WO2022058878A1 - Nouveaux composés picolinamide pour lutter contre des champignons phytopathogènes - Google Patents

Nouveaux composés picolinamide pour lutter contre des champignons phytopathogènes Download PDF

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Publication number
WO2022058878A1
WO2022058878A1 PCT/IB2021/058347 IB2021058347W WO2022058878A1 WO 2022058878 A1 WO2022058878 A1 WO 2022058878A1 IB 2021058347 W IB2021058347 W IB 2021058347W WO 2022058878 A1 WO2022058878 A1 WO 2022058878A1
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ethyl
carbamoyl
oxadiazol
methoxypyridin
methoxy
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PCT/IB2021/058347
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English (en)
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Sachin Baban NARUTE
Chandrashekhar Lilachand PATIL
Rohit Saxena
Ruchi GARG
Santosh Shridhar AUTKAR
Alexander G.M. KLAUSENER
Ramdas Balu GADAKH
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Pi Industries Limited
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Priority to EP21798096.0A priority Critical patent/EP4214203A1/fr
Publication of WO2022058878A1 publication Critical patent/WO2022058878A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D498/04—Ortho-condensed systems

Definitions

  • the present invention relates to novel picolinamide compounds which are useful in combating phytopathogenic fungi, and to a process for preparing these picolinamide compounds.
  • the present invention also relates to a composition, a combination comprising these novel picolinamide compounds, and a method for combating phytopathogenic fungi using the same.
  • Picolinamide compounds are described as fungicidal agents in WO2016109288, WO2016109289, WO2016109300, WO2016109301, WO2016109302, WO2016109303, WO200114339, and WO2016122802.
  • the picolinamide compounds reported in the above cited literature have disadvantages in certain aspects, such as that they exhibit a narrow spectrum of efficacy or that they do not have satisfactory fungicidal activity, particularly at low application rates.
  • fungicidal compounds including such that are belonging to the class of the above cited picolinamides, so as to provide compounds being effective against a broader spectrum of fungi, having lower toxicity, higher selectivity, being used at lower dosage rate to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective and long-lasting control. Therefore, it is an objective of the present invention to provide compounds having an improved/enhanced activity and/or a broader efficacy spectrum against phytopathogenic fungi. This objective is achieved by using a compound of formula (I) of the present invention for combating phytopathogenic fungi.
  • the present invention relates to a compound of formula (I), Formula (I) wherein, R 1 , R 1a , R 2 , W, R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and A are as defined in the detailed description.
  • the present invention also relates to a process for preparing the compound of formula (I).
  • the compounds of formula (I) have been found to be advantageous over the compounds reported in the literature in either of improved fungicidal activity, broader spectrum of biological efficacy, lower application rates, more favourable biological, environmental properties or enhanced plant compatibility.
  • the present invention further relates to an agrochemical composition comprising a compound of formula (I) or a compound of formula (I) in combination with a further pesticidally active substance for controlling and/or preventing plant diseases, particularly caused by phytopathogenic fungi.
  • the present invention still further relates to a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a fungicidally effective amount of a compound of formula (I), a composition or a combination thereof, is applied to the plants, to parts thereof or the locus thereof.
  • transitional phrase “consisting of” excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith.
  • 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.
  • invertebrate pest includes arthropods, gastropods and nematodes, helminths, fungi, bacteria and viruses of economic importance as pests.
  • arthropod includes insects, mites, spiders, scorpions, centipedes, millipedes, pill bugs and symphylans.
  • gastropod includes snails, slugs and other Stylommatophora.
  • nematode refers to a living organism of the Phylum Nematoda.
  • helminths includes roundworms, heartworms, phytophagous nematodes (Nematoda), flukes (Tematoda), acanthocephala and tapeworms (Cestoda).
  • 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, feed 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.
  • 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), 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.
  • a compound of the present invention typically in the form of a composition formulated for veterinary use, to the animal to be protected.
  • parasitic 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.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” or - N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched C 1 to C 24 alkyl, preferably C 1 to C 15 alkyl, more preferably C 1 to C 10 alkyl, most preferably C 1 to C 6 alkyl.
  • Non- limiting examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylprop
  • 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, hydroxy, halogen, carbonyl, carbonyloxy and the like, are at the end.
  • alkenyl used either alone or in compound words includes straight-chain or branched C 2 to C 24 alkenes, preferably C 2 to C 15 alkenes, more preferably C 2 to C 10 alkenes, most preferably C 2 to C 6 alkenes.
  • Non-limiting examples of alkenes include ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2 -propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1- butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3- butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2 -propenyl, 1-ethyl-1-propenyl, 1-ethyl-2
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. This definition also applies to alkenyl as a part of a composite substituent, for example haloalkenyl and the like, unless defined specifically elsewhere.
  • Non-limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3- butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1- methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl -2- propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3- pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-penty
  • alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere.
  • alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • cycloalkyl means alkyl closed to form a ring. Non-limiting examples include cyclopropyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl etc., unless specifically defined elsewhere.
  • cycloalkenyl means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non-limiting examples include cyclopropenyl, cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as a part of a composite substituent, for example cycloalkenylalkyl etc., unless specifically defined elsewhere.
  • cycloalkynyl means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. Non-limiting examples include cyclopropynyl, cyclopentynyl and cyclohexynyl.
  • cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere.
  • cycloalkoxy “cycloalkenyloxy” and the like are defined analogously. Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl etc., unless specifically defined elsewhere.
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • haloalkyl when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2- fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 1,1-dichloro
  • haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.
  • haloalkenyl “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, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2- dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and 1,1,1-trifluoroprop-2-oxy.
  • haloalkylthio means straight-chain or branched alkylthio groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above.
  • Non-limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1- bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio, pentafluoroethylthio and 1,1,1-triflu
  • haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere.
  • haloalkylsulfinyl include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • hydroxy means —OH
  • Amino means —NRR, wherein R can be H or any possible substituent such as alkyl.
  • sulfinyl means SO
  • sulfonyl means S(O) 2 .
  • alkoxy used either alone or in compound words included C 1 to C 24 alkoxy, preferably C 1 to C 15 alkoxy, more preferably C 1 to C 10 alkoxy, most preferably C 1 to C 6 alkoxy.
  • alkoxy examples include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy, 1,1- dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2-dimethylpropoxy, 1- ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1-methylpentoxy, 2- methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3- dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2- ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy and 1-ethyl-2- methylpropoxy and the different isomers.
  • alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1- dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2- dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio,
  • Halocycloalkyl, halocycloalkenyl, alkylcycloalkyl, cycloalkylalkyl, cycloalkoxyalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, haloalkylcarbonyl, cycloalkylcarbonyl, haloalkoxylalkyl, and the like, are defined analogously to the above examples.
  • alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include -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 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 methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1- methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2-methylpropylsulphinyl, 1,1- dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2-methylbutylsulphinyl, 3- methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1- dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl, 1-methylpentylsulphinyl, 2- methylpentylsulphinyl, 3-methylpentylsulphinyl, 4-methylp
  • 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 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-methylpentylsulphony
  • arylsulfonyl includes Ar-S(O) 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. “Alkylamino”, “dialkylamino”, and the like, are defined analogously to the above examples.
  • carrier or carbocyclic includes “aromatic carbocyclic ring system” and “non-aromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not statisfied).
  • 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; non-limiting examples thietanyl, oxetanyl, oxiranyl, azetidinyl, aziridinyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3- tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-pyr
  • heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere.
  • heteroaryl or “aromatic heterocyclic” means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom; 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, non-limiting examples furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazoly
  • 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, non-limiting examples 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4- pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin- 3-yl and 1,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: non-limiting examples indol-1-yl, indol- 2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol
  • 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.
  • “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.
  • 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.
  • the total number of carbon atoms in a substituent group is indicated by the “C i -C j ” prefix where i and j are numbers from 1 to 21.
  • C 1 -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • the inventive compound of the present invention may, if appropriate, be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example E and Z, threo and erythro, and also optical isomers, but if appropriate also of tautomers. Both the E and the Z isomers, and also the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers and the possible tautomeric forms are disclosed and claimed.
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • beneficial effects e.g., suitability for preparation of useful formulations, improved biological performance
  • the preparation and isolation of a particular polymorph of a compound represented by formula (I) can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • the term “pest” for the purpose of the present disclosure includes but is not limited to fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and rodents.
  • the term “plant” is understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • the term “plant” includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, ferns, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis.
  • Examples of “plant” for the purpose of the present invention include but are not limited to agricultural crops such as wheat, rye, barley, triticale, oats or rice; beet, e.g.
  • sugar beet or fodder beet fruits and fruit trees, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit and citrus trees, such as oranges, lemons, grapefruits or mandarins; any horticultural plants, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; cucurbitaceae; oleaginous plants; energy and raw material plants, such as
  • the plant for the purpose of the present invention includes but is not limited to cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and vegetables, ornamentals, any floricultural plants and other plants for use of human and animals.
  • plant parts is understood to mean all parts and organs of plants above and below the ground.
  • plant parts includes but is not limited to cuttings, leaves, twigs, tubers, flowers, seeds, branches, roots including taproots, lateral roots, root hairs, root apex, root cap, rhizomes, slips, shoots, fruits, fruit bodies, bark, stem, buds, auxillary buds, meristems, nodes and internodes.
  • locus thereof includes soil, surroundings of plant or plant parts and equipment or tools used before, during or after sowing/planting a plant or a plant part.
  • compositions optionally comprising other compatible compounds to a plant or a plant material or locus thereof include application by a technique known to a person skilled in the art which include but is not limited to spraying, coating, dipping, fumigating, impregnating, injecting and dusting.
  • applied means adhered to a plant or plant part either physically or chemically including impregnation.
  • the present invention provides a novel compound of formula (I), Formula (I) wherein, R 1 is selected from the group consisting of hydroxy, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 - cycloalkyl, C 1 -C 6 -alkoxy, C 3 -C 6 -cycloalkyloxy, C 1 -C 6 -alkylthio, C 1 -C 6 -cycloalkylthio, -NHR 9 and - N(R 9 ) 2 ; R 1a is selected from the group consisting of hydroxy, halogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 - haloalkyl and C 1 -C 6 -alkoxy; R 2 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C
  • the compound of formula (I) is represented by compound of formula (Ia); Formula (Ia) In another embodiment, the compound of formula (I) is represented by compound of formula (Ib); Formula (Ib) In yet another embodiment, the compound of formula (I) is represented by compound of formula (Ic); Formula (Ic) In still another embodiment, the compound of formula (I) is represented by compound of formula (Id); Formula (Id) In yet still another embodiment, the compound of formula (I) is represented by compound of formula (Ie); Formula (Ie) In yet still another embodiment, the compound of formula (I) is represented by compound of formula (If); Formula (If) In yet still another embodiment, the compound of formula (I) is represented by compound of formula (Ig); Formula (Ig) In preferred embodiment, the present invention provides a compound of formula (I) wherein, R 1 is selected from the group consisting of hydroxy, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C
  • the present invention provides a compound of formula (I), wherein R 1 is selected from the group consisting of hydroxy, halogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 3 -C 6 - cycloalkyl, C 1 -C 6 -alkoxy and C 3 -C 6 -cycloalkyloxy; R 2 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 -alkoxy-C 1 - C 6 -alkyl, -C(O)-R 9 , -C(O)-OR 9 and –(CH 2 ) m -O-C(O)-R 9 ; R 3 is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxy;
  • R 1 is selected from the group consisting of hydroxy, C 1 -C 6 - alkoxy and C 3 -C 6 -cycloalkyloxy.
  • R 2 is selected from the group consisting of hydrogen, C 1 -C 6 - alkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, -C(O)-R 9 , -C(O)-OR 9 and –(CH 2 ) m -O-C(O)-R 9 .
  • R 3 is selected from the group consisting of hydrogen, C 1 -C 6 - alkyl and C 3 -C 6 -cycloalkyl.
  • R 4 and R 5 are independently selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl and C 3 -C 6 - cycloalkyl; or R 4 and R 5 together with the atoms to which they are attached may form a 3 to 6 membered non-aromatic carbocyclic ring; the ring may be optionally substituted with one or more identical or different groups of R 4a .
  • the compound of formula (I) is selected from (S)-3-hydroxy-4- methoxy-N-(1-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)picolinamide, (S)-4-methoxy-2-((1-(5-phenyl- 1,2,4-oxadiazol-3-yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate, (S)-4-methoxy-2-((1-(5-phenyl-1,2,4- oxadiazol-3-yl)ethyl)carbamoyl)pyridin-3-yl acetate, (S)-ethyl (2-((1-(5-(4-fluorophenyl)-1,2,4- oxadiazol-3-yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl) carbonatecarbonate, (S)-2-
  • the agriculturally acceptable salts of the compounds of formula (I) encompass especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the fungicidal action of the compounds of formula (I).
  • Suitable cations are thus in particular the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, of the transition metals, preferably manganese, copper, zinc and iron, and also the ammonium ion which, if desired, may carry one to four C 1 -C 4 -alkyl substituents and/or one phenyl or benzyl substituent, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(C 1 -C 4 -alkyl)sulfonium, and sulfoxonium ions, preferably tri(C 1 - C 4 -alkyl)sulfoxonium.
  • the salts obtainable in this way likewise have fungicidal properties.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of C 1 -C 4 -alkanoic acids. They can be formed by reacting a compound of formula (I) with an acid of the corresponding anion, such as hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, nitric acid etc.
  • the compounds of the present invention may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers e.g. a racemate, individual stereoisomers, or constitutional isomers or as an optically active form.
  • 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).
  • the compounds of formula (I) can be present in different crystal modifications whose biological activity may differ. They also form part of the subject matter of the present invention.
  • the compounds of formula (I) can be present in atropisomers arising from restricted rotation about a single bond of asymmetric groups. They also form part of the subject matter of the present invention.
  • the compound selected from formula (I), (including all stereoisomers, N-oxides, and salts thereof), typically may exist in more than one form.
  • the compounds of formula (I) thus includes all crystalline and non-crystalline forms of the compound that formula (I) represents.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • the present invention provides a process for synthesis of compound of formula (I).
  • the following schemes illustrate approaches for preparing compounds of formula (I). The following descriptions and examples are provided for illustrative purposes and should not be construed as limiting in terms of substituents or substitution patterns. Further, the mentioned reagents, solvents and reaction conditions are intended for the purpose of exemplification only and should not be construed as limiting.
  • the compounds of the present invention as defined by formula (I) and/or in the tables 1 may be prepared, in known manner, in a variety of ways as described in the schemes 1-5.
  • the definitions of W, R 1 , R 1a , R 2 , R 3 , R 4 , A, R 5 , R 6 , R 7 and R 8 in the compounds of formula (I), II , III and compounds of formula 1 to 15 are as defined in the detailed description of the invention unless otherwise specifically stated.
  • a compound of formula (I), wherein W is O can be prepared by coupling of an acid of formula 1 (or it’s salt) with an amine (or its acid salt) of formula II in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, and optionally in a suitable solvent such as dichloromethane, N,N-dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethyl
  • a compound of formula (I) can also be prepared by protection or O-alkylation of hydroxyl group in compound of formula III which can be prepared by coupling of an acid of formula 2 (or it’s salt) with requisite amine of formula II (or it’s acid salt) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, and optionally in a solvent such as dichloromethane, N,N-dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-
  • a compound of formula Ia can also be prepared by the protection or O-alkylation of hydroxyl group in compound of formula 10 which in turn can be constructed by coupling of an acid of formula 2 (or it’s salt) with a suitably substituted amine of formula 3 (or it’s acid salt) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, and optionally in a solvent such as dichloromethane, N,N-dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl
  • Amine of formula 3 (or it’s acid salt) can be obtained by the deprotection of compound of formula 8.
  • the compound of formula 8 can be obtained by coupling of hydroxyimino compound of formula 5 and an acid or acid halide of formula 6 in the presence of a suitable coupling reagent such as such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, followed by acid (such as acetic acid, p-toluene sulfonic acid and the like) mediated cyclization of a compound of formula 7 in a high boiling solvent such as toluene.
  • a suitable coupling reagent such as such as hexafluorophosphate
  • the hydroxyimino compound of formula 5 can be prepared from a suitably substituted cyano compound of formula 4 by treatment with hydroxylamine hydrochloride in the presence of an alcoholic solvent such as ethanol. These reactions are carried out at a temperature between 25 °C to 80 °C.
  • a compound of formula Ia can also be prepared by coupling of an acid or acid halide of formula 6 with hydroxyimino compound of formula 14 in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or a suitable alkyl chloroformates such as ethyl chloroformate, isobutyl chloroformate and the like, followed by acid (such as acetic acid, p-toluene sulfonic acid and the like) mediated cyclization.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or
  • the coupling reactions are carried out in a suitable solvent such as dichloromethane, tetrahydrofuran, N,N- dimethylformamide and the like, at a temperature between 0 °C to 25 °C, whereas cyclization was carried out in high boiling solvent such as toluene at 70 °C to 100 °C.
  • a suitable solvent such as dichloromethane, tetrahydrofuran, N,N- dimethylformamide and the like
  • cyclization was carried out in high boiling solvent such as toluene at 70 °C to 100 °C.
  • the hydroxyimino compound of formula 14 can be prepared from a corresponding cyano compound of formula 13 in the presence of hydroxylamine hydrochloride and or a solvent such as ethanol.
  • the cyano compound of formula 13 can be obtained by coupling of an acid of formula 1 (or it’s salt) and an amine of formula 12 (or it’s acid salt) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, and optionally in a solvent such as dichloromethane, N,N- dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodi
  • the suitably substituted amine of formula 12 can be prepared from a compound of formula 4 by deprotection of protecting group such as tert-butoxy carbonyl.
  • the requisite cyano compound of formula 4 can be synthesized from a protected amine of formula 11 in the presence of an acid anhydride and optionally in a solvent such as tetrahydrofuran. These reactions are carried out at a temperature between 0 °C to 25 °C.
  • the protected amine of formula 11 can be prepared from suitably substituted amide of formula 10 by protection of amines.
  • the compound of formula Ib (Scheme-6) can be synthesized by coupling of an acid of formula 1 (or it’s salt) and an amine of formula 15 (or it’s acid salt) using a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or acid chlorides such as acetyl chloride, isobutyrylchloride and the like, and optionally in a solvent such as dichloromethane, N,N- dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl
  • a compound of formula Ib can also be prepared by protection of hydroxyl group or O-alkylation in compound of formula 16 which in turn can be constructed by coupling of an acid of formula 2 (or it’s salt) with suitably substituted amine of formula 15 (or it’s acid salt) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or acid chlorides such as acetyl chloride, isobutyryl chloride and the like, and optionally in a solvent such as dichloromethane, N,
  • a compound of formula Ib can also be prepared by coupling of an acid of formula 18 (or it’s acid halide) with hydroxyimino compound of formula 20 in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, followed by acid (such as acetic acid, p-toluene sulfonic acid and the like) mediated cyclization.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochlor
  • the coupling reactions are carried out in a solvent such as dichloromethane, tetrahydrofuran, N,N-dimethylformamide and the like, at a temperature between 0 °C to 25 °C, whereas cyclization was carried out in high boiling solvent such as toluene at a temperature between 70 °C to 100 °C.
  • the hydroxyimino compound of formula 20 can be prepared from a corresponding cyano compound of formula 19 in the presence of hydroxylamine hydrochloride and optionally in a solvent such as ethanol. These transformations are carried out at a temperature between 50 °C to 70 °C.
  • the acid compound of formula 18 can be prepared via acid or base mediated hydrolysis of an ester of formula 17.
  • the ester compound of formula 17 can be obtained by coupling of an acid of formula 1 (or it’s acid chloride) and an amine of formula 16 by using a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like followed by acid (such as acetic acid, p-toluene sulfonic acid and the like) mediated cyclization.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or a
  • the compound of formula 23 in turn can be synthesized by coupling of acid or acid halide of formula 6 and hydroxyimino compound of formula 20 in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or a suitable alkyl chloroformates such as ethyl chloroformate, isobutyl chloroformate and the like followed by acid (such as acetic acid, p-toluene sulfonic acid and the like) mediated cyclization.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like or
  • the coupling reactions are carried out in a solvent such as dichloromethane, tetrahydrofuran, N,N-dimethylformamide and the like, at a temperature between 0 °C to 25 °C, whereas cyclization was carried out in high boiling solvent such as toluene at a temperature between 70 °C to 100 °C.
  • a solvent such as dichloromethane, tetrahydrofuran, N,N-dimethylformamide and the like
  • the compound of formula Ic (Scheme-10) can be synthesized by coupling of an acid of formula 1 (or it’s salt) and an amine of formula 24 (or it’s acid salt) using a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformates such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyrylchloride and the like, and optionally in a solvent such as dichloromethane, N,N- dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole t
  • a compound of formula Ic can also be prepared by protection of hydroxyl group or O-alkylation of compound of formula 25 which in turn can be obtained by coupling of an acid of formula 2 (or it’s salt) with a suitably substituted amine of formula 24 (or it’s acid salt) in presence of a coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or acid chlorides such as acetyl chloride, isobutyryl chloride and the like, and optionally in a solvent such as dichloromethane, N,
  • the suitably substituted amine of formula 24 can be prepared from the compound of formula 28 under suitable deprotection conditions (Scheme 12).
  • the compound of formula 28 in turn can be obtained by coupling of acid of formula 27 and imidohydrazide of formula 26 in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyryl chloride and the like, and optionally in a solvent such as dichloromethane, N,N-dimethylformamide, tetrahydro
  • a suitable coupling reagent such as hexafluorophosphate
  • the imidohydrazide compound of formula 26 can be obtained from alkyl imidate of formula 25 (or it’s acid salts) by treating it with methyl hydrazine (or it’s acid salts). These reactions are carried out in an alcoholic solvent such as ethanol at a temperature between 50°C to 80°C.
  • the suitable imidate substrate of formula 25 can be prepared by heating a suitably substituted cyano compound of formula 19 in alcohol such as ethanol in presence of a suitable acid or acid chloride such as hydrochloric acid, acetyl chloride etc. These reactions are typically carried out at a temperature between 0°C to 25°C.
  • a compound of formula Ic can also be prepared by coupling of imidohydrazide of formula 26 with an acid of formula 18 in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyryl chloride and the like, and optionally in a suitable solvent such as dichloromethane, N,N-dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethyla
  • the acid compound of formula 18 can be synthesized by hydrolysis of an ester of formula 17 under acidic or basic conditions.
  • Scheme: 13 The compound of formula If and Ig (Scheme-14) can be synthesized by coupling of an acid of formula 1 (or it’s salt) and an amine of formula 29 (or it’s acid salt) using a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyrylchloride and the like, and optionally in a solvent such as dichloromethane
  • a suitable coupling reagent such as hexafluor
  • the compounds of formula If and Ig can also be prepared by protection of hydroxyl group or O-alkylation of compound of formula 30 which in turn can be constructed by coupling of an acid of formula 2 (or it’s salt) with suitably substituted amine of formula 29 (or it’s acid salt) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyryl chloride and the like, and optionally in a suitable solvent such as dichlor
  • a compound of formula If can also be prepared by cyclization of hydrazide compound of formula 32 using a suitable reagent such as phosphorus pentoxide, CBr4/PPh3 and the like, and a compound of formula Ig can be prepared by same cyclization using phosphorus pentasulfide.
  • the compound of formula 32 can be synthesized by coupling of hydrazide compound of formula 31 with an acid of formula 6 (or it’s acid chloride) in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3- dimethylaminopropyl)-N′-ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyryl chloride and the like, and or a solvent such as dichloromethane, N,N-dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3
  • the suitable hydrazide compound of formula 31 can be synthesized from corresponding ester compound of formula 17 by treating it with hydrazine hydrate in a suitable alcoholic solvent such as ethanol, methanol etc. This transformation is carried out at a temperature between 50°C to 80°C.
  • Scheme: 16 The suitably substituted amine of formula 29 can be prepared from a compound of formula 35 under suitable deprotection conditions (Scheme 17).
  • the compound of formula 35 in turn can be obtained by cyclization of compound of formula 34 employing a suitable reagent such as phosphorus pentoxide, CBr4/PPh3, phosphorus pentasulfide and the like.
  • the required hydrazide substrate of formula 34 can be prepared by coupling of an acid of formula 6 (or it’s acid chloride) with a suitably substituted hydrazide in the presence of a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl uronium, N-(3-dimethylaminopropyl)-N′- ethylcarbodiimide hydrochloride and the like, or a suitable alkyl chloroformate such as ethyl chloroformate, isobutyl chloroformate and the like, or a suitable acid chloride such as acetyl chloride, isobutyryl chloride and the like, and optionally in a solvent such as dichloromethane, N,N- dimethylformamide, tetrahydrofuran and the like.
  • a suitable coupling reagent such as hexafluorophosphate azabenzotriazole tetramethyl
  • the compounds of the present disclosure are applied in the form of a formulation, comprising one or more of the compounds of formula (I) with a phytologically acceptable carrier.
  • Concentrated formulations may be dispersed in water, or other liquids, for application, or formulations may be dust-like or granular, which may then be applied without further treatment.
  • the formulations can be prepared according to procedures that are conventional in the agricultural chemical art.
  • the present disclosure contemplates all vehicles by which one or more of the compounds may be formulated for delivery and use as a fungicide.
  • formulations are applied as aqueous suspensions or emulsions.
  • Such suspensions or emulsions may be produced from water-soluble, water-suspendible, or emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates.
  • emulsifiable formulations which are solids, usually known as wettable powders; or liquids, usually known as emulsifiable concentrates, aqueous suspensions, or suspension concentrates.
  • any material to which these compounds may be added may be used, provided it yields the desired utility without significant interference with the activity of these compounds as antifungal agents.
  • the present invention provides a agrochemical composition
  • a agrochemical composition comprising the compound of formula (I), agriculturally acceptable salts, metal complexes, constitutional isomers, stereo-isomers, diastereoisomers, enantiomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, geometric isomers, or N-oxides thereof, optionally with one or more additional active ingredient with the auxiliary such as inert carrier or any other essential ingredient such as surfactants, additives, solid diluents and liquid diluents.
  • An agrochemical composition comprises a fungicidally effective amount of a compound of formula (I).
  • the term "effective amount” denotes an amount of the composition or of the compound of formula (I), which is sufficient for controlling harmful fungi on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the fungal species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound of formula (I) used.
  • the present invention provides a composition comprising at least one compound of formula (I) and seed.
  • the amount of the compound of formula (I) in the composition ranges from 0.1 g ai (gram per active ingredient) to 1 kg ai (kilogram per active ingredient) per 100 kg of seeds.
  • compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e. g. EW, EO, ES, ME), capsules (e. g. CS, ZC), pastes, pastilles, wettable powders or dusts (e. g.
  • compositions are prepared in a known manner, such as described by Mollet and Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product Formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries for the formulations and/or the agrochemicals compositions according to the inventions are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e. g.
  • kerosene diesel oil
  • oils of vegetable or animal origin aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes
  • alcohols e. g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol
  • glycols DMSO; ketones, e. g. cyclohexanone
  • esters e. g. lactates, carbonates, fatty acid esters, gamma- butyrolactone; fatty acids; phosphonates; amines; amides, e. g.
  • Suitable solid carriers or fillers are mineral earths, e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulphate, magnesium sulphate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulphate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e. g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulphate, magnesium sulphate, magnesium oxide
  • polysaccharides e. g. cellulose, starch
  • fertilizers
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emulsifier, dispersant, solubilizer, wetter, penetration enhancer, protective colloid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1: Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulphates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl-and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulphates are sulphates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinyl pyrrolidone, vinyl alcohols, or vinyl acetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases.
  • polyacids are alkali salts of polyacrylic acid or polyacid comb polymers.
  • polybases are polyvinyl amines or polyethylene amines.
  • Suitable adjuvants are compounds, which have a negligible or even no pesticidal activity themselves, and which improve the biological performance of the compound of Formula (I) on the target. Examples are surfactants, mineral or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e. g.
  • xanthan gum carboxymethyl cellulose
  • inorganic clays organic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazolinones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e. g. in red, blue, or green
  • examples are inorganic colorants (e. g.
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • Examples for composition types and their preparation are: i) Water-soluble concentrates (SL, LS) 10-60 wt% of a compound of formula (I) and 5-15 wt% wetting agent (e. g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e. g.
  • Dispersible concentrates 5-25 wt% of a compound of formula (I) and 1-10 wt% dispersant (e. g. polyvinyl pyrrolidone) are dissolved in organic solvent (e. g. cyclohexanone) ad 100 wt%. Dilution with water gives a dispersion.
  • Emulsifiable concentrates EC 15-70 wt% of a compound of formula (I) and 5-10 wt% emulsifiers (e. g.
  • binder e. g. polyvinyl alcohol
  • binder e. g. polyvinyl alcohol
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • Water-dispersible powders and water-soluble powders (WP, SP, WS) 50-80 wt% of a compound of Formula (I) are ground in a rotor-stator mill with addition of 1-5 wt% dispersants (e. g. sodium lignosulfonate), 1-3 wt% wetting agents (e. g. alcohol ethoxylate) and solid carrier (e. g. silica gel) ad 100 wt%. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e. g. sodium lignosulfonate
  • wetting agents e. g. alcohol ethoxylate
  • solid carrier e. g. silica gel
  • Microcapsules An oil phase comprising 5-50 wt% of a compound of formula (I), 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e. g. methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.
  • a protective colloid e.
  • an oil phase comprising 5-50 wt% of a compound of Formula (I) according to the invention, 0-40 wt% water insoluble organic solvent (e. g. aromatic hydrocarbon), and an isocyanate monomer (e. g. diphenylmethene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e. g. polyvinyl alcohol).
  • a polyamine e. g. hexamethylenediamine
  • the monomers amount to 1-10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS) 1-10 wt% of a compound of formula (I) are ground finely and mixed intimately with solid carrier (e. g. finely divided kaolin) ad 100 wt%.
  • Granules (GR, FG) 0.5-30 wt% of a compound of formula (I) are ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray-drying or fluidized bed.
  • Ultra-low volume liquids (UL) 1-50 wt% of a compound of formula (I) are dissolved in organic solvent (e.
  • compositions types i) to xiii) may optionally comprise further auxiliaries, such as 0.1-1 wt% bactericides, 5-15 wt% anti-freezing agents, 0.1-1 wt% anti-foaming agents, and 0.1-1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and in particular between 0.5 and 75%, by weight of active ingredient (ai).
  • the active ingredients (ai) are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • compositions in question give, after two-to-tenfold dilution, active substance concentrations from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 1.0 kg per ha, and in particular from 0.1 to 1.0 kg per ha.
  • amounts of active substance from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kg of plant propagation material (preferably seeds) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect.
  • Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • These agents can be mixed with the composition according to the invention in a weight ratio of 1:100 to 100:1, preferably 1:20 to 20:1.
  • a pesticide is generally a chemical or biological agent (such as pesticidally active ingredient, compound, composition, virus, bacterium, antimicrobial or disinfectant) that through its effect deters, incapacitates, kills or otherwise discourages pests.
  • Target pests can include insects, plant pathogens, weeds, mollusks, birds, mammals, fish, nematodes (roundworms), and microbes that destroy property, cause nuisance, spread disease or are vectors for disease.
  • pesticide includes also plant growth regulators that alter the expected growth, flowering, or reproduction rate of plants; defoliants that cause leaves or other foliage to drop from a plant, usually to facilitate harvest; desiccants that promote drying of living tissues, such as unwanted plant tops; plant activators that activate plant physiology for defense against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology e.g. to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • the user applies the composition according to the invention usually from a predosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • the present invention provides a combination comprising the compound of formula (I) and at least one further pesticidally active substance selected from the group consisting of fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertilizers and nutrients.
  • the compound of formula (I), the combination and the composition thereof comprising them in the use as fungicides with other fungicides may result in an expansion of the fungicidal spectrum of activity being obtained or in a prevention of fungicide resistance development. Furthermore, in many cases, extraordinary and unexpected effects are obtained.
  • the present invention also relates to the combination comprising at least one compound of formula (I) and at least one further pesticidally active substance selected from the group of fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, safeners, plant growth regulators, antibiotics, fertiliers and nutrients.
  • the pesticidally active substances reported in WO2015185485 pages 36-43 and WO2017093019 pages 42-56 can be used in conjunction with the compound of formula (I).
  • the active substances referred to as component 2, their preparation and their activity e. g. against harmful fungi 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 present invention furthermore relates to agrochemical mixtures comprising at least one compound of formula (I) (component 1) and at least one further active substance useful for plant protection.
  • agrochemical mixtures comprising at least one compound of formula (I) (component 1) and at least one further active substance useful for plant protection.
  • an additional effect can be obtained.
  • This can be obtained by applying the compound of formula (I) and at least one further pesticidally active substance simultaneously, either jointly (e. g. as tank-mix) or separately, or in succession, wherein the time interval between the individual applications is selected to ensure that the active substance applied first still occurs at the site of action in a sufficient amount at the time of application of the further pesticidally active substance(s).
  • the order of application is not essential for working of the present invention.
  • the time between both applications may vary e. g. between 2 hours to 7 days. Also a broader range is possible ranging from 0.25 hour to 30 days, preferably from 0.5 hour to 14 days, particularly from 1 hour to 7 days or from 1.5 hours to 5 days, even more preferred from 2 hours to 1 day.
  • the weight ratio of the component 1) and the component 2) generally depends on the properties of the active components used, usually it is in the range of 1:1000 to 1000:1, often in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1, even more preferably in the range of 1:4 to 4:1 and in particular in the range of 1:2 to 2:1.
  • the weight ratio of the component 1) and the component 2) usually is in the range of 1000:1 to 1:1000, often in the range of 100:1 to 1:100, regularly in the range of 50:1 to 1:50, preferably in the range of 20:1 to 1:20, more preferably in the range of 10:1 to 1:10, even more preferably in the range of 4:1 to 1:4 and in particular in the range of 2:1 to 1:2.
  • the ternary mixtures i.e.
  • the weight ratio of component 1) and component 2) depends from the properties of the active substances used, usually it is in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1 and in particular in the range of 1:4 to 4:1, and the weight ratio of component 1) and component 3) usually it is in the range of 1:100 to 100:1, regularly in the range of 1:50 to 50:1, preferably in the range of 1:20 to 20:1, more preferably in the range of 1:10 to 10:1 and in particular in the range of 1:4 to 4:1.
  • any further active components are, if desired, added in a ratio of 20:1 to 1:20 to the component 1. These ratios are also suitable for inventive mixtures applied by seed treatment.
  • individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank or any other kind of vessel used for applications (e. g. seed treater drums, seed pelleting machinery, knapsack sprayer) and further auxiliaries may be added, if appropriate.
  • one embodiment of the invention is a kit for preparing a usable pesticidal composition, the kit comprising a) a composition comprising component 1) as defined herein and at least one auxiliary; and b) a composition comprising component 2) as defined herein and at least one auxiliary; and optionally c) a composition comprising at least one auxiliary and optionally a further active component 3) as defined herein.
  • Application of the compound of formula (I), the combination and the composition thereof can be carried out before or during sowing.
  • Methods for applying the compound of formula (I), the combination and the composition thereof, respectively, are application onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in- furrow application methods.
  • the compound of formula (I), the combination and the composition thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the present invention provides a method for controlling or preventing infestation of plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops wherein an effective amount of at least one compound of formula (I) or the combination or the composition, is applied to the plants, to parts thereof or locus thereof.
  • the present invention provides a method for controlling or preventing infestation of plants by phytopathogenic microorganisms in agricultural crops and or horticultural crops wherein an effective amount of at least one compound of formula (I) or the combination or the composition, is applied to the seeds of plants.
  • the compound of formula (I) and the composition according to the invention are suitable as fungicides. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn.
  • Oomycetes Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).
  • Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the compound of formula (I) and the composition according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g. wheat, rye, barley, triticale, oats or rice; beet, e. g.
  • sugar beet or fodder beet fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; banana
  • the compound of formula (I) and the composition according to the invention are important in the control of phytopathogenic fungi on soybeans and on the plant propagation material, such as seeds, and the crop material of soybeans.
  • the compound of formula (I) and composition thereof, respectively are used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • plant propagation material is to be understood to denote all the generative or reproductive parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant.
  • vegetative plant material such as cuttings and tubers (e. g. potatoes)
  • These young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • cultivación of plant propagation materials with the compound of formula (I), the combination and or the composition thereof, respectively is used for controlling a multitude of fungi on cereals, such as wheat, rye, barley and oats; rice, corn, cotton and soybeans.
  • cultivated plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf. http://cera-gmc.org/, see GM crop database therein).
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo-or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • auxin herbicides such as dicamba or 2,4-D
  • bleacher herbicides such as hydroxylphenylpyruvate dioxygenase (HPPD) inhibitors or phytoene desaturase (PDS) inhibitors
  • acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones
  • glutamine synthetase (GS) inhibitors such as glufosinate
  • protoporphyrinogen-IX oxidase inhibitors lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i.
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61, 2005, 246; 61, 2005, 258; 61, 2005, 277; 61, 2005, 269; 61, 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci.
  • mutagenesis e.g. Clearfield ® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun ® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron.
  • the Bacillus are particularly from Bacillus thuringiensis, such as ⁇ - endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • ⁇ - endotoxins e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry9c
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA- reductase
  • ion channel blockers such as blockers of sodium or calcium channels
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO02/015701).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP374753, WO93/007278, WO95/34656, EP427529, EP451878, WO03/18810 und WO03/52073.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • insecticidal proteins contained in the genetically modified plants impart to the plants, producing these proteins, tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens by the use of recombinant DNA techniques are also within the scope of the present invention. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, e. g.
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
  • plants capable to synthesize one or more proteins, by the use of recombinant DNA techniques, to increase the productivity e. g.
  • plants that contain a modified amount of substances of content or new substances of content, by the use of recombinant DNA techniques, to improve human or animal nutrition e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada) are also within the scope of the present invention.
  • plants that contain a modified amount of substances of content or new substances of content by the use of recombinant DNA techniques, to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany) are also within the scope of the present invention.
  • the compounds of formula (I) may be, for example, effective against fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses. These fungi and fungal vectors of disease as well as phytopathogenic bacteria and viruses are for example: Absidia corymbifera, Alternaria spp, Aphanomyces spp, Ascochyta spp, Aspergillus spp. including A.
  • cichoracearum Eutypa lata, Fusarium spp. including F. culmorum, F. graminearum, F. langsethiae, F. moniliforme, F. oxysporum, F. proliferatum, F. subglutinans, F. solani, Gaeumannomyces graminis, Gibberella fujikuroi, Gloeodes pomigena, Gloeosporium musarum, Glomerella cingulate, Guignardia bidwellii, Gym nosporangium juniperi-virginianae, Helminthosporium spp, Hemileia spp, Histoplasma spp. including H.
  • capsulatum Laetisaria fuciformis, Leptographium lindbergi, Leveillula taurica, Lophodermium seditiosum, Microdochium nivale, Microsporum spp, Monilinia spp, Mucor spp, Mycosphaerella spp. including M. graminicola, M. pomi, Oncobasidium theobromaeon, Ophiostoma piceae, Paracoccidioides spp, Penicillium spp. including P. digitatum, P. italicum, Petriellidium spp, Peronosclerospora spp. Including P. maydis, P.
  • leucotricha Polymyxa graminis, Polymyxa betae, Pseudocercosporella herpotrichoides, Pseudomonas spp, Pseudoperonospora spp. including P. cubensis, P. humuli, Pseudopeziza tracheiphila, Puccinia spp. including P. hordei, P. recondita, P. striiformis, P. triticina, Pyrenopeziza spp, Pyrenophora spp, Pyricularia spp. including P. oryzae, Pythium spp. including P.
  • Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia sorghi, Puccinia striiformis f.sp. Hordei, Puccinia striiformis f.sp.
  • Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include the diseases caused by rust disease pathogens, for example Gymnosporangium species, for example Gymnosporangium sabinae; Hemileia species, for example Hemileia vastatrix; Phakopsora species, for example Phakopsora pachyrhizi or Phakopsora meibomiae; Puccinia species, for example Puccinia recondita, Puccinia graminis oder Puccinia striiformis; Uromyces species, for example Uromyces appendiculatus.
  • rust disease pathogens for example Gymnosporangium species, for example Gymnosporangium sabinae
  • Hemileia species for example Hemileia vastatrix
  • Phakopsora species for example Phakopsora pachyrhizi or Phakopsora meibomiae
  • Cronartium ribicola White pine blister rust
  • Gymnosporangium juniperi-virginianae Cedar-apple rust
  • Hemileia vastatrix Coffee rust
  • Phakopsora meibomiae and P. pachyrhizi Soybean rust
  • Puccinia coronata Crown Rust of Oats and Ryegrass
  • Puccinia graminis Stetem rust of wheat and Kentucky bluegrass, or black rust of cereals
  • Puccinia hemerocallidis Daylily rust
  • Puccinia persistens subsp.
  • Puccinia sorghi rust in corn
  • Puccinia striiformis 'Yellow rust' in cereals
  • Uromyces appendiculatus rust of beans
  • Uromyces phaseoli Bean rust
  • Puccinia melanocephala 'Brown rust' in sugarcane
  • Puccinia kuehnii 'Orange rust' in sugarcane
  • the present invention further relates to the use of the compound of formula (I), the combination or the composition thereof for controlling or preventing against phytopathogenic fungi such as Septoria spp., powdery mildews, Botrytis spp., anthracnose, Alternaria spp., scab and Monilinia spp. of agricultural crops and or horticultural crops.
  • the present invention further relates to the use of the compound of formula (I), the combination or the composition thereof for controlling or preventing against phytopathogenic fungi such as Septoria spp., powdery mildews, Botrytis spp., anthracnose, Alternaria spp., scab and Monilinia spp.
  • Plants which can be treated in accordance with the invention include the following: cotton, flax, grapevine, fruits, vegetables, such as Rosaceae sp (for example pome fruits such as apples, pears, apricots, cherries, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp for example pome fruits such as apples, pears, apricots, cherries, almonds and peaches
  • Rosaceae sp for example pome fruits such as apples, pears, apricots, cherries, almonds and peaches
  • Ribesioidae sp. Juglandaceae
  • Rubiaceae sp. for example coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for example lemons, oranges and grapefruit
  • Vitaceae sp. for example grapes
  • Solanaceae sp. for example tomatoes, peppers
  • Liliaceae sp. for example lettuce
  • Umbelliferae sp. for example Cruciferae sp., Chenopodiaceae sp.
  • Cucurbitaceae sp. for example cucumber
  • Alliaceae sp. for example leek, onion
  • peas for example peas
  • major crop plants such as Poaceae/Gramineae sp.
  • Poaceae/Gramineae sp. for example maize, turf, cereals such as wheat, rye, rice, barley, oats, millet and triticale
  • Asteraceae sp. for example sunflower
  • Brassicaceae sp. for example white cabbage, red cabbage, broccoli, cauliflower, Brussels sprouts, pak choi, kohlrabi, radishes, and oilseed rape, mustard, horseradish and cress
  • Fabacae sp. for example bean, peanuts
  • Papilionaceae sp. for example soya bean
  • phytophthora rot (Phytophthora megasperma), brown stem rot (Phialophora gregata), pythium rot (Pythium aphanidennatum, Pythium irregulare, Pythium debaryanum, Pythium myriotylum, Pythium ultimum), rhizoctonia root rot, stem decay, and damping-off (Rhizoctonia solani), sclerotinia stem decay (Sclerotinia sclerotiorum), sclerotinia southern blight (Sclerotinia rolfsii), thielaviopsis root rot (Thielaviopsis basicola).
  • the present invention also relates to the use of the compound of formula (I), the combination or the composition thereof for controlling or preventing the following plant diseases: Puccinia spp. (rusts) on various plants, for example, but not limited to 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 and Phakopsoraceae spp. on various plants, in particular Phakopsora pachyrhizi and P.
  • Puccinia spp. rusts
  • rusts rusts
  • P. triticina brown or leaf rust
  • P. striiformis stripe or yellow rust
  • P. hordei dwarf rust
  • the compound, the combination and the composition of the present invention can be used for controlling or preventing plant diseases.
  • the compound of formula (I), the combination and/or the composition 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. solani or A. alternata), tomatoes (e. g. A. solani or 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. maydis) or Northern leaf blight (B.
  • zeicola on corn, e. g. spot blotch (C. 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 (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn.
  • Ophiostoma Ophiostoma
  • spp. rot or wilt
  • 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. kikuchii) and rice
  • graminicola Anthracnose stalk rot
  • soft fruits e. g. C. coccodes: black dot
  • beans e. g. C. lindemuthianum
  • soybeans e. g. C. truncatum or C. gloeosporioides
  • Corticium spp. e. g. C. sasakii (sheath blight) on rice
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g.
  • teleomorph Nectria or Neonectria spp.
  • vines e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease
  • Dematophora teleomorph: Rosellinia
  • necatrix root and stem rot
  • Diaporthe spp. e. g. D. phaseolorum (damping off) on soybeans
  • Drechslera ser. Helminthosporium, teleomorph: Pyrenophora
  • spp. on corn, cereals, such as barley e. g. D.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets £. betae
  • vegetables e. g. E. pisi
  • cucurbits e. g. E. cichoracearum
  • cabbages e. g. E. cruciferarum
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn.
  • G. 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
  • Macrophomina phaseolina syn. phaseoli
  • root and stem rot on soybeans and cotton
  • Microdochium syn. Fusarium
  • nivale pink snow mold
  • 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
  • Mycosphaerella spp. 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 brassicae
  • rape e. g. P. parasitica
  • onions e. g. P. destructor
  • tobacco P. tabacina
  • soybeans e. g. P. manshurica
  • Phakopsora pachyrhizi and P. meibomiae staybean rust
  • 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
  • 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. capsici), soybeans (e. g. P. megasperma, syn. P. sojae), soybeans, potatoes and tomatoes (e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • 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.
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • Pseudopezicula tracheiphila red fire disease or .rotbrenner', anamorph: Phialophora) on vines
  • 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, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia 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
  • S. solani silk and stem rot
  • S. solani silk and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot) on rice
  • Sclerotinia spp e. g.
  • R. solani root and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • Sarocladium oryzae and S. attenuatum sheath rot
  • Sclerotinia spp Sclerotinia spp.
  • seed rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or 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 prowdery mildew, anamorph: Oidium tuckeri
  • 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.
  • S. nodorum Stagonospora blotch, teleomorph: Leptosphaeria [syn. Phaeosphaeria] nodorum
  • 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
  • tobacco, pome fruits, vegetables, soybeans and cotton e. g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • the compounds of formula (I) have broad ranges of activity against fungal pathogens.
  • Exemplary pathogens may include, but are not limited to, causing agent of wheat leaf blotch (Zymoseptoria tritici), wheat brown rust (Puccinia triticina), wheat stripe rust (Puccinia striiformis), scab of apple (Venturia inaequalis), powdery mildew of grapevine (Uncinula necator), barley scald (Rhynchosporium secalis), blast of rice (Pyricularia oryzae), rust of soybean (Phakopsora pachyrhizi), glume blotch of wheat (Leptosphaeria nodorum), powdery mildew of wheat (Blumeria graminis f. sp.
  • the exact amount of the active material to be applied is dependent not only on the specific active material being applied, but also on the particular action desired, the fungal species to be controlled, and the stage of growth thereof, as well as the part of the plant or other product to be contacted with the compound. Thus, all the compounds, and formulations containing the same, may not be equally effective at similar concentrations or against the same fungal species.
  • the compound of formula (I), the combination and the composition thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • protection of materials is to be understood to denote the protection of technical and non-living materials, such as adhesives, glues, wood, paper and paperboard, textiles, leather, paint dispersions, plastics, cooling lubricants, fiber or fabrics, against the infestation and destruction by harmful microorganisms, such as fungi and bacteria.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Pora spp., Serpula spp.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.
  • Basidiomycetes such as Coniophora spp
  • the present invention provides a method for controlling or preventing phytopathogenic fungi.
  • the method comprises treating the fungi or the materials, plants, plant parts, locus thereof, soil or seeds to be protected against fungal attack, with an effective amount of at least one compound of formula (I) or a combination or a composition comprising at least one compound of formula (I).
  • the method of treatment according to the invention can also be used in the field of protecting stored products or harvest against attack of fungi and microorganisms.
  • the term "stored products” is understood to denote natural substances of plant or animal origin and their processed forms, which have been taken from the natural life cycle and for which long-term protection is desired.
  • Stored products of crop plant origin such as plants or parts thereof, for example stalks, leafs, tubers, seeds, fruits or grains
  • timber whether in the form of crude timber, such as construction timber, electricity pylons and barriers, or in the form of finished articles, such as furniture or objects made from wood.
  • Stored products of animal origin are hides, leather, furs, hairs and the like. The combination according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
  • stored products is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • fungicide as used herein means a compound that controls, modifies, or prevents the growth of fungi.
  • the compound of formula (I), the combination and the composition thereof, respectively, may be used for improving the health of a plant.
  • the invention also relates to a method for improving plant health by treating a plant, its propagation material and/or the locus where the plant is growing or is to grow with an effective amount of compound of formula (I) and the composition thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e. g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e. g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e. g. improved content or composition of certain ingredients
  • the compound of formula (I) are employed as such or in the form of composition for treating the fungi or the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with a compound of formula (I), the combination and the composition thereof protectively either at or before planting or transplanting. Any range or desired value given herein may be extended or altered without losing the effects sought, as is apparent to the skilled person for an understanding of the teachings herein.
  • Example-1 Preparation of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)picolinamide
  • Step-A Preparation of tert-butyl (S)-(1-amino-1-oxopropan-2-yl)carbamate
  • Boc-anhydride 15.8 mL, 68.1 mmol
  • reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with water (20 mL) and extracted with dichloromethane (3 x 150 mL). The combined organic layers were dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain tert-butyl (S)-(1-amino-1-oxopropan-2-yl)carbamate (8.0 g, 42.5 mmol, 75% yield).
  • Step-B Preparation of tert-butyl (S)-(1-cyanoethyl)carbamate
  • tert-butyl (S)-(1-amino-1-oxopropan-2-yl)carbamate 3.0 g, 15.9 mmol
  • pyridine 5.2 mL, 63.8 mmol
  • trifluoroacetic anhydride 6.7 g, 31.9 mmol
  • Step-C Preparation of tert-butyl (S)-(1-(hydroxyamino)-1-iminopropan-2-yl)carbamate
  • tert-butyl (S)-(1-cyanoethyl)carbamate 0.5 g, 2.9 mmol
  • sodium bicarbonate 0.37 g, 4.4 mmol
  • hydroxylamine hydrochloride 0.31 g, 4.4 mmol
  • Step-D Preparation of tert-butyl (S)-(1-(5-phenyl-1,2,4-oxadiazol-3-yl)ethyl)carbamate
  • tert-butyl (S)-(1-(hydroxyamino)-1-iminopropan-2-yl)carbamate 4.8 g, 23.7 mmol
  • triethylamine 10 mL, 71.1 mmol
  • dichloromethane 20 mL
  • benzoyl chloride 3.3 mL, 28.5 mmol
  • reaction mixture was quenched with ice-cold water (50 mL) and extracted with dichloromethane (3 x 200 mL). The combined organic layer was washed with brine solution (100 mL), dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain a crude compound. This crude compound was further dissolved in toluene (250 mL), followed by the addition of acetic acid (1.4 mL, 23.7 mmol) at 25 °C. The resulting reaction mixture was stirred at 100 °C for 24 h.
  • Step-F Preparation of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)picolinamide
  • (1) To a stirred solution of (S)-1-(5-phenyl-1,2,4-oxadiazol-3-yl)ethan-1-amine hydrochloride (1.0 g, 4.6 mmol) and 3-hydroxy-4-methoxypicolinic acid (0.7 g, 4.1 mmol) in dichloromethane (30 mL), diisopropylethylamine (3.6 mL, 20.7 mmol) was added at 25 °C.
  • Example-2 Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (2): To a stirred solution of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)picolinamide (0.4 g, 1.2 mmol) and triethylamine (0.5 mL, 3.5 mmol) in dichloromethane (5 mL), isobutyryl chloride (0.2 mL, 1.4 mmol) was added slowly at 0 °C.
  • Example-3 Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)carbamoyl)pyridin-3-yl acetate (3): To a stirred solution of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,2,4-oxadiazol-3- yl)ethyl)picolinamide (0.4 g, 1.2 mmol) and triethylamine (0.8 mL, 5.9 mmol) in dichloromethane (5 mL), acetyl chloride (140 mg, 1.8 mmol) was added slowly at 0 °C.
  • Example-4 Preparation of (S)-4-methoxy-2-((1-(3-phenyl-1,2,4-oxadiazol-5- yl)ethyl)carbamoyl)pyridin-3-yl acetate (37): a) Step-A: Preparation of N-hydroxybenzimidamide. To a stirred solution of benzonitrile (3.0 g, 29.1 mmol) and sodium bicarbonate (3.7 g, 43.6 mmol) in ethanol (30 mL), hydroxylamine hydrochloride (2.2 g, 32.0 mmol) was added at 25 °C. The resulting reaction mixture was stirred at 50 °C for 12 h. The reaction mixture was evaporated under reduced pressure.
  • Step-B Preparation of tert-butyl (S)-(1-(benzimidamidooxy)-1-oxopropan-2-yl)carbamate.
  • N-hydroxybenzimidamide 2.0 g, 14.69 mmol
  • (tert-butoxycarbonyl)-L- alanine 2.8 g, 14.7 mmol
  • diisopropylethylamine 7.7 mL, 44.1 mmol
  • Step-C Preparation of tert-butyl (S)-(1-(3-phenyl-1,2,4-oxadiazol-5-yl)ethyl)carbamate
  • tert-butyl (S)-(1-(benzimidamidooxy)-1-oxopropan-2-yl)carbamate 4.5 g, 14.6 mmol
  • acetic acid 0.8 mL, 14.6 mmol
  • Step-D Preparation of (S)-1-(3-phenyl-1,2,4-oxadiazol-5-yl)ethan-1-amine hydrochloride
  • Step-E Preparation of (S)-4-methoxy-2-((1-(3-phenyl-1,2,4-oxadiazol-5- yl)ethyl)carbamoyl)pyridin-3-yl acetate (37): To a stirred solution of 3-acetoxy-4-methoxypicolinic acid (200 mg, 0.9 mmol) and triethylamine (0.4 mL, 2.8 mmol) in dichloromethane (5 mL), ethyl chloroformate (0.1 mL, 1.042 mmol) was added slowly at 0 °C. The resulting reaction mixture was stirred at 0 °C for 30 min.
  • Example-5 Preparation of (S)-4-methoxy-2-((1-(3-phenyl-1,2,4-oxadiazol-5- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (51): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (200 mg, 1.2 mmol) and triethylamine (0.5 mL, 3.6 mmol) in dichloromethane (10 mL), isobutyryl chloride (0.2 mL, 2.5 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-6 Preparation of (S)-3-hydroxy-4-methoxy-N-(1-(3-phenyl-1,2,4-oxadiazol-5- yl)ethyl)picolinamide (60): To a stirred solution of (S)-4-methoxy-2-((1-(3-phenyl-1,2,4-oxadiazol-5-yl)ethyl)carbamoyl)pyridin- 3-yl isobutyrate (350 mg, 0.9 mmol) in methanol (10 mL), potassium carbonate (236 mg, 1.7 mmol) was added slowly at 0 °C.
  • Step-B Preparation of N'-methylbenzimidohydrazide
  • ethyl benzimidate hydrochloride 3.0 g, 16.2 mmol
  • methylhydrazine sulfate 2.6 g, 17.8 mmol
  • triethylamine 11.3 mL, 81 mmol
  • the reaction mixture was stirred for 2 h at same temperature. After completion of the reaction, the reaction mixture was evaporated, residue was washed with methyl tert-butyl ether (200 mL) to afford crude N'-methylbenzimidohydrazide (3.0 g, 20.1 mmol, 100% yield).
  • N-methylbenzimidohydrazide (473 mg, 3.2 mmol) was added at 0 °C and stirred for 30 min. The reaction mixture was allowed to warm up to 25 °C and stirred for 3 h at the same temperature. After completion of the reaction, the reaction mixture was quenched with water (10 mL) and extracted with dichloromethane (2 x 30 mL). The combined organic layers were dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain crude tert-butyl (S)-(1-(2- (imino(phenyl)methyl)-1-methylhydrazinyl)-1-oxopropan-2-yl)carbamate (0.9 g, 2.8 mmol, 100% yield).
  • Step-D Preparation of tert-butyl (S)-(1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5- yl)ethyl)carbamate
  • tert-butyl (S)-(1-(2-(imino(phenyl)methyl)-2-methylhydrazinyl)-1-oxopropan- 2-yl)carbamate 4.0 g, 12.5 mmol
  • acetic acid 0.7 mL, 12.5 mmol
  • reaction mixture was stirred at 100 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure to isolate a crude compound which was purified through flash column chromatography to obtain tert-butyl (S)-(1-(1-methyl-3-phenyl-1H- 1,2,4-triazol-5-yl)ethyl)carbamate (2.0 g, 6.6 mmol, 53% yield).
  • Step-E Preparation of (S)-1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)ethan-1-amine hydrochloride
  • Step-F Preparation of (S)-isobutyl (4-methoxy-2-((1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5- yl)ethyl)carbamoyl)pyridin-3-yl) carbonate (103): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (500 mg, 3.0 mmol) and triethylamine (0.7 mL, 5.2 mmol) in dichloromethane (10 mL), isobutyl chloroformate (0.8 mL, 6.2 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-9 Preparation of (S)-3-hydroxy-4-methoxy-N-(1-(1-methyl-3-phenyl-1H-1,2,4-triazol- 5-yl)ethyl)picolinamide (127): To a stirred solution of (S)-1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5-yl)ethan-1-amine hydrochloride (388 mg, 1.6 mmol) and 3-hydroxy-4-methoxypicolinic acid (250 mg, 1.5 mmol) in dichloromethane (10 mL), diisopropylethylamine (1.3 mL, 7.4 mmol) was added at 25 °C.
  • Example-10 Preparation of (S)-4-methoxy-2-((1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5- yl)ethyl)carbamoyl)pyridin-3-yl acetate (126): To a stirred solution of (S)-3-hydroxy-4-methoxy-N-(1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5- yl)ethyl)picolinamide (300 mg, 0.9 mmol) and triethylamine (0.4 mL, 2.6 mmol) in dichloromethane (10 mL), acetyl chloride (0.1 mL, 1.3 mmol) was added slowly at 0 °C.
  • Example-11 Preparation of (S)-4-methoxy-2-((1-(1-methyl-3-phenyl-1H-1,2,4-triazol-5- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (108): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (150 mg, 0.9 mmol) and triethylamine (0.2 mL, 1.5 mmol) in dichloromethane (10 mL), isobutyryl chloride (0.2 mL, 1.8 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-12 Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (84): a) Step-A: Preparation of tert-butyl (S)-(1-(2-benzoylhydrazineyl)-1-oxopropan-2-yl)carbamate To a stirred solution of benzohydrazide (3.0 g, 22.0 mmol) and (tert-butoxycarbonyl)-L-alanine (4.6 g, 24.2 mmol) in N,N-dimethylformamide (25 mL), diisopropylethylamine (11.6 mL, 66.1 mmol) was added at 0 °C.
  • Step-B Preparation of tert-butyl (S)-(1-(5-phenyl-1,3,4-oxadiazol-2-yl)ethyl)carbamate
  • tert-butyl (S)-(1-(2-benzoylhydrazinyl)-1-oxopropan-2-yl)carbamate 2.2 g, 7.2 mmol
  • triethylamine 2.5 mL, 17.9 mmol
  • dichloromethane 30 mL
  • triphenylphosphine 3.8 g, 14.3 mmol
  • carbon tetrabromide 4.8 g, 14.3 mmol
  • Step-C Preparation of (S)-1-(5-phenyl-1,3,4-oxadiazol-2-yl)ethan-1-amine
  • tert-butyl (S)-(1-(5-phenyl-1,3,4-oxadiazol-2-yl)ethyl)carbamate 1.2 g, 4.2 mmol
  • dichloromethane 10 mL
  • trifluoracetic acid 3.2 mL, 41.5 mmol
  • Step-D Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (84): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (300 mg, 1.8 mmol) and triethylamine (0.3 ml, 2.1 mmol) in dichloromethane (15 mL), isobutyryl chloride (0.3 mL, 2.9 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-13 Preparation of (S)-isobutyl (4-methoxy-2-((1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl) carbonate (83): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (500 mg, 3.0 mmol) and triethylamine (0.5 mL, 3.4 mmol) in dichloromethane (20 mL), isobutyl chloroformate (0.7 mL, 5.0 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-14 Preparation of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)picolinamide (96): To a stirred solution of (S)-isobutyl (4-methoxy-2-((1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl) carbonate (500 mg, 1.1 mmol) in tetrahydrofuran (6 mL) and water (3 mL), lithium hydroxide monohydrate (143 mg, 3.4 mmol) was added at 0 °C.
  • Example-15 Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl acetate (97): To a stirred solution of (S)-3-hydroxy-4-methoxy-N-(1-(5-phenyl-1,3,4-oxadiazol-2- yl)ethyl)picolinamide (200 mg, 0.6 mmol) and triethylamine (0.3 mL, 1.8 mmol) in dichloromethane (10 mL), acetyl chloride (0.1 mL, 1.2 mmol) was added slowly at 0 °C.
  • Example-16 Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,3,4-thiadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (124): a) Step-A: Preparation of tert-butyl (S)-(1-(2-benzoylhydrazinyl)-1-oxopropan-2-yl)carbamate To a stirred solution of (tert-butoxycarbonyl)-L-alanine (4.0 g, 21.1 mmol) and triethylamine (6.1 mL, 44.0 mmol) in dichloromethane (25 mL), ethyl chloroformate (2.2 mL, 22.9 mmol) was added slowly at 0 °C.
  • Step-B Preparation of tert-butyl (S)-(1-(5-phenyl-1,3,4-thiadiazol-2-yl)ethyl)carbamate
  • tert-butyl (S)-(1-(2-benzoylhydrazinyl)-1-oxopropan-2-yl)carbamate 1.5 g, 4.9 mmol
  • Lawson’s reagent 2.4 g, 5.9 mmol
  • Step-C Preparation of (S)-1-(5-phenyl-1,3,4-thiadiazol-2-yl)ethan-1-amine
  • tert-butyl (S)-(1-(5-phenyl-1,3,4-thiadiazol-2-yl)ethyl)carbamate 2.0 g, 6.6 mmol
  • dichloromethane 10 mL
  • trifluoracetic acid 5.1 mL, 65.5 mmol
  • Step-D Preparation of (S)-4-methoxy-2-((1-(5-phenyl-1,3,4-thiadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl isobutyrate (124): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (206 mg, 1.2 mmol) and triethylamine (0.4 mL, 3.0 mmol) in dichloromethane (15 mL), isobutyryl chloride (0.3 mL, 2.7 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-17 Preparation of (S)-isobutyl (4-methoxy-2-((1-(5-phenyl-1,3,4-thiadiazol-2- yl)ethyl)carbamoyl)pyridin-3-yl) carbonate (125): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (206 mg, 1.2 mmol) and triethylamine (0.4 mL, 3.0 mmol) in dichloromethane (20 mL), isobutyl chloroformate (0.4 mL, 2.7 mmol) was added slowly at 0 °C. The reaction mixture was stirred at 0 °C for 30 min.
  • Example-18 Preparation of N-((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)-3-hydroxy-4-methoxypicolinamide (163): a) Step-A: Preparation of 1-(4-fluorobenzyl)tetrahydro-1H-thiophen-1-ium bromide: To a stirred solution of 1-(bromomethyl)-4-fluorobenzene (2.6 mL, 20.8 mmol) in acetone (50 mL), tetrahydrothiophene (1.8 mL, 20.8 mmol) was added at 25 °C.
  • Step-B Preparation of ethyl (E)-3-(4-fluorophenyl)acrylate: To a stirred solution of (E)-3-(4-fluorophenyl)acrylic acid (5 g, 30.1 mmol) in ethanol (50 mL), thionyl chloride (3.3 mL, 45.1 mmol) was added at 0 °C. The resulting reaction mixture was allowed to stir at 75 °C for 2 h. After completion of the reaction, the reaction mixture was evaporated under reduced pressure. The residue obtained was diluted with water (40 mL) and basified with saturated solution of sodium bicarbonate (30 mL). The reaction mass extracted with dichloromethane (2 x 50 mL).
  • Step-C Preparation of ethyl 2,3-bis(4-fluorophenyl)cyclopropane-1-carboxylate : To a stirred solution of ethyl (E)-3-(4-fluorophenyl)acrylate (1.0 g, 5.2 mmol) in mixture of dichloromethane (15 mL) and tetrahydrofuran (6 mL), 1-(4-fluorobenzyl)tetrahydro-1H-thiophen-1- ium bromide (1.6 g, 5.9 mmol) was added at 25 °C.
  • reaction mixture was then cooled to -78 °C and to this cold solution lithium bis(trimethylsilyl)amide (7.7 mL, 7.8 mmol) was added dropwise.
  • the resulting reaction mixture was allowed to warm up to 25 °C and stirred further for 20 h. After completion of the reaction, the reaction mixture was quenched with water (10 mL) and twice with dichloromethane (2 x 20 mL).
  • Step-D Preparation of 2,3-bis(4-fluorophenyl)cyclopropane-1-carboxylic acid: To a stirred solution of ethyl 2,3-bis(4-fluorophenyl)cyclopropane-1-carboxylate (4.6 g, 15.8 mmol) in tetrahydrofuran (40 mL) and water (6.7 mL), lithium hydroxide monohydrate (1.1 g, 47.1 mmol) was added at 25 °C. The resulting reaction mixture was stirred at 55 °C for 20 h. After completion of the reaction, the reaction mixture was diluted with water (30 mL) and acidified with 1 N HCl.
  • Step-E Preparation of tert-butyl ((2S)-1-(((2,3-bis(4-fluorophenyl)cyclopropane-1- carbonyl)oxy)amino)-1-iminopropan-2-yl)carbamate: To a stirred solution of 2,3-bis(4-fluorophenyl)cyclopropane-1-carboxylic acid (3.8 g, 13.7 mmol) in N,N-dimethylformamide (30 mL), tert-butyl (S)-(1-(hydroxyamino)-1-iminopropan-2-yl)carbamate (3.4 g, 16.5 mmol), diisopropylethylamine (7.2 mL, 41.1 mmol) and hexafluorophosphate azabenzotriazole tetramethyl uronium (7.8 g, 20.6 mmol) were added at 0 °C.
  • Step-F Preparation of tert-butyl ((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4- oxadiazol-3-yl)ethyl)carbamate: To a stirred solution of tert-butyl ((2S)-1-(((2,3-bis(4-fluorophenyl)cyclopropane-1- carbonyl)oxy)amino)-1-iminopropan-2-yl)carbamate (6.2 g, 13.5 mmol) in toluene (60 mL), acetic acid (0.8 mL, 13.5 mmol) was added at 25 °C and stirred at 100 °C for 24 h.
  • reaction mixture was concentrated under reduced pressure to isolate a crude compound, which was purified by column chromatography using 10-20 % ethyl acetate in hexane as an eluent to obtain tert-butyl ((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)carbamate (4.4 g, 10 mmol, 74 % yield).
  • Step-G Preparation of (1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethan-1-amine : To a stirred solution of tert-butyl ((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)carbamate (4.4 g, 10.0 mmol) in dichloromethane (40 mL), hydrochloric acid (12.5 mL, 50.2 mmol) was added at 0 °C and the reaction mixture was stirred at 25 °C for 24 h.
  • Step-H Preparation of 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl acetate (159): To a stirred solution of 3-acetoxy-4-methoxypicolinic acid (200 mg, 0.9 mmol) in tetrahydrofuran (5 mL), diisopropylethylamine (0.5 mL, 2.8 mmol) and isobutyl chloroformate (0.1 mL, 0.9 mmol) were added at 0 °C.
  • reaction mixture was stirred at 0 °C for 10 min followed by dropwise addition of a solution of (1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3-yl)ethan-1-amine (388 mg, 1.1 mmol) in tetrahydrofuran (1 mL).
  • the resulting reaction mixture was stirred at 25 °C for 30 min. After completion of the reaction, the reaction mixture was diluted with water (6 mL) and extracted with ethyl acetate (2 x 25 mL).
  • Step-I Preparation of N-((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)-3-hydroxy-4-methoxypicolinamide (163): To a stirred solution of 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl acetate (1.4 g, 2.6 mmol) in methanol (15 mL), potassium carbonate (724 mg, 5.2 mmol) was added at 0 °C and stirred at same temperature for 30 min.
  • Example-19 Preparation of 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol- 3-yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl isobutyrate (142): To a stirred solution of 3-hydroxy-4-methoxypicolinic acid (100 mg, 0.6 mmol) in dichloromethane (4 mL), triethylamine (0.2 mL, 1.8 mmol) and isobutyryl chloride (0.1 mL, 1.2 mmol) were added at 0 °C.
  • Example-20 Preparation of 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol- 3-yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl butyrate (160): To a solution of N-((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3-yl)ethyl)-3- hydroxy-4-methoxypicolinamide (200 mg, 0.4 mmol) in dichloromethane (4 mL), triethylamine (0.2 mL, 1.2 mmol) and butyryl chloride (0.
  • Example-21 Preparation of 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol- 3-yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl benzoate (161): To a stirred solution of N-((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4-oxadiazol-3- yl)ethyl)-3-hydroxy-4-methoxypicolinamide (200 mg, 0.4 mmol) in dichloromethane (4 mL), triethylamine (0.1 mL, 0.8 mmol) and benzoyl chloride (0.05 mL, 0.4 mmol) were added sequentially at 0 °C.
  • reaction mixture was warmed to 25 °C and stirred for 1 h. After completion of the reaction, the reaction mixture was diluted water (5 mL) and extracted with dichloromethane (2 x 10 mL). The combined organic layers were washed with brine (4 mL), dried over anhydrous sodium sulphate and evaporated under reduced pressure to isolate a crude compound, which was purified by column chromatography to obtain 2-(((1S)-1-(5-(2,3-bis(4-fluorophenyl)cyclopropyl)-1,2,4- oxadiazol-3-yl)ethyl)carbamoyl)-4-methoxypyridin-3-yl benzoate (93 mg, 0.2 mmol, 38 % yield).
  • BIOLOGY EXAMPLES As described herein the compounds of general formula (I) show fungicidal activities which are exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops.
  • the compounds of the present invention were assessed for their activity as described in the following tests:
  • 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 test concentration was dispensed into 60 mm sterile petri-plates.
  • each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • Example 2 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 an actively growing virulent culture plate. Plates were incubated in growth chambers at 22 °C temperature and 90% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • Example 3 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.
  • each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • Example 4 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 an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • Example 5 Corynespora cassiicola (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 an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 70% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • 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 a compound in the desired test concentration was dispensed into 60 mm sterile petri-plates.
  • each plate was seeded with a 5 mm size mycelial disc taken from the periphery of an actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control. Compounds 1 2 9 16 17 35 54 61 71 72 73 74 87 at 300ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive pathogen growth.
  • Example 7 Phytophthora infestans (Late blight of potato & tomato): The compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Rye Agar medium just prior to dispensing it into petri dishes. 5 mL medium with the compound in the desired test 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 an actively growing virulent culture plate. Plates were incubated in growth chambers at 18 oC temperature and 95% relative humidity for seven days and the radial growth was measured and compared to the one of the untreated control.
  • test media-solution 100 ⁇ l of the test media-solution was added to a 96-well microtiter plate, consequently, the same volume (100 ⁇ l) of spore suspension was added to the well making the final test concentrations and the plate was incubated at 18°C for 15-18 days.
  • the growth inhibition was evaluated by measuring the OD600.
  • Example 9 Venturia inaequalis (VENTIN) Potato dextrose (PDB) liquid medium containing a VENTIN (10 5 spores/ml) spore suspension was prepared.
  • VENTIN Potato dextrose
  • PDB Potato dextrose
  • 100 ⁇ l of test media-solution was added to a 96-well microtiter plate, consequently, the same volume (100 ⁇ l) of spore suspension was added to the well making the final test concentrations and the treated plate was incubated at 18 °C for 15-18 days. The growth inhibition was evaluated by measuring the OD600.
  • Example 10 Botrytis cinerea (Gray mold) liquid testing Yeast bacterial peptone and sodium acetate (YBA) liquid medium containing a BOTRCI (10 4 spores/ml) spore suspension was prepared.
  • each test compound was solved in dimethyl sulfoxide. 100 ⁇ l of the test media-solution was added to a 96-well microtiter plate, consequently, the same volume (100 ⁇ l) of spore suspension was added to each well providing the final test concentration and the plate was incubated at 22 °C for 15-18 days. The growth inhibition was evaluated by measuring the OD600.
  • Example 1 Botrytis cinerea test in tomato Compounds were dissolved in 2% dimethyl sulfoxide/acetone and then mixed with water containing an emulsifier to the calibrated spray volume of 50 mL. Each spray solution was poured into a spray bottle for further application.
  • To test the preventive activity of the compound healthy young bean/chilli plants, raised in the greenhouse, were sprayed with the active compound preparation at the stated application rate inside the spray cabinets using hollow cone nozzles. One day after treatment, the plants were inoculated with a spore suspension containing 1.2 x 10 6 Botrytis cinerea inoculum.
  • the inoculated plants were then kept in a greenhouse chamber at 18-20 °C temperature and 90-100 % relative humidity for disease expression.
  • a visual assessment of the compound’s performance was carried out by rating the disease severity (0- 100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compound was calculated by comparing the disease rating in the treatment with the one of the untreated control.
  • the sprayed plants were also assessed for plant damage by recording symptoms like necrosis, chlorosis and stunting.
  • Example 3 Phytophthora infestans test on Tomato Compounds were dissolved in 2 % dimethyl sulfoxide/acetone and then mixed with water containing an emulsifier to the calibrated spray volume of 50 mL. Each spray solution was poured into a spray bottle for further application. To test the preventive activity of the compound, healthy young tomato plants, raised in the greenhouse, were sprayed with the active compound preparation at the stated application rate inside the spray cabinets using hollow cone nozzles.
  • the plants were inoculated with a sporangial suspension containing 0.24x10 6 Phytophthora infestans inoculum. After inoculation, the plants were kept in darkness at 15 °C during 24 h, and then transferred to a greenhouse chamber at 18 o C temperature and 95-100 % relative humidity for disease expression.
  • a visual assessment of the compound’s performance was carried out by rating the disease severity (0- 100% scale) on treated plants 3, 7, 10 and 15 days after application. Efficacy (% control) of the compound was calculated by comparing the disease rating in the treatment with the one of the untreated control. The sprayed plants were also assessed for plant damage by recording symptoms like necrosis, chlorosis and stunting.

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Abstract

La présente invention concerne un composé de formule (I), Formule (I), dans laquelle R1, R1a, R2, W, R3, R4, R5, A, R6, R7 et R8 sont tels que définis dans la description détaillée, ainsi qu'un procédé de préparation du composé de formule (I). La présente invention concerne également un procédé de lutte contre des champignons phytopathogènes.
PCT/IB2021/058347 2020-09-15 2021-09-14 Nouveaux composés picolinamide pour lutter contre des champignons phytopathogènes WO2022058878A1 (fr)

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