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WO2025177310A1 - Composés hétérocycliques fusionnés et leurs utilisations - Google Patents

Composés hétérocycliques fusionnés et leurs utilisations

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Publication number
WO2025177310A1
WO2025177310A1 PCT/IN2025/050264 IN2025050264W WO2025177310A1 WO 2025177310 A1 WO2025177310 A1 WO 2025177310A1 IN 2025050264 W IN2025050264 W IN 2025050264W WO 2025177310 A1 WO2025177310 A1 WO 2025177310A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
group
trifluoromethyl
compound
cycloalkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/IN2025/050264
Other languages
English (en)
Inventor
Narasimha Murthy Cheemala
Dipankar Roy
Ankit VAISHNAV
Viraj SINGH
Ajay Singh Yadav
Pankajkumar Vishwas PATIL
Alexander G.M. KLAUSENER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
PI Industries Ltd
Original Assignee
PI Industries Ltd
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Filing date
Publication date
Application filed by PI Industries Ltd filed Critical PI Industries Ltd
Publication of WO2025177310A1 publication Critical patent/WO2025177310A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P7/00—Arthropodicides
    • A01P7/04—Insecticides

Definitions

  • the present invention relates to compounds of formula (I). 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 composition comprising those compounds, and to their use as pest control agents. BACKGROUND OF THE INVENTION
  • the currently available modern insecticides and acaricides have to satisfy many requirements, for example, regarding level of activity, long lasting efficacy, broadness of insecticidal spectrum as well as environmental and toxicological safeness, additional beneficial effects, and the possible use thereof.
  • the present invention envisages such compounds that satisfy or overcome drawbacks associated with the prior art.
  • certain novel pesticidally active fused heterocyclic compounds with sulfur containing substituents being subject of this invention have favorable properties as pesticides and are environmentally safer, as desired.
  • invertebrate pest includes arthropods, gastropods and nematodes of economic importance as pests.
  • arthropod includes but is not limited to insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes but is not limited to snails, slugs and other Stylommatophora.
  • nematode refers to a living organism of the Phylum Nematoda.
  • helminths includes but is not limited to roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Tematoda), acanthocephala and tapeworms (Cestoda).
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of corn, soybeans and other legumes, rice, cereal (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 fruit (berries, cherries) and other specialty crops (e.g., canola, sunflower, olives).
  • wheat 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 e.g., sweet potatoes, grapes, cotton, tree fruits (e.g.
  • 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” refer 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 necrosis, 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-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-e
  • 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
  • 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.
  • 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.
  • alkynyl used either alone or in compound words includes straight-chain or branched C 2 to C 24 alkynes, preferably C 2 to C 15 alkynes, more preferably C 2 to C 10 alkynes, most preferably C 2 to C 6 alkynes.
  • Non-limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2- butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1- ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1- methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-penty
  • 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.
  • cycloalkylalkyl denotes cycloalkyl substitution on an alkyl group. It refers to a cycloalkyl group attached via an alkyl linkage to the rest of the molecule.
  • C3-C6-cycloalkyl-C1-Cn-alkyl- refers to a C1-Cn-alkyl radical as generally defined above substituted by one or more C3-C6-cycloalkyl groups as generally defined above.
  • C3-C6-cycloalkyl-C1-C3-alkyl is to be construed accordingly.
  • Examples include but are not limited to, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclopentylethyl and cyclohexylmethyl.
  • 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. This definition also applies to 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.
  • 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 one or more 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-dichloro-2,2,2-trifluoroethyl, and 1,1,1-trifluoroprop-2-yl.
  • 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 1,1,1-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 1,1,1-triflu
  • carbonyl means -C(O)-
  • carbonyloxy means -OC(O)-
  • oxo O
  • sulfinyl means SO
  • sulfonyl means S(O)2.
  • alkoxy used either alone or in compound words included C1 to C24 alkoxy, preferably C1 to C 15 alkoxy, more preferably C 1 to C 10 alkoxy, most preferably C 1 to C 6 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 1-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-dimethylbutylthio,
  • Halocycloalkyl halocycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, and the like, are defined analogously to the above examples.
  • alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include -CH2SCH2, -CH2SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2.
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • cycloalkylalkylamino denotes 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 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 methylsulfinyl, ethylsulfinyl, propylsulfinyl, 1-methylethylsulfinyl, butylsulfinyl, 1-methylpropylsulfinyl, 2-methylpropylsulfinyl, 1,1-dimethylethylsulfinyl, pentylsulfinyl, 1-methylbutylsulfinyl, 2-methylbutylsulfinyl, 3- methylbutylsulfinyl, 2,2-dimethylpropylsulfinyl, 1-ethylpropylsulfinyl, hexylsulfinyl, 1,1- dimethylpropylsulfinyl, 1,2-dimethylpropylsulfinyl, 1-methylpentylsulfinyl, 2-methylpentylsulfiny
  • alkylsulfonyl include but are not limited to methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 1-methylpropylsulfonyl, 2- methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, pentylsulfonyl, 1-methylbutylsulfonyl, 2- methylbutylsulfonyl, 3-methylbutylsulfonyl, 2,2-dimethylpropylsulfonyl, 1-ethylpropylsulfonyl, hexylsulfonyl, 1,1-dimethylpropylsulfonyl, 1,2-dimethylpropylsulfonyl, 1-methylpentylsulfonyl, 2- methyl
  • arylsulfonyl includes Ar-S(O)2, wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulfonyl as a part of a composite substituent, for example alkylsulfonylalkyl etc., unless defined elsewhere. "Alkylamino”, “dialkylamino”, and the like, are defined analogously to the above examples.
  • C1-C6-hydroxyalkyl denotes a radical of the formula in which C1-C6 alkyl is substituted with hydroxy group. Non-limiting examples include -CH2OH, -CH(CH3)-OH, CH2CH2-OH.
  • C3-C4-cycloalkyl is optionally substituted with 1 or 2 halo atoms
  • C3-C4-cycloalkyl is optionally substituted with 1 or 2 halo atoms
  • C3-C4-cycloalkyl substituted with 1 halo atom and C3- C4-cycloalkyl substituted with 2 halo atoms.
  • optionally substituted can be used interchangeably with “unsubstituted or substituted”.
  • carrier includes "aromatic carbocyclic ring system” and “nonaromatic carbocyclic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which 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).
  • 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.
  • 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) oxiranyl, aziridinyl,oxetanyl, thietanyl, azetidinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl,
  • 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, thiazoly
  • 6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-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) indol-1-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol
  • heteroarylalkyl denotes heteroaryl substitution on an alkyl group. It refers to a heteroaryl group attached via an alkyl linkage to the rest of the molecule.
  • heteroaryl-C1-C3-alkyl refers to a C1-C3-alkyl radical, as generally defined above, substituted by one 5- or 6- membered heteroaryl ring.
  • Examples include but are not limited to, imidazolyl methyl, oxadiazolyl methyl, thiadiazolyl methyl, pyridinyl ethyl, pyrazinyl ethyl, pyridinyl methyl, pyrazinyl methyl, pyrimidinyl methyl and pyrimidinyl ethyl.
  • the term “3-4 membered heterocyclyl-C1-C3-alkyl” refers to a C1-C3-alkyl radical, as generally defined above, substituted by one 3- to 4- membered heterocyclyl ring.
  • 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.
  • Hydrophilickylsilyl 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.
  • the term “trialkylsilyloxy” denotes a trialkylsilyl moiety attached through oxygen.
  • alkylcarbonyl 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.
  • 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.
  • 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.
  • 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 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.
  • 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.
  • Embodiments according to the invention are provided as set out below: Embodiment 01: Accordingly, the present invention provides fused heterocyclic compounds of formula (I), wherein, R 1 is C 1 -C 6 -alkyl; Y is selected from O or NR Y ; R Y is selected from the group consisting of hydrogen, cyano, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 - C 6 -alkynyl, C 1 -C 6 -haloalkyl, C 2 -C 6 -haloalkenyl, C 3 -C 5 -cycloalkyl, C 3 -C 5 -cycloalkyl-C 1 -C 3 - alkyl and -C(O)R 1a ; R 1a is selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 5 - cyclo
  • Embodiment-02 In an embodiment of the present invention, the compounds of formula (I) are represented by the compounds of formula (I-1), (I-2) or (I-3); wherein, m is 1 or 2; R 2x is selected from hydrogen, halogen, cyano, C1-C6-alkyl, C3-C6-cycloalkyl, C1- C 6 -alkoxy, C 1 -C 6 -alkoxy-C 3 -C 6 -cycloalkyl, C 1 -C 6 -haloalkyl or C 1 -C 6 -haloalkoxy; R 1 , Q, R 2 , and R Y are as defined above for the compounds of formula (I).
  • Q is selected from the group consisting of Q is selected from the group consisting of Q1a, Q1b, Q1c, Q1d, Q1e, Q1f and Q1g; wherein, # denotes the point of attachment to pyrazolopyrimidine ring.
  • Embodiment-06 According to embodiment 05, preferably Q is selected from the group consisting of Q1a-1, Q1b-1, Q1c-1, Q1d-1, Q1e-1, Q1e-2, Q1f-1, Q1f-2 and Q1g-1: wherein, # denotes the point of attachment to pyrazolopyrimidine ring.
  • Embodiment-07 According to embodiments 05 or 06, R 3 is selected from the group consisting of halogen, C 1 -C 3 -haloalkyl, -S(O) 0-2 C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy.
  • Embodiment-08 According to embodiments 05 or 06 or 07, for Q1a to Q1f and Q1a-1 to Q1f-2, preferably R 3 is C 1 -C 3 -haloalkyl and for Q1g and Q1g-1, preferably R 3 is -S(O) 0-2 C 1 -haloalkyl.
  • Embodiment-09 According to embodiments 05 or 06 or 07 or 08, for Q1a to Q1f and Q1a-1 to Q1f- 2, preferably R 3 is selected from fluoromethyl group, a difluoromethyl group, a chlorofluoromethyl group, a dichlorofluoromethyl group, a chlorodifluoromethyl group or a trifluoromethyl group; more preferably R 3 is trifluoromethyl. For Q1g and Q1g-1, more preferably R 3 is -S(O) 0-2 CF 3 .
  • Embodiment-10 According to embodiment 05, R 13 is selected from hydrogen or C 1 -C 6 -alkyl.
  • Embodiment-11 According to embodiments 05 or 10, preferably R 13 is selected from hydrogen or C 1 - C 3 -alkyl more preferably R 13 is methyl.
  • Embodiment-12 According to any of the above embodiments, R 1 is C 1 -C 3 -alkyl.
  • Embodiment-13 According to embodiment 12, preferably R 1 is ethyl.
  • Embodiment-14 According to any of the above embodiments, preferably Y is oxygen (O).
  • Embodiment-15 According to any of the above embodiments, preferably Y is 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-haloalkenyl, C3-C5- cycloalkyl, C3-C5-cycloalkyl-C1-C3-alkyl and -C(O)R 1a .
  • R 1a is selected from the group consisting of C1-C4- alkyl, C1-C4-haloalkyl, C3-C5-cycloalkyl and C3-C5-cycloalkyl-C1-C3-alkyl.
  • Embodiment-18 According to any of the above embodiment, preferably R 2 is cyclopropyl, wherein said cyclopropyl ring may optionally be substituted with one or more groups of R 2a .
  • R 2 is pyrimidinyl, wherein said pyrimidinyl ring may optionally be substituted with one or more groups of R 2a .
  • Embodiment-20 According to any of the above embodiments, preferably R 2 is CR 2b R 2c R 2d .
  • Embodiment-21 According to any of the above embodiments, preferably R 2 is NR 11 R 12 .
  • Embodiment-23 According to embodiments 18 or 19 or 22, R 2a is selected from the group consisting of halogen, cyano, C 1 -C 3 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, OR 4 , C 1 -C 3 -haloalkyl and C 3 -C 6 - cycloalkyl.
  • Embodiment-24 According to embodiment 20, R 2b is selected from the group consisting of halogen, hydroxy and C1-C3-haloalkyl.
  • Embodiment-25 According to embodiment 20, R 2c is selected from the group consisting of hydrogen, halogen and C1-C3-alkyl.
  • Embodiment-26 According to embodiment 20, R 2d is selected from the group consisting of hydrogen and C1-C3-alkyl.
  • Embodiment-27 According to embodiment 26, R 2d is selected from the group consisting of hydrogen and C1-C2-alkyl.
  • R 11 is selected from the group consisting of C2- C6-alkyl, cyano, C2-C6-alkenyl, C2-C6-alkynyl, C1-C4-cyanoalkyl, C1-C4-haloalkyl, C2-C6-haloalkenyl, C1-C4-alkoxy, C3-C6-cycloalkyl, C3-C6-cycloalkyl-C1-C3-alkyl, 3- to 6- membered non aromatic heterocyclic ring, 3- to 4- membered non aromatic heterocyclyl-C1-C3-alkyl, 5- to 6- membered heteroaryl-C1-C3-alkyl, NR 5 R 6 , C1-C3-alkylsulfonyl, -C(O)R 7 and C1-C3-alkyl-C(O)R 8 ; wherein each group may optionally be substituted
  • R 11 is selected from the group consisting of C2-C4-alkyl, cyano, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4-cyanoalkyl, C1-C4-haloalkyl, C1- C 4 -alkoxy, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkyl-C 1 -C 3 -alkyl, 3- to 6- membered non aromatic heterocyclic ring, 3- to 4- membered non aromatic heterocyclyl-C 1 -C 3 -alkyl, 5- to 6- membered heteroaryl-C1-C3-alkyl, NR 5 R 6 , C1-C3-alkylsulfonyl, -C(O)R 7 and C1-C3-alkyl-C(O)R 8 ; wherein each group may optionally be substituted
  • Embodiment-31 According to any of the above embodiments 28 to 30, R 11a is independently selected from the group consisting of halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 - cycloalkyl, -C(O)O-C 1 -C 3 alkyl, oxo, hydroxy and C 1 -C 4 -hydroxyalkyl.
  • R 11a is independently selected from the group consisting of halogen, cyano, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, C 3 -C 6 - cycloalkyl, -C(O)O-C 1 -C 3 alkyl, oxo, hydroxy and C 1 -C 4 -hydroxyalkyl.
  • Embodiment-32 According to any of the above embodiments 28 to 31, R 11a is independently selected from the group consisting of halogen, cyano, C 1 -C 3 -alkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -alkylthio, C 3 -C 5 - cycloalkyl, -C(O)O-C 1 -C 3 alkyl, oxo, hydroxy and C 1 -C 3 -hydroxyalkyl.
  • R 12 is selected from the group consisting of hydrogen, C 1 -C 4 -alkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -haloalkyl, C 2 -C 4 -haloalkenyl and C 3 -C 6 -cycloalkyl.
  • R 12 is selected from the group consisting of hydrogen, C1-C3-alkyl, C2-C3-alkenyl, C2-C3-alkynyl, C1-C3-haloalkyl, C2-C3-haloalkenyl and C3-C5- cycloalkyl.
  • Embodiment-35 According to embodiment 21, R 11 and R 12 together with the nitrogen atom to which they are attached may form a 3- to 6-membered non aromatic heterocyclic ring; wherein said heterocyclic ring optionally contains 1 or 2 heteroatoms independently selected from N, O or S(O)0- 2; said heterocyclic ring is optionally substituted by one or more substituents independently selected from halogen, cyano, oxo, C1-C4-alkyl, C1-C4-alkoxy or C1-C4-haloalkyl.
  • Embodiment-36A According to embodiment 36, R X and R Xa together with the sulfur atom to which they are attached may form a 6-membered non aromatic heterocyclic ring; wherein said heterocyclic ring optionally contains 1 or 2 heteroatoms independently selected from N, O or S(O)0- 2; said heterocyclic ring is optionally substituted by one or more substituents independently selected from halogen, cyano, oxo, C1-C3-alkyl, C1-C3-alkoxy or C1-C3-haloalkyl.
  • R 2x is independently selected from the group consisting of halogen, cyano, C1-C4-alkyl, C3-C5-cycloalkyl, C1-C4-alkoxy, C1-C4-alkoxy-C3-C5- cycloalkyl, C1-C4-haloalkyl and C1-C4-haloalkoxy.
  • Embodiment-38 According to embodiment 37, R 2x is independently selected from the group consisting of halogen, cyano, C 1 -C 3 -alkyl, C 3 -C 5 -cycloalkyl, C 1 -C 3 -alkoxy, C 1 -C 3 -alkoxy-C 3 -C 5 - cycloalkyl, C 1 -C 3 -haloalkyl and C 1 -C 3 -haloalkoxy.
  • Embodiment-39 According to embodiments 37 or 38, preferably R 2x is absent.
  • R 5 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, C3- C8-cycloalkyl-C1-C6-alkyl, 3- to 6- membered non aromatic heterocyclic ring, phenyl and phenyl-C1- C6-alkyl; wherein each group may optionally be substituted with one or more groups of R 5b .
  • Embodiment-44 According to embodiments 42 or 43, R 5 is selected from the group consisting of hydrogen, C1-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C3-haloalkyl and C3-C6-cycloalkyl;
  • Embodiment-45 According to any of the above embodiments 42 to 43, R 5a is selected from the group consisting of C1-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, benzyl and 3- to 6- membered non aromatic heterocyclic ring.
  • Embodiment-46 According to any of the above embodiments 42 to 43, R 5b is selected from the group consisting of halogen, cyano, C1-C3-alkyl and C1-C3-alkoxy.
  • Embodiment-47 According to any of the above embodiments, R 6 is selected from the group consisting of hydrogen, C1-C3-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C3-haloalkyl, C2-C4-haloalkenyl and C3-C6- cycloalkyl.
  • Embodiment-58 the compounds of formula (I) or (IA) are preferably represented by the compounds of formula (ID); wherein, R 1 , R11, R 12 , Q and Y are as defined above for compound of formula (I) or as defined in any of the above embodiments.
  • Embodiment-59 According to this embodiment, for the compounds of formula (I) or (IA) or (IA-1) to (IA-3), (IA-1 x to IA-3 x ) or (IB) to (IE), Q is preferably selected from embodiment 08.
  • Embodiment-60 According to this embodiment, the present invention provides the compounds of formula (Z); wherein, R 1 , Q, R 2 and R 2x are as defined above for the compounds of formula (I) or as defined in any of the above embodiments with the proviso that 2-(ethylthio)-N-methyl-3-(3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine is excluded from the definition of compound of formula (Z).
  • Embodiment-61 According to this embodiment, the compound of formula (Z) is an intermediate for preparing the compounds of formula (I).
  • Embodiment-62 According to a preferred embodiment of the present invention, the compound of formula (I) of the present invention disclosed in Table-A are selected from N-(2-(ethylsulfonyl)-3-(3- methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)-O- methylhydroxylamine; N-cyclopropyl-2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H- imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine; N-cyclopropyl-2-(ethylsulfonyl)-N- methyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-
  • 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.
  • organic cation part of the salt examples include but are not limited to pyridine, methyl amine, imidazole, benzimidazole, hitidine, phosphazene, tetramethyl ammonium, tetrabutylammonium, choline and trimethylamine.
  • Metal ions in metal complexes of the compound of formula (I) are especially the ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main group, especially aluminium, tin and lead, and also of the first to eighth transition groups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period and the first to eighth transition groups.
  • the metals can be present in the various valencies that they can assume.
  • the present invention provides a compound of formula (I), salts, metal complexes, stereo-isomers, 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.
  • Salts of the compounds of the formula (I) are preferably veterinary and/or agriculturally acceptable salts, preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula (I) has a basic functionality.
  • N-oxide includes any compound of formula (I) which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments that represent essentially a single crystal type and embodiments that 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. 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.
  • 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.
  • the present invention provides a process for preparing the compound of formula (I) or salts thereof.
  • 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).
  • the compound of formula (I) can be prepared according to schemes: 1-10 and chemistry examples described herein.
  • the process for preparing a compound of formula (Z), more specifically compound of formula (Za), comprises reacting a compound of formula (2a), with a compound of formula (3), wherein M is NR 13 to obtain the compound of formula (Za).
  • the compound of formula (3) is either commercially available or can be prepared by using the methods known or analogously described in WO200665703, WO2009131237, WO2010125985, WO2011043404, WO2011040629, WO2012086848, WO2013018928 and WO2015000715.
  • the carboxylic acid group present in the compound of formula (2a) can be converted to a more reactive functional group, such as an acyl halide, mixed anhydride, acyl azide, N- Acylbenzotriazoles, active esters, or via an in situ activation by peptide coupling reagents such as bis(2- oxo-3-oxazolidinyl)phosphinic chloride (BOP-Cl); dicyclohexyl carbodiimide (DCC) or 1-ethyl-3-(3- dimethylaminopropyl)carbodiimide (EDC), followed by amide bond formation with compound of formula (3) in solvents such as dichloromethane, dichloroethane, N,N-dimethylacetamide, tetrahydrofuran or acetonitrile or a mixture thereof to obtain the compound of formula (4).
  • a more reactive functional group such as an acyl halide, mixed anhydride, acyl azide,
  • Organic non- nucleophilic bases such as triethyl amine, ethyldiisopropyl amine, pyridine, N-methyl pyrrolidine, 1,8- diazabicyclo[5.4.0]undec-7-ene may be used.
  • the reaction can be carried out in a temperature in the range of 0 °C to 150 °C.
  • the compound of formula (4) can be converted to the compound of formula (Za) by dehydration, following conventional or under microwave conditions, in the presence of an acid catalyst, for example, methane sulfonic acid, or para-toluene sulfonic acid, in an inert solvent such as N-methyl pyrrolidine at a temperature in the range of 25 °C to 185 °C.
  • an acid catalyst for example, methane sulfonic acid, or para-toluene sulfonic acid
  • an inert solvent such as N-methyl pyrrolidine
  • the compound of formula (4) can be converted to the compound of formula (Za) wherein M is oxygen under Mitsunobu reaction conditions well known to those skilled in the art using di- isopropyl azodicarboxylate and triphenyl phosphine, in an inert solvent such as diethyl ether or tetrahydrofuran at a temperature in the range of 25 °C to 50 °C.
  • an inert solvent such as diethyl ether or tetrahydrofuran at a temperature in the range of 25 °C to 50 °C.
  • the carboxylic acid of formula (2a) can be converted to Weinreb amide of formula (5) upon reaction with N,O-dimethylhydroxylamine by methods described in WO201175643 and EP2671582.
  • the compound of formula (6) can be converted to a compound of the formula (8), wherein X is a halogen (preferably chlorine or bromine) with a halogenating agent such as N-chloro succinimide, N-bromo succinimide, N-iodo succinimide, I2, CuBr2, Br2 in acetic acid or PhNMe3 + Br3- typically in a solvent such as methanol, acetonitrile, tetrahydrofuran, ethylacetate, chloroform or dichloromethane, or mixtures thereof, at a temperature in the range of 0 °C to 150 °C, preferably between 25 °C to 120 °C, optionally under microwave heating conditions.
  • a halogenating agent such as N-chloro succinimide, N-bromo succinimide, N-iodo succinimide, I2, CuBr2, Br2 in acetic acid or PhNMe3 + Br3- typically in
  • the compound of formula (Zb) can be obtained by condensing the compound of formula (8) with the compound of formula (7), in an inert solvent, for example, ethanol or acetonitrile, optionally in the presence of a suitable base, such as sodium, potassium or cesium carbonate, at a temperature in the range of 80 °C to 150 °C, optionally under microwave heating conditions.
  • a suitable base such as sodium, potassium or cesium carbonate
  • the compound of formula (Zc) can be prepared by reacting a compound of formula (9) in which Y- is a halide ion or mesityl sulfonate with a compound of formula (11), optionally in the presence of a suitable base and an inert solvent.
  • the compound of formula (Zd) can be prepared by reacting a compound of formula (10), in which Y- is a halide ion or mesityl sulfonate with a compound of formula (11), optionally in the presence of a suitable base and an inert solvent.
  • the compound of formula (9) or (10) can be prepared via N-amination by reacting a compound of formula (7) with O-mesitylenesulfonylhydroxylamine (MSH) as an amination reagent or one of its equivalent, as described for example in WO201334506 and US201359833.
  • Schemes 4 to 10 provide processes for the preparation of pyrzolo pyrimidine.
  • Schemes 4a-c depict a process for the synthesis of the compounds of formula (2aa-2ac): Scheme: 4a
  • the pyrazole derivative of formula (12) can undergo a cyclocondensation reaction when treated with a dielectrophilic compound of formula (13) or it’s protected/masked (e.g. aldehyde masked as a ketal) version to provide a compound of formula (14).
  • the condensation can be carried out in a solvent and in the presence of an acid.
  • an acid include but are not limited to acetic acid, sulfonic acid (e.g. PTSA), sulfuric acid or hydrochloric acid, which liberate the reactive functional group.
  • Examples of the solvent include but are not limited to methanol, ethanol, isopropanol or ethylene glycol or the like.
  • the reaction can be carried out at a temperature in the range of 0 °C to 150 °C.
  • the compound of formula (15) can be obtained by treating a compound of formula (14) with a halogenating agent and 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 or N,N- dimethylformamide or the like.
  • halogenating agents include but are not limited to phosphorus oxychloride, thionyl chloride, phosphorus pentachloride or oxalyl chloride or the like.
  • the base include but are not limited to N,N-dimethylaniline, diisopropylethylamine or N- methylmorpholine or the like.
  • the reaction can be carried out at a temperature in the range of 50-200 °C.
  • the halo compound of formula (15) can conveniently be coupled under standard Suzuki cross-coupling conditions with boronic acids or a boronic ester compound of formula (16) to obtain the compound of formula (18).
  • 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 or 1,4-dioxane or a solvent system such as a mixture of tetrahydrofuran (THF)/water, 1,2-dimethoxyethane/water or 1,4-dioxane/water or the like.
  • a suitable solvent for example, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), 1,2-dimethoxyethane or 1,4-dioxane or a solvent system such as a mixture of te
  • the reaction is usually carried out in the presence of a suitable base, for example, potassium carbonate, cesium carbonate or potassium phosphate.
  • a suitable 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 precedent in the literature, see for example Chem. Soc. Rev.2014, 43, 412-443 or in WO2014070978.
  • the compound of formula (15) may be coupled with a stannous compound of formula (17), 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 catalyst such as copper(I) iodide and copper(I) chloride, in the presence of a base such as alkali metal hydrides, alkali metal carbonates or organic bases, in a suitable solvent such as acetonitrile, tetrahydrofuran (THF), N,N-dimethylformamide (DMF), 1,2-d
  • a ligand and/or an inorganic halogenated compound may be added to the reaction as needed.
  • ligand 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 or 1,10-phenanthroline.
  • Examples of inorganic halogenated compounds include alkali metal fluorides such as potassium fluoride or sodium fluoride; and alkali metal halides such as lithium chloride, sodium chloride or sodium chloride.
  • the hydrolysis of a compound of formula (18) can be carried out by using a base such as sodium hydroxide, potassium hydroxide, lithium hydroxide or Bis(tributyltin) oxide or the like, in a solvent such as tetrahydrofuran, water, methanol, ethanol or toluene or a mixture(s) thereof, to obtain a compound of formula (2aa).
  • the reaction can be carried out at a temperature in the range of 50 °C to 150 °C.
  • a process for the synthesis of a compound of formula (2ab) is depicted in scheme 4b: Scheme: 4b wherein, R 1 and R 2 have the meanings as described above.
  • the compound of formula (20) can be prepared by the cyclization of the pyrazole derivative of formula (12) with commercially available 2-halo-malonaldehydes of formula (19) under acid catalyzed conditions.
  • Examples of an acid include but not limited to acetic acid, sulfonic acid (e.g PTSA), sulfuric acid or hydrochloric acid.
  • the solvents include but are not limited to methanol, ethanol, isopropanol or ethyleneglycol or the like.
  • the reaction can be carried out at a temperature in the range of 0 °C to 150 °C.
  • the compound of formula (20) can be coupled under standard Suzuki cross-coupling conditions or Stille cross-coupling conditions using the reagents of formula (21) to obtain the compound of formula (22) as described in step 3 or step 4 of scheme 4a.
  • Subsequent alkaline hydrolysis of the compound of formula (22) as described in step 5 of scheme 4a can provide a compound of formula (2ab).
  • the compound of formula (2ac) can be prepared according to the following scheme 4c: Scheme: 4c wherein, R 1 and R 2 have the meanings as described above.
  • Pyrazole derivative compound of formula (12) can undergo a cyclocondensation with 1,3- dimethyluracil of formula (23) or alkoxyacrylate derivatives of formula (24) in the presence of a suitable base to obtain pyrimidin-5-one derivatives of formula (25).
  • a suitable base include sodium ethoxide, sodium methoxide, potassium tert-butoxide, potassium carbonate, sodium carbonate, cesium carbonate or potassium phosphate or the like.
  • the solvent include methanol, ethanol, isopropanol, ethyleneglycol, N,N-dimethylacetamide or N,N-dimethylformamide or the like.
  • the reaction can be carried out at a temperature in the range of 50 °C to 150 °C.
  • Compounds of formula (29a-c) can be prepared by reacting compounds of formula (15/20/26) with a reagent of formula (28), in the presence of a base and solvent.
  • a base include sodium, potassium or cesium carbonate, or sodium or potassium tert-butylate, or diisopropylethylamine or triethylamine or DBU, or pyridine.
  • the solvents include tetrahydrofuran, N,N- dimethylformamide, acetonitrile or dimethyl sulfoxide. The reaction can be carried out at a temperature in the range of 25 °C to 130 °C.
  • compounds of formula (29a-c) can be prepared by reacting compounds of formula (15/20/26) under transition metal catalyzed conditions.
  • the reaction can be catalyzed by a palladium based catalyst, for example, bis(dibenzylideneacetone)palladium(0) (Pd(dba)2) or 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′-d
  • the reaction temperature can preferentially range from 25 o C 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.
  • the compound of formula (29a-c) can be prepared by copper or nickel catalysis.
  • Examples of the base include but is not limited to alklaimetal carbonates, or diisopropylethylamine or pyridine or 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 a temperature in the range of 25 o C to 120 o C.
  • Subsequent alkaline hydrolysis of the compound of formula (29a-c) as described in step 5 of scheme 4a can provide the compound of formula (2a-c).
  • Scheme: 6 wherein, Q, R 1 , R 2 , R 11 and R 12 have the meanings as described above.
  • the compound of formula (Z-1) can be prepared according to scheme-6 by reacting the compound of formula (30a-c) using conditions described in step-3 or step-4 of scheme-4a.
  • the compound of formula (Z-2) can be prepared from the compound of formula (28) using the conditions described in step-1 of scheme-5.
  • a process for the synthesis of compounds of formula (30a-c) is depicted in the scheme–7.
  • Scheme: 7 wherein, R 1 and Q have the meanings as described above.
  • Organo sulfanylalkenes of formula (32) can be formed by reacting a compound of formula (31) with CS 2 in the presence of a base such as alkali metal carbonates, alkali metal hydrides, lithium, sodium or potassium hexamethyl disilazane, sodium or potassium hydroxide, in an appropriate solvent such as tetrahydrofuran, acetonitrile or N,N-dimethylfromamide, at a temperature in the range of 0 o C to 50 °C.
  • the compound of formula (32) can be cyclized to aminopyrazole derivative of formula (33) using hydrazine.
  • Such methods are described in the literature, for example, Russian Journal of Organic Chemistry, 2014, 50(3), 412-421.
  • a compound of formula (Z-1A) can be prepared by reacting the pyrazole derivative of formula (33) with a compound of formula (34) under cyclocondensation conditions, in the presence of a solvent and an acid.
  • an acid include acetic acid, sulfonic acid (e.g. PTSA), sulfuric acid or hydrochloric acid which liberate the reactive functional group.
  • the solvents include but are not limited to methanol, ethanol, isopropanol or ethylene glycol or the like.
  • the reaction can be carried out at a temperature in the range of 50 °C to 150 °C.
  • Synthetic methods to prepare the reagents of formula (34) are known in the literature, For e.g. Organic Chemistry Frontiers (2022), 9(16), 4416-4420. Scheme: 9 wherein, Q, R 1 , R 2 , R 2x and R 2a have the meanings as described above. R 2x also includes hydrogen.
  • 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 or other organic peracids or the like can be used for this, at a temperature in the range of 0 o C to 100 °C.
  • mCPBA m- chloroperoxybenozic acid
  • hydrogenperoxide/glacial acetic acid hydrogenperoxide/trifluroacetic acid
  • hydrogenperoxide/potassium permanganate hydrogenperoxide/p-toluenesuflonylimidazole
  • urea hydrogen peroxide/ trifluroacetic acid ox
  • solvents used in this reaction include aliphatic halogenated hydrocarbons such as dichloromethane or chloroform and alcohols such as methanol or ethanol or the mixtures thereof.
  • a suitable nitrogen source such for example, ammonia, ammonium carbamate or ammonium acetate
  • hypervalent iodine reagents such as diacetoxyiodobenzene PhI(OAc) 2
  • solvents such as toluene, ace
  • the compound of formula (I-3) wherein R Y is other than ‘H’ can be prepared using a reagent R Y -X, wherein X is a leaving group, for example, halides such as chloro, bromo or iodo, or an aryl or alkylsulfonate such as trifluoromethanesulfonate.
  • Alkylation reaction can be performed in the presence of a base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate or triethylamine and in the presence of solvent such as dichloromethane, dichloroethane, DMF, DMSO, ethanol or methanol and at a temperature in the range of 0 o C to 150 °C.
  • a base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, cesium carbonate or triethylamine
  • solvent such as dichloromethane, dichloroethane, DMF, DMSO, ethanol or methanol
  • Step-1 2-Cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide
  • 2-cyanoacetic acid 33.4 g, 392 mmol
  • dichloromethane 300 mL
  • 1-(3- dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride 48.1 g, 251 mmol
  • N,N- diisopropylethylamine 82 mL, 471 mmol
  • the resulting reaction mixture was stirred at 25 °C for 24 h under nitrogen atmosphere. After the completion of the reaction, the reaction mixture was evaporated and diluted with water (500 mL). The aqueous layer was extracted with ethyl acetate (4 x 250 mL). The combined organic layers were washed with water (250 mL), brine (250 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a residue which was further washed with hexane to obtain 2-cyano-N-(2- (methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (39 g, 151 mmol; 96 % yield).
  • Step-2 2-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)acetonitrile
  • a solution of 2-cyano-N-(2-(methylamino)-5-(trifluoromethyl)pyridin-3-yl)acetamide (39 g, 151 mmol) in acetic acid (230 mL) was heated at 110 °C for 2 h. After the completion of the reaction, the reaction mixture was evaporated under reduced pressure, diluted with ethyl acetate (250 mL) and water (250 mL).
  • the resulting reaction mixture was heated at 95 °C for 6 h.
  • the reaction mixture was cooled to 25 °C and then quenched with ice cold water (200 mL), pH was adjusted to 7 ⁇ 8 using aqueous saturated NaHCO 3 solution, and extracted with ethyl acetate (4 x 100 mL).
  • Step-7 2-(7-Bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine
  • 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine 3- chloroperoxybenzoic acid (4.15 g, 14.4 mmol) was added at 0 °C.
  • reaction mixture was stirred at 25 °C for 6 h. After the completion of the reaction, the reaction mixture was diluted with dichloromethane (200 mL), washed with saturated aqueous sodium bicarbonate solution (100 mL), and aqueous sodium thiosulfate solution (100 mL).
  • Step-8 2-(2-(Ethylsulfonyl)-7-(pyrimidin-2-yl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine
  • 2-(7-bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine 2.7 g, 5.5 mmol
  • 2-(tributylstannyl)pyrimidine (2.63 mL, 8.3mmol) in tetrahydrofuran (THF) (50 mL)
  • tetrakis(triphenylphosphine)palladium(0) (0.64 g, 0.5 mmol
  • copper (I) bromide (0.16 g, 1.1 mmol
  • Example-2 Synthesis of N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5- b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)- ⁇ 6-sulfaneylidene)cyanamide (Compound-38) Step-1: 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine To a stirred solution of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine (2.0 g, 4.4 mmol) in 1,4-dioxan
  • Step-2 (7-Cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- ⁇ 6-sulfanone
  • 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine 3.4 g, 8.1 mmol
  • methanol 80 mL
  • acetonitrile 40 mL
  • the resulting reaction mixture was cooled to 0 °C followed by the addition of ammonium carbamate (1.90 g, 24.4 mmol) in portions at same temperature over 0.5 h.
  • the resulting reaction mixture was stirred at 25 °C for 15 h.
  • reaction mixture was evaporated under reduced pressure to obtain a crude product which was purified by flash column chromatography to obtain (7-cyclopropyl- 3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-2- yl)(ethyl)(imino)- ⁇ 6-sulfanone (1.8 g, 4.0 mmol, 49.3% yield).
  • Step-3 N-((7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(oxo)- ⁇ 6-sulfaneylidene)cyanamide
  • (7-cyclopropyl-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- ⁇ 6-sulfanone 200 mg, 0.4 mmol
  • dichloromethane 5 mL
  • DMAP 109 mg, 0.9 mmol
  • cyanogen bromide 141 mg, 1.3 mmol
  • Example-3 Synthesis of 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5- b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (Compound-23) Step-1: tert-Butyl 2-cyano-2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5- b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetate To a stirred solution of 2-(7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine (1.0 g, 2.2 mmol) in N,N-dimethyl
  • Step-2 (2-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile
  • a stirred solution of tert-butyl 2-cyano-2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H- imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetate 600 mg, 1.1 mmol
  • sodium chloride (0.34 ml, 5.8 mmol
  • Step-3 1-(2-(Ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile
  • 2-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)acetonitrile 500 mg, 1.2 mmol
  • cesium carbonate (1.17 g, 3.6 mmol
  • 1,2-dibromoethane (0.31 mL, 3.6 mmol
  • Step-4 1-(2-(Ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile
  • the titled compound 1-(2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin- 2-yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonitrile (90 mg, 0.2 mmol, 52.5% yield) was prepared from 1-(2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)cyclopropane-1-carbonit
  • Example-4 Synthesis of N-cyclopropyl-2-(ethylsulfonyl)-N-methyl-3-(3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2-yl)pyrazolo[1,5-a]pyrimidin-7-amine (Compound- 3)
  • 2-(7-bromo-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine 200 mg, 0.4 mmol
  • N,N-dimethyl formamide 3 mL
  • N-Methylcyclopropanamine (0.09 mL, 1mmol
  • Example-5 Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3- methyl-6-(trifluoromethyl)-3H-imidazo[4,5-c]pyridine (Compound-52)
  • Step-1 7-Cyclopropyl-2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4- yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide
  • HATU 646 mg, 1.70 mmol
  • Step-2 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-c]pyridine
  • 7-cyclopropyl-2-(ethylthio)-N-(5-(methylamino)-2-(trifluoromethyl)pyridin-4- yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide 300 mg, 0.69 mmol
  • acetic acid 20 mL
  • Step-3 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-c]pyridine
  • the titled compound 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-c]pyridine 62 mg, 0.14 mmol, 52.4% yield
  • 2- (7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6-(trifluoromethyl)-3H- imidazo[4,5-c]pyridine 110 mg, 0.26 mmol
  • Example-6 Synthesis of 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7- methyl-3-(trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (Compound-50)
  • Step-1 7-Cyclopropyl-2-(ethylthio)-N-(3-(methylamino)-6-(trifluoromethyl)pyridazin-4- yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide
  • 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid (1.64 g, 6.25 mmol) in N,N-dimethylformamide (10 mL), HATU (2.57 g, 6.77 mmol)) and N,N- diisopropylethylamine
  • Step-2 6-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3- (trifluoromethyl)-7H-imidazo[4,5-c]pyridazine
  • 7-cyclopropyl-2-(ethylthio)-N-(3-(methylamino)-6-(trifluoromethyl)pyridazin- 4-yl)pyrazolo[1,5-a]pyrimidine-3-carboxamide 0.7 g, 1.60 mmol
  • acetic acid 10 mL
  • Step-3 6-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3- (trifluoromethyl)-7H-imidazo[4,5-c]pyridazine: The titled compound 6-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3- (trifluoromethyl)-7H-imidazo[4,5-c]pyridazine (145 mg, 0.321 mmol, 67.4 % yield) was prepared from 6-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-methyl-3-(trifluoromethyl)-7H- imidazo[4,5-c]pyridazine (200 mg, 0.48 mmol) following the reaction conditions as described in step
  • Example-7 Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7- (trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (Compound-8) Step-1: 1,2-Diamino-4-(trifluoromethyl)pyridin-1-ium diphenylphosphinate. To a stirred solution of 4-(trifluoromethyl)pyridin-2-amine (2.0 g, 12.3 mmol) in dichloromethane (40 mL), (aminooxy)diphenylphosphine oxide (4.03 g, 17.3 mmol) was added at 25 °C.
  • Step-2 2-(7-Cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine
  • 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid 600 mg, 2.3 mmol
  • dichloromethane 20 mL
  • triethylamine (0.95 mL, 6.8 mmol
  • 1-(3- dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (481 mg, 2.5 mmol)
  • 1- hydroxybenzotriazole (339 mg, 2.5 mmol) were added.
  • Step-3 2-(7-Cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-7-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine
  • 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7- (trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine 200 mg, 0.49 mmol
  • dichloromethane 20 mL
  • chloroperoxybenzoic acid 276 mg, 1.04 mmol
  • reaction mixture was stirred at 25 °C for 6 h. After completion of the reaction, the reaction mixture was quenched with aqueous sodium thiosulphate solution (100 mL) and extracted with dichloromethane (2x 50 mL).
  • Example-8 Synthesis of (7-cyclopropyl-3-(7-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-2-yl)(ethyl)(imino)- ⁇ 6-sulfanone (Compound-36) To a stirred solution of 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-7- (trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (500 mg, 1.24 mmol) in methanol (10 mL) and acetonitrile (10 mL), iodobenzene diacetate (1.19 g, 3.71 mmol) was added followed by carbamic acid ammonium salt (290 mg, 3.71 mmol) at 25 °C.
  • Example-9 Synthesis of 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylic acid
  • Step-1 Ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3-carboxylate
  • acetic acid 250 mL
  • methyl 3,3-dimethoxypropanoate 9.9 mL, 69.7 mmol
  • Step-2 Ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate
  • the titled compound ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (5 g, 15.1 mmol, 81% yield) was prepared from ethyl 2-(ethylthio)-7-hydroxypyrazolo[1,5-a]pyrimidine-3- carboxylate (5 g, 18.7 mmol) following the reaction conditions as described in step 6 for example-1.
  • Step-3 Ethyl 7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate To a stirred solution of ethyl 7-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidine-3-carboxylate (7 g, 21.2 mmol), cyclopropylboronic acid (7.28 g, 85 mmol) and potassium phosphate tribasic (13.45 g, 63.6 mmol) in 1,4-dioxane (70 ml), 1,1'-bis(diphenylphosphino)ferrocene-palladium(II)dichloride dichloromethane adduct (1.73 g, 2.1 mmol) was added under nitrogen purging.
  • Step-4 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 resulting reaction mixture was stirred at 60 °C for 4 h.
  • reaction mixture was cooled to 25 °C and evaporated under reduced pressure to obtain a residue which was acidified with concentrated HCl.
  • the solid obtained 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).
  • reaction mixture was poured into aqueous saturated sodium bicarbonate (400 mL) solution.
  • aqueous layer was extracted with ethyl acetate (2 X 200 mL).
  • the combined organic layers were washed with brine solution (200 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product.
  • the crude product was purified by flash column chromatography to obtain 2-(chloromethyl)- 6-(trifluoromethyl)imidazo[1,2-a]pyridine (10.54 g, 44.9 mmol, 56 % yield) as a liquid.
  • Step-3 3,3-bis(Ethylthio)-2-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acrylonitrile
  • potassium hydroxide 7.47 g, 133 mmol
  • 2- (6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)acetonitrile (15.0 g, 66.6 mmol) was added.
  • the resulting reaction mixture was stirred for 1 h at 25 °C and it was cooled to -5 °C followed by dropwise addition of carbon disulfide (4.0 mL, 66.6 mmol) over 10 minutes.
  • Step-4 3-(Ethylthio)-4-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)-1H-pyrazol-5-amine
  • acetonitrile 200 mL
  • ethanol 200 mL
  • hydrazine hydrate 3.9 mL, 80.0 mmol
  • the resulting reaction mixture was heated at 130 °C for 6 h. After the completion of the reaction, the reaction mixture was cooled to 25 °C, the solvent was removed under reduced pressure. Water (200 mL) was added to the residue, extracted with DCM (2 x 100 mL).
  • Step-6 7-Bromo-2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5- a]pyrimidine
  • 2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2-yl)pyrazolo[1,5- a]pyrimidin-7(4H)-one 9.8 g, 25.8 mmol
  • phosphorus oxybromide 29.6 g, 103 mmol
  • potassium carbonate 14.28 g, 103.0 mmol
  • the resulting reaction mixture was stirred at 95 °C for 16 h. After completion of the reaction, the reaction mixture was cooled to 25 °C, and poured into saturated aqueous sodium bicarbonate solution (400 mL). The aqueous layer was extracted with ethyl acetate (2 X 500 mL) and the combined organic layers were washed with brine solution (100 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude solid.
  • Step-7 7-Bromo-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidine
  • 7-bromo-2-(ethylthio)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidine (2.84 g, 6.42 mmol) in dichloromethane (120 mL)
  • 3- chloroperoxybenzoic acid (4.43 g, 15.41 mmol) was added and the resulting reaction mixture was stirred at 25 °C for 6 h.
  • the rection mixture was diluted with dichloromethane (200 mL). The organic layer was washed with saturated aqueous sodium bicarbonate solution (2 x 50 mL), sodium thiosulfate (2 x 30 mL), saturated brine solution (2 x 50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain the crude compound.
  • Step-8 N-(tert-butyl)-2-(ethylsulfonyl)-N-methyl-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-amine
  • 7-bromo-2-(ethylsulfonyl)-3-(6-(trifluoromethyl)imidazo[1,2-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidine 250 mg, 0.53 mmol
  • triethylamine (0.22 mL, 1.58 mmol
  • N-methyl-tert-butylamine 115 mg; 1.32 mmol
  • the resulting reaction mixture was stirred at 25 °C for 4 h. After the completion of the reaction, the reaction mixture was poured into water (25 mL). The aqueous layer was extracted with ethyl acetate (3 X 10 mL), the combined organic layers were washed with brine solution (10 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude compound.
  • Example-11 Synthesis of 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3- yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (Compound-115)
  • Step-1 1,2-diamino-5-(trifluoromethyl)pyridin-1-ium diphenylphosphinate
  • 5-(trifluoromethyl)pyridin-2-amine 30 g, 185 mmol) in dichloromethane (500 mL)
  • (aminooxy)diphenylphosphine oxide (43.2 g, 185 mmol) was added at 25 °C, and the resulting reaction mixture was stirred for 18 h.
  • Step-2 2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2-yl)pyrazolo[1,5- a]pyrimidin-7(4H)-one
  • 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid 15.13 g, 63.2 mmol
  • 1,2-diamino-5-(trifluoromethyl)pyridin-1-ium diphenylphosphinate 25 g, 63.2 mmol
  • 1-[3-(Dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride (18.18 g, 95 mmol) and 1H-1,2,3-benzotriazol-1-ol hydrate (10.82 g, 63.2 mmol)
  • the resulting reaction mixture was stirred at 85 °C for 16 h, After the completion of the reaction, the reaction mixture was cooled to 25 °C, and the volatiles were removed under reduced pressure. The residue was diluted with water (1000 mL) and the aqueous layer was extracted with ethyl acetate (3 x 500 mL).
  • Step-3 2-(7-chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine
  • 2-(ethylthio)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7(4H)-one 9 g, 23.66 mmol) in toluene (100 ml) and acetonitrile (100 mL), POCl 3 (22.05 mL, 237 mmol) was added.
  • Step-4 2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine
  • 2-(7-chloro-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)- [1,2,4]triazolo[1,5-a]pyridine (6 g, 15.05 mmol) in dichloromethane (120 mL), m-CPBA (8.79 g, 33.1 mmol) was added at 0 °C, and the resulting reaction mixture was stirred at 25 °C for 3 h.
  • reaction mixture was quenched with 10% aqueous sodium thiosulfate solution (100 mL).
  • the aqueous layer was extracted with dichloromethane (2 x 250 mL), the combined organic layers were washed with saturated sodium bicarbonate solution (2 x 250 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to get a crude product which was purified by flash column chromatography to obtain 2-(7-chloro-2- (ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine (6.1 g, 14.16 mmol, 94 % yield).
  • Step-5 1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one
  • 2-(7-chloro-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6- (trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine 800 mg, 1.86 mmol
  • 1,4-dioxane (20 mL) tributyl(1-ethoxyvinyl)stannane (805 mg, 2.228 mmol) was added.
  • the resulting mixture was purged with nitrogen for 5 minutes treated withtetrakis(triphenylphosphine)palladium(0) (129 mg, 0.111 mmol), and stirred at 90 °C for 2 h.
  • the reaction mixture was filtered and concentrated under reduced pressure to get a residue, which was taken in 4.0 M hydrochloric acid in dioxane (112 mL), and the resulting reaction mixture was stirred at 25 °C for 2 h, diluted with ethyl acetate (100 mL), and washed with saturated brine solution (2 x 100 mL).
  • Step-6 2-(7-(1,1-difluoroethyl)-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-6- (trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridine
  • 1-(2-(ethylsulfonyl)-3-(6-(trifluoromethyl)-[1,2,4]triazolo[1,5-a]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-7-yl)ethan-1-one 200 mg, 0.46 mmol
  • dichloromethane 10 mL
  • DAST (0.24 ml, 1.83 mmol
  • Example-12 Synthesis of 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid
  • Step-1 ethyl 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylate
  • acetic acid 250 mL
  • Step-2 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylic acid
  • ethyl 2-(ethylthio)-7-oxo-4,7-dihydropyrazolo[1,5-a]pyrimidine-3-carboxylate 20 g, 74.8 mmol
  • sodium hydroxide 29.9 g, 748 mmol
  • water 250 mL
  • Example-13 Synthesis of 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3- yl)-5-((trifluoromethyl)sulfonyl)benzo[d]oxazole (Compound-198)
  • Step-1 2-nitro-4-((trifluoromethyl)thio)phenol
  • 4-((trifluoromethyl)thio)phenol 40 g, 206 mmol
  • acetic acid 177 mL, 0.309 mol
  • sulfuric acid (12.3 mL, 227 mmol
  • Step-2 2-amino-4-((trifluoromethyl)thio)phenol
  • 2-nitro-4-((trifluoromethyl)thio)phenol 40 g, 167 mmol
  • iron powder 20 g, 502 mmol
  • ammonium chloride 89 g, 1.67 mol
  • water 400 mL
  • the reaction mixture was stirred at 70 °C for 18 h.
  • the reaction mixture was filtered through a pad of celite ® , washed with ethyl acetate (2 L).
  • Step-3 2-cyano-N-(2-hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide
  • 2-cyanoacetic acid 30.5 g, 359 mmol
  • dichloromethane 500 mL
  • N,N- diisopropylethylamine 75 mL, 430 mmol
  • 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (41.2 g, 215 mmol)
  • 2-amino-4-((trifluoromethyl)thio)phenol (30 g, 143 mmol) were added in sequence at 25 °C.
  • the reaction mixture was stirred for 18 h at 25 °C.
  • reaction mixture was diluted with water (1 L) and extracted with dichloromethane (2 x 500 mL) and the combined organic layers were washed with water (500 mL) and saturated brine solution (500 mL), dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to get a crude compound which was purified by flash column chromatography to obtain 2-cyano-N-(2- hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide (13 g, 47.1 mmol, 32.8 % yield).
  • Step-4 2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acetonitrile
  • 2-cyano-N-(2-hydroxy-5-((trifluoromethyl)thio)phenyl)acetamide 11 g, 39.8 mmol
  • POCl3 37.1 mL, 398 mmol
  • reaction mixture was stirred at 100 °C for 8 h.
  • the reaction mixture was cooled to 25 °C and concentrated under reduced pressure, residue was diluted with water (500 mL) and extracted with ethyl acetate (2 x 500 mL).
  • Step-5 3,3-bis(ethylthio)-2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acrylonitrile
  • 2-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)acetonitrile 7 g, 27.1 mmol
  • potassium hydroxide 3.19 g, 56.9 mmol
  • reaction mixture was cooled to 0 °C and carbon disulfide (1.96 mL, 32.5 mmol) was added dropwise over 10 minutes.
  • the reaction mixture was stirred for 1 h at 25 °C and then ethyl iodide (8.75 mL, 108 mmol) was added at 0 o C in dropwise manner over 10 minutes, thereafter reaction mixture was stirred for 16 h at 25 °C. After the completion of the reaction, the reaction mixture was diluted with water (500 mL).
  • Step-6 3-(ethylthio)-4-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)-1H-pyrazol-5-amine
  • acetonitrile 100 mL
  • ethanol 100 mL
  • hydrazine hydrate 5.1 mL, 102 mmol
  • Step-7 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5- ((trifluoromethyl)thio)benzo[d]oxazole
  • 3-(ethylthio)-4-(5-((trifluoromethyl)thio)benzo[d]oxazol-2-yl)-1H-pyrazol-5- amine 800 mg, 2.22 mmol
  • acetic acid 20 mL
  • E -1-cyclopropyl-3- (dimethylamino)prop-2-en-1-one (618 mg, 4.44 mmol) at 25 °C and the resulting reaction mixture was stirred at 110 °C for 3 h.
  • reaction mixture was cooled to 25 °C and concentrated under reduced pressure to obtain a residue.
  • the residue was diluted with water (200 mL) and the precipitated solid was filtered, washed with water (200 mL), diethyl ether (50 mL) and dried under reduced pressure to obtain 2-(7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)- 5-((trifluoromethyl)thio)benzo[d]oxazole (800 mg, 1.833 mmol, 83 % yield).
  • Step-8 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5- ((trifluoromethyl)sulfonyl)benzo[d]oxazole
  • the titled compound 2-(7-cyclopropyl-2-(ethylsulfonyl)pyrazolo[1,5-a]pyrimidin-3-yl)-5- ((trifluoromethyl)sulfonyl)benzo[d]oxazole (150 mg, 0.300 mmol, 32.7 % yield) was prepared from 2- (7-cyclopropyl-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-5-((trifluoromethyl)thio)benzo[d]oxazole (400 mg, 0.916 mmol) following the reaction conditions as described in step 7 for example-1.
  • Step-2 ((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl- ⁇ 6-sulfanone
  • 2-(6-bromo-2-(ethylthio)pyrazolo[1,5-a]pyrimidin-3-yl)-3-methyl-6- (trifluoromethyl)-3H-imidazo[4,5-b]pyridine (0.20 g, 0.44 mmol) in toluene (6 mL), iminodimethyl- ⁇ 6-sulfanone (0.06 g, 0.66 mmol), potassium phosphate, tribasic (0.186 g, 0.87 mmol) were added in sequence, and the reaction mixture was degassed under nitrogen flow for 5 minutes.
  • Step-3 ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl- ⁇ 6-sulfanone
  • the titled compound ((2-(ethylsulfonyl)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin-6-yl)imino)dimethyl- ⁇ 6-sulfanone (64 mg, 0.128 mmol, 37.4 % yield) was prepared from ((2-(ethylthio)-3-(3-methyl-6-(trifluoromethyl)-3H-imidazo[4,5-b]pyridin-2- yl)pyrazolo[1,5-a]pyrimidin
  • 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) and at least one additional component selected from the group consisting of surfactants and auxiliaries.
  • 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.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed.
  • the present invention provides an agrochemical compositions compound of formula (I), which comprise 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 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 compounds 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.
  • compound 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.
  • Treatment of plant propagation materials such as seeds, e.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 500 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 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.
  • 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.
  • compositions according to the present invention are applied per hectare of 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.
  • 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, fish and plants.
  • 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).
  • helminths such as: roundworms, heartworms, and phytophagous nematodes (Nematoda), flukes (Tematoda), Acanthocephala, and tapeworms (Cestoda).
  • 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 pests in forest, greenhouse, nursery, ornamentals, turfgrass, food and
  • 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 in the order of 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 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).
  • Thysanoptera e.g., Frankliniella occidentalis Pergande (western flower thrip), Scirthoth ⁇ ps citri Moulton (citrus thrip), Sericothrips variabilis Beach (soybean thrip), and Thrips tabaci Lindeman (onion thrip)
  • order Coleoptera
  • 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; Ring
  • 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) 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, Chrysom
  • 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 present invention provides 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 or 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.
  • 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, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural utility.
  • additional biological active compatible compound which includes but is not limited to insecticides, fungicides, nematocides, bactericides, acaricides, growth regulators such as rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum
  • 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 compounds or agents having a similar spectrum of control but a different mode of action.
  • the biologically effective amount of the compound of formula (I) in the composition ranges from 0.1 % to 99% by weight with respect to the total weight of the composition, preferably from 5% to 50% by weight with respect to the total weight of the composition.
  • the present invention furthermore provides a method of combating invertebrate pests, said method comprising contacting the invertebrate pests, their habitat, breeding ground, food supply, plant, seed, soil, area, material or environment in which the invertebrate pests are growing or may grow, or the materials, plants, seeds, soils, surfaces or spaces to be protected from pest attack or infestation with a biologically effective amount of the compound or the composition of the present invention.
  • 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 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 piperonyl butpxide often enhance compound efficacy.
  • the rate of application required for effective control i.e. "biologically effective amount" will depend on such factors as the species of invertebrate to be controlled, the pest′s life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.0001 kg/ hectare may be sufficient or as much as 8 kg/hectare may be required.
  • 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 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 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 to 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.
  • 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 semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to particular necessities in terms of stickyness, moisture retention or aging characteristics.
  • 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 weight % to 15 weight %, desirably from 0.001 weight % 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, N,N-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
  • 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, (2-hydroxymethylcyclohexyl) 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 Eucalyp
  • 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, electrie wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (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.
  • the present invention provides 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 compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof, composition and combination thereof comprising the compound of formula (I).
  • the present invention provides a method for protecting crops from attack or infestation by insects and mite pests comprises contacting the crop with the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof according to claim 1, composition and combination thereof comprising the compound of formula (I).
  • the present invention provides a method, wherein said method comprises applying effective dosages of the compound of formula (I) in amounts ranging from 1 gai to 5000 gai per hectare in agricultural or horticultural crops.
  • the present invention provides a method for the protection of seeds, plants and plant parts from soil insects and of the seedlings roots and shoots from soil and foliar insects comprising contacting the seeds before sowing and/or after pre-germination with the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof, composition and combination thereof comprising the compound of formula (I).
  • the present invention provides use of the compound of formula (I) or salts, stereoisomers, polymorphs, metal complexes or N-oxides thereof, composition and combination thereof comprising compound of formula (I), for combating insects and mite pests in agricultural crops, horticultural crops, household and vector control and parasites on animals.
  • the present invention further provides a treated seed comprising the compounds of the present invention, particularly in an amount ranging from about 0.0001% to about 1% by weight of the seed before treatment.
  • the compounds of the present invention are also suitable for the treatment of seeds in order to protect the seed from insect pest, in particular from soil-living insect and mite pests and the resulting plant′s roots and shoots against soil pests and foliar insects.
  • 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.
  • 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, fruit, 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.
  • seed coating compositions reported in EP3165092, EP3158864, WO2016198644, WO2016039623, WO2015192923, CA2940002, US2006150489, US2004237395, WO2011028115, EP2229808, WO2007067042, EP1795071, EP1273219, WO200178507, EP1247436, NL1012918 and CA2083415.
  • 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.
  • the compounds of the present invention may be used for treating seed from plants, which tolerate the action of herbicides or fungicides or insecticides owing to breeding, including genetic engineering methods.
  • the compound 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
  • compositions which are especially useful for seed treatment are e.g.: A. Soluble concentrates (SL, LS) B. Emulsions (EW, EO, ES) C. Suspensions (SC, OD, FS) D.
  • Water-dispersible granules and water-soluble granules E. Water-dispersible powders and water-soluble powders (WP, SP, WS) F. Gel-Formulations (GF) G. 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.
  • 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 also 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. For specific crops such as lettuce the rate can be higher.
  • the present invention provides a seed comprising a compound of formula (I) or salts, metal complexes, N-oxides, stereoisomers, polymorphs thereof, composition and combination thereof comprising the compound of formula (I), wherein the amount of compound of formula (I) in said seed ranging from about 0.0001 % to about 1 % by weight.
  • Animal health also provides an agricultural and/or veterinary composition comprising at least one compound of the present invention.
  • the present invention still further relates to a use of the compound, N-oxide or veterinarily acceptable salt thereof or the composition of the present invention in the preparation of a medicament for treating or protecting animals against infestation or infection by invertebrate pests or parasites.
  • 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 residual 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.
  • 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
  • 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 compositions containing them for combating mosquitoes. In one embodiment, the present invention provides use of the compounds of formula (I) and compositions containing them for combating flies. In one embodiment, the present invention provides use of the compounds of of formula (I) and compositions containing them for combating fleas. The use of the compounds of the present invention and 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.
  • 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 mg/kg to 100 mg/kg of animal body weight per day of the compound of the present invention, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • 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 mg/kg to 100 mg/kg of animal body weight per day of the compound of the present invention.
  • the compounds of the present invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on formulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compound of the present invention.
  • 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.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N-methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active compounds can optionally be dissolved in physiologically tolerable vegetable or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation.
  • Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester. Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n- butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the used concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary. 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.
  • Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, methylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, N, N-dimethylformamide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
  • Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment-like consistency result.
  • the thickeners employed are the thickeners given above. 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.
  • Suitable solvents which are for example, water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or noctylpyrrolidone, N-methylpyrrolidone, 2-pyrrolidon
  • Suitable colorants are, for example, all colorants permitted for use on animals and which can be dissolved or suspended.
  • Suitable absorption-promoting substances are for example, dimethyl sulfoxide, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides or fatty alcohols.
  • Suitable antioxidants are for example, sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole or tocopherol.
  • Suitable light stabilizers are for example, novantisolic acid.
  • Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacrylates or natural polymers such as alginates, gelatin.
  • Emulsions can be administered orally, dermally, or as injections.
  • Emulsions are either of the water-in- oil type or of the oil-in-water type. 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.
  • Suitable hydrophobic phases are: Liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length C 1 -C 12 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, monoand diglycerides of the Cs- do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C 16 -C 18 , isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C 12 -C
  • Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
  • Suitable emulsifiers are for example, non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monooleate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p- iminodipropionate or lecithin.
  • Suitable anionic surfactants are for example, sodium lauryl sulfate, fatty alcohol ether sulfates, mono/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; suitable cation-active surfactants are cetyltrimethylammonium chloride.
  • Suitable further auxiliaries are for example, substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
  • 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. Suitable wetting agents (dispersants) are the emulsifiers given above. Other auxiliaries which may be mentioned are those given above. Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above 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 are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances.
  • Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates.
  • Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches. Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
  • auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyrrolidone, and dry binders such as microcrystalline cellulose.
  • "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 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 per cent by weight, preferably from 0.1 to 65 per cent by weight, more preferably from 1 to 50 per cent by weight, most preferably from 5 to 40 per cent by weight.
  • Preparations are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 per cent by weight, preferably of 1 to 50 per cent by weight.
  • the preparations comprise the compounds of the present invention against endoparasites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 per cent by weight, very particularly preferably of 0.005 to 0.25 per cent by weight.
  • compositions comprising the compounds of the present invention are applied dermally/topically.
  • 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.
  • solid formulations which release compounds of the present invention in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • 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 tolerant to drought, high salt, high temperature, chill, forst or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality plant product, more number of 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 tolerant to drought, high salt, high temperature, chill, forst or light radiation, improved flowering, enhanced nutrient utilization (such as improved nitrogen assimilation), enhanced quality plant product, more number of productive tillers, enhanced resistance to fungi, insects, pests and the like, which results in higher yields.
  • the compounds of formula (I) show insecticidal activities which are exerted with respect to numerous insects which attack on important agricultural crops.
  • Example A Helicoverpa armigera 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 60 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 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 65%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of the larvae. The moribund larvae were considered dead while calculating the percent mortality.
  • the compounds 5, 8, 9, 22, 32, 33, 39, 41, 49, 50, 51, 52, 103, 108, 109, 112, and 127 recorded ⁇ 70 per cent mortality @ 300 PPM.
  • Example B Spodoptera litura 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 60 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 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 65%. Observations on dead, moribund and alive larvae were recorded 96 h after the release of larvae. The moribund larvae were considered as dead while calculating the percent mortality. The compounds 5, 8, 22, 24, 25, 33, 34, 39, 41, 49, 52, 104, and 108 recorded ⁇ 70 per cent mortality @ 300 PPM.
  • Example C Plutella xylostella 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 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 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 65%. Observations on dead, moribund and alive larvae were recorded 72 hr after the release. The moribund larvae were considered dead while calculating the percent mortality.
  • Example D Bemisia tabaci 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 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 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 kept in a plant growth chamber at a temperature of 25 o C and relative humidity of 65%. Observations on dead, moribund and alive adults were recorded 72 h after the release. The moribund adults were considered dead while calculating the percent mortality.
  • the compounds 5, 6, 9, 24, 27, 33, 34, 38, 40, 41, 49, 50, 51, 52, 53, 58, 66, 70, 73, 76, 81, 86, 94, 95, 104, 109, 125, 127, 135, 156, 160, 165, 171, 175, 180, 195 and 196 recorded ⁇ 70 per cent mortality @ 300 PPM.
  • Example E Myzus persicae 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 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 1 % agar-agar solution.
  • Example F Nilaparvata lugens 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 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 the seedlings were placed in glass test tubes with the roots kept in water.15 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 65%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Health & Medical Sciences (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

La présente invention concerne un composé hétérocyclique fusionné de formule (I), ou des sels, des stéréoisomères, des polymorphes, des complexes métalliques ou des N-oxydes de ceux-ci, (I), Q, R1, Y, R2 et R2x étant tels que définis dans la description détaillée. La présente invention concerne également des procédés pour leur préparation et l'utilisation des composés de formule (I) en tant qu'agent de lutte contre des nuisibles.
PCT/IN2025/050264 2024-02-23 2025-02-21 Composés hétérocycliques fusionnés et leurs utilisations Pending WO2025177310A1 (fr)

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