WO2022208370A1 - Fused heterocyclic compounds and their use as pest control agents - Google Patents

Fused heterocyclic compounds and their use as pest control agents Download PDF

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Publication number
WO2022208370A1
WO2022208370A1 PCT/IB2022/052918 IB2022052918W WO2022208370A1 WO 2022208370 A1 WO2022208370 A1 WO 2022208370A1 IB 2022052918 W IB2022052918 W IB 2022052918W WO 2022208370 A1 WO2022208370 A1 WO 2022208370A1
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group
alkyl
haloalkyl
cycloalkyl
alkenyl
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PCT/IB2022/052918
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French (fr)
Inventor
Narasimha Murthy Cheemala
Rohit NIRANIYA
Gagan Kukreja
Ankur Aniruddh UPADHYAY
Alexander G. M. KLAUSENER
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Pi Industries Ltd.
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Publication of WO2022208370A1 publication Critical patent/WO2022208370A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems

Definitions

  • the present invention relates to fused heterocyclic compounds. More particularly, the present invention relates to fused heterocyclic compounds of formula (I) and a process for the preparation thereof. The present invention further relates to the use of fused heterocyclic compounds of formula (I) as pest control agents.
  • BACKGROUND OF THE INVENTION The currently available modern insecticides and acaricides must satisfy many requirements, for example regarding spectrum and level of efficacy, long lasting activity, beneficial side effects, and possible use thereof.
  • the present invention provides a fused heterocyclic compound of formula (I) or agriculturally acceptable salts, isomers/structural isomers, stereoisomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof.
  • Q, Z, Y, m, R 1 , A, G 1 , G 2 , D and E are as defined in the detailed description.
  • the present invention provides a process for preparing a compound of formula (I) or agriculturally acceptable salts thereof.
  • the present invention provides a composition for controlling or preventing invertebrate pests comprising a biologically effective amount of a compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries.
  • the composition comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients.
  • the present invention provides the use of a compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereoisomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides, compositions or combinations thereof, for combating invertebrate pests in agricultural crops and/or horticultural crops or parasites on animals.
  • 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 a compound of formula (I) or agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N- oxides thereof and a composition or combination thereof.
  • a compound of formula (I) or agriculturally acceptable salts isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N- oxides thereof and a composition or combination thereof.
  • 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.
  • 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 "invertebrate pest” includes arthropods, gastropods and nematodes of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes snails, slugs and other Stylommatophora.
  • nematode refers to a living organism of the Phylum Nematoda.
  • helminths includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Tematoda), acanthocephala and tapeworms (Cestoda).
  • agronomic refers to the production of field crops such as for food, feed and fiber and includes the growth of corn, 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, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruits (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).
  • 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 product, 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.
  • Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e.
  • 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.
  • 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 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).
  • 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.
  • 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 C 1 to C 24 alkyl, preferably C 1 to C 15 alkyl, more preferably C 1 to C 10 alkyl, most preferably C 1 to C 6 alkyl.
  • alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1- methylpropyl and l-ethyl-2-methylpropyl or the different isomers.
  • 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
  • other radicals for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.
  • alkenyl used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably C2 to C15 alkenes, more preferably C2 to C10 alkenes, most preferably C2 to C6 alkenes.
  • 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, l-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-1-propenyl, 1,2-dimethyl-2 -propenyl, 1-ethyl-1-propenyl,
  • 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.
  • Non-limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l- methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, l-methyl-3-pentynyl, 1- methyl-4-pentynyl, 2-methyl-3-pentynyl
  • alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere.
  • alkynyl can also include moieties comprised of multiple triple bonds such as 2,5- hexadiynyl.
  • cycloalkyl means alkyl closed to form a ring. Non-limiting examples include but are not limited to cyclopropyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere.
  • 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.
  • cycloalkynyl means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. Non-limiting examples include but are not limited to cyclopropynyl, cyclopentynyl and cyclohexynyl.
  • cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere.
  • cycloalkoxy "cycloalkenyloxy” and the like are defined analogously. Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl etc., unless specifically defined elsewhere.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • haloalkyl 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.
  • haloalkyl include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2- trichloroethyl, pentafluoroethyl, 1,1-dichlor
  • haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.
  • haloalkenyl haloalkynyl
  • haloalkoxy means straight-chain or branched alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above.
  • Non-limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro- 2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trifluoroprop-2-oxy.
  • haloalkylthio means straight-chain or branched alkylthio groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above.
  • Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and l,l,l
  • haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere.
  • haloalkylsulfinyl include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O).
  • haloalkylsulfonyl include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2.
  • 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 S(O)2
  • oxa means O.
  • alkoxy used either alone or in compound words include C1 to C24 alkoxy, preferably C1 to C15 alkoxy, more preferably C1 to C10 alkoxy, most preferably C1 to C6 alkoxy.
  • alkoxy examples 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.
  • alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1- ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutyl
  • Halocycloalkyl halocycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, and the like, are defined analogously to the above examples.
  • alkylthioalkyl denotes an alkylthio substitution on alkyl.
  • alkylthioalkyl include -CH2SCH2, -CH2SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2.
  • alkylthioalkoxy denotes an alkylthio substitution on alkoxy.
  • cycloalkylalkylamino denotes a cycloalkyl substitution on alkyl amino.
  • alkoxyalkoxyalkyl alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl and the like, are defined analogously to "alkylthioalkyl” or cycloalkylalkylamino.
  • alkoxycarbonyl is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as a part of a composite substituent, for example cycloalkylalkoxycarbonyl and the like, unless specifically defined elsewhere.
  • alkoxycarbonylalkylamino denotes an alkoxy carbonyl substitution on alkyl amino.
  • Alkylcarbonylalkylamino denotes alkyl carbonyl substitution on alkyl amino.
  • alkylthioalkoxycarbonyl, cycloalkylalkylaminoalkyl and the like are defined analogously.
  • alkylsulfinyl include but are not limited to methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2- methylpropylsulphinyl, 1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl, 1-methylpentylsulphinyl, 2- methylpentylsulphinyl, 3-methylpentylsulfonyl,
  • arylsulfinyl includes Ar-S(O), wherein Ar can be any carbocycle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
  • alkylsulfonyl include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl, 1-methylpropylsulphonyl, 2- methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1-methylpentylsulphonyl, 2- methylpentylsulphonyl, 3-methylpentylsulfonyl,
  • arylsulfonyl includes Ar-S(O)2, wherein Ar can be any carbocycle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere. "Alkylamino”, “dialkylamino”, and the like, are defined analogously to the above examples.
  • carrier or “carbocyclic” or “carbocyclyl” include an “aromatic carbocyclic ring system” and a “nonaromatic carbocylic ring system” 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).
  • Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbornyl and the like.
  • Non limiting examples of aromatic carbocyclic ring systems are phenyl, naphthyl and the like.
  • 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.
  • 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.
  • aryl also comprises “aralkyl” refers to aryl hydrocarbon radicals including an alkyl portion as defined above.
  • Examples include benzyl, phenylethyl, and 6-napthylhexyl.
  • 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.
  • 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.
  • heterocycle indicates that the Huckel rule is satisfied and the term “non-aromatic” indicates that the Huckel rule is not satisfied.
  • non-aromatic heterocycle or “non-aromatic heterocyclic” means three- to fifteen-membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to 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) oxetanyl, oxiranyl, aziridinyl, azetidinyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidin
  • heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere.
  • heteroaryl or "aromatic heterocyclic” means 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 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
  • 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) pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indolyl, benzimidazolyl, indazolyl, benzofuranyl, benzothiophenyl, benzothiazolyl, and benzoxazolyl; benzofused 6-membered heteroaryl which contains one to three nitrogen atoms: for example
  • Bicyclic 5-6 heteroaryl systems with one bridgehead (ring junction) nitrogen atom containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom for example (but not limited to) imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, [1,2,4]triazolo[1,5-a]pyrimidine, [1,2,4]triazolo[1,5- b]pyridazine, [1,2,4]triazolo[1,5-a]pyrazine, [1,2,4]triazolo[1,5-a]pyridine, imidazo[1,2-c]pyrimidine, imidazo[1,2-b]pyridazine, [1,2,4]triazolo[1,5-c]pyrimidine, 1-methyl-1H-indole, imidazo[1,2-a]pyrazine, pyrazolo[1,5-a]pyridine and [1,2,4]triazolo[4,3-a]pyr
  • 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.
  • Hydrotrialkylsilyl denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different.
  • 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.
  • trialkylsilyloxy denotes a trialkylsilyl moiety attached through oxygen.
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • haloalkylsufonylaminocarbonyl, alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously.
  • 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.
  • C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C2 alkoxyalkyl designates CH3OCH2
  • C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2
  • 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.
  • inventive compound 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 Z isomers, 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.
  • 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.
  • 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.
  • plant includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, ferns, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis.
  • 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.
  • 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, corn, soybean, other leguminous plants, rape, sugar cane or oil palm; tobacco; nuts; coffee; tea;
  • the plant for the purpose of the present invention includes but is not limited to cereals, corn, 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 for use of human and animals.
  • plant parts is understood to mean all parts and organs of plants above and below the ground.
  • 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, auxillary buds, meristems, nodes and internodes.
  • 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.
  • compositions optionally comprising other compatible compounds to a plant or a plant material or locus thereof include application 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.
  • applied means adhered to a plant or plant part either physically or chemically including impregnation.
  • WO2020/250183 describes the fused heterocyclic compounds and their use as pest control agents in which Q is described as a fused bicyclic ring.
  • the present invention provides the compound of formula (I) wherein Q is monocyclic 6-membered heterocyclic ring.
  • the present invention provides a compound of formula (I), ormu a ( ) wherein, R 1 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C3-C8-cycloalkyl-C1-C6-alkyl; Y is independently selected from O or NR Y ; R Y is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-halo
  • the following embodiments provide definitions, including preferred definitions, for substituents with reference to the compounds of formula (I) according to the 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 document. Further, embodiments of this disclosure described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula (I) but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula (I).
  • the compound of formula (I) is represented by a compound of formula (IA); wherein, R 1 , Q, Z, A, G 1 , G 2 , E and m have the meanings as described above.
  • the compound of formula (I) is represented by a compound of formula (IB); Formula (IB) wherein, R 1 , Q, Z, R Y , A, G 1 , G 2 , E and m have the meanings as described above.
  • One embodiment of the present invention provides the compound of formula (I); wherein, Z is direct bond and R 1 , Q, Y, A, G 1 , G 2 , E and m are same as defined herein above.
  • Another embodiment of the present invention provides a compound of formula (I); wherein, Z represent O (oxygen atom) and R 1 , Q, Y, A, G 1 , G 2 , E and m are as defined herein above.
  • the present invention provides a compound of formula (I), wherein the fused ring system DE contains at least one nitrogen atom.
  • Q is selected from Q1, Q2 or Q3.
  • Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom represented as Q1, A 3 are independently selected from C or N provided that at least one of A 1 , A 2 , A 3 is not nitrogen at the same time; the symbol represents the point of attachment to ring DE.
  • Q1 is selected from Q1a, Q1b, Q1c, Q1d and Q1e.
  • Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, Z represents O (oxygen atom); and said Q is attached through Z to the ring DE.
  • Q1 represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, Z represents O (oxygen atom); and said Q1Z group is selected from: ; wherin QZ group is optionally substituted with one or more R 3 .
  • Q represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom and is represented as Q2 ; p is optionally substituted with one or more R 3 ; the symbol represents the point of attachment to the ring DE.
  • Q2 represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom, Z represents a direct bond and said Q2 is attached to ring DE through nitrogen atom.
  • Q2 is selected from: wherein the symbol represent the point of attachment to the ring DE.
  • Q2 represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom
  • Z represents a direct bond and said Q2 is attached to ring DE through a nitrogen atom.
  • Q2 is selected from: Q2a, Q2c, Q2d and Q2f, more preferably from Q2a and Q2c.
  • Q represents a six membered non-aromatic partially unsaturated heterocyclic ring containing at least one nitrogen atom and being represented as Q3 p Q3 is optionally substituted with one or more R 3 ; the symbol represents the point of attachment to the ring DE.
  • Q3 is selected from: tachment t o e r ng .
  • Q3 is selected from Q3a, Q3b, Q3c and Q3f
  • R 5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C3-C8-cycloalkyl and C3-C8-cycloalkyl-C1-C6- alkyl; wherein R 5 is optionally substituted with one or more halogen.
  • Q3 is selected from Q3aa, Qba, Q3ca and Q3fa. .
  • Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, and Z represents a direct bond.
  • the more preferred Q is selected from Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c and Q3f.
  • the fused ring system DE is selected from the group consisting of DE-1 to DE- 15: whe e , e oes e po o a ac e o e g a e o es e po o a achment to the group -S(Y) m R 1 .
  • the DE ring is selected from DE-1, DE-7 and DE-11, even more preferably from DE-7.
  • R 3 is selected from halogen, -S(O) 0-2 C 1 -C 6 -haloalkyl, -S(O)(NR Y ) C 1 -C 6 -haloalkyl, C 1 -C 4 haloalkyl and C 1 -C 4 haloalkoxy,
  • R 3 is selected from C 1 -C 4 haloalkyl, preferably C 1 -C 2 haloalkyl, and more preferably is CF 3 .
  • R 3 is selected from C 1 -C 4 haloalkoxy, C 2 -C 4 haloalkenyloxy, preferably C 1 -C 3 haloalkoxy, and more preferably is -O-CH 2 CF 2 CF 3 .
  • R 3 is -S(O) 0-2 C 1 -C 6 -haloalkyl, more preferably -S(O) 0-2 CF 3
  • the compound of formula (I) is represented by a compound of formula (I-1); wherein, R 1 is C1-C6 alkyl or C3-cycloalkyl; Y is NR Y or O; R Y is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl; Z represents a direct bond or O; Q represents a 6-membered heterocyclic ring which may optionally be substituted by one or more groups of R 3 ; R 3 is selected from the group consisting of halogen, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C4- cycloalkyl, C 1
  • the compound of formula (I-1); wherein, -S(Y) m R 1 group represents, S(O) 0-2 R 1 or S(O)( NR Y ) R 1 ; preferably S(O) 2 C 1 -C 3 (cyclo)alkyl; wherein more preferred (cyclo)alkyl is selected from ethyl, isopropyl and cyclopropyl.
  • R 1 is C1-C3 alkyl or C3 cycloalkyl
  • Z is direct bond or O
  • Q is selected from Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c or Q3f
  • R 3 is selected from halogen, -S(O)0-2C1-C4-haloalkyl, -S(O)(NR Y ) C1-C6-haloalkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; more preferably C1-C4 haloalkoxy
  • R 11 is selected from halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C2-C6-haloalkeny
  • the compounds of formula (I-1), wherein R 11 is selected from CHF 2 , CF 3 , CH 2 CF 3 , -NHCH 2 CH 3 , -N(CH 3 )CH 2 CH 3, -NH(C(CH 3 ) 3 ), -N(CH 3 )(C(CH 3 ) 3 ), -N(CH 3 )COCH 3 , - N(CH 3 )CO(cyclopropyl), -N S(O)(CH 3 ) 2 , cyclopropyl, cyanocyclopropyl, 3-chloro-pyrazol-1-yl, 3- trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl, pyrimidin-2-yl, pyridazyn-2-yl or pyridazyn-3-yl; wherein R 11 is optionally substituted with F, Cl, CN, methyl or methoxy.
  • the compounds of formula (I-1), wherein -S(Y)mR 1 group represents, S(O)( NR Y ) R 1 ;
  • R Y is hydrogen or C1-C3-alkyl, more preferably hydrogen, methyl, ethyl or isopropyl; and
  • R 1 is C1- C3-alkyl; more preferably R 1 is methyl, ethyl, isopropyl; most preferably R 1 is ethyl.
  • particularly compound of formula (I) is selected form 2-(ethylthio)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one; 7-bromo-2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylsulfonyl)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylthio)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine;
  • the term (un)substituted is referred as said groups are unsubstituted, or said groups are independently substituted with the substitutents selected from the group consisting of halogen, cyano, C 1 -C 6 -alkyl, C 2 - C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy and -S(O)0-2C1-C6-alkyl.
  • the compounds of the present invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • 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 to 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.
  • An anion part of the respective salt, in case the compound of formula (I) is represented by a cationic moiety or capable of forming a cationic moiety, can be inorganic or organic.
  • the cation part of the respective salt in case the compound of formula (I) is an ionic compound or is capable of forming an anion can be inorganic or organic.
  • inorganic anion parts of the respective salt include but are not limited to chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, hydrogen carbonates and hydrogen sulfate.
  • organic anion parts of the respective salt include but are not limited to formate, alkanoates, carbonates, acetates, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, maleate, citrates, benzoates, cinnamates, oxalates, alkylsulphates, alkylsulphonates, arylsulphonates aryldisulphonates, alkylphosphonates, arylphosphonates, aryldiphosphonates, p-toluenesulphonate, and salicylate.
  • inorganic cation parts of the respective salt include but are not limited to alkali and alkaline earth metals.
  • organic cation parts of the respective salt include but are not limited to pyridinium, methyl ammonium, imidazolium, benzimidazolium, histidinium, phosphonium, tetramethyl ammonium, tetrabutylammonium, cholinium and trimethylamonium.
  • the present invention provides a compound of formula (I), or an agrochemically acceptable salt, 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.
  • Non-crystalline forms include embodiments which are solids such as waxes, gums and glassy species 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).
  • 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.
  • 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.
  • beneficial effects e.g., suitability for preparation of useful formulations, improved biological performance
  • 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.
  • the present invention provides a process for preparing the compound of formula (I) or agriculturally acceptable salts thereof.
  • the compounds of the present invention as defined by formula (I) and/or in table (I) may be prepared, in a known manner, in a variety of ways as described in the schemes 1-15.
  • the compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I).
  • a compound of general formula (I) wherein Z represents a direct bond, represented by formula (IAa), may be obtained from a compound of formula (Int-2b) under standard Suzuki cross coupling conditions with boronic acids or a boronic ester compound of formula (Int-1d).
  • the Suzuki cross coupling reaction can be catalyzed by a palladium based catalyst, including but not limited to 1,1′- bis(diphenylphosphino)ferrocene]dichloropalladium(II) or tetrakis(triphenylphosphine) palladium(0), in a suitable solvent, for example tetrahydrofuran (THF), N,N’,dimethylformamide (DMF), 1,2- dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of tetrahydrofuran (THF)/water, 1,2- dimethoxyethane/water, 1,4-dioxane/water, or the like.
  • a suitable solvent for example tetrahydrofuran (THF), N,N’,dimethylformamide (DMF), 1,2- dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of t
  • the reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate or potassium phosphate.
  • a base for example potassium carbonate, cesium carbonate or potassium phosphate.
  • the reaction temperature can preferentially range from ambient temperature (20 °C) to the boiling point of the reaction mixture, or under microwave irradiation at a temperature between 70 °C and 150 °C to produce the compound of formula (I) as cited in the literature, see for example Chem. Soc. Rev. 2014, 43, 412-443 or in WO2014070978.
  • the compound of formula (Int-2b) may be coupled with a hetroaryl tin compound of formula (Int-1d), in the presence of a catalyst such as bis(triphenylphosphine)palladium(II)dichloride, tetrakis(triphenylphosphine)palladium(0), 1,1’-bis(diphenylphosphino)ferrocene palladium(II)chloride, tris(dibenzylideneacetone)dipalladium(0), and palladium(II)acetate; nickel catalysts such as bis(cyclooctadiene)nickel(0) and nickel(II) chloride; and copper catalysts such as copper(I) iodide and copper(I) chloride, in the presence of a base such as alkali metal hydrides, alkali metal carbonates, and organic bases, in a suitable solvent such as acetonitrile, tetrahydrofuran (THF), N
  • a ligand and/or an inorganic halogenated compound may be added to the reaction as needed.
  • ligands to be used in the reaction include triphenylphosphine, Xantphos, 2,2’-bis(diphenylphosphino)-1,1’- binaphthyl, 1,1’-bis(diphenylphosphino)ferrocene, 2-(dicyclohexylphosphino)-2’, 4’, 6’-triisopropyl-1,1’- biphenyl, 2-aminoethanol, 8-hydroxyquinoline and 1,10-phenanthroline.
  • Scheme-2 represents the process for preparing compounds of formula (Int-2b).
  • Compounds of formula (Int-2) which can be prepared by literature methods (WO2020/250183) can be further converted into compounds of formula (22) under Curtius rearrangement conditions.
  • This rearrangement can be performed using sodium azide or diphenyl phosphorazidate in the presence of a base such as triethylamine or diisopropylethylamine, in a solvent such as methanol, ethanol, tert-butyl alcohol or benzyl alcohol, carried out at temperatures ranging from about 25 and 150 °C.
  • a base such as triethylamine or diisopropylethylamine
  • a solvent such as methanol, ethanol, tert-butyl alcohol or benzyl alcohol
  • R” Me or Et
  • basic conditions can be implemented such as lithium hydroxide or sodium hydroxide or potassium hydroxide, in the presence of methanol or ethanol or 2-methylpropanol, at temperatures ranging from 0 and 120 °C.
  • Deprotection can be carried out under hydrogenation such as by hydrogen gas in the presence of palladium metal such as palladium on charcoal or palladium(II) hydroxide, in the presence of methanol or ethanol or ethylacetate at pressure, usually ranging from 1 to 10 bar at 25 °C.
  • the amine derivative (Int-2a) can be converted into a compound of formula (Int-2b), where X is a halogen, by diazotation using e.g.
  • Scheme-3 s of general formula (Int-1d) from appropriate halides or triflates of compounds of formula (Int-1a) by reaction with a reagent such as hexamethylditin or triethyltin chloride in presence of a catalyst such as tetrakis(triphenylphosphine)palladium(0), in the presence of a base such as potassium carbonate, in a suitable solvent such as N,N’,dimethylformamide (DMF), or a mixture of two or more appropriate solvents, at a temperature between 25 °C and the reflux temperature of the respective solvent, or under microwave irradiation at a temperature between 70 °C and 160 °C.
  • a reagent such as hexamethylditin or triethyltin chloride
  • a catalyst such as tetrakis(triphenylphosphine)palladium(0)
  • a base such as potassium carbonate
  • a suitable solvent such as N,N’,
  • compounds of general formula (Int-1d) may be obtained from compounds of formula (Int- 1a) by reacting with a reagent such as n-butyllithium in a suitable aprotic solvent such as tetrahydrofuran (THF) at temperature between -100 °C and 25 °C and then reacted with a reagent such as hexamethylditin or triethyltin chloride in a suitable aprotic solvent such as tetrahydrofuran (THF) at temperature between - 100 °C and 50 °C.
  • a reagent such as n-butyllithium in a suitable aprotic solvent such as tetrahydrofuran (THF) at temperature between -100 °C and 25 °C
  • a reagent such as hexamethylditin or triethyltin chloride
  • THF tetrahydrofuran
  • This reaction may be catalyzed by nickel(II)chloride hexahydrate, anhydrous nickel(II)chloride, nickel(II)iodide, nickel(II) chloride ethylene glycol dimethyl ether complex, bis(triphenylphosphine)nickel(II) dichloride, or bis(1,5- cyclooctadiene)nickel(0), in the presence of an equivalent to excess amount of zinc or manganese metal.
  • a ligand can be used in case it is needed or recommended to support the respected catalyst.
  • Examples of the ligand include but are not limited to 1,10-phenanthroline, 4,7-dimethyl-1,10-phenathroline or 4,7- dimethoxy-1,10-phenathrolin 3,4-dimethyl-1,10-phenanthroline or 2,2'-bipyridine or 4,4'-dimethyl-2,2'- bipyridine or 4,4'-ditert-butyl-2,2'-bipyridine or triphenyl phosphine or 1,2-bis(diphenylphosphino)ethane or 1,3-bis(diphenylphosphino)propane. Any additive may or may not be required in the above reaction.
  • examples of the additive include but are not limited to sodium or potassium iodide, lithium chloride, lithium methoxide, trimethylchlorosilane or magnesium (II) chloride.
  • the reaction can be carried out in an appropriate solvent such as N,N-dimethyl formamide, N,N-dimethylacetamide, N- methyl-2-pyrrolidone or N,N′-Dimethylpropyleneurea (DMPU), at temperatures ranges between 25 °C and 100 °C.
  • DMPU N,N′-Dimethylpropyleneurea
  • a compound of formula (IAa-1) can be prepared by reacting a compound of formula (Int-2b) with a cyclic amide compound of formula (Q2) (which can be prepared by literature procedure as described in US2019/0327970).
  • the above mentioned conversion can be performed using a base such as alkalimetal carbonate, alkalimetal hydride, sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyldisilazane, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4- (dimethylamino)pyridine, in an appropriate solvent such as acetonitrile, tetrahydrofuran, dimethyl slufoxide, N,N-dimethylformamide, N,N-dimethyl acetamide, or N-methyl-2-pyrrolidone, at a temperature range between 25 °C and 120 °C.
  • a base such as alkalimetal carbonate, alkalimetal hydride, sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyldisilazane, diisopropylethylamine, pyridine, 1,8-d
  • a compound of formula (IAa-1) can be prepared by metal catalysis.
  • the metal catalyst include but are not limited to copper catalysts such as copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I)oxide, trifluromethanesulfonicacid copper(I)salt benzene complex, or 2- thiophenecarboxylic acid copper(I)salt; and nickel catalysts such as bis(cyclooctadiene)nickel(0) and nickel chloride, and a ligand, for example 1,10-phenanthroline, 8-hydroquinoline, trans-1,2- cyclohexanediamine, trans-1,2-bis(methylamino)cyclohexane, N,N-dimethylethylenediamine, 2,2'- bipyridine, 2-aminoethanol, triphenyl phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3- bis(diphenylpho
  • appropriste bases include but are not limited to alkalimetal carbonates, diisopropylethylamine, pyridine, 1,8-Diazabicyclo[5.4.0]undec-7-ene or 4-(dimethylamino)pyridine, in an appropriate solvent such as acetonitrile, dimethyl slufoxide, N,N- dimethylformamide, N,N-dimethyl acetamide, or N-methyl-2-pyrrolidone, at temperatures ranges between 25 °C and 120 °C.
  • Scheme-6 w ere n Q, , , , , , an m ave the meanings as described above.
  • Compounds of formula (IAa-2) can be obtained by reacting a compound of formula (Int-2b) with a hydroxy compound of formula (Int-1c). The reaction is usually carried out in the presence of a base such as alkali metal carbonates and alkali metal hydrides, in an appropriate solvent including but not limited to acetonitrile, tetrahydrofuan N,N-dimethylformaide, at temperatures ranges between 0 and 150 °C.
  • a base such as alkali metal carbonates and alkali metal hydrides
  • an appropriate solvent including but not limited to acetonitrile, tetrahydrofuan N,N-dimethylformaide, at temperatures ranges between 0 and 150 °C.
  • Compounds of formula (Int-3c) can be prepared following methods as described in WO2005/018557, WO2009/149188, WO2010/104818, and WO2015/153304.
  • compounds of formula (IAa-2) can be prepared by reacting a hydroxy derivative (Int-1c) and a compound of formula (Int-2b), in the presence of a metal catalyst and a base.
  • the metal catalyst include but are not limited to copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I) oxide, copper(I)trifluoromethanesulfonate benzene complex, and tetrakis (acetoform) copper (I), copper(I) 2-thiophene carboxylate; nickel catalysts such as bis (cyclooctadien) nickel (0) and nickel(II)chloride, preferably supported by a ligand such as 1,10-phenanthroline, 8-hydroquinoline, trans- 1,2-cyclohexanediamine, trans-1,2-bis(methylamino)cyclohexane, N,N-dimethylethylenediamine, 2,2'- bipyridine, 2-amino
  • Examples of the base include but are not limited to alkalimetal carbonates, alkalimetal hydrides, triethylamine, diisopropylethylamine, pyridine and 4- (dimethylamino) pyridine.
  • Appropriate solvents for carrying out these reactions are such as acetonitrile, tetrahydrofuan, N,N-dimethylformaide, or aromatic hydrocarbons. Typical temperatures for carrying out these reactions are between 0 and 130 ° C.
  • Scheme-7 wherein Q, Z, R 1 , R Y , A, G 1 , G 2 , E, and n have the meanings as described above.
  • Compounds of formula (3) can be formed by reacting a compound of formula (Int-1a) with a compound of formula (2) (R” is preferably lower alkyl such as methyl, ethyl or tert-butyl ester in this case) in the presence of a base such as alkali metal carbonates (such as sodium, potassium or cesium carbonate) (hereinafter, collectively referred to as alkali metal carbonates); and alkali metal hydrides such as sodium or potassium hydride (hereinafter, collectively referred to as alkali metal hydrides), sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyl disilazane, in an appropriate solvent such as tetrahydrofuran, dioxane, acetonitrile, dimethylsulfoxide, N,N-dimethylfromamide, or N,N- dimethylacetamide, at temperatures between 0 and 120 °C.
  • a base such as alkali metal carbonates (such as
  • compounds of formula (4) can be prepared under metal catalysis in the presence of a base.
  • Applicable metal catalysts are such as palladium(II)acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3 optionally in form of its chloroform adduct; tetrakis(triphenylphosphine)palladium(0); copper catalysts such as copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I)oxide, trifluromethanesulfonicacid copper(I)salt benzene complex , 2-thiophenecarboxylic acid copper(I)salt, and a ligand, for example triphenylphosphine, 1,1’- bis(diphenylphosphino)ferrocene, XantPhos ((
  • Compounds of formula (4) can be obtained from a compound of formula (3) by a decarboxylation reaction carried out under basic or acidic conditions converting the alkyl ester group.
  • Acidic conditions can be realized by the use of reagents such as p-toluenesulfonic acid, trifluroacetic acid, hydrochloric acid; basic conditions can be realized by the use of lithium, sodium or potassium hydroxide.
  • Appropriate solvents for conducting such reactions are such as acetonitrile, dioxane, dimethylsulfoxide, dichloromethane, 1,2-dichloroethane, methanol, ethanol, 2-propanol and water, at temperature ranges between 25 °C and 150 °C.
  • compounds of formula (4) can be formed in a single step, by reacting a compound of formula (1) with acetonitrile in the presence of a base.
  • a base examples include such as n-butyl lithium or t-butyl lithium, methyllithium, or phenyl lithium, or lithium, sodium or potassium hexamethyl disilazane.
  • Appropriate solvents for such reactions are such as tetrahydrofuran, methyl tetrahydrofuran, diethyl ether, at temperatures between -78 and 0 °C.
  • Scheme-9 A process for the synthesis of compounds of formula (Q-Int-1aa) is depicted in scheme-9.
  • (Organo sulfanyl) alkenes of formula (5) can be formed by reacting cyano compounds of formula (4) with CS 2 in the presence of a base such as alkalimetal carbonates, alkalimetal hydrides, lithium, sodium or potassium hexamethyl disilazane, sodium or potassium hydroxide, in an appropriate solvent such as tetrahydrofuran, acetonitrile and N,N-dimethylfromamide, at temperatures between 0 and 50 °C.
  • a base such as alkalimetal carbonates, alkalimetal hydrides, lithium, sodium or potassium hexamethyl disilazane, sodium or potassium hydroxide
  • an appropriate solvent such as tetrahydrofuran, acetonitrile and N,N-dimethylfromamide, at temperatures between 0 and 50 °C.
  • the compounds of formula (5) can be cyclized to the aminopyrazole derivatives (6) using hydrazine. Such methods are described in the literature, for example in Russian Journal of Organic Chemistry, 2014, 50(3), 412-421.
  • the respective aminopyrazole derivatives can be converted in to the compounds of formula (8) using reagents such as (7) under acidic medium using acids such as acetic acid, or p-toluenesulfonic acid, in an appropriate solvent such as ethanol, 2-propanol, toluene, xylene, N,N-dimethylformamide, at temperatures between 80 and 130 °C. (Journal of Medicinal Chemistry, 58(18), 7140-7163; 2015).
  • the conversion of compounds of formula (8) into compounds of formula (9) can be carried out in a solvent and in the presence of a halogenating agent, in the presence or absence of a base.
  • a solvent include but are not limited to acetonitrile, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, N,N- dimethylformamide and the like.
  • halogenating agents include but are not limited to phosphorous oxychloride, thionyl chloride, phosphorous pentachloride, oxalyl chloride, and the like.
  • Examples of base include but are not limited to N,N-dimethylaniline, diisopropylethylamine, N- methylmorpholine and the like.
  • the reaction can be carried out at temperatures ranging from 50-200 °C.
  • Oxidizing agents such as m-chloroperoxybenozic acid (mCPBA), hydrogenperoxide/glacial acetic acid, hydrogenperoxide/trifluroacetic acid, hydrogenperoxide/potassium permanganate, hydrogenperoxide/p- toluenesuflonylimidazole, urea hydrogen peroxide/ trifluroacetic acid, oxone, sodium periodate, sodium hypochlorite and other orgnaic peracids and the like can be used for this.
  • solvents useful in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform: alcohols such as mehnaol and ethanol and the mixtures thereof.
  • solvents being useful in this process include methanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, N,N-dimethylformamide, and the like.
  • the respective reaction can be carried out at temperatures ranging from about 50 °C to about 150 °C.
  • Such reactions are well known, and also alternative reactions are well described in the literature, for example in J. Org. Chem. 2007, 72, 1046, or in WO2018081417.
  • Halogenation of compounds of formula (12) using phosphorous oxychloride or phosphorous oxybromide allows to obtain compounds of formula (13) as described in WO201108689, for example.
  • the compounds of formula (Q-Int-1ab) can be obtained from (13) in a similar manner as described in step-5 of scheme-9.
  • Bisacetal protected malonaldehyde compounds of formula (14) can be activated by halogenation with a halogenating agent, such as bromine, iodine, chlorine, N-bromosuccinimide, N-iodosuccinimide, or N- chlorosuccinimide under acidic conditions, established by utilizing an acid independently selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, tetrafluoroboric acid or p- toluenesulfonic acid in a suitable solvent, e.g., water, to obtain a halogenated aldehyde, such as chloro-, iodo- or bromomalonaldehyde
  • step 2 compounds of formula (15) can be reacted with pyrazole derivatives of formula (6) under suitable condensation conditions to obtain compounds of formula (17).
  • the solvent being useful during this step include but are not limited to dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and to mixtures thereof.
  • the reaction can be carried out at temperatures ranging from about 50 °C to about 150 °C.
  • compounds of formula (17) can also be prepared by cyclization of pyrazole derivatives of formula (6) with commercially available 2-halo-malonaldehydes of formula (16) under acid catalyzed conditions.
  • acids include but are not limited to acetic acid, sulfonic acids (e.g., PTSA), sulfuric acid, and hydrochloric acid.
  • solvents being useful in this step include but are not limited to methanol, ethanol, isopropanol, ethylene glycol, and the like.
  • the respective reactions can be carried out at temperatures ranging from about 0 °C to about 150 °C. (J. Het. Chem.1974, 44, 51).
  • the Suzuki cross coupling reaction can be catalyzed by a palladium based catalyst, including but not limited to 1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or tetrakis(triphenylphosphine) palladium(0), in a suitable solvent as for example tetrahydrofuran (THF), N,N′-dimethylformamide (DMF), 1,2-dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of tetrahydrofuran (THF)/water, 1,2-dimethoxyethane/water, 1,4-dioxane/water, or the like.
  • a suitable solvent as for example tetrahydrofuran (THF), N,N′-dimethylformamide (DMF), 1,2-dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of
  • the reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate or potassium phosphate.
  • a base for example potassium carbonate, cesium carbonate or potassium phosphate.
  • the reaction temperature can preferentially range from ambient temperature (20 °C) to the boiling point of the reaction mixture as precedented in the literature, see for example Chem. Soc. Rev.2014, 43, 412-443 or in WO2014070978.
  • scompounds of formula (Q-1aa) can also be formed by subjecting corresponding sulfides to Suzuki conditions mentioned as above, and followed by oxidation under any of the given conditions for step-5 in scheme-9.
  • the reaction may be catalyzed by a palladium based catalyst, involving for example bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3; optionally in form of its chloroform adduct), or palladium(II)acetate, and a ligand, for example XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen-4yl)diphenylphosphane), XPhos (2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), RuPhos (2-Dicyclohexylphosphino-2′,6′- diisopropoxybiphenyl), or BINAP (2,2’-bis(diphenylphosphino)-1,1’-bin
  • reaction temperature can prefrentially range from room temperaturte to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation.
  • Such reactions, and alternative conditions such as iron or copper catalysis, have been described, for example, in WO2018/099812.
  • Scheme-14 Wherein Q, R 1 , R 5 , R 6 , X, Y, and m have the meanings as described above
  • Compounds of formula (Q-1ac) can be prepared by reacting compounds of formula (Q-Int-1aa/1ab/1ac) with a reagent of formula (20), wherein R 5 and R 6 are as defined in formula (I), in the presence of a base.
  • Examples of the base include but are not limited to sodium carbonate, potassium carbonate or cesium carbonate, sodium tert-butylate or potassium tert-butylate, diisopropylethylamine, triethylamine or DBU, in a solvent selected from tetrahydrofuran, N,N-dimethylformamide or acetonitrile.
  • the reaction can be carried out at temperatures ranging from about 25 to about 130 °C.
  • compounds of formula (Q-1ac) can be prepared by reacting compounds of formula Q-Int- 1aa/1ab/1ac), under catalyzed conditions mentioned in step-1 of scheme-13.
  • Compounds of formula (Q-1ad) can be prepared by reacting compounds of formula (Q-Int-1aa/1ab/1ac) with a reagent of formula (21), wherein R 4 is as defined in formula X, in the presence of a base.
  • a base include but are not limited to alkalimetal hydrides, alkalimetal carbonates, sodium or potassium tert-butylate, diisopropylethylamine, triethylamine or DBU, thereby using a solvent such as tetrahydrofuran, N,N-dimethylformamide or acetonitrile.
  • reaction can be carried out at temperatures ranging from about 25 to about 130 °C.
  • compounds of formula (Q-1ad) can be prepared from compounds of formula (Q-Int- 1aa/1ab/1ac) using copper catalyzed conditions.
  • Copper based catalyst used for this purpose involve for example copper(I) iodide, copper(I) bromide, copper(I) chloride or copper(I) acetate and a ligand, for example 1,10-phenanthroline, 4,7-dimethyl-1,10-phenathroline, 4,7-dimethoxy-1,10-phenathrolin, 4,7- diphenyl-1,10-phenathrolin, or L-proline, in the presence of a base, like sodium carbonate, potassium carbonate or cesium carbonate, or sodium or potassium tert-butylate, in a solvent or a solvent mixture as for example dioxane, 1,2-dimethoxyethane, toluene, acetonitrile, or N,N-dimethylformamide preferably under inert atmosphere.
  • a base like sodium carbonate, potassium carbonate or cesium carbonate, or sodium or potassium tert-butylate
  • solvent or a solvent mixture as for example dioxane
  • the reaction temperature can range preferably from room temperature to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation.
  • the present invention provides a process for the preparation of compounds of formula (I) or salts thereof.
  • the compounds of formula (I) including their stereoisomers, salts, and N-oxides, and their precursors in the mentioned synthesic processes, 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 respective precursors, or by customary modifications of the synthesis routes described.
  • 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.
  • 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.
  • purification can also be carried out by recrystallization or digestion.
  • individual target compounds of formula (I) cannot be obtained by the routes described above, they can be prepared by derivatization of other compounds of formula (I).
  • a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g., under the action of light, acids or bases). Such conversions may also take place during or after use, e.g., during the treatment of plants or within the treated plant, or even in the harmful fungus to be controlled.
  • Table A-1 provides 28 compounds A-1.001 to A-1.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • A-1.015 is initions of R 11 Sr.
  • Table A-2 provides 28 compounds A-2.001 to A-2.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-3 provides 28 compounds A-3.001 to A-3.028 of formula (I-1) wherein Q , Z is 10 direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-4 provides 28 compounds A-4.001 to A-4028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-5 provides 28 compounds A-5.001 to A-5.028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-6 provides 28 compounds A-6.001 to A-6.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-7 provides 28 compounds A-7.001 to A-7.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-8 provides 28 compounds A-8.001 to A-8.028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-9 provides 28 compounds A-9.001 to A-9.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-10 provides 28 compounds A-10.001 to A-10.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-11 provides 28 compounds A-11.001 to A-11.028 of formula (I-1) wherein , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-12 provides 28 compounds A-12.001 to A-12.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-13 provides 28 compounds A-13.001 to A-13.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-14 provides 28 compounds A-14.001 to A-14.028 of formula (I-1) wherein Q a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-15 provides 28 compounds A-15.001 to A-15.028 of formula (I-1) wherein direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-16 provides 28 compounds A-16.001 to A-16.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-17 provides 28 compounds A-17.001 to A-17.028 of formula (I-1) wherein , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-18 provides 28 compounds A-18.001 to A-18.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-19 provides 28 compounds A-19.001 to A-19.028 of formula (I-1) wherein Z is a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-20 provides 28 compounds A-20.001 to A-20.028 of formula (I-1) wherein Z is a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-21 provides 28 compounds A-21.001 to A-21.028 of formula (I-1) wherein Q a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-22 provides 28 compounds A-22.001 to A-22.028 of formula (I-1) wherein s a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-23 provides 28 compounds A-23.001 to A-23.028 of formula (I-1) wherein Q a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-24 provides 28 compounds A-24.001 to A-24.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-25 provides 28 compounds A-25.001 to A-25.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-26 provides 28 compounds A-26.001 to A-26.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-27 provides 28 compounds A-27.001 to A-27.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-28 provides 28 compounds A-28.001 to A-28.028 of formula (I-1) wherein Q and Z together represen , -S(Y) m R 1 is -S(O) 2 Et, and R 11 are as defined in table B.
  • Table A-29 provides 28 compounds A-29.001 to A-29.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-30 provides 28 compounds A-30.001 to A-30.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-31 provides 28 compounds A-31.001 to A-31.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR 1 is -S(O)2Et, and R 11 are as defined in table B.
  • Table A-63 provides 28 compounds A-63.001 to A-63.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B
  • Table A-64 provides 28 compounds A-64.001 to A-64.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B
  • Table A-65 provides 28 compounds A-65.001 to A-65.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-66 provides 28 compounds A-66.001 to A-66.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-67 provides 28 compounds A-67.001 to A-67.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-68 provides 28 compounds A-68.001 to A-68.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-69 provides 28 compounds A-69.001 to A-69.028 of formula (I-1) wherein , m 1 (NMe)Et, and R 11 Z is a direct bond, -S(Y) R is S(O) are as defined in table B.
  • Table A-70 provides 28 compounds A-70.001 to A-70.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-71 provides 28 compounds A-71.001 to A-71.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-72 provides 28 compounds A-72.001 to A-72.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-73 provides 28 compounds A-73.001 to A-73.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-74 provides 28 compounds A-74.001 to A-74.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-75 provides 28 compounds A-75.001 to A-75.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-76 provides 28 compounds A-76.001 to A-76.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-77 provides 28 compounds A-77.001 to A-77.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-78 provides 28 compounds A-78.001 to A-78.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R11 are as defined in table B.
  • Table A-79 provides 28 compounds A-79.001 to A-79.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-80 provides 28 compounds A-80.001 to A-80.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-81 provides 28 compounds A-81.001 to A-81.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-82 provides 28 compounds A-82.001 to A-82.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-83 provides 28 compounds A-83.001 to A-83.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-84 provides 28 compounds A-84.001 to A-84.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-85 provides 28 compounds A-85.001 to A-85.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-86 provides 28 compounds A-86.001 to A-86.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-87 provides 28 compounds A-87.001 to A-87.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-88 provides 28 compounds A-88.001 to A-88.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y) m R 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-89 provides 28 compounds A-89.001 to A-89.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-90 provides 28 compounds A-90.001 to A-90.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-91 provides 28 compounds A-91.001 to A-91.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-92 provides 28 compounds A-92.001 to A-92.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • Table A-93 provides 28 compounds A-93.001 to A-93.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR 1 is S(O)(NMe)Et, and R 11 are as defined in table B.
  • 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) agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries.
  • the composition additionally comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers or nutrients.
  • the present invention provides a compound of formula (I) or its N-oxides and salts into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • agrochemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g.
  • EC emulsions
  • EW e.g. EW
  • EO EO
  • ES emulsions
  • ME 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
  • gel formulations for the treatment of plant propagation materials e.g. GF.
  • compositions 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, Agrow Reports DS243, T and F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers or binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g.
  • Suitable solid carriers or fillers are mineral earths, e.g.
  • silicates silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon′s, Vol.1: Emulsifiers and Detergents, McCutcheon′s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyland tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • phosphates are phosphate esters.
  • carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar- based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugarbased surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are homeor copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases.
  • polyacids are alkali salts of polyacrylic acid or polyacid comb polymers.
  • polybases are polyvinylamines or polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, TandF Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azoand phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are: i) Water-soluble concentrates (SL, LS) 10-60 wt% of a compound (I) or an N-oxide or salt thereof and 5-15 wt% of a wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
  • a wetting agent e.g. alcohol alkoxylates
  • Dispersible concentrates DC 5-25 wt% of a compound (I) or an N-oxide or salt thereof and 1-10 wt% of a dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% of an organic solvent (e.g. cyclohexanone). Dilution with water gives dispersion.
  • a dispersant e.g. polyvinylpyrrolidone
  • an organic solvent e.g. cyclohexanone
  • Emulsifiable concentrates EC 15-70 wt% of a compound (I) or an N-oxide or salt thereof and 5-10 wt% emulsifiers (e.g.
  • Emulsions (EW, EO, ES) 5-40 wt% of a compound (I) or an N-oxide or salt thereof and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% of a water-insoluble organic solvent (e.g. aromatic hydrocarbon).
  • Suspensions SC, OD, FS
  • 20-60 wt% of a compound (I) or an N-oxide or salt thereof are comminuted with the addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 0,1 -2 wt% thickener e.g. xanthan gum
  • WG, SG Water-dispersible granules and water-soluble granules (WG, SG) 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed).
  • a binder e.g. polyvinylalcohol
  • Dilution with water gives a stable dispersion or solution of the active substance.
  • WP, SP, WS Water-dispersible powders and water-soluble powders 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% of a solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • wetting agents e.g. alcohol ethoxylate
  • a solid carrier e.g. silica gel
  • Microcapsules An oil phase comprising 5-50 wt% of a compound (I) or an N-oxide or salt thereof, 0-40 wt% of a water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% of acrylic monomers (e.g.
  • methylmethacrylate, methacrylic acid and a dior triacrylate are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization, initiated by a radical initiator, results in the formation of poly(methyl acrylate) microcapsules.
  • a protective colloid e.g. polyvinyl alcohol
  • Radical polymerization, initiated by a radical initiator, results in the formation of poly(methyl acrylate) microcapsules results in the formation of poly(methyl acrylate) microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the present invention, 0-40 wt% of a water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol
  • a polyamine e.g. hexamethylenediamine
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition
  • Dustable powders (DP, DS) 1-10 wt% of a compound I or an N-oxide or salt thereof are ground finely and mixed intimately with up to 100 wt% of a solid carrier, e.g. finely divided kaolin.
  • xii) Granules (GR, FG) 0.5-30 wt% of a compound I or an N-oxide or salt thereof is ground finely and associated with up to 100 wt% of a solid carrier (e.g. silicate).
  • a solid carrier e.g. silicate
  • Ultra-low volume liquids 1-50 wt% of a compound (I) or an N-oxide or salt thereof are dissolved in up to 100 wt% of an organic solvent, e.g. aromatic hydrocarbon.
  • the compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% of bactericides, 5-15 wt% of anti-freezing agents, 0.1-1 wt% of anti-foaming agents, and 0.1 -1 wt% of colorants.
  • the present invention provides agrochemical compositions of a compound of formula (I), which comprise the active substance between 0.01 and 95% by weight, preferably between 0.1 and 90%, and more preferably between 1 and 70 %, in particular between 10 and 60 by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • 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 the treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating a compound of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in- furrow application methods of the propagation material.
  • the compound of formula (I) or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
  • 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 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of the active substance from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • 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 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides 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).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the compounds of the present invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a spectrum of agronomic and non-agronomic invertebrate pests.
  • invertebrate pest control means inhibition of invertebrate pest development (including mortality) that causes significant reduction in feeding or other injury or damage caused by the pest (related expressions are defined analogously).
  • invertebrate pest includes arthropods, gastropods and nematodes of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes snails, slugs and other stylommatophora.
  • nematode includes all of the helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests.
  • 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.
  • 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.
  • insects are 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 (Panonychus 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.
  • Tetranychidae e.g., European red mite (Panonychus ulmi Koch), two spotted spider mite (Tetranychus urticae Koch), McDaniel mite (Tetranychus mcdaniel
  • 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).
  • spiders in the order Araneae such as the brown recluse spider (Loxosceles reclusa Gertsch and Mulaik) and the black widow spider (Latrodectus mactans Fabricius)
  • 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.
  • the compounds of the present invention show particularly high activity against pests of the order Lepidoptera (e.g., Alabama argillacea Hubner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A.
  • Lepidoptera e.g., Alabama argillacea Hubner (cotton leaf worm), Archips argyrospila Walker (fruit tree leaf roller), A.
  • E. Smith (fall armyworm), Trichoplusia ni H ⁇ bner (cabbage looper) and Tula absolutea Meyrick (tomato leafminer)).
  • Compounds of the present invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiplionpisum 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 a
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthoth ⁇ ps citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci
  • the compounds of formula (I), their N-oxides, their isomers, 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 ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Chilo infuscatellus, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Earias vittella, Elasmopalpus lignosellus, E
  • 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.
  • 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, Campo
  • Narceus spp. Earwigs (Dermaptera), e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon allinae, Menacanthus stramineus and Solenopotes capillatus. 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;
  • 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.
  • arachnoidea such as acarians
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis.
  • the present invention provides the compound of formula (I) which is useful for controlling insects selected form sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species: Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, 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, Chrysanoptera and Franklini
  • 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 and nutrients.
  • the compounds used in the composition and in combination with the compound of formula (I) are also termed as active compatible compounds.
  • 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.
  • fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients disclosed and reported in WO2016156129 and/or WO2017153200 can be combined with at least one compound of formula (I) of the present disclosure.
  • the fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients reported in WO2016156129 and or WO2017153200 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.
  • the compounds of the present invention can be mixed with at least one additional biological 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 and virus or fungi to form a multi- component pesticide giving an even broader spectrum of agricultural utility.
  • additional biological active compatible compound 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 and virus or fungi to form a multi- component pesticide giving an even broader spectrum of agricultural utility
  • 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.
  • 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.
  • the biologically effective amount of the compound of formula (I) in the compositions ranges from 0.1-99% by weight with respect to the total weight of the composition, preferably from 5-50% 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 or agriculturally acceptable salts, isomers/structural isomers, stereo- isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof as well as composition or combination thereof.
  • 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.
  • 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.
  • 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 the application of a compound or a composition of the present invention by direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • 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 piperonylbutoxide often enhance the 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.
  • invertebrate pest control i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the compounds of formula (I), their N-oxides and salts or composition(s) containing them by any application method known in the art.
  • 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).
  • 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 or arachnids by contacting the plant/crop with a pesticidally effective amount of at least one compound of the present invention.
  • crop refers both to growing and harvested crops.
  • the present invention provides a method for protecting crops from attack or infestation by invertebrate pests, which comprises contacting the crop with a biologically effective amount of the compound or the composition of the present invention, isomer, polymorph, N-oxide or salt thereof.
  • the compounds of the present invention are employed as such or in the 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.
  • the present invention provides a method for the protection of seeds 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. 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, isomer, polymorph, N-oxide or veterinary acceptable salt thereof.
  • the rate of application (applying effective dosages) of the compound of the present invention may be in the range of 1 gai to 5000 gai per hectare in agricultural or horticultural crops, preferably from 25 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 corn), 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.
  • the compound or the composition of the present invention are useful in protecting agricultural crops such as cereals, corn, 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 other vegetables, and ornamentals.
  • 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).
  • 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.
  • non-crop invertebrate pests such as ants, termites, wasps, flies, mosquitos, crickets, or cockroaches.
  • compounds of the present invention are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semi-solid 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- or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickiness, moisture retention or aging characteristics.
  • 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.
  • the typical content of active ingredient is from 0.001 to 15 weight %, desirably from 0.001 to 5 weight % of active compound.
  • Formulations of compounds of the present invention as aerosols 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 ethoxylate having 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.
  • emulsifiers such as sorbitol monooleate, oleyl ethoxylate having 3-7 mol of
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • 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 %.
  • the compounds of the present invention and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • the methods to control infectious diseases transmitted by insects e.g.
  • Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for example are ⁇ , ⁇ -diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1-yl- carbonyl)-2-methylpiperine, (2hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as ⁇ (+/-)-3-allyl- 2-methyl4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l-epi-eucamalol or crude plant extracts from plants like Eucal
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, monoand di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets.
  • the compounds of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human beings (e.g. when the pests invade into houses and public facilities).
  • the compounds of the present invention are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc.
  • 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.
  • Seed treatment 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 insects and the resulting plant′s roots and shoots against soil pests and foliar insects.
  • 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.
  • 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.
  • 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.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corms, bulbs, fruits, tubers, grains, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds.
  • 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.
  • 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 as for example, seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918 and CA2083415.
  • 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.
  • 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 corn), 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.
  • 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.
  • 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) (WO92/00377) (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 (EP142924, EP193259),
  • 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 example by traditional breeding methods and/or the generation of
  • 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).
  • 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 emergence of the plants.
  • compositions which are especially useful for seed treatment are e.g.: Soluble concentrates (SL, LS) Emulsions (EW, EO, ES) Suspensions (SC, OD, FS) Water-dispersible granules and water-soluble granules (WG, SG) Water-dispersible powders and water-soluble powders (WP, SP, WS) Gel-Formulations (GF) Dustable powders (DP, DS)
  • 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.
  • a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • 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/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a 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.
  • 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
  • colorants can be included in the formulation.
  • Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • the application rates of the compounds of the present invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g 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 I, as defined herein.
  • the amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed.
  • Digital Technologies 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.
  • 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.
  • 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.
  • 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.
  • input sensors such as e.g. a camera
  • 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.
  • GPS geographic information systems
  • pests can be detected from imagery acquired by a camera.
  • the pests can be identified and/or classified based on that imagery.
  • identification and / classification can make use of image processing algorithms.
  • 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.
  • Animal health also provides an agricultural and/or veterinary composition comprising at least of one compound of the present invention.
  • the present invention provides use of the compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides, composition or combination thereof, for combating invertebrate pests in agricultural crops and/or horticultural crops or parasites in or on animals.
  • 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.
  • One object of the present invention is therefore to provide new methods to control parasites in and on animals.
  • Another object of the present invention is to provide safer pesticides for animals.
  • Another object of the present invention is to provide pesticides for animals that may be used in lower doses than existing pesticides. Another object of the present invention is to provide pesticides for animals, which provide a long lasting control of parasites.
  • the present invention also relates to 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.
  • 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.
  • 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 requires, for example, low, non-emetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
  • compounds of the present invention are suitable for combating endo and ectoparasites in and on animals.
  • the 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 (including humans) 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 such as trout, carp and eels.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals such as mink, chinchilla and raccoon
  • birds such
  • the 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. 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.
  • the compounds of the present invention are especially useful for combating ectoparasites.
  • 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.
  • 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.
  • 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.
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp, Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp
  • Roundworms Nematoda 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.
  • 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.
  • 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. 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.
  • the compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the present invention provides use of the compounds of formula (I) and the compositions containing them for combating mosquitoes. In one embodiment, the present invention provides use of the compounds of formula (I) and the compositions containing them for combating flies. In one embodiment, the present invention provides use of the compounds of formula (I) and the compositions containing them for combating fleas. The use of the compounds of the present invention and the compositions containing them for combating ticks is still another embodiment of the present invention. The compounds of the present invention are also especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians). In one embodiment, the administration of the compounds of the present invention can be carried out both prophylactically and therapeutically.
  • administration of the compounds of the present invention is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • the 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.
  • the compounds of the present invention may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 to 100 mg/kg of animal body weight per day of the compound of the present invention, preferably with 0.5 to 100 mg/kg of animal body weight per day.
  • 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.
  • the compounds of the present invention may be formulated into an implant for subcutaneous administration.
  • the compound of the present invention may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 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.
  • dips and sprays usually contain 0.5 to 5,000 ppm and preferably 1 to 3,000 ppm of the compound of the present invention.
  • the compounds of the present invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • 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-inwater 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.
  • 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.
  • the solutions are filtered and filled sterile.
  • 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. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. 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. Gels are applied to or spread on the skin or introduced into body cavities.
  • Gels are prepared by treating solutions which have been prepared according to the state of the art for injection solutions with sufficient thickener that a clear material having an ointment-like consistency result.
  • 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, adhesives are added.
  • 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.
  • 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. Liquid suspending agents are all homogeneous solvents and solvent mixtures.
  • Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions only by their higher viscosity.
  • the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
  • suitable excipients if appropriate with addition of auxiliaries, and brought into the desired form.
  • parasiticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, 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 from about 0.001 to 95% of the compound of the present invention. Generally, it is favorable to apply the compounds of the present invention in total amounts of 0.5 to 100 mg/kg per day, preferably 1 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% by weight, preferably from 0.1 to 65% by weight, more preferably from 1 to 50% by weight, most preferably from 5 to 40% by weight.
  • Preparations diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90% by weight, preferably of 1 to 50% by weight. Furthermore, the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2% by weight, preferably of 0.05 to 0.9% by weight, very particularly preferably of 0.005 to 0.25% by weight.
  • the compositions comprising the compounds of the present invention are applied dermally/topically.
  • 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.
  • 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 2003/086075.
  • Positive crop response The compounds of the present invention not only control insect and mite pests effectively but also show positive crop response such as plant growth enhancement effects like enhanced root growth, enhanced tolerance to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality of plant products, more productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields.
  • plant growth enhancement effects like enhanced root growth, enhanced tolerance to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality of plant products, more productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields.
  • CHEMISTRY EXAMPLES The following examples set forth the manner and process of making compounds of the present invention without being a limitation thereof and include the best mode contemplated by the inventors for carrying out the invention.
  • reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was poured into ice water (200 mL) and extracted with ethyl acetate (3 x 100 mL). The combined ethyl acetate layers were washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 5-(2,2,3,3,3-pentafluoropropoxy)pyrazine-2-carboxylic acid (9 g, z, 52.4 % yield) as a solid.
  • Step-2 5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)methanol
  • 5-(2,2,3,3,3-pentafluoropropoxy)pyrazine-2-carboxylic acid (1 g, 3.67 mmol) in tetrahydrofuran (THF) (30 mL)
  • 1,1'-carbonyldiimidazole (CDI) (0.89 g, 5.51 mmol
  • Step-3 2-(chloromethyl)-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine
  • thionyl chloride 8.5 ml, 116 mmol
  • the reaction mixture was stirred at 100 °C for 2 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and poured into water.
  • the aqueous layer was extracted with ethyl acetate (EtOAc) (2 x 50 mL) and the combined ethyl acetate layers were washed with aqueous saturated sodium bicarbonate solution (50 mL), brine (50 mL), dried over anhydrous sodium sulfate, and concentrated to obtain the crude product.
  • the crude product was purified by flash column chromatography on silica gel using 10 % ethyl acetate in hexane as an eluent to obtain 2-(chloromethyl)-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine (4.7 g, 16.99 mmol, 73.1 % yield).
  • reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were washed with brine solution (50 mL), dried over sodium sulfate, and concentrated to obtain the crude which was purified by flash column chromatography on silica gel using 20 % ethyl acetate in hexane as an eluent to obtain 2-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acetonitrile (3.2 g, 11.98 mmol; 66.3 % yield).
  • Step-5 3,3-bis(ethylthio)-2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acrylonitrile
  • 2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acetonitrile 3 g, 11.23 mmol
  • potassium hydroxide 1.32 g, 23.58 mmol
  • the resulting reaction mixture was stirred for 1 h at 25 °C.
  • reaction mixture was cooled to -5 °C and carbon disulfide (0.81 ml, 13.48 mmol) was added dropwise, over 10 min. After complete addition, the reaction mixture was stirred for 1 h at -5 °C. Then ethyl iodide (2.0 mL, 24.70 mmol) was added in dropwise manner to the reaction mixture, at the same temperature over 15 min. The resultant reaction mixture was stirred for 2 h at 0 °C and then at 25 °C for 16 h.
  • reaction mixture was concentrated under reduced pressure and the crude product obtained was purified by flash column chromatography on silica gel using 10 % ethyl acetate in hexane as an eluent to obtain 3,3-bis(ethylthio)-2-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)acrylonitrile (2.6 g, 6.51 mmol; 58.0 % yield).
  • Step-6 3-(ethylthio)-4-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-1H-pyrazol-5-amine
  • hydrazine hydrate (0.63 mL, 10.27 mmol (79% w/v)
  • Step-7 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin- 7(4H)-one
  • 3-(ethylthio)-4-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-1H-pyrazol-5- amine 2.5 g, 6.77 mmol
  • acetic acid 25 mL
  • methyl 3,3-dimethoxypropanoate (1.50 g, 10.15 mmol
  • Step-8 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine
  • 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-7(4H)-one 1.6 g, 3.80 mmol
  • potassium carbonate (1.05 g, 7.59 mmol)
  • phosphorus oxybromide (2.18 g, 7.59 mmol
  • reaction mixture was heated at 90 °C for 6 h. After completion of the reaction, the reaction mixture was cooled to 0 °C and diluted with ice-water mixture (50 mL). The pH of the mixture was adjusted to 7-8 by slow addition of saturated aqueous sodium bicarbonate solution.
  • aqueous layer was extracted with ethyl acetate (3 x 100 mL) and the combined ethyl acetate layers were washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product which was purified by flash column chromatography on silica gel using 50 % ethyl acetate in hexane as an eluent to obtain 7- bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine (0.6 g, 1.162 mmol, 30.6 % yield).
  • the resultant reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was diluted with aqueous sodium thiosulfate solution and extracted with dichloromethane (2 x 15 mL). The combined dichloromethane layers were washed with a saturated aqueous sodium bicarbonate solution (50 mL) and water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product which was purified by flash column chromatography on silica gel using 35 % ethyl acetate in hexane as an eluent to obtain 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (210 mg, 0.41 mmol, 65.7 % yield).
  • reaction mixture was thoroughly deoxygenated by subjecting it to vacuum/nitrogen cycles three times. Then 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (23.8 mg, 0.03 mmol) was added to the reaction mixture which then was heated at 90 °C for 2 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and filtered through a pad of celite.
  • Example-2 Synthesis of N-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine (Compound 7) -(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (Step-08; Example-1) (0.15 g, 0.310 mmol) in N,N-dimethylformamide (DMF) (2 mL), cyclopropanamine (0.09 g, 1.55 mmol) was added drop wise at 0 °C.
  • DMF N,N-dimethylformamide
  • the reaction mixture was stirred at 25 °C for 3 h.
  • the reaction mixture was diluted with ice cold water (10 mL) and the aqueous layer was extracted with ethyl acetate (3 x 10 mL).
  • the combined ethyl acetate layers were washed with water (20 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product which was was purified by flash column chromatography on silica gel using 1% methanol in dichloromethane to obtain N-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (90 mg, 0.195 mmol; 63.1 % yield) as solid.
  • Example-3 Synthesis of 7-ethoxy-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (Compound 11) tetrahydrofuran (THF) (5 mL), sodium hydride (0.03 g, 0.77 mmol) was added at 0 C, and the reaction mixture was stirred for 30 min at the same temperature after which 7-bromo-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (0.25 g, 0.52 mmol) in tetrahydrofuran (THF) (5 ml) was added.
  • THF tetrahydrofuran
  • Example-4 Synthesis of ((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl- ⁇ 6 -sulfanone (Compound 6) -(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (200 mg, 0.39 mmol) in toluene (6 mL), iminodimethyl- ⁇ 6 -sulfanone (72.2 mg, 0.77 mmol), potassium phosphate, tribasic (164 mg, 0.77 mmol), and 2-dicyclohexylphosphino- 2',4',6'-triisopropylbiphenyl (36.9 mg, 0.077 mmol) were added, and the reaction mixture was degassed under nitrogen for
  • the crude product was purified by flash chromatography on silica gel using 1-2% methanol in dichloromethane to obtain ((2-(ethylsulfonyl)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-l6- sulfanone (90 mg, 0.17 mmol, 44.0 % yield) as a solid.
  • Step 2 Synthesis of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate To a stirred solution of ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 18.7 mmol) in acetonitrile (100 ml), potassium carbonate (K2CO3) (7.76 g, 56.1 mmol) and phosphorus oxybromide (16.1 g, 56.1 mmol) were added at 25 °C, and the resulting mixture was heated at 95 °C for 4 h.
  • K2CO3 potassium carbonate
  • phosphorus oxybromide (16.1 g, 56.1 mmol
  • Step 3 Synthesis of ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate
  • a mixture of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (7 g, 21.20 mmol), cyclopropylboronic acid (7.28 g, 85 mmol) and potassium phosphate tribasic (13.45 g, 63.6 mmol) in dioxane (70 mL) were purged under nitrogen gas for 10 min followed by the addition of 1,1'- bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane adduct (1.73 g, 2.12 mmol).
  • the resulting reaction mixture was heated at 90 °C for 3 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, filtered through a bed of celite and washed with ethylacetate. The organic layer was washed with water (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get the crude product which was purified by flash column chromatography using 50 % ethyl acetate in hexane on silica gel to obtain ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5- a]pyrimidine-3-carboxylate (3 g, 10.3 mmol, 48.6 % yield).
  • Step 4 Synthesis of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid
  • ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate 3 g, 10.3 mmol
  • lithium hydroxide, monohydrate 4.32 g, 103 mmol
  • the reaction mixture was stirred at 60 °C for 4 h.
  • reaction mixture was heated at 100 °C for 8 h. After completion of the reaction, the reaction mixture was cooled to 25 °C followed by the addition of a mixture of 15% aqueous sodium thiosulphate solution and saturated aqueous NaHCO 3 solution under stirring.
  • aqueous layer was extracted with dichloromethane (4 x 25 mL), and the combined organic layers were dried under reduced pressure to give a crude product, which was purified by flash column chromatography using 20-40 % ethyl acetate in hexane on silica gel to obtain 7- cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine (5 g, 14.48 mmol, 76 % yield) as a grey powder.
  • reaction mixture was diluted with dichloromethane (15 mL).
  • the organic layer was washed with 1N sodium hydroxide (NaOH) (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get a crude product which was purified by flash column chromatography using 20-40 % ethyl acetate in hexane on silica gel to obtain 7-cyclopropyl-2- (ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine (150 mg, 0.398 mmol, 68.6 % yield) as a solid.
  • NaOH sodium hydroxide
  • Example-6 Synthesis of 3-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 110) .
  • Step 1 Synthesis of 1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)-3-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)pyridin-2(1H)-one
  • 3-bromo-1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one 500 mg, 1.49 mmol
  • bis(pinacolato)diboron 756 mg, 2.98 mmol
  • potassium acetate 292 mg, 2.98 mmol
  • Step 2 Synthesis of 3-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 110)
  • a stirred mixture of 7-cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine (1 g, 2.90 mmol)
  • potassium carbonate (K2CO3) (1.20 g, 8.69 mmol) in 1,4-dioxane (10 mL) and water (1 mL) was purged with nitrogen gas
  • the resulting reaction mixture was heated at 110 °C for 4 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, filtered through a bed of celite, and washed with ethyl acetate. The ethyl acetate layer was washed with water (25 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get a crude product which was purified by flash column chromatography on silicagel using 80% ethylacetate in hexane to get 3-(7-cyclopropyl-2- (ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (150 mg, 0.316 mmol, 10.91 % yield).
  • Example-7 Synthesis of 3-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl- 6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 119)
  • the title compound 3-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (170 mg, 0.34 mmol, 12.7 % yield) was prepared from 7-cyclopropyl-2-(ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine (1.0 g, 2.65 mmol) using the procedure mentioned in step-2 of example-6.
  • Example A Helicoverpa armigera
  • the diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 o C in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray.
  • a single starved Helicoverpa armigera third instar larva was released into each of the cells of the bioassay trays and the tray was covered with the lid.
  • the bio-assay trays were then kept under laboratory conditions at a temperature of 25 o C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of the larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control.
  • the compounds 3 5 6 16 21 43 44 45 48 52 101 103 108 120 and 121 recorded ⁇ 70 per cent mortality @ 300PPM.
  • Example B Spodoptera litura The diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 o C in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray. A single starved Spodoptera litura third instar larva was released into each of the cells of the bioassay trays and the tray was covered with the lid.
  • the bio- assay trays were then kept under laboratory conditions at a temperature of 25 o C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control.
  • the compounds 3 4 5 14 16 21 43 45 48 52 70 72 103 116 119 and 121 recorded ⁇ 70 per cent mortality @ 300PPM.
  • Example C Plutella xylostella The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution.
  • the tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to get the desired test concentration.
  • Cabbage leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then transferred into the cells of bioassay trays.
  • a single Plutella xylostella second instar larva was released into each cell and the tray was covered with a lid.
  • the bio-assay trays were then kept under laboratory conditions at a temperature of 25 o C and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control.
  • the leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to get the desired test concentration. Brinjal leaves were dipped in the compound solution for 10 seconds; shade dried for 20 min and then placed, with the abaxial side of the leaf up, on 4 ml of a solidified 1 % agar- agar solution in respective perforated container caps. Known numbers of freshly emerged whitefly adults were collected, using a modified aspirator, and released into a perforated container in which the cap containing the treated leaf was placed.
  • Example E Myzus persicae 2. The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to the desired test concentration.
  • Capsicum leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then placed, with the abaxial side of the leaf up, in single cells of a bio-assay tray containing 4 ml of a solidified 1 % agar-agar solution.
  • the trays were kept in a plant growth chamber at a temperature of 25 o C and a relative humidity of 70%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release.
  • Percent mortality was calculated by combining dead and moribund nymphs and comparing the result with the one of the untreated control.
  • Example F Nilaparvata lugens The seedling dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to the desired test concentration.
  • Paddy seedlings were dipped in the compound solution for 10 seconds, shade dried for 20 min and then placed in glass test tubes with the roots kept in water. 15 Nilaparvata lugens third instar nymphs were released into each test tube and the tubes were kept in a plant growth chamber at a temperature of 25 o C and relative humidity of 75%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund nymphs and comparing the result to the one of the untreated control. The compound 36 12 13 21 23 24 28 29 43 52 58 59 76 93 108 and 109 recorded ⁇ 70 per cent mortality @ 300PPM.

Abstract

The present invention discloses a fused heterocyclic compound of formula (I), Formula (I) wherein, Q, R1, Z, A, G1, G2, E, Y and m are as defined in the detailed description. The present invention further discloses methods for their preparation and use of the compounds of formula (I) as a pest control agent.

Description

Title of the Invention: FUSED HETEROCYCLIC COMPOUNDS AND THEIR USE AS PEST CONTROL AGENTS FIELD OF THE INVENTION: The present invention relates to fused heterocyclic compounds. More particularly, the present invention relates to fused heterocyclic compounds of formula (I) and a process for the preparation thereof. The present invention further relates to the use of fused heterocyclic compounds of formula (I) as pest control agents. BACKGROUND OF THE INVENTION: The currently available modern insecticides and acaricides must satisfy many requirements, for example regarding spectrum and level of efficacy, long lasting activity, beneficial side effects, and 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. Heterocyclic compounds with pesticidal activity are known and described in prior art, for example, in WO2020250183, WO2018221720 and WO201765228. There is a continuous need for new compounds which are more effective, less toxic, and environmentally safer and/or have different modes of action. In view of the above, the present invention envisages such compounds that satisfy or overcome drawbacks associated with the prior art. It has now surprisingly been found that certain novel pesticidally active fused heterocyclic compounds with sulfur containing substituents, being subject of this invention, have better favorable properties as pesticides, as desired. SUMMARY OF THE INVENTION: Accordingly, the present invention provides a fused heterocyclic compound of formula (I) or agriculturally acceptable salts, isomers/structural isomers, stereoisomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof. wherein, Q, Z, Y, m, R1, A, G1, G2,
Figure imgf000003_0001
D and E are as defined in the detailed description. In one embodiment, the present invention provides a process for preparing a compound of formula (I) or agriculturally acceptable salts thereof. In another embodiment, the present invention provides a composition for controlling or preventing invertebrate pests comprising a biologically effective amount of a compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries. In yet another embodiment, the composition comprises at least one additional biologically active and compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers, or nutrients. In still another embodiment, the present invention provides the use of a compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereoisomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides, compositions or combinations thereof, for combating invertebrate pests in agricultural crops and/or horticultural crops or parasites on animals. In yet 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 a compound of formula (I) or agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N- oxides thereof and a composition or combination thereof. DETAILED DESCRIPTION OF THE INVENTION: 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. 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. 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". 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). 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 (Tematoda), 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 corn, 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, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruits (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives). 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 product, 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. 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. 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. The meaning of various terms used in the description shall now be illustrated. 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. 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 C1 to C24 alkyl, preferably C1 to C15 alkyl, more preferably C1 to C10 alkyl, most preferably C1 to C6 alkyl. Representative examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1- methylpropyl and 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. The term “alkenyl”, used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably C2 to C15 alkenes, more preferably C2 to C10 alkenes, most preferably C2 to C6 alkenes. Representative examples of alkenes include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-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, l-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-1-propenyl, 1,2-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-1-pentenyll,l,2-trimethyl-2-propenyl, 1-ethyl-l-methyl-2-propenyl, l-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. Non-limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2-butynyl, l- methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, l-methyl-3-pentynyl, 1- methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l-pentynyl, 3-methyl-4- pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, 1,1-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. The term "cycloalkyl" means alkyl closed to form a ring. Non-limiting examples include but are not limited to cyclopropyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere. 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. The term "cycloalkynyl" means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. Non-limiting examples include but are not limited to cyclopropynyl, cyclopentynyl and cyclohexynyl. This definition also applies to cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere. The term "cycloalkoxy", "cycloalkenyloxy" and the like are defined analogously. Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl etc., unless specifically defined elsewhere. 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, 1,1-dichloro-2,2,2-trifluoroethyl, and 1,1,1-trifluoroprop-2-yl. This definition also applies to haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere. 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. The term "haloalkoxy" means straight-chain or branched alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non-limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro- 2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trifluoroprop-2-oxy. This definition also applies to haloalkoxy as a part of a composite substituent, for example haloalkoxyalkyl etc., unless specifically defined elsewhere. The term "haloalkylthio" means straight-chain or branched alkylthio groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1-bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio and l,l,l-trifluoroprop-2-ylthio. This definition also applies to haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere. Non-limiting examples of "haloalkylsulfinyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. 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 S(O)2, oxa means =O. The term "alkoxy" used either alone or in compound words include C1 to C24 alkoxy, preferably C1 to C15 alkoxy, more preferably C1 to C10 alkoxy, most preferably C1 to C6 alkoxy. Examples of alkoxy include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1- dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1- ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2- dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2- trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 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. The term "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Non-limiting examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. The term "alkoxyalkoxy" denotes alkoxy substitution on alkoxy. The term "alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1- ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2- methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1- ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio, 1-ethyl-1- methylpropylthio and l-ethyl-2-methylpropylthio and the different isomers. Halocycloalkyl, halocycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, and the like, are defined analogously to the above examples. The term "alkylthioalkyl" denotes an alkylthio substitution on alkyl. Representative examples of "alkylthioalkyl" include -CH2SCH2, -CH2SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes an alkylthio substitution on alkoxy. The term "cycloalkylalkylamino" denotes a cycloalkyl substitution on alkyl amino. The terms alkoxyalkoxyalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl and the like, are defined analogously to "alkylthioalkyl" or cycloalkylalkylamino. The term "alkoxycarbonyl" is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as a part of a composite substituent, for example cycloalkylalkoxycarbonyl and the like, unless specifically defined elsewhere. The term "alkoxycarbonylalkylamino" denotes an alkoxy carbonyl substitution on alkyl amino. "Alkylcarbonylalkylamino" denotes alkyl carbonyl substitution on alkyl amino. The terms alkylthioalkoxycarbonyl, cycloalkylalkylaminoalkyl and the like are defined analogously. Non-limiting examples of "alkylsulfinyl" include but are not limited to methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2- methylpropylsulphinyl, 1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl, 1-methylpentylsulphinyl, 2- methylpentylsulphinyl, 3-methylpentylsulphinyl, 4-methylpentylsulphinyl, 1,1-dimethylbutylsulphinyl, 1,2-dimethylbutylsulphinyl, 1,3-dimethylbutylsulphinyl, 2,2-dimethylbutylsulphinyl, 2,3- dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl, 1-ethylbutylsulphinyl, 2-ethylbutylsulphinyl, 1,1,2- trimethylpropylsulphinyl, 1,2,2-trimethylpropylsulphinyl, 1-ethyl-1-methylpropylsulphinyl and 1-ethyl-2- methylpropylsulphinyl and the different isomers. The term "arylsulfinyl" includes Ar-S(O), wherein Ar can be any carbocycle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere. Non-limiting examples of "alkylsulfonyl" include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl, 1-methylpropylsulphonyl, 2- methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1-ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1-methylpentylsulphonyl, 2- methylpentylsulphonyl, 3-methylpentylsulphonyl, 4-methylpentylsulphonyl, 1,1-dimethylbutylsulphonyl, 1,2-dimethylbutylsulphonyl, 1,3-dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl, 2,3- dimethylbutylsulphonyl, 3,3-dimethylbutylsulphonyl, 1-ethylbutylsulphonyl, 2-ethylbutylsulphonyl, 1,1,2-trimethylpropylsulphonyl, 1,2,2-trimethylpropylsulphonyl, 1-ethyl-1-methylpropylsulphonyl and l- ethyl-2-methylpropylsulphonyl and the different isomers. The term "arylsulfonyl" includes Ar-S(O)2, wherein Ar can be any carbocycle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere. "Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples. The terms “carbocycle” or “carbocyclic” or “carbocyclyl” include an “aromatic carbocyclic ring system” and a “nonaromatic carbocylic ring system” 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). Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbornyl and the like. Non limiting examples of aromatic carbocyclic ring systems are phenyl, naphthyl and the like. 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. The term “aryl” also comprises “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. The term "aromatic" indicates that the Huckel rule is satisfied and the term "non-aromatic" indicates that the Huckel rule is not satisfied. The term "heterocycle" or "heterocyclic" or "heterocyclic ring system" includes an "aromatic heterocycle" or "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 one of the C atoms of the ring member is replaced with at least one heteroatom selected from N, O, S(O)0-2, and/or one of the C atom of the ring member of the heterocycle may be replaced by C(=O), C(=S), C(=CR*R*) and C=NR*, * indicates integers. The term "non-aromatic heterocycle" or "non-aromatic heterocyclic" means three- to fifteen-membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to 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) oxetanyl, oxiranyl, aziridinyl, azetidinyl, thietanyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothiazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, l,2,4-thiadiazolidinyl, l,2,4-triazolidin-1-yl, l,2,4-triazolidin-3-yl, l,2,3-triazolidinyl, l,3,4-oxadiazolidinyl, l,3,4-thiadiazolidinyl, 1,3,4-triazolidinyl, dihydrofuryl, dihydrothienyl, pyrrolinyl, isoxazolinyl, isothiazolinyl, dihydropyrazolyl, dihydrooxazolyl, dihydrothiazolyl,piperidinyl, pyrazynyl, morpholinyl, thiomorphlinyl, l,3-dioxan-5-yl, tetrahydropyranyl, tetrahydrothienyl, hexahydropyridazinyl, hexahydropyrimidinyl, piperazinyl and cycloserines. This definition also applies to heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere. The term "heteroaryl" or "aromatic heterocyclic" means 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 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, l,2,4-oxadiazolyl, l,2,4-thiadiazolyl, l,2,4-triazolyl, l,3,4-oxadiazolyl, l,3,4-thiadiazolyl, l,3,4-triazolyl, tetrazolyl; nitrogen-bonded 5-membered heteroaryl containing one to four nitrogen atoms, or benzofused nitrogen-bonded 5-membered heteroaryl 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-l- yl, 1- imidazolyl, 1,2,3-triazol-l-yl and 1,3,4-triazol-l-yl. 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) pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, l,3,5-triazin-2-yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indolyl, benzimidazolyl, indazolyl, benzofuranyl, benzothiophenyl, benzothiazolyl, and benzoxazolyl; benzofused 6-membered heteroaryl which contains one to three nitrogen atoms: for example (but not limited to) quinolinyl, isoquinolinyl, quinoxalinyl, phthalazinyl, quinazolinyl and cinnolinyl. Bicyclic 5-6 heteroaryl systems with one bridgehead (ring junction) nitrogen atom containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) imidazo[1,2-a]pyridine, imidazo[1,2-a]pyrimidine, [1,2,4]triazolo[1,5-a]pyrimidine, [1,2,4]triazolo[1,5- b]pyridazine, [1,2,4]triazolo[1,5-a]pyrazine, [1,2,4]triazolo[1,5-a]pyridine, imidazo[1,2-c]pyrimidine, imidazo[1,2-b]pyridazine, [1,2,4]triazolo[1,5-c]pyrimidine, 1-methyl-1H-indole, imidazo[1,2-a]pyrazine, pyrazolo[1,5-a]pyridine and [1,2,4]triazolo[4,3-a]pyridine. 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. Non-limiting examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Non- limiting examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. Non-limiting examples of "alkylaminocarbonyl" include CH3NHC(=O), CH3CH2NHC(=O), CH3CH2CH2NHC(=O), (CH3)2CHNHC(=O) and the different butylamino -or pentylaminocarbonyl isomers. Non-limiting examples of "dialkylaminocarbonyl" include (CH3)2NC(=O), (CH3CH2)2NC(=O), CH3CH2(CH3)NC(=O), CH3CH2CH2(CH3)NC(=O) and (CH3)2CHN(CH3)C(=O). Non-limiting examples of "alkoxyalkylcarbonyl" include CH3OCH2C(=O), CH3OCH2CH2C(=O), CH3CH2OCH2C(=O), CH3CH2CH2CH2OCH2C(=O) and CH3CH2OCH2CH2C(=O). Non-limiting examples of "alkylthioalkylcarbonyl" include CH3SCH2C(=O), CH3SCH2CH2C(=O), CH3CH2SCH2C(=O), CH3CH2CH2CH2SCH2C(=O) and CH3CH2SCH2CH2C(=O). The term haloalkylsufonylaminocarbonyl, alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously. Non-limiting examples of "alkylaminoalkylcarbonyl" include CH3NHCH2C(=O), CH3NHCH2CH2C(=O), CH3CH2NHCH2C(=O), CH3CH2CH2CH2NHCH2C(=O) and CH3CH2NHCH2CH2C(=O). The term "amide" means A-R′C=ONR′′-B, wherein R′ and R′′ indicates substituents and A and B indicate any group. The term "thioamide" means A-R′C=SNR′′-B, wherein R′ and R′′ indicates substituents and A and B indicate any group. 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 replacement of a hydrogen on said carbon or nitrogen. 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 group of defined substituents. Further, when the subscript m in (R)m indicates 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 un-substituted. 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 so as 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 of skilled in the art to practice the embodiments herein. Accordingly, the examples should not be construed as limiting the scope of the embodiments herein. 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. 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. 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 compound 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 Z isomers, 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. 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. 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. For the purpose of the present disclosure the term "plant" includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, ferns, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis. 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, corn, 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. Preferably, the plant for the purpose of the present invention includes but is not limited to cereals, corn, 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 for use of human 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, auxillary buds, meristems, nodes and internodes. 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. 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 application 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. The term "applied" means adhered to a plant or plant part either physically or chemically including impregnation. In prior art, particularly WO2020/250183 describes the fused heterocyclic compounds and their use as pest control agents in which Q is described as a fused bicyclic ring. The present invention provides the compound of formula (I) wherein Q is monocyclic 6-membered heterocyclic ring. It has now surprisingly been found out that new compounds wherein Q represent monocyclic 6-membered heterocyclic ring are effective on broader range of pathogens as compare to the compounds disclosed in the prior art. Accordingly, the present invention provides a compound of formula (I),
Figure imgf000016_0001
ormu a ( ) wherein, R1 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C3-C8-cycloalkyl-C1-C6-alkyl; Y is independently selected from O or NRY; RY is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl; A represents N or CR2; G1 and G2 represents N or C; provided that both G are not nitrogen simultaneously; R2 is selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0- 2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R2a and cyclic groups of R2 may be optionally substituted with one or more groups of R2b; R2a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0- 1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R2b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0- 2R7, C(=O)R8, Si(R′′)3, S(O)0-1R9=NR10 and N=S(O)0-1(R9)2; or two R2a or two R2b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′)2, may form a 3- to 7-membered ring, which for its part may be substituted by one or more groups of R2ab; R2ab is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR5R6, S(O)0- 2R7, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; Q represents 6-membered heterocyclic ring which may optionally be substituted by one or more groups of R3; R3 is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R3a and cyclic groups of R3 may be optionally substituted with one or more groups of R3b; R3a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0- 1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R3b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2-NR5R6, C(R′′)2- OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; two R3a or two R3b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)m and Si(R′′)2, may form a 3- to 7-membered ring, which for its part may be substituted by one or more groups of R3ab; wherein R3ab is selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, NR5R6, S(O)0-2R7; Z represents a direct bond or O; ring E represents a 5- or 6-membered heterocyclic ring fused with ring D; wherein ring E is optionally substituted by one or more groups of R11; R11 is selected from the group consisting of halogen, cyano, oxa, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R11a and cyclic groups of R11 may be optionally substituted with one or more groups of R11b; R11a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3- C10-heterocyclyl; R11b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2- NR5R6, C(R′′)2-OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0- 1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, S(O)2R7, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R4a and cyclic groups of R4 may be optionally substituted with one or more groups of R4b; R4a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR′R′′, S(O)0-2R7, C(=O)R8, Si(R′′)3, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R5a and cyclic groups of R5 may be optionally substituted with one or more groups of R5b; R5a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, Si(R′′)3, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R6 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C1-C6-cycloalkyl and C(=O)R8; or R5 and R6 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R7 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, NR5R6, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R7a and cyclic groups of R7 may be optionally substituted with one or more groups of R7b; R7a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R7b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR5R6, N=S(O)0-1(R9)2, C6-C10-aryl, C7-C14- aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R8a and cyclic groups of R8 may be optionally substituted with one or more groups of R8b; R8a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R8b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C(=O)R8; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, Si(R′′)3, S(O)0-2R7 and C(=O)R8; two R9 substituents or R9 and R10 substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R′ is selected from the group consisting of R′′, OR′′, N(R′′)2, S(O)0-2R′′, C(=O)R′′, C(=O)OR′′ and C(=O)N(R′′)2; R′′ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl and C3-C8-cycloalkyl; wherein each may be optionally substituted with halogen; each group of R1 to R11, R2a, R2b, R2ab, R3a, R3b, R3ab, R4a, R4b, R5a, R5b, R7a, R7b, R8a and R8b may be optionally substituted by one or more groups selected from the group consisting of halogen, cyano, R′′, OR′′, SR′′, N(R′′)2, COOR′′ and CON(R′′)2; "m" is an integer ranging from 0 to 2; or stereoisomers, and salts thereof. The following embodiments provide definitions, including preferred definitions, for substituents with reference to the compounds of formula (I) according to the 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 document. Further, embodiments of this disclosure described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula (I) but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula (I). In one embodiment, the compound of formula (I) is represented by a compound of formula (IA);
Figure imgf000021_0001
wherein, R1, Q, Z, A, G1, G2, E and m have the meanings as described above. In another embodiment, the compound of formula (I) is represented by a compound of formula (IB);
Figure imgf000021_0002
Formula (IB) wherein, R1, Q, Z, RY, A, G1, G2, E and m have the meanings as described above. One embodiment of the present invention provides the compound of formula (I); wherein, Z is direct bond and R1, Q, Y, A, G1, G2, E and m are same as defined herein above. Another embodiment of the present invention provides a compound of formula (I); wherein, Z represent O (oxygen atom) and R1, Q, Y, A, G1, G2, E and m are as defined herein above. In one embodiment, the present invention provides a compound of formula (I), wherein the fused ring system DE contains at least one nitrogen atom. In one embodiment, Q is selected from Q1, Q2 or Q3. In one embodiment, Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom represented as Q1,
Figure imgf000022_0001
A3 are independently selected from C or N provided that at least one of A1, A2, A3 is not nitrogen at the same time; the symbol represents the point of attachment to ring DE.
Figure imgf000022_0002
In a preferred embodiment, Q1 is selected from Q1a, Q1b, Q1c, Q1d and Q1e.
Figure imgf000022_0003
In one embodiment, Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, Z represents O (oxygen atom); and said Q is attached through Z to the ring DE. In a preferred embodiment, Q1 represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, Z represents O (oxygen atom); and said Q1Z group is selected from:
Figure imgf000023_0001
; wherin QZ group is optionally substituted with one or more R3. In another embodiment, Q represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom and is represented as Q2 ;
Figure imgf000023_0002
p is optionally substituted with one or more R3; the symbol represents the point of attachment to the ring DE.
Figure imgf000023_0003
In a preferred embodiment, Q2 represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom, Z represents a direct bond and said Q2 is attached to ring DE through nitrogen atom. In a preferred embodiment, Q2 is selected from:
Figure imgf000023_0004
wherein the symbol represent the point of attachment to the ring DE. In one embodiment, Q2 represents a six membered non-aromatic heterocyclic ring containing at least one nitrogen atom, Z represents a direct bond and said Q2 is attached to ring DE through a nitrogen atom. In a preferred embodiment, Q2 is selected from: Q2a, Q2c, Q2d and Q2f, more preferably from Q2a and Q2c. In yet another embodiment, Q represents a six membered non-aromatic partially unsaturated heterocyclic ring containing at least one nitrogen atom and being represented as Q3
Figure imgf000024_0001
p Q3 is optionally substituted with one or more R3; the symbol represents the point of attachment to the ring DE.
Figure imgf000024_0002
In a preferred embodiment, Q3 is selected from: tachment t
Figure imgf000024_0003
o e r ng . In a preferred embodiment, Q3 is selected from Q3a, Q3b, Q3c and Q3f, and R5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C3-C8-cycloalkyl and C3-C8-cycloalkyl-C1-C6- alkyl; wherein R5 is optionally substituted with one or more halogen. In another more preferred embodiment, Q3 is selected from Q3aa, Qba, Q3ca and Q3fa. .
Figure imgf000024_0004
According to an even more preferred embodiment, Q represents a six membered heteroaromatic ring (aromatic heterocyclic ring) containing at least one nitrogen atom, and Z represents a direct bond. According to a most preferred embodiment, the more preferred Q is selected from Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c and Q3f. In another embodiment, the fused ring system DE is selected from the group consisting of DE-1 to DE- 15: whe
Figure imgf000025_0001
e , e oes e po o a ac e o e g a e o es e po o a achment to the group -S(Y)mR1. In a preferred embodiment, the DE ring is selected from DE-1, DE-7 and DE-11, even more preferably from DE-7. In one embodiment, R3 is selected from halogen, -S(O)0-2C1-C6-haloalkyl, -S(O)(NRY) C1-C6-haloalkyl, C1-C4 haloalkyl and C1-C4 haloalkoxy, In another embodiment, R3 is selected from C1-C4 haloalkyl, preferably C1-C2 haloalkyl, and more preferably is CF3. In yet another embodiment, R3 is selected from C1-C4 haloalkoxy, C2-C4 haloalkenyloxy, preferably C1-C3 haloalkoxy, and more preferably is -O-CH2CF2CF3. In yet another embodiment, R3 is -S(O)0-2C1-C6-haloalkyl, more preferably -S(O)0-2CF3 In one embodiment, R11 is selected from halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C2- C6-haloalkenyl, C3-C8-cycloalkyl, C3-C8-cyanocycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, phenyl, 4-6 membered heterocyclyl, and preferably from 5 membered nitrogen containing heterocycles . In one embodiment, the compound of formula (I) is represented by a compound of formula (I-1);
Figure imgf000026_0001
wherein, R1 is C1-C6 alkyl or C3-cycloalkyl; Y is NRY or O; RY is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl; Z represents a direct bond or O; Q represents a 6-membered heterocyclic ring which may optionally be substituted by one or more groups of R3; R3 is selected from the group consisting of halogen, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C4- cycloalkyl, C1-C6-haloalkoxy S(O)0-2 C1-C6-haloalkyl, -S(O)0-1R9=NR10, and C3-C10-heterocyclyl; wherein C3-C10-heterocyclyl of R3 may be optionally substituted with one or more groups of R3b; R3b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3- C8-cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, S(O)0-2C1-C6-alkyl and S(O)0-2C1-C6-haloalkyl; R11 is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, -S(O)0-1R9=NR10, -N=S(O)0-1(R9)2, -P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R11a, and cyclic groups of R11 may be optionally substituted with one or more groups of R11b; R11a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3- C10-heterocyclyl; R11b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2- NR5R6, C(R′′)2-OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0- 1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, S(O)2R7, Si(R′′)3, phenyl, benzyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with R4a and cyclic groups of R4 may be optionally substituted with one or more groups of R4b; R4a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR′R′′, S(O)0-2R7, C(=O)R8, Si(R′′)3, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R5a and cyclic groups of R5 may be optionally substituted with one or more groups of R5b; R5a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, Si(R′′)3, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R6 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C1-C6-cycloalkyl and C(=O)R8; or R5 and R6 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part may optionally be substituted by one or more groups of R’; R7 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, NR5R6, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R7a and cyclic groups of R7 may be optionally substituted with one or more groups of R7b; R7a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R7b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR5R6, N=S(O)0-1(R9)2, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R8a and cyclic groups of R8 may be optionally substituted with one or more groups of R8b; R8a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R8b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C(=O)R8; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, Si(R′′)3, S(O)0-2R7 and C(=O)R8; two R9 or R9 and R10 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R′ is selected from the group consisting of R′′, OR′′, N(R′′)2, C(=O)R′′, C(=O)OR′′ and C(=O)N(R′′)2; R′′ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl and C3-C8-cycloalkyl; wherein each may be optionally substituted with halogen; "m" is an integer ranging from 0 to 2; or stereoisomers, and salts thereof. In one embodiment, the compound of formula (I-1); wherein, -S(Y)mR1 group represents, S(O)0-2R1 or S(O)(=NRY) R1; preferably S(O)2C1-C3 (cyclo)alkyl; wherein more preferred (cyclo)alkyl is selected from ethyl, isopropyl and cyclopropyl. In a preferred embodiment-A, the compound of formula (I-1); wherein, R1 is C1-C3 alkyl or C3 cycloalkyl; Z is direct bond or O; more preferably Z is direct bond Q is selected from Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c or Q3f; more preferably Q1a, Q1d, Q1e R3 is selected from halogen, -S(O)0-2C1-C4-haloalkyl, -S(O)(NRY) C1-C6-haloalkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; more preferably C1-C4 haloalkoxy; R11 is selected from halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C3-C8-cyanocycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, -S(O)0- 1R9=NR10, -N=S(O)0-1(R9)2, (un)substituted phenyl or (un)substituted 4-6 membered heterocyclyl; R5 is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, -C(=O)R8, (un)substituted phenyl or (un)substituted C3-C10-heterocyclyl; and R8 is selected from C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl; R6 is selected from hydrogen, C1-C6-alkyl, C1-C6-cycloalkyl or C(=O) C1-C6 alkoxy; R7 is selected from C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, NR5R6, (un)substituted phenyl, (un)substituted benzyl or (un)substituted 4-6 membered heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl and C3-C8-cycloalkyl; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8- cycloalkyl, and C(=O)R8. In one more preferred embodiment, the compounds of formula (I-1), wherein R11 is selected from CHF2, CF3, CH2CF3, -NHCH2CH3, -N(CH3)CH2CH3, -NH(C(CH3)3), -N(CH3)(C(CH3)3), -N(CH3)COCH3, - N(CH3)CO(cyclopropyl), -N=S(O)(CH3)2, cyclopropyl, cyanocyclopropyl, 3-chloro-pyrazol-1-yl, 3- trifluoromethyl-pyrazol-1-yl, 1,2,4-triazol-1-yl, pyrimidin-2-yl, pyridazyn-2-yl or pyridazyn-3-yl; wherein R11 is optionally substituted with F, Cl, CN, methyl or methoxy. In another preferred embodiment, the compounds of formula (I-1), wherein R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl; wherein R4 may optionally be substituted with R4a and R4a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6- haloalkyl, C3-C8-cycloalkyl, OR′′; In yet another preferred embodiment, the compounds of formula (I-1), wherein -S(Y)mR1 group represents, S(O)0-2R1; preferably S(O)2C1-C2 alkyl; more preferably S(O)2 ethyl. In yet another preferred embodiment, the compounds of formula (I-1), wherein -S(Y)mR1 group represents, S(O)(=NRY) R1; RY is hydrogen or C1-C3-alkyl, more preferably hydrogen, methyl, ethyl or isopropyl; and R1 is C1- C3-alkyl; more preferably R1 is methyl, ethyl, isopropyl; most preferably R1 is ethyl. In yet another preferred embodiment-A, the compounds of formula (I-1), wherein Z is O. In one embodiment, particularly compound of formula (I) is selected form 2-(ethylthio)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one; 7-bromo-2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylsulfonyl)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylthio)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; ((2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-l6-sulfanone; ((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7- yl)imino)dimethyl-l6-sulfanone; N-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin- 2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylthio)-N-methyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylthio)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine; 2- (ethylthio)-7-methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 7- ethoxy-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 2- (ethylsulfonyl)-N-methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7- amine; 2-(ethylsulfonyl)-N,N-dimethyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-7-amine; N-(cyclopropylmethyl)-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-N-isobutyl-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(cyclopropylmethyl)-2- (ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2- (ethylthio)-N,N-dimethyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7- amine; N-cyclopropyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-7-amine; N-ethyl-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-ethyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; (7-cyclopropyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; 6-bromo-2- (ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)- 7-methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 6-cyclopropyl-2- (ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylthio)-3- (5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; (6-cyclopropyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; 2- (ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; N-(tert- butyl)-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-6- amine; 6-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; 6-cyclopropyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine; ((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-l6-sulfanone; ethyl((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)(methyl)-l6-sulfanone; 2- (ethylsulfonyl)-6-methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; ethyl((2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-6- yl)imino)(methyl)-l6-sulfanone; ((2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl-l6-sulfanone; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)-6-(pyrimidin-5-yl)pyrazolo[1,5-a]pyrimidine; 7-bromo-2-(ethylthio)-3- (6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine; 6-(3,5-difluorophenyl)-2- (ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 2- (ethylsulfonyl)-6-(4-fluorophenyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; 1-(2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-6-yl)ethan-1-one; 7-bromo-2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin- 3-yl)pyrazolo[1,5-a]pyrimidine; 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine; N-(tert-butyl)-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine; 2- (ethylsulfonyl)-7-(4-fluorophenyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-7-amine; 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-5(4H)-one; 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-7-(pyrimidin-2- yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylthio)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin- 3-yl)pyrazolo[1,5-a]pyrimidine; 5-bromo-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine; N-(2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide; 7-cyclopropyl-2-(ethylsulfonyl)-3-(6- (2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylthio)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(tert- butyl)-2-(ethylthio)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7- amine; 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 5-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 2- (ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5- a]pyrimidin-7-amine; N-(tert-butyl)-2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3- yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)- 7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidine; N-(2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetamide N-(2-(ethylsulfonyl)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)pivalamide 2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-5-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidine; 2- (ethylsulfonyl)-N,N-dimethyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin- 5-amine 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-5-(pyrimidin-2- yl)pyrazolo[1,5-a]pyrimidine; N-(2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-5-yl)cyclopropanecarboxamide; 5-cyclopropyl-2-(ethylsulfonyl)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; 5-cyclopropyl-2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; (5-cyclopropyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; N-(2- (ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-5- yl)acetamide; 2-(ethylsulfonyl)-N-neopentyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-7- (trifluoromethyl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)-7-(trifluoromethyl)pyrazolo[1,5-a]pyrimidine; N-((5-cyclopropyl-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-l6- sulfaneylidene)cyanamide; 2-(ethylthio)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5- a]pyrimidin-7(4H)-one; 2,7-bis(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; (7-cyclopropyl-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5- a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; 2-(ethylsulfonyl)-N-methyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-5-amine; 2-(ethylsulfonyl)-N-neopentyl-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-5-amine; 2-(ethylsulfonyl)-5- methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; ((2-(ethylsulfonyl)-3- (5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-5-yl)imino)dimethyl-l6- sulfanone; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-N-(2,2,2- trifluoroethyl)pyrazolo[1,5-a]pyrimidin-5-amine; 2-(ethylsulfonyl)-N-isobutyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-5-amine; 2-(ethylsulfonyl)-5-(5-methyl-3- (trifluoromethyl)-1H-pyrazol-1-yl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-5-(1H-1,2,4-triazol-1- yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-5-(3- (trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidine; ((2-(ethylsulfonyl)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-l6-sulfanone; ethyl((2- (ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7- yl)imino)(methyl)-l6-sulfanone; diethyl((2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin- 3-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)-l6-sulfanone; N-(2-(ethylsulfonyl)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetamide; N-(2-(ethylsulfonyl)-3-(6- (2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropanecarboxamide; 2-(ethylsulfonyl)-N-methyl-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin- 7-amine; 2-(ethylsulfonyl)-N-isopropyl-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5- a]pyrimidin-7-amine; 2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)-7-(pyrimidin- 2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-7- (1H-1,2,4-triazol-1-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)-7-(3-(trifluoromethyl)-1H-1,2,4-triazol-1-yl)pyrazolo[1,5- a]pyrimidine; 2-(ethylsulfonyl)-7-(1-methyl-1H-pyrazol-5-yl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine; N-cyclopropyl-2-(ethylsulfonyl)-3-(6- (2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylsulfonyl)-7-(1- methyl-1H-pyrazol-5-yl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-7-(1-methyl-3- (trifluoromethyl)-1H-pyrazol-5-yl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine; 2-(ethylsulfonyl)-7-(1-methyl-3-(trifluoromethyl)-1H-pyrazol-5-yl)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl-2-(ethylthio)-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-7-(1-methyl-1H- pyrazol-5-yl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine; 7-cyclopropyl- 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidine; (7-(tert- butylamino)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-2- yl)(ethyl)(imino)-l6-sulfanone; 7-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2- yl)pyrazolo[1,5-a]pyrimidine; 2-(ethylsulfonyl)-N-methyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-(tert-butyl)-2-(ethylsulfonyl)-3-(6-(2,2,3,3,3- pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine; (7-cyclopropyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; 3-(7- cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6-(2,2,3,3,3- pentafluoropropoxy)pyridin-2(1H)-one; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2- yl)-N-(2,2,2-trifluoroethyl)pyrazolo[1,5-a]pyrimidin-7-amine; N-ethyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-ethyl-2-(ethylsulfonyl)-3-(6- (2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7-amine; (7-cyclopropyl-3-(5- (2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)-l6-sulfanone; N-ethyl-2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidin-7- amine; N-((7-cyclopropyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2- yl)(ethyl)(oxo)-l6-sulfaneylidene)cyanamide; N-((7-cyclopropyl-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)-l6- sulfaneylidene)cyanamide; 2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)-7- (pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidine; 3-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin- 3-yl)-1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one; N-cyclopropyl-2-(ethylsulfonyl)-3- (5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N- (cyclopropylmethyl)-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5- a]pyrimidin-7-amine; 2-(ethylsulfonyl)-N-isopropyl-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine; 2-(ethylthio)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)-7- (trifluoromethyl)pyrazolo[1,5-a]pyrimidine; ((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-l6-sulfanone; ethyl 2- (ethylthio)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5-a]pyrimidine-7-carboxylate; 2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)-7-(trifluoromethyl)pyrazolo[1,5- a]pyrimidine and ethyl 2-(ethylsulfonyl)-3-(6-(2,2,3,3,3-pentafluoropropoxy)pyridazin-3-yl)pyrazolo[1,5- a]pyrimidine-7-carboxylate. The term (un)substituted is referred as said groups are unsubstituted, or said groups are independently substituted with the substitutents selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2- C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, C1-C6-alkoxy and -S(O)0-2C1-C6-alkyl. 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 to 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. An anion part of the respective salt, in case the compound of formula (I) is represented by a cationic moiety or capable of forming a cationic moiety, can be inorganic or organic. Alternatively, the cation part of the respective salt, in case the compound of formula (I) is an ionic compound or is capable of forming an anion can be inorganic or organic. Examples of inorganic anion parts of the respective salt include but are not limited to chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, hydrogen carbonates and hydrogen sulfate. Examples of organic anion parts of the respective salt include but are not limited to formate, alkanoates, carbonates, acetates, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, maleate, citrates, benzoates, cinnamates, oxalates, alkylsulphates, alkylsulphonates, arylsulphonates aryldisulphonates, alkylphosphonates, arylphosphonates, aryldiphosphonates, p-toluenesulphonate, and salicylate. Examples of inorganic cation parts of the respective salt include but are not limited to alkali and alkaline earth metals. Examples of organic cation parts of the respective salt include but are not limited to pyridinium, methyl ammonium, imidazolium, benzimidazolium, histidinium, phosphonium, tetramethyl ammonium, tetrabutylammonium, cholinium and trimethylamonium. In one embodiment, the present invention provides a compound of formula (I), or an agrochemically acceptable salt, 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. The compounds of formula (I), including all stereoisomers, N-oxides, and salts thereof, typically exist in more than one physical form, and formula (I) thus includes all crystalline and non-crystalline forms of the compounds that formula (I) may represent. Non-crystalline forms include embodiments which are solids such as waxes, gums and glassy species 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 compound of formula (I) or agriculturally acceptable salts thereof. The compounds of the present invention as defined by formula (I) and/or in table (I) may be prepared, in a known manner, in a variety of ways as described in the schemes 1-15. The compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I). Scheme-1:
Figure imgf000037_0001
ave the meanings as described above A compound of general formula (I) wherein Z represents a direct bond, represented by formula (IAa), may be obtained from a compound of formula (Int-2b) under standard Suzuki cross coupling conditions with boronic acids or a boronic ester compound of formula (Int-1d). The Suzuki cross coupling reaction can be catalyzed by a palladium based catalyst, including but not limited to 1,1′- bis(diphenylphosphino)ferrocene]dichloropalladium(II) or tetrakis(triphenylphosphine) palladium(0), in a suitable solvent, for example tetrahydrofuran (THF), N,N’,dimethylformamide (DMF), 1,2- dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of tetrahydrofuran (THF)/water, 1,2- dimethoxyethane/water, 1,4-dioxane/water, or the like. The reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate or potassium phosphate. The reaction temperature can preferentially range from ambient temperature (20 °C) to the boiling point of the reaction mixture, or under microwave irradiation at a temperature between 70 °C and 150 °C to produce the compound of formula (I) as cited in the literature, see for example Chem. Soc. Rev. 2014, 43, 412-443 or in WO2014070978. Alternatively, the compound of formula (Int-2b) may be coupled with a hetroaryl tin compound of formula (Int-1d), in the presence of a catalyst such as bis(triphenylphosphine)palladium(II)dichloride, tetrakis(triphenylphosphine)palladium(0), 1,1’-bis(diphenylphosphino)ferrocene palladium(II)chloride, tris(dibenzylideneacetone)dipalladium(0), and palladium(II)acetate; nickel catalysts such as bis(cyclooctadiene)nickel(0) and nickel(II) chloride; and copper catalysts such as copper(I) iodide and copper(I) chloride, in the presence of a base such as alkali metal hydrides, alkali metal carbonates, and organic bases, in a suitable solvent such as acetonitrile, tetrahydrofuran (THF), N,N’,dimethylformamide (DMF), 1,2-dimethoxyethane, 1,4-dioxane, at a temperature between 25 °C and the reflux temperature of the solvent, or under microwave irradiation at a temperature between 70 °C and 150 °C. A ligand and/or an inorganic halogenated compound may be added to the reaction as needed. Examples of such ligands to be used in the reaction include triphenylphosphine, Xantphos, 2,2’-bis(diphenylphosphino)-1,1’- binaphthyl, 1,1’-bis(diphenylphosphino)ferrocene, 2-(dicyclohexylphosphino)-2’, 4’, 6’-triisopropyl-1,1’- biphenyl, 2-aminoethanol, 8-hydroxyquinoline and 1,10-phenanthroline. Examples of inorganic halogenated compounds to be used include alkali metal fluorides such as potassium fluoride and sodium fluoride; and alkali metal halides such as lithium chloride, sodium chloride and sodium chloride. Scheme-2:
Figure imgf000038_0001
Scheme-2 represents the process for preparing compounds of formula (Int-2b). Compounds of formula (Int-2) which can be prepared by literature methods (WO2020/250183) can be further converted into compounds of formula (22) under Curtius rearrangement conditions. This rearrangement can be performed using sodium azide or diphenyl phosphorazidate in the presence of a base such as triethylamine or diisopropylethylamine, in a solvent such as methanol, ethanol, tert-butyl alcohol or benzyl alcohol, carried out at temperatures ranging from about 25 and 150 °C. Compounds of formula (Int-2a) can be obtained by simple deprotection of the corresponding carbamates under basic or acidic or hydrogenation conditions depending upon the nature of the respective carbamate. Acidic conditions such as hydrochloride or trifluoroacetic acid, in the presence of dioxane or dichloromethane or dichlorethane or chloroform, at temperatures ranging from 0 and 120 °C can be implemented for cases where R” = tert- butyl. When R” = Me or Et, basic conditions can be implemented such as lithium hydroxide or sodium hydroxide or potassium hydroxide, in the presence of methanol or ethanol or 2-methylpropanol, at temperatures ranging from 0 and 120 °C. Deprotection can be carried out under hydrogenation such as by hydrogen gas in the presence of palladium metal such as palladium on charcoal or palladium(II) hydroxide, in the presence of methanol or ethanol or ethylacetate at pressure, usually ranging from 1 to 10 bar at 25 °C. The amine derivative (Int-2a) can be converted into a compound of formula (Int-2b), where X is a halogen, by diazotation using e.g. sodium nitrite or tert-butyl nitrite and subsequent substitution using a suitable copper halide, in an appropriate solvent such as dichloromethane, 1,2-dichloroethane, toluene or water, at temperatures ranges between 0 and 100 °C. Scheme-3:
Figure imgf000039_0001
s of general formula (Int-1d) from appropriate halides or triflates of compounds of formula (Int-1a) by reaction with a reagent such as hexamethylditin or triethyltin chloride in presence of a catalyst such as tetrakis(triphenylphosphine)palladium(0), in the presence of a base such as potassium carbonate, in a suitable solvent such as N,N’,dimethylformamide (DMF), or a mixture of two or more appropriate solvents, at a temperature between 25 °C and the reflux temperature of the respective solvent, or under microwave irradiation at a temperature between 70 °C and 160 °C. Alternatively, compounds of general formula (Int-1d) may be obtained from compounds of formula (Int- 1a) by reacting with a reagent such as n-butyllithium in a suitable aprotic solvent such as tetrahydrofuran (THF) at temperature between -100 °C and 25 °C and then reacted with a reagent such as hexamethylditin or triethyltin chloride in a suitable aprotic solvent such as tetrahydrofuran (THF) at temperature between - 100 °C and 50 °C. Scheme-4:
Figure imgf000039_0002
wherein Q, R1, A, G1, G2, E, and m have the meanings as described above Alternatively, compounds of formula (I), wherein Z represents a direct bond, represented by compounds of formula (IAa), can be obtained by reacting compounds of formula (Int-2b) with compounds of formula (Int-1a) under Ni-catalyzed reductive coupling reactions. This reaction may be catalyzed by nickel(II)chloride hexahydrate, anhydrous nickel(II)chloride, nickel(II)iodide, nickel(II) chloride ethylene glycol dimethyl ether complex, bis(triphenylphosphine)nickel(II) dichloride, or bis(1,5- cyclooctadiene)nickel(0), in the presence of an equivalent to excess amount of zinc or manganese metal. A ligand can be used in case it is needed or recommended to support the respected catalyst. Examples of the ligand include but are not limited to 1,10-phenanthroline, 4,7-dimethyl-1,10-phenathroline or 4,7- dimethoxy-1,10-phenathrolin 3,4-dimethyl-1,10-phenanthroline or 2,2'-bipyridine or 4,4'-dimethyl-2,2'- bipyridine or 4,4'-ditert-butyl-2,2'-bipyridine or triphenyl phosphine or 1,2-bis(diphenylphosphino)ethane or 1,3-bis(diphenylphosphino)propane. Any additive may or may not be required in the above reaction. In such cases examples of the additive include but are not limited to sodium or potassium iodide, lithium chloride, lithium methoxide, trimethylchlorosilane or magnesium (II) chloride. The reaction can be carried out in an appropriate solvent such as N,N-dimethyl formamide, N,N-dimethylacetamide, N- methyl-2-pyrrolidone or N,N′-Dimethylpropyleneurea (DMPU), at temperatures ranges between 25 °C and 100 °C. Such reactions have been described in the literature, for example, J. Org. Chem., 2014, 79, 777-782 or Top. Curr. Chem. (2016) 374:43. Scheme-5:
Figure imgf000040_0001
wherein Q, Z, R1, A, G1, G2, E, and m have the meanings as described above A compound of formula (IAa-1) can be prepared by reacting a compound of formula (Int-2b) with a cyclic amide compound of formula (Q2) (which can be prepared by literature procedure as described in US2019/0327970). The above mentioned conversion can be performed using a base such as alkalimetal carbonate, alkalimetal hydride, sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyldisilazane, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undec-7-ene, 4- (dimethylamino)pyridine, in an appropriate solvent such as acetonitrile, tetrahydrofuran, dimethyl slufoxide, N,N-dimethylformamide, N,N-dimethyl acetamide, or N-methyl-2-pyrrolidone, at a temperature range between 25 °C and 120 °C. Alternatively a compound of formula (IAa-1) can be prepared by metal catalysis. Examples of the metal catalyst include but are not limited to copper catalysts such as copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I)oxide, trifluromethanesulfonicacid copper(I)salt benzene complex, or 2- thiophenecarboxylic acid copper(I)salt; and nickel catalysts such as bis(cyclooctadiene)nickel(0) and nickel chloride, and a ligand, for example 1,10-phenanthroline, 8-hydroquinoline, trans-1,2- cyclohexanediamine, trans-1,2-bis(methylamino)cyclohexane, N,N-dimethylethylenediamine, 2,2'- bipyridine, 2-aminoethanol, triphenyl phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3- bis(diphenylphosphino)propane, XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen- 4yl)diphenylphosphane), XPhos (2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), RuPhos (2- Dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl), BINAP (2,2’-bis(diphenylphosphino)-1,1’- binaphthalene), or 1,1’-bis(diphenylphosphino)ferrocene. Examples appropriste bases include but are not limited to alkalimetal carbonates, diisopropylethylamine, pyridine, 1,8-Diazabicyclo[5.4.0]undec-7-ene or 4-(dimethylamino)pyridine, in an appropriate solvent such as acetonitrile, dimethyl slufoxide, N,N- dimethylformamide, N,N-dimethyl acetamide, or N-methyl-2-pyrrolidone, at temperatures ranges between 25 °C and 120 °C. Scheme-6:
Figure imgf000041_0001
w ere n Q, , , , , , , an m ave the meanings as described above. Compounds of formula (IAa-2) can be obtained by reacting a compound of formula (Int-2b) with a hydroxy compound of formula (Int-1c). The reaction is usually carried out in the presence of a base such as alkali metal carbonates and alkali metal hydrides, in an appropriate solvent including but not limited to acetonitrile, tetrahydrofuan N,N-dimethylformaide, at temperatures ranges between 0 and 150 °C. Compounds of formula (Int-3c) can be prepared following methods as described in WO2005/018557, WO2009/149188, WO2010/104818, and WO2015/153304. Alternatively, compounds of formula (IAa-2) can be prepared by reacting a hydroxy derivative (Int-1c) and a compound of formula (Int-2b), in the presence of a metal catalyst and a base. Examples of the metal catalyst include but are not limited to copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I) oxide, copper(I)trifluoromethanesulfonate benzene complex, and tetrakis (acetoform) copper (I), copper(I) 2-thiophene carboxylate; nickel catalysts such as bis (cyclooctadien) nickel (0) and nickel(II)chloride, preferably supported by a ligand such as 1,10-phenanthroline, 8-hydroquinoline, trans- 1,2-cyclohexanediamine, trans-1,2-bis(methylamino)cyclohexane, N,N-dimethylethylenediamine, 2,2'- bipyridine, 2-aminoethanol, triphenyl phosphine, 1,2-bis(diphenylphosphino)ethane, 1,3- bis(diphenylphosphino)propane, XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen- 4yl)diphenylphosphane), XPhos (2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), RuPhos (2- Dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl), BINAP (2,2’-bis(diphenylphosphino)-1,1’- binaphthalene), or 1,1’-bis(diphenylphosphino)ferrocene. Examples of the base include but are not limited to alkalimetal carbonates, alkalimetal hydrides, triethylamine, diisopropylethylamine, pyridine and 4- (dimethylamino) pyridine. Appropriate solvents for carrying out these reactions are such as acetonitrile, tetrahydrofuan, N,N-dimethylformaide, or aromatic hydrocarbons. Typical temperatures for carrying out these reactions are between 0 and 130 ° C. Scheme-7:
Figure imgf000042_0001
wherein Q, Z, R1, RY, A, G1, G2, E, and n have the meanings as described above. Compounds of formua (IB) can be obtained by sulfimination/sulfoximination of a compound of formula (IA) wherein n=0, as described in Chem.Commun., 2017, 53, 2064; Tertahedron Lett.2005, 46, 8007 and WO2015071180A1. Scheme-8:
Figure imgf000042_0002
According to scheme-8, the present invention provides a method for the preparation of intermediate compounds of formula (4) starting from appropriate halides or triflates of formula (Int-1a) wherein Q is as defined above. Compounds of formula (3) can be formed by reacting a compound of formula (Int-1a) with a compound of formula (2) (R” is preferably lower alkyl such as methyl, ethyl or tert-butyl ester in this case) in the presence of a base such as alkali metal carbonates (such as sodium, potassium or cesium carbonate) (hereinafter, collectively referred to as alkali metal carbonates); and alkali metal hydrides such as sodium or potassium hydride (hereinafter, collectively referred to as alkali metal hydrides), sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyl disilazane, in an appropriate solvent such as tetrahydrofuran, dioxane, acetonitrile, dimethylsulfoxide, N,N-dimethylfromamide, or N,N- dimethylacetamide, at temperatures between 0 and 120 °C. Alternatively, compounds of formula (4) can be prepared under metal catalysis in the presence of a base. Applicable metal catalysts are such as palladium(II)acetate, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3 optionally in form of its chloroform adduct; tetrakis(triphenylphosphine)palladium(0); copper catalysts such as copper(I)iodide, copper(I)bromide, copper(I)chloride, copper(I)oxide, trifluromethanesulfonicacid copper(I)salt benzene complex , 2-thiophenecarboxylic acid copper(I)salt, and a ligand, for example triphenylphosphine, 1,1’- bis(diphenylphosphino)ferrocene, XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen- 4yl)diphenylphosphane), XPhos (2-Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), RuPhos (2- Dicyclohexylphosphino-2′,6′-diisopropoxybiphenyl), BINAP (2,2’-bis(diphenylphosphino)-1,1’- binaphthalene), L-proline, 2-Pyridinecarboxylic acid, optinally in form of its HCl salt; examples of the base include but are not limited to alkali metal carbonates, sodium or potassium tert-butoxide, lithium, sodium or potassium hexamethyl disilazane, in an appropriate solvent such as tetrahydrofuran, dioxane, dimethylsulfoxide, N,N-dimethylfromamide and N,N-dimethylacetamide, at temperatures between 0 and 150 °C. Compounds of formula (4) can be obtained from a compound of formula (3) by a decarboxylation reaction carried out under basic or acidic conditions converting the alkyl ester group. Acidic conditions can be realized by the use of reagents such as p-toluenesulfonic acid, trifluroacetic acid, hydrochloric acid; basic conditions can be realized by the use of lithium, sodium or potassium hydroxide. Appropriate solvents for conducting such reactions are such as acetonitrile, dioxane, dimethylsulfoxide, dichloromethane, 1,2-dichloroethane, methanol, ethanol, 2-propanol and water, at temperature ranges between 25 °C and 150 °C. Such examples are described in the literature, as for instance in EP1674455, EP1548007. Alternatively, compounds of formula (4) can be formed in a single step, by reacting a compound of formula (1) with acetonitrile in the presence of a base. Examples for such a base are such as n-butyl lithium or t-butyl lithium, methyllithium, or phenyl lithium, or lithium, sodium or potassium hexamethyl disilazane. Appropriate solvents for such reactions are such as tetrahydrofuran, methyl tetrahydrofuran, diethyl ether, at temperatures between -78 and 0 °C. Such examples are described in the literature, as for instance in Tetrahedron Letters, 2014, 55, 5963. Scheme-9:
Figure imgf000044_0001
A process for the synthesis of compounds of formula (Q-Int-1aa) is depicted in scheme-9. (Organo sulfanyl) alkenes of formula (5) can be formed by reacting cyano compounds of formula (4) with CS2 in the presence of a base such as alkalimetal carbonates, alkalimetal hydrides, lithium, sodium or potassium hexamethyl disilazane, sodium or potassium hydroxide, in an appropriate solvent such as tetrahydrofuran, acetonitrile and N,N-dimethylfromamide, at temperatures between 0 and 50 °C. The compounds of formula (5) can be cyclized to the aminopyrazole derivatives (6) using hydrazine. Such methods are described in the literature, for example in Russian Journal of Organic Chemistry, 2014, 50(3), 412-421. The respective aminopyrazole derivatives can be converted in to the compounds of formula (8) using reagents such as (7) under acidic medium using acids such as acetic acid, or p-toluenesulfonic acid, in an appropriate solvent such as ethanol, 2-propanol, toluene, xylene, N,N-dimethylformamide, at temperatures between 80 and 130 °C. (Journal of Medicinal Chemistry, 58(18), 7140-7163; 2015). The conversion of compounds of formula (8) into compounds of formula (9) can be carried out in a solvent and in the presence of a halogenating agent, in the presence or absence of a base. Examples of the solvent include but are not limited to acetonitrile, chloroform, tetrahydrofuran, 1,4-dioxane, toluene, N,N- dimethylformamide and the like. Examples of halogenating agents include but are not limited to phosphorous oxychloride, thionyl chloride, phosphorous pentachloride, oxalyl chloride, and the like. Examples of base include but are not limited to N,N-dimethylaniline, diisopropylethylamine, N- methylmorpholine and the like. The reaction can be carried out at temperatures ranging from 50-200 °C. The compounds of formula (Q-Int-1aa) wherein Y=O, m=1 (sulfoxide) and/or m=2 (sulfone), can be obtained by the oxidation of the corresponding sulfide compounds of formula (9) while applying appropriate oxidizing agents and conditions well known to those skilled in the art. Oxidizing agents such as m-chloroperoxybenozic acid (mCPBA), hydrogenperoxide/glacial acetic acid, hydrogenperoxide/trifluroacetic acid, hydrogenperoxide/potassium permanganate, hydrogenperoxide/p- toluenesuflonylimidazole, urea hydrogen peroxide/ trifluroacetic acid, oxone, sodium periodate, sodium hypochlorite and other orgnaic peracids and the like can be used for this. Examples of solvents useful in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane, chloroform: alcohols such as mehnaol and ethanol and the mixtures thereof. Scheme-10:
Figure imgf000045_0001
wherein Q, R1, R2, R4, X, Y, and m have the meanings as described above Pyrazole derivativeas of formula (6) can undergo cyclocondensations with 1,3-dimethyl uracil type compounds of formula (10) or alkoxyacrylate derivatives of formula (11) in the presence of a base to obtain pyrimidin-5-one derivatives of formula (12). Examples of the base include sodium ethoxide, sodium methoxide, sodium or potassium tert-butoxide, alkalimetal carbonates, potassium phosphate, and the like. Examples of solvents being useful in this process include methanol, ethanol, isopropanol, ethylene glycol, N,N-dimethylacetamide, N,N-dimethylformamide, and the like. The respective reaction can be carried out at temperatures ranging from about 50 °C to about 150 °C. Such reactions are well known, and also alternative reactions are well described in the literature, for example in J. Org. Chem. 2007, 72, 1046, or in WO2018081417. Halogenation of compounds of formula (12) using phosphorous oxychloride or phosphorous oxybromide allows to obtain compounds of formula (13) as described in WO201108689, for example. The compounds of formula (Q-Int-1ab) can be obtained from (13) in a similar manner as described in step-5 of scheme-9. Scheme-11:
Figure imgf000046_0001
wherein Q, R1, X, Y, and m have the meanings as described above Bisacetal protected malonaldehyde compounds of formula (14) can be activated by halogenation with a halogenating agent, such as bromine, iodine, chlorine, N-bromosuccinimide, N-iodosuccinimide, or N- chlorosuccinimide under acidic conditions, established by utilizing an acid independently selected from hydrochloric acid, sulfuric acid, methanesulfonic acid, trifluoroacetic acid, tetrafluoroboric acid or p- toluenesulfonic acid in a suitable solvent, e.g., water, to obtain a halogenated aldehyde, such as chloro-, iodo- or bromomalonaldehyde of formula (15). Following step 2, compounds of formula (15) can be reacted with pyrazole derivatives of formula (6) under suitable condensation conditions to obtain compounds of formula (17). Examples of the solvent being useful during this step include but are not limited to dimethyl sulfoxide, N,N-dimethylacetamide, N,N-dimethylformamide, and to mixtures thereof. The reaction can be carried out at temperatures ranging from about 50 °C to about 150 °C. Compounds of formula (17) can be further conveniently oxidized to the corresponding sulfoxide Y=O, m=1 or sulfone Y=O, m=2 under the mentioned reaction conditions of step-5 in scheme 9 to obtain compounds of formula (Q-Int-1ac). Alternatively, compounds of formula (17) can also be prepared by cyclization of pyrazole derivatives of formula (6) with commercially available 2-halo-malonaldehydes of formula (16) under acid catalyzed conditions. Examples of such acids include but are not limited to acetic acid, sulfonic acids (e.g., PTSA), sulfuric acid, and hydrochloric acid. Examples of solvents being useful in this step include but are not limited to methanol, ethanol, isopropanol, ethylene glycol, and the like. The respective reactions can be carried out at temperatures ranging from about 0 °C to about 150 °C. (J. Het. Chem.1974, 44, 51). Scheme-12:
Figure imgf000047_0001
w ere n Q, , , , , an m ave e mean ngs as escr e above Compounds of formula (Q-Int-1aa/1ab/1ac) can be coupled under standard Suzuki cross coupling conditions with boronic acids or boronic ester compounds of formula (18) to obtain compounds of formula (Q-1aa). The Suzuki cross coupling reaction can be catalyzed by a palladium based catalyst, including but not limited to 1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) or tetrakis(triphenylphosphine) palladium(0), in a suitable solvent as for example tetrahydrofuran (THF), N,N′-dimethylformamide (DMF), 1,2-dimethoxyethane, 1,4-dioxane or a solvent system such as a mixture of tetrahydrofuran (THF)/water, 1,2-dimethoxyethane/water, 1,4-dioxane/water, or the like. The reaction is usually carried out in the presence of a base, for example potassium carbonate, cesium carbonate or potassium phosphate. The reaction temperature can preferentially range from ambient temperature (20 °C) to the boiling point of the reaction mixture as precedented in the literature, see for example Chem. Soc. Rev.2014, 43, 412-443 or in WO2014070978. Alternatively scompounds of formula (Q-1aa) can also be formed by subjecting corresponding sulfides to Suzuki conditions mentioned as above, and followed by oxidation under any of the given conditions for step-5 in scheme-9. Scheme-13:
Figure imgf000048_0001
meanings as described above Compounds of formula (Q-1ab) can be prepared by reacting compounds of formula (Q-Int-1aa/1ab/1ac), with a reagent NH=S(O)R5R6 represented by formula (19), wherein R5 and R6 are as defined in formula (I). The reaction may be catalyzed by a palladium based catalyst, involving for example bis(dibenzylideneacetone)palladium(0) (Pd(dba)2), tris(dibenzylideneacetone)dipalladium(0) (Pd2(dba)3; optionally in form of its chloroform adduct), or palladium(II)acetate, and a ligand, for example XantPhos ((5-di-phenylphosphanyl-9,9-dimethyl-xanthen-4yl)diphenylphosphane), XPhos (2- Dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl), RuPhos (2-Dicyclohexylphosphino-2′,6′- diisopropoxybiphenyl), or BINAP (2,2’-bis(diphenylphosphino)-1,1’-binaphthalene), in presence of a base, as sodium, potassium or cesium carbonate, sodium or potassium tert-butylate, or potassium phosphate, using a solvent or a solvent mixture, as for example dioxane, 1,2-dimethoxyethane or toluene, preferably under inert atmosphere. The reaction temperature can prefrentially range from room temperaturte to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation. Such reactions, and alternative conditions such as iron or copper catalysis, have been described, for example, in WO2018/099812. Scheme-14:
Figure imgf000048_0002
Wherein Q, R1, R5, R6, X, Y, and m have the meanings as described above Compounds of formula (Q-1ac) can be prepared by reacting compounds of formula (Q-Int-1aa/1ab/1ac) with a reagent of formula (20), wherein R5 and R6 are as defined in formula (I), in the presence of a base. Examples of the base include but are not limited to sodium carbonate, potassium carbonate or cesium carbonate, sodium tert-butylate or potassium tert-butylate, diisopropylethylamine, triethylamine or DBU, in a solvent selected from tetrahydrofuran, N,N-dimethylformamide or acetonitrile. The reaction can be carried out at temperatures ranging from about 25 to about 130 °C. Alternatively, compounds of formula (Q-1ac) can be prepared by reacting compounds of formula Q-Int- 1aa/1ab/1ac), under catalyzed conditions mentioned in step-1 of scheme-13. Scheme-15:
Figure imgf000049_0001
, , , , meanings as described above Compounds of formula (Q-1ad) can be prepared by reacting compounds of formula (Q-Int-1aa/1ab/1ac) with a reagent of formula (21), wherein R4 is as defined in formula X, in the presence of a base. Examples of the base include but are not limited to alkalimetal hydrides, alkalimetal carbonates, sodium or potassium tert-butylate, diisopropylethylamine, triethylamine or DBU, thereby using a solvent such as tetrahydrofuran, N,N-dimethylformamide or acetonitrile. The reaction can be carried out at temperatures ranging from about 25 to about 130 °C. Alternatively, compounds of formula (Q-1ad) can be prepared from compounds of formula (Q-Int- 1aa/1ab/1ac) using copper catalyzed conditions. Copper based catalyst, used for this purpose involve for example copper(I) iodide, copper(I) bromide, copper(I) chloride or copper(I) acetate and a ligand, for example 1,10-phenanthroline, 4,7-dimethyl-1,10-phenathroline, 4,7-dimethoxy-1,10-phenathrolin, 4,7- diphenyl-1,10-phenathrolin, or L-proline, in the presence of a base, like sodium carbonate, potassium carbonate or cesium carbonate, or sodium or potassium tert-butylate, in a solvent or a solvent mixture as for example dioxane, 1,2-dimethoxyethane, toluene, acetonitrile, or N,N-dimethylformamide preferably under inert atmosphere. The reaction temperature can range preferably from room temperature to the boiling point of the reaction mixture, or the reaction may be performed under microwave irradiation. In another embodiment, the present invention provides a process for the preparation of compounds of formula (I) or salts thereof. The compounds of formula (I) including their stereoisomers, salts, and N-oxides, and their precursors in the mentioned synthesic processes, 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 respective precursors, 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. 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. If individual target compounds of formula (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, a separation is generally not necessarily required since in some cases the individual isomers can be interconverted during work-up for use or during application (e.g., under the action of light, acids or bases). Such conversions may also take place during or after use, e.g., during the treatment of plants or within the treated plant, or even in the harmful fungus to be controlled. The compounds of formula (I) according to the following Tables A-1 to A-93 can be prepared according to the methods described above. The examples which follow are intended to illustrate the invention and show preferred compounds of formula (I), in the form of a compound of formula (I-1).
Figure imgf000050_0001
Formula (I-1) Table A-1 provides 28 compounds A-1.001 to A-1.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000051_0001
For example, A-1.015 is initions of R11
Figure imgf000051_0002
Sr. 11 21 R11 No
Figure imgf000051_0006
Figure imgf000051_0007
Figure imgf000051_0005
Table A-2 provides 28 compounds A-2.001 to A-2.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000051_0003
Table A-3 provides 28 compounds A-3.001 to A-3.028 of formula (I-1) wherein Q , Z is 10 direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000051_0004
Table A-4 provides 28 compounds A-4.001 to A-4028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0001
Table A-5 provides 28 compounds A-5.001 to A-5.028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0002
Table A-6 provides 28 compounds A-6.001 to A-6.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0003
Table A-7 provides 28 compounds A-7.001 to A-7.028 of formula (I-1) wherein Q , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0004
Table A-8 provides 28 compounds A-8.001 to A-8.028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0005
Table A-9 provides 28 compounds A-9.001 to A-9.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0006
Table A-10 provides 28 compounds A-10.001 to A-10.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0007
Table A-11 provides 28 compounds A-11.001 to A-11.028 of formula (I-1) wherein , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0008
Table A-12 provides 28 compounds A-12.001 to A-12.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0009
Table A-13 provides 28 compounds A-13.001 to A-13.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000052_0010
Table A-14 provides 28 compounds A-14.001 to A-14.028 of formula (I-1) wherein Q a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0002
Table A-15 provides 28 compounds A-15.001 to A-15.028 of formula (I-1) wherein direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0003
Table A-16 provides 28 compounds A-16.001 to A-16.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0001
Table A-17 provides 28 compounds A-17.001 to A-17.028 of formula (I-1) wherein , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0004
Table A-18 provides 28 compounds A-18.001 to A-18.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0005
Table A-19 provides 28 compounds A-19.001 to A-19.028 of formula (I-1) wherein Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B. Table A-20 provides 28 compounds A-20.001 to A-20.028 of formula (I-1) wherein Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B. Table A-21 provides 28 compounds A-21.001 to A-21.028 of formula (I-1) wherein Q a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0006
Table A-22 provides 28 compounds A-22.001 to A-22.028 of formula (I-1) wherein s a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0007
Table A-23 provides 28 compounds A-23.001 to A-23.028 of formula (I-1) wherein Q a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000053_0008
Table A-24 provides 28 compounds A-24.001 to A-24.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0001
Table A-25 provides 28 compounds A-25.001 to A-25.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0002
Table A-26 provides 28 compounds A-26.001 to A-26.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0003
Table A-27 provides 28 compounds A-27.001 to A-27.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0004
Table A-28 provides 28 compounds A-28.001 to A-28.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0005
Table A-29 provides 28 compounds A-29.001 to A-29.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0006
Table A-30 provides 28 compounds A-30.001 to A-30.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0007
Table A-31 provides 28 compounds A-31.001 to A-31.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR1 is -S(O)2Et, and R11 are as defined in table B.
Figure imgf000054_0008
Table A-32 provides 28 compounds A-32.001 to A-32.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000054_0009
Table A-33 provides 28 compounds A-33.001 to A-33.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B
Figure imgf000055_0001
Table A-34 provides 28 compounds A-34.001 to A-34.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0002
Table A-35 provides 28 compounds A-35.001 to A-35.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0003
Table A-36 provides 28 compounds A-36.001 to A-36.028 of formula (I-1) wherein Q is , Z is direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0004
Table A-37 provides 28 compounds A-37.001 to A-37.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0005
Table A-38 provides 28 compounds A-38.001 to A-38.028 of formula (I-1) wherein , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0006
Table A-39 provides 28 compounds A-39.001 to A-39.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0007
Table A-40 provides 28 compounds A-40.001 to A-40.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000055_0008
Table A-41 provides 28 compounds A-41.001 to A-41.028 of formula (I-1) wherein , direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R1
Figure imgf000055_0009
Z is a 1 are as defined in table B. Table A-42 provides 28 compounds A-42.001 to A-42.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0001
Table A-43 provides 28 compounds A-43.001 to A-43.028 of formula (I-1) where , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0002
Table A-44 provides 28 compounds A-44.001 to A-44.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0003
Table A-45 provides 28 compounds A-45.001 to A-45.028 of formula (I-1) wherein Q i Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0004
Table A-46 provides 28 compounds A-46.001 to A-46.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0005
Table A-47 provides 28 compounds A-47.001 to A-47.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0006
Table A-48 provides 28 compounds A-48.001 to A-48.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0007
Table A-49 provides 28 compounds A-49.001 to A-49.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0008
Table A-50 provides 28 compounds A-50.001 to A-50.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0009
Table A-51 provides 28 compounds A-51.001 to A-51.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000056_0010
Table A-52 provides 28 compounds A-52.001 to A-52.028 of formula (I-1) wherein Q i Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0001
Table A-53 provides 28 compounds A-53.001 to A-53.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0002
Table A-54 provides 28 compounds A-54.001 to A-54.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0003
Table A-55 provides 28 compounds A-55.001 to A-55.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0004
Table A-56 provides 28 compounds A-56.001 to A-56.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0005
Table A-57 provides 28 compounds A-57.001 to A-57.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0006
Table A-58 provides 28 compounds A-58.001 to A-58.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0007
Table A-59 provides 28 compounds A-59.001 to A-59.028 of formula (I-1) wherein Q and Z together represen , -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0008
Table A-provides 28 compounds A-33.001 to A-3360.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000057_0009
Table A-61 provides 28 compounds A-61.001 to A-61.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B. Table A
Figure imgf000058_0001
ompounds A-62.001 to A-62.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(=NH)Et, and R11 are as defined in table B.
Figure imgf000058_0002
Table A-63 provides 28 compounds A-63.001 to A-63.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B
Figure imgf000058_0003
Table A-64 provides 28 compounds A-64.001 to A-64.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B
Figure imgf000058_0004
Table A-65 provides 28 compounds A-65.001 to A-65.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000058_0005
Table A-66 provides 28 compounds A-66.001 to A-66.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000058_0006
Table A-67 provides 28 compounds A-67.001 to A-67.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000058_0007
Table A-68 provides 28 compounds A-68.001 to A-68.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000058_0008
Table A-69 provides 28 compounds A-69.001 to A-69.028 of formula (I-1) wherein , m 1 (NMe)Et, and R11
Figure imgf000058_0009
Z is a direct bond, -S(Y) R is S(O) are as defined in table B. Table A-70 provides 28 compounds A-70.001 to A-70.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000058_0010
Table A-71 provides 28 compounds A-71.001 to A-71.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0001
Table A-72 provides 28 compounds A-72.001 to A-72.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0002
Table A-73 provides 28 compounds A-73.001 to A-73.028 of formula (I-1) wherein Q i , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0003
Table A-74 provides 28 compounds A-74.001 to A-74.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0004
Table A-75 provides 28 compounds A-75.001 to A-75.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0005
Table A-76 provides 28 compounds A-76.001 to A-76.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0006
Table A-77 provides 28 compounds A-77.001 to A-77.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0007
Table A-78 provides 28 compounds A-78.001 to A-78.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0008
Table A-79 provides 28 compounds A-79.001 to A-79.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0009
Table A-80 provides 28 compounds A-80.001 to A-80.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000059_0010
Table A-81 provides 28 compounds A-81.001 to A-81.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0001
Table A-82 provides 28 compounds A-82.001 to A-82.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0002
Table A-83 provides 28 compounds A-83.001 to A-83.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0003
Table A-84 provides 28 compounds A-84.001 to A-84.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0004
Table A-85 provides 28 compounds A-85.001 to A-85.028 of formula (I-1) wherein Q is , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0005
Table A-86 provides 28 compounds A-86.001 to A-86.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0006
Table A-87 provides 28 compounds A-87.001 to A-87.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0007
Table A-88 provides 28 compounds A-88.001 to A-88.028 of formula (I-1) wherein Q , Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0008
Table A-89 provides 28 compounds A-89.001 to A-89.028 of formula (I-1) wherein Q Z is a direct bond, -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000060_0009
Table A-90 provides 28 compounds A-90.001 to A-90.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000061_0001
Table A-91 provides 28 compounds A-91.001 to A-91.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B. Table A-92 provides 28 compounds A-92.001 to A-92.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000061_0002
Table A-93 provides 28 compounds A-93.001 to A-93.028 of formula (I-1) wherein Q and Z together represent , -S(Y)mR1 is S(O)(NMe)Et, and R11 are as defined in table B.
Figure imgf000061_0003
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) agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof and at least one additional component selected from the group consisting of surfactants and auxiliaries. In 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, antibiotics, fertilizers or nutrients. In yet another embodiment, the present invention provides a compound of formula (I) or its N-oxides and salts into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or 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 types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No.2, 6th Ed. May 2008, CropLife International. The compositions 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, Agrow Reports DS243, T and F Informa, London, 2005. Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers or binders. Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof. Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof. Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon′s, Vol.1: Emulsifiers and Detergents, McCutcheon′s Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.). Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylarylsulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyland tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates. Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar- based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugarbased surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homeor copolymers of vinylpyrrolidone, vinylalcohols, or vinylacetate. Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or polyethyleneamines. Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, TandF Informa UK, 2006, chapter 5. Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates. Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones. Suitable anti- freezing agents are ethylene glycol, propylene glycol, urea and glycerin. Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and watersoluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin-, azoand phthalocyanine colorants). Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers. Examples for composition types and their preparation are: i) Water-soluble concentrates (SL, LS) 10-60 wt% of a compound (I) or an N-oxide or salt thereof and 5-15 wt% of a wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water. ii) Dispersible concentrates (DC) 5-25 wt% of a compound (I) or an N-oxide or salt thereof and 1-10 wt% of a dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% of an organic solvent (e.g. cyclohexanone). Dilution with water gives dispersion. iii) Emulsifiable concentrates (EC) 15-70 wt% of a compound (I) or an N-oxide or salt thereof and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% of a water insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES) 5-40 wt% of a compound (I) or an N-oxide or salt thereof and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% of a water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion. v) Suspensions (SC, OD, FS) In an agitated ball mill, 20-60 wt% of a compound (I) or an N-oxide or salt thereof are comminuted with the addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% of a binder (e.g. polyvinylalcohol) is added. vi) Water-dispersible granules and water-soluble granules (WG, SG) 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of a compound (I) or an N-oxide or salt thereof are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1-3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% of a solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance. viii) Gel (GW, GF) In an agitated ball mill, 5-25 wt% of a compound (I) or an N-oxide or salt thereof are comminuted with the addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, ix) Microemulsion (ME) 5-20 wt% of a compound (I) or an N-oxide or salt thereof are added to 5-30 wt% of an organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% of a surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion. x) Microcapsules (CS) An oil phase comprising 5-50 wt% of a compound (I) or an N-oxide or salt thereof, 0-40 wt% of a water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% of acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a dior triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization, initiated by a radical initiator, results in the formation of poly(methyl acrylate) microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the present invention, 0-40 wt% of a water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylmethene-4,4′-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition, xi) Dustable powders (DP, DS) 1-10 wt% of a compound I or an N-oxide or salt thereof are ground finely and mixed intimately with up to 100 wt% of a solid carrier, e.g. finely divided kaolin. xii) Granules (GR, FG) 0.5-30 wt% of a compound I or an N-oxide or salt thereof is ground finely and associated with up to 100 wt% of a solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed. xiii) Ultra-low volume liquids (UL) 1-50 wt% of a compound (I) or an N-oxide or salt thereof are dissolved in up to 100 wt% of an organic solvent, e.g. aromatic hydrocarbon. The compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% of bactericides, 5-15 wt% of anti-freezing agents, 0.1-1 wt% of anti-foaming agents, and 0.1 -1 wt% of colorants. In one another embodiment, the present invention provides agrochemical compositions of a compound of formula (I), which comprise the active substance between 0.01 and 95% by weight, preferably between 0.1 and 90%, and more preferably between 1 and 70 %, in particular between 10 and 60 by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). 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 the treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating a compound of formula (I) and compositions thereof, respectively, on to plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, soaking and in- furrow 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 germination is not induced, e.g. by seed dressing, pelleting, coating and dusting. 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 0.05 to 0.9 kg per ha, in particular from 0.1 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 the active substance from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required. 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 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material. Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) 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. 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. 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. 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. The compounds of the present invention are characterized by favorable metabolic and/or soil residual patterns and exhibit activity controlling a 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 as well as fish and plants. In the context of the present invention "invertebrate pest control" means inhibition of invertebrate pest development (including mortality) that causes 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. The term "gastropod" includes snails, slugs and other stylommatophora. The term "nematode" includes all of the helminths, such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda). Those skilled in the art will recognize that not all compounds are equally effective against all pests. 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 corn borer (Ostrinia nubilalis Hubner), navel orangeworm (Amyelois transitella Walker), corn root webworm (Crambus caliginosellus Clemens), sod webworm (Herpetogramma licarsisalis Walker)); leafrohers, 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 (Lymantria dispar Linnaeus)); nymphs and adults of the order Blattodea mcluding 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 corn 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, whitefiies 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 (Panonychus 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., Chiysomya spp., Phonnia spp.), and other muscoid fly pests, horse flies (e.g., Tabanus spp.), botflies (e.g., Gastrophilus spp., Oestrus spp.), cattle grubs (e.g., Hypoderma spp.), deer flies (e.g., Chrysops spp.), keds (e.g., Melophagus ovinus Linnaeus) and other Brachycera, mosquitoes (e.g., Aedes spp., Anopheles spp., Culex spp.), black flies (e.g., Prosimulium spp., Simulium spp.), biting midges, sand flies, sciarids, and other Nematocera; 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 Fδrster), 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 cams De Geer), fluff louse (Goniocotes gallinae De Geer), sheep body louse (Bovicola ovis Schrank), short-nosed cattle louse (Haematopinus eurystemus Nitzsch), long-nosed cattle louse (Linognathus vituli Linnaeus) and other sucking and 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 (Ctenocephatides 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, Dirofllaria immitis Leidy in dogs, Anoplocephala peifoliata in horses, Fasciola hepatica Linnaeus in ruminants, etc.). The compounds of the present invention show particularly high activity against pests of 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 (corn root webworm), Crambus teterrellus Zincken (bluegrass webworm), Cydia pomonella Linnaeus (codling moth), Earias insulana Boisduval (spiny bollworm), Earias vittella Fabricius (spotted bollworm), Helicoveipa armigera Hύbner (American bollworm), Helicoverpa zea Boddie (corn earworm), Heliothis virescens Fabricius (tobacco budworm), Herpetogramma licarsisalis Walker (sod webworm), Lobesia botrana Denis and Schiffeπnύller (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 armyworm), Spodoptera litura Fabricius (tobacco cutworm, cluster caterpillar), Spodoptera frugiperda J. E. Smith (fall armyworm), Trichoplusia ni Hύbner (cabbage looper) and Tula absoluta Meyrick (tomato leafminer)). Compounds of the present invention also have commercially significant activity on members from the order Homoptera including: Acyrthisiplionpisum Harris (pea aphid), Aphis craccivora Koch (cowpea aphid), Aphis fabae Scopoli (black bean aphid), Aphis gossypii Glover (cotton aphid, melon aphid), Aphis pomi De Geer (apple aphid), Aphis spiraecola Patch (spirea aphid), Aulacorthum solani Kaltenbach (foxglove aphid), Chaetosiphon fragaefolii Cockerell (strawberry aphid), Diuraphis noxia Kurdjumov/Mordvilko (Russian wheat aphid), Dysaphis plantaginea Paaserini (rosy apple aphid), Eriosoma lanigerum Hausmann (woolly apple aphid), Hyalopterus pruni Geoffroy (mealy plum aphid), Lipaphis erysimi Kaltenbach (tarnip aphid), Metopolophium dirrhodum Walker (cereal aphid), Macrosipum euphorbiae Thomas (pqtato aphid), Myzus persicae Sulzer (peach-potato aphid, green peach aphid), Nasonovia ribisnigri Mosley (lettuce aphid), Pemphigus spp. (root aphids and gall aphids), Rhopalosiphum maidis Fitch (corn leaf aphid), Rhopalosiphum padi Linnaeus (bird cherry-oat aphid), Schizaphis graminum Rondani (greenbug), Sitobion avenae Fabricius (English grain aphid), Therioaphis maculata Buckton (spotted alfalfa aphid), Toxoptera aurantii, Boyer de Fonscolombe (black citrus aphid), and Toxoptera citiicida Kirkaldy (brown citrus aphid); Adelges spp. (adelgids); Phylloxera devastatrix Pergande (pecan phylloxera); Bemisia tabaci Gennadius (tobacco whitefly, 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 (corn 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); Planococcus citri Risso (citrus mealybug); Pseudococcus spp. (other mealybug complex); Cacopsylla pyricola Foerster (pear psylla), Trioza diospyri Ashmead (persimmon psylla). 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), Graptόsthetus 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 DaEas (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), Scirthothήps 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). Particularly, the compounds of formula (I), their N-oxides, their isomers, 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 ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Chilo infuscatellus, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Earias vittella, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Helicoverpa armigera, Helicoverpa virescens, Helicoverpa zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Leucinodes orbonalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, 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 Beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica longicornis, Diabrotica semipunctata, Diabrotica undecimpunctata Diabrotica speciosa, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria; 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 allinae, 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. 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. In one embodiment of the present invention, the present invention provides the compound of formula (I) which is useful for controlling insects selected form sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species: Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, Diptera: Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Contarinia sorghicola Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia titillanus, Mayetiola destructor, Musca autumnalis, Musca domestica, Muscina stabulans, Oestrus ovis, Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophora columbiae, Psila rosae, Psorophora discolor, Prosimulium mixtum, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis, Sarcophaga spp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea, and Tipula paludosa; 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. 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 and nutrients. The compounds used in the composition and in combination with the compound of formula (I) are also termed as active compatible compounds. 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 WO2017153200 can be combined with at least one compound of formula (I) of the present disclosure. The fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, fertilizers and nutrients reported in WO2016156129 and or WO2017153200 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. Particularly, the compounds of the present invention can be mixed with at least one additional biological 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 and virus or fungi to form a multi- component pesticide giving an even broader spectrum of agricultural utility. 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 the WO2019072906A1 (page 27 to 37). 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 genetically modified plant 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. In one embodiment of the present invention, the biologically effective amount of the compound of formula (I) in the compositions ranges from 0.1-99% by weight with respect to the total weight of the composition, preferably from 5-50% 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 or agriculturally acceptable salts, isomers/structural isomers, stereo- isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides thereof as well as composition or combination thereof. 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 the application of a compound or a composition of the present invention by direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. 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 piperonylbutoxide often enhance the 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. The animal pest, i.e. the insects, arachnids and nematodes, the plant, soil or water in which the plant is growing can be contacted with the compounds of formula (I), their N-oxides and salts or composition(s) containing them by any application method known in the art. As such, "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). 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 or arachnids 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. In one embodiment, the present invention provides a method for protecting crops from attack or infestation by invertebrate pests, which comprises contacting the crop with a biologically effective amount of the compound or the composition of the present invention, isomer, polymorph, N-oxide or salt thereof. The compounds of the present invention are employed as such or in the 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. In one embodiment, the present invention provides a method for the protection of seeds 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. 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, isomer, polymorph, N-oxide or veterinary acceptable salt thereof. 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 1 gai to 5000 gai per hectare in agricultural or horticultural crops, preferably from 25 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 corn), 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. Particularly, the compound or the composition of the present invention are useful in protecting agricultural crops such as cereals, corn, 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 other vegetables, and ornamentals. 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). 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. The bait can be a liquid, a solid or a semi-solid 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- or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickiness, moisture retention or aging characteristics. 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. For use in bait compositions, the typical content of active ingredient is from 0.001 to 15 weight %, desirably from 0.001 to 5 weight % of active compound. 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 ethoxylate having 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. 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 %. The compounds of the present invention and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vaporizers and also in moth papers, moth pads or other heat-independent vaporizer systems. The methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula (I) and its respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like. Insecticidal compositions for application to fibers, fabric, knitgoods, nonwovens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for example are Ν,Ν-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1 -(3-cyclohexan-1-yl- carbonyl)-2-methylpiperine, (2hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl- 2-methyl4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant extracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-l-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic acids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, monoand di-ethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene. The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the insecticide or spraying them onto the nets. The compounds of the present invention and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human beings (e.g. when the pests invade into houses and public facilities). The compounds of the present invention are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywoods, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets and heat insulating material such as styrene foams etc.. In case of application against ants doing harm to crops 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. Seed treatment 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 insects and the resulting plant′s roots and shoots against soil pests and foliar insects. 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. 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, fruits, tubers, grains, cuttings, cut shoots and the like and means, in a preferred embodiment, true seeds. 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. 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 as for example, seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918 and CA2083415. 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. 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 corn), 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. 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. 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) (WO92/00377) (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 (EP142924, EP193259), 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 example by 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). 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 emergence of the plants. Compositions which are especially useful for seed treatment are e.g.: Soluble concentrates (SL, LS) Emulsions (EW, EO, ES) Suspensions (SC, OD, FS) Water-dispersible granules and water-soluble granules (WG, SG) Water-dispersible powders and water-soluble powders (WP, SP, WS) Gel-Formulations (GF) Dustable powders (DP, DS) 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. In a one embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water. 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/l) of the active ingredient, from 0.1 to 20 % by weight (1 to 200 g/l) of at least one surfactant, e.g. 0.05 to 5 % by weight of a 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 Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108. An example of a gelling agent is carrageen (Satiagel®) In the treatment of seed, the application rates of the compounds of the present invention are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, more preferably from 1 g to 1000 g per 100 kg of seed and in particular from 1 g to 200 g 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 I, as defined herein. The amount of the compound I or the agriculturally useful salt thereof will in general vary from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 1000 g per 100 kg of seed. Digital Technologies 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. 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. 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. In an 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. Animal health The present invention also provides an agricultural and/or veterinary composition comprising at least of one compound of the present invention. In one embodiment, the present invention provides use of the compound of formula (I), agriculturally acceptable salts, isomers/structural isomers, stereo-isomers, diastereomers, enantiomers, tautomers, metal complexes, polymorphs, or N-oxides, composition or combination thereof, for combating invertebrate pests in agricultural crops and/or horticultural crops or parasites in or on animals. 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. One object of the present invention is therefore to provide new methods to control parasites in and on animals. Another object of the present invention is to provide safer pesticides for animals. Another object of the present invention is to provide pesticides for animals that may be used in lower doses than existing pesticides. Another object of the present invention is to provide pesticides for animals, which provide a long lasting control of parasites. The present invention also relates to 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. 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. 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 requires, 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. The 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 (including humans) 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 such as trout, carp and eels. The 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. 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. The compounds of the present invention are especially useful for combating ectoparasites. 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, Culicoides furens, 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. Roundworms Nematoda: 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., Dirofilari 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. The compounds of formula (I) and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida. In one embodiment, the present invention provides use of the compounds of formula (I) and the compositions containing them for combating mosquitoes. In one embodiment, the present invention provides use of the compounds of formula (I) and the compositions containing them for combating flies. In one embodiment, the present invention provides use of the compounds of formula (I) and the compositions containing them for combating fleas. The use of the compounds of the present invention and the compositions containing them for combating ticks is still another embodiment of the present invention. The compounds of the present invention are also especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians). 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. For oral administration to warm-blooded animals, the 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 to 100 mg/kg of animal body weight per day of the compound of the present invention, preferably with 0.5 to 100 mg/kg of animal body weight per day. 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 adition 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 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 to 5,000 ppm and preferably 1 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. 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-inwater 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. 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. The solutions are filtered and filled sterile. 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. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on. 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. Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared according to the state of the art for injection solutions with sufficient thickener that a clear material having an ointment-like consistency result. 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, adhesives are added. 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. 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. 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. Liquid suspending agents are all homogeneous solvents and solvent mixtures. Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions only by their higher viscosity. 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. In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, 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 from about 0.001 to 95% of the compound of the present invention. Generally, it is favorable to apply the compounds of the present invention in total amounts of 0.5 to 100 mg/kg per day, preferably 1 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% by weight, preferably from 0.1 to 65% by weight, more preferably from 1 to 50% by weight, most preferably from 5 to 40% by weight. Preparations diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90% by weight, preferably of 1 to 50% by weight. Furthermore, the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2% by weight, preferably of 0.05 to 0.9% by weight, very particularly preferably of 0.005 to 0.25% by weight. In a one embodiment, the compositions comprising the compounds of the present invention are applied dermally/topically. 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 to 300 mg/kg, preferably 20 to 200 mg/kg, most preferably 25 to 160 mg/kg body weight of the treated animal in the course of three weeks. 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 2003/086075. Positive crop response: The compounds of the present invention not only control insect and mite pests effectively but also show positive crop response such as plant growth enhancement effects like enhanced root growth, enhanced tolerance to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality of plant products, more productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields. CHEMISTRY EXAMPLES: The following examples set forth the manner and process of making compounds of the present invention without being a limitation thereof and include the best mode contemplated by the inventors for carrying out the invention.
Figure imgf000094_0001
,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine (Compound 3) Step-1: 5-(2,2,3,3,3-pentafluoropropoxy)pyrazine-2-carboxylic acid To a stirred solution of 5-chloropyrazine-2-carboxylic acid (10 g, 63.1 mmol), 2,2,3,3,3- pentafluoropropan-1-ol (14.20 g, 95 mmol) in N,N-dimethylformamide (DMF) (300 mL) being kept under nitrogen, sodium hydride (NaH) (6.31 g, 158 mmol) was added at 25 °C. The reaction mixture was stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was poured into ice water (200 mL) and extracted with ethyl acetate (3 x 100 mL). The combined ethyl acetate layers were washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain 5-(2,2,3,3,3-pentafluoropropoxy)pyrazine-2-carboxylic acid (9 g, z, 52.4 % yield) as a solid. 1H- NMR (400 MHz, DMSO-d6) δ 13.47 (s, 1H), 8.85-8.84 (m, 1H), 8.57 (d, J = 1.2 Hz, 1H), 5.21 (td, J = 13.7, 1.0 Hz, 2H); ESI MS (m/z) 270.85(M-H)-. Step-2: 5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)methanol To a stirred solution of 5-(2,2,3,3,3-pentafluoropropoxy)pyrazine-2-carboxylic acid (1 g, 3.67 mmol) in tetrahydrofuran (THF) (30 mL), 1,1'-carbonyldiimidazole (CDI) (0.89 g, 5.51 mmol) was added at 25 °C. The reaction mixture was stirred to 25 °C for 12 h. Sodiumborohydride (NaBH4) (0.28 g, 7.35 mmol) as a solution in water (10 mL) was added to the reaction mixture and the resultant mixture was strried at 25 °C for 2 h. After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate (EtOAc) (2 x 100 mL). The combined ethyl acetate layers were washed with brine (100 mL), dried over sodium sulfate, and concentrated to get the crude product which was purified by flash column chromatography on silica gel using 20 % ethyl acetate in hexane as an eluent to obtain (5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)methanol (650 mg, 2.52 mmol; 68.5 % yield) as an oily substance. 1H- NMR (400 MHz, DMSO-d6) δ 8.39 (d, J = 1.5 Hz, 1H), 8.26 (t, J = 0.7 Hz, 1H), 5.49 (t, J = 5.7 Hz, 1H), 5.13 (td, J = 13.8, 1.1 Hz, 2H), 4.58-4.57 (m, 2H); ESI MS (m/z) 258.55 (M-H)+. Step-3: 2-(chloromethyl)-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine To a stirred solution of (5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)methanol (6 g, 23.24 mmol) in toluene (100 mL), thionyl chloride (8.5 ml, 116 mmol) was added at 25 °C. The reaction mixture was stirred at 100 °C for 2 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and poured into water. The aqueous layer was extracted with ethyl acetate (EtOAc) (2 x 50 mL) and the combined ethyl acetate layers were washed with aqueous saturated sodium bicarbonate solution (50 mL), brine (50 mL), dried over anhydrous sodium sulfate, and concentrated to obtain the crude product. The crude product was purified by flash column chromatography on silica gel using 10 % ethyl acetate in hexane as an eluent to obtain 2-(chloromethyl)-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine (4.7 g, 16.99 mmol, 73.1 % yield). 1H-NMR (400 MHz, DMSO-d6) δ 8.50-8.46 (m, 1H), 8.42-8.38 (m, 1H), 5.19-5.05 (m, 2H), 4.88-4.80 (m, 2H). Step-4: 2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acetonitrile To a stirred solution of 2-(chloromethyl)-5-(2,2,3,3,3-pentafluoropropoxy)pyrazine (5.0 g, 18.08 mmol) in acetonitrile (5 mL), trimethylsilyl cyanide (4.9 mL, 36.2 mmol) and tetra-n-butylammonium fluoride (TBAF) (36.2 mL, 36.2 mmol) were added respectively and the resulting mixture was stirred at 25 °C for 14 h. After completion of the reaction, the reaction mixture was poured into water and the aqueous layer was extracted with ethyl acetate (2 x 100 mL). The combined organic layers were washed with brine solution (50 mL), dried over sodium sulfate, and concentrated to obtain the crude which was purified by flash column chromatography on silica gel using 20 % ethyl acetate in hexane as an eluent to obtain 2-(5- (2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acetonitrile (3.2 g, 11.98 mmol; 66.3 % yield).1H-NMR (400 MHz, DMSO-d6) δ 8.50 (d, J = 1.2 Hz, 1H), 8.28 (t, J = 0.6 Hz, 1H), 5.18-5.09 (m, 2H), 4.23 (s, 2H); ESI MS (m/z) 265.85 (M-H)-. Step-5: 3,3-bis(ethylthio)-2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acrylonitrile To a stirred solution of 2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acetonitrile (3 g, 11.23 mmol) in acetonitrile (60 mL), potassium hydroxide (1.32 g, 23.58 mmol) was added at 25 °C. The resulting reaction mixture was stirred for 1 h at 25 °C. Then reaction mixture was cooled to -5 °C and carbon disulfide (0.81 ml, 13.48 mmol) was added dropwise, over 10 min. After complete addition, the reaction mixture was stirred for 1 h at -5 °C. Then ethyl iodide (2.0 mL, 24.70 mmol) was added in dropwise manner to the reaction mixture, at the same temperature over 15 min. The resultant reaction mixture was stirred for 2 h at 0 °C and then at 25 °C for 16 h. The reaction mixture was concentrated under reduced pressure and the crude product obtained was purified by flash column chromatography on silica gel using 10 % ethyl acetate in hexane as an eluent to obtain 3,3-bis(ethylthio)-2-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)acrylonitrile (2.6 g, 6.51 mmol; 58.0 % yield). 1H-NMR (400 MHz, CHCl3-d) δ 8.44 (d, J = 1.5 Hz, 1H), 8.39 (d, J = 1.5 Hz, 1H), 4.91-4.85 (m, 2H), 3.10 (q, J = 7.3 Hz, 2H), 2.96 (q, J = 7.4 Hz, 2H), 1.42 (q, J = 7.3 Hz, 3H), 1.29-1.24 (m, 3H); ESI MS (m/z) 399.85 (MH)+. Step-6: 3-(ethylthio)-4-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-1H-pyrazol-5-amine To a stirred solution of 3,3-bis(ethylthio)-2-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)acrylonitrile (4.1 g, 10.27 mmol) in a mixture of acetonitrile (30 mL) and ethanol (30 mL), hydrazine hydrate (0.63 mL, 10.27 mmol (79% w/v)) was added drop wise at 0 °C. The resultant mixture was stirred at 0 °C for 1 h. The reaction mixture was diluted with ice cold water (20 mL) and the precipitated solid was filtered. The solid was washed with water and dried under reduced pressure to obtain the crude product which was purified by column chromatography on silica gel using 100% ethyl acetate as an eluent to obtain 3- (ethylthio)-4-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-1H-pyrazol-5-amine (2.8 g, 7.58 mmol; 73.9 % yield). 1H-NMR (400 MHz, DMSO-d6) δ 11.91 (s, 1H), 8.64 (d, J = 26.7 Hz, 1H), 8.39 (s, 1H), 6.05 (d, J = 11.5 Hz, 2H), 5.19-5.08 (m, 2H), 3.05-2.82 (m, 2H), 1.33-1.20 (m, 3H); ESI MS (m/z) 370.10 (MH)+. Step-7: 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin- 7(4H)-one To a stirred solution of 3-(ethylthio)-4-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)-1H-pyrazol-5- amine (2.5 g, 6.77 mmol) in acetic acid (25 mL), methyl 3,3-dimethoxypropanoate (1.50 g, 10.15 mmol) was added. The reaction mixture was heated at 100 °C for 16 h. It was then cooled to 25 °C and concentrated under reduced pressure. Water (20 mL) was added to the above crude mixture which then was extracted with ethyl acetate (3 x 100 mL). The combined ethyl acetate layers were washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product which was purified by flash column chromatography on silica gel using 5% methanol in dichloromethane as an eluent to obtain 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one (1.5 g, 3.56 mmol; 52.6 % yield.1H-NMR (400 MHz, DMSO-d6) δ 12.05 (s, 1H), 8.58 (d, J = 1.5 Hz, 1H), 8.49 (d, J = 1.5 Hz, 1H), 7.81 (d, J = 7.6 Hz, 1H), 5.85 (d, J = 7.3 Hz, 1H), 5.19 (dd, J = 13.7, 13.0 Hz, 2H), 3.25 (q, J = 7.3 Hz, 2H), 1.37 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 421.50 (M-H)+. Step-8: 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine To a stirred solution of 2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidin-7(4H)-one (1.6 g, 3.80 mmol) in acetonitrile (30 mL), potassium carbonate (1.05 g, 7.59 mmol) and phosphorus oxybromide (2.18 g, 7.59 mmol) were added at 25 °C. The reaction mixture was heated at 90 °C for 6 h. After completion of the reaction, the reaction mixture was cooled to 0 °C and diluted with ice-water mixture (50 mL). The pH of the mixture was adjusted to 7-8 by slow addition of saturated aqueous sodium bicarbonate solution. The aqueous layer was extracted with ethyl acetate (3 x 100 mL) and the combined ethyl acetate layers were washed with water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude product which was purified by flash column chromatography on silica gel using 50 % ethyl acetate in hexane as an eluent to obtain 7- bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine (0.6 g, 1.162 mmol, 30.6 % yield). 1H-NMR (400 MHz, DMSO-d6) δ 8.77 (t, J = 1.1 Hz, 1H), 8.55 (d, J = 1.5 Hz, 1H), 8.48 (d, J = 4.6 Hz, 1H), 7.65 (d, J = 4.6 Hz, 1H), 3.92 (s, 3H), 3.25 (q, J = 7.3 Hz, 2H), 1.40 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 483.95 (MH; 79Br)+, 485.95 (MH; 81Br)+ Step-9: 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine To a stirred solution of 7-bromo-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (0.3 g, 0.62 mmol) in dichloromethane (10 mL), m-chloroperbenzoic acid (0.3 g, 1.30 mmol) was added portion wise at 0-5 °C. The resultant reaction mixture was stirred at 25 °C for 2 h. After completion of the reaction, the reaction mixture was diluted with aqueous sodium thiosulfate solution and extracted with dichloromethane (2 x 15 mL). The combined dichloromethane layers were washed with a saturated aqueous sodium bicarbonate solution (50 mL) and water (50 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product which was purified by flash column chromatography on silica gel using 35 % ethyl acetate in hexane as an eluent to obtain 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (210 mg, 0.41 mmol, 65.7 % yield).1H-NMR (400 MHz, DMSO-d6) δ 8.69 (d, J = 1.5 Hz, 1H), 8.63-8.62 (m, 2H), 7.90 (d, J = 4.4 Hz, 1H), 5.23 (t, J = 13.7 Hz, 2H), 3.78-3.73 (m, 2H), 1.27-1.22 (m, 3H); ESI MS (m/z) 517.90 (MH; 79Br)+, 519.90 (MH; 81Br)+ Step-10: 7-cyclopropyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine To a stirred solution of 7-bromo-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (150 mg, 0.29 mmol) and cyclopropylboronic acid (125 mg, 1.45 mmol) in a mixture of dioxane (6 mL) and water (2 mL), potassium phosphate tribasic (154 mg, 0.73 mmol) was added. The reaction mixture was thoroughly deoxygenated by subjecting it to vacuum/nitrogen cycles three times. Then 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane complex (23.8 mg, 0.03 mmol) was added to the reaction mixture which then was heated at 90 °C for 2 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and filtered through a pad of celite. The filtrate was concentrated under reduced pressure and the crude product was purified by flash column chromatography on silica gel using 20 % ethyl acetate in hexane as an eluent to obtain 7- cyclopropyl-2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidine (65 mg, 0.136 mmol; 46.9 % yield).1H-NMR (400 MHz, DMSO-d6) δ 8.71 (d, J = 1.5 Hz, 1H), 8.66 (d, J = 4.4 Hz, 1H), 8.61 (d, J = 1.5 Hz, 1H), 7.06 (d, J = 4.6 Hz, 1H), 5.22 (t, J = 13.3 Hz, 2H), 3.76 (q, J = 7.4 Hz, 2H), 2.90-2.84 (m, 1H), 1.43-1.38 (m, 2H), 1.27-1.16 (m, 5H); ESI MS (m/z), 478.15 (MH)+. Example-2: Synthesis of N-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine (Compound 7)
Figure imgf000098_0001
-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (Step-08; Example-1) (0.15 g, 0.310 mmol) in N,N-dimethylformamide (DMF) (2 mL), cyclopropanamine (0.09 g, 1.55 mmol) was added drop wise at 0 °C. The reaction mixture was stirred at 25 °C for 3 h. The reaction mixture was diluted with ice cold water (10 mL) and the aqueous layer was extracted with ethyl acetate (3 x 10 mL). The combined ethyl acetate layers were washed with water (20 mL), dried over anhydrous sodium sulfate and concentrated under reduced pressure to obtain the crude product which was was purified by flash column chromatography on silica gel using 1% methanol in dichloromethane to obtain N-cyclopropyl-2-(ethylthio)-3-(5-(2,2,3,3,3- pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (90 mg, 0.195 mmol; 63.1 % yield) as solid.1H-NMR (400 MHz, DMSO-d6) δ 9.24 (d, J = 1.5 Hz, 1H), 8.45 (d, J = 1.5 Hz, 1H), 8.30 (d, J = 5.4 Hz, 1H), 8.23 (s, 1H), 6.44 (d, J = 5.4 Hz, 1H), 5.18-5.11 (m, 2H), 3.26 (t, J = 7.3 Hz, 2H), 2.73 (dt, J = 8.7, 3.4 Hz, 1H), 1.34 (t, J = 7.3 Hz, 3H), 0.92-0.85 (m, 2H), 0.78-0.74 (m, 2H); ESI MS (m/z) 460.50 [(MH)+]. Example-3: Synthesis of 7-ethoxy-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (Compound 11) tetrahydrofuran (THF) (5 mL), sodium hydride
Figure imgf000099_0001
(0.03 g, 0.77 mmol) was added at 0 C, and the reaction mixture was stirred for 30 min at the same temperature after which 7-bromo-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (0.25 g, 0.52 mmol) in tetrahydrofuran (THF) (5 ml) was added. After 15 minutes of stirring the reaction at 0 °C, the reaction mixture was warmed to 25 °C and stirred for further 2 h. After completion of the reaction, ice-cold water (10 mL) was added to the reaction mixture and the resulting precipitate was filtered off, followed by washing with water (10 mL) and drying under reduced pressure to obtain the crude product. The crude product was further purified by washing with diethylether to obtain 7-ethoxy-2-(ethylthio)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5- a]pyrimidine (85 mg, 0.189 mmol; 36.6 % yield). 1H-NMR (400 MHz, DMSO-d6) δ 9.21 (d, J = 1.5 Hz, 1H), 8.53 (d, J = 5.1 Hz, 1H), 8.50 (d, J = 1.5 Hz, 1H), 6.73 (d, J = 5.4 Hz, 1H), 5.16 (dd, J = 13.8, 12.8 Hz, 2H), 4.58 (q, J = 7.0 Hz, 2H), 3.19 (q, J = 7.4 Hz, 2H), 1.49 (t, J = 7.1 Hz, 3H), 1.36 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 450.60 [(MH)+]. Example-4: Synthesis of ((2-(ethylsulfonyl)-3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-λ6-sulfanone (Compound 6)
Figure imgf000099_0002
-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2- yl)pyrazolo[1,5-a]pyrimidine (200 mg, 0.39 mmol) in toluene (6 mL), iminodimethyl-λ6-sulfanone (72.2 mg, 0.77 mmol), potassium phosphate, tribasic (164 mg, 0.77 mmol), and 2-dicyclohexylphosphino- 2',4',6'-triisopropylbiphenyl (36.9 mg, 0.077 mmol) were added, and the reaction mixture was degassed under nitrogen for 5 minutes. Then tris(dibenzylideneacetone)dipalladium(0) (35.5 mg, 0.04 mmol) was added, degassing was continued for another 5 minutes and the reaction mixuture was heated to 110 °C for 2 h. After completion of the reaction, the reaction mixture was filtered through a bed of celite and washed with ethyl acetate. The combined organic layers were washed with water (50 mL), dried over sodium sulfate, concentrated under reduced pressure to get the crude product. The crude product was purified by flash chromatography on silica gel using 1-2% methanol in dichloromethane to obtain ((2-(ethylsulfonyl)- 3-(5-(2,2,3,3,3-pentafluoropropoxy)pyrazin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)imino)dimethyl-l6- sulfanone (90 mg, 0.17 mmol, 44.0 % yield) as a solid. 1H -NMR (400 MHz, DMSO-d6) δ 8.72 (d, J = 1.5 Hz, 1H), 8.57 (d, J = 1.5 Hz, 1H), 8.41 (d, J = 5.1 Hz, 1H), 6.82 (d, J = 5.1 Hz, 1H), 5.25-5.18 (m, 2H), 3.74 (t, J = 7.5 Hz, 2H), 3.69 (s, 6H), 1.22 (t, J = 7.5 Hz, 3H); ESI MS (m/z), 528.90 (MH)+ Example-5: Synthesis of 7-cyclopropyl-2-(ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine
Figure imgf000100_0001
A mixture of ethyl 5-amino-3-(ethylthio)-1H-pyrazole-4-carboxylate (10 g, 46.5 mmol) and methyl 3,3- dimethoxypropanoate (9.9 ml, 69.7 mmol) in acetic acid (250 ml) was heated at 120 °C for 18 h. After completion of the reaction, acetic acid was removed under reduced pressure and the crude reaction mixture was diluted with cold water to give a light yellow precipitate. This yellow solid material was filtered off and washed with water (500 mL) and hexane (500 mL), followed by drying under reduced pressure to obtain ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (10 g, 37.4 mmol, 81 % yield). 1H-NMR (400 MHz, DMSO-d6) δ 11.87 (s, 1H), 7.76 (d, J = 7.6 Hz, 1H), 5.91 (d, J = 7.6 Hz, 1H), 4.29 (q, J = 7.1 Hz, 2H), 3.10-3.17 (m, 2H), 1.32-1.37 (m, 3H), 1.26-1.32 (m, 3H); ESI MS (m/z) 268 (MH)+. Step 2: Synthesis of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate To a stirred solution of ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 18.7 mmol) in acetonitrile (100 ml), potassium carbonate (K2CO3) (7.76 g, 56.1 mmol) and phosphorus oxybromide (16.1 g, 56.1 mmol) were added at 25 °C, and the resulting mixture was heated at 95 °C for 4 h. The reaction mixture was cooled to 25 °C and poured into an ice-water mixture (250 mL) and basified with saturated sodium bicarbonate solution (adjusted to pH = 7~8) and extracted with ethyl acetate (2 x 250 mL). The combined organic layers were washed with saturated brine solution, dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to provide the crude compound which was purified by flash column chromatography on silicagel using 50 % ethyl acetate in hexane as an eluent to obtain ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 15.1 mmol, 81 % yield).1H-NMR (400 MHz, CHLOROFORM-d) δ 8.43 (d, J = 4.6 Hz, 1H), 7.20 (d, J = 4.6 Hz, 1H), 4.47 (q, J = 7.1 Hz, 2H), 3.30 (q, J = 7.4 Hz, 2H), 1.47-1.51 (m, 3H), 1.42-1.60 (m, 3H); ESI MS (m/z) 331.75 (MH)+. Step 3: Synthesis of ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate A mixture of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (7 g, 21.20 mmol), cyclopropylboronic acid (7.28 g, 85 mmol) and potassium phosphate tribasic (13.45 g, 63.6 mmol) in dioxane (70 mL), were purged under nitrogen gas for 10 min followed by the addition of 1,1'- bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane adduct (1.73 g, 2.12 mmol). The resulting reaction mixture was heated at 90 °C for 3 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, filtered through a bed of celite and washed with ethylacetate. The organic layer was washed with water (100 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get the crude product which was purified by flash column chromatography using 50 % ethyl acetate in hexane on silica gel to obtain ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5- a]pyrimidine-3-carboxylate (3 g, 10.3 mmol, 48.6 % yield). 1H-NMR (400 MHz, CHLOROFORM-d) δ 8.55 (d, J = 4.8 Hz, 1H), 6.39 (d, J = 4.8 Hz, 1H), 4.53-4.44 (m, 2H), 3.35-3.24 (m, 2H), 1.50-1.37 (m, 8H), 1.22-1.12 (m, 2H); ESI MS (m/z) 291.95 (MH)+. Step 4: Synthesis of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid To a stirred solution of ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (3 g, 10.3 mmol) in ethanol (30 mL), lithium hydroxide, monohydrate (4.32 g, 103 mmol) in water (30 mL) was added. The reaction mixture was stirred at 60 °C for 4 h. After completion of the reaction, the reaction mixture was concentrated under reduced pressure to obtain a residue which was was acidified with concentrated hydrochloric acid (HCl) (adjusted PH= 1). The obtained solid was filtered and dried under reduced pressure to obtain 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (2.2 g, 8.4 mmol, 81 % yield).1H-NMR (400 MHz, DMSO-d6) δ 8.51 (d, J = 4.9 Hz, 1H), 6.81 (d, J = 4.8 Hz, 1H), 3.20-3.14 (m, 2H), 2.85-2.73 (m, 1H), 1.38 (t, J = 7.3 Hz, 3H), 1.35-1.31 (m, 2H), 1.24-1.20 (m, 2H); ESI MS (m/z) 264.00 (MH)+ Step 5: Synthesis of 7-cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine To a stirred solution of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (5 g, 18.99 mmol) in N,N-dimethylformamide (50 mL), iodine (9.64 g, 38.0 mmol) and potassium phosphate, (3.31 g, 18.99 mmol) were added under nitrogen atmospshere at 0 oC. The reaction mixture was heated at 100 °C for 8 h. After completion of the reaction, the reaction mixture was cooled to 25 °C followed by the addition of a mixture of 15% aqueous sodium thiosulphate solution and saturated aqueous NaHCO3 solution under stirring. The aqueous layer was extracted with dichloromethane (4 x 25 mL), and the combined organic layers were dried under reduced pressure to give a crude product, which was purified by flash column chromatography using 20-40 % ethyl acetate in hexane on silica gel to obtain 7- cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine (5 g, 14.48 mmol, 76 % yield) as a grey powder. 1H-NMR (400 MHz, CHLOROFORM-d) δ 8.34 (d, J = 4.8 Hz, 1H), 6.25 (d, J = 4.4 Hz, 1H), 3.29-3.23 (m, 2H), 2.95-2.84 (m, 1H), 1.46 (t, J = 7.6 Hz, 3H), 1.36-1.30 (m, 2H), 1.15-1.11 (m, 2H); Step 6: Synthesis of 7-cyclopropyl-2-(ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine To a stirred solution of 7-cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine (200 mg, 0.58 mmol) in dichloromethane (10 mL), meta-chloroperoxybenzoic acid (mCPBA) (286 mg, 1.16 mmol) was added at 25 °C and the reaction mixture was further stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was diluted with dichloromethane (15 mL). The organic layer was washed with 1N sodium hydroxide (NaOH) (10 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get a crude product which was purified by flash column chromatography using 20-40 % ethyl acetate in hexane on silica gel to obtain 7-cyclopropyl-2- (ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine (150 mg, 0.398 mmol, 68.6 % yield) as a solid.1H-NMR (400 MHz, CHLOROFORM-d) δ 8.56 (d, J = 4.6 Hz, 1H), 6.54 (d, J = 4.6 Hz, 1H), 3.48 (q, J = 7.4 Hz, 2H), 3.02-2.95 (m, 1H), 1.49-1.45 (m, 2H), 1.44-1.37 (m, 3H), 1.16-1.12 (m, 2H); ESI MS (m/z) 377.85 (MH)+. Example-6: Synthesis of 3-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 110) .
Figure imgf000102_0001
Step 1: Synthesis of 1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)-3-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)pyridin-2(1H)-one To a stirred solution of 3-bromo-1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (500 mg, 1.49 mmol) in toluene (1 mL), bis(pinacolato)diboron (756 mg, 2.98 mmol) and potassium acetate (292 mg, 2.98 mmol) were added, and the resulting mixture was freed from oxygen under a nitrogen stream for 10 minutes. Then PdCl2(dppf)-CH2Cl2 adduct (60.8 mg, 0.074 mmol) was added to the above reaction mixture and the resulting mixture was stirred at 100 °C for 1 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (50 mL) and water (50 mL). The aqueous layer was extracted with ethyl acetate (2 X 30 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to get a crude product 1-methyl-6-(2,2,3,3,3- pentafluoropropoxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2(1H)-one (400 mg, 1.488 mmol, 70.2 % yield) which was used in the next step without any further purification. ESI MS (m/z) 301.90 (MH)+. Step 2: Synthesis of 3-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 110) A stirred mixture of 7-cyclopropyl-2-(ethylthio)-3-iodopyrazolo[1,5-a]pyrimidine (1 g, 2.90 mmol), 1- methyl-6-(2,2,3,3,3-pentafluoropropoxy)-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridin-2(1H)- one (2.22 g, 5.79 mmol), potassium carbonate (K2CO3) (1.20 g, 8.69 mmol) in 1,4-dioxane (10 mL) and water (1 mL) was purged with nitrogen gas for 10 minutes and then dichloro[1,1'- bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.24 g, 0.29 mmol) was added to it. The resulting reaction mixture was heated at 110 °C for 4 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, filtered through a bed of celite, and washed with ethyl acetate. The ethyl acetate layer was washed with water (25 mL), dried over anhydrous sodium sulfate, filtered and concentrated under reduced pressure to get a crude product which was purified by flash column chromatography on silicagel using 80% ethylacetate in hexane to get 3-(7-cyclopropyl-2- (ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (150 mg, 0.316 mmol, 10.91 % yield).1H-NMR (400 MHz, DMSO-d6) δ 8.28 (d, J = 4.4 Hz, 1H), 7.50 (d, J = 8.1 Hz, 1H), 6.61 (d, J = 4.4 Hz, 1H), 6.04 (d, J = 8.1 Hz, 1H), 5.07 (t, J = 12.6 Hz, 2H), 3.37 (d, J = 9.5 Hz, 3H), 3.10 (q, J = 7.3 Hz, 2H), 2.81-2.77 (m, 1H), 1.32-1.28 (m, 5H), 1.22-1.16 (m, 2H); ESI MS (m/z) 475.55 (MH)+. Example-7: Synthesis of 3-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl- 6-(2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (compound 119)
Figure imgf000103_0001
The title compound 3-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-1-methyl-6- (2,2,3,3,3-pentafluoropropoxy)pyridin-2(1H)-one (170 mg, 0.34 mmol, 12.7 % yield) was prepared from 7-cyclopropyl-2-(ethylsulfonyl)-3-iodopyrazolo[1,5-a]pyrimidine (1.0 g, 2.65 mmol) using the procedure mentioned in step-2 of example-6. 1H-NMR (400 MHz, DMSO-d6) δ 8.52 (d, J = 4.6 Hz, 1H), 7.55 (d, J = 8.3 Hz, 1H), 6.96 (d, J = 4.6 Hz, 1H), 6.08 (d, J = 7.9 Hz, 1H), 5.11 (t, J = 12.7 Hz, 2H), 3.54 (q, J = 7.4 Hz, 2H), 3.38-3.36 (m, 4H), 2.83-2.79 (m, 1H), 1.39-1.34 (m, 2H), 1.25-1.18 (m, 5H); ESI MS (m/z) 506.70 (MH)+. The below compounds in table-1 were obtained using appropriate starting materials and following analogues procedures as described in the examples 1-7 or according to general schemes 1-15 as described in description. Table: 1 mp Compound Name Data No = ), = 0, ), = ), )+ ), = ), SI ), = ), ); ), = = 90 ), = 69 .
Figure imgf000104_0001
N-cyclopropyl-2-(ethylthio)-3- 1H -NMR (400 MHz, DMSO-d6) δ 9.24 (d, J = 1.5 Hz, 1H), (5-(2,2,3,3,3- 8.45 (d, J = 1.5 Hz, 1H), 8.30 (d, J = 5.4 Hz, 1H), 8.23 (s, 1H), 644 (d J = 54 H 1H) 518511 ( 2H) 326 (t J = 73 Hz, ), 50 ), = .8 36 ), z, 27 z) ), = .4 z) ), = .0 6 ), = ), = ), = ), 95 ), ), = 2- 00 ), = 78 .1 SI
Figure imgf000105_0001
amine MS (m/z) 509.00 [(MH)+]. N-(ccloro lmethl)-2- 1H -NMR (400 MHz DMSO-d6) δ 925 (d J = 15 Hz 1H), z, , J z, m, ), = 16 z) .2 65 .4 88 ), = .3 J 95 ), = 0- S ), = 60 .3 ), m, m, ), 3, .4 00 ), = .4 96 , J .1
Figure imgf000106_0001
yl)pyrazolo[1,5-a]pyrimidine Hz, 1H), 5.21-5.14 (m, 2H), 3.19 (q, J = 7.3 Hz, 2H), 1.37 (t, J = 7.3 Hz, 3H); ESI MS (m/z) 406.15 (MH)+. 1H NMR 400 MH DMSO d6 δ 911 dd J = 22 05 Hz, d, ), m, z, d, .6 SI ), ), 23 SI ), = .4 +. z, d, = 9- +. 60 ), ); 60 ), ), z) ), = ), z) ), = ), SI ), = .3 +.
Figure imgf000107_0001
2-(ethylsulfonyl)-3-(5- 1H-NMR (400 MHz, DMSO-d6) δ 9.98 (d, J = 2.2 Hz, 1H), (2,2,3,3,3- 9.37 (s, 2H), 9.33 (d, J = 2.2 Hz, 1H), 9.31 (s, 1H), 8.75 (d, J = t fl ) i 2 12 H 1H) 865 (d J = 15 H 1H) 524 (t J = 133 H 2H), z) ), = 42 ), = ), = ), = J .5 ), = ), z) ), m, ), ), 7, ); z, s, ), ); 74 .1 d, .5 ), m, = z, , J
Figure imgf000108_0001
(2,2,3,3,3- = 1.5 Hz, 1H), 8.32-8.27 (m, 2H), 6.38 (d, J = 5.4 Hz, 2H), 5.21 pentafluoropropoxy)pyrazin-2- (dd, J = 14.3, 13.3 Hz, 2H), 3.77 (q, J = 7.3 Hz, 2H), 1.24 (t, J = l) l 15 i idi 7 73 H 3H) ESI MS ( /) 45290 (MH)+ ), ), z) ), = ), = ), = 9- 0- ), = ), m, , J ), m, ), = 0- S , J z, 4- .8 ), ), 24 SI ), ), = . ), 23 =
Figure imgf000109_0001
2-(ethylsulfonyl)-3-(6- 1H-NMR (400 MHz, DMSO-d6) δ 8.92 (t, J = 6.6 Hz, 1H), 8.48 (2,2,3,3,3- (d, J = 5.4 Hz, 1H), 8.28 (d, J = 9.3 Hz, 1H), 7.55 (d, J = 9.3 t fl ) id i H 1H) 686 (d J = 54 H 1H) 534 (t J = 137 H 2H), z, ), ), = S ), = ), = m, , J J .9 82 .3 z) z, d, z, ), , J z, z, ), = ), ); = ), z, 89 ), z, 5- +.
Figure imgf000110_0001
1 5-cyclopropyl-2-(ethylthio)-3- H-NMR (400 MHz, DMSO-d6) δ 9.15 (d, J = 1.5 Hz, 1H), (5-(2,2,3,3,3- 8.97 (d, J = 7.1 Hz, 1H), 8.48 (d, J = 1.5 Hz, 1H), 7.07 (d, J = 71 H 1H) 520513 ( 2H) 328 ( 1H) 315 ( J = 7.4 14 ), = 55 13 = ), z, z) ), = 79 .9 ), = .3 +. ), = .3 +. ), = 0- SI = 89 = 10 ), 8, ), ), = 66 .3
Figure imgf000111_0001
sulfanone Hz, 3H), 1.29-1.25 (m, 2H); ESI MS (m/z) 477.45 (MH)+. 2-(ethylsulfonyl)-N-methyl-3- 1H-NMR (400 MHz, DMSO-d6) δ 8.87 (s, 1H), 8.65 (d, J = 7.6 5 22333 H 1H 851 d J = 12 H 1H 807 d J = 46 H 1H 654 ), . .3 z, d, ); 25 3- z) 74 6- z) ), = ), , J ), = ), m, z) ), = = S , J J z, ), = ), z) ), z,
Figure imgf000112_0001
pentafluoropropoxy)pyridazin- 1H), 5.34 (t, J = 13.4 Hz, 2H), 3.83 (q, J = 7.4 Hz, 2H), 3.70 (s, 3-yl)pyrazolo[1,5-a]pyrimidin- 6H), 1.23 (t, J = 7.5 Hz, 3H); ESI MS (m/z) 529.00 (MH)+. 7 l)i i )di thll6 ), = s, S ), = 38 z) = ), z, z) = ), z, m, ), = .8 24 , J J ), ); 00 z, , J SI = ), ), z) = ), =
Figure imgf000113_0001
a]pyrimidine 2-(ethylsulfonyl)-7-(1-methyl- 1H-NMR (400 MHz, DMSO-d6) δ 8.91 (d, J = 4.3 Hz, 1H), 1H l5 l 35 873 d J = 15 H 1H 864 d J = 15 H 1H 774 d J = ), z, .4 66 .4 2- ), = 37 z, ), m, s, S ), = 03 SI ), = ), = 20 ), = 1- S ), = z, m, d, = z, ), ), ), SI
Figure imgf000114_0001
2-yl)(ethyl)(imino)-l6- MS (m/z) 508.50 (MH)+. sulfanone 1HNMR 400 MH DMSOd6 δ 860 d J = 44 H 1H), = z, S 7- 8, ), = ), = 5- = ), 3- 1- 22 ), = ), ), ), 6, ), z, ), 65 = 24 35 .0 ), z, ), 8, 2- m, , J
Figure imgf000115_0001
(2,2,3,3,3- = 9.3 Hz, 1H), 6.39 (d, J = 5.1 Hz, 1H), 5.37-5.30 (m, 2H), 3.86 pentafluoropropoxy)pyridazin- (q, J = 7.4 Hz, 2H), 1.27-1.21 (m, 3H); ESI MS (m/z) 452.85 3 l) l 15 i idi (MH)+ ), z, ), z, ), = z, 5- , J .5 = ); ), = ), 5- m, z, ), = . ), 8, ), m, z) ), = z, = ); ), = .3 +.
Figure imgf000116_0001
a]pyrimidine 1 ((2-(ethylsulfonyl)-3-(5- H-NMR (400 MHz, DMSO-d6) δ 8.47 (d, J = 2.7 Hz, 1H), 840 d J = 51 H 1H 800798 1H 765 dd J = 88, ), ); ), = 25
Figure imgf000117_0001
As described herein, the compounds of formula (I) show insecticidal activities which are exerted with respect to numerous insects which attacks on important agricultural crops. The compounds of the present invention were assessed for their activity as described in the following tests: BIOLOGY EXAMPLES: Example A: Helicoverpa armigera The diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 oC in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray. A single starved Helicoverpa armigera third instar larva was released into each of the cells of the bioassay trays and the tray was covered with the lid. The bio-assay trays were then kept under laboratory conditions at a temperature of 25 oC and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of the larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 3 5 6 16 21 43 44 45 48 52 101 103 108 120 and 121 recorded ≥ 70 per cent mortality @ 300PPM. Example B: Spodoptera litura The diet incorporation method was used, in which the required quantity of the test compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing. Semi-synthetic diet was incorporated into this solution when the temperature was approximately 50 oC in the bioassay containers. Compound and diet were stirred thoroughly for proper mixing and allowed to cool for 30 min. The solidified diet was cut into equal pieces, and then each piece was transferred into one cell of a bio-assay tray. A single starved Spodoptera litura third instar larva was released into each of the cells of the bioassay trays and the tray was covered with the lid. The bio- assay trays were then kept under laboratory conditions at a temperature of 25 oC and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of larvae. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 3 4 5 14 16 21 43 45 48 52 70 72 103 116 119 and 121 recorded ≥ 70 per cent mortality @ 300PPM. Example C: Plutella xylostella The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to get the desired test concentration. Cabbage leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then transferred into the cells of bioassay trays. A single Plutella xylostella second instar larva was released into each cell and the tray was covered with a lid. The bio-assay trays were then kept under laboratory conditions at a temperature of 25 oC and a relative humidity of 70%. Observations on dead, moribund and alive larvae were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund larvae and comparing the result to the one of the untreated control. The compounds 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 33 36 39 40 42 43 44 45 46 48 49 51 52 54 55 57 58 59 60 61 63 64 68 69 70 71 72 73 75 76 77 79 81 84 86 87 88 89 90 91 92 93 94 96 97 98 100 101 102 103 105 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124 and 125 recorded ≥ 70 per cent mortality @ 300PPM. Example D: Bemisia tabaci 1. The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to get the desired test concentration. Brinjal leaves were dipped in the compound solution for 10 seconds; shade dried for 20 min and then placed, with the abaxial side of the leaf up, on 4 ml of a solidified 1 % agar- agar solution in respective perforated container caps. Known numbers of freshly emerged whitefly adults were collected, using a modified aspirator, and released into a perforated container in which the cap containing the treated leaf was placed. The containers were sealed with a perforated lid and kept in a plant growth chamber at a temperature of 25 oC and relative humidity of 70%. Observations on dead, moribund and alive adults were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund adults and comparing the result to the one of the untreated control. The compounds 52 108 and 119 recorded ≥ 70 per cent mortality @ 300PPM. Example E: Myzus persicae 2. The leaf dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to the desired test concentration. Capsicum leaves were dipped in the compound solution for 10 seconds, shade dried for 20 min and then placed, with the abaxial side of the leaf up, in single cells of a bio-assay tray containing 4 ml of a solidified 1 % agar-agar solution. Known numbers of third instar nymphs of Myzus persicae, collected in petri plates, were released into the cell with the treated leaf and the cell was covered with a perforated lid for better aeration. The trays were kept in a plant growth chamber at a temperature of 25 oC and a relative humidity of 70%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund nymphs and comparing the result with the one of the untreated control. The compounds 3 6 12 13 15 20 23 27 43 46 48 52 58 59 72 76 86 93 96 103 110 114 116 118 119 and 124 recorded ≥ 70 per cent mortality @ 300PPM. Example F: Nilaparvata lugens The seedling dip method was used for testing, wherein the required quantity of the compound was weighed and dissolved in a tube containing solvent solution. The tube was put on a vortex at 2000 rpm for 90 min for proper mixing, then diluted with a 0.01% Triton-X solution to the desired test concentration. Paddy seedlings were dipped in the compound solution for 10 seconds, shade dried for 20 min and then placed in glass test tubes with the roots kept in water. 15 Nilaparvata lugens third instar nymphs were released into each test tube and the tubes were kept in a plant growth chamber at a temperature of 25 oC and relative humidity of 75%. Observations on dead, moribund and alive nymphs were recorded 72 h after the release. Percent mortality was calculated by combining dead and moribund nymphs and comparing the result to the one of the untreated control. The compound 36 12 13 21 23 24 28 29 43 52 58 59 76 93 108 and 109 recorded ≥ 70 per cent mortality @ 300PPM. Having described the invetion with reference to certain preferred embodiments, other embodiments will become apparent to one skilled in the art from the consideration of the specification. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.

Claims

CLAIMS: 1. A compound of formula (I),
Figure imgf000121_0001
wherein, R1 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C3-C8-cycloalkyl-C1-C6-alkyl; Y is independently selected from O or NRY; RY is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl; A represents N or CR2; G1 and G2 represent N or C; provided that both G are not nitrogen simultaneously; R2 is selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0- 2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R2a and cyclic groups of R2 may be optionally substituted with one or more groups of R2b; R2a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0- 1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R2b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0- 2R7, C(=O)R8, Si(R′′)3, S(O)0-1R9=NR10 and N=S(O)0-1(R9)2; or two R2a or two R2b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′)2, may form a 3- to 7-membered ring, which for its part may be substituted by one or more groups of R2ab; R2ab is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR5R6, S(O)0- 2R7, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; Q represents a 6-membered heterocyclic ring which may optionally be substituted by one or more groups of R3; R3 is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C R′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R3a and cyclic groups of R3 may be optionally substituted with one or more groups of R3b; R3a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0- 1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R3b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2-NR5R6, C(R′′)2- OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; two R3a or two R3b substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)m and Si(R′′)2, may form a 3- to 7-membered ring, which for its part may be substituted by one or more groups of R3ab; wherein R3ab is selected from the group consisting of hydrogen, halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, NR5R6, S(O)0-2R7; Z represents a direct bond or O; ring E represents a 5- or 6-membered heterocyclic ring fused with ring D; wherein ring E is optionally substituted by one or more groups of R11; R11 is selected from the group consisting of halogen, cyano, oxa, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R11a and cyclic groups of R11 may be optionally substituted with one or more groups of R11b; R11a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3- C10-heterocyclyl; R11b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2- NR5R6, C(R′′)2-OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0- 1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, S(O)2R7, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R4a and cyclic groups of R4 may be optionally substituted with one or more groups of R4b; R4a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR′R′′, S(O)0-2R7, C(=O)R8, Si(R′′)3, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R5a and cyclic groups of R5 may be optionally substituted with one or more groups of R5b; R5a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10- aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, Si(R′′)3, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R6 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C1-C6-cycloalkyl and C(=O)R8; or R5 and R6 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R7 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, NR5R6, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R7a and cyclic groups of R7 may be optionally substituted with one or more groups of R7b; R7a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R7b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR5R6, N=S(O)0-1(R9)2, C6-C10-aryl, C7-C14- aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R8a and cyclic groups of R8 may be optionally substituted with one or more groups of R8b; R8a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R8b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C(=O)R8; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, Si(R′′)3, S(O)0-2R7 and C(=O)R8; two R9 substituents or R9 and R10 substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R′ is selected from the group consisting of R′′, OR′′, N(R′′)2, S(O)0-2R′′, C(=O)R′′, C(=O)OR′′ and C(=O)N(R′′)2; R′′ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl and C3-C8-cycloalkyl; wherein each may be optionally substituted with halogen; each group of R1 to R11, R2a, R2b, R2ab, R3a, R3b, R3ab, R4a, R4b, R5a, R5b, R7a, R7b, R8a and R8b may be optionally substituted by one or more groups selected from the group consisting of halogen, cyano, R′′, OR′′, SR′′, N(R′′)2, COOR′′ and CON(R′′)2; "m" is an integer ranging from 0 to 2; or agrochemically acceptable salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof.
2. The compound of formula (I) according to claim 1, wherein said compound of formula (I) is represented by compound of formula (I-1);
Figure imgf000125_0001
wherein, R1 is C1-C6 alkyl or C3-cycloalkyl; Y is NRY or O; RY is selected from the group consisting of hydrogen, cyano, C1-C4-alkyl, C2-C4-alkenyl, C2-C4- alkynyl, C1-C4-haloalkyl, C2-C4-haloalkenyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl; Z represents a direct bond or O; Q represents a 6-membered heterocyclic ring which may optionally be substituted by one or more groups of R3; R3 is selected from the group consisting of halogen, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C4- cycloalkyl, C1-C6-haloalkoxy S(O)0-2 C1-C6-haloalkyl, -S(O)0-1R9=NR10, and C3-C10-heterocyclyl; wherein C3-C10-heterocyclyl of R3 may be optionally substituted one or more groups of R3b; R3b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3-C8- cycloalkyl, C1-C6-alkoxy, C1-C6-haloalkoxy, S(O)0-2C1-C6-alkyl and S(O)0-2C1-C6-haloalkyl; R11 is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, -S(O)0-1R9=NR10, -N=S(O)0-1(R9)2, -P(=O)(OR′′)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R11a and cyclic groups of R11 may be optionally substituted with one or more groups of R11b; R11a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0- 1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R11b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, C(R′′)2-NR5R6, C(R′′)2-OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, Si(R′′)3, C6-C10-aryl, C7- C14-aralkyl and C3-C10-heterocyclyl; R4 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, S(O)2R7, Si(R′′)3, phenyl, benzyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with R4a and cyclic groups of R4 may be optionally substituted with one or more groups of R4b; R4a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R4b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR4, NR′R′′, S(O)0-2R7, C(=O)R8, Si(R′′)3, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with R5a and cyclic groups of R5 may be optionally substituted with one or more groups of R5b; R5a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, Si(R′′)3, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R5b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, Si(R′′)3, C(=O)R′, C6-C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R6 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C1-C6-cycloalkyl and C(=O)R8; or R5 and R6 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part may optionally be substituted by one or more groups of R’; R7 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, NR5R6, C6-C10-aryl, C7-C14-aralkyl and C3-C10- heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R7a and cyclic groups of R7 may be optionally substituted with one or more groups of R7b; R7a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14- aralkyl and C3-C10-heterocyclyl; R7b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R8 is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR5R6, N=S(O)0-1(R9)2, C6-C10-aryl, C7-C14- aralkyl and C3-C10-heterocyclyl; wherein each aliphatic group may be optionally substituted with one or more groups of R8a and cyclic groups of R8 may be optionally substituted with one or more groups of R8b; R8a is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6-C10-aryl, C7-C14- aralkyl and C3-C10-heterocyclyl; R8b is selected from the group consisting of halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, OR′′, NR′R′′, S(O)0-2R′, C(=O)R′, C6- C10-aryl, C7-C14-aralkyl and C3-C10-heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl and C(=O)R8; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C2-C6- alkynyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, Si(R′′)3, S(O)0-2R7 and C(=O)R8; two R9 or R9 and R10 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, C(=O), C(=S), S(O)0-2 and Si(R′′)2, may form a 4- to 7-membered ring, which for its part is optionally substituted by one or more groups of R’; R′ is selected from the group consisting of R′′, OR′′, N(R′′)2, C(=O)R′′, C(=O)OR′′ and C(=O)N(R′′)2; R′′ is selected from the group consisting of hydrogen, C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1- C6-haloalkyl and C3-C8-cycloalkyl; wherein each may be optionally substituted with halogen; "m" is an integer ranging from 0 to 2; or stereoisomers, and salts thereof.
3. The compound of formula (I) as claimed in claim 1 or 2, wherein, Q is selected from Q1, Q2 or Q3, R5 are as defined in claim 1.
Figure imgf000128_0001
4. The compound of formula (I) as claimed in claim 3, wherein, Q1, Q2 or Q3 are selected from, Q1a, Q1b, Q1c, Q1d, Q1e, Q2a, Q2b, Q2c, Q2d, Q2e, Q2f, Q2g, Q3a, Q3b, Q3c, Q3d, Q3e, Q3f, or Q3g,
5.
Figure imgf000129_0001
The compound of formula (I) as claimed in claim 3, wherein, Q1, Q2 or Q3 are selected from, Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c or Q3f.
6. The compound of formula (I) according to claim 1 or 2, wherein R3 is selected from halogen, -S(O)0- 2C1-C6-haloalkyl, C1-C4 haloalkyl and C1-C4 haloalkoxy.
7. The compound of formula (I) according to claim 1 or 2, wherein R11 is selected from halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C3-C8- cyanocycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, S(O)0-1R9=NR10, N=S(O)0-1(R9)2, phenyl, 4-6 membered heterocyclyl; wherein R11 is optionally substituted with F, Cl, CN, methyl or methoxy.
8. The compound of formula (I-1) according to claim 2, wherein, R1 is C1-C4 alkyl; Z represents a direct bond or O; Q is selected from Q1a, Q1d, Q1e, Q2a, Q2c, Q3a, Q3b, Q3c or Q3f; R3 is selected from halogen, -S(O)0-2C1-C4-haloalkyl, -S(O)(NRY) C1-C6-haloalkyl, C1-C4 haloalkyl or C1-C4 haloalkoxy; R11 is selected from halogen, cyano, C1-C6-alkyl, C2-C6-alkenyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, C3-C8-cyanocycloalkyl, OR4, CR′′=NR5, NR5R6, S(O)0-2R7, C(=O)R8, -S(O)0- 1R9=NR10, -N=S(O)0-1(R9)2, (un)substituted phenyl or (un)substituted 4-6 membered heterocyclyl; R5 is selected from hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, C2-C6-haloalkenyl, C3-C8-cycloalkyl, (un)substituted phenyl or (un)substituted C3-C10-heterocyclyl; R6 is selected from hydrogen, C1-C6-alkyl, C1-C6-cycloalkyl or C(=O)R8; and R8 is selected from C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl; R7 is selected from C1-C6-alkyl, C1-C6-haloalkyl, C3-C8-cycloalkyl, NR5R6, (un)substituted phenyl, (un)substituted benzyl or (un)substituted 4-6 membered heterocyclyl; R9 is selected from the group consisting of C1-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C6- haloalkyl, C2-C6-haloalkenyl and C3-C8-cycloalkyl; R10 is selected from the group consisting of hydrogen, cyano, C1-C6-alkyl, C1-C6-haloalkyl, C3- C8-cycloalkyl, and C(=O)R8.
9. The compound of formula (I-1) according to claim 2, wherein R11 is selected from CHF2, CF3, CH2CF3, -NHCH2CH3, -N(CH3)CH2CH3, -NH(C(CH3)3), -N(CH3)(C(CH3)3), -N(CH3)COCH3, - N(CH3)CO(cyclopropyl), -N=S(O)(CH3)2, cyclopropyl, 3-chloro-pyrazol-1-yl, 3-trifluoromethyl- pyrazol-1-yl, 1,2,4-triazol-1-yl, pyrimidin-2-yl, pyridazyn-2-yl or pyridazyn-3-yl; wherein R11 optionally substituted with F, Cl, CN, methyl or methoxy.
10. A composition comprising the compound of formula (I) or agronomically acceptable salts, stereo- isomers, polymorphs or N-oxides thereof according to claim 1 and at least one additional component selected from the group consisting of surfactants and auxiliaries.
11. The composition according to claim 10, wherein the 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.
12. The composition according to claim 10, wherein the said compound of formula (I) ranges from 0.1 % to 99 % by weight with respect to the total weight of the composition, preferably ranges from 5 to 50 % by weight with respect to the total weight of the composition.
13. A combination comprising a biologically effective amount of the compound of formula (I) 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 and nutrients.
14. A method for combating insects and mite pests comprising contacting the insects and mite pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the insect and mite 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), salts, stereoisomers, polymorphs, metal complexes, N-oxides composition or combination thereof according to claim 1 or 10 or 13.
15. A method for protecting crops from attack or infestation by insects and mite pests comprising contacting the crop with the compound of formula (I), agronomically acceptable salts, stereo-isomers, polymorphs, metal complexes, N-oxides composition or combination thereof according to claim 1 or 10 or 13.
16. The method according to claim 14 or 15, wherein the said method comprises applying an effective dosages of a compound of formula (I) in amounts ranging from 1 gai to 5000 gai per hectare in agricultural or horticultural crops.
17. 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), salts, stereoisomers, polymorphs, metal complexes, N-oxides composition or combination thereof according to claim 1 or 10 or 13.
18. Use of a compound of formula (I), salts, N-oxides, isomers, polymorphs, composition or combination thereof according to claim 1 or 10 or 13, for combating insects and mite pests in agricultural crops, horticultural crops, household and vector control and parasites on animals.
19. A seed comprising a compound of formula (I) or salts, metal complexes, N-oxides, stereoisomers, polymorphs, composition or combination thereof according to claim 1 or 10 or 13, wherein the amount of the compound of formula (I) in the said seed is ranging from about 0.0001 % to about 1 % by weight.
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