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WO2020095161A1 - Nitrone compounds and use thereof - Google Patents

Nitrone compounds and use thereof Download PDF

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Publication number
WO2020095161A1
WO2020095161A1 PCT/IB2019/059386 IB2019059386W WO2020095161A1 WO 2020095161 A1 WO2020095161 A1 WO 2020095161A1 IB 2019059386 W IB2019059386 W IB 2019059386W WO 2020095161 A1 WO2020095161 A1 WO 2020095161A1
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WO
WIPO (PCT)
Prior art keywords
oxide
thiazol
methanimine
trifluorobut
difluorobut
Prior art date
Application number
PCT/IB2019/059386
Other languages
French (fr)
Inventor
Renugadevi Gurusamy
Sathishkumar MURUGAN
Robindro SARANGTHEM
Kamble Maruti MADHAVRAO
Vikram Singh JHALA
Suresh ASHAMONI
Uzma KHAN
Deepak Lahanya EBHAD
Anil Kumar Verma
Ruchi GARG
Hagalavadi M VENKATESHA
Alexander G.M. KLAUSENER
Original Assignee
Pi Industries Ltd.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Pi Industries Ltd. filed Critical Pi Industries Ltd.
Publication of WO2020095161A1 publication Critical patent/WO2020095161A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/84—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/36—Sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical

Definitions

  • the present invention relates to novel nitrone compounds. More particularly, the present invention relates to a nitrone compound of formula (I) and to a process for preparation thereof. The present invention further relates to a use of nitrone compound of formula (I) as a crop protection agent for the control of phytopathogenic microorganisms such as plant parasitic nematodes and plant pathogens.
  • Heterocyclic compounds carrying a fluroalkenyl chain have been described in literature for use as pesticides and, in particular, as nematicides.
  • JP500037/1988 discloses polyhaloalkene compounds which have nematicidal activity.
  • JP176141/1997 discloses thiazole compounds having insecticidal and acaricidal activity.
  • Nitrones are the N-oxide of imines, they are first used as agents to trap free-radicals (known as spin trapping) in chemical systems and subsequently, in biochemical systems.
  • US3834073 discloses phenyl nitrone derivatives for controlling plant pathogens in soil by soil treatment or by treatment of the crop plant seeds.
  • the present invention describes compounds of formula (I) which possess the above mentioned effects or advantages.
  • the present invention provides a novel nitrone compound of formula (I),
  • R 1 , R 2 , R 3 , R 4 , A, A 1 and n are as defined in the detailed description.
  • the present invention provides a process for the preparation of compounds of formula (I).
  • the present invention provides a use of compound of formula (I) as crop protection agent for the control of phytopathogenic microorganisms such as plant parasitic nematodes and plant pathogens.
  • compositions comprising, “comprising”, “includes”, “including”, “has”, “having”, “contains”,“containing”,“characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • transitional phrase“consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term“consisting essentially of’ occupies a middle ground between“comprising” and“consisting of’.
  • “or” refers to an inclusive“or” and not to an exclusive “or”. For example, a condition A“or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • indefinite articles“a” and“an” preceding an element or component of the present invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore“a” or“an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
  • the term“pesticide” in each case also always comprises the term “crop protection agent”.
  • the term“invertebrate pest” includes arthropods, gastropods and nematodes of economic importance as pests.
  • the term“arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • the term“gastropod” includes snails, slugs and other Stylommatophora.
  • the term“nematode” refers to a living organism of the Phylum Nematoda.
  • the term“helminths” includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Trematoda), acanthocephala and tapeworms (Cestoda).
  • undesired microorganisms or“phytopathogenic microorganisms” such as f ingal or bacterial pathogens includes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae respectively.
  • invertebrate pest control means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.
  • 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” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include 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). Additionally, the person skilled in the art knows processes or methods or technology to separate, enrich, and/or to selectively prepare said isomers.
  • the term“alkyl”, used either alone or in compound words such as“alkylthio” or“haloalkyl” or -N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched Ci to C24 alkyl, preferably Ci to C15 alkyl, more preferably Ci to C10 alkyl, most preferably Ci to G, alkyl.
  • Non limiting examples of alkyl include methyl, ethyl, propyl, 1 -methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, l,l-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, l,l-dimethylpropyl, 1 ,2-dimethylpropyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, 1 ,2-dimethylbutyl, l,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2- ethylbutyl, l,l
  • the alkyl is at the end of a composite substituent, as, for example, in alkylcycloalkyl
  • the part of the composite substituent at the start for example the cycloalkyl
  • other radicals for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.
  • alkenyl used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably C2 to C15 alkenes, more preferably C2 to C10 alkenes, most preferably C2 to G > alkenes.
  • Non limiting examples of alkenes include ethenyl, l-propenyl, 2-propenyl, l-methylethenyl, l-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- l-propenyl, 2-methyl-l-propenyl, l-methyl-2 -propenyl, 2- methyl-2-propenyl, l-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl- l-butenyl, 2-methyl- 1- butenyl, 3-methyl- l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, l,l-dimethyl-2-propenyl, 1, 2-dimethyl- l-propenyl, 1
  • Alkenyl also includes polyenes such as l,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 branched or straight-chain G to C 24 alkynes, preferably C 2 to C 15 alkynes, more preferably C 2 to C 10 alkynes, most preferably C 2 to G > alkynes.
  • Non limiting examples of alkynes include ethynyl, l-propynyl, 2-propynyl, l-butynyl, 2- butynyl, 3-butynyl, l-methyl-2-propynyl, l-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2- butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, l,l-dimethyl-2-propynyl, 1- ethyl -2-propynyl, l-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1- methyl-3-pentynyl, l-methyl-4-penty
  • alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere.
  • the term“Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • cyclic alkyl or“cycloalkyl” means alkyl closed to form a ring.
  • Non limiting examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere.
  • cycloalkenyl means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non limiting examples include but are not limited to 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. 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. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl etc., unless specifically defined elsewhere.
  • alkoxy used either alone or in compound words included Ci to C24 alkoxy, preferably Ci to C15 alkoxy, more preferably Ci to C10 alkoxy, most preferably Ci to O, alkoxy.
  • alkoxy include methoxy, ethoxy, propoxy, 1 -methylethoxy, butoxy, l-methylpropoxy, 2-methylpropoxy, 1,1- dimethylethoxy, pentoxy, l-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1- ethylpropoxy, hexoxy, l,l-dimethylpropoxy, l,2-dimethylpropoxy, l-methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, l,l-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, l-e
  • alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio, 1,1- dimethylethylthio, pentylthio, l-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2- dimethylpropylthio, l-ethylpropylthio, hexylthio, l,l-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, l,l-dimethylbutylthio, 1 ,2-dimethylbutylthio, l,3-di
  • “hydroxy” means -OH,“amino” means -NRR, wherein R can be H or any possible substituent such as alkyl;“carbonyl” means -C(O)- ,“carbonyloxy” means -OC(O)-,“sulfinyl” means SO,“sulfonyl” means S(0) 2 -
  • halogen either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as“haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, l-bromoethyl, l-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 l,l,l,l-trifluoroprop-2-yl.
  • This definition also
  • haloalkenyl and“haloalkynyl” are defined analogously except that, instead of alkyl groups, alkenyl and alkynyl groups are present as a part of the substituent.
  • 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, l-chloroethoxy, l-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
  • haloalkylthio or“haloalkylsulfanyl” 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, l-chloroethylthio, 1- bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difLuoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio, pentafluoroethylthio and l,
  • Non limiting examples of “haloalkylsulfinyl” include CF 3 S(0), CCFStO), CFsCthStO) and CF 3 CF 2 S(0).
  • Non limiting examples of “haloalkylsulfonyl” include CF 3 S(0) 2 , CCl 3 S(0) 2 , CF 3 CH 2 S(0) 2 and CF 3 CF 2 S(0) 2 .
  • alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include -CH 2 SCH 2 , -CH 2 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy 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 methylsulphinyl, ethylsulphinyl, propylsulphinyl, l-methylethylsulphinyl, butylsulphinyl, l-methylpropylsulphinyl, 2- methylpropylsulphinyl, l,l-dimethylethylsulphinyl, pentylsulphinyl, l-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, l-ethylpropylsulphinyl, hexylsulphinyl, 1 , 1 -dimethylpropylsulphiny
  • arylsulfinyl includes Ar-S(O), wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
  • alkylsulfonyl include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1 -methylethylsulphonyl, butylsulphonyl, 1 -methylpropylsulphonyl, 2-methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1- ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1- methylpentylsulphonyl, 2-methylpentylsulphonyl, 3-methylpent
  • arylsulfonyl includes Ar-S(0) 2 , wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere.
  • the term“Alkylamino”,“dialky lamino”, and the like, are defined analogously to the above examples.
  • the term“ring” or“ring system” or“Cy” as a component of formula I is carbocyclyl or heterocyclyl.
  • the term“ring system” denotes one or more rings.
  • bicyclic ring or ring system denotes a ring system consisting of two or more common atom.
  • aromatic indicates that the Hueckel rule is satisfied and the term“non-aromatic” indicates that the Hueckel rule is not satisfied.
  • “carbocycle” or“carbocyclic” or“carbocyclyl” include“aromatic carbocyclic ring system” and“nonaromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not satisfied).
  • Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbornyl and the like.
  • Non limiting examples of aromatic carbocyclic ring system are phenyl, naphthyl and the like.
  • aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to phenyl, naphthalene, biphenyl, anthracene, and the like.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.
  • aralkyl refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Examples include benzyl, phenylethyl, and 6-napthylhexyl.
  • aralkenyl refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Examples include styryl, 3 -(benzyl) prop-2-enyl, and 6-napthylhex-2-enyl.
  • hetero in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • 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, azetidinyl, thietanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2- tetrahydrothienyl, 3-tetrahydrothienyl, 1 -pyrrolidinyl, 2-pyrrolidinyl,
  • heteroaryl means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, l,2,4-oxadiazolyl, l,2,4-thiadiazolyl, l,2,4-triazolyl, l,3,
  • 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-l,3-diene-l,4-diyl group in which one or two carbon atoms may be replaced by nitrogen atoms, where these rings are attached to the skeleton via one of the nitrogen ring members, for example (but not limited to) 1 - pyrrolyl, l-pyrazolyl, l,2,4-triazolyl, l-imidazolyl, l,2,3-triazolyl and l,3,4-triazolyl.
  • 6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2- yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-l-yl, indol-2-yl, indol-3-yl, indol-4
  • Non-limiting examples of fused 6-5-membered heteroaryl include Indolizinyl; pyrazolo[l,5- ajpyridinyl; imidazo[l,2-a]pyridinyl; pyrrolo[l,2-a]pyrimidinyl; pyrazolo[l,5-a]pyrimidinyl; imidazo[l,2-a]pyrimidinyl; pyrrolo[l,2-a]pyrazinyl; pyrazolo[l,5-a]pyrazinyl; imidazo[l,2- ajpyrazinyl and the like.
  • heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl.
  • the term “Halotrialkylsilyl” denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different.
  • the term“Alkoxytrialkylsilyl” denotes at least one of the three alkyl radicals is substituted with one or more alkoxy radicals which may be the same or different.
  • Trialkylsilyloxy denotes a trialkylsilyl moiety attached through oxygen.
  • alkylcarbonyl examples include C(0)CH 3 , C C ⁇ CtbCtbCtb and C(0)CH(CH 3 ) 2 -
  • haloalkylsufonylaminocarbonyl alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously.
  • the total number of carbon atoms in a substituent group is indicated by the“Ci- ” prefix where i and j are numbers from 1 to 21.
  • C1-C3 alkoxy designates methoxy through propoxy.
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e. g. (R)i- j , then the number of substituents may be selected from the integers between i and j inclusive.
  • A represents O, NR 5 or S
  • a 1 represents C or N
  • R 1 is selected from the group consisting of CVCValkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C i -CV haloalkyl, C 2 -C 6 -haloalkenyl, C 3 -C 6 -cycloalkyl, CVCVcycloal kyl-C i -CVal kyl , CVC io-aryl-C i -Co al kyl and C 4 -Cio-heterocyclyl-Ci-C 6 -alkyl; each group of R 1 may be optionally substituted by one or more groups selected from the group consisting of X, CVC io-aryl, C 4 -Cio-heterocyclyl, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , COOR 5a , CN and CON(R 5a ) 2 ;
  • R 3 is selected from the group consisting of hydrogen, CVCValkyl, CVCVhaloalkyl, C 3 -Cio-cycloalkyl, CVCio-aryl and C 4 -Cio-heterocyclyl; each group of R 3 may be optionally substituted by one or more groups selected from the group consisting of X, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 4 is selected from the group consisting of CVCValkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce- haloalkyl, C 3 -Ci 2 -cycloalkyl, C 3 -Cio-halocycloalkyl and CVCVcycloal kyl-C i -O,-al kyl ; each group of R 4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 5 is selected from the group consisting of hydrogen, CVCValkyl, Ci-Ce-haloalkyl, C 3 -Ci 2 -cycloalkyl, Ce-Cio-aryl, C 4 -C 6 -heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R 5b ; and each group of R 5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R 5a , OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , and CON(R 5a ) 2 ;
  • R 5a is selected from the group consisting of hydrogen, CVCValkyl and C 3 -C 6 -cycloalkyl;
  • R 5b is selected from the group consisting of hydrogen, X, CN, OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CON(R 5a ) 2 , CVCValkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-haloalkyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -haloalkynyl, and C 3 -C 6 -cycloalkyl;
  • X represents halogen;
  • the compounds of formula (I) and wherever appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the present invention provides a compound of formula (la),
  • A represents Oor S
  • R 3 is selected from the group consisting of hydrogen, Ci-Ci 2 -alkyl, Ci-Ci 2 -haloalkyl, C3-C10- cycloalkyl, Ce-Cio-aryl and C 4 -Cio-heterocyclyl; each group of R 3 may be optionally substituted by one or more groups selected from the group consisting of X, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 4 is selected from the group consisting of Ci-CValkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-haloalkyl C 3 -Ci 2 -cycloalkyl, C 3 -Cio-halocycloalkyl and CVCVcycloal kyl-C 1 -G,-al kyl ; each group of R 4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 5 is selected from the group consisting of hydrogen, Ci-G, -alkyl, Ci-Ce-haloalkyl, C 3 -Ci 2 -cycloalkyl, Ce-Cio-aryl and C 4 -C 6 -heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R 5b ; each group of R 5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R 5a , OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CN, and CON(R 5a ) 2 ; R 5a is selected from the group consisting of hydrogen, X, Ci-Ce-alkyl and CYCYcycloalkyl;
  • R 5b is selected from the group consisting of hydrogen, X, CN, OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CON(R 5a ) 2 , Ci-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-haloalkyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -haloalkynyl and CYCYcycloalkyl;
  • X represents halogen
  • the present invention provides a compound of formula (lb),
  • A represent O or S
  • R 3 is selected from the group consisting of hydrogen, Ci-Ci 2 -alkyl, Ci-Ci 2 -haloalkyl, C3-C10- cycloalkyl, CYCio-aryl and C 4 -Cio-heterocyclyl; each group of R 3 may be optionally substituted by one or more groups selected from the group consisting of X, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 4 is selected from the group consisting of CVCYalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-haloalkyl C 3 -Ci 2 -cycloalkyl, C 3 -Cio-halocycloalkyl and CYCYcycloal kyl-C 1 -G,-al kyl ; each group of R 4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R 5a , OR 5a , SR 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 5 is selected from the group consisting of hydrogen, CVCYalkyl, Ci-Ce-haloalkyl, C 3 -Ci 2 -cycloalkyl, Ce-Cio-aryl and C 4 -C 6 -heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R 5b ; each group of R 5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R 5a , OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CN, and CON(R 5a ) 2 ;
  • R 5a is selected from the group consisting of hydrogen, X, CVCYalkyl and C 3 -C 6 -cycloalkyl;
  • R 5b is selected from the group consisting of hydrogen, X, CN, OR 5a , S(0) n R 5a , N(R 5a ) 2 , Si(R 5a ) 3 , COOR 5a , CON(R 5a ) 2 , Ci-Ce-alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, Ci-Ce-haloalkyl, C 2 -C 6 -haloalkenyl, C 2 -C 6 -haloalkynyl and C 3 -C 6 -cycloalkyl;
  • X represents halogen
  • the compound of formula (I) is selected from (Z)-N-methyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2- ((3,4,4-trifluorobut-3-en- 1 -yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 - (2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut- 3-en- 1 -yl)thio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- 1 -(2-((4,4-difluoro
  • the present invention provides a process for the synthesis of compound of formula (I) comprising at least one of the following steps:
  • the compound of formula 1 can be prepared by the oxidation of substituted sulfide or sulfoxide derivatives of formula 2a or 2b with an suitable oxidizing reagent preferably selected from meto-chloroperbenzoic acid or oxone in the presence of a suitable solvent selected from methanol, dichloromethane etc.
  • the compound of formula 2b can be prepared by the oxidation of substituted sulfide of formula 2a with a suitable oxidizing reagent preferably selected from meta- chloroperbenzoic acid or oxone in the presence of a suitable solvent selected from methanol, dichloromethane etc.
  • a suitable oxidizing reagent preferably selected from meta- chloroperbenzoic acid or oxone in the presence of a suitable solvent selected from methanol, dichloromethane etc.
  • the compound of formula 2a can be prepared by the condensation of substituted hydroxyl amine with the compound of formula 3 optionally in the presence a suitable base selected from sodium acetate or potassium acetate; and a suitable solvent selected from methanol or ethanol.
  • the compound of formula 2a can also be prepared by alkylation of compound of formula 4 in the presence of a suitable base e.g. potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide etc.
  • a suitable base e.g. potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide etc.
  • the corresponding compound of formula 4 can be prepared by condensation of compound of formula 3 with hydroxyl amine hydrochloride optionally in the presence a suitable base selected from sodium acetate or potassium acetate; and a suitable solvent selected from methanol or ethanol.
  • the compound of formula 3a can be prepared from the compound of formula 6 by Vilsmeier-Haack reaction.
  • the corresponding compound of formula 6 can be prepared by thiol- alkylation of compound of formula 5 with alkyl/alkenyl halide in the presence of a suitable base selected from potassium carbonate or triethylamine in a suitable solvents such as ethanol, acetonitrile or /V,/V-Dimcthyl form amide under heating conditions.
  • the compound of formula 8 can be prepared alkylation of thiol compound of formula 7 with suitable alkyl/alkenyl halide in the presence of potassium carbonate or triethylamine in solvents such as ethanol, acetonitrile or /V,/V-d i mcth y I form am i dc under heating conditions.
  • the resulting compound of formula 8 can be reduced to compound of formula 9 using reducing agent such as sodium borohydride in appropriate solvent e.g. methanol.
  • compound of formula 9 can be converted to compound of formula 3a using oxidizing agent such as dess-martin periodinane in appropriate solvent e.g. dichloromethane.
  • the compound of formula iii can be prepared by the hydrolyzing the compound of formula ii in the presence of a suitable hydrolyzing agent and optionally in the presence of a suitable solvent.
  • the compound of formula ii can be prepared by N-alkylation of compound of formula i in the presence of a suitable alkylating reagent such as alkyl halide and a suitable base selected from potassium carbonate or triethylamine.
  • any of the compounds according to the invention can exist in one or more optical, geometric or chiral isomer forms depending on the number of asymmetric centres in the compound.
  • the invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term “scalemic” denotes a mixture of enantiomers in different proportions), and to the mixtures of all the possible stereoisomers, in all proportions.
  • the diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by a person ordinary skilled in the art.
  • any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by a person ordinary skilled in the art.
  • any of the compounds according to the invention can also exist in one or more amorphic or isomorphic or polymorphic forms, depending on their preparation, purification storage and various other influencing factors.
  • the invention thus relates all the possible amorphic, isomorphic and polymorphic forms, in all proportions.
  • the amorphic, isomorphic and polymorphic forms can be prepared and/or separated and/or purified according to general methods, which are known per se by a person ordinary skilled in the art.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, N,N- diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, /V,/V-diethylaniline, pyridine, 4-(/V,/V-di methyl am inojpyndine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • DBU diazabicyclo[5.4.0]undec-7-ene
  • the reaction according to scheme- 1 to 13 is preferably carried out in a solvent selected from standard solvents which are inert under the prevailing reaction conditions.
  • a solvent selected from standard solvents which are inert under the prevailing reaction conditions.
  • aliphatic, alicyclic or aromatic hydrocarbons such as, petroleum ether, hexane, toluene; halogenated hydrocarbons, such as, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride or dichloroethane
  • ethers such as, diethyl ether, diisopropyl ether, methyl /-butyl ether (MTBE), dioxane, tetrahydrofuran or 1,2 -dime thoxy ethane
  • nitriles such as, acetonitrile or propionitrile, or
  • amides such as, /V, /V-di mcthylformam idc (
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent.
  • the reaction is advantageously carried out in a temperature range from approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, in many cases in the range between ambient temperature and approximately +80 °C.
  • a compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula (I) can be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent.
  • a salt is chosen depending on its tolerances for compound's use, such as agricultural or physiological tolerance. Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the present invention provides use of compound of formula (I), stereoisomers, agriculturally acceptable salts, tautomers or N-oxides thereof or composition or combination thereof for controlling or preventing agricultural crops and/or horticultural crops against phytopathogenic fungi, bacteria, insects, nematodes or mites.
  • the present invention provides use of compound of formula (I), stereoisomers, agriculturally acceptable salts, tautomers or N-oxides thereof or composition or combination thereof for controlling or preventing agricultural crops and/or horticultural crops against nematodes and phytopathogenic fungi.
  • the agricultural crops are selected from cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, 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, other vegetables or ornamentals.
  • the compounds according to the invention can be used for controlling or destroying pests such as nematodes and/or fungi which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • pests such as nematodes and/or fungi which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
  • the compounds of formula (I) according to the 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 pesticide resistant pests such as insects and fungi, which compounds of formula (I) have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. Accordingly, the present invention also makes available a pesticidal composition comprising compounds of the invention, such as formula (I). It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting animals and useful plants against attack and damage by nematodes and phytopathogenic microorganisms like fungi or bacteria.
  • the present invention also makes available a nematicidal composition comprising compounds of the invention, such as formula (I). It has also now been found that the compounds of formula I according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting animals and useful plants against attack and damage by fungi. Accordingly, the present invention also makes available a fungicidal composition comprising compounds of the invention, such as formula (I).
  • the compounds of the formula (I) can possess potent microbicidal activity and can be used for the control of unwanted microorganisms, such as fungi, nematodes and bacteria, in agricultural or horticultural crop protection and in the protection of such materials.
  • the compounds of the formula (I) can possess very good fungicidal properties and can be used in crop protection, for example for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • the compounds of the formula (I) can be used as nematicides in crop protection, for example, for control of Tylenchida, Rhabditida, Dorylaimida, and Tryplonchida.
  • the compounds of the formula (I) can be used as bactericides in crop protection, for example, for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • the compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
  • the compounds of the formula (I) can be used for controlling or preventing against phytopathogenic fungi, bacteria, nematodes of agricultural crops and or horticultural crops.
  • the compounds of the formula (I) can be used in crop protection, wherein the agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, 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 agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, 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 invention also relates to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic, Semiendoparasitic and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria 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, Ap
  • the nematode species Meloidogyne spp., Heterodera spp., Rotylenchus spp., Pratylenchus spp. and Radopholus spp. can be controlled by compounds of the invention.
  • the compound of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • the compound of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • Albugo spp. white rust on ornamentals, vegetables (e.g. A C andida ) and sunflowers (e.g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solanior A. alternata), tomatoes (e.g. A. solanior A. alternata ) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici(anthracnose) on wheat and A.
  • Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. niaydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.
  • strawberries vegetables
  • vegetables eg. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • Bremialactucae downy mildew
  • Ceratocystis syn. Ophiostoma
  • Cercospora spp. rot or wilt
  • corn e. g. Gray leaf spot: C. zeae-maydis
  • rice sugar beets
  • C.beticola sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchil) and rice
  • Cladosporium spp. on tomatoes e. g. C. fu/vum: leaf mold
  • cereals e.g. C. herbarum (black ear) on wheat
  • Claviceps purpurea ergot
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn ( C. carbonum), cereals (e. g. C. sativus, anamorph:#. sorokiniana) and rice (e.g. C.
  • Cylindrocarpon spp. e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • liriodendri Neonectria liriodendrf Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g. D. D.
  • tritici- repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyn), soft fruits (E.
  • sabinae rust on pears
  • Helminthosporium spp. syn. Drechslera, teleomorph: Cochliobolus
  • Hemileia spp. e.g. H. vastatrix( coffee leaf rust) on coffee
  • Isariopsis clavispora syn. Cladosporium vitis
  • Macrophominaphaseolina syn. phaseo/1
  • soybeans and cotton e.g.
  • Microsphaera diffusa (powdery mildew) on soybeans
  • Monilinia spp. e.g. M laxa, M fructicola and M fructigena( bloom and twig blight, brown rot) on stone fruits and other rosaceous plants
  • Mycosphaerellaspp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M fijiensis (black Sigatoka disease) on bananas
  • Peronospora spp. downy mildew) on cabbage (e. g. P. brassicae), rape (e.g. P.
  • soybeans e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum
  • Physoderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsid
  • soybeans e. g. P.megasperma, syn. P. sojae
  • potatoes and tomatoes e. g. P. infestans: late blight
  • broad-leaved trees e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples
  • Polymyxa spp. e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P.
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia ya/lundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or, rotbrenner', anamorph: Phialophora
  • Puccinia spp. rusts
  • oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, grape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramu/aria spp., e.g. R. collo-cygni(Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • R. solani sheath blight
  • R. cerealis Rhizoctonia spring blight
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot
  • seed rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e.g. S. rolfsiior S. sclerotiorum); Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn.
  • S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum ) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • the present invention provides a composition for controlling or preventing phytopathogenic microorganisms comprising a compound of general formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof and one or more inert carriers.
  • the composition may additionally comprises one or more active compatible compounds selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
  • active compatible compounds selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
  • the concentration of the compound of general formula (I) ranges from 1 to 90% 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 further relates to a composition for controlling unwanted microorganisms comprising at least one of the compounds of the formula (I) and one or more inert carrier.
  • the inert carrier further comprises agriculturally suitable auxiliaries, solvents, diluents, surfactants and/or extenders and the like.
  • the present invention further relates to a composition for controlling unwanted microorganisms, comprising at least one of the compounds of the formula (I) and/or one or more active compatible compound selected from fungicides, bactericides, acaricides, insecticides, nematicides, herbicides, biopesticides, plant growth regulators, antibiotics, fertilizers and/or mixtures thereof.
  • a compound of the present invention is used in the form of a composition (e.g.formulation) containing a carrier.
  • a compound of the invention and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ulv) liquid, ultra-low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or
  • a formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
  • auxiliaries for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
  • composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.
  • a fertilizer such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.
  • the present invention also makes available a composition
  • a composition comprising a compound of the invention and an agronomical carrier and optionally one or more customary formulation auxiliaries.
  • the compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries).
  • the grinding/milling of the compounds is to ensure specific particle size.
  • compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - a compound according to the invention and the type of composition is to be selected to suit the intended aims and the prevailing circumstances.
  • suitable liquid carriers are unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions Cs to C12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N- dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxid
  • solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silicas or highly disperse absorbtive polymers are also possible to add highly disperse silicas or highly disperse absorbtive polymers.
  • Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand.
  • a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues.
  • Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties.
  • the surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature.
  • Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or (cyclo) aliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols.
  • water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups.
  • the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit.
  • nonylphenoxypolyethoxyethanol castor oil poly glycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol.
  • fatty acid esters of polyoxyethylene sorbitan such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 Carbon atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.
  • Suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface- active compounds.
  • suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 Carbon atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates.
  • synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates.
  • the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 Carbon atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulphuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulphuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulphonyl groups and a fatty acid radical of approximately 8 to approximately 22 Carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate.
  • suitable phosphates such as salts of the phosphoric ester of a p- nonylphenol/(4-l4)ethylene oxide adduct, or phospholipids.
  • the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of compound according to the present invention and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight).
  • surfactants % in each case meaning percent by weight.
  • foliar formulation types for pre-mix compositions are:
  • examples of seed treatment formulation types for pre-mix compositions are:
  • formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.
  • the methods of application such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries.
  • a solvent for example, water
  • Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 15%, of the desired ingredients, and 99.9 to 80%, especially 99.9 to 85%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20%, especially 0.1 to 15%, based on the tank-mix formulation.
  • auxiliaries including, for example, a solvent such as water
  • a pre mix formulation for foliar application comprises 0.1 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation.
  • auxiliaries including, for example, a solvent such as water
  • a pre-mix formulation for seed treatment application comprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation whereas commercial products will preferably be formulated as concentrates (e.g., pre-mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition).
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • Preferred seed treatment pre-mix formulations are aqueous suspension concentrates.
  • the formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, roto static seed treaters, and drum coaters. Other methods, such as spouted beds may also be useful.
  • the seeds may be pre sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art.
  • the compounds of the present invention are particularly suited for use in soil and seed treatment applications.
  • the pre-mix compositions of the invention contain 0.5 to 99.9% especially 1 to 95%, advantageously 1 to 50%, by mass of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, by mass based on the mass of the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • a compound of the formula (I) in a preferred embodiment, independent of any other embodiments, is in the form of a plant propagation material treating (or protecting) composition, wherein said plant propagation material protecting composition may comprises additionally a coloring agent.
  • the plant propagation material protecting composition or mixture may also comprise at least one polymer from water-soluble and water-dispersible film-forming polymers that improve the adherence of the active ingredients to the treated plant propagation material, which polymer generally has an average molecular weight of at least 10,000 to about 100,000.
  • the present invention provides a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof, is applied to the plants, to parts thereof or a locus thereof.
  • the present invention provides a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof is applied to a seeds of plants.
  • the present invention provides a method of controlling or preventing phytopathogenic microorganisms in agricultural crops and/or horticultural crops using the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 1 g to 5 kg per hectare of agricultural and/or horticultural crops.
  • Examples of application methods for the compounds of the invention and compositions thereof, that is the methods of controlling pests in the agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring which are to be selected to suit the intended aims of the prevailing circumstances.
  • the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application).
  • systemic action by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application).
  • granules can be metered into the flooded paddy-field.
  • the application of the compounds of the present invention to the soil is a preferred application method.
  • Typical rates of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha, such as 50 to 300 g/ha.
  • the present invention provides a seed comprising compound of formula (I) and/or stereoisomers, agriculturally acceptable salts, tautomers, N-oxides thereof or composition or combination thereof, wherein the amount of the compound of the formula (I) or an N-oxide or an agriculturally acceptable salt thereof is ranging from 0.1 g to 10 kg per 100 kg of seed.
  • the compounds of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type.
  • the propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • the application of the compounds of the present invention to seeds is a preferred application method.
  • seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula I.
  • the term“coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the said seed product When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • 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 seed treatment application of the compound formula I which is a preferred application method, can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts,
  • plant is to be understood as including also plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus and also plants which have been selected or hybridized to preserve and / or attain a desired trait, such as insect, fungi and /or nematode resistance.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae ⁇ , or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vip e.g. Vipl, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus, toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdys
  • 8-endotoxins for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Flybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculexl® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricine N-acetyltransferase(PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a
  • transgenic plants are: i) Btl l Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btl l maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; ii)Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810; iv)MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects; v) IPC 531 Cotton from Monsanto Europe S.A.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • CP4 EPSPS obtained from Agrobacterium sp. strain CP4
  • Roundup® contains glyphosate
  • CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
  • the present invention provides a combination comprising the compound of general formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof and one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertili ers.
  • Compounds of this invention are effective for controlling nematodes and/or fungal pathogens of agronomic plants, both growing and harvested, when employed alone, they may also be used in combination with other biological active agents used in agriculture, such as one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activator, molluscicide, and pheromones (whether chemical or biological). Mixing the compounds of the invention or the compositions thereof in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
  • formula (I) compounds of this invention may be used effectively in conjunction or combination with pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cyclodienes, formamidines, phenol tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles and the like.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding, for example, one or more insecticidally, acaricidally, nematicidally and/or fungicidally active agents.
  • the combinations compounds of formula (I) with other insecticidally, acaricidally, nematicidally and/or fungicidally active agents may also have further surprising advantages. For example, better tolerance by plants, reduced phytotoxicity, pests or fungi can be controlled in their different development stages or better behavior during their production, for example during grinding or mixing, during their storage or during their use.
  • the known and reported active compounds such as fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients can be combined with at least one compound of formula I of the present invention.
  • active compounds such as fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients
  • WO2017076739 A to O
  • the present invention also relates to such combinations comprising the compound of the present invention and active compatible compounds reported in WO2017076739.
  • the compounds of formula (I) of the present invention can also be combined with other insecticidal active compounds of unknown or uncertain mode of action: afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, l l-(4-chloro-2,6-dimethylphenyl)-l2- hydroxy-l,4-dio
  • the active substances referred above, their preparation and their activity e.g. against harmful fungi/insect/nematode is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available.
  • the compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci.
  • the mass ratio of any two ingredients in each combination is selected as to give the desired effect, for example, enhanced activity. In general, the mass ratio would vary depending on the specific ingredient and how many ingredients are present in the combination. Generally, the mass ratio between any two ingredients in any combination of the present invention, independently of one another, is from 100:1 to 1:100, including from 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23,
  • Preferred mass ratios between any two components of present invention are from 75:1 to 1:75, more preferably, 50:1 to 1.50, especially 25:1 to 1:25, advantageously 10:1 to 1:10, such as 5:1 to 1:5, for example 1:3 to 3:1.
  • the mixing ratios are understood to include, on the one hand, ratios by mass and also, on other hand, molar ratios.
  • combinations of the present invention i.e. those comprising a compound of the present invention and one or more other biological active agents
  • the ingredients of a combination are applied sequentially (i.e., one after the other), the ingredients are applied sequentially within a reasonable period of each other to attain the biological performance, such as within a few hours or days.
  • the order of applying the ingredients in the combination i.e., whether the compounds of formula (I) should be applied first or not is not essential for working the present invention.
  • ingredients of the combinations may be applied as a composition containing the combination, in which case (A) the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready-to-apply, spray broth, or slurry), or (B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
  • A the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready-to-apply, spray broth, or slurry), or
  • B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
  • a compound according to the present invention is applied as a combination. Accordingly, the present invention also provides a composition comprising a compound according to the invention as herein described and one or more other biological active agents, and optionally one or more customary formulation auxiliaries; which may be in the form of a tank-mix or pre-mix composition.
  • the compounds of formula (I) are particularly useful for controlling and preventing helminth and nematode endo and ecto-parasitic infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, fish, rabbits, goats, mink, fox, chinchillas, dogs and cats as well as humans.
  • compounds of invention are especially useful for the control of helminths and nematodes.
  • helminths are members of the class Trematoda, commonly known as flukes or flatworms, especially members of the genera Fasciola, Fascioloides, Paramphistomu, Dicrocoelium, Eurytrema, Ophisthorchis, Fasciolopsis, Echinostoma and Paragonimus.
  • Nematodes which can be controlled by the formula (I) compounds include the genera Haemonchus, Ostertagia, Cooperia, Oesphagastomu, Nematodirus, Dictyocaulus, Trichuris, Dirofilaria, Ancyclostoma, Ascaria and the like.
  • the compounds of the 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 invention may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 g/kg of animal body weight per day of the compound of the invention.
  • the compounds of the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds of the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds of the invention may be formulated into an implant for subcutaneous administration.
  • the compounds of the invention may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of the invention.
  • the compounds of the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays and pour-on formulations.
  • dips and sprays usually contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to 3,000 ppm of the compound of the invention.
  • the compounds of the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
  • a compound of formula (I) is an anti helminth compound.
  • a compound of formula (I) is a pesticidal compound, preferably a nematicidal compound. Temperatures are given in degrees Celsius.
  • the compounds of the present invention not only control insect pests effectively but also show positive crop response such as plant growth enhancement effects like enhanced crop vigor, enhanced root growth, enhanced tolerant to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, efficient water & 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.
  • Step 2 Preparation of 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde:
  • Step 4 Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide
  • reaction mixture was diluted with water (30 mL) and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to yield a crude product.
  • the obtained crude product was purified by column chromatography using 60-100 % ethyl acetate/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide (0.26 g, 48 % yield).
  • Step 5 Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)methanimine oxide
  • the ethyl acetate layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography using 80-100 % ethyl hexane/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide. (0.14 g, 68 % yield).
  • Step 6 Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5- yl)methanimine oxide
  • the ethyl acetate layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography using 80-100 % ethyl acetate/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide (0.17 g, 76% yield).
  • Step 1 Preparation of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde oxime:
  • Step 2 Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2- yl)methanimine oxide
  • reaction mixture was diluted with water (30 mL) and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography using 60-100% ethyl acetate/hexane to yield N-methyl-l-(5-((3,4,4-trifluorobut-3-en- l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide (0.5 g, 48 % yield).
  • Step 3 Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfmyl)-l,3,4-thiadiazol-2- yl)methanimine oxide:
  • Step 4 Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2- yl)methanimine oxide
  • Step 1 Preparation of tert-butyl ((tert-butoxycarbonyl)oxy)(alkyl/haloalkyl/benzyl/alkene)- carbamate intermediate
  • Step 2 Preparation of N-alkyl/haloalkyl/alkene/benzyl - hydrox lamine hydrochloride
  • Step 1 Preparation of tert-butyl ((tert-butoxycarbonyl)oxy)(ethyl)carbamate
  • the intermediate tert-butyl ((tert-butoxycarbonyl)oxy)(ethyl)carbamate was prepared by following the general procedure as described in example-3, step-l, using ethyl iodide (100 % yield).
  • Step 1 Preparation of ethyl 5-bromo-l,3,4-thiadiazole-2-carboxylate
  • Step 2 Preparation of ethyl 5-mercapto-l,3,4-thiadiazole-2-carboxylate: To a stirred solution of ethyl 5-bromo- 1 ,3,4-thiadiazolc-2-carboxylatc (10 g, 42.2 mmol) in methanol (40 mL), thiourea (4.8 g, 63.3 mmol) was added portion wise at 25 °C and slowly heated to 70 °C for 3 h. After completion of the reaction, the reaction mixture was concentrated and acidified with dilute hydrochloric acid (30 mL) at 0 °C.
  • Step 3 Preparation of ethyl 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2- car boxy late:
  • reaction mixture was diluted with ethyl acetate (30 mL) and water (30 mL) and acidified to pH 4 using 1N hydrochloric acid.
  • the organic layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography using 20% ethyl acetate/hexane to yield the titled compound (6.6 g, 70 % yield); LCMS (M+l): 298.80.
  • Step 4 Preparation of (5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanol:
  • Step 5 Preparation of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde:
  • the aldehyde/ketone (1 mmol) (e.g example- 1, step-3 and example-4, step-5) was dissolved in methanol (5 mL) then sodium acetate (2.5 mmol) and N-alkyl hydroxylamine hydrochloride (1.5 mmol) were added.
  • the reaction mixture was stirred for 1 h.
  • the reaction mixture was diluted with ethyl acetate (10 mL).
  • the reaction mixture was quenched with water (10 mL) and extracted twice with ethyl acetate.
  • the combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography using 60-100% ethyl acetate/hexane to yield the titled compound (70-90 % yield).
  • Table-I illustrates in a non-limiting manner examples of compounds according to the invention that were prepared using analogous procedures as mentioned in the examples above.
  • ⁇ -NMR data of selected examples are written in form of 'H-NMR-peak lists. To each signal peak are listed the d-value in ppm and the no of proton in round brackets.
  • tetramethylsilane For calibrating the chemical shift for 1 H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in dimethyl sulfoxide. Therefore in 'NMR peak lists, tetramethylsilane peak can occur but not necessarily.
  • the compounds of formula (I) show high nematicidal activity which is exerted with respect to nematodes which attack on important agricultural crops.
  • the compounds of the present invention were also showing high fungicidal activity which is exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops.
  • the compounds of the present invention were assessed for their activity against one or more of the following nematodes and fungal diseases.
  • Example 1 Meloidogyne incognita (Root-knot nematode ): IN VITRO TEST
  • test compounds at a concentration of 300 ppm were introduced into 500 pL of distilled water containing 50 Meloidogyne incognita juveniles into 24-well plates. The suspension was lightly shaken for uniform mixing of compounds. The test plates were covered with lids, and were kept for incubation at 25 °C and 90% relative humidity. Dead/inactive nematodes were counted at an interval of 48, 72 and 96 hours under a microscope and the percent mortality was calculated. After 96 hours after treatment following compounds, 1 2 3 4 5 6 7
  • Cucumber plants were grown in seedling trays containing a mixture of Sand:Soil:FYM:Cocopeat in ratio of 1:1: 1:1.
  • One mL of test compounds at the desired concentrations was applied into the soil mixture with the help of a micropipette when the cucumber seedlings were ten days old and inoculated with approximately 2000 freshly hatched second-stage juveniles of Meloidogyne incognita.
  • the treated plants were allowed to grow at 27 °C under greenhouse conditions. Observation of gall rating was recorded after 15 days of application. Plants were carefully uprooted and roots were washed thoroughly. The gall rating was observed on 0-10 scale as described by Zeck (1971) as mentioned below:
  • Example 1 Pyricularia oryzae (Rice blast):
  • Rhizoctonia solani (Rice sheath blight/Potato black scurf):

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Abstract

The present invention relates to novel nitrone compounds of formula (I), wherein, A, A1, R1, R2, R3, R4 and n are as defined in the description. The present invention further relates to their preparation and use to protect crops against undesired phytopathogenic microorganisms, phytopathogenic fungi and pests such as nematodes.

Description

NITRONE COMPOUNDS AND USE THEREOF
FIELD OF THE INVENTION
The present invention relates to novel nitrone compounds. More particularly, the present invention relates to a nitrone compound of formula (I) and to a process for preparation thereof. The present invention further relates to a use of nitrone compound of formula (I) as a crop protection agent for the control of phytopathogenic microorganisms such as plant parasitic nematodes and plant pathogens.
BACKGROUND OF THE INVENTION
Heterocyclic compounds carrying a fluroalkenyl chain have been described in literature for use as pesticides and, in particular, as nematicides. For example, W02017002100, DE10254876, W02004005268, W02003049541, W02003029231, W02002006259, W02002006257,
W02002006256, W02001066529, W0200102378, WO95/24403 and W086/07590.
JP500037/1988 discloses polyhaloalkene compounds which have nematicidal activity. JP176141/1997 discloses thiazole compounds having insecticidal and acaricidal activity.
Nitrones are the N-oxide of imines, they are first used as agents to trap free-radicals (known as spin trapping) in chemical systems and subsequently, in biochemical systems.
US3834073 discloses phenyl nitrone derivatives for controlling plant pathogens in soil by soil treatment or by treatment of the crop plant seeds.
The control of damages to crops caused by phytopathogenic microorganisms and pests is extremely important in achieving high crop efficiency. For instance, plant disease damage to ornamental, vegetable, field, cereal and fruit crops can cause significant reduction in productivity and thereby result in increased cost to the consumer. Many products are commercially available to control such damages. The need continues for new compounds which are more effective, less costly, less toxic, environmentally safer and/or have different modes of action.
The effectiveness of the diflurobutenes, trifluorobutenes and other compounds described in the prior art is not fully satisfactory in various cases. Therefore, it is always of high interest in agriculture to find novel pesticidal compounds in order to avoid and/or control the development of microorganisms such as fungal or bacterial pathogens or pests being resistant to known active ingredients. It is therefore of high interest to use novel compounds being more active than those already known, with the aim of decreasing the amounts of active compound to be used, whilst at the same time maintaining an effectiveness at least equivalent to the already known compounds.
The present invention describes compounds of formula (I) which possess the above mentioned effects or advantages. Such compounds of formula (I), namely nitrone compounds wherein the heterocyclic ring is substituted according to the invention, show unexpected and significantly higher activity against undesired microorganisms such as fungal or bacterial pathogens or against pests such as nematodes or insects.
SUMMARY OF THE INVENTION
The present invention provides a novel nitrone compound of formula (I),
Figure imgf000003_0001
Formula (I)
wherein, R1, R2, R3, R4, A, A1 and n are as defined in the detailed description.
In one embodiment, the present invention provides a process for the preparation of compounds of formula (I).
In another embodiment, the present invention provides a use of compound of formula (I) as crop protection agent for the control of phytopathogenic microorganisms such as plant parasitic nematodes and plant pathogens.
DESCRIPTION
The terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure.
As used herein, the terms “comprises”, “comprising”, “includes”, “including”, “has”, “having”, “contains”,“containing”,“characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
The transitional phrase“consisting of’ excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase“consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
The transitional phrase“consisting essentially of’ is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term“consisting essentially of’ occupies a middle ground between“comprising” and“consisting of’. Further, unless expressly stated to the contrary,“or” refers to an inclusive“or” and not to an exclusive “or”. For example, a condition A“or” B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, the indefinite articles“a” and“an” preceding an element or component of the present invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore“a” or“an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
As referred to in this disclosure, the term“pesticide” in each case also always comprises the term “crop protection agent”.
The term“invertebrate pest” includes arthropods, gastropods and nematodes of economic importance as pests. The term“arthropod” includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans. The term“gastropod” includes snails, slugs and other Stylommatophora. The term“nematode” refers to a living organism of the Phylum Nematoda. The term“helminths” includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Trematoda), acanthocephala and tapeworms (Cestoda).
The term “undesired microorganisms” or“phytopathogenic microorganisms” such as f ingal or bacterial pathogens includes Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae respectively.
In the context of this disclosure“invertebrate pest control” means inhibition of invertebrate pest development (including mortality, feeding reduction, and/or mating disruption), and related expressions are defined analogously.
The term“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).
The term “nonagronomic” refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications. Nonagronomic applications include protecting an animal from an invertebrate parasitic pest by administering a parasiticidally effective (i.e. biologically effective) amount of a compound of the present invention, typically in the form of a composition formulated for veterinary use, to the animal to be protected. As referred to in the present disclosure and claims, the terms“parasiticidal” and “parasiticidally” refers to observable effects on an invertebrate parasite pest to provide protection of an animal from the pest. Parasiticidal effects typically relate to diminishing the occurrence or activity of the target invertebrate parasitic pest. Such effects on the pest include 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 skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s). Additionally, the person skilled in the art knows processes or methods or technology to separate, enrich, and/or to selectively prepare said isomers.
The meaning of various terms used in the description shall now be illustrated:
In the above description, the term“alkyl”, used either alone or in compound words such as“alkylthio” or“haloalkyl” or -N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched Ci to C24 alkyl, preferably Ci to C15 alkyl, more preferably Ci to C10 alkyl, most preferably Ci to G, alkyl. Non limiting examples of alkyl include methyl, ethyl, propyl, 1 -methylethyl, butyl, 1- methylpropyl, 2-methylpropyl, l,l-dimethylethyl, pentyl, l-methylbutyl, 2-methylbutyl, 3- methylbutyl, 2,2-dimethylpropyl, 1 -ethylpropyl, hexyl, l,l-dimethylpropyl, 1 ,2-dimethylpropyl, 1- methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, l,l-dimethylbutyl, 1 ,2-dimethylbutyl, l,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, l-ethylbutyl, 2- ethylbutyl, l,l,2-trimethylpropyl, l,2,2-trimethylpropyl, 1 -ethyl- l-methylpropyl and l-ethyl-2- methylpropyl or the different isomers. If the alkyl is at the end of a composite substituent, as, for example, in alkylcycloalkyl, the part of the composite substituent at the start, for example the cycloalkyl, may be mono- or polysubstituted identically or differently and independently by alkyl. The same also applies to composite substituents in which other radicals, for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.
The term“alkenyl”, used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably C2 to C15 alkenes, more preferably C2 to C10 alkenes, most preferably C2 to G> alkenes. Non limiting examples of alkenes include ethenyl, l-propenyl, 2-propenyl, l-methylethenyl, l-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- l-propenyl, 2-methyl-l-propenyl, l-methyl-2 -propenyl, 2- methyl-2-propenyl, l-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl- l-butenyl, 2-methyl- 1- butenyl, 3-methyl- l-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, l,l-dimethyl-2-propenyl, 1, 2-dimethyl- l-propenyl, 1 ,2-dimethyl-2 -propenyl, 1 -ethyl- l-propenyl, l-ethyl-2-propenyl, l-hexenyl, 2-hexenyl, 3-hexenyl, 4- hexenyl, 5-hexenyl, 1 -methyl- l-pentenyl, 2-methyl- l-pentenyl, 3-methyl- l-pentenyl, 4-methyl- 1- pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1- methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4- pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, l,l-dimethyl-2-butenyl,
1.1-dimethyl-3-butenyl, 1 ,2-dimethyl-l-butenyl, 1 ,2-dimethyl-2-butenyl, l,2-dimethyl-3-butenyl, 1 ,3- dimethyl- 1 -butenyl, l,3-dimethyl-2-butenyl, l,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3- dimethyl- l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-l-butenyl, 3,3- dimethyl-2-butenyl, 1 -ethyl- l-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl- l-butenyl, 2- ethyl-2-butenyl, 2-ethyl-3-butenyl, l,l,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2- methyl-l-propenyl and l-ethyl-2-methyl-2-propenyl and the different isomers. The term“Alkenyl” also includes polyenes such as l,2-propadienyl and 2,4-hexadienyl. This definition also applies to alkenyl as a part of a composite substituent, for example haloalkenyl and the like, unless defined specifically elsewhere.
The term“alkynyl”, used either alone or in compound words includes branched or straight-chain G to C24 alkynes, preferably C2 to C15 alkynes, more preferably C2 to C10 alkynes, most preferably C2 to G> alkynes. Non limiting examples of alkynes include ethynyl, l-propynyl, 2-propynyl, l-butynyl, 2- butynyl, 3-butynyl, l-methyl-2-propynyl, l-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2- butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, l,l-dimethyl-2-propynyl, 1- ethyl -2-propynyl, l-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, l-methyl-2-pentynyl, 1- methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-l- pentynyl, 3-methyl-4-pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, l,l-dimethyl-2-butynyl,
1.1-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, 1- ethyl-2-butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl and the different isomers. This definition also applies to alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere. The term“Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
The term“cyclic alkyl” or“cycloalkyl” means alkyl closed to form a ring. Non limiting examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere.
The term“cycloalkenyl” means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non limiting examples include but are not limited to cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as a part of a composite substituent, for example cycloalkenylalkyl etc., unless specifically defined elsewhere.
The term“cycloalkynyl” means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. This definition also applies to cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere.
The term“cycloalkoxy”,“cycloalkenyloxy” and the like are defined analogously. Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl etc., unless specifically defined elsewhere.
The term“alkoxy” used either alone or in compound words included Ci to C24 alkoxy, preferably Ci to C15 alkoxy, more preferably Ci to C10 alkoxy, most preferably Ci to O, alkoxy. Examples of alkoxy include methoxy, ethoxy, propoxy, 1 -methylethoxy, butoxy, l-methylpropoxy, 2-methylpropoxy, 1,1- dimethylethoxy, pentoxy, l-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1- ethylpropoxy, hexoxy, l,l-dimethylpropoxy, l,2-dimethylpropoxy, l-methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, l,l-dimethylbutoxy, 1 ,2-dimethylbutoxy, 1,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, l-ethylbutoxy, 2- ethylbutoxy, 1 , 1 ,2-trimethylpropoxy, l,2,2-trimethylpropoxy, 1 -ethyl- l-methylpropoxy and l-ethyl-2- methylpropoxy and the different isomers. This definition also applies to alkoxy as a part of a composite substituent, for example haloalkoxy, alkynylalkoxy, etc., unless specifically defined elsewhere.
The term“alkylthio” includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, l-methylethylthio, butylthio, l-methylpropylthio, 2-methylpropylthio, 1,1- dimethylethylthio, pentylthio, l-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2- dimethylpropylthio, l-ethylpropylthio, hexylthio, l,l-dimethylpropylthio, 1 ,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, l,l-dimethylbutylthio, 1 ,2-dimethylbutylthio, l,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3- dime thy lbu tylthio , 1 -ethylbutylthio, 2-ethylbutylthio, 1 , 1 ,2-trimethylpropylthio, 1,2,2- trimethylpropylthio, 1 -ethyl- l-methylpropylthio and l-ethyl-2-methylpropylthio and the different isomers.
The term“hydroxy” means -OH,“amino” means -NRR, wherein R can be H or any possible substituent such as alkyl;“carbonyl” means -C(O)- ,“carbonyloxy” means -OC(O)-,“sulfinyl” means SO,“sulfonyl” means S(0)2-
The term“halogen”, either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as“haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
Non-limiting examples of “haloalkyl” include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1 -chloroethyl, l-bromoethyl, l-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 l,l,l-trifluoroprop-2-yl. This definition also applies to haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.
The terms“haloalkenyl” and“haloalkynyl” are defined analogously except that, instead of alkyl groups, alkenyl and alkynyl groups are present as a part of the substituent.
The term“haloalkoxy” means straight-chain or branched alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non-limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, l-chloroethoxy, l-bromoethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2- dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trifluoroprop-2-oxy. This definition also applies to haloalkoxy as a part of a composite substituent, for example haloalkoxyalkyl etc., unless specifically defined elsewhere.
The terms“haloalkylthio” or“haloalkylsulfanyl” 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, l-chloroethylthio, 1- bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difLuoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio, pentafluoroethylthio and l,l,l-trifluoroprop-2-ylthio. This definition also applies to haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere.
Non limiting examples of “haloalkylsulfinyl” include CF3S(0), CCFStO), CFsCthStO) and CF3CF2S(0). Non limiting examples of “haloalkylsulfonyl” include CF3S(0)2, CCl3S(0)2, CF3CH2S(0)2 and CF3CF2S(0)2.
The term “alkylthioalkyl” denotes alkylthio substitution on alkyl. Non limiting examples of “alkylthioalkyl” include -CH2SCH2, -CH2SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. The term“Alkylthioalkoxy” denotes alkylthio substitution on alkoxy. The term “cycloalkylalkylamino” denotes cycloalkyl substitution on alkyl amino.
The terms alkoxyalkoxyalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl and the like, are defined analogously to “alkylthioalkyl” or cycloalkylalkylamino.
The term“alkoxycarbonyl” is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as a part of a composite substituent, for example cycloalkylalkoxycarbonyl and the like, unless specifically defined elsewhere.
The term“alkoxycarbonylalkylamino” denotes alkoxy carbonyl substitution on alkyl amino.
The term“Alkylcarbonylalkylamino” denotes alkyl carbonyl substitution on alkyl amino.
The terms alkylthioalkoxycarbonyl, cycloalkylalkylaminoalkyl and the like are defined analogously. Non limiting examples of “alkylsulfinyl” include but are not limited to methylsulphinyl, ethylsulphinyl, propylsulphinyl, l-methylethylsulphinyl, butylsulphinyl, l-methylpropylsulphinyl, 2- methylpropylsulphinyl, l,l-dimethylethylsulphinyl, pentylsulphinyl, l-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, l-ethylpropylsulphinyl, hexylsulphinyl, 1 , 1 -dimethylpropylsulphinyl, 1 ,2-dimethylpropylsulphinyl, 1 -methylpentylsulphinyl, 2-methylpentylsulphinyl, 3-methylpentylsulphinyl, 4-methylpentylsulphinyl, 1,1- dimethylbutylsulphinyl, l,2-dimethylbutylsulphinyl, l,3-dimethylbutylsulphinyl, 2,2- dimethylbutylsulphinyl, 2,3-dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl, 1- ethylbutylsulphinyl, 2-ethylbutylsulphinyl, l,l,2-trimethylpropylsulphinyl, 1,2,2- trimethylpropylsulphinyl, 1 -ethyl- l-methylpropylsulphinyl and l-ethyl-2-methylpropylsulphinyl and the different isomers. The term“arylsulfinyl” includes Ar-S(O), wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
Non limiting examples of “alkylsulfonyl” include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1 -methylethylsulphonyl, butylsulphonyl, 1 -methylpropylsulphonyl, 2-methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1- ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1- methylpentylsulphonyl, 2-methylpentylsulphonyl, 3-methylpentylsulphonyl, 4- methylpentylsulphonyl, 1,1-dimethylbutylsulphonyl, 1 ,2-dimethylbutylsulphonyl, 1,3- dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl, 2,3-dimethylbutylsulphonyl, 3,3- dimethylbutylsulphonyl, 1-ethylbutylsulphonyl, 2-ethylbutylsulphonyl, 1,1,2- trimethylpropylsulphonyl, 1,2,2-trimethylpropylsulphonyl, 1 -ethyl- 1 -methylpropylsulphonyl and 1- ethyl-2-methylpropylsulphonyl and the different isomers.
The term“arylsulfonyl” includes Ar-S(0)2, wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere.
The term“Alkylamino”,“dialky lamino”, and the like, are defined analogously to the above examples. The term“ring” or“ring system” or“Cy” as a component of formula I is carbocyclyl or heterocyclyl. The term“ring system” denotes one or more rings.
The term“bicyclic ring or ring system” denotes a ring system consisting of two or more common atom. The term“aromatic” indicates that the Hueckel rule is satisfied and the term“non-aromatic” indicates that the Hueckel rule is not satisfied.
The terms“carbocycle” or“carbocyclic” or“carbocyclyl” include“aromatic carbocyclic ring system” and“nonaromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not satisfied).
Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbornyl and the like.
Non limiting examples of aromatic carbocyclic ring system are phenyl, naphthyl and the like.
The term“aryl” as used herein is a group that contains any carbon-based aromatic group including, but not limited to phenyl, naphthalene, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.
The term“aralkyl” refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Examples include benzyl, phenylethyl, and 6-napthylhexyl. As used herein, the term“aralkenyl” refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Examples include styryl, 3 -(benzyl) prop-2-enyl, and 6-napthylhex-2-enyl.
The term“hetero” in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
The terms “heterocycle” or “heterocyclic” includes “aromatic heterocycle” or “heteroaryl ring system” and“nonaromatic heterocycle ring system” or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds in which ring may be aromatic or non-aromatic, wherein the heterocycle ring contains at least one heteroatom selected from N, O, S(0)o 2, and or C ring member of the heterocycle may be replaced by C(=0), C(=S), C(=CR*R*) and C=NR*, * indicates integers.
The terms “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, azetidinyl, thietanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2- tetrahydrothienyl, 3-tetrahydrothienyl, 1 -pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1- pyrazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5- oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, l-imidazolidinyl, 2-imidazolidinyl, 4- imidazolidinyl, l,2,4-oxadiazolidin-3-yl, l,2,4-oxadiazolidin-5-yl, l,2,4-thiadiazolidin-3-yl, 1,2,4- thiadiazolidin-5-yl, l,2,4-triazolidin-l-yl, l,2,4-triazolidin-3-yl, l,3,4-oxadiazolidin-2-yl, 1,3,4- thiadiazolidin-2-yl, l,3,4-triazolidin-l-yl, l,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, pyrrolinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3- isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2- isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4- isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-l-yl,
2.3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,
3.4-dihydropyrazol-l-yl, 3 ,4-dihydropyrazol-3-yl, 3 ,4-dihydropyrazol-4-yl, 3 ,4-dihydropyrazol-5-yl,
4.5-dihydropyrazol-l-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4- dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4- dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, piperidinyl, 2-piperidinyl, 3- piperidinyl, 4-piperidinyl, pyrazynyl, morpholinyl, thiomorphlinyl, l,3-dioxan-5-yl, 2- tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4- hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2- piperazinyl, l,3,5-hexahydrotriazin-2-yl, l,2,4-hexahydrotriazin-3-yl, cycloserines, 2, 3, 4, 5- tetrahydro[lH]azepin-l- or -2- or -3- or -4- or -5- or -6- or -7-yl, 3,4,5,6-tetra-hydro[2H]azepin-2- or - 3- or -4- or -5- or -6- or-7-yl, 2,3,4,7-tetrahydro[lH]azepin-l- or -2- or -3- or -4- or -5- or -6- or-7-yl, 2,3,6,7-tetrahydro[lH]azepin-l- or -2- or -3- or -4- or -5- or -6- or -7-yl, hexahydroazepin-l- or -2- or -3- or -4-yl, tetra- and hexahydrooxepinyl such as 2,3,4,5-tetrahydro[lH]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, 2,3,4,7-tetrahydro[lH]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, 2, 3,6,7- tetrahydro[lH]oxepin-2- or -3- or -4- or -5- or -6- or -7-yl, hexahydroazepin-l- or -2- or -3- or -4-yl, tetra- and hexahydro-l,3-diazepinyl, tetra- and hexahydro-l,4-diazepinyl, tetra- and hexahydro-1,3- oxazepinyl, tetra- and hexahydro-l,4-oxazepinyl, tetra- and hexahydro-l,3-dioxepinyl, tetra- and hexahydro-l,4-dioxepinyl. This definition also applies to heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere.
The term“heteroaryl” means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, l,2,4-oxadiazolyl, l,2,4-thiadiazolyl, l,2,4-triazolyl, l,3,4-oxadiazolyl, l,3,4-thiadiazolyl, l,3,4-triazolyl, tetrazolyl; nitrogen-bonded 5-membered heteroaryl containing one to four nitrogen atoms, or benzofused nitrogen-bonded 5-membered heteroaryl containing one to three nitrogen atoms:
5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-l,3-diene-l,4-diyl group in which one or two carbon atoms may be replaced by nitrogen atoms, where these rings are attached to the skeleton via one of the nitrogen ring members, for example (but not limited to) 1 - pyrrolyl, l-pyrazolyl, l,2,4-triazolyl, l-imidazolyl, l,2,3-triazolyl and l,3,4-triazolyl.
6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2- yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-l-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-l-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-l-yl, indazol-3- yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, l-benzofuran-2-yl, 1- benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5-yl, 1 -benzofuran- 6-yl, l-benzofuran-7-yl, 1- benzothiophen-2-yl, l-benzothiophen-3-yl, l-benzothiophen-4-yl, l-benzothiophen-5-yl, 1- benzothiophen-6-yl, l-benzothiophen-7-yl, l,3-benzothiazol-2-yl, l,3-benzothiazol-4-yl, 1,3- benzothiazol-5-yl, l,3-benzothiazol-6-yl, l,3-benzothiazol-7-yl, l,3-benzoxazol-2-yl, l,3-benzoxazol-4- yl, l,3-benzoxazol-5-yl, l,3-benzoxazol-6-yl and l,3-benzoxazol-7-yl; benzofused 6-membered heteroaryl which contains one to three nitrogen atoms: for example (but not limited to) quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-l- yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.
Non-limiting examples of fused 6-5-membered heteroaryl include Indolizinyl; pyrazolo[l,5- ajpyridinyl; imidazo[l,2-a]pyridinyl; pyrrolo[l,2-a]pyrimidinyl; pyrazolo[l,5-a]pyrimidinyl; imidazo[l,2-a]pyrimidinyl; pyrrolo[l,2-a]pyrazinyl; pyrazolo[l,5-a]pyrazinyl; imidazo[l,2- ajpyrazinyl and the like.
This definition also applies to heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.
The term“Trialkylsilyl” includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl. The term “Halotrialkylsilyl” denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different. The term“Alkoxytrialkylsilyl” denotes at least one of the three alkyl radicals is substituted with one or more alkoxy radicals which may be the same or different. The term“Trialkylsilyloxy” denotes a trialkylsilyl moiety attached through oxygen.
Non limiting examples of “alkylcarbonyl” include C(0)CH3, C C^CtbCtbCtb and C(0)CH(CH3)2- Examples of “alkoxycarbonyl” include CH30C(=0), CtbCtbOC^O), CtbCtbCtbOC^O), (CH3)2CH0C(=0) and the different butoxy or pentoxycarbonyl isomers. Examples of “alkylaminocarbonyl” include CH3NHC(=0), CH3CH2NHC(=0), CH3CH2CH2NHC(=0), (CH3)2CHNHC(=0) and the different butylamino -or pentylaminocarbonyl isomers. Examples of “dialkylaminocarbonyl” include (CH3)2NC(=0), (CH3CH2)2NC(=0), CH3CH2(CH3)NC(=0), CH3CH2CH2(CH3)NC(=0) and (CH3)2CHN(CH3)C(=0). Examples of“alkoxyalkylcarbonyl” include CH30CH2C(=0), CH30CH2CH2C(=0), CH3CH20CH2C(=0), CH3CH2CH2CH20CH2C(=0) and CH3CH20CH2CH2C(=0). Examples of “alkylthioalkylcarbonyl” include CtbSCtbC^O), CH3SCH2CH2C(=0), CH3CH2SCH2C(=0), CH3CH2CH2CH2SCH2C(=0) and
CtbCtbSCtbCtbC^O). The term haloalkylsufonylaminocarbonyl, alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously.
Non limiting examples of “alkylaminoalkylcarbonyl” include CtbNHCtbC^O), CH3NHCH2CH2C(=0), CH3CH2NHCH2C(=0), CH3CH2CH2CH2NHCH2C(=0) and
CH3CH2NHCH2CH2C(=0).
The term“amide” means A-R'C=ONR"-B, wherein R' and R" indicates substituents and A and B indicate any group.
The term“thioamide” means A-R'C=SNR"-B, wherein R' and R" indicates substituents and A and B indicate any group.
The total number of carbon atoms in a substituent group is indicated by the“Ci- ” prefix where i and j are numbers from 1 to 21. For example, C1-C3 alkoxy designates methoxy through propoxy. In the above recitations, when a compound of formula (I) is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e. g. (R)i-j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R1 or R2, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Accordingly, the present invention provides a compound of formula (I),
Figure imgf000014_0001
Formula (I)
wherein,
A represents O, NR5 or S;
A1 represents C or N;
R1 is selected from the group consisting of CVCValkyl, C2-C6-alkenyl, C2-C6-alkynyl, C i -CV haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkyl, CVCVcycloal kyl-C i -CVal kyl , CVC io-aryl-C i -Co al kyl and C4-Cio-heterocyclyl-Ci-C6-alkyl; each group of R1 may be optionally substituted by one or more groups selected from the group consisting of X, CVC io-aryl, C4-Cio-heterocyclyl, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN and CON(R5a)2;
R2 is selected from the group consisting of hydrogen, X, CN, (C=0)-R5b, OR4, N(R4)2, S(0)nR5b, Ci- Ce-alkyl, Ci-Ce-haloalkyl and CVCVcycloalkyl; each group of R2 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R3 is selected from the group consisting of hydrogen, CVCValkyl, CVCVhaloalkyl, C3-Cio-cycloalkyl, CVCio-aryl and C4-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of CVCValkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce- haloalkyl, C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and CVCVcycloal kyl-C i -O,-al kyl ; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, CVCValkyl, Ci-Ce-haloalkyl, C3-Ci2-cycloalkyl, Ce-Cio-aryl, C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; and each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, and CON(R5a)2;
R5a is selected from the group consisting of hydrogen, CVCValkyl and C3-C6-cycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, CVCValkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl, and C3-C6-cycloalkyl; X represents halogen;
n represents integers wherein n=0-2;
or agriculturally acceptable salts, stereoisomer, tautomers or N-oxides thereof.
It can be advantageous to isolate or synthesize in each case the biologically more effective isomer, for example enantiomer or diastereomer, or isomeric mixture, for example enantiomeric mixture or diastereomeric mixture, if the individual components have a different biological activity.
The compounds of formula (I) and wherever appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
In preferred embodiment, the present invention provides a compound of formula (la),
Figure imgf000015_0001
Formula (la)
wherein;
A represents Oor S;
R2 is selected from the group consisting of hydrogen, X, CN, (C=0)-R5b, OR4, N(R4)2, S(0)nR5b, Ci- Ce-alkyl, Ci-Ce-haloalkyl and CVCVcycloalkyl; each group of R2 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R3 is selected from the group consisting of hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C3-C10- cycloalkyl, Ce-Cio-aryl and C4-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of Ci-CValkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and CVCVcycloal kyl-C 1 -G,-al kyl ; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, Ci-G, -alkyl, Ci-Ce-haloalkyl, C3-Ci2-cycloalkyl, Ce-Cio-aryl and C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2; R5a is selected from the group consisting of hydrogen, X, Ci-Ce-alkyl and CYCYcycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, Ci-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl and CYCYcycloalkyl;
X represents halogen;
n represents integers wherein n=0-2.
In another preferred embodiment, the present invention provides a compound of formula (lb),
Figure imgf000016_0001
Formula (lb)
wherein;
A represent O or S;
R3 is selected from the group consisting of hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C3-C10- cycloalkyl, CYCio-aryl and C4-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of CVCYalkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and CYCYcycloal kyl-C 1 -G,-al kyl ; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, CVCYalkyl, Ci-Ce-haloalkyl, C3-Ci2-cycloalkyl, Ce-Cio-aryl and C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5a is selected from the group consisting of hydrogen, X, CVCYalkyl and C3-C6-cycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, Ci-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl and C3-C6-cycloalkyl;
X represents halogen;
n represents integers wherein n=0-2.
In more preferred embodiment, the compound of formula (I) is selected from (Z)-N-methyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2- ((3,4,4-trifluorobut-3-en- 1 -yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 - (2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut- 3-en- 1 -yl)thio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3-en- 1 - yl)sulfinyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en- l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-5- yl)-N-isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N- ethyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl- 1 - (2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l- (2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)- l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-
(cyclobutylmethyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N- (cyclopropylmethyl)-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N- (cyclopropylmethyl)- 1 -(2-((4,4-difluorobut-3-en- 1 -yl)thio)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2- ((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N-isobutylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)-N-isobutylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut- 3-en-l-yl)sulfonyl)thiazol-5-yl)-N-isobutylmethanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2-((4,4- difluorobut-3-en- 1 -yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((4,4- difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-(butylthio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(butylthio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2- (butylsulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- N-methyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-isopropyl- 1 - (2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3,4,4- trifluorobut-3-en-l-yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4- trifluorobut-3-en- 1 -yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl- 1 -(2-((3,4,4-trifluorobut- 3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut- 3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut- 3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-methyl-2-((3,4,4-trifluorobut-3- en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl- 1 -(4-methyl-2-((3,4,4-trifluorobut-3-en- 1 - yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol- 5-yl)ethan- 1 -imine oxide, (Z)-N-ethyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)thio)thiazol-5-yl)ethan- 1 - imine oxide, (Z)-N-ethyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfonyl)thiazol-5-yl)ethan- 1 -imine oxide, (Z)-N-isopropyl- 1 -(2-((3,4,4-trifluorobut-3-cn- 1 -yl )thio)thiazol-5-yl )cthan- 1 -imine oxide, (Z)- N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)ethan-l-imine oxide, (Z)-N- methyl- 1 -(2-((3 ,4,4-tifluorobut-3-en- 1 -yl)sulfinyl)thiazol-5-yl)ethan- 1 -imine oxide, (Z)- 1 -(2-
(butylthio)thiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l-(2-((3-fluoropropyl)thio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-N-isopropyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-4- yl)methanimine oxide, (Z)-l-(2-(benzylthio)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2- (benzylthio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2-(benzylsulfinyl)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(benzylsulfinyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- 1 -(2-(benzylsulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- 1 -(2-(benzylsulfonyl)thiazol- 5-yl)-N-methylmethanimine oxide, (Z)-N-ethyl- 1 -(2-((3-fluoropropyl)thio)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-((3-fluoropropyl)thio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-N-isopropyl- l-(2-((2,2,2-trifluoroethyl)thio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-(butylsulfinyl)thiazol-5-yl)- N-ethylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l- (2-((3-fluoropropyl)sulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-((3- fluoropropyl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)- 1 -(2-((3- fluoropropyl)sulfinyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- 1 -(2-((3- fluoropropyl)sulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-N-ethyl- 1 -(2-((3- fluoropropyl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3- fluoropropyl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl- 1 -(2-(prop-2-yn- 1 - ylthio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)-4-methylthiazol-5- yl)-N-methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)-4-methylthiazol-5-yl)-N- ethylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)-4-methylthiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)-4-methylthiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((3,4,4-tifluorobut-3-en-l-yl)thio)thiazol-5-yl)- N-methylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)- 1 -(4-cyclopropyl-2-((4,4-difluorobut-3-en- 1 -yl)sulfinyl)thiazol-5-yl)- N-methylmethanimine oxide, (Z)- 1 -(4-cyclopropyl-2-((4,4-difluorobut-3-en- 1 -yl)sulfonyl)thiazol-5- yl)-N-methylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((3,4,4-trifluorobut-3- en-l-yl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-(allylthio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-N-methyl- 1 -(2-(prop-2-yn-l -ylsulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-(prop-2-yn-l-ylthio)thiazol-5-yl)methanimine oxide, (Z)-l-(2- (allylsulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-ethyl- 1 -(2-(prop-2-yn- 1 - ylsulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl- 1 -(2-((4,4-difluorobut-3-en- 1 - yl)thio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-N-benzyl-l -(2-((4,4-difluorobut-3-en- 1 -yl)thio)thiazol-4- yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-4- yl)methanimine oxide, (Z)-N-benzyl- 1 -(2-((4,4-difluorobut-3-en- 1 -yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3-en- 1 -yl)thio)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N- benzyl- 1 -(2-((4,4-difluorobut-3-en- 1 -yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-((4,4- difluorobut-3-en-l-yl)thio)-4-phenylthiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)thio)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)-4-phenylthiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfonyl)-4-phenylthiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfonyl)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)-N-cyclohexyl- l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((3,4,4- trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(2-methoxyethyl)-l-(2-((3,4,4- trifluorobut-3-en- 1 -yl)thio)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3-en- 1 - yl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-4-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2-((3,4,4-trifluorobut-3-en- 1 -yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfinyl)thiazol-4-yl)methanimine oxide, (Z)-N-cyclohexyl- 1 -(2-((4,4-difluorobut-3-en- 1 - yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2-((3,4,4-trifluorobut-3- en- 1 -yl)sulfonyl)thiazol-4-yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3-en- 1 - yl)sulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-phenyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2-methoxyethyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)-N-phenyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N-(2- methoxyethyl)methanimine oxide, (Z)-N-(2-methoxyethyl)- 1 -(2-((3,4,4-trifluorobut-3-en- 1 - yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)-N-(2-methoxyethyl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((3,4,4-trifluorobut-3- en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-allyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2-chloroethyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, l-(4-chloro-2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)-N-methylmethanimine oxide, (Z)-N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)- N-methylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2-yl)-N- methylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N- methylmethanimine oxide, (Z)-N-isopropyl- 1 -(5-((3,4,4-trifluorobut-3-en- 1 -yl)thio)- 1 ,3,4-thiadiazol- 2-yl)methanimine oxide, (Z)-N-isopropyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)- N-ethylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2-yl)-N- ethylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N- ethylmethanimine oxide, (Z)-N-cyclohexyl-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol- 2-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-
2-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-cyclohexyl- 1 -(5-((3,4,4-trifluorobut-3-en- 1 -yl)sulfonyl)- l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(5-((3,4,4-trifluorobut-3-en-l- yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(5-((3,4,4- trifluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-
(cyclopropylmethyl)- 1 -(5-((3,4,4-trifluorobut-3-en- 1 -yl)sulfonyl)- 1 ,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-benzyl-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)- N-(2-methoxyethyl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)-N-(2-methoxyethyl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l- yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N-(2-methoxyethyl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-
3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)-N-phenylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l- yl)sulfinyl)-l,3,4-thiadiazol-2-yl)-N-phenylmethanimine oxide, N-isopropyl-l-(2-((3,4,4-trifluorobut- 3-en- 1 -yl)thio)oxazol-5-yl)methanimine oxide, N-ethyl- 1 -(2-((3,4,4-trifluorobut-3-en- 1 - yl)thio)oxazol-5-yl)methanimine oxide, N-ethyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)oxazol-5- yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en-l-yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en-l-yl)sulfmyl)oxazol-5- yl)methanimine oxide, (Z)-N-isopropyl- 1 -(4-methyl -2-((3, 4, 4-trifluorobut-3-en- 1 -yl)sulfinyl)oxazol- 5-yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)oxazol-5- yl)methanimine oxide, (Z)-N-ethyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en-l-yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -( 1 -methyl-2-((3 ,4,4-trifluorobut-3-en- 1 -yl)thio)- 1 H-imidazol- 5-yl)methanimine oxide, (Z)-N-ethyl- 1 -( 1 -methyl-2-((3,4,4-trifluorobut-3-en- 1 -yl)thio)- lH-imidazol- 5-yl)methanimine oxide, (Z)-N-methyl- 1 -( 1 -methyl-2-((3,4,4-trifluorobut-3-en- 1 -yl)sulfinyl)- 1H- imidazol-5-yl)methanimine oxide, (Z)-N-isopropyl- 1 -( 1 -methyl -2-((3, 4, 4-trifluorobut-3-en- 1 -yl)thio)- lH-imidazol-5-yl)methanimine oxide and (Z)-N-methyl-l-(4-methyl-5-((3,4,4-trifluorobut-3-en-l- yl)thio) -4H- 1 ,2 ,4-triazol-3 -yl)methanimine oxide .
In one embodiment, the present invention provides a process for the synthesis of compound of formula (I) comprising at least one of the following steps:
a) reacting a compound of formula 3 with substituted hydroxyl amine salt, optionally in the presence of a suitable base and suitable solvent to afford compound of formula 2a, according to the reaction scheme as depicted below;
Figure imgf000022_0001
b) oxidizing the compound of formula 2a in the presence of a suitable oxidizing agent to afford compound formula 2b according to the reaction scheme as depicted below;
Figure imgf000022_0002
c) oxidizing the compound of formula 2b in the presence of a suitable oxidizing agent to afford compound formula (I) according to the reaction scheme as depicted below;
Figure imgf000022_0003
The compounds of the present invention as defined by formula (I) and/or in table (I) may be prepared, in known manner, in a variety of ways as described in the schemes. Compounds of the present invention can be made as shown in the following schemes, in which, unless otherwise stated, the definition of each variable is as defined above for a compound of formula (I). Scheme: 1
Figure imgf000023_0001
As shown in scheme 1, the compound of formula 1 can be prepared by the oxidation of substituted sulfide or sulfoxide derivatives of formula 2a or 2b with an suitable oxidizing reagent preferably selected from meto-chloroperbenzoic acid or oxone in the presence of a suitable solvent selected from methanol, dichloromethane etc.
Scheme: 2
Figure imgf000023_0002
As shown in scheme 2, the compound of formula 2b can be prepared by the oxidation of substituted sulfide of formula 2a with a suitable oxidizing reagent preferably selected from meta- chloroperbenzoic acid or oxone in the presence of a suitable solvent selected from methanol, dichloromethane etc.
Scheme: 3
Figure imgf000023_0003
As shown in scheme 3, the compound of formula 2a can be prepared by the condensation of substituted hydroxyl amine with the compound of formula 3 optionally in the presence a suitable base selected from sodium acetate or potassium acetate; and a suitable solvent selected from methanol or ethanol.
Scheme: 4
Figure imgf000023_0004
As shown in scheme 4, the compound of formula 2a can also be prepared by alkylation of compound of formula 4 in the presence of a suitable base e.g. potassium carbonate, sodium hydroxide, potassium hydroxide, potassium tert-butoxide etc. The corresponding compound of formula 4 can be prepared by condensation of compound of formula 3 with hydroxyl amine hydrochloride optionally in the presence a suitable base selected from sodium acetate or potassium acetate; and a suitable solvent selected from methanol or ethanol.
Scheme: 5
Figure imgf000024_0001
As shown in scheme 5, the compound of formula 3a can be prepared from the compound of formula 6 by Vilsmeier-Haack reaction. The corresponding compound of formula 6 can be prepared by thiol- alkylation of compound of formula 5 with alkyl/alkenyl halide in the presence of a suitable base selected from potassium carbonate or triethylamine in a suitable solvents such as ethanol, acetonitrile or /V,/V-Dimcthyl form amide under heating conditions.
Scheme: 6
Figure imgf000024_0002
As shown in scheme 6, the compound of formula 8 can be prepared alkylation of thiol compound of formula 7 with suitable alkyl/alkenyl halide in the presence of potassium carbonate or triethylamine in solvents such as ethanol, acetonitrile or /V,/V-d i mcth y I form am i dc under heating conditions. The resulting compound of formula 8 can be reduced to compound of formula 9 using reducing agent such as sodium borohydride in appropriate solvent e.g. methanol. Further, compound of formula 9 can be converted to compound of formula 3a using oxidizing agent such as dess-martin periodinane in appropriate solvent e.g. dichloromethane.
Scheme: 7
Figure imgf000024_0003
As shown in scheme 7, the compound of formula iii can be prepared by the hydrolyzing the compound of formula ii in the presence of a suitable hydrolyzing agent and optionally in the presence of a suitable solvent. The compound of formula ii can be prepared by N-alkylation of compound of formula i in the presence of a suitable alkylating reagent such as alkyl halide and a suitable base selected from potassium carbonate or triethylamine.
Any of the compounds according to the invention can exist in one or more optical, geometric or chiral isomer forms depending on the number of asymmetric centres in the compound. The invention thus relates equally to all the optical isomers and to their racemic or scalemic mixtures (the term “scalemic” denotes a mixture of enantiomers in different proportions), and to the mixtures of all the possible stereoisomers, in all proportions. The diastereoisomers and/or the optical isomers can be separated according to the methods which are known per se by a person ordinary skilled in the art.
Any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by a person ordinary skilled in the art.
Any of the compounds according to the invention, can also exist in one or more amorphic or isomorphic or polymorphic forms, depending on their preparation, purification storage and various other influencing factors. The invention thus relates all the possible amorphic, isomorphic and polymorphic forms, in all proportions. The amorphic, isomorphic and polymorphic forms can be prepared and/or separated and/or purified according to general methods, which are known per se by a person ordinary skilled in the art.
There are large number of suitable known standard methods, such as alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction. The choice of the preparation methods which are suitable are depending on the properties (reactivity) of the substituents in the intermediates. These reactions can be conveniently performed in a solvent. These reactions can be conveniently performed at various temperatures. These reactions can be conveniently performed in an inert atmosphere. The reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, N,N- diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, /V,/V-diethylaniline, pyridine, 4-(/V,/V-di methyl am inojpyndine, quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction according to scheme- 1 to 13 is preferably carried out in a solvent selected from standard solvents which are inert under the prevailing reaction conditions. Preference is given to aliphatic, alicyclic or aromatic hydrocarbons, such as, petroleum ether, hexane, toluene; halogenated hydrocarbons, such as, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride or dichloroethane; ethers, such as, diethyl ether, diisopropyl ether, methyl /-butyl ether (MTBE), dioxane, tetrahydrofuran or 1,2 -dime thoxy ethane; nitriles, such as, acetonitrile or propionitrile, or; amides, such as, /V, /V-di mcthylformam idc (DMF), /V, /V- d i m c t h y 1 ac c t a m i dc , N- mcthylfonnanilidc, N- methylpyrrolidone (NMP) or hexamethylenephosphoric triamide; esters, such as, for example, methyl acetate or ethyl acetate; sulfoxides, such as, dimethyl sulfoxide (DMSO); sulfones, such as, sulfolane; alcohols, such as, methanol, ethanol, nor isopropanol, 1 ,1-, iso-, sec- or tert-butanol, ethanediol, propane- l,2-diol, ethoxy ethanol, methoxy ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or mixtures of these.
The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. The reaction is advantageously carried out in a temperature range from approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, in many cases in the range between ambient temperature and approximately +80 °C.
A compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention. Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchanger reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchanger reagent. A salt is chosen depending on its tolerances for compound's use, such as agricultural or physiological tolerance. Salts of compounds of formula (I) can be converted in the customary manner into the free compounds I, acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchanger reagent. Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
In one embodiment, the present invention provides use of compound of formula (I), stereoisomers, agriculturally acceptable salts, tautomers or N-oxides thereof or composition or combination thereof for controlling or preventing agricultural crops and/or horticultural crops against phytopathogenic fungi, bacteria, insects, nematodes or mites. In preferred embodiment, the present invention provides use of compound of formula (I), stereoisomers, agriculturally acceptable salts, tautomers or N-oxides thereof or composition or combination thereof for controlling or preventing agricultural crops and/or horticultural crops against nematodes and phytopathogenic fungi.
The agricultural crops are selected from cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, 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, other vegetables or ornamentals.
The compounds according to the invention can be used for controlling or destroying pests such as nematodes and/or fungi which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these pests.
The compounds of formula (I) according to the 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 pesticide resistant pests such as insects and fungi, which compounds of formula (I) have a very favorable biocidal spectrum and are well tolerated by warm-blooded species, fish and plants. Accordingly, the present invention also makes available a pesticidal composition comprising compounds of the invention, such as formula (I). It has now been found that the compounds of formula (I) according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting animals and useful plants against attack and damage by nematodes and phytopathogenic microorganisms like fungi or bacteria. Accordingly, the present invention also makes available a nematicidal composition comprising compounds of the invention, such as formula (I). It has also now been found that the compounds of formula I according to the invention have, for practical purposes, a very advantageous spectrum of activities for protecting animals and useful plants against attack and damage by fungi. Accordingly, the present invention also makes available a fungicidal composition comprising compounds of the invention, such as formula (I).
The compounds of the formula (I) can possess potent microbicidal activity and can be used for the control of unwanted microorganisms, such as fungi, nematodes and bacteria, in agricultural or horticultural crop protection and in the protection of such materials.
The compounds of the formula (I) can possess very good fungicidal properties and can be used in crop protection, for example for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The compounds of the formula (I) can be used as nematicides in crop protection, for example, for control of Tylenchida, Rhabditida, Dorylaimida, and Tryplonchida.
The compounds of the formula (I) can be used as bactericides in crop protection, for example, for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
The compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seed, the plant or plant parts, the fruit or the soil in which the plants grow.
The compounds of the formula (I) can be used for controlling or preventing against phytopathogenic fungi, bacteria, nematodes of agricultural crops and or horticultural crops.
The compounds of the formula (I) can be used in crop protection, wherein the agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, 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 formula (I) are especially useful for the control of nematodes. Thus, in a further aspect, the invention also relates to a method of controlling damage to plant and parts thereof by plant parasitic nematodes (Endoparasitic, Semiendoparasitic and Ectoparasitic nematodes), especially plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, Meloidogyne arenaria 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, Eelonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Pratylenchus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species, such as Subanguina spp., Hypsoperine spp., Macroposthonia spp., Melinius spp., Punctodera spp., and Quinisulcius spp..
Particularly, the nematode species Meloidogyne spp., Heterodera spp., Rotylenchus spp., Pratylenchus spp. and Radopholus spp. can be controlled by compounds of the invention.
The compound of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The compound of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp. (white rust) on ornamentals, vegetables (e.g. A Candida ) and sunflowers (e.g. A. tragopogonis); Altemaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassicae), sugar beets (A. tenuis), fruits, rice, soybeans, potatoes (e. g. A. solanior A. alternata), tomatoes (e.g. A. solanior A. alternata ) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e.g. A. tritici(anthracnose) on wheat and A. hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. niaydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (eg. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremialactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C.beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchil) and rice; Cladosporium spp. on tomatoes (e. g. C. fu/vum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helminthosporium of Bipolaris) spp. (leaf spots) on corn ( C. carbonum), cereals (e. g. C. sativus, anamorph:#. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypil ), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C.lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides); Corticium spp., e.g. C. sasakiil sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e.g. C. liriodendri, teleomorph: Neonectria liriodendrf Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e.g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e.g. D. teres, net blotch) and wheat (e.g. D. tritici- repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyn), soft fruits (E. veneta: anthracnose) and vines (E.ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e.g. E. pis,), such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme) and F. tucumani-ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gibberella spp. on cereals (e.g. G. zeae) and rice (e. g. G. fujikurof Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e.g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix( coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophominaphaseolina (syn. phaseo/1 ) (root and stem rot) on soybeans and cotton; Microdochium (syn .Fusarium) nivale (pink snow mold) on cereals (e.g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e.g. M laxa, M fructicola and M fructigena( bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerellaspp. on cereals, bananas, soft fruits and ground nuts, such as e.g. M graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e.g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina ) and soybeans (e.g. P. manshurica); Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e.g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Physoderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsid), soybeans (e. g. P.megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad-leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia ya/lundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or, rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, P. kuehnii( orange rust) on sugar cane and P. asparagion asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, grape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramu/aria spp., e.g. R. collo-cygni(Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani ( sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer( black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sarocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e.g. S. rolfsiior S. sclerotiorum); Septoria spp. on various plants, e.g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) nodorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator(powdery mildew, anamorph: Oidium tucken) on vines; Setospaeria spp. (leaf blight) on corn (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum ) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa(dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. U. phaseo/J) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut)on cereals (e.g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes. In one embodiment, the present invention provides a composition for controlling or preventing phytopathogenic microorganisms comprising a compound of general formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof and one or more inert carriers.
In another embodiment, the composition may additionally comprises one or more active compatible compounds selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
The concentration of the compound of general formula (I) ranges from 1 to 90% 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 further relates to a composition for controlling unwanted microorganisms comprising at least one of the compounds of the formula (I) and one or more inert carrier. The inert carrier further comprises agriculturally suitable auxiliaries, solvents, diluents, surfactants and/or extenders and the like.
The present invention further relates to a composition for controlling unwanted microorganisms, comprising at least one of the compounds of the formula (I) and/or one or more active compatible compound selected from fungicides, bactericides, acaricides, insecticides, nematicides, herbicides, biopesticides, plant growth regulators, antibiotics, fertilizers and/or mixtures thereof.
Generally, a compound of the present invention is used in the form of a composition (e.g.formulation) containing a carrier. A compound of the invention and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ulv) liquid, ultra-low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder.
A formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers. The composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.
Accordingly, the present invention also makes available a composition comprising a compound of the invention and an agronomical carrier and optionally one or more customary formulation auxiliaries. The compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries). In the case of solid compounds of the invention, the grinding/milling of the compounds is to ensure specific particle size. These processes for the preparation of the compositions and the use of the compounds of the invention for the preparation of these compositions are also a subject of the invention.
Examples of compositions for use in agriculture are emulsifiable concentrates, suspension concentrates, microemulsions, oil dispersibles, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymeric substances, which comprise - at least - a compound according to the invention and the type of composition is to be selected to suit the intended aims and the prevailing circumstances.
Examples of suitable liquid carriers are unhydrogenated or partially hydrogenated aromatic hydrocarbons, preferably the fractions Cs to C12 of alkylbenzenes, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols and their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N- dimethylformamide, water, unepoxidized or epoxidized vegetable oils, such as unexpodized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils. Examples of solid carriers which are used for example for dusts and dispersible powders are, as a rule, ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add highly disperse silicas or highly disperse absorbtive polymers. Suitable particulate adsorptive carriers for granules are porous types, such as pumice, brick grit, sepiolite or bentonite, and suitable non-sorptive carrier materials are calcite or sand. In addition, a large number of granulated materials of inorganic or organic nature can be used, in particular dolomite or comminuted plant residues. Suitable surface-active compounds are, depending on the type of the active ingredient to be formulated, non-ionic, cationic and/or anionic surfactants or surfactant mixtures which have good emulsifying, dispersing and wetting properties. The surfactants mentioned below are only to be considered as examples; a large number of further surfactants which are conventionally used in the art of formulation and suitable according to the invention are described in the relevant literature. Suitable non-ionic surfactants are, especially, polyglycol ether derivatives of aliphatic or (cyclo) aliphatic alcohols, of saturated or unsaturated fatty acids or of alkyl phenols which may contain approximately 3 to approximately 30 glycol ether groups and approximately 8 to approximately 20 carbon atoms in the (cyclo)aliphatic hydrocarbon radical or approximately 6 to approximately 18 carbon atoms in the alkyl moiety of the alkyl phenols. Also suitable are water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol or alkyl polypropylene glycol having 1 to approximately 10 carbon atoms in the alkyl chain and approximately 20 to approximately 250 ethylene glycol ether groups and approximately 10 to approximately 100 propylene glycol ether groups. Normally, the abovementioned compounds contain 1 to approximately 5 ethylene glycol units per propylene glycol unit. Examples which may be mentioned are nonylphenoxypolyethoxyethanol, castor oil poly glycol ether, polypropylene glycol/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol or octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. The cationic surfactants are, especially, quarternary ammonium salts which generally have at least one alkyl radical of approximately 8 to approximately 22 Carbon atoms as substituents and as further substituents (unhalogenated or halogenated) lower alkyl or hydroxyalkyl or benzyl radicals. The salts are preferably in the form of halides, methylsulfates or ethylsulfates. Examples are stearyltrimethylammonium chloride and benzylbis(2-chloroethyl)ethylammonium bromide.
Examples of suitable anionic surfactants are water-soluble soaps or water-soluble synthetic surface- active compounds. Examples of suitable soaps are the alkali, alkaline earth or (unsubstituted or substituted) ammonium salts of fatty acids having approximately 10 to approximately 22 Carbon atoms, such as the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which are obtainable for example from coconut or tall oil; mention must also be made of the fatty acid methyl taurates. However, synthetic surfactants are used more frequently, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylaryl sulfonates. As a rule, the fatty sulfonates and fatty sulfates are present as alkali, alkaline earth or (substituted or unsubstituted) ammonium salts and they generally have an alkyl radical of approximately 8 to approximately 22 Carbon atoms, alkyl also to be understood as including the alkyl moiety of acyl radicals; examples which may be mentioned are the sodium or calcium salts of lignosulfonic acid, of the dodecylsulphuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. This group also includes the salts of the sulphuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulphonyl groups and a fatty acid radical of approximately 8 to approximately 22 Carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of decylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid/formaldehyde condensate. Also possible are, furthermore, suitable phosphates, such as salts of the phosphoric ester of a p- nonylphenol/(4-l4)ethylene oxide adduct, or phospholipids.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of compound according to the present invention and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.
Examples of foliar formulation types for pre-mix compositions are:
Figure imgf000035_0001
Whereas, examples of seed treatment formulation types for pre-mix compositions are:
Figure imgf000035_0002
Examples of formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.
As with the nature of the formulations, the methods of application, such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries. Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
Generally, a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 15%, of the desired ingredients, and 99.9 to 80%, especially 99.9 to 85%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20%, especially 0.1 to 15%, based on the tank-mix formulation. Typically, a pre mix formulation for foliar application comprises 0.1 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation.
Normally, a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75%, of the desired ingredients, and 99.75 to 20%, especially 99 to 25%, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40%, especially 0.5 to 30%, based on the tank-mix formulation.
Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9%, especially 1 to 95%, of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, based on the pre-mix formulation whereas commercial products will preferably be formulated as concentrates (e.g., pre-mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition).
Preferred seed treatment pre-mix formulations are aqueous suspension concentrates. The formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, roto static seed treaters, and drum coaters. Other methods, such as spouted beds may also be useful. The seeds may be pre sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art. The compounds of the present invention are particularly suited for use in soil and seed treatment applications.
In general, the pre-mix compositions of the invention contain 0.5 to 99.9% especially 1 to 95%, advantageously 1 to 50%, by mass of the desired ingredients, and 99.5 to 0.1%, especially 99 to 5%, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50%, especially 0.5 to 40%, by mass based on the mass of the pre-mix formulation.
A compound of the formula (I) in a preferred embodiment, independent of any other embodiments, is in the form of a plant propagation material treating (or protecting) composition, wherein said plant propagation material protecting composition may comprises additionally a coloring agent. The plant propagation material protecting composition or mixture may also comprise at least one polymer from water-soluble and water-dispersible film-forming polymers that improve the adherence of the active ingredients to the treated plant propagation material, which polymer generally has an average molecular weight of at least 10,000 to about 100,000.
In an embodiment, the present invention provides a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof, is applied to the plants, to parts thereof or a locus thereof.
In another embodiment, the present invention provides a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof is applied to a seeds of plants. In yet another embodiment, the present invention provides a method of controlling or preventing phytopathogenic microorganisms in agricultural crops and/or horticultural crops using the compound of general formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 1 g to 5 kg per hectare of agricultural and/or horticultural crops.
Examples of application methods for the compounds of the invention and compositions thereof, that is the methods of controlling pests in the agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring which are to be selected to suit the intended aims of the prevailing circumstances.
One method of application in agriculture is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest or fungi in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application). In the case of paddy rice plants, such granules can be metered into the flooded paddy-field. The application of the compounds of the present invention to the soil is a preferred application method.
Typical rates of application per hectare is generally 1 to 2000 g of active ingredient per hectare, in particular 10 to 1000 g/ha, preferably 10 to 600 g/ha, such as 50 to 300 g/ha.
In one embodiment, the present invention provides a seed comprising compound of formula (I) and/or stereoisomers, agriculturally acceptable salts, tautomers, N-oxides thereof or composition or combination thereof, wherein the amount of the compound of the formula (I) or an N-oxide or an agriculturally acceptable salt thereof is ranging from 0.1 g to 10 kg per 100 kg of seed.
The compounds of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the abovementioned type. The propagation material can be treated with the compound prior to planting, for example seed can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds. The application of the compounds of the present invention to seeds is a preferred application method.
The term seed embraces seeds and plant propagules of all kinds including but not limited to true seeds, seed pieces, suckers, corns, bulbs, fruit, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term“coated or treated with and/or containing” generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
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 seed treatment application of the compound formula I, which is a preferred application method, can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pomaceous fruit, stone fruit or soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals (such as flowers, and lawn grass or turf). In an embodiment, the plant is selected from cereals, corn, soybean, rice, sugarcane, vegetables and oil plants.
The term“plant” is to be understood as including also plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesizing one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus and also plants which have been selected or hybridized to preserve and / or attain a desired trait, such as insect, fungi and /or nematode resistance. Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae·, or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus, toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl- transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the context of the present invention there are to be understood by 8-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Flybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin-G- recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073. The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367474, EP-A-0 401 979 and WO 90/13651. The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera). Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculexl® (maize variety that expresses a CrylFa2 toxin and the enzyme phosphinothricine N-acetyltransferase(PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); Newleaf® (potato variety that expresses a Cry3A toxin); NatureGard®, 25Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Btl l corn borer (CB) trait) and Protecta®. Further examples of such transgenic plants are: i) Btl l Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Btl l maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; ii)Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European corn borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; iii) MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect -resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810; iv)MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects; v) IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02; vi) 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein CrylF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium; vii) NK603 x MON 810 Maize from Monsanto Europe S.A. 270- 272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally breed hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European corn borer.
In one embodiment, the present invention provides a combination comprising the compound of general formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof and one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertili ers.
Compounds of this invention are effective for controlling nematodes and/or fungal pathogens of agronomic plants, both growing and harvested, when employed alone, they may also be used in combination with other biological active agents used in agriculture, such as one or more nematicides, insecticides, acaricides, fungicides, bactericides, plant activator, molluscicide, and pheromones (whether chemical or biological). Mixing the compounds of the invention or the compositions thereof in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action. For example, the formula (I) compounds of this invention may be used effectively in conjunction or combination with pyrethroids, neonicotinoids, macrolides, diamides, phosphates, carbamates, cyclodienes, formamidines, phenol tin compounds, chlorinated hydrocarbons, benzoylphenyl ureas, pyrroles and the like.
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding, for example, one or more insecticidally, acaricidally, nematicidally and/or fungicidally active agents. The combinations compounds of formula (I) with other insecticidally, acaricidally, nematicidally and/or fungicidally active agents may also have further surprising advantages. For example, better tolerance by plants, reduced phytotoxicity, pests or fungi can be controlled in their different development stages or better behavior during their production, for example during grinding or mixing, during their storage or during their use.
The known and reported active compounds such as fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients can be combined with at least one compound of formula I of the present invention. For example, fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients disclosed and reported in WO2017076739 (A to O) can be combined with compound of Formula I of the present invention. The present invention also relates to such combinations comprising the compound of the present invention and active compatible compounds reported in WO2017076739.
The compounds of formula (I) of the present invention can also be combined with other insecticidal active compounds of unknown or uncertain mode of action: afidopyropen, afoxolaner, azadirachtin, amidoflumet, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, dicloromezotiaz, dicofol, flufenerim, flometoquin, fluensulfone, fluhexafon, fluopyram, flupyradifurone, fluralaner, metoxadiazone, piperonyl butoxide, pyflubumide, pyridalyl, pyrifluquinazon, sulfoxaflor, tioxazafen, triflumezopyrim, l l-(4-chloro-2,6-dimethylphenyl)-l2- hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-l0-one, 3-(4' -fluoro-2,4-dimethylbiphenyl-3- yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-one, l-[2-fluoro-4-methyl-5-[(2,2,2- trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-l Fl-l,2,4-triazole-5-amine, Bacillus firmus;(E/Z)- N-[l-[ (6-ch loro-3-pyridyl) methyl] -2-pyridylidene ]-2,2,2-trifluoro-acetamide; (E/Z)-N-[l-[(6- chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; (E/Z)-2,2,2-trifluoro-N- [l-[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; (E/Z)-N-[l-[(6-bromo-3-pyridyl)methyl]- 2-pyridylidene]-2,2,2-trifluoroacetamide; (£/Z)-N-[l-[l-(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]- 2,2,2-trifluoroacetamide; (E/Z)-N-[l-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2-difluoro- acetamide; (E/Z)- 2-chloro-N-[ l-[ ( 6-chloro-3-pyridyl) methyl] -2-pyridylidene] -2, 2-difluoro- acetamide; (E/Z)-N-[l-[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; (E/Z)-N-[l-[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propanamide); N-[l-[ (6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-thioacetamide; N-[l-[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-N'-isopropyl-acetamidine; fluazaindolizine; 4-[5-(3,5- dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(l-oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-lH-pyrazole; 3- (benzoylmethylamino)-N-[2-bromo-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl)propyl]-6- (trifluoromethyl)phenyl]-2-fluoro-benzamide; 3-(benzoylmethylamino)-2-fluoro-N-[2-iodo-4-
1 1 ,2,2,2-tetrafluoro- 1 -(trifluoromcthyljcthyl ]-6-(triflu iomcthyl )phcnyl ]-bcnzamidc; N-[3-[[[2-iodo- 4-[l ,2,2,2-tetrafluoro- 1 -(trifluoromethyl)ethyl] -6-(tifluoromethyl)phenyl] amino] carbonyl] phenyl] -N- methyl-benzamide; N-[3-[[[2-bromo-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]-6-
(trifluoromethyl)phenyl] amino] carbonyl] -2-fluorophenyl] -4-fluoro-N -methylbenzamide ; 4-fluoro-N - |2-fluoro-3-| 112-iodo-4-| 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl jethyl ]-6-
(trifluoromethyl)phenyl] amino] carbonyl] phenyl] -N -methyl-benzamide ; 3 -fluoroN - [2-fluoro-3 - [ [ [2- iodo-4-| 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl jethyl ]-
6(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; 2-chloro-N-[3-[[[2-iodo-4- 1 1 ,2,2,2-tetrafluoro- 1 -(trifluoromethyl jethyl ]-6-(trifluoiOmcthyl )phcnyl ]amino]carbonyl Iphcnyl ]-3- pyridinecarboxamide; 4-cyano-N-| 2-cyano-5-| |2,6-dibromo-4-| 1 ,2,2,3,3,3-hcxafluoro- 1 -
(trifluoromethyl) propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;4-cyano-3-[(4-cyano-2- mcthyl-bcnzoyl )amino]-N-|2,6-dichloro-4-| 1 ,2,2,3,3,3-hcxafluoro- 1 -(tnfluoromcthyl ) propyl]phenyl]-
2-fluoro-benzamide; N-|5-| |2-chloro-6-cyano-4-| 1 ,2,2,3,3,3-hcxafluoro- 1 -
(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; N-[5-[[2- bromo-6-chloro-4- [2,2,2-trifluoro- 1 -hydroxy- 1 -(trifluoromethyl)ethyl]phenyl] carbamoyl] -2-cyano- phcnyl ]-4-cyano-2-mcthyl-bcnzamidc;N-|5-| 12-bromo-6-chloro-4-| 1 ,2,2,3,3,3-hcxafluoro- 1 - (trifluoromethyl) propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-cyano- N-|2-cyano-5-| |2,6-dichloro-4-| 1 ,2,2,3,3,3-hcxafluoro- 1 -(ti ifluoromcthyl )propyl Iphcnyl ]carbamoyl ] phenyl] -2-methyl-benzamide; 4-cyano-N-[2-cyano-5-[[2,6-dichloro-4-[l,2,2,2-tetrafluoro-l-
(trifluoromethyl)ethyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; N-[5-[[2-bromo-6-chloro-4- 1 1 ,2,2,2-tetrafluoro- 1 -(trifluoromcthyl)cthyl ] phenyl]carbamoyl] -2-cyan o-phenyl]-4-cyano-2-methyl- benzamide; 2-(l,3-dioxan-2-yl)-6-[2-(3-pyridinyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3- pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]- pyrimidine; N-methylsulfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; N- methylsLilfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2-carboxamide; N-ethyl-N-[4-methyl-2-(3- pyridyl)thiazol-5-yl]-3-methylthio-propan amide; N-methyl-N-[ 4-methyl-2-( 3-pyridyl)thiazol-5-yl]-
3-methylthio-propanamide;N,2-dimethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3- methylthiopropanamide; N-ethyl-2-methyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio- propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2-methyl-3-methylthio-propanamide; N-[ 4-chloro-2-(3-pyridyl )thiazol-5-yl]-N ,2-dimethyl-3-methylthio-propanamide;N-[4-chloro-2-(3- pyridyl)thiazol-5-yl]-N-methyl-3-methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N- ethyl-3-methylthio-propanamide; l-[(6-chloro-3-pyridinyl)methyl]-l,2,3,5,6,7-hexahydro-5-methoxy- 7-methyl-8-nitro-imidazo[l,2-a]pyridine;l-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro- l,2,3,5,6,7-hexahydroimidazo[l,2-a]pyridin-5-ol; l-isopropyl-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide;l-(l,2-dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; N,5-dimethyl-N-pyridazin-4-yl- 1 -(2,2,2-trifluoro- 1 -methyl-ethyl)pyrazole-4- carhox amide ; 1-[1-(1 -cyanocyclopropyl)ethyl] -N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; N-ethyl-l-(2-fluoro-l-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4- carboxamide; l-(l,2-dimethylpropyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; l-[l- (1 -cyanocyclopropyl)ethyl] -N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide;N-methyl- 1 -(2- fluoro-l-methyl-propyl]-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; l-(4,4- difluorocyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; l-(4,4- difluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide, N-( l-methylethyl)-2- (3-pyridinyl)-2H-indazole-4-carboxamide;N-cyclopropyl-2-(3-pyridinyl)-2H-indazole-4- carboxamide; N-cyclohexyl-2-(3-pyridinyl)- 2H-indazole-4-carboxamide; 2-(3-pyridinyl)-N-(2,2,2- trifluoroethyl)-2H-indazole-4-carboxamide; 2-(3-pyridinyl)-N-[(tetrahydro-2-furanyl)methyl]-2H- indazole-5-carboxamide; methyl 2-[[2-(3-pyridinyl)-2H-indazol-5-yl]carbonyl]hydrazinecarboxylate; N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)-2H-indazole-5-carboxamide; N-(2,2- difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; 2-(3-pyridinyl )N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; N-[(5-methyl-2-pyrazinyl)methyl]-2-(3-pyridinyl)-2H-indazole-5- carboxamide, N-[3-chloro-l-(3-pyridyl)pyrazol-4-yl]N-ethyl-3-(3, 3 ,3-trifluoropropylsulfanyl) propanamide ; N- [3 -chloro- 1 -(3 -pyridyl)pyrazol-4-yl] -N -ethyl-3 -(3 , 3 ,3 -trifluoropropylsulfinyl) propanamide; N-[3-chloro-l-(3-pyridyl)pyrazol-4-yl]-3-[(2,2-difluorocyclopropyl)methylsulfanyl]-N- ethyl-propanamide ; N- [3 -chloro- 1 -(3 -pyridyl)pyrazol-4-yl] -3 - [(2 ,2-difluorocyclopropyl) methylsulfinyl]-N-ethyl-propanamide; sarolaner, lotilaner.
The active substances referred above, their preparation and their activity e.g. against harmful fungi/insect/nematode is known (cf.: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141 317; EP- A 152 031; EP-A 226 917; EP-A 243 970; EP-A 256 503; EP-A 428 941; EP-A 532 022; EP-A 1 028 125; EP-A1 035 122; EP-A 1 201 648; EP-A 1 122 244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO 00/46148; WO 00/65913; WO 01/54501; WO
01/56358; WO 02/22583; WO 02/40431; WO 03/10149; WO 03/11853; WO 03/14103; WO
03/16286; WO 03/53145; WO 03/61388; WO 03/66609; WO 03/74491; WO 04/49804; WO
04/83193; WO 05/120234; WO 05/123689; WO 05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07 /90624, WO
10/139271, WO 11 /028657, WO 12/168188, WO 07 /006670, WO 11/77514; WO 13/047749, WO
10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO
13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224, WO
11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, WO 15/65922, WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441).
The mass ratio of any two ingredients in each combination is selected as to give the desired effect, for example, enhanced activity. In general, the mass ratio would vary depending on the specific ingredient and how many ingredients are present in the combination. Generally, the mass ratio between any two ingredients in any combination of the present invention, independently of one another, is from 100:1 to 1:100, including from 99:1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90:10, 89:11, 88:12, 87:13, 86:14, 85:15, 84:16, 83:17, 82:18, 81:19, 80:20, 79:21, 78:22, 77:23,
76:24, 75:25, 74:26, 73:27, 72:28, 71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:45, 64:46, 63:47,
62:48, 61:49, 60:40, 59:41, 58:42, 57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49, 50:50, 49:51,
48:52, 47:53, 46:54, 45:55, 44:56, 43:57, 42:58, 41:59, 40:60, 39:61, 38:62, 37:63, 36:64, 35:65,
34:66, 33:67, 32:68, 31:69, 30:70, 29:71, 28:72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21:79,
20:80, 19:81, 18:82, 17:83, 16:84, 15:85, 14:86, 13:87, 12:88, 11:89, 10:90, 9:91, 8:92, 7:93, 6:94, 5:95, 4:96, 3:97, 2:98, to 1:99. Preferred mass ratios between any two components of present invention are from 75:1 to 1:75, more preferably, 50:1 to 1.50, especially 25:1 to 1:25, advantageously 10:1 to 1:10, such as 5:1 to 1:5, for example 1:3 to 3:1. The mixing ratios are understood to include, on the one hand, ratios by mass and also, on other hand, molar ratios.
The combinations of the present invention (i.e. those comprising a compound of the present invention and one or more other biological active agents) may be applied simultaneously or sequentially.
In the event, the ingredients of a combination are applied sequentially (i.e., one after the other), the ingredients are applied sequentially within a reasonable period of each other to attain the biological performance, such as within a few hours or days. The order of applying the ingredients in the combination, i.e., whether the compounds of formula (I) should be applied first or not is not essential for working the present invention.
In the event ingredients of the combinations are applied simultaneously in the present invention, they may be applied as a composition containing the combination, in which case (A) the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready-to-apply, spray broth, or slurry), or (B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
In an embodiment, independent of other embodiments, a compound according to the present invention is applied as a combination. Accordingly, the present invention also provides a composition comprising a compound according to the invention as herein described and one or more other biological active agents, and optionally one or more customary formulation auxiliaries; which may be in the form of a tank-mix or pre-mix composition.
The compounds of formula (I) are particularly useful for controlling and preventing helminth and nematode endo and ecto-parasitic infestations and infections in warm-blooded animals such as cattle, sheep, swine, camels, deer, horses, poultry, fish, rabbits, goats, mink, fox, chinchillas, dogs and cats as well as humans. In the context of control and prevention of infestation and infections in warm blooded animals, compounds of invention are especially useful for the control of helminths and nematodes. Examples for helminths are members of the class Trematoda, commonly known as flukes or flatworms, especially members of the genera Fasciola, Fascioloides, Paramphistomu, Dicrocoelium, Eurytrema, Ophisthorchis, Fasciolopsis, Echinostoma and Paragonimus. Nematodes which can be controlled by the formula (I) compounds include the genera Haemonchus, Ostertagia, Cooperia, Oesphagastomu, Nematodirus, Dictyocaulus, Trichuris, Dirofilaria, Ancyclostoma, Ascaria and the like. For oral administration to warm-blooded animals, the compounds of the invention may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of the invention may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 g/kg of animal body weight per day of the compound of the invention. Alternatively, the compounds of the invention may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of the invention may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of the invention may be formulated into an implant for subcutaneous administration. In addition the compounds of the invention may be transdermally administered to animals. For parenteral administration, the dosage form chosen should provide the animal with about 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compound of the invention.
The compounds of the invention may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays and pour-on formulations. For topical application, dips and sprays usually contain about 0.5 ppm to 5,000 ppm and preferably about 1 ppm to 3,000 ppm of the compound of the invention. In addition, the compounds of the invention may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep.
In an embodiment, independent of any other embodiments, a compound of formula (I) is an anti helminth compound.
In an embodiment, independent of any other embodiments, a compound of formula (I) is a pesticidal compound, preferably a nematicidal compound. Temperatures are given in degrees Celsius. The compounds of the present invention not only control insect pests effectively but also show positive crop response such as plant growth enhancement effects like enhanced crop vigor, enhanced root growth, enhanced tolerant to drought, high salt, high temperature, chill, frost or light radiation, improved flowering, efficient water & 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.
CHEMISTRY EXAMPLES:
The following examples set forth the manner and process of making compounds of the present invention without being a limitation thereof and include the best mode contemplated by the inventors for carrying out the invention.
Example 1: N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide Step 1: Preparation of 2-((3, 4, 4-trifluorobut-3-en-l-yl)thio)thiazole
To a solution of thiazole-2-thiol (1 g, 8.5 mmol) in acetonitrile (10 mL), potassium carbonate (1.8 g, 12.8 mmol) was added at 25 °C and stirred for 30 min. To the resulting reaction mixture, 4-Chloro- 1,1, 2-trifluorobut-l-ene (1.3 g, 9.4 mmol) was added and stirred at 60 °C for 4 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (30 mL) followed by water (30 mL) and acidified to pH 4 using 1 N hydrochloric acid. The ethyl acetate layer was separated and the aqueous layer was extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 10 % ethyl acetate/hexane to yield 2-((3, 4, 4-trifluorobut-3-en-l-yl)thio)thiazole (1.6 g, 85 % yield) as pale yellow liquid; LCMS (M+l): 225.6.
Step 2: Preparation of 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde:
To an ice cooled dry /V,/V-di mcthylformam idc (2.4 g, 33.3 mmol), phosphoryl chloride (5.1 g, 33.3 mmol) was added drop wise and stirred for 30 min. A solution of 2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazole (1.5 g, 6.6 mmol) in dry /V, /V- D i m c t h y 1 f r m a m i d c (10 mL) was added drop wise to the reaction mixture and stirred for 20 min. The reaction mixture was allowed to reach 25 °C and heated to 80 °C for 12 h. After completion of the reaction, phosphoryl chloride was evaporated and the reaction mixture was neutralized using 1 N sodium hydroxide solution at 25 °C. The reaction mixture was diluted with water (30 mL) and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 10 % ethyl acetate/hexane to yield 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde (1.0 g, 60 % yield). 'H-NMR (400 MHz, CDCL) d 9.66 (s, 1H), 7.80 (s, 1H), 3.41-3.49 (m, 2H), 2.86-2.91 (m, 2H). Step 3: Preparation of 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde oxime
To a solution of 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde (1 g, 3.9 mmol) in methanol (10 mL), sodium acetate (0.6 g, 7.9 mmol) was added at 0 °C and stirred for 15 min. To the resulting reaction mixture, hydroxylamine hydrochloride (0.3 g, 3.9 mmol) was added and stirred at 0 °C. The reaction mixture was allowed to reach 25 °C and stirred further for 2 h. After completion of the reaction, the reaction mixture was evaporated and diluted with water, extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 30 % ethyl acetate/hexane to yield 2-((3,4,4-trifluorobut-3- en-l-yl)thio)thiazole-5-carbaldehyde oxime (0.92 g, 87 % yield); LCMS (M+l): 268.75.
Step 4: Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide
To a solution of 2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazole-5-carbaldehyde oxime (0.5 g, 1.8 mmol) in /V, /V- d i m e th y 1 f r m a m i dc (10 mL), potassium carbonate (0.5 g, 3.7 mmol) was added at 25 °C and stirred for 30 min. To the resulting reaction mixture, methyl iodide (0.3 g, 2.2 mmol) was added and stirred further at 50 °C for 6 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to yield a crude product. The obtained crude product was purified by column chromatography using 60-100 % ethyl acetate/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide (0.26 g, 48 % yield). ' H-NMR (400 MHz, DMSO-c/6) d 8.42 (s, 1H), 8.19 (s, 1H), 3.76 (s, 3H), 3.43-3.46 (m, 2H), 2.76-2.87 (m, 2H); LCMS (M+l): 283.10.
Step 5: Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)methanimine oxide
To a solution of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide (0.2 g, 0.7 mmol) in methanol (10 mL), oxone (0.48 g, 0.7 mmol) was added at 0 °C. The reaction mixture was slowly allowed to reach at 25 °C and stirred for 4 h. After completion of the reaction, the reaction mixture was concentrated, the crude material was taken in ethyl acetate (30 mL) and washed with water and brine solution (20 mL). The ethyl acetate layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 80-100 % ethyl hexane/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide. (0.14 g, 68 % yield). 'H-NMR (400 MHz, DMSO-d6) d 8.64 (s, 1H), 8.52 (s, 1H), 3.82 (s, 3H), 3.53-3.61 (m, 1H), 3.34-3.37 (m, 1H), 2.76-2.89 (m, 1H), 2.58-2.67 (m, 1H); LCMS (M+l): 299.05.
Step 6: Preparation of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5- yl)methanimine oxide
To a solution of N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide (0.2 g, 0.7 mmol) in methanol (10 mL), oxone (0.9g, 1.4 mmol) was added at 0 °C. The reaction mixture was slowly allowed to reach 25 °C and stirred for 16 h. After completion of the reaction, the reaction mixture was concentrated, the crude material was taken in ethyl acetate (30 mL) and washed with water and brine solution (20 mL). The ethyl acetate layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 80-100 % ethyl acetate/hexane to yield N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide (0.17 g, 76% yield). Tf-NMR (400 MHz, DMSO-d6) d 8.82 (s, 1H), 8.66 (s, 1H), 3.94 (s, 3H), 3.86 (t, J = 7.0 Hz, 2H), 2.78-2.88 (m, 2H); LCMS (M+l): 315.05.
Example 2: N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2- yl)methanimine oxide
Step 1: Preparation of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde oxime:
To a solution of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde (2 g, 7.8 mmol) in methanol (10 mL), sodium acetate (1.6 g, 19.7 mmol) was added at 0 °C and stirred for 15 min. To the resulting reaction mixture, hydroxylamine hydrochloride (0.8 g, 11.8 mmol) was added at 0 °C. The reaction mixture was allowed to reach 25 °C and stirred further for 2 h. After completion of the reaction, the reaction mixture was evaporated and diluted with ethyl acetate (30 mL) and water (30 mL). The organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 20 % ethyl acetate/hexane to yield 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazole-2-carbaldehyde oxime (1.7 g, 80 % yield); LCMS (M+l): 269.9.
Step 2: Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2- yl)methanimine oxide
To a solution of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde oxime (1 g, 3.71 mmol) in /V, /V- d i m c th y 1 fo r m a m i dc (10 mL), potassium hydroxide (0.313 g, 5.57 mmol) was added at 25 °C and stirred for 30 min. To the resulting reaction mixture, methyl iodide (0.23 ml, 3.7 mmol) was added and stirred further at 25 °C for 6 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 60-100% ethyl acetate/hexane to yield N-methyl-l-(5-((3,4,4-trifluorobut-3-en- l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide (0.5 g, 48 % yield). 1 H-NMR (400 MHz, DMSO- d6) d 8.94 (d, J = 0.7 Hz, 1H), 3.96 (d, J = 0.7 Hz, 3H), 3.57 (t, J = 6.8 Hz, 2H), 2.83-2.94 (m, 2H); LCMS (M+l): 284.1.
Step 3: Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfmyl)-l,3,4-thiadiazol-2- yl)methanimine oxide:
To a solution of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide (0.2 g, 0.7 mmol) in methanol (6 mL) and water (3 mL), oxone (0.35 g, 0.6 mmol was added ) at 0 °C. The reaction mixture was slowly allowed to reach 25 °C and stirred further for 2 h. After completion of the reaction, the reaction mixture was concentrated, neutralized using 10% sodium bicarbonate solution and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 30% ethyl acetate/hexane to yield N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide (0.14 g, 66 % yield). 'H-NMR (400 MHz, CDCL): d 9.15 (s, 1H), 4.04 (d, J = 0.5 Hz, 3H), 3.67-3.74 (m, 1H), 3.51-3.56 (m, 1H), 2.81-2.92 (m, 1H), 2.66-2.76 (m, 1H); LCMS (M+l): 300.1.
Step 4: Preparation of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2- yl)methanimine oxide
To a solution of N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide (0.2 g, 0.7 mmol) in methanol (6 mL) and water (3 mL), oxone (0.9 g, 1.4 mmol) was added at 0 °C. The reaction mixture was slowly allowed to reach 25 °C and stirred for 4 h. After completion of the reaction, the reaction mixture was concentrated, neutralized using 10% sodium bicarbonate solution and extracted twice with ethyl acetate (60 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 30 % ethyl hexane/hexane to yield N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2- yl)methanimine oxide (0.15 g, 65 % yield). 'H-NMR (400 MHz, CDCL): d 9.33 (d, J = 0.7 Hz, 1H), 4.06-4.09 (m, 3H), 4.05 (d, J = 7.1 Hz, 2H), 2.85-2.96 (m, 2H); LCMS (M+l): 315.95.
Example 3: General procedure for synthesis of N-Alkyl/haloalkyl/benzyl/alkene-hydroxylamine hydrochloride
Step 1: Preparation of tert-butyl ((tert-butoxycarbonyl)oxy)(alkyl/haloalkyl/benzyl/alkene)- carbamate intermediate
To a solution of tert-butyl ((tert-butoxycarbonyl)oxy)carbamate (2.0 mmol) in dimethylformamide, sodium hydride (2.8 mmol, 60% in oil) was added slowly portion-wise at 0 °C over a period of 1 min. The reaction mixture was stirred for 1 h at 25 °C and alkyl iodide or alkyl bromide (4.0 mmol) was added at 0 °C. The reaction mixture was stirred 1 h at 25 °C. After completion of the reaction, the reaction mixture was poured into ice-water slowly. The product was appeared slightly non-polar compared to starting material on thin-layer chromatography. The compound was extracted with ethyl acetate, washed with water and brine. The ethyl acetate layer was separated, dried over sodium sulphate and concentrated to obtain a N-alkylated desired crude product, tert-butyl ((tert- butoxycarbonyl)oxy)(alkyl)carbamate (100 % yield) which was used for next step.
Step 2: Preparation of N-alkyl/haloalkyl/alkene/benzyl - hydrox lamine hydrochloride
To a solution of crude material from step-l, tert-butyl ((tert-butoxycarbonyl)oxy)(alkyl)carbamate in dioxane (5 mL), 4 M hydrochloric acid in dioxane (4 mL, 16 mmol) was added and stirred for 16 h. After completion of the reaction, the reaction mixture was concentrated to obtain desired product as N-alkyl/haloalkyl/alkene/benzyl clothi- hydroxylamine as a hydrochloride salt (100 % yield).
Example 4: Preparation of N-ethylhydroxylamine hydrochloride
Step 1: Preparation of tert-butyl ((tert-butoxycarbonyl)oxy)(ethyl)carbamate
The intermediate tert-butyl ((tert-butoxycarbonyl)oxy)(ethyl)carbamate was prepared by following the general procedure as described in example-3, step-l, using ethyl iodide (100 % yield). Tf-NMR (400 MHz, DMSO-d6) d 3.52-3.50 (m, 2H), 1.45 (s, 9H), 1.39 (s, 9H), 1.1 (d, / = 2.4, 7.2 Hz, 2H).
Step 2: Preparation of N-ethylhydroxylamine hydrochloride
The compound N-ethylhydroxylamine hydrochloride was prepared by following the general procedure as described in example-3, step-2, (100 % yield). 1 H-NMR (400 MHz, DMSO-c/6) d 11.34 (s, 1H), 10.7 (s, 1H), 3.17 - 3.06 (m, 2H), 1.22 - 1.11 (m, 3H).
Example 5: Preparation of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2- carbaldehyde
Step 1: Preparation of ethyl 5-bromo-l,3,4-thiadiazole-2-carboxylate
To a solution of tert- butyl nitrite (6.9 mL, 87 mmol) in acetonitrile (100 mL), copper (II) bromide (15.5 g, 69.3 mmol) was added at 0 °C and stirred for 15 min. To the reaction mixture, ethyl 5-amino- l,3,4-thiadiazole-2-carboxylate (10 g, 57.7 mmol) was added slowly and heated to 60 °C for 30 min. After completion of the reaction, the resulting reaction mixture was quenched by adding saturated ammonium chloride solution (50 mL), extracted twice with ethyl acetate (100 mL) and washed with brine (50 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 10 % ethyl acetate/hexane mixture to yield ethyl 5-bromo- l,3,4-thiadiazole-2-carboxylate (10.3 g, 75 % yield), which was used for next step without characterization.
Step 2: Preparation of ethyl 5-mercapto-l,3,4-thiadiazole-2-carboxylate: To a stirred solution of ethyl 5-bromo- 1 ,3,4-thiadiazolc-2-carboxylatc (10 g, 42.2 mmol) in methanol (40 mL), thiourea (4.8 g, 63.3 mmol) was added portion wise at 25 °C and slowly heated to 70 °C for 3 h. After completion of the reaction, the reaction mixture was concentrated and acidified with dilute hydrochloric acid (30 mL) at 0 °C. Precipitated solid was filtered off to obtain ethyl 5-mercapto-l,3,4- thiadiazole-2-carboxylate (6.4 g, 80 % yield) which was used for next step without further purification; LCMS (M+): 190.15.
Step 3: Preparation of ethyl 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2- car boxy late:
To a solution of ethyl 5-mercapto-l,3,4-thiadiazole-2-carboxylate (6 g, 31.5 mmol) in acetonitrile (40 mL), /V,/V-di isopropyl ethyl amine (8.3 ml, 47.3 mmol) was added at 25 °C and stirred for 30 min. To the reaction mixture, 4-Chloro-l,l,2-trifluorobut-l-ene (4.4 ml, 37.8 mmol) was added and stirred further at 80 °C for 12 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (30 mL) and water (30 mL) and acidified to pH 4 using 1N hydrochloric acid. The organic layer was dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 20% ethyl acetate/hexane to yield the titled compound (6.6 g, 70 % yield); LCMS (M+l): 298.80.
Step 4: Preparation of (5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanol:
To a solution of ethyl 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carboxylate (6 g, 20.1 mmol) in tetrahydrofuran (40 mL), sodium borohydride (2.3 g, 60.3 mmol) was added portion wise at 0 °C. The reaction mixture was heated to 55 °C, then methanol (20 mL) was added drop wise to the reaction mixture and stirred for 15 min. After completion of the reaction, the reaction mixture was cooled to 25 °C and acidified using dilute hydrochloric acid (50 mL) and extracted twice with ethyl acetate (100 mL). The ethyl acetate layer was washed with water, brine (50 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 50% ethyl acetate/hexane mixture to yield (5-((3,4,4-trifluorobut-3-en-l- yl)thio)-l,3,4-thiadiazol-2-yl)methanol (4.1 g, 80 % yield); LCMS (M+l): 256.60.
Step 5: Preparation of 5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazole-2-carbaldehyde:
To a cooled solution of (5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanol (3.5 g, 13.7 mmol) in dichloromethane (30 mL), Dess-Martin periodinone (8.7 g, 20.5 mmol) was added portion wise and stirred at 25 °C for 12 h. After completion of the reaction, the reaction mixture was filtered through celite, filtrate was washed with saturated sodium bicarbonate solution (50 mL). The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 10% ethyl acetate/hexane mixture to yield 5-((3,4,4-trifluorobut-3-en-l- yl)thio)-l,3,4-thiadiazole-2-carbaldehyde (2.5 g, 72 % yield). 'H-NMR (400 MHz, CDCI3): d 10.07 (s, 1H), 3.69-3.62 (m, 2H), 2.96-2.86 (m, 2H).
Example 6: General procedure for the synthesis of N-oxide (N-oxide of imine)
The aldehyde/ketone (1 mmol) (e.g example- 1, step-3 and example-4, step-5) was dissolved in methanol (5 mL) then sodium acetate (2.5 mmol) and N-alkyl hydroxylamine hydrochloride (1.5 mmol) were added. The reaction mixture was stirred for 1 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (10 mL). The reaction mixture was quenched with water (10 mL) and extracted twice with ethyl acetate. The combined organic layers were dried over anhydrous sodium sulphate, filtered and concentrated under reduced pressure to obtain a crude product. The obtained crude product was purified by column chromatography using 60-100% ethyl acetate/hexane to yield the titled compound (70-90 % yield).
Example 7: Preparation of (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- ethylmethanimine oxide:
The compound (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N-ethylmethanimine oxide (78 % yield) was prepared by following the general procedure as described in example 6. 1 H-NMR (400 MHz, DMSO-d6) d 8.47 (d, J = 0.5 Hz, 1H), 8.22 (t, J = 6.8 Hz, 1H), 4.60 (dtd, J = 26.6, 7.9, 2.5 Hz, 1H), 3.98 (q, J = 7.3 Hz, 2H), 3.31 (d, J = 7.1 Hz, 2H), 2.42 (ddt, J = 14.8, 7.0, 1.7 Hz, 2H), 1.36 (t, J = 7.2 Hz, 3H); LCMS (M+): 278.1.
Example 8: Preparation of (Z)-N-benzyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide
The compound (Z)-N-benzyl- 1 -(5-((3,4,4-trifluorobut-3-en- 1 -yl)thio)- 1 ,3,4-thiadiazol-2- yl)methanimine oxide was prepared (76 % yield) by following the general procedure as described in example 6. 'H-NMR (400 MHz, DMSO-d6) d 9.17 (s, 1H), 7.48-7.51 (m, 2H), 7.37-7.42 (m, 3H), 5.30 (s, 2H), 3.54 (t, J = 6.7 Hz, 2H), 2.80-2.91 (m, 2H); LCMS (M+l): 360.0.
Example 9: Preparation of (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)oxazol-5- yl)methanimine oxide
The compound (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)oxazol-5-yl)methanimine oxide was prepared (78 % yield) by following the general procedure as described in example 6. 'H-NMR (400 MHz, DMSO-d6) d 8.18 (s, 1H), 8.11 (s, 1H), 3.78 (s, 3H), 3.34-3.46 (m, 2H), 2.81-2.92 (m, 2H); LCMS (M+l): 266.70.
The following Table-I illustrates in a non-limiting manner examples of compounds according to the invention that were prepared using analogous procedures as mentioned in the examples above.
In the following examples, Ή-NMR data of selected examples are written in form of 'H-NMR-peak lists. To each signal peak are listed the d-value in ppm and the no of proton in round brackets.
For calibrating the chemical shift for 1 H spectra, we use tetramethylsilane and/or the chemical shift of the solvent used, especially in the case of spectra measured in dimethyl sulfoxide. Therefore in 'NMR peak lists, tetramethylsilane peak can occur but not necessarily.
5 Table-I:
Figure imgf000053_0001
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
* Compound names generated using Chemdraw Professional 17.1
As described herein the compounds of formula (I) show high nematicidal activity which is exerted with respect to nematodes which attack on important agricultural crops. The compounds of the present invention were also showing high fungicidal activity which is exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops. The compounds of the present invention were assessed for their activity against one or more of the following nematodes and fungal diseases.
Biological examples
Biological Test Examples for Plant parasitic nematodes
Example 1: Meloidogyne incognita (Root-knot nematode ): IN VITRO TEST
The test compounds at a concentration of 300 ppm were introduced into 500 pL of distilled water containing 50 Meloidogyne incognita juveniles into 24-well plates. The suspension was lightly shaken for uniform mixing of compounds. The test plates were covered with lids, and were kept for incubation at 25 °C and 90% relative humidity. Dead/inactive nematodes were counted at an interval of 48, 72 and 96 hours under a microscope and the percent mortality was calculated. After 96 hours after treatment following compounds, 1 2 3 4 5 6 7
9 10 11 12 13 14 15 16 17 18 19 20
21 22 23 24 25 26 27 28 29 30 36 37
38 39 40 41 42 43 44 45 46 47 49 50
51 54 55 74 75 76 77 78 79 80 81 83
84 85 86 92 94 95 96 97 98 99 100 101
102 103 104 105 106 107 108 109 110 111 112 114
115 116 118 119 121 122 124 125 126 127 128 129
130 131 132 133 134 135 136 137 138 139 140 141
142 143 144 145 146 147 150 151 155 156 157 158
159 161 162 163 164 165 166 167 168 169 170 171
172 173 174 175 176 177 178 179 180 181 182 183
184 185 186 187 188 189 190 191 192 193 194 195
196 197 198 199 203 204 at 300 ppm showed more than 70% mortality in the tests, where there was no mortality in the untreated check.
Meloidogyne incognita: IN VIVO TEST
Cucumber plants were grown in seedling trays containing a mixture of Sand:Soil:FYM:Cocopeat in ratio of 1:1: 1:1. One mL of test compounds at the desired concentrations was applied into the soil mixture with the help of a micropipette when the cucumber seedlings were ten days old and inoculated with approximately 2000 freshly hatched second-stage juveniles of Meloidogyne incognita. The treated plants were allowed to grow at 27 °C under greenhouse conditions. Observation of gall rating was recorded after 15 days of application. Plants were carefully uprooted and roots were washed thoroughly. The gall rating was observed on 0-10 scale as described by Zeck (1971) as mentioned below:
0 = no galls
1 = very few small galls
2 = numerous small galls
3 = numerous small galls of which some are grown together
4 = numerous small and some big galls
5 = 25% of roots severely galled
6 = 50% of roots severely galled
7 = 75% of roots severely galled
8 = no healthy roots but plant is still green
9 = roots rotting and plant dying
10 = plant and roots dead Compounds 1 3 4 5 6 9 10 13 15 16 19 20 21 22 24 25 26 27 28 30 38 40
42 74 75 77 79 80 83 84 102 106 108 109
110 114 115 122 136 140 144 156 159 161 162 163
164 166 167 168 170 180 182 188 194 195 196 197
198 at 300 ppm recorded less than 3 gall rating in the tests, where there was extensive galling (up to 8) in untreated check.
Biological Test Examples for fungal pathogens (IN VITRO TEST)
Example 1: Pyricularia oryzae (Rice blast):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 1 2 3 4 6 7
8 9 11 12 13 14 15 16 17 18 19 20
21 22 23 24 26 28 30 32 33 34 37 40 41
42 43 44 45 46 47 48 49 52 56 57 58
60 64 65 66 67 68 71 72 73 74 75 76
78 81 82 85 86 88 90 92 93 97 98 99
100 101 102 103 107 108 109 110 112 118 119 120
122 123 124 125 129 130 135 136 137 138 139 140
141 142 143 146 149 150 151 155 156 157 158 159
160 161 162 163 164 165 166 167 168 169 170 171
172 173 174 175 176 179 180 181 182 183 184 185
187 188 189 191 192 194 197 199 200 205 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 2: Rhizoctonia solani (Rice sheath blight/Potato black scurf):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 25 °C and 60% relative humidity for seven days and radial growth was measured. Compounds 14 21 22 23 27 38 46 47 48 74 81 82 125 135 137 155 156 157 158 159
160 161 162 163 166 170 173 176 179 180 181 182
184 185 188 189 191 194 205 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 3: Botrytis cinerea (Gray mold):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 22 °C and 90% relative humidity for seven days and radial growth was measured. Compounds 2 20 21 30 48 74 75 76
81 82 119 125 137 151 157 158 160 163 166 170
171 173 175 176 179 180 184 185 187 188 191 205 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 4: Alternaria solani (early blight of tomato/potato):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 25 °C and 60% relative humidity for seven days and radial growth was measured. Compounds 3 7 9 11 16 21 28 30
40 43 44 56 57 120 137 148 160 162 163 168
170 173 176 179 180 182 184 185 189 190 191 194
199 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 5: Colletotrichum capsici (anthracnose):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 25 °C and 60% relative humidity for seven days and radial growth was measured. Compounds 14 40 41 44 76 81 82 85
103 123 135 137 138 142 156 157 159 160 162 163
167 168 170 178 179 181 182 184 185 188 189 194 199 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 6: Corynespora cassicola (Leaf spot of tomato):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to potato dextrose agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 25 °C and 70% relative humidity for seven days and radial growth was measured. Compounds 13 44 56 76 81 82 135 161 163 167 168 180 194 205 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Having described the invention with reference to certain preferred aspects, other aspects will become apparent to one skilled in the art from consideration of the specification. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.

Claims

CLAIMS:
1) A compound of formula (I),
Figure imgf000075_0001
Formula (I)
wherein;
A represent O, NR5 or S;
A1 represents C or N;
R1 is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-Ce- haloalkyl, C2-C6-haloalkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkyl-Ci-C6-alkyl, C6-Cio-aryl-Ci-C6- alkyl and C4-Cio-heterocyclyl-Ci-C6-alkyl; each group of R1 may be optionally substituted by one or more groups selected from the group consisting of X, C6-Cio-aryl, CVCi -hctcrocyclyl. R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN and CON(R5a)2;
R2 is selected from the group consisting of hydrogen, X, CN, (C=0)-R5b, OR4, N(R4)2. S(0)nR5b, Ci- C6-alkyl, Ci-C6-haloalkyl and C3-C6-cycloalkyl; each group of R2 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R3 is selected from the group consisting of hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C3-C10- cycloalkyl, C6-Cio-aryl and Ci-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and C3-C6-cycloalkyl-Ci-C6-alkyl; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-Ci2-cycloalkyl, C6-Cio-aryl and C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)„R5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5a is selected from the group consisting of hydrogen, X, Ci-C6-alkyl and C3-C6-cycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl and C3-C6-cycloalkyl;
X represents halogen;
n represents integers wherein n=0-2;
or agriculturally acceptable salts, stereoisomer, tautomers or N-oxides thereof.
2) The compound as claimed in claim 1, wherein said compound of formula (I) is represented by formula (la)
Figure imgf000076_0001
Formula (la)
wherein;
A represents O or S;
R2 is selected from the group consisting of hydrogen, X, CN, (C=0)-R5b, OR4, N(R4)2, S(0)nR5b, Ci- C6-alkyl, Ci-C6-haloalkyl and C3-C6-cycloalkyl; each group of R2 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R3 is selected from the group consisting of hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C3-C10- cycloalkyl, C6-Cio-aryl and Ci-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and C3-C6-cycloalkyl-Ci-C6-alkyl; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-C6-haloalkyl, C3-Ci2-cycloalkyl, C6-Cio-aryl and C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)„R5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5a is selected from the group consisting of hydrogen, X, Ci-Gi-alkyl and C3-C6-cycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl and C3-C6-cycloalkyl; X represents halogen;
n represents integers wherein n=0-2.
3) The compound as claimed in claim 1, wherein said compound of formula (I) is represented by formula (lb)
Figure imgf000077_0001
Formula (lb)
wherein;
A represent O or S;
R3 is selected from the group consisting of hydrogen, Ci-Ci2-alkyl, Ci-Ci2-haloalkyl, C3-C10- cycloalkyl, C6-Cio-aryl and Ci-Cio-heterocyclyl; each group of R3 may be optionally substituted by one or more groups selected from the group consisting of X, R5a, OR5a, SR5a, N(R5a)2, COOR5a, CN, and CON(R5a)2;
R4 is selected from the group consisting of Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C6-haloalkyl C3-Ci2-cycloalkyl, C3-Cio-halocycloalkyl and C3-C6-cycloalkyl-Ci-C6-alkyl; each group of R4 may be optionally substituted by one or more groups selected from the group consisting of X, aryl, heteroaryl, R5a, OR5a, SR5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5 is selected from the group consisting of hydrogen, Ci-Ce-alkyl, Ci-C6-haloalkyl, C3-Ci2-cycloalkyl, C6-Cio-aryl and C4-C6-heterocyclyl; wherein aryl and heterocyclyl groups are further substituted with R5b; each group of R5 is optionally substituted by one or more groups selected from the group consisting of X, CN, R5a, OR5a, S(0)„R5a, N(R5a)2, Si(R5a)3, COOR5a, CN, and CON(R5a)2;
R5a is selected from the group consisting of hydrogen, X, Ci-Gi-alkyl and C3-G5-cycloalkyl;
R5b is selected from the group consisting of hydrogen, X, CN, OR5a, S(0)nR5a, N(R5a)2, Si(R5a)3, COOR5a, CON(R5a)2, Ci-C6-alkyl, C2-C6-alkenyl, Cz-G.-alkynvl. Ci-C6-haloalkyl, C2-C6-haloalkenyl, C2-C6-haloalkynyl and C3-C6-cycloalkyl;
X represents halogen;
n represents integers wherein n=0-2.
4) The compound of formula (I) as claimed in claim 1, wherein said compound of formula (I) is selected from (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- isopropylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)sulfmyl)thiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-N-methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)thiazol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfonyl)thiazol-5- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)sulfmyl)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -cn-l -yl)suironyl)thiazol-5-yl)-N- ethylmethanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-N-ethyl- 1 -(2-((3 ,4,4-trilluorobut-3 -en-1 -yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N- ethyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl-l- (2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)-l- (2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)- 1 -(2-((3 ,4,4-trifluorobut-3 -en-1 -yl)sulfony l)thiazol-5-yl)methanimine oxide, (Z)-N-
(cyclobutylmethyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N- (cyclopropylmethyl)-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N- (cyclopropylmethyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-l-(2- ((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N-isobutylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)-N-isobutylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut- 3 -en- 1 -yl)sulfonyl)thiazol-5-yl)-N-isobuty lmethanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((4,4- difluorobut-3 -en- 1 -y l)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((4,4- difluorobut-3 -en- 1 -y l)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)- 1 -(2-((4,4- difluorobut-3 -en- 1 -y l)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclobutylmethyl)- 1 -(2-((4,4- difluorobut-3 -en- 1 -y l)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-(butylthio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(butylthio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2- (butylsulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- N-methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en-1 -yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-isopropyl- 1 - (2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3,4,4- trilluorobut-3 -en- 1 -yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-methyl- 1 -(4-methyl-2-((3 ,4,4- trilluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut- 3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut- 3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-methyl-2-((3,4,4-trifluorobut- 3 -en- 1 -yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl- 1 -(4-methyl-2-((3 ,4,4-trifluorobut-3 - en- 1 -yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl- 1 -(4-methyl-2-((3 ,4,4-trifluorobut-3 -en- l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol- 5-yl)ethan- 1 -imine oxide, (Z)-N-ethyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)thiazol-5 -yl)ethan-l - imine oxide, (Z)-N-ethyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfonyl)thiazol-5-yl)ethan-l -imine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)ethan-l-imine oxide, (Z)- N-methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en-1 -yl)sulfonyl)thiazol-5-yl)ethan- 1 -imine oxide, (Z)-N- methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en-1 -yl)sulfinyl)thiazol-5-yl)ethan- 1 -imine oxide, (Z)- 1 -(2-
(butylthio)thiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l-(2-((3-lluoropropyl)thio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)-N-isopropyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)thiazol-4- yl)methanimine oxide, (Z)-l-(2-(benzylthio)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2- (benzylthio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2-(benzylsulfinyl)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-(benzylsulfinyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)- l-(2-(benzylsulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2-(benzylsulfonyl)thiazol- 5-yl)-N-methylmethanimine oxide, (Z)-N-ethyl-l-(2-((3-fluoropropyl)thio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((3-fluoropropyl)thio)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-N-isopropyl- l-(2-((2,2,2-trifluoroethyl)thio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-(butylsulfmyl)thiazol-5-yl)- N-ethylmethanimine oxide, (Z)-l-(2-(butylsulfonyl)thiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l- (2 -((3 -fluoropropyl)sulfinyl)thiazol-5 -yl)-N-methylmethanimine oxide, (Z)- 1 -(2-((3 - fluoropropyl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-((3- fluoropropyl)sulfinyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-l-(2-((3- fluoropropyl)sulfonyl)thiazol-5-yl)-N-isopropylmethanimine oxide, (Z)-N-ethyl-l-(2-((3- fluoropropyl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-((3- fluoropropyl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(2-(prop-2-yn-l- ylthio)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)-4-methylthiazol-5- yl)-N-methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)-4-methylthiazol-5-yl)-N- ethylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)thio)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)-4-methylthiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)-4-methylthiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)-4-methylthiazol-5-yl)-N- isopropylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((3,4,4-trilluorobut-3-en-l-yl)thio)thiazol-5-yl)- N-methylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-l-(4-cyclopropyl-2-((4,4-difluorobut-3-en-l-yl)sulfmyl)thiazol-5-yl)- N-methylmethanimine oxide, (Z)- 1 -(4-cyclopropyl-2-((4,4-difluorobut-3 -en- 1 -yl)sulfonyl)thiazol-5- yl)-N-methylmethanimine oxide, (Z)- 1 -(4-cyclopropyl-2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)sulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)- 1 -(4-cyclopropyl-2-((3 ,4,4-trifluorobut-3 - en-l-yl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-l-(2-(allylthio)thiazol-5-yl)-N- methylmethanimine oxide, (Z)-N-methyl-l-(2-(prop-2-yn-l-ylsulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl-l-(2-(prop-2-yn-l-ylthio)thiazol-5-yl)methanimine oxide, (Z)-l-(2- (allylsulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-ethyl- 1 -(2-(prop-2-yn- 1 - ylsulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl-l-(4-phenyl-2-((3,4,4-trifluorobut-3-en-l- y l)thio)thiazol-5 -y l)methanimine oxide, (Z) -N-ethy 1- 1 -(4 -pheny l-2-((3 ,4 ,4-trifluorobut-3 -en- 1 - yl)thio)thiazol-5-y l)methanimine oxide, (Z)-N-methyl- 1 -(4-phenyl-2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-ethyl- 1 -(4-phenyl-2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-methyl- 1 -(4-phenyl-2-((3 ,4,4-trifluorobut-3 -en- 1 - y l)sulfony l)thiazol-5 -y l)methanimine oxide, (Z) -N-ethy 1- 1 -(4 -pheny l-2-((3 ,4 ,4-trifluorobut-3 -en- 1 - yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzy 1- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l- yl)thio)thiazol-5-y l)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)thio)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-N-benzyl- 1 -(2-((4,4-difluorobut-3 -en- 1 -y l)thio)thiazol-4- yl)methanimine oxide, (Z)-N-methyl-l -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfmyl)thiazol-4-yl)-N- methylmethanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-4- yl)methanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-4- yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)thio)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N- benzyl-l-(2-((4,4-difluorobut-3-en-l-yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4- difluorobut-3 -en- 1 -y l)thio)-4-phenylthiazol-5-yl)-N-methylmethanimine oxide, (Z)- 1 -(2 -((4, 4- difluorobut-3 -en- 1 -y l)thio)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)- 1 -(2 -((4,4- difluorobut-3-en-l-yl)sulfinyl)-4-phenylthiazol-5-yl)-N -methylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3-en-l-yl)sulfinyl)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)-l-(2-((4,4- difluorobut-3 -en- 1 -y l)sulfonyl)-4-phenylthiazol-5-yl)-N-methylmethanimine oxide, (Z)- 1 -(2-((4,4- difluorobut-3-en-l-yl)sulfonyl)-4-phenylthiazol-5-yl)-N-ethylmethanimine oxide, (Z)-N-cyclohexyl- l-(2-((3,4,4-trifluorobut-3-en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2- ((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((3,4,4- trifluorobut-3 -en- 1 -yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(2-methoxy ethyl)- 1 -(2-((3 ,4,4- trifhiorobut-3 -en- 1 -yl)thio)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en-1 - yl)sulfonyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-benzy 1- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-benzyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-4-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)thiazol-4-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((3 ,4,4-trifluorobut-3 -en- l-yl)sulfinyl)thiazol-4-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((4,4-difluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(2-((3 ,4,4-trifluorobut-3 - en- 1 -yl)sulfonyl)thiazol-4-yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 - yl)sulfinyl)thiazol-5-yl)-N-methylmethanimine oxide, (Z)-N-phenyl-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2-methoxyethyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -en- 1 -yl)thio)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)- 1 -(2-((4,4-difluorobut-3 -cn- l -yl)suironyl)thiazol-5-yl)-N- phenylmethanimine oxide, (Z)-N-phenyl-l-(2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5- yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)thio)thiazol-5-yl)-N-(2- methoxyethyl)methanimine oxide, (Z)-N-(2-methoxyethyl)-l -(2-((3 ,4,4-trilluorobut-3 -en- 1 - yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-l-(2-((4,4-difluorobut-3-en-l-yl)sulfinyl)thiazol-5- yl)-N-(2-methoxyethyl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfinyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(4-chlorobenzyl)-l-(2-((3,4,4-trifluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((3,4,4-trilluorobut-3- en-l-yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2-chlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)thio)thiazol-5-yl)methanimine oxide, (Z)-N-(2,6-dichlorobenzyl)-l-(2-((4,4-difluorobut-3-en-l- yl)sulfonyl)thiazol-5-yl)methanimine oxide, (Z)-N-allyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 - yl)thio)thiazol-5-y l)methanimine oxide, (Z)-N-(2-chloroethyl)- 1 -(2-((3 ,4,4-trilluorobut-3 -en- 1 - yl)thio)thiazol-5-yl)methanimine oxide, l-(4-chloro-2-((3,4,4-trilluorobut-3-en-l-yl)thio)thiazol-5- yl)-N-methylmethanimine oxide, (Z)-N-methyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-methyl- 1 -(5-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfonyl)-l ,3 ,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-methyl- 1 -(5-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)-l ,3 ,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl-l-(5-((3,4,4-trilluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl- 1 -(5-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)-l ,3 ,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-ethyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)- 1-(5 -((4,4-difluorobut-3 -en-1 -yl)thio)- 1 ,3 ,4-thiadiazol-2-y 1)- N-methylmethanimine oxide, (Z)- 1-(5 -((4,4-difluorobut-3 -en- 1 -yl)sulfinyl)-l ,3 ,4-thiadiazol-2-yl)-N- methylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N- methylmethanimine oxide, (Z)-N-isopropyl- 1 -(5-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)-l ,3 ,4-thiadiazol- 2-yl)methanimine oxide, (Z)-N-isopropyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)- l-(5-((4,4-difluorobut-3 -en-1 -yl)thio)- 1 ,3 ,4-thiadiazol-2-y 1)- N-ethylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2-yl)-N- ethylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N- ethylmethanimine oxide, (Z)-N-cyclohexyl-l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-cyclohexyl- 1 -(5 -((4,4-difluorobut-3 -en- 1 -yl)sulfonyl)-l ,3 ,4-thiadiazol- 2-yl)methanimine oxide, (Z)-N-cyclohexyl- 1 -(5-((3 ,4,4-trifluorobut-3 -en-1 -yl)thio)- 1 ,3,4-thiadiazol-
2-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((3,4,4-trilluorobut-3-en-l-yl)thio)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-cyclohexyl-l-(5-((3,4,4-trifluorobut-3-en-l-yl)sulfonyl)- 1 ,3 ,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(5-((3 ,4,4-trilluorobut-3 -en- 1 - yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((3,4,4-trifluorobut-3-en-l- yl)sulfinyl)- 1 ,3 ,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-benzy 1- 1 -(5-((3 ,4,4-trilluorobut-3 -en-1 - yl)sulfonyl)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)-l-(5-((3,4,4- trilluorobut-3 -en- 1 -yl)sulfinyl)-l ,3 ,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- l-(5-((4,4-difluorobut-3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-
(cyclopropylmethyl)- 1 -(5-((3 ,4,4-trifluorobut-3 -en- l-yl)sulfonyl)- 1 ,3 ,4-thiadiazol-2-yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(5-((4,4-difluorobut-3 -en- 1 -yl)sulfinyl)- 1 ,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-benzyl- 1 -(5 -((4,4-difluorobut-3 -en-1 -yl)thio)- 1 ,3,4-thiadiazol-2- yl)methanimine oxide, (Z)-N-(cyclopropylmethyl)- 1 -(5-((4,4-difluorobut-3 -en- 1 -yl)sulfonyl)-l ,3 ,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)-N-benzyl-l-(5-((4,4-difluorobut-3-en-l-yl)sulfonyl)-l,3,4- thiadiazol-2-yl)methanimine oxide, (Z)- 1-(5 -((4,4-difluorobut-3 -en-1 -yl)thio)- 1 ,3 ,4-thiadiazol-2-y 1)- N-(2-methoxyethyl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l-yl)sulfinyl)-l,3,4- thiadiazol-2-yl)-N-(2-methoxyethyl)methanimine oxide, (Z)- 1 -(5-((4,4-difluorobut-3 -en- 1 - yl)sulfonyl)-l,3,4-thiadiazol-2-yl)-N-(2-methoxyethyl)methanimine oxide, (Z)-l-(5-((4,4-difluorobut-
3-en-l-yl)thio)-l,3,4-thiadiazol-2-yl)-N-phenylmethanimine oxide, (Z)-l-(5-((4,4-difluorobut-3-en-l- yl)sulfinyl)- 1 ,3 ,4-thiadiazol-2-yl)-N-phenylmethanimine oxide, N-isopropyl- 1 -(2-((3 ,4,4-trifluorobut- 3 -en- 1 -yl)thio)oxazol-5-y l)methanimine oxide, N-ethy 1- 1 -(2-((3 ,4,4-trilluorobut-3-en-l - yl)thio)oxazol-5-yl)methanimine oxide, N-ethy 1- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)o\azol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -(4-methyl-2-((3 ,4,4-trifluorobut-3-en- 1 -yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -(4-methyl-2-((3 ,4,4-trifluorobut-3 -en- 1 -y l)sullinyl)oxazol-5- yl)methanimine oxide, (Z)-N-isopropyl-l-(4-methyl-2-((3,4,4-trifluorobut-3-en-l-yl)sulfinyl)oxazol- 5-yl)methanimine oxide, (Z)-N-methyl- 1 -(2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -(2 -((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)oxazol-5- yl)methanimine oxide, (Z)-N -ethyl- 1 -(4-methyl-2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)oxazol-5- yl)methanimine oxide, (Z)-N-methyl- 1 -( 1 -methyl-2 -((3 ,4,4-trifluorobut-3 -en- 1 -y l)thio)-lH-imidazol- 5-yl)methanimine oxide, (Z)-N-ethyl-l-(l-methyl-2-((3,4,4-trifluorobut-3-en-l-yl)thio)-lH-imidazol- 5-yl)methanimine oxide, (Z)-N-methyl-l -( 1 -methyl-2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)sulfinyl)-lH- imidazol-5-yl)methanimine oxide, (Z)-N-isopropyl- 1 -( 1 -methyl-2-((3 ,4,4-trifluorobut-3 -en- 1 -yl)thio)- lH-imidazol-5-yl)methanimine oxide and (Z)-N-methyl-l-(4-methyl-5-((3,4,4-trifluorobut-3-en-l- yl)thio)-4H- 1 ,2,4-triazol-3 -yl)methanimine oxide.
5) A process for preparing a compound of formula (I) and/or a salt thereof as claimed in claim 1, wherein said process comprises at least one of the following steps (a) to (c):
a) reacting a compound of formula 3 with a substituted hydroxyl amine salt optionally in the presence of a suitable base and a suitable solvent to afford a compound of formula 2a, according to the reaction scheme as depicted below;
Figure imgf000083_0001
Solvent I X - ’
2a
b) oxidizing the compound of formula 2a in the presence of a suitable oxidizing agent to afford compound formula 2b according to the reaction scheme as depicted below;
Q
Q o
v -
©»? 1 A . ' N \\ i Oxidizing © I
Figure imgf000083_0002
ft r1
R4 N^^ x^~-S/ R4 Ύ cΉ
reagent
R4
2a 2b
c) oxidizing the compound of formula 2b in the presence of a suitable oxidizing agent to afford compound formula (I) according to the reaction scheme as depicted below;
Figure imgf000083_0003
6) A composition for controlling or preventing phytopathogenic microorganisms comprising a compound of formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof as claimed in claim 1 and one or more inert carriers.
7) The composition as claimed in claim 6, wherein said composition may additionally comprises one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers. 8) The composition as claimed in claim 6 or 7, wherein the concentration of the compound of general formula (I) ranges from 1 to 90% 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.
9) A combination comprising the compound of formula (I), stereoisomer, agriculturally acceptable salts, tautomers or N-oxides thereof as claimed in claim 1 and one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients and fertilizers.
10) Use of compound of formula (I), stereoisomers, agriculturally acceptable salts, tautomers or N- oxides thereof or composition or combination thereof as claimed in claim 1 or 6 or 9, for controlling or preventing agricultural crops and/or horticultural crops against phytopathogenic fungi, bacteria, insects, nematodes, mites.
11) The use of compound of general formula (I) as claimed in claim 10, for controlling or preventing agricultural crops and/or horticultural crops against nematodes and phytopathogenic fungi.
12) The use of the compounds of general formula (I) as claimed in claim 10 or 11, wherein said agricultural crops are selected from cereals, com, rice, soybean and other leguminous plants, fruits and fruit trees, 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, other vegetables and ornamentals.
13) A seed comprising compound of formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof as claimed in claim 1 or 6 or 9, wherein the amount of the compound of the formula (I) or an N-oxide or an agriculturally acceptable salt thereof is ranging from 0.1 g to 10 kg per 100 kg of seed.
14) A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof as claimed in claim 1 or 6 or 9, is applied to the plants, to parts thereof or a locus thereof.
15) A method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof as claimed in claim 1 or 6 or 9 is applied to the seeds of plants.
16) A method of controlling or preventing phytopathogenic microorganisms in agricultural crops and or horticultural crops using the compound of formula (I) and/or stereoisomers or agriculturally acceptable salts or tautomers or N-oxides thereof or composition or combination thereof as claimed in claim 1 or 6 or 9 comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 1 g to 5 kg per hectare of agricultural and/or horticultural crops.
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