WO2022038500A1 - Novel heterocyclic compounds for combating phytopathogenic fungi - Google Patents

Novel heterocyclic compounds for combating phytopathogenic fungi Download PDF

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Publication number
WO2022038500A1
WO2022038500A1 PCT/IB2021/057545 IB2021057545W WO2022038500A1 WO 2022038500 A1 WO2022038500 A1 WO 2022038500A1 IB 2021057545 W IB2021057545 W IB 2021057545W WO 2022038500 A1 WO2022038500 A1 WO 2022038500A1
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oxadiazol
chlorodifluoromethyl
ethyl
methyl
amide
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PCT/IB2021/057545
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English (en)
French (fr)
Inventor
Paras Raybhan BHUJADE
Maruti N Naik
Santosh Shridhar AUTKAR
Ruchi GARG
Alexander G.M. KLAUSENER
Parsaram Dadasaheb ASWALE
Visannagari RAMAKRISHNA
Rohit Arvind DENGALE
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Pi Industries Limited
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Publication of WO2022038500A1 publication Critical patent/WO2022038500A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/653—Five-membered rings
    • C07F9/65306—Five-membered rings containing two nitrogen atoms
    • C07F9/65318—Five-membered rings containing two nitrogen atoms having the two nitrogen atoms in positions 1 and 3
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having alternatively specified atoms bound to the phosphorus atom and not covered by a single one of groups A01N57/10, A01N57/18, A01N57/26, A01N57/34
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
    • A01N57/12—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals
    • 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/30—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing aromatic radicals
    • 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
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
    • C07F9/65583—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system each of the hetero rings containing nitrogen as ring hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings

Definitions

  • the present invention relates to novel heterocyclic compounds which are useful in combating phytopathogenic fungi, a process for preparing the heterocyclic compounds, a combination and a composition comprising the novel heterocyclic compounds.
  • the present invention also relates to a method for combating phytopathogenic fungi.
  • Oxadiazole compounds are known to be useful in the pharmaceutical field. For instance, WO2013066835 discloses oxadiazole compounds as pharmaceutically active agents.
  • Oxadiazole compounds are also known to be useful as crop protection agents to combat or prevent microorganism’s infestations.
  • EP0276432, WO2015185485, EP3165093, EP3167716, EP3165093, WO2017110861, WO2017110862, WO2017110864, WO2017211652, WO2017220485, WO2017072247, WO2017076742, WO2018065414, WO2018118781 and WO2018202491 disclose the oxadiazole compounds which are used as fungicides.
  • oxadiazole 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. Therefore, the need remains for the development of new fungicidal compounds, so as to provide compounds being effective against a broader spectrum of fungi, having lower toxicity, higher selectivity, and being used at lower dosage rates to reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective and long-lasting pest control. Therefore, it is an object of the present invention to provide compounds having an improved/enhanced activity and/or a broader efficacy spectrum against phytopathogenic fungi.
  • the present invention relates to a compound of formula (I), wherein, Het, A, L 1 , R 6 and R 7 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 or environmental properties, or enhanced plant compatibility.
  • the present invention further relates to a combination comprising the compound of formula (I) of the present invention and at least one further pesticidally active substance for effectively controlling or preventing phytopathogenic fungi which are difficult to combat.
  • the present invention still further relates to a composition comprising the compound of formula (I) as such or the compound of formula (I) in combination with a pesticidally active substance.
  • the present invention still further relates to a method and use of the compound of formula (I) as such or the combination or the composition thereof for combating plant diseases, particularly phytopathogenic fungi.
  • 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 pests includes but is not limited to fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and nematodes of economic importance.
  • pest control means inhibition of invertebrate pest development (including necrosis, retarded growth and/or death), 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, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products stored product
  • agro-forestry and vegetation management e.g., 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
  • fungicidal and “fungicidally” refers to observable effects on a fungal pathogen to provide protection of an animal from the disease. Fungicidal effects typically relate to diminishing the occurrence or activity of the target pathogen. Such effects on the pathogens include necrosis, death, retarded growth, or lessened ability to grow on or in the host animal. These effects on pathogens provide control (including prevention, reduction or elimination) of infestation or infection of the animal.
  • 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
  • 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 oxiranyl, aziridinyl, thietanyl, oxetanyl, azetidinyl, 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 .
  • inventive compound of the present invention may, if appropriate, be present as mixtures of different possible isomeric forms, especially of stereoisomers, for example E and Z, threo and erythro, and also optical isomers, but if appropriate also of tautomers. Both the E and the Z isomers, and also the threo and erythro isomers, and the optical isomers, any desired mixtures of these isomers and the possible tautomeric forms are disclosed and claimed.
  • pest for the purpose of the present disclosure includes but is not limited to fungi, stramenopiles (oomycetes), bacteria, nematodes, mites, ticks, insects and rodents.
  • Plant is understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants).
  • Crop plants may be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which are protectable and non-protectable by plant breeders’ rights.
  • plant includes a living organism of the kind exemplified by trees, shrubs, herbs, grasses, ferns, and mosses, typically growing in a site, absorbing water and required substances through its roots, and synthesizing nutrients in its leaves by photosynthesis.
  • plants for the purpose of the present invention include but are not limited to agricultural crops such as wheat, rye, barley, triticale, oats or rice; beet, e.g. sugar beet or fodder beet; fruits and fruit trees, such as pomes, stone fruits or soft fruits, e.g.
  • leguminous plants such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit and citrus trees, such as oranges, lemons, grapefruits or mandarins; any horticultural plants, vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; cucurbitaceae; oleaginous plants; energy and raw material plants, such as cereals, corn, soybean, other leguminous plants, rape, sugar cane or oil palm; tobacco; nuts; coffee; tea;
  • the plant for the purpose of the present invention includes but is not limited to cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, grapes, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and vegetables, ornamentals, any floricultural plants and other plants for use of human and animals.
  • plant parts is understood to mean all parts and organs of plants above and below the ground.
  • plant parts include but is not limited to cuttings, leaves, twigs, tubers, flowers, seeds, branches, roots including taproots, lateral roots, root hairs, root apex, root cap, rhizomes, slips, shoots, fruits, fruit bodies, bark, stem, buds, auxillary buds, meristems, nodes and internodes.
  • locus thereof includes soil, surroundings of plant or plant parts and equipment or tools used before, during or after sowing/planting a plant or a plant part.
  • compositions optionally comprising other compatible compounds to a plant or a plant material or locus thereof include application by a technique known to a person skilled in the art which 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.
  • Het is selected from the group consisting of Het-1 to Het-6; wherein, # indicates the point of attachment to A.
  • the present invention provides a compound of formula (IA), wherein, R 1 , A, L 1 , R 6 and R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A),
  • the present invention provides a compound of formula (IA-A1), wherein, m is an integer selected from 0 to 4, and R 1 , R A , R 6 , R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A2), wherein, m is an integer selected from 0 to 4; and R 1 , R A , R 4 , R 5 , R 6 , R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A3), wherein, m is an integer selected from 0 to 4; and R 1 , R A , R 6 , R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A4), wherein, m is an integer selected from 0 to 4; and R 1 , R A , R 4 , R 5 , R 6 , R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A5), wherein, m is an integer selected from 0 to 4; and R 1 , R A , R 4 , R 5 , R 6 , R ’ , R 7 are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A6), ( ) wherein, R 1 , R A , R 4 , R 5 , R 6 , R 7 and m are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-A7), wherein, R 1 , R A , R 4 , R 5 , R 6 , R 7 and m are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-B), wherein, R 1 , R A , R 6 , R 7 and m are as defined in the above detailed description.
  • the present invention provides a compound of formula (IA-B1), Formula (IA-B1) wherein, R 1 , R A , R 6 , R 7 and m are as defined in the above detailed description.
  • the present invention provides the compound of formula (I), wherein R 1 is selected from the group consisting of CF 3 , CF 2 H and CF 2 Cl.
  • R 1 is selected from the group consisting of CF 3 , CF 2 H and CF 2 Cl.
  • the present invention provides the compound of formula (I), wherein A is phenyl, napthalenyl, furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, imidazolyl, oxadiazolyl, triazolyl, pyridinyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, indolyl, benzimidazolyl, indazolyl, benzofuranyl, benzothiophenyl, benzothiazolyl, benzoxazolyl, quinolinyl, isoquinolinyl, quin
  • the present invention provides the compound of formula (I), wherein R A is selected from the group consisting of halogen, cyano, nitro, thiol, amino, hydroxy, C 1 - C 6 -alkyl, C 3 -C 8 -cycloalkyl, C 3 -C 8 -cycloalkylalkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, C 1 -C 6 - hydroxyalkyl, C 3 -C 8 -halocycloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 1 -C 6 -haloalkoxycarbonyl.
  • R A is selected from the group consisting of halogen, cyano, nitro, thiol, amino, hydroxy, C 1 - C 6 -alkyl, C 3 -C 8 -cycloal
  • the present invention provides the compound of formula (I), wherein R 4 and R 5 are selected from the group consisting of hydrogen, halogen, hydroxy, cyano, C 1 - C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy and C 1 -C 6 -haloalkoxy.
  • the present invention provides the compound of formula (I), wherein R 6 and R 7 are selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -cycloalkenyl, C 1 -C 6 -haloalkyl, –OR 8 , -NR 9 R 10 , C 6 -C 10 -aryl, C 7 -C 14 - aralkyl, C 3 -C 10 -heterocyclyl and C 3 -C 10 -heterocyclyl-C 1 -C 6 -alkyl; wherein the ring member atoms of the heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from N, O and S; and wherein the aliphatic or cyclic groups of R 6 and R 7 are unsubstit
  • the present invention provides the compound of formula (I), wherein R 7a is selected from the group consisting of C 1 -C 6 -alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 - C 6 -haloalkoxy, C 6 -C 10 -aryl, C 7 -C 14 -aralkyl, C 3 -C 10 -heterocyclyl and C 3 -C 10 -heterocyclyl-C 1 -C 6 -alkyl; wherein the aliphatic or cyclic moieties of R 7a may optionally be substituted with one or more groups of R 7aa selected from the group consisting of halogen, cyano, nitro, hydroxyl, thiol, amino, C 1 -C 6 - alkyl, C 1 -C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6
  • the present invention provides the compound of formula (I), wherein R 8 is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl and C 1 -C 6 -haloalkyl.
  • the present invention provides the compound of formula (I), wherein R 9 and R 10 are selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, C 6 -C 10 -aryl, C 7 -C 14 -aralkyl, C 3 -C 10 -heterocyclyl, C 3 -C 10 - heterocyclyl-C 1 -C 6 -alkyl; wherein the aliphatic or cyclic groups of R 9 are unsubstituted or substituted by 1, 2, 3 or up to the maximum possible number of identical or different groups R 9a .
  • the present invention provides the compound of formula (I), wherein R 9 and R 10 together with the N atom to which they are attached may form a saturated or partially unsaturated monocyclic 5 to 6 membered heterocycle, wherein the heterocycle includes beside one nitrogen atom and one or more carbon atoms 1, 2 or 3 heteroatoms independently selected from N and O as ring member atoms.
  • the present invention provides the compound of formula (I), wherein R 9a is selected from the group consisting of halogen, cyano, nitro, hydroxyl, C 1 -C 6 -alkyl, C 1 - C 6 -haloalkyl, C 1 -C 6 -alkoxy, C 1 -C 6 -haloalkoxy and C 3 -C 8 -cycloalkyl.
  • the present invention provides the compound of formula (I), wherein R’ is selected from the group consisting of hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 1 -C 6 - haloalkyl, C 1 -C 6 -alkoxy and C 1 -C 6 -haloalkoxy.
  • the compound of formula (I) of the present invention is selected from ethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinate, ethyl bis(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphinate, diethyl (4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)benzyl)phosphonate, methyl(piperidin-1-yl)(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphine oxide, methyl(piperidin-1-yl)(1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)ethyl)phosphine oxide, ethyl methyl(4-
  • the compounds of the present disclosure may be present either in pure form or as mixtures of different possible isomeric forms such as stereoisomers or constitutional isomers.
  • the various stereoisomers include enantiomers, diastereomers, chiral isomers, atropisomers, conformers, rotamers, tautomers, optical isomers, polymorphs, and geometric isomers. Any desired mixtures of these isomers fall within the scope of the claims of the present disclosure.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s).
  • An anion part of the salt in case the compound of Formula (I) is a cationic or capable of forming a cation can be inorganic or organic.
  • a cation part of the salt in case the compound of formula (I) is an anionic or capable of forming anion can be inorganic or organic.
  • examples of inorganic anion part of the salt include but are not limited to chloride, bromide, iodide, fluoride, sulfate, phosphate, nitrate, nitrite, hydrogen carbonates, hydrogen sulfate.
  • organic anion part of the salt examples include but are not limited to formate, alkanoates, carbonates, acetates, trifluoroacetate, trichloroacetate, propionate, glycolate, thiocyanate, lactate, succinate, malate, citrates, benzoates, cinnamates, oxalates, alkylsulphates, alkylsulphonates, arylsulphonates aryldisulphonates, alkylphosphonates, arylphosphonates, aryldiphosphonates, p-toluenesulphonate, and salicylate.
  • inorganic cation part of the salt examples include but are not limited to alkali and alkaline earth metals.
  • organic cation part of the salt examples include but are not limited to pyridine, methyl amine, imidazole, benzimidazole, hitidine, phosphazene, tetramethyl ammonium, tetrabutylammonium, choline and trimethylamine.
  • Metal ions in metal complexes of the compound of formula (I) are especially the ions of the elements of the second main group, especially calcium and magnesium, of the third and fourth main group, especially aluminium, tin and lead, and also of the first to eighth transition groups, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Particular preference is given to the metal ions of the elements of the fourth period and the first to eighth transition groups.
  • the metals can be present in the various valencies that they can assume.
  • 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).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by formula (I) can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by formula (I).
  • Preparation and isolation of a particular polymorph of a compound represented by formula (I) can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • the present invention provides a process for the synthesis of a compound of formula (I), wherein the definitions of Het, A, L 1 , R 6 , R 7 , R 9 and R 10 in the compounds of formula (I) and in the compounds of formula 1 to 16 are as defined in the above detailed description of the invention unless otherwise specifically stated.
  • the present invention provides a process for preparing the compound of formula (I) comprising the steps of: a) reacting a compound of formula 3 with a compound of formula R 6 -X wherein X is Cl, Br or I; to affford a compound of formula 4; b) reacting a compound of formula 4 with hydroxyl amine to afford a compound of formula 5; c) reacting a compound of formula 5 with a suitable carboxylic acid anhydride of formula (a) or a suitable acid chloride of formula (b) to afford a compound of formula 6, wherein Het is Het- 1; d) reacting a compound of formula 6 with a suitable chlorinating reagent to afford a compound of formula 7; wherein, R 6 is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - alkynyl, C 3 -C 6 -cycloalkyl and C 3 -C
  • the process for the synthesis of compound of formula (I) further comprising the steps of: f) reacting a compound of formula 15 with a suitable chlorinating reagent to afford a compound of formula (I); wherein, R 6 is -OEt; Het, A, L 1 , R 6 , R 9 and R 10 are as defined in claim 1; g) reacting a compound of formula 14 with a compound of formula HNR 9 R 10 to afford a compound of formula (I); wherein, R 6 is -OEt; R 7 is -NR 9 R 10 .
  • the present invention provides a process for preparing the compound of formula (I) comprising the steps of: a) reacting a compound of formula 9 with hydroxyl amine to afford a compound of formula 10; b) reacting a compound of formula 10 with a suitable carboxylic acid anhydride of formula (a) or acid chloride of formula (b) to obtain a compound of formula 11, wherein Het is Het-1; c) reacting a compound of formula 11 with suitable halogenating reagent to afford a compound of formula 12; d) reacting the compound of formula 12 with a suitable reagent to afford a compound of formula 13; e) reacting the compound of formula 13 with suitable chlorinating reagent to afford a compound of formula 14; f) reacting a compound of formula 14 with a compound of formula HNR 9 R 10 to afford a compound of formula (I);
  • the following schemes illustrate approaches to generate compounds of formula (I).
  • the compounds of the present invention as defined by formula (I) and/or in the tables 1 to 8 may be prepared, in known manner, in a variety of ways as described in the schemes 1-6; General scheme: 1 wherein, L 1 is CH 2 ; X is Cl, Br or I; and Het is ; R 6 is selected from the group consisting of C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl and C 3 -C 6 -cycloalkenyl; A, R 1 , R 7 , R 9 and R 10 are as defined in the detailed description above.
  • the compound of formula 2 can be obtained by reacting the compound of formula 1 with a preformed complex of anilinium hypophosphite and hexamethyldisilazane. This reaction is typically carried out in a suitable aprotic solvent such as dichloromethane, toluene, acetonitrile, tetrahydrofuran, and the like at a suitable temperature ranging from 0 to 35 °C.
  • a suitable aprotic solvent such as dichloromethane, toluene, acetonitrile, tetrahydrofuran, and the like at a suitable temperature ranging from 0 to 35 °C.
  • the complex of anilinium hypophosphite and hexamethyldisilazane can be prepared by reacting an equimolar mixture of anilinium hypophosphite and hexamethyldisilazane at a suitable temperature ranging from 100 to 110 °C.
  • the compound of formula 3 can be obtained by esterification of the compound of formula 2 with ethanol in the presence of a suitable esterification reagent such as pivaloyl chloride and a suitable solvent such as pyridine. This reaction can be carried out at a temperature ranging from 0 to 35 °C.
  • the compound of formula 3 can also be obtained by reacting the compound of formula 2 with ethanol in the presence of a suitable coupling reagent such as N,N′-dicyclohexylcarbodiimide (DCC), 4-dimethylaminopyridine (DMAP), and the like at an ambient temperature (Tetrahedron Letters, 2005, vol.46, issue: 19, p.3359 – 3362).
  • Step: 3 The compound of formula 4 can be obtained by alkylating the compound of formula 3 with a compound of formula R 6 -X wherein X is Cl, Br or I, in the presence of a suitable base such as lithium bis(trimethylsilyl)amide and in a suitable aprotic solvent such as tetrahydrofuran, at a temperature ranging from -78 °C to 25 °C.
  • a suitable base such as lithium bis(trimethylsilyl)amide
  • a suitable aprotic solvent such as tetrahydrofuran
  • Step: 5 The compound of formula 6 wherein Het is ; can be obtained by reacting the compound of formula 5 with carboxylic acid anhydride of formula (a) or acid chloride of formula (b).
  • Step: 6 The compound of formula 7 can be obtained by reacting the compound of formula 6 with a suitable reagent such as oxalyl chloride or thionyl chloride. This reaction can be carried out in a suitable solvent such as dichloromethane at a temperature ranging from 0 to 40 °C.
  • Step: 7 The compound of formula (I) wherein L 1 is CH 2 ; Het is and R 6 is methyl can be obtained by reacting the compound of formula 7 with the compound of formula HNR 9 R 10 in the presence of a suitable base such as triethylamine, N,N-diisopropylethylamine, and the like at a temperature ranging from 0 to 50 °C. This reaction is carried out in a suitable solvent such as dichloromethane, tetrahydrofuran, ethyl acetate, and the like.
  • a suitable base such as triethylamine, N,N-diisopropylethylamine, and the like at a temperature ranging from 0 to 50 °C.
  • a suitable solvent such as dichloromethane, tetrahydrofuran, ethyl acetate, and the like.
  • Step 1 The compound of formula 4 wherein L 1 is CH 2 can be directly obtained by reacting the compound of formula 1 wherein L 1 is CH 2 and X is Cl, Br or I, with compound of formula (iii) (Arbuzov reaction) optionally in the presence of a suitable base such as sodium hydroxide. This reaction may optionally be carried out in a suitable solvent such as toulene, acetonitrile, N,N-dimethylformamide, and the like at a temperature ranging from 90 to 120 °C. [Tetrahedron, 1984, 40, p. 2731; Australian Journal of Chemistry, 1983, 36, 12, p.2517 – 2536].
  • Step: 1 The compound of formula 10 can be obtained by reacting the compound of formula 9 with hydroxyl amine in a suitable polar protic solvent such as ethanol, methanol, and the like. Alternatively, this reaction can also be carried out by using hydroxylamine hydrochloride in the presence of suitable organic and/or inorganic bases such as triethylamine, N,N-diisopropylethylamine, sodium bicarbonate, and the like.
  • Step: 2 The compound of formula 11 wherein Het is ; can be obtained by reacting the compound of formula 10 with carboxylic acid anhydride of formula (a) or acid chloride of formula (b). These reactions are typically performed in a suitable aprotic solvent such as tetrahydrofuran, 1,4-dioxane, dichloromethane, and the like optionally in the presence of a suitable base such as triethylamine, N,N- diisopropylethylamine, and the like at temperature ranging from 0 to 50 °C.
  • a suitable aprotic solvent such as tetrahydrofuran, 1,4-dioxane, dichloromethane, and the like
  • a suitable base such as triethylamine, N,N- diisopropylethylamine, and the like at temperature ranging from 0 to 50 °C.
  • Step: 3 The compound of formula 12 wherein Het is or in which R 1 is CF 3 ; can be obtained by radical halogenation of compound of formula 11 with a suitable halogenating reagent such as N-bromosuccinimide or N-chlorosuccinimide in the presence of a suitable radical initiator such as azobisisobutyronitrile or benzoyl peroxide.
  • a suitable radical initiator such as azobisisobutyronitrile or benzoyl peroxide.
  • This reaction can be carried out in a suitable solvent such as chloroform, carbon tetrachloride and the like at refluxing temperatures.
  • Step: 4 The compound of formula 13 wherein L 1 is CH 2 ; Het is or in which R 1 is CF 3 can be obtained by reacting the compound of formula 12 wherein L 1 is CH 2 ; Het is o wherein R 1 is CF 3 , with triethyl phosphite at a temperature ranging from 30 to 110 °C.
  • the compound of formula 13 wherein L 1 is a direct bond; Het is or wherein R 1 is CF 3 can be obtained by reacting the compound of formula 12 wherein L 1 is a direct bond; Het is wherein R 1 is CF 3 , with diethyl phosphonate in the presence of Pd (0) catalyst such as tetrakis(triphenylphosphine)palladium. This reaction is typically carried out in presence of a suitable base such as triethylamine, diisopropyl ethyl amine, and the like at temperature ranging from 50 °C to 90 °C.
  • Pd (0) catalyst such as tetrakis(triphenylphosphine)palladium.
  • Step: 5 The compound of formula 14 wherein L 1 is CH 2 or a direct bond; Het is or wherein R 1 is CF 3 ; can be obtained by reacting the compound of formula 13 with a suitable chlorinating reagent such as phosphorous oxychloride at temperature ranging from 0 to 80 °C.
  • a suitable chlorinating reagent such as phosphorous oxychloride at temperature ranging from 0 to 80 °C.
  • Step: 6 The compound of formula (I) wherein L 1 is CH 2 or a direct bond; Het is or wherein R 1 is CF 3 ; R 6 is -OEt; R 7 is -NR 9 R 10 ; can be obtained by reacting the compound of formula 14 with the compound of formula HNR 9 R 10 in the presence of a suitable base such as triethylamine, N,N- diisopropylethylamine, and the like at a temperature ranging from 0 to 50 °C. This reaction is carried out in a suitable solvent such as dichloromethane, tetrahydrofuran, ethyl acetate, and the like.
  • a suitable base such as triethylamine, N,N- diisopropylethylamine, and the like
  • the compound of formula 15 can be obtained by reacting the compound of formula 6 with a suitable chlorinating reagent such as oxalyl chloride to obtain the chloride derivative of compound of formula 15 which was hydrolysed with water at 0-5 °C to obtain compound of formula 15.
  • a suitable chlorinating reagent such as oxalyl chloride
  • This reaction is typically carried out in a suitable solvent such as dichloromethane.
  • this reaction can also be carried out by reacting the compound of formula 6 with trimethylsilyl bromide as reported in the Journal of Medicinal Chemistry, 1998, vol. 41, # 5, p. 752 – 759.
  • Step: 2 The compound of formula (I) wherein R 7 is -NR 9 R 10 is obtained by reacting compound of formula 15 with a suitable amine of formula HNR 9 R 10 in the presence of a suitable coupling reagent such as 1-(3- dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 4-dimethylaminopyridine. This reaction is carried out in a suitable solvent such as tetrahydrofuran at refluxing temperature.
  • Step: 1 The compound of formula 15 can be obtained by reacting the compound of formula 6 with lithium bromide. This reaction is typically carried out in a suitable solvent such as 2-pentanone at refluxing temperature.
  • Step: 2 The compound of formula 14 can be obtained by reacting the compound of formula 15 with a suitable chlorinating reagent such as oxalyl chloride or thionyl chloride. This reaction can be carried out in a suitable solvent such as dichloromethane at a temperature ranging from 0 to 40 °C optionally in the presence of a suitable catalyst such as dimethylformamide.
  • a suitable chlorinating reagent such as oxalyl chloride or thionyl chloride.
  • the present invention relates to an agrochemical composition
  • an 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.
  • the compound of formula (I) and the composition according to the invention, respectively, are suitable as fungicides.
  • Plasmodiophoromycetes Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).
  • 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.
  • 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.
  • 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 10 kg ai (kilogram per active ingredient) per 100 kg of seeds.
  • 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.
  • treatment 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.
  • cultiva 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.
  • auxin herbicides such as dicamba or 2,4-D
  • bleacher herbicides such as hydroxylphenylpyruvate dioxygena
  • 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. Cry1A(b), Cry1A(c), Cry1F, Cry1F(a2), Cry11A(b), Cry111A, Cry111B(b1) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1A(b), Cry1A(c), Cry1F, Cry1F(a2), Cry11A(b), Cry111A, Cry111B(b1) or Cry9c vegetative insecticidal proteins (VIP), e. g. VIP1, VIP2, VIP3 or VIP3A
  • insecticidal proteins of bacteria colonizing nematodes e. g. Photorhabdus spp.
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibitors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA- reductase
  • ion channel blockers such as blockers of sodium or calcium channels
  • 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 Cry1Ac 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.
  • PR proteins pathogenesis-related proteins
  • 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 present invention also relates to a method for combating infestation of plants by phytopathogenic micro-organisms in agricultural crops and or horticultural crops wherein an effective amount of at least one compound of formula (I) or the combination of the present invention or the composition of the present invention, is applied to the seeds of plants.
  • the compound, the combination and the composition of the present invention can be used for combating 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.
  • Albugo spp. white rust
  • vegetables e. g. A. Candida
  • sunflowers e. g. A. tragopogonis
  • Altemaria spp. Alternaria leaf spot
  • rape A. brass
  • 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) spp. (rot or wilt) on broad-leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cercospora leaf spots) on corn (e. g.
  • Gray leaf spot C. zeae-maydis
  • rice sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice
  • Cladosporium spp. on tomatoes e. g. C. fulvum: leaf mold
  • cereals e. g. C. herbarum (black ear) on wheat
  • Cochliobolus anamorph: Helminthosporium of Bipolaris
  • spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C.
  • sativus anamorph: B. sorokiniana
  • rice e. g. C. miyabeanus, anamorph: H. oryzae
  • Colletotrichum teleomorph: Glomerella
  • spp. anthracnose on cotton (e. g. C. gossypii), corn (e. g. C. graminicola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. C.
  • sasakii sheath blight
  • Corynespora cassiicola leaf spots
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleomorph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. D.
  • tritici-repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£.
  • 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.
  • Non-limiting examples of pathogens of fungal diseases which can be treated in accordance with the invention include: Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae, rusts for example those caused by Pucciniales such as Cerotelium fici, Chrysomyxa arctostaphyli, Coleosporium ipomoeae, Hemileia vastatrix, Puccinia arachidis, Puccinia cacabata, Puccinia graminis, Puccinia recondita, Puccinia sorghi, Puccinia hordei, Puccinia striiformis f.sp.
  • Ustilaginales such as Ustilaginoidea virens, Ustilago nuda, Ustilago tritici, Ustilago zeae
  • rusts for example those caused by Pucciniales such as
  • Puccinia striiformis f.sp. Secalis Pucciniastrum coryli, or Uredinales such as Cronartium ribicola, Gymnosporangium juniperi-viginianae, Melampsora medusae, Phakopsora pachyrhizi, Phragmidium mucronatum, Physopella ampelosidis, Tranzschelia discolor and Uromyces viciae-fabae; and other rots and diseases such as those caused by Cryptococcus spp., Exobasidium vexans, Marasmiellus inoderma, Mycena spp., Sphacelotheca reiliana, Typhula ishikariensis, Urocystis agropyri, ltersonilia perplexans, Corticium invisum, Laetisaria fuciformis, Waitea circinata, Rhizoctonia solani
  • Blastocladiomycetes such as Physoderma maydis.
  • Mucoromycetes such as Choanephora cucurbitarum; Mucor spp.; and Rhizopus arrhizus
  • 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; In particular, Cronartium ribicola (White pine blister rust); Gymnosporangium juniperi-virginianae (Cedar-apple rust); Hemileia vast
  • 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
  • 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. (for example banana trees and plantations), Rubiaceae sp.
  • Rosaceae sp for example pome fruits such as apples, pears, apricots, cherries, almonds and peaches
  • Ribesioidae sp. Juglandaceae sp.
  • Betulaceae sp. Ana
  • Theaceae 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 combating 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 present invention further relates to the use of the compound of formula (I), the combination or the composition thereof for combating against phytopathogenic fungi such as Phakopsora pachyrhizi, Phakopsora meibomiae, of agricultural crops and or horticultural crops.
  • 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
  • Candida spp. and Saccharomyces cerevisae are particularly suitable for controlling the following plant diseases: Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans.
  • the present invention further relates to a method for combating 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 the combination or the 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 to 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.
  • 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 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.
  • the above identified indicators for the health condition of a plant may be interdependent or may result from each other.
  • the compound of formula (I) can be present in different crystal modifications or polymorphs whose biological activity may differ. They are likewise subject matter of the present invention.
  • the compounds of formula (I) are employed as such or in the form of a 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 ingredients.
  • 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.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound of formula (I).
  • An agrochemical composition comprises a fungicidally effective amount of a compound of formula (I).
  • 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 compound of formula (I), their -oxides, metal complexes, isomers, polymorphs or the agriculturally acceptable salts thereof can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • agrochemical compositions e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e. g. SC, OD, FS), emulsifiable concentrates (e. g. EC), emulsions (e.
  • compositions types are defined in the "Catalogue of pesticide Formulation types and international coding system", Technical Monograph No.2, 6 th Ed.
  • 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.
  • Suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifiers 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.
  • Suitable solid carriers or fillers are mineral earths, e. g.
  • silicates silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides, e. g. cellulose, starch; fertilizers, e. g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e. g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as 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, sulfates, 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.
  • sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • phosphates are phosphate esters.
  • carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-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. Application 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 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.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate, not until immediately prior to use (tank mix).
  • pesticides e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • the invention disclosed in the present disclosure shall now be elaborated with the help of non-limiting examples.
  • Example 1 Preparation of methyl(piperidin-1-yl)(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphine oxide (Compound no 4) and methyl(piperidin-1-yl)(1-(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)phosphine oxide (Compound no 5) a) Step 1: (4-cyanobenzyl)phosphinic acid A mixture of Anilinium hypophosphite (11.44 g, 72 mmol) and hexamethyldisilazane (15.1 mL, 72 mmol) were taken together and was heated at 110 °C under nitrogen for 3 h till the reaction mixture became clear.
  • reaction mixture was then cooled to 0 °C, and dichloromethane (50 mL) was added followed by the addition of 4-(bromomethyl) benzonitrile (9.9 g, 50.3 mmol).
  • the resulting reaction mixture was stirred at 25 °C for 16 h.
  • 10 % aqueous sodium hydroxide solution 50 mL was added drop wise to the reaction mixture at 0-5 °C to adjust it to pH 10, and stirring was continued for 10 min.
  • the aqueous layer was separated and acidified to pH 3 by adding of a 4 M aqueous hydrochloric acid solution. This aqueous layer was concentrated to dryness.
  • Step 2 ethyl (4-cyanobenzyl)phosphinate (4-Cyanobenzyl) phosphinic acid (8.5g, 47 mmol) was dissolved in ethanol (80 mL) and cooled to 0 °C. Pyridine (8.73 mL, 108 mmol) was added and the reaction mixture was stirred for 10 minutes.
  • Step 3 ethyl (4-cyanobenzyl)(methyl)phosphinate and ethyl (1-(4- cyanophenyl)ethyl)(methyl)phosphinate
  • Ethyl (4-cyanobenzyl)phosphinate (3 g, 14.3 mmol) was dissolved in anhydrous tetrahydrofuran (10 mL) under nitrogen atmosphere. The solution was cooled to -78 °C and purged with nitrogen for 5 min. Lithium bis(trimethylsilyl)amide (14.3 mL, 14.3 mmol) was added at -78 °C, and the reaction mixture was stirred for 10 min.
  • Methyl iodide (0.9 mL, 14.3 mmol) was added and the resulting reaction mixture was slowly allowed to warm to 25 °C within 3 h. After completion of the reaction, the reaction mixture was quenched with aqueous saturated ammonium chloride solution (20 mL). The product was extracted twice with ethyl acetate (60 mL). The combined ethyl acetate layers were dried over anhydrous sodium sulphate and concentrated under reduced pressure.
  • the resulting crude product was purified by column chromatography to obtain a 2:1 mixture of ethyl (4- cyanobenzyl)(methyl)phosphinate and ethyl (1-(4-cyanophenyl)ethyl)(methyl)phosphinate (2 g).
  • Step 4 ethyl (4-(N'-hydroxycarbamimidoyl)benzyl)(methyl)phosphinate and ethyl (1-(4-(N'- hydroxycarbamimidoyl)phenyl)ethyl)(methyl)phosphinate
  • a solution of a 2:1 mixture of ethyl (4-cyanobenzyl)(methyl)phosphinate and ethyl (1-(4- cyanophenyl)ethyl)(methyl)phosphinate 1.7 g
  • 50 % aqueous hydroxylamine solution 0.06 mL, 14.8 mmol
  • Step 5 ethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinate (Compound no.
  • the reaction mixture was diluted with 50 mL of ethyl acetate and washed with a saturated aqueous solution of sodium bicarbonate (25 mL).
  • the ethyl acetate layer was dried over anhydrous sodium sulphate and concentrated to obtain 2.3 g of a crude product containing a mixture of ethyl methyl(1- (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)phosphinate and ethyl methyl(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinate.
  • 0.4 g of the crude product was purified by prep-HPLC to isolate two pure compounds.
  • Ethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinate (compound no. 1): 1 H- NMR (400 MHz, DMSO-d6) ⁇ 8.00 (d, 2H), 7.51 (dd, 2H), 3.87-4.00 (m, 2H), 3.35 (s, 1H), 1.32-1.37 (m, 3H), 1.18 (t, , 3H); LCMS (M+H): 334.95. Ethyl methyl(1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)phosphinate (compound no.
  • Step 6 methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinic chloride and methyl(1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)phosphinic chloride
  • a solution of a 2:1 mixture of ethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphinate and ethyl methyl(1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)ethyl)phosphinate 1.5 g) in dichloromethane (5 mL), oxalyl chloride (2 M in dichloromethane) (4.3 mL, 8.6 mmol) was added at 0 °C, and the
  • reaction mixture was concentrated under reduced pressure to obtain a crude product containing a 2:1 mixture of methyl(4-(5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl)benzyl)phosphinic chloride and methyl(1-(4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)phenyl)ethyl)phosphinic chloride (1.4 g). It was used as such in the next step without purification.
  • Step 7 methyl(piperidin-1-yl)(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphine oxide (Compound no 4) and methyl(piperidin-1-yl)(1-(4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)phenyl)ethyl)phosphine oxide (Compound no 5)
  • piperidine 0.293 mL, 2.9 mmol
  • triethylamine 1.0 mL, 7.4 mmol
  • dichloromethane 7.4 mmol
  • the resulting reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with dichloromethane (10 mL) and washed with a saturated aqueous solution of sodium bicarbonate (20 mL). The dichloromethane layer was separated, dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain crude product.
  • the obtained crude product was purified by prep-HPLC to obtain methyl(piperidin-1-yl)(4- (5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphine oxide (65 mg) and methyl(piperidin-1- yl)(1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)ethyl)phosphine oxide (110 mg).
  • Example 2 Preparation of ethyl bis(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)phosphinate (Compound no.2) a) Step 1: ethyl bis(4-cyanophenyl)phosphinate To a stirred mixture of 1-bromo-4-iodobenzene (0.3 g, 1.1 mmol) and anilinium hypophosphite (0.337 g, 2.1 mmol) in acetonitrile (10 mL), (3-aminopropyl)triethoxysilane (0.494 mL, 2.1 mmol) was added at 25 °C.
  • reaction mixture was degassed by nitrogen gas for 10 min.
  • [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) complex with dichloromethane (0.07 g, 0.085 mmol) was added and the mixture was degassed again for 5 min.
  • the reaction mixture was heated at 80 °C for 3 h.
  • the reaction mixture was basified using sodium bicarbonate and extracted with 10 % ethyl acetate in hexane.
  • the aqueous layer was acidified using 10 % aqueous hydrochloric acid to pH 3 and extracted by 10 % methanol in dichloromethane (20 mL).
  • the organic layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by column chromatography on silica gel using 70 % ethyl acetate in hexane as an eluent to obtain ethyl bis(4- cyanophenyl)phosphinate (0.156 g, 50 % yield).
  • Step 2 ethyl bis(4-(N'-hydroxycarbamimidoyl)phenyl)phosphinate
  • a solution of ethyl bis(4-cyanophenyl)phosphinate (0.35 g, 1.2 mmol) in ethanol (10 mL) hydroxylamine (50 % aqueous solution) (0.762 mL, 5.9 mmol) was added at 25 °C and stirred for 16 h. After completion of the reaction, the reaction mixture was concentrated to obtain ethyl bis(4-(N'- hydroxycarbamimidoyl)phenyl)phosphinate (0.42 g, 98 % yield).
  • Step 3 ethyl bis(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphinate
  • ethyl bis(4-(N'-hydroxycarbamimidoyl)phenyl)phosphinate 0.428 g, 1.2 mmol
  • trifluoroacetic anhydride 0.5 mL, 3.5 mmol
  • the reaction mixture was poured into ice cold saturated solution of sodium bicarbonate in water (20 mL).
  • the product was extracted by ethyl acetate (20 mL). The ethyl acetate layer was dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography on silica gel using 50 % ethyl acetate in hexane as an eluent to obtain ethyl bis(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphinate (0.25 g, 41 % yield).
  • Example 3 Preparation of ethyl N-isobutyl-P-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphonamidate (Compound no.20) a) Step 1: diethyl (4-cyanobenzyl)phosphonate A solution of 4-(bromomethyl)benzonitrile (5 g, 25.5 mmol) and triethyl phosphite (8.92 mL, 51 mmol) was stirred at 110 °C for 16 h.
  • Step 2 (4-(N'-hydroxycarbamimidoyl)benzyl)phosphonate
  • diethyl (4-cyanobenzyl)phosphonate 5 g, 19.7 mmol
  • hydroxylamine 50% aqueous solution
  • the resulting reaction mixture was stirred at 60 °C for 10 h.
  • the reaction mixture was concentrated under reduced pressure to remove the volatiles and to obtain diethyl (4-(N'- hydroxycarbamimidoyl)benzyl)phosphonate (5 g, 88 % yield).
  • Step 3 diethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphonate (compound no.3)
  • diethyl (4-(N'-hydroxycarbamimidoyl)benzyl)phosphonate (5 g, 17.47 mmol)
  • trifluoroacetic anhydride (4.44 mL, 31.4 mmol) was added slowly at 0-5 °C under nitrogen atmosphere.
  • the resulting reaction mixture was stirred for 12 h at 25 °C.
  • Step 4 ethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphonochloridate Phosphorous oxychloride (138 ⁇ l, 1.482 mmol) was added to diethyl (4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)benzyl)phosphonate (450 mg, 1.235 mmol) at 5-10 °C. To this reaction mixture, N,N- dimethylformamide (0.053 mL, 0.686 mmol) was added and the resulting reaction mixture was stirred at 80 °C for 6 h under nitrogen atmosphere.
  • N,N- dimethylformamide 0.053 mL, 0.686 mmol
  • Step 5 ethyl N-isobutyl-P-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphonamidate
  • ethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphonochloridate 150 mg, 0.423 mmol
  • dichloromethane 5 mL
  • 2-methylpropan-1-amine 0.63 mL, 0.6 mmol
  • triethylamine 0.088 mL, 0.6 mmol
  • the resulting reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was diluted with ethyl acetate (10 mL) and washed twice with water (10 mL). The ethyl acetate layer was separated, dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by flash column chromatography on silica gel using eluent 60 % ethyl acetate/hexane to obtain ethyl N-isobutyl-P-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol- 3-yl)benzyl)phosphonamidate (60 mg, 36 % yield).
  • Example 4 Preparation of N-(4-fluorophenyl)-P-methyl-P-(4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)benzyl)phosphinic amide (Compound no.46) a) Step 1 : methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinic acid To a solution of ethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinate (8.2 g, 24.5 mmol) in dichloromethane (60 mL), oxalyl chloride (5.37 mL, 61.3 mmol) was added at 0 °C.
  • reaction mixture was stirred at 25 °C for 16 h. After completion of reaction, the reaction mixture was cooled to 0 °C, water (6 mL) was added dropwise until all the effervescences ceases. Volatiles were removed under reduced pressure and the crude was co-distilled with toluene to remove traces of water to obtain methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinic acid (7 g, 93 % yield).
  • Step 2 N-(4-fluorophenyl)-P-methyl-P-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphinic amide (Compound no.46)
  • 4-fluoroaniline (0.44 g, 3.9 mmol)
  • methyl(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphinic acid 0.4 g, 1.3 mmol
  • 4- dimethylaminopyridine 0.319 g, 2.6 mmol
  • Example 5 Preparation of N-phenyl-P-(4-(5-(trifluoromethyl)-1,3,4-oxadiazol-2- yl)benzyl)phosphonamidate (Compound no.52) a) Step 1: 5-(p-tolyl)-1H-tetrazole To a stirred solution of 4-methylbenzonitrile (40 g, 341 mmol) in N,N-dimethylformamide (150 mL), sodium azide (24.42 g, 376 mmol) was added at 25 °C and cooled to 0 °C. To the obtained mixture, ceric ammonium nitrate (28 g, 51 mmol) was slowly added.
  • 4-methylbenzonitrile 40 g, 341 mmol
  • N,N-dimethylformamide 150 mL
  • sodium azide 24.42 g, 376 mmol
  • ceric ammonium nitrate 28 g, 51 mmol
  • the resulting reaction mixture was stirred at 120 °C for 6 h. After completion of the reaction, the reaction mixture was cooled to 25 °C and crushed ice (300g) was added portion wise into it under stirring. Stirring was continued for 10 minutes to obtain a precipitate. The precipitate was filtered, washed with water and dried under reduced pressure to obtain 5-(p-tolyl)-1H-tetrazole (42 g, 77 % yield).
  • Step 3 2-(4-(bromomethyl)phenyl)-5-(trifluoromethyl)-1,3,4-oxadiazole
  • 2-(p-tolyl)-5-(trifluoromethyl)-1,3,4-oxadiazole 15 g, 66 mmol
  • chloroform 200 mL
  • N-bromosuccinimide (12.87 g, 72.3 mmol) was added and stirred at 70 °C for 10 minutes.
  • 2,2′-azobis(2-methylpropionitrile) 1.295 g, 7.89 mmol
  • Step 4 diethyl (4-(5-(trifluoromethyl)-1,3,4-oxadiazol-2-yl)benzyl)phosphonate
  • a mixture of triethyl phosphate (1 g, 5.5 mmol) and 2-(4-(bromomethyl)phenyl)-5-(trifluoromethyl)- 1,3,4-oxadiazole (1.69 g, 5.49 mmol) was stirred at 70 °C for 2 h. The mixture was concentered under reduced pressure to obtain diethyl (4-(5-(trifluoromethyl)-1,3,4-oxadiazol-2-yl)benzyl)phosphonate (1.6 g, 80 % yield).
  • Step 5 (4-(5-(trifluoromethyl)-1,3,4-oxadiazol-2-yl)benzyl)phosphonochloridate Phosphorus oxychloride (1.54 mL, 16.47 mmol) was added dropwise at 0 °C to diethyl (4-(5- (trifluoromethyl)-1,3,4-oxadiazol-2-yl)benzyl)phosphonate (2 g, 5.5 mmol) and stirred for 15 min. Then to this solution, N,N-dimethylformamide (0.043 mL, 0.55 mmol) was added dropwise at 0 °C, and the resulting reaction mixture was stirred at 80 °C for 4 h.
  • N,N-dimethylformamide 0.043 mL, 0.55 mmol
  • the resulting reaction mixture was stirred at 25 °C for 48 h. After completion of the reaction, the reaction mixture was quenched by pouring into 10 % aqueous hydrochloric acid solution (50 mL) at 0-5 °C. The product was extracted by ethyl acetate (150 mL). The ethyl acetate layer was washed with water (50 mL), dried over anhydrous sodium sulphate and concentrated under reduce pressure to obtain a crude product.
  • Example 6 Preparation of ethyl N-(2,4-difluorophenyl)-P-((7-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)imidazo[1,2-a]pyridin-2-yl)methyl)phosphonamidate (Compound no.66) a) Step 1: 2-(Chloromethyl)imidazo[1,2-a]pyridine-7-carbonitrile To a stirred solution of 2-aminoisonicotinonitrile (5 g, 42.0 mmol) in ethanol (30 mL), 1,3- dichloropropan-2-one (10.66 g, 84 mmol) was added, and stirred was continued at 90 °C for 36 h.
  • Step 4 Diethyl ((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)imidazo[1,2-a]pyridin-2- yl)methyl)phosphonate (Compound no.64) To a stirred solution of diethyl ((7-(N'-hydroxycarbamimidoyl)imidazo[1,2-a]pyridin-2- yl)methyl)phosphonate (0.4 g, 1.2 mmol) in tetrahydrofuran (10 mL), trifluoroacetic anhydride (0.312 mL, 2.2 mmol) was added slowly at 0-5 °C under nitrogen atmosphere and stirred for 18 h at 25 °C.
  • the reaction mixture was quenched by pouring in saturated aqueous sodium bicarbonate solution (20 mL) at 0-5 °C.
  • the product was extracted with ethyl acetate (20 mL).
  • the ethyl acetate layer was washed with water (20 mL), dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography on silica gel to obtain diethyl ((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)imidazo[1,2-a]pyridin-2- yl)methyl)phosphonate (0.12 g, 24% yield).
  • Step 5 Ethyl hydrogen ((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)imidazo[1,2-a]pyridin- 2-yl)methyl)phosphonate
  • diethyl ((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)imidazo[1,2-a]pyridin-2- yl)methyl)phosphonate (0.200 g, 0.5 mmol) in 2-pentanone (3 mL)
  • lithium bromide (0.052 g, 0.6 mmol) was added in one portion at 25 °C and stirred for 2 h at 110 °C.
  • Step 7 Ethyl N-(2,4-difluorophenyl)-P-((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)imidazo[1,2-a]pyridin-2-yl)methyl)phosphonamidate (Compound no.66) To a stirred solution of ethyl ((7-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)imidazo[1,2-a]pyridin-2- yl)methyl)phosphonochloridate (0.3 g, 0.7 mmol) in dichloromethane (3 mL), triethylamine (0.212 mL, 1.5 mmol) and 2,4-difluoroaniline (0.118 g, 0.9 mmol) were added at 0 °C.
  • Example 7 Preparation of ethyl N-(2-methoxyethyl)-P-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol- 3-yl)phenyl)phosphonamidate (Compound no.78) a) Step 1: N'-hydroxy-4-iodobenzimidamide To a stirred solution of 4-iodobenzonitrile (5 g, 21.8 mmol) in methanol (50 mL), hydroxylamine (7.4 mL, 26.2 mmol) was added slowly at 25 °C under nitrogen atmosphere and stirred for 12 h at 25 °C.
  • Step 3 diethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphonate (compound no.76)
  • diethyl phosphonate 6.38 mL, 49.4 mmol
  • triethylamine 7.19 mL, 41.2 mmol
  • tetrakis(triphenylphosphine)palladium 1.9 g, 1.6 mmol
  • the reaction mixture was allowed to stir for 3 h at 90 °C.
  • the reaction mixture was diluted with water 50 mL, extracted with ethyl acetate (3 x 35 mL) and washed with saturated aqueous sodium chloride solution.
  • the combined ethyl acetate layer was dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography to obtain diethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)phosphonate (7 g, 49 % yield).
  • Step 4 ethyl hydrogen (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphonate (Compound no.75)
  • diethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphonate 4.5 g, 12.85 mmol
  • 2-pentanone 30 mL
  • lithium bromide 103 mg, 1.2 mmol
  • Step 5 ethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)phosphonochloridate
  • ethyl hydrogen (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)phosphonate
  • oxalyl chloride (0.17 mL, 1.9 mmol) was added at 0 °C.
  • the reaction mixture was stirred for 30 min at 0 °C and stirred for 2 h at 25 °C. Then the volatiles were removed under reduced pressure.
  • Example 8 Preparation of diethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphoramidate (Compound no.88) a) Step 1: tert-butyl (tert-butoxycarbonyl)(4-cyanobenzyl)carbamate To a stirred solution of di-tert-butyl iminodicarbonate (22.16g, 102 mmol) in N,N-dimethylformamide (200 mL), potassium carbonate (21.15 g, 153 mmol) was added at 0 °C, and the reaction mixture was stirred at same temperature for 15 min.
  • Step 2 tert-butyl-(tert-butoxycarbonyl)(4-(N'-hydroxycarbamimidoyl)benzyl)carbamate
  • hydroxylamine 50% aq solution
  • 12.15 mL, 199 mmol was added at 0 °C and stirred at same temperature for 16 h. Volatiles were evaporated under reduced pressure to dryness.
  • Step 3 tert-butyl (tert-butoxycarbonyl)(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)carbamate
  • tert-butyl-(tert-butoxycarbonyl)(4-(N'-hydroxycarbamimidoyl)benzyl)carbamate 20 g, 55 mmol
  • trifluoroacetic anhydride 15.46 mL, 109 mmol
  • Step 4 (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride
  • tert-butyl (tert-butoxycarbonyl)(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)carbamate (20 g, 45.1 mmol) in tetrahydrofuran (200 mL)
  • hydrogen chloride (4M in 1,4- dioxane) (45.1 mL, 180 mmol) was added at 0 °C.
  • the resulting reaction mixture was stirred at 70 °C for 16 h.
  • reaction mixture was then cooled to 20 °C and evaporated to dryness under reduced pressure.
  • residue was co-distilled twice with toluene (20 mL) to obtain (4-(5-(trifluoromethyl)- 1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride (9 g, 71 % yield) as a white solid.
  • reaction mixture was quenched by addition of water (100 mL) and extracted with ethyl acetate (2 x 100 mL). The combined organic layer was dried over anhydrous sodium sulphate and evaporated to dryness under reduced pressure to obtain a crude product.
  • the crude product was purified by prep-HPLC to afford diethyl (4- (5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphoramidate (0.278 g, 68 % yield).
  • Example 9 Preparation of dimethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphoramidate (Compound no.89) To a stirred solution of (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride (0.3 g, 1.1 mmol) in tetrahydrofuran (10 mL), triethylamine (0.45 mL, 3.2 mmol) was added, followed by dimethyl phosphorochloridate (0.202 g, 1.4 mmol) at 0 °C. The reaction mixture was stirred at 25 °C for 2 h.
  • Example 10 Preparation of dimethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphoramidate (Compound no.90) a) Step 1: N'-hydroxy-4-methylbenzimidamide To a stirred solution of 4-methylbenzonitrile (5 g, 42.7 mmol) in ethanol (50 mL), 50% aqueous solution of hydroxylamine (3.92 mL, 64 mmol) was added. The reaction mixture was heated to 70 °C under nitrogen atmosphere for 16 h. The reaction mixture was evaporated under reduced pressure to dryness to obtain N'-hydroxy-4-methylbenzimidamide (6 g, 94 % yield) as a white solid.
  • Step 2 3-(p-tolyl)-5-(trifluoromethyl)-1,2,4-oxadiazole
  • N'-hydroxy-4-methylbenzimidamide 6 g, 40 mmol
  • trifluoroacetic anhydride 8.46 mL, 59.9 mmol
  • the resulting reaction mixture was stirred at 25 °C for 16 h.
  • the reaction mixture was diluted with water (100 mL) and the product was extracted with ethyl acetate (3 X 50 mL).
  • Step 3 3-(4-(bromomethyl)phenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole
  • N-bromosuccinimide (6.67 g, 37.5 mmol) followed by 2,2′-azobis(2- methylpropionitrile) (0.32 g, 1.97 mmol) were added.
  • the reaction mixture was heated to 48 °C for 10 h.
  • the reaction mixture was cooled to 25 °C, diluted with water (100 mL) and extracted with dichloromethane (3 X 50 mL). The combined dichloromethane layer were dried over anhydrous sodium sulphate and evaporated under reduced pressure to obtain a crude product.
  • the obtained crude product was purified by flash column chromatography to obtain 3-(4-(bromomethyl)phenyl)-5- (trifluoromethyl)-1,2,4-oxadiazole (6.57 g, 54.2 % yield) as white solid.
  • Step 4 N-methyl-1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine
  • 3-(4-(bromomethyl)phenyl)-5-(trifluoromethyl)-1,2,4-oxadiazole (1 g, 3.26 mmol) in tetrahydrofuran (10 mL) 2 M methanamine in tetrahydrofuran solution (8.14 mL, 16.28 mmol) was added at 0 °C .
  • the resulting solution was allowed to stir for 24 h at 25 °C. After completion of the reaction, the volatiles were evaporated.
  • Step 5 dimethyl methyl(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphoramidate (Compound no.90)
  • N-methyl-1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride 0.3 g, 1.12 mmol
  • triethylamine (0.71 mL, 5.1 mmol
  • dimethyl phosphorochloridate 0.186 mL, 1.5 mmol
  • the resulting reaction mixture was stirred at 25 °C for 2 h.
  • the reaction was quenched with water (100 mL) and extracted twice with ethyl acetate (100 mL).
  • the combined ethyl acetate layer was dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography to obtain dimethyl methyl(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphoramidate (0.204 g, 55 % yield).
  • Example 11 Preparation of ethyl N-(2,4-difluorobenzyl)-P-(4-(5-(trifluoromethyl)-1,2,4- oxadiazol-3-yl)benzyl)phosphonamidate (Compound no.91)
  • N-methyl-1-(4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)phenyl)methanamine hydrochloride 0.4 g, 1.3 mmol
  • triethylamine 0.49 mL, 6.8 mmol
  • diethyl phosphorochloridate 0.296 mL, 2.0 mmol
  • the resulting reaction mixture was stirred at 25 °C for 2 h.
  • the reaction mixture was quenched with water (100 mL) and extracted with ethyl acetate (2 x 100 mL).
  • the combined organic layer was dried over anhydrous sodium sulfate and evaporated to dryness under reduced pressure to obtain a crude product.
  • the crude product was purified by column chromatography to obtain diethyl methyl(4-(5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphoramidate (0.16 g, 30 % yield).
  • Example 12 Preparation of ethyl (1-(4-(5-(chlorodifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)ethyl)(methyl)phosphinate (compound no.87) a) Step 1: ethyl (1-(4-cyanophenyl)ethyl)(methyl)phosphinate To a degassed solution of ethyl (4-cyanobenzyl)phosphinate (0.8 g, 3.4 mmol) in anhydrous tetrahydrofuran (10 mL), lithium bis(trimethylsilyl)amide (4.85 mL, 5.2 mmol) was added at -78 °C under nitrogen atmosphere.
  • Step 2 ethyl-(1-(4-(N'-hydroxycarbamimidoyl)phenyl)ethyl)(methyl)phosphinate
  • ethyl (1-(4-cyanophenyl)ethyl)(methyl)phosphinate (0.57 g, 2.403 mmol) in ethanol (60 mL)
  • a 50% aqueous solution of hydroxylamine 0.08 mL, 4.8 mmol
  • reaction mixture was concentrated and three times co-evaporated with ethyl acetate (each 30 mL) under reduced pressure to obtain ethyl-(1-(4-(N'- hydroxycarbamimidoyl)phenyl)ethyl)(methyl)phosphinate (0.43 g, 66 % yield).
  • Step 3 ethyl (1-(4-(5-(chlorodifluoromethyl)-1,2,4-oxadiazol-3- yl)phenyl)ethyl)(methyl)phosphinate (Compound no.87)
  • ethyl-(1-(4-(N'-hydroxycarbamimidoyl)phenyl)ethyl)(methyl)phosphinate (0.350 g, 1.295 mmol)
  • 2-chloro-2,2-difluoroacetic anhydride 0.315 g, 1.3 mmol
  • the resulting reaction mixture was stirred at 25 °C for 16 h. After completion of the reaction, the reaction mixture was poured into a mixture of ethyl acetate (100 mL) and an aqueous saturated solution of sodium bicarbonate (75 mL) and stirred for 10 min. The organic layer was isolated, washed by saturated solution of sodium bicarbonate (100 mL), dried over anhydrous sodium sulphate and concentrated under reduced pressure to obtain a crude product.
  • Example 13 Preparation of ethyl methyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3- yl)benzyl)phosphonate (compound no.95) To a stirred solution of ethyl (4-(5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl)benzyl)phosphonochloridate (0.25 g, 0.71 mmol) in dichloromethane (3 ml), 4-dimethylaminopyridine (0.09 g, 0.71 mmol) and methanol (0.027 g, 0.85 mmol) were added at 0 °C.
  • 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):
  • 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.
  • 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. Compounds 4 5 27 34 35 38 46 74 91 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 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.
  • 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.
  • the sprayed plants were also assessed for plant damage by recording symptoms like necrosis, chlorosis and stunting.
  • Compounds 1 2 3 4 5 6 7 8 12 13 14 15 16 17 18 20 21 22 23 24 25 26 27 28 29 31 32 34 35 36 39 41 42 43 45 48 49 50 58 59 60 61 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81 82 83 87 88 89 90 91 at 300 ppm gave more than or equal to 70% control in these tests when compared to the untreated check which showed extensive disease development.

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WO2024068517A1 (en) 2022-09-28 2024-04-04 Bayer Aktiengesellschaft 3-(hetero)aryl-5-chlorodifluoromethyl-1,2,4-oxadiazole as fungicide
WO2024068519A1 (en) 2022-09-28 2024-04-04 Bayer Aktiengesellschaft 3-(hetero)aryl-5-chlorodifluoromethyl-1,2,4-oxadiazole as fungicide

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