WO2019150311A1 - 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms - Google Patents

1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms Download PDF

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Publication number
WO2019150311A1
WO2019150311A1 PCT/IB2019/050807 IB2019050807W WO2019150311A1 WO 2019150311 A1 WO2019150311 A1 WO 2019150311A1 IB 2019050807 W IB2019050807 W IB 2019050807W WO 2019150311 A1 WO2019150311 A1 WO 2019150311A1
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WIPO (PCT)
Prior art keywords
dithiolo
cyano
pyrazine
dicarbonitrile
ylidene
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PCT/IB2019/050807
Other languages
French (fr)
Inventor
Rohit Saxena
Sandip Appaji PUJARI
Sambhaji Shivnath THOK
Sankha DEBNATH
Jella Rama RAJU
Rupesh Kumar Mishra
Ruchi GARG
Santosh Shridhar AUTKAR
Hagalavadi M VENKATESHA
Alexander G.M. KLAUSENER
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Pi Industries Ltd.
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Publication of WO2019150311A1 publication Critical patent/WO2019150311A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems

Definitions

  • the present invention relates to 1-3 dithiol compounds of general formula (I). More particularly, the present invention relates to 1-3 dithiol compounds of general formula (I) which are used to protect crops by fighting against phytopathogenic microorganisms, preferably fungal pathogens.
  • Patent applications JP2009292967 and JP2002189295 discloses 1-3 dithiol class of compounds which are used for coloring and photopolymerizable compositions, however the use of 1-3 dithiol class of compounds as crop protecting agent is not disclosed in these applications.
  • the present invention envisages such compounds that satisfy or overcomes drawbacks associated with the prior art.
  • the present invention provides a 1-3 dithiol compound of general formula (I),
  • R 1 , R 2 , R 3 and R 4 are defined in detailed description.
  • the present invention provides use of compound of general formula (I) as crop protection agent for control of phytopathogenic microorganisms, preferably of fungal pathogens.
  • transitional phrase “comprises”, “comprising”, “includes”, “including”, “has”, “having”, “contains”, “containing”, “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • transitional phrase "consisting essentially of is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of’.
  • the term "pesticide” in each case also always comprises the term "crop protection agent”.
  • undesired microorganisms or "phytopathogenic microorganisms” such as fungal or bacterial pathogens includes namely Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae respectively.
  • agronomic refers to the production of field crops such as for food, fuels, biofuels, any biomaterials and fiber and includes namely the growth of com, 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), biofuel production crops such as com, sugar/starch crops, sugar-beet and sweet sorghum, cellulosic crops such as switchgrass, miscanthus, com stover, poplar, biodiesel crops rapeseed (canola), soybeans, palm oil, mustard, camelina, safflower, sunflower and jatropha and other specialty crops (e.g.,
  • alkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl groups are optionally substituted (e.g., "substituted” or “unsubstituted” alkyl, “substituted” or “unsubstituted” alkenyl, "substituted” or “unsubstituted” alkynyl, "substituted” or “unsubstituted” carbocyclyl, "substituted” or “unsubstituted” heterocyclyl, "substituted” or “unsubstituted” aryl or “substituted” or “unsubstituted” heteroaryl group).
  • substituted means that at least one hydrogen present on a group (e.g., a carbon or nitrogen atom etc.) is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction under normal conditions (temperature, pressure, air etc.).
  • a "substituted" group has a substituent at one or more substitutable positions of the group, and when more than one position in any given stmcture is substituted, the substituent is either the same or different at each position.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” or - N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched Ci to C M alkyl, preferably Ci to C15 alkyl, more preferably Ci to C10 alkyl, most preferably Ci to G, alkyl.
  • Non limiting examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 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,
  • alkyl is at the end of a composite substituent, as, for example, in alkylcycloalkyl, the part of the composite substituent at the start, for example the cycloalkyl, may be mono- or poly substituted identically or differently and independently by alkyl.
  • other radicals for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.
  • alkenyl used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably Ci to C15 alkenes, more preferably Ci to C10 alkenes, most preferably Ci to C6 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-l-propenyl, l-methyl-2 -propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl- 1-butenyl, 2-methyl-l- butenyl, 3 -methyl- 1-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3 -methyl-2 -butenyl, l-methyl-3- butenyl, 2 -methyl-3 -butenyl, 3 -methyl-3 -butenyl, 1,1 -dimethyl-2 -propenyl, 1,2-dimethyl- 1-propenyl,
  • 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.
  • alkenyloxy refers to an alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C6-alkenyloxy is a C2-C6-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-Cs-alkenyloxy is a C2- Cs-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • alkenyloxy include, but are not limited to, allyloxy, 2-butenyloxy, 3- butenyloxy and 3-pentenyloxy.
  • haloalkenyloxy refers to a haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C6-haloalkenyloxy is a C2-C6-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C8- haloalkenyloxy is a C2-Cs-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • Non limiting examples of haloalkenyloxy include, but are not limited to, 3-bromo-2-propenyloxy and 4-bromo-3-butenyloxy.
  • alkenylthio refers to an alkenyl group, as defined above, attached via an sulphur atom to the remainder of the molecule.
  • C2-C6-alkenylthio is a C2-C6-alkenyl group, as defined above, attached via a sulphur atom to the remainder of the molecule.
  • C2-Cs-alkenyloxy is a C2- G-alkcnvl group, as defined above, attached via a sulphur atom to the remainder of the molecule.
  • alkenylthio include, but are not limited, allylsulfanyl, 2-butenylsulfanyl, 3- butenylsulfanyl and 3-pentenylsulfanyl.
  • alkynyl used either alone or in compound words includes branched or straight-chain C2 to C24 alkynes, preferably C2 to C15 alkynes, more preferably C2 to C10 alkynes, most preferably C2 to G, alkynes.
  • Non limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- butynyl, 3-butynyl, 1 -methyl-2 -propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2- butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1 -dimethyl-2 -propynyl, 1- ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2 -pentynyl, 1- methyl-3-pentynyl, l-methyl-4-pentynyl, 2-me
  • 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.
  • alkynyloxy refers to a alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C6-alkynyloxy is a C2-C6-alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-Cs-alkynyloxy is a C2-C8- alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • Non limiting examples of alkynyloxy include, but are not limited to, 3-pentynyloxy, 3-butynyloxy and 2- propynyloxy.
  • haloalkynyloxy refers to a haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C6-haloalkynyloxy is a C2-C6-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • C2-C8- haloalkynyloxy is a C2-Cs-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule.
  • Non limiting examples of haloalkynyloxy include, but are not limited to, (3-bromo-2-propynyl)oxy and (4-bromo-3-butynyl)oxy.
  • alkynylthio refers to a alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule.
  • C2-C6-alkynyloxy is a C2-C6-alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule.
  • C2-Cs-alkynyloxy is a C2-C8- alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule.
  • alkynylthio include, but are not limited, 2-propynylsulfanyl, 3-butynylsulfanyl and 3-pentynylsulfanyl.
  • cyclic alkyl or "cycloalkyl” means alkyl closed to form a ring. Non limiting examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl, cycloalkyl alkoxy or cycloalkyl alkyloxy, cycloalkyl alkylthio etc., unless specifically defined elsewhere.
  • alky ley cloalkyl refers to mono-, bi- or tricyclic alkylcycloalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, for example methylcyclopropyl, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is also given to alkylcycloalkyls having 4, 5 or 7 carbon atoms such as, inter alia, ethylcyclopropyl or 4- methylcyclohexyl.
  • the inventive alkylcycloalkyls may be substituted by one or more identical or different radicals.
  • cycloalkylalkyl refers to mono-, bi- or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is also given to cycloalkylalkyls having 4, 5 or 7 carbon atoms such as, inter alia, cyclopropylmethyl or cyclobutylmethyl.
  • the inventive cycloalkylalkyls may be substituted by one or more identical or different radicals.
  • cycloalkenyl means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non limiting examples include but are not limited to cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as a part of a composite substituent, for example cycloalkenylalkyl etc., unless specifically defined elsewhere.
  • cycloalkynyl means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. This definition also applies to cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere.
  • cycloalkoxy or "cycloalkyloxy”, “cycloalkenyloxy” and the like are defined analogously.
  • Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl, etc., unless specifically defined elsewhere.
  • alkoxy used either alone or in compound words included Ci to CM alkoxy, preferably Ci to C15 alkoxy, more preferably Ci to Cio alkoxy, most preferably Ci to G, alkoxy.
  • alkoxy include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2- methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2- dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1- methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2- dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,
  • 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,
  • hydroxy means -OH
  • amino means -NRR, wherein R can be H or any possible substituent such as alkyl
  • carbonyl means -C(O)-
  • carbonyloxy means -OC(O)-
  • sulfinyl means SO
  • sulfonyl means S(0) 2 .
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 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, l,l-dichloro-2,2,2-trifluoroethyl, and l,l,l,l-trifluoroprop-2-yl. This definition also applies to haloalkyl
  • haloalkenyl and “haloalkynyl” are defined analogously except that, instead of alkyl groups, alkenyl and alkynyl groups are present as a part of the substituent.
  • haloalkoxy means straight-chain or branched alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above.
  • Non limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2- dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l
  • haloalkylthio or "haloalkylsulfanyl” means straight-chain or branched alkylthio groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above.
  • Non limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1- bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio, pentafluoroethylthio and l,l,l
  • haloalkenylthio or "haloalkenylsulfanyl” means straight-chain or branched alkenylthio 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 "haloalkylsulfinyl” include CF 3 S(0), CCTS(O). CF 3 CH 2 S(0) and CF 3 CF 2 S(0).
  • Non limiting examples of "haloalkylsulfonyl” include CF 3 S(0) 2 , CC1 3 S(0) 2 , CF 3 CH 2 S(0) 2 and CF 3 CF 2 S(0) 2 .
  • alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include -CH 2 SCH 2 , -CH 2 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • cycloalkylalkylamino denotes cycloalkyl substitution on alkyl amino.
  • alkoxyalkoxyalkyl alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl and the like, are defined analogously to "alkylthioalkyl” or cycloalkylalkylamino .
  • alkoxycarbonyl is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as a part of a composite substituent, for example cycloalkylalkoxycarbonyl and the like, unless specifically defined elsewhere.
  • alkoxycarbonylalkylamino denotes alkoxy carbonyl substitution on alkyl amino.
  • alkylcarbonylalkylamino denotes alkyl carbonyl substitution on alkyl amino.
  • alkylthioalkoxycarbonyl cycloalky lalkylaminoalkyl and the like are defined analogously.
  • alkylsulfinyl include but are not limited to methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2- methylpropylsulphinyl, 1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphin
  • arylsulfinyl includes Ar-S(O), wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
  • alkylsulfonyl include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl, 1-methylpropylsulphonyl, 2-methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1- ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1- methylpentylsulphonyl, 2-methylpentylsulphonyl, 3-methylpentylsulfonyl,
  • arylsulfonyl includes Ar-S(0) 2 , wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere.
  • alkylamino dialkylamino
  • ring system as a component of formula I is carbocyclyl or heterocyclyl.
  • ring system denotes one or more rings.
  • bicyclic ring or ring system denotes a ring system consisting of two or more common atom.
  • carrier or “carbocyclic” or “carbocyclyl” include “aromatic carbocyclic ring system” and “nonaromatic carbocylic ring system” or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not satisfied).
  • Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbomyl and the like.
  • Non limiting examples of aromatic carbocyclic ring system are phenyl, naphthyl and the like.
  • aryl as used herein is a group that contains any carbon-based aromatic group including, but not limited to phenyl, naphthalene, biphenyl, anthracene, and the like.
  • the aryl group can be substituted or unsubstituted.
  • the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.
  • aralkyl refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Non limiting examples include benzyl, phenylethyl, and 6-napthylhexyl.
  • aralkenyl refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Non limiting examples include styryl, 3 -(benzyl) prop-2 -enyl, and 6- napthy lhex-2 -eny 1.
  • hetero in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • non-aromatic heterocycle or “non-aromatic heterocyclic” means three- to fifteen- membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to carbon ring members, one to three nitrogen atoms and/or one oxygen or sulphur atom or one or two oxygen and/or sulphur atoms; if the ring contains more than one oxygen atom, they are not directly adjacent; for example (but not limited to) oxiranyl, aziridinyl, oxetanyl, azetidinyl, thietanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2- tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyr
  • heteroaryl means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl
  • 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1, 3 -diene-1, 4-diyl group in which one or two carbon atoms may be replaced by nitrogen atoms, where these rings are attached to the skeleton via one of the nitrogen ring members, for example (but not limited to) 1- pyrrolyl, 1-pyrazolyl, 1,2,4-triazolyl, 1-imidazolyl, 1,2,3-triazolyl and 1,3,4-triazolyl.
  • 6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2- yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-l-yl, indol-2-yl, indol-3-yl, indol-4
  • Non limiting examples of fused 6-5-membered heteroaryl include Indolizinyl; pyrazolo[l,5- ajpyridinyl; imidazo[l,2-a]pyridinyl; pyrrolo[l,2-a]pyrimidinyl; pyrazolo[l,5-a]pyrimidinyl; imidazo[l,2-a]pyrimidinyl; pyrrolo[l,2-a]pyrazinyl; pyrazolo[l,5-a]pyrazinyl; imidazo[l,2- ajpyrazinyl and the like.
  • This definition also applies to heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl.
  • Hallotrialkylsilyl denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different.
  • Alkoxytrialkylsilyl denotes at least one of the three alkyl radicals is substituted with one or more alkoxy radicals which may be the same or different.
  • Trialkylsilyloxy denotes a trialkylsilyl moiety attached through oxygen.
  • alkylcarbonyl examples include C(0)CH 3 , C/O/CThCFbCTh and C(0)CH(CH3) 2 .
  • haloalkylsufonylaminocarbonyl alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously.
  • the total number of carbon atoms in a substituent group is indicated by the "G- " prefix where i and j are numbers from 1 to 21.
  • Ci-C 3 alkoxy designates methoxy through propoxy.
  • substituents When a compound is substituted with a substituent bearing a subscript indicates that the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e. g. (R)i- j , then the number of substituents may be selected from the integers between i and j inclusive.
  • the present invention provides a compound of general formula (I),
  • R 1 and R 2 are independently selected from the group consisting of cyano, nitro, Ci-G, -alkyl. C 2 - G, -alkenyl. G-G,-alkynyk G-G-haloalkyk G-G,-haloalkcnvl. G-G.-haloalkvnvl.
  • R 1 is selected from the group consisting of cyano, nitro, G-G, -alkyl.
  • R 2 is selected from the group consisting of S(0)o-iR 7 , G,-Gn-aryl and C3-C10- heterocyclyl; said G,- Go -aryl.
  • C 3 -Cio-heterocyclyl group may be optionally substituted with at least one group selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G,- alkyl, C 2 -Cs-alkenyl, G-Cs-alkynyl, G-G,-haloalkyl.
  • R' is selected from the group consisting of hydrogen, halogen, G-G.-alkyl and G3 ⁇ 4-G,- cycloalkyl.
  • R" is selected from the group consisting of hydrogen, N(R')2, G-G, -alkyl.
  • G-G-haloalkyl and C3-C8-cycloalkyl, each group of R'' is optionally substituted by one or more groups selected from the group consisting of halogen, cyano, R', OR', SR', N(R') 2 , Si(R') 3 , COOR', CON(R') 2 and C -Ci 2 -aryl which is optionally substituted by one or more group R'.
  • R 7 is selected from the group consisting of hydrogen, Ci-G, -alkyl. G-G-alkcnvl. C 2 -Cs- alkynyl, Ci-Ci-haloalkyl, G-Cs-haloalkenyl, C3-Cio-cycloalkyl, G-Go-cycloalkyl-G- Ci-alkyl, C3-Cio-halocycloalkyl, amino, mono-(Ci-C 6 -alkyl)amino, di-(Ci-C 6 - alkyl)amino, G-G ' -aralkyk Ci- o aryl and C3-Cio-heterocyclyl.
  • Each group of R 1 , R 2 , R 7 may optionally be substituted with one or more groups selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, Ci-G, -alkyl.
  • R 5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl.
  • C 3 -Go-heterocyclyl said aryl or heterocyclyl group may optionally be substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, C 1 -G -alkyl and C 1 -G,- alkoxy.
  • R 5a is selected from the group consisting of hydrogen, cyano, G-G, -alkyl.
  • each group of R 5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR'', SR'', N(R") 2 , Si(R'') 3 , COOR", cyano and CON(R") 2 .
  • R 5a is selected from the group consisting of hydrogen, G-G, -alkyl.
  • each group of R 5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R") 2 , Si(R") 3 , COOR'', cyano and CON(R") 2 .
  • R 6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl.
  • the compound of general formula (I) is selected from 2-(5-methyl-4,6- dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, 2-(4,6-dioxo-5,6-dihydro- 4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, diethyl 2-(5-methyl-4,6-dioxo-5,6-dihydro-4H- [l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, diethyl 2-(4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5- c]pyrrol-2-ylidene)malonate, ethyl 2-cyano-2-(5-methyl-4,6-dioxo-5,6
  • the compounds of the present disclosure may be used 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.
  • the person skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s). Additionally, the person skilled in the art knows processes or methods or technology to separate, enrich, and/or to selectively prepare said isomers.
  • the biologically more effective isomer for example specific enantiomers or diastereomers, or isomeric mixture, for example enantiomeric mixtures or diastereomeric mixtures, if the individual components have a different biological activity.
  • the compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound.
  • the invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions.
  • the geometric isomers can be separated according to general methods, which are known per se by a person ordinary skilled in the art.
  • any of the compounds according to the invention can also exist in one or more amorphic or isomorphic or polymorphic forms, depending on their preparation, purification storage and various other influencing factors.
  • the invention thus relates all the possible amorphic, isomorphic and polymorphic forms, in all proportions.
  • the amorphic, isomorphic and polymorphic forms can be prepared and/or separated and/or purified according to general methods, which are known per se by a person ordinary skilled in the art.
  • the present invention provides use of compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, for controlling or preventing agricultural crops and/or horticultural crops against phytopathogenic fungi, bacteria, insects, nematodes or mites.
  • the present invention provides use of compound of general formula (I), bi- oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, for controlling or preventing against phytopatho genic fungi of agricultural crops and/or horticultural crops.
  • the compounds according to the invention can be used for controlling undesired phytopathogenic microorganisms preferably fungal pathogens which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these microorganisms.
  • undesired phytopathogenic microorganisms preferably fungal pathogens which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these microorganisms.
  • the compounds of the formula (I) can possess potent microbicidal activity and can be used for the control of unwanted microorganisms, such as fungi, and bacteria, in agricultural or horticultural crop protection and in the protection of such materials.
  • the compounds of the formula (I) possess very good fungicidal properties and can be used in crop protection, for example for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
  • the compounds of the formula (I) can be used as bactericides in crop protection, for example, for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
  • the compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi.
  • the invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seeds, to plants or plant parts, to fruit or to the soil in which the respective plants grow.
  • the compounds of the formula (I) can be used for controlling or preventing against phytopathogenic fungi, bacteria, of agricultural crops and or horticultural crops.
  • the compounds of the formula (I) can be used in crop protection, wherein the agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and other vegetables, and ornamentals.
  • the agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and other vegetables, and ornamentals.
  • the present invention provides a process for preparing compounds of the formula (I).
  • the present invention provides a composition for controlling or preventing phytopathogenic microorganisms, comprising a compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salts thereof and one or more inert carriers.
  • the composition may additionally comprises one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
  • active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
  • the concentration of the compound of general formula (I) ranges from 1 to 90% by weight with respect to the total weight of the composition, preferably from 5 to 50% by weight with respect to the total weight of the composition.
  • the present invention provides an agrochemical composition, comprising at least one compound of formula (I) and/or N-oxide or S-oxide or an agriculturally acceptable salt thereof.
  • the present invention provides a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein said compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, is applied to the plants, to parts thereof or a locus thereof.
  • the present invention provides a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and or horticultural crops, wherein the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof is applied to the seeds of plants.
  • the present invention provides a method for controlling or preventing phytopathogenic microorganisms in agricultural crops and/or horticultural crops using the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof, which comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 1 g to 5 kg per hectare of agricultural or horticultural crops.
  • the present invention provides a method for combating harmful fungi, comprising treating, plants, the soil, seeds or the materials to be protected against fungal attack with an effective amount of at least one compound of formula (I) or with a composition.
  • the present invention provides a seed comprising compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salt or composition or combination thereof, wherein the amount of the compound of general formula (I), or an N-oxide or S-oxide or an agriculturally acceptable salt thereof, is from 0.1 g to 10 kg per 100 kg of seed.
  • the compound of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • the compounds of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
  • 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.
  • Botrytis cinerea teleomorph: Botryotinia fuckeliana: grey mold
  • fruits and berries e.g. strawberries
  • vegetables e.g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and
  • zeaemaydis rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchil) and rice; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph: B.
  • tomatoes e.g. C. fulvum: leaf mold
  • cereals e.g. C. herbarum (black ear) on wheat
  • Claviceps purpurea ergot
  • Cochliobolus anamorph: Helmin
  • sorokiniana and rice (e.g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypit), corn (e.g. C. gramini cola: Anthracnose stalk rot), fruits, potatoes (e. g. C. coccodes: black dot), vegetables like beans (e.g. C. lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides) ; Corticium spp., e.g. 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 (E. pyn), soft fruits (E.
  • 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 on sugar beets
  • Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsid), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P.
  • 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 rosa ceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples
  • Polymyxa spp. e.g. on cereals, such as barley and wheat (P.
  • P. betae sugar beets
  • Pseudocercosporella herpotrichoides eyespot, teleomorph: Tapesia yallundae
  • Pseudoperonospora downy mildew
  • P. cubensis on cucurbits or P. humili on hop
  • 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) ; Ramu/aria spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp.
  • R. solani root and stem rot
  • S. solani silk and stem rot
  • S. solani silk blight
  • R. cerealis Rhizoctonia spring blight
  • Rhizopus stolonifer black mold, soft rot
  • Rhynchosporium secalis scald
  • stem rot or white mold on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soy beans (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) no dorum (Stagonospora blotch) on cereals; Uncinula (syn.
  • Erysiphe necator prowdery mildew, anamorph: Oidium tucken
  • Setospaeria spp. leaf blight
  • com e.g. S. turcicum, syn. Helminthosporium turcicum
  • turf e.g. Sphacelotheca spp. (smut) on com, (e.g. S. reiliana: head smut), sorghum und sugar cane
  • Sphaerotheca fuliginea prowdery mildew
  • Spongospora subterranea powdery scab
  • S. nodorum Stagonospora blotch, teleomorph: Lepto sphaeria [syn. Phaeosphaeria] nodorum
  • wheat Synchytrium endobioticum on potatoes (po tato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fmits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp.
  • U. nuda and U. avaenae com (e. g. U. maydis: com smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fmits and ornamentals, vines, soft fmits, vegetables and field crops, e.g. V dahliae on strawberries, rape, potatoes and tomatoes.
  • the present invention provides use of compounds of formula (I) and compositions thereof, for controlling and/or preventing plant diseases caused by pathogens such as: Pyricularia oryzae, Rhizoctonia solani, Botrytis cinerea, Alternaria solani, Colletotrichum capsici, Septoria lycopersici, Fusarium culmorum, Phakopsora pachyrhizi, Sphaerotheca fuliginea, Pseudoperonospora cubensis, Puccinia triticina, Septoria tritici, Phytopthora infestans, Plasmopara viticola, Uncinula necator.
  • pathogens such as: Pyricularia oryzae, Rhizoctonia solani, Botrytis cinerea, Alternaria solani, Colletotrichum capsici, Septoria lycopersici, Fusarium culmorum, Phakopsora pachyrhizi, Sphaerothe
  • the present invention provides a method for combating phytopathogenic fungi, comprising treating plants, soil, seeds or materials to be protected against fungal attack with an effective amount of the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof as disclosed in the present invention.
  • the compounds of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
  • 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 Coni ophora spp., Corio/us spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser pula spp.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.
  • Basidiomycetes such as Coni
  • yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
  • 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, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment.
  • 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 combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold.
  • stored products is understood to denote natural substances of plant origin and their processed forms, more preferably fruits and their processed forms, such as pomes, stone fruits, soft fruits and citrus fruits and their processed forms.
  • the compound of formula (I) and compositions 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 compounds of formula (I) and compositions thereof, respectively.
  • plant health is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress.
  • yield e. g. increased biomass and/or increased content of valuable ingredients
  • plant vigor e.g. improved plant growth and/or greener leaves ("greening effect")
  • quality e. g. improved content or composition of certain ingredients
  • tolerance to abiotic and/or biotic stress e.g. improved content or composition of certain ingredients
  • seed embraces seeds and plant propagules of all kinds including but not limited to hue seeds, seed pieces, suckers, corns, bulbs, fruits, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
  • the present invention also comprises seeds coated or treated with or containing a compound of formula I.
  • coated or treated with and/or containing generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application.
  • the seed product When the said seed product is (re)planted, it may absorb the active ingredient.
  • the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
  • Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting.
  • the seed treatment application of the compound formula I which is a preferred application method, can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
  • Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pome fruit, stone fruit or soft fmit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts
  • plant is to be understood as including also plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus and also plants which have been selected or hybridised to preserve and/or attain a desired trait, such as insect, fungi and /or nematode resistance.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g.
  • Vip vegetative insecticidal proteins
  • Vipl e.g. Vipl, Vip2, Vip3 or Vip3A
  • insecticidal proteins of bacteria colonising nematodes for example Photorhabdus spp.
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosomeinactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdy
  • 8-endotoxins for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A
  • Vip vegetative insecticidal proteins
  • Hybrid toxins are produced recombinant by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • Truncated toxins for example a truncated CrylAb, are known.
  • modified toxins one or more amino acids of the naturally occurring toxin are replaced.
  • preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin- G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367474, EP-A-0 401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects.
  • Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculexl® (maize variety that expresses a Cry lFa2 toxin and the enzyme phosphinothricine N-acetyltransferase(PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses
  • transgenic plants are: i) Bill Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European com borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bil l maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; ii)Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
  • This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence.
  • the preparation of such transgenic maize plants is described in WO 03/018810; iv)MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9.
  • MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects; v) IPC 531 Cotton from Monsanto Europe S.A.
  • registration number C/GB/02/M3/03 consists of conventionally breed hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European com borer.
  • the compounds of formula (I) can be present in different crystal modifications 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 form of compositions by treating the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances.
  • the application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
  • Plant propagation materials may be treated with compounds of formula (I) as such or a composition comprising at least one compound of formula (I) 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) according to the invention.
  • An agrochemical composition comprises a fungicidally effective amount of a compound of formula (I).
  • the term "effective amount” denotes an amount of the composition or of the compounds 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.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 61h Ed. May 2008, Croplife International.
  • compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F lnforma, 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. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e. g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e.g. toluene, paraffin, tetrahydronaphthalene, alkylated n
  • lactates carbonates, fatty acid esters, gamma- butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; 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.
  • 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
  • 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.l : 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.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-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 homo- 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. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of 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, minerals or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F lnforma UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic 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 antifoaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants e.g. in red, blue, or green
  • Suitable colorants are pigments of low water solubility and water soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinyl pyrrolidones, polyvinyl acetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound of formula (I) and 5-15 wt% wetting agent e.g. alcohol alkoxylates
  • a water-soluble solvent e. g. alcohols
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • water-insoluble organic solvent e. g. aromatic hydro carbon
  • Emulsions (EW, EO, ES)
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water insoluble organic solvent e.g. aromatic hydrocarbon
  • This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
  • a compound of formula (I) 20-60 wt% of a compound of formula (I) are comminuted with addition of 2- 10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e. g. sodium lignosulfonate and alcohol ethoxylate
  • 0.1-2 wt% thickener e.g. xanthan gum
  • a compound of formula (I) 50-80 wt% of a compound of formula (I) are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • 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
  • a compound of formula (I) In an agitated ball mill, 5-25 wt% of a compound of formula (I) are comminuted with addition of 3- 10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1-5 wt% thickener e.g. carboxymethyl cellulose
  • wt% of a compound of formula (I) are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontane ously a thermodynamically stable microemulsion.
  • organic solvent blend e. g. fatty acid dimethyl amide and cyclohexanone
  • surfactant blend e. g. alcohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound of formula (I), 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or tri-acrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules.
  • 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 protective colloid e. g. polyvinyl alcohol.
  • the addition of a polyamine results in the formation of polyurea microcapsules.
  • the monomers amount to 1- 10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • a compound of formula (I) is ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
  • solid carrier e.g. finely divided kaolin
  • a compound of formula (I) is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%.
  • solid carrier e. g. silicate
  • Granulation is achieved by extrusion, spray -drying or fluidized bed.
  • organic solvent e.g. aromatic hydrocarbon
  • 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.
  • 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 substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed.
  • the com positions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready -to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying compound of formula (I) and compositions thereof, respectively, onto plant propagation material, especially seeds include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods.
  • compound of formula (I) or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably 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
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1: 10 to 10: 1.
  • a pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, vims, 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.
  • pesticides 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 of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
  • Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programs.
  • IPM integrated pest management
  • Biopesticides fall into two major classes, microbial and biochemical pesticides:
  • Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce) entomopathogenic nematodes are also classed as microbial pesticides, even though they are multicellular.
  • Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals
  • the user applies the composition according to the invention usually from a pre dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • the present invention further relates to a composition for controlling unwanted microorganisms comprising at least one of the compounds of the formula (I) and one or more inert carrier.
  • the inert carrier further comprises agriculturally suitable auxiliaries, solvents, diluents, surfactants and/or extenders and the like.
  • the present invention further relates to a composition for controlling unwanted microorganisms, comprising at least one of the compounds of the formula (I) and/or one or more active compatible compound selected from fungicides, bactericides, acaricides, insecticides, nematicides, herbicides, biopesticides, plant growth regulators, antibiotics, fertilizers and/or mixtures thereof.
  • a compound of the present invention is used in the form of a composition (e.g. formulation) containing a carrier.
  • a compound of the invention and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ulv) liquid, ultra-low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets
  • a formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
  • auxiliaries for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers.
  • the composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides.
  • the present invention also makes available a composition comprising a compound of the invention and an agronomical carrier and optionally one or more customary formulation auxiliaries.
  • compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries).
  • auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention
  • at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries).
  • the grinding/milling of the compounds is to ensure specific particle size.
  • the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of compound according to the present invention and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight).
  • surfactants % in each case meaning percent by weight.
  • foliar formulation types for pre-mix compositions are:
  • examples of seed treatment formulation types for pre-mix compositions are:
  • formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.
  • the methods of application such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries.
  • a solvent for example, water
  • Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
  • a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 15 %, of the desired ingredients, and 99.9 to 80 %, especially 99.9 to 85 %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20 %, especially 0.1 to 15 %, based on the tank-mix formulation.
  • auxiliaries including, for example, a solvent such as water
  • a pre-mix formulation for foliar application comprises 0.1 to 99.9 %, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1 %, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75 %, of the desired ingredients, and 99.75 to 20 %, especially 99 to 25 %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40 %, especially 0.5 to 30 %, based on the tank-mix formulation.
  • auxiliaries including, for example, a solvent such as water
  • a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 %, especially 1 to 95 %, of the desired ingredients, and 99.5 to 0.1 %, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre-mix formulation whereas commercial products will preferably be formulated as concentrates (e.g., pre-mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition).
  • Preferred seed treatment pre-mix formulations are aqueous suspension concentrates.
  • the formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, rotostatic seed treaters, and dram coaters. Other methods, such as spouted beds may also be useful.
  • the seeds may be pre sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art.
  • the compounds of the present invention are particularly suited for use in soil and seed treatment applications.
  • the pre-mix compositions of the invention contain 0.5 to 99.9 especially 1 to 95, advantageously 1 to 50 %, by mass of the desired ingredients, and 99.5 to 0.1, especially 99 to 5%, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50, especially 0.5 to 40 %, by mass based on the mass of the pre-mix formulation.
  • a solid or liquid adjuvant including, for example, a solvent such as water
  • a compound of the formula (I) in a preferred embodiment, independent of any other embodiments, is in the form of a plant propagation material treating (or protecting) composition, wherein said plant propagation material protecting composition may comprises additionally a colouring agent.
  • the plant propagation material protecting composition or mixture may also comprise at least one polymer from water-soluble and water-dispersible film-forming polymers that improve the adherence of the active ingredients to the treated plant propagation material, which polymer generally has an average molecular weight of at least 10,000 to about 100,000.
  • Examples of application methods for the compounds of the invention and compositions thereof, that is the methods of controlling pests in the agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring which are to be selected to suit the intended aims of the prevailing circumstances.
  • the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application).
  • systemic action by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application).
  • granules can be metered into the flooded paddy-field.
  • the application of the compounds of the present invention to the soil is a preferred application method.
  • Typical rates of application per hectare are generally 1 to 5000 g of active ingredient per hectare.
  • the compounds of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the above mentioned type.
  • the propagation material can be treated with the compound prior to planting, for example seeds can be treated prior to sowing.
  • the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling.
  • Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds.
  • the application of the compounds of the present invention to seeds is a preferred application method.
  • compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding, for example, one or more insecticidally, acaricidally, nematicidally and/or fungicidally active agents.
  • the combinations compounds of formula (I) with other insecticidally, acaricidally, nematicidally and/or fungicidally active agents may also have further surprising advantages which can also be described, in a wider sense, improved properties, for example, better tolerance by plants, reduced phytotoxicity, pests or fungi can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
  • A) Inhibitors of the ergosterol biosynthesis for example (A01) aldimorph, (A02) azaconazole, (A03) bitertanol, (A04) bromuconazole, (A05) cyproconazole, (A06) diclobutrazole, (A07) difenoconazole, (A08) diniconazole, (A09) diniconazole-M, (A10) dodemorph, (Al l) dodemorph acetate, (A12) epoxiconazole, (A13) etaconazole, (A14) fenarimol, (A15) fenbuconazole, (A16) fenhexamid, (A17) fenpropidin, (A18) fenpropimorph, (A19) fluquinconazole, (A20) llurprimidol, (A21) flusilazole, (A22) ll
  • B) Inhibitors of the respiratory chain at complex I or II for example (B01) bixafen, (B02) boscalid, (B03) carboxin, (B04) cypropamide, (B05) diflumetorim, (B06) fenfuram, (B07) fluopyram, (B08) flutolanil, (B09) fluxapyroxad, (B 10) furametpyr, (B l l) furmecyclox, (B12) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (B 13) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (B 14) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (B 15) isopyrazam (anti-epimeric enantiomer 1S,4
  • C) Inhibitors of the respiratory chain at complex III for example (C01) ametoctradin, (C02) amisulbrom, (C03) azoxystrobin, (C04) cyazofamid, (C05) coumethoxystrobin, (C06) coumoxystrobin, (C07) dimoxystrobin, (C08) enoxastrobin, (C09) famoxadone, (CIO) fenamidone, (Cl l) fenaminstrobin, (C12) flufenoxystrobin, (C13) fluoxastrobin, (C14) kresoxim-methyl, (C15) metominostrobin, (C16) mandestrobin, (C17) orysastrobin, (C18) picoxystrobin, (C19) pyraclostrobin, (C20) pyrametostrobin, (C21) pyraoxystrobin, (C22) pyrib
  • D) Inhibitors of the mitosis and cell division for example (D01) benomyl, (D02) carbendazim, (D03) chlorfenazole, (D04) diethofencarb, (D05) ethaboxam, (D06) fluopicolide, (D07) fiiberidazole, (D08) pencycuron, (D09) thiabendazole, (D10) thiophanate-methyl, (D l l) thiophanate, (D 12) zoxamide, (D13) 5-chloro-7-(4-methylpiperidin-l-yl)-6-(2,4,6-trifluorophenyl)[l,2,4]triazolo[l,5-a]pyrimidine, (D14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6- trifluorophenyl) pyridazine, (D15) 3-
  • E) Compounds capable to have a multisite action for example (E01) bordeaux mixture, (E02) captafol, (E03) captan, (E04) chlorothalonil, (E05) copper hydroxide, (E06) copper naphthenate, (E07) copper oxide, (E08) copper oxychloride, (E09) copper(2+) sulfate, (E10) dichlofluanid, (El l) dithianon, (E12) dodine, (E13) dodine free base, (E14) ferbam, (E15) fluorofolpet, (E16) folpet, (E17) guazatine, (E18) guazatine acetate, (E19) iminoctadine, (E20) iminoctadine albesilate, (E21) iminoctadine triacetate, (E22) mancopper, (E23) mancozeb, (E24)
  • F Compounds capable to induce a host defence, for example (F01) acibenzolar-S -methyl, (F02) isotianil, (F03) probenazole, (F04) tiadinil, (F05) laminarin, (F06) 4-cyclopropyl-N-(2,4- dimethoxyphenyl)thiadiazole-5 -carboxamide .
  • G) Inhibitors of the amino acid and/or protein biosynthesis for example (G01) andoprim, (G02) blasticidin-S, (G03) cyprodinil, (G04) kasugamycin, (G05) kasugamycin hydrochloride hydrate, (G06) mepanipyrim, (G07) pyrimethanil, (G08) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihy droisoquinolin- 1 -y l)quinoline, (G09)oxytetracy cline, (G 10) streptomycin.
  • G01 andoprim for example (G01) andoprim, (G02) blasticidin-S, (G03) cyprodinil, (G04) kasugamycin, (G05) kasugamycin hydrochloride hydrate, (G06) mepanipyrim, (G07) pyrimethanil, (G08) 3-(5-fluor
  • H Inhibitors of the ATP production, for example (H01) fentin acetate, (H02) fentin chloride, (H03) fentinhydroxide, (H04) silthiofam.
  • I) Inhibitors of the cell wall synthesis for example (101) benthiavalicarb, (102) dimethomorph, (103) flumorph, (104) iprovalicarb, (105) mandipropamid, (106) polyoxins, (107) polyoxorim, (108) validamycin A, (109) valifenalate, (110) polyoxin B, (Il l) (2E)-3-(4-tert-butylphenyl)-3-(2- chloropyridin-4-yl)- l-(morpholin-4-yl)prop-2-en- 1 -one, (112) (2Z)-3 -(4-tert-butylphenyl)-3 -(2- chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one.
  • J) Inhibitors of the lipid and membrane synthesis for example (JO 1) biphenyl, (J02) chloroneb, (J03) dicloran, (J04) edifenphos, (J05) etridiazole, (J06) iodocarb, (J07) iprobenfos, (J08) isoprothiolane, (J09) propamocarb, (J10) propamocarb hydrochloride, (J 11) prothiocarb, (J12) pyrazophos, (J13) quintozene, (J14) tecnazene, (J15) toclofos-methyl.
  • JO 1 biphenyl
  • J02 chloroneb
  • J03 dicloran
  • J04 edifenphos
  • J05 etridiazole
  • J06 iodocarb
  • J07 iprobenfos
  • J08 isoprothiolane
  • K) Inhibitors of the melanin biosynthesis for example (KOI) carpropamid, (K02) diclocymet, (K03) fenoxanil, (K04) phthalide, (K05) pyroquilon, (K06) tolprocarb, (K07)tricyclazole.
  • L) Inhibitors of the nucleic acid synthesis for example (L01) benalaxyl, (L02) benalaxyl-M (kiralaxyl), (L03) bupirimate, (L04) clozylacon, (L05) dimethirimol, (L06) ethirimol, (L07) furalaxyl, (L08) hymexazol, (L09) metalaxyl, (L10) metalaxyl-M (mefenoxam), (LI 1) ofurace, (L12) oxadixyl, (L13) oxolinic acid, (L14)octhilinone.
  • M Inhibitors of the signal transduction, for example (M01) chlozolinate, (M02) fenpiclonil, (M03) fludioxonil, (M04) iprodione, (M05) procymidone, (M06) quinoxyfen, (M07) vinclozolin, (M08) proquinazid.
  • N Compounds capable to act as an uncoupler, for example (N01) binapacryl, (N02) dinocap, (N03) ferimzone, (N04) fluazinam, (N05) meptyldinocap.
  • growth regulators for example abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine.
  • the compound of formula (I) can be mixed with one or more active compatible compound selected from insecticides/acaricides/nematicides class, which are specified herein by their common names that are known and described, for example in The Pesticide Manual 17th Ed. , or can be searched in the internet (e.g. under www.alanwood.net/pesticides) .
  • Acetylcholinesterase (AChE) inhibitors such as carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb or organophosphates, such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifo
  • GABA-gated chloride channel antagonists such as cyclodiene organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
  • Sodium channel modulators/voltage-dependent sodium channel blockers such as pyrethroids, for example acrinathrin, allethrin, d -cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin
  • pyrethroids for example a
  • deltamethrin empenthrin [(EZ)-(lR)-isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, fluey thrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin
  • prallethrin pyrethrins (pyrethmm), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) -isomers)], tralomethrin and transfluthrin or DDT or methoxychlor.
  • Nicotinic acetylcholine receptor (nAChR) competitive modulators such as neonicotinoids, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
  • nAChR Nicotinic acetylcholine receptor
  • Nicotinic acetylcholine receptor (nAChR) allosteric modulators such as spinosyns, for example spinetoram and spinosad.
  • Glutamate-gated chloride channel (GluCl) allosteric modulators such as avermectins / milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
  • Juvenile hormone mimics such as juvenile hormone analogues, for example hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen.
  • Active compounds with unknown or non-specific mechanisms of action such as alkyl halides for example as methyl bromide and other alkyl halides or chloropicrin or fluorides or borates or tartar emetic or methyl isocyanate generators.
  • Chordotonal organ TRPV channel modulators such as pyridine azomethine derivatives, for example pymetrozine and pyrifluquinazon or flonicamid.
  • Mite growth inhibitors for example clofentezine, hexythiazox and diflovidazin or etoxazole.
  • Microbial disruptors of insect gut midgut for example Bacillus thuringiensis subspecies israelensis, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and Bacillus sphaericus and BT crop proteins: CrylAb, CrylAc, CrylFa, CrylA 105, Cry2Ab, Vip3a, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl / Cry35Abl.
  • Inhibitors of mitochondrial ATP synthase such as organotin miticides, for example azocyclotin, cyhexatin and fenbutatin oxide or diafenthiuron or propargite or tetradifon.
  • organotin miticides for example azocyclotin, cyhexatin and fenbutatin oxide or diafenthiuron or propargite or tetradifon.
  • Nicotinic acetylcholine receptor (nAChR) channel blockers such as bensultap, cartap- hydrochloride, thiocyclam and thiosultap-sodium.
  • Inhibitors of chitin biosynthesis, type 0, such as bistrifluoron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and trillumuron.
  • Ecdysone receptor agonists such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
  • Octopamine receptor agonists such as amitraz.
  • Mitochondrial complex III electron transport inhibitors such as hydramethylnon or acequinocyl or fluacrypyrim or bifenazate.
  • Mitochondrial complex I electron transport inhibitors for example, METI acaricides and insecticides, for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
  • Inhibitors of acetyl CoA carboxylase such as tetronic and tetramic acid derivatives, for example spirodiclofen, spiromesifen and spirotetramat.
  • Mitochondrial complex IV electron transport inhibitors such as phosphides, for example aluminum phosphide, calcium phosphide, zinc phosphide and phosphine or cyanides.
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen and cyflumetofen or carboxanilides.
  • Ryanodine receptor modulators such as diamides, for example chlorantraniliprole, cyantraniliprole, flubendiamide, tetraniliprole, (R)-3-chloro-N-l- ⁇ 2-methyl-4-[l,2,2,2-tetrafluoro-l- (trifluoromethyl)ethyl]phenyl ⁇ -N2-(l-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-Nl- ⁇ 2-methyl-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]phenyl ⁇ -N2-(l-methyl-2- methylsulfonylethyl)phthalamide, methyl-2-[3,5-dibromo-2-( ⁇ [3-bromo-l-(3-chloropyridin-2-yl)-lH- pyrazol-5-yl]carbonyl ⁇ amino)benz
  • fluazaindolizine 4-[5 -(3 ,5-dichlorophenyl)-5 -(trifluoromethyl)-4H-isoxazol-3 -yl] -2 -methyl -N-( 1- oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3- dichloroallyloxy)phenoxy]propoxy]-lH-pyrazole; 3-(benzoylmethylamino)-N-[2-bromo-4-
  • the mass ratio of any two ingredients in each combination is selected as to give the desired effect. In general, the mass ratio would vary depending on the specific ingredient and how many ingredients are present in the combination. Generally, the mass ratio between any two ingredients in any combination of the present invention, independently of one another, is from 100: 1 to 1 : 100, including from 99: 1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90: 10, 89: 11, 88: 12, 87: 13, 86: 14, 85: 15, 84: 16, 83: 17, 82: 18, 81: 19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28,
  • the combination of the present invention i.e. those comprising a compound of the present invention and one more other biological active agent
  • the ingredients of a combination are applied sequentially (i.e., one after the other), the ingredients are applied sequentially within a reasonable period of each other to attain the biological performance, such as within a few horns or days.
  • the order of applying the ingredients in the combination i.e., whether the compounds of formula (I) should be applied first or not is not essential for working the present invention.
  • ingredients of the combinations may be applied as a composition containing the combination, in which case (A) the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready -to-apply, spray broth, or slurry), or (B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
  • A the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready -to-apply, spray broth, or slurry), or
  • B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
  • a compound according to the present invention is applied as a combination. Accordingly, the present invention also provides a composition comprising a compound according the invention as herein described and one or more other biological active agents, and optionally one or more customary formulation auxiliaries; which may be in the form of a tank-mix or pre-mix composition.
  • the mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds of formula (I), respectively.
  • suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines.
  • Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, Y. Y-dictbvlanilinc. pyridine, 4-( Y, Y-dimcthylamino)pyridinc. quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • the reaction according to scheme-1 is preferably carried out in a solvent selected from standard solvents which are inert under the prevailing reaction conditions.
  • a solvent selected from standard solvents which are inert under the prevailing reaction conditions.
  • aliphatic, alicyclic or aromatic hydrocarbons such as, petroleum ether, hexane, toluene; halogenated hydrocarbons, such as, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride or dichloroethane ; ethers, such as, diethyl ether, diisopropyl ether, methyl /-butyl ether (MTBE), dioxane, tetrahydrofuran or 1,2-dimethoxy ethane; nitriles, such as, acetonitrile or propionitrile, or; amides, such as, Y, Y-d i m c t h v 1 fo rm a m
  • N- methylpyrrolidone (NMP) or hexamethylenephosphoric triamide N- methylpyrrolidone (NMP) or hexamethylenephosphoric triamide
  • esters such as, for example, methyl acetate or ethyl acetate
  • sulfoxides such as, dimethyl sulfoxide (DMSO)
  • sulfones such as, sulfolane
  • alcohols such as, methanol, ethanol, nor isopropanol, 1,1-, iso-, sec- or tert-butanol, ethanediol, propane- 1,2-diol, ethoxy ethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or mixtures of these.
  • the reactants can be reacted with each other as such, i.e. without adding a solvent or diluent.
  • the reaction is advantageously carried out in a temperature range from approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, in many cases in the range between ambient temperature and approximately +80 °C.
  • a compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention.
  • Salts of compounds of formula (I) can be prepared in a manner known per se.
  • acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent.
  • a salt is chosen depending on its tolerances for compound's use, such as agricultural or physiological tolerance.
  • Salts of compounds of formula (I) can be converted in the customary manner into the free compounds of formula (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
  • a salt of inorganic acid such as hydrochloride
  • a suitable metal salt such as a sodium, barium or silver
  • Example 6 2-(Cyano(m-tolyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile: To a stirred suspension of sodium hydride (60% in mineral oil, 335 mg, 8.39 mmol) in tetrahydrofuran (10 mL), a solution of 2-(m-tolyl)acetonitrile (500 mg, 3.81 mmol) in L ' ,L - dimethylformamide (5 mL) was added and stirred for 2 h at 0 °C. To this reaction mixture, carbon disulfide (0.25 mL, 4.19 mmol) was added and allowed to stir for 2 h at 25 °C.
  • Example 12 2-((6-Chloropyridazin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile: To a stirred solution of 2-(6-chloropyridazin-3-yl)acetonitrile (0.2 g, 1.30 mmol) in L ' ,L - dimethylformamide (4.0 mL), sodium hydride (60% in mineral oil, 0.11 g, 2.73 mmol) and carbon disulfide (0.1 mL, 1.56 mmol) were added successively and stirred for 10 min at 0 °C.
  • M+l means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopy
  • 3 ⁇ 4-NMR data of selected examples are written in the form of 'H-NMR-pcak lists. To each signal peaks the d-value in ppm and the no of proton in round brackets are listed.
  • tetramethylsilane and/or the chemical shift of the respective solvent especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur, but not necessarily.
  • the compounds of general formula (I) shown fungicidal activity which is exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops.
  • Compounds of the present invention were assessed for biological activity against one or more of the following pathogens: Biological Test Examples for fungal pathogens
  • Example 1 Pyricularia oryzae (Rice blast):
  • Rhizoctonia solani (Rice sheath blight/Potato black scurf):
  • Example 7 Fusarium culmorum (Foot rot of cereals):
  • Example 8 Phytophthora infestans (Late blight of potato & tomato):

Abstract

The present invention disclosed 1-3 dithiol compounds of general formula (I), wherein, R1 to R4 have the meanings as defined in description. The present invention further discloses methods for their preparation and use thereof for the protection of crops from phytopathogenic microorganisms.

Description

1-3 DITHIOL COMPOUNDS AND THEIR USE FOR THE PROTECTION OF CROPS
FROM PHYTOPATHOGENIC MICROORGANISMS
FIELD OF THE INVENTION
The present invention relates to 1-3 dithiol compounds of general formula (I). More particularly, the present invention relates to 1-3 dithiol compounds of general formula (I) which are used to protect crops by fighting against phytopathogenic microorganisms, preferably fungal pathogens.
BACKGROUND OF THE INVENTION
The control of damages to crops caused by phytopathogenic microorganisms is extremely important in achieving high crop efficiency. For instance, plant disease damage to ornamental, vegetable, field, cereal and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Many products are commercially available to control such damages. The need continues for new compounds which are more effective, less costly, less toxic, environmentally safer and/or have different modes of action. Certain 1-3 dithiol compounds are disclosed in literature as microbicidal active ingredients in pesticides. For example DE2700869, US4075204, US4075205, US4052394, DE19630229, WO2015150343 discloses the use of 1-3 dithiol compounds, either alone or as part of composition, as fungicides.
Patent applications JP2009292967 and JP2002189295 discloses 1-3 dithiol class of compounds which are used for coloring and photopolymerizable compositions, however the use of 1-3 dithiol class of compounds as crop protecting agent is not disclosed in these applications.
Phosphorus, Sulfur Silicon Relat. Elem. (1981), 9(3), pp. 329-35 journal article, describes the alkylation and arylation reactions with geminal dithiolates in which certain 1-3 dithiol compounds are disclosed.
The drawback associated with these compounds is that the fungicidal activity of these compounds particularly at low application rates is unsatisfactory.
Therefore, there is a continuous need for new compounds which are more effective, less costly, less toxic, and environmentally safer and/or have different modes of action.
In view of the above, the present invention envisages such compounds that satisfy or overcomes drawbacks associated with the prior art.
Considering this, it is an object of the present invention to provide compounds having enhanced activity and/or a broader activity spectrum against phytopathogenic harmful fungi.
Surprisingly, this objective is achieved by the use of 1-3 dithiol class of compounds being disclosed in this invention of having favorable fungicidal activity against phytopathogenic fungi. SUMMARY OF THE INVENTION
The present invention provides a 1-3 dithiol compound of general formula (I),
Figure imgf000003_0001
wherein, R1, R2, R3 and R4 are defined in detailed description.
In an embodiment, the present invention provides use of compound of general formula (I) as crop protection agent for control of phytopathogenic microorganisms, preferably of fungal pathogens.
DESCRIPTION
DEFINITIONS:
The definitions provided for the terminologies used in the present disclosure are for illustrative purpose only and in no manner limit the scope of the present invention disclosed in the present disclosure.
The transitional phrase "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
The transitional phrase "consisting of excludes any element, step or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited, except for impurities ordinarily associated therewith. When the phrase "consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
The transitional phrase "consisting essentially of is used to define a composition or method that includes materials, steps, features, components or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of" occupies a middle ground between "comprising" and "consisting of’.
Further, unless expressly stated to the contrary, "or" refers to an inclusive "or" and not to an exclusive "or". For example, a condition "A" or "B" is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B is true (or present).
Also, the indefinite articles "a" and "an" preceding an element or component of the present invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
As referred to in this disclosure, the term "pesticide" in each case also always comprises the term "crop protection agent".
The term "undesired microorganisms" or "phytopathogenic microorganisms" such as fungal or bacterial pathogens includes namely Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes and Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae respectively.
The term "agronomic" refers to the production of field crops such as for food, fuels, biofuels, any biomaterials and fiber and includes namely the growth of com, 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), biofuel production crops such as com, sugar/starch crops, sugar-beet and sweet sorghum, cellulosic crops such as switchgrass, miscanthus, com stover, poplar, biodiesel crops rapeseed (canola), soybeans, palm oil, mustard, camelina, safflower, sunflower and jatropha and other specialty crops (e.g., canola, sunflower, olives).
The terms alkyl, alkenyl, alkynyl, carbocyclyl, heterocyclyl, aryl and heteroaryl groups, as defined herein, are optionally substituted (e.g., "substituted" or "unsubstituted" alkyl, "substituted" or "unsubstituted" alkenyl, "substituted" or "unsubstituted" alkynyl, "substituted" or "unsubstituted" carbocyclyl, "substituted" or "unsubstituted" heterocyclyl, "substituted" or "unsubstituted" aryl or "substituted" or "unsubstituted" heteroaryl group). In general, the term "substituted", whether preceded by the term "optionally" or not, means that at least one hydrogen present on a group (e.g., a carbon or nitrogen atom etc.) is replaced with a permissible substituent, e.g., a substituent which upon substitution results in a stable compound, e.g., a compound which does not spontaneously undergo transformation such as by rearrangement, cyclization, elimination, or other reaction under normal conditions (temperature, pressure, air etc.). Unless otherwise indicated, a "substituted" group has a substituent at one or more substitutable positions of the group, and when more than one position in any given stmcture is substituted, the substituent is either the same or different at each position.
The meaning of various terms used in the description shall now be illustrated. The term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" or - N(alkyl) or alkylcarbonylalkyl or alkylsuphonylamino includes straight-chain or branched Ci to CM alkyl, preferably Ci to C15 alkyl, more preferably Ci to C10 alkyl, most preferably Ci to G, alkyl. Non limiting examples of alkyl include methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2- methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2- dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,
1.1.2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 -ethyl- 1-methylpropyl and l-ethyl-2-methylpropyl or the different isomers. If the alkyl is at the end of a composite substituent, as, for example, in alkylcycloalkyl, the part of the composite substituent at the start, for example the cycloalkyl, may be mono- or poly substituted identically or differently and independently by alkyl. The same also applies to composite substituents in which other radicals, for example alkenyl, alkynyl, hydroxyl, halogen, carbonyl, carbonyloxy and the like, are at the end.
The term "alkenyl", used either alone or in compound words includes straight-chain or branched C2 to C24 alkenes, preferably Ci to C15 alkenes, more preferably Ci to C10 alkenes, most preferably Ci to C6 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-l-propenyl, l-methyl-2 -propenyl, 2- methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1 -methyl- 1-butenyl, 2-methyl-l- butenyl, 3 -methyl- 1-butenyl, l-methyl-2-butenyl, 2-methyl-2-butenyl, 3 -methyl-2 -butenyl, l-methyl-3- butenyl, 2 -methyl-3 -butenyl, 3 -methyl-3 -butenyl, 1,1 -dimethyl-2 -propenyl, 1,2-dimethyl- 1-propenyl,
1.2-dimethyl-2 -propenyl, 1 -ethyl- 1-propenyl, l-ethyl-2 -propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4- hexenyl, 5-hexenyl, 1-methyl-l-pentenyl, 2-methyl- 1-pentenyl, 3 -methyl- 1-pentenyl, 4-methyl-l- pentenyl, 1 -methyl-2 -pentenyl, 2-methyl-2-pentenyl, 3 -methyl-2 -pentenyl, 4-methyl-2-pentenyl, 1- methyl-3-pentenyl, 2 -methyl-3 -pentenyl, 3 -methyl-3 -pentenyl, 4-methyl -3 -pentenyl, l-methyl-4- pentenyl, 2-methy 1-4 -pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1 -dimethyl-2 -butenyl, l,l-dimethyl-3 -butenyl, 1,2-dimethyl-l-butenyl, 1,2 -dimethyl-2 -butenyl, l,2-dimethyl-3 -butenyl, 1,3- dimethyl- 1-butenyl, l,3-dimethyl-2-butenyl, 1,3 -dimethyl-3 -butenyl, 2, 2-dimethy 1-3 -butenyl, 2,3- dimethyl- 1-butenyl, 2,3 -dimethyl-2 -butenyl, 2,3 -dimethyl-3 -butenyl, 3,3-dimethyl-l-butenyl, 3,3- dimethyl-2-butenyl, 1 -ethyl- 1-butenyl, l-ethyl-2-butenyl, l-ethyl-3 -butenyl, 2-ethyl- 1-butenyl, 2- ethy 1-2 -butenyl, 2-ethyl-3 -butenyl, l,l,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2 -propenyl, l-ethyl-2- methyl-l-propenyl and l-ethyl-2 -methyl-2 -propenyl and the different isomers. "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. The term "alkenyloxy" as used herein refers to an alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-alkenyloxy is a C2-C6-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-Cs-alkenyloxy is a C2- Cs-alkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. Non limiting examples of alkenyloxy include, but are not limited to, allyloxy, 2-butenyloxy, 3- butenyloxy and 3-pentenyloxy.
The term "haloalkenyloxy" as used herein refers to a haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-haloalkenyloxy is a C2-C6-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C8- haloalkenyloxy is a C2-Cs-haloalkenyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. Non limiting examples of haloalkenyloxy include, but are not limited to, 3-bromo-2-propenyloxy and 4-bromo-3-butenyloxy.
The term "alkenylthio" as used herein refers to an alkenyl group, as defined above, attached via an sulphur atom to the remainder of the molecule. C2-C6-alkenylthio is a C2-C6-alkenyl group, as defined above, attached via a sulphur atom to the remainder of the molecule. C2-Cs-alkenyloxy is a C2- G-alkcnvl group, as defined above, attached via a sulphur atom to the remainder of the molecule. Non limiting examples of alkenylthio include, but are not limited, allylsulfanyl, 2-butenylsulfanyl, 3- butenylsulfanyl and 3-pentenylsulfanyl.
The term "alkynyl", used either alone or in compound words includes branched or straight-chain C2 to C24 alkynes, preferably C2 to C15 alkynes, more preferably C2 to C10 alkynes, most preferably C2 to G, alkynes. Non limiting examples of alkynes include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2- butynyl, 3-butynyl, 1 -methyl-2 -propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, l-methyl-2- butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-l-butynyl, 1,1 -dimethyl-2 -propynyl, 1- ethyl -2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1 -methyl-2 -pentynyl, 1- methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methy 1-3 -pentynyl, 2-methyl-4-pentynyl, 3-methyl-l- pentynyl, 3-methyl-4-pentynyl, 4-methyl-l-pentynyl, 4-methyl-2-pentynyl, l,l-dimethyl-2-butynyl, l,l-dimethyl-3-butynyl, l,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-l-butynyl, 1- ethyl-2-butynyl, l-ethyl-3-butynyl, 2 -ethyl-3 -butynyl and l-ethyl-l-methyl-2 -propynyl and the different isomers. This definition also applies to alkynyl as a part of a composite substituent, for example haloalkynyl etc., unless specifically defined elsewhere. The term "alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
The term "alkynyloxy" as used herein refers to a alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-alkynyloxy is a C2-C6-alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-Cs-alkynyloxy is a C2-C8- alkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. Non limiting examples of alkynyloxy include, but are not limited to, 3-pentynyloxy, 3-butynyloxy and 2- propynyloxy.
The term "haloalkynyloxy" as used herein refers to a haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C6-haloalkynyloxy is a C2-C6-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. C2-C8- haloalkynyloxy is a C2-Cs-haloalkynyl group, as defined above, attached via an oxygen atom to the remainder of the molecule. Non limiting examples of haloalkynyloxy include, but are not limited to, (3-bromo-2-propynyl)oxy and (4-bromo-3-butynyl)oxy.
The term "alkynylthio" as used herein refers to a alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule. C2-C6-alkynyloxy is a C2-C6-alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule. C2-Cs-alkynyloxy is a C2-C8- alkynyl group, as defined above, attached via an sulphur atom to the remainder of the molecule. Non limiting examples of alkynylthio include, but are not limited, 2-propynylsulfanyl, 3-butynylsulfanyl and 3-pentynylsulfanyl.
The term "cyclic alkyl" or "cycloalkyl" means alkyl closed to form a ring. Non limiting examples include but are not limited to cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. This definition also applies to cycloalkyl as a part of a composite substituent, for example cycloalkylalkyl, cycloalkyl alkoxy or cycloalkyl alkyloxy, cycloalkyl alkylthio etc., unless specifically defined elsewhere.
The term“alky ley cloalkyl” as used herein refers to mono-, bi- or tricyclic alkylcycloalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, for example methylcyclopropyl, ethylcyclopropyl, isopropylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. Preference is also given to alkylcycloalkyls having 4, 5 or 7 carbon atoms such as, inter alia, ethylcyclopropyl or 4- methylcyclohexyl. The inventive alkylcycloalkyls may be substituted by one or more identical or different radicals.
The term“cycloalkylalkyl” as used herein refers to mono-, bi- or tricyclic cycloalkylalkyl preferably having 4 to 10 or 4 to 7 carbon atoms, for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl and cyclopentylethyl. Preference is also given to cycloalkylalkyls having 4, 5 or 7 carbon atoms such as, inter alia, cyclopropylmethyl or cyclobutylmethyl. The inventive cycloalkylalkyls may be substituted by one or more identical or different radicals.
The term "cycloalkenyl" means alkenyl closed to form a ring including monocyclic, partially unsaturated hydrocarbyl groups. Non limiting examples include but are not limited to cyclopentenyl and cyclohexenyl. This definition also applies to cycloalkenyl as a part of a composite substituent, for example cycloalkenylalkyl etc., unless specifically defined elsewhere. The term "cycloalkynyl" means alkynyl closed to form a ring including monocyclic, partially unsaturated groups. This definition also applies to cycloalkynyl as a part of a composite substituent, for example cycloalkynylalkyl etc., unless specifically defined elsewhere.
The term "cycloalkoxy" or "cycloalkyloxy", "cycloalkenyloxy" and the like are defined analogously. Non limiting examples of cycloalkoxy include cyclopropyloxy, cyclopentyloxy and cyclohexyloxy. This definition also applies to cycloalkoxy as a part of a composite substituent, for example cycloalkoxy alkyl, etc., unless specifically defined elsewhere.
The term "alkoxy" used either alone or in compound words included Ci to CM alkoxy, preferably Ci to C15 alkoxy, more preferably Ci to Cio alkoxy, most preferably Ci to G, alkoxy. Non limiting examples of alkoxy include methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2- methylpropoxy, 1,1-dimethylethoxy, pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2,2- dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 1- methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1,1-dimethylbutoxy, 1,2- dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, 1 -ethyl- 1- methylpropoxy and l-ethyl-2-methylpropoxy and the different isomers. This definition also applies to alkoxy as a part of a composite substituent, for example haloalkoxy, alkynylalkoxy, etc., unless specifically defined elsewhere.
The term "alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1- dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2- dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2-dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3- dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2- trimethylpropylthio, 1 -ethyl- 1-methylpropylthio and l-ethyl-2-methylpropylthio and the different isomers.
The term "hydroxy" means -OH, "amino" means -NRR, wherein R can be H or any possible substituent such as alkyl; "carbonyl" means -C(O)- , "carbonyloxy" means -OC(O)-, "sulfinyl" means SO, "sulfonyl" means S(0)2.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
Non limiting examples of "haloalkyl" include chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 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, l,l-dichloro-2,2,2-trifluoroethyl, and l,l,l-trifluoroprop-2-yl. This definition also applies to haloalkyl as a part of a composite substituent, for example haloalkylaminoalkyl etc., unless specifically defined elsewhere.
The terms "haloalkenyl" and "haloalkynyl" are defined analogously except that, instead of alkyl groups, alkenyl and alkynyl groups are present as a part of the substituent.
The term "haloalkoxy" means straight-chain or branched alkoxy groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non limiting examples of haloalkoxy include chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2- difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2- dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and l,l,l-trilluoroprop-2-oxy. This definition also applies to haloalkoxy as a part of a composite substituent, for example haloalkoxy alkyl etc., unless specifically defined elsewhere.
The term "haloalkylthio" or "haloalkylsulfanyl" means straight-chain or branched alkylthio groups where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as specified above. Non limiting examples of haloalkylthio include chloromethylthio, bromomethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio, dichlorofluoromethylthio, chlorodifluoromethylthio, 1-chloroethylthio, 1- bromoethylthio, 1- fluoroethylthio, 2-fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2- chloro-2- fluoroethylthio, 2-chloro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2- trichloroethylthio, pentafluoroethylthio and l,l,l-trifluoroprop-2-ylthio. This definition also applies to haloalkylthio as a part of a composite substituent, for example haloalkylthioalkyl etc., unless specifically defined elsewhere.
The term "haloalkenylthio" or "haloalkenylsulfanyl" means straight-chain or branched alkenylthio 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 "haloalkylsulfinyl" include CF3S(0), CCTS(O). CF3CH2S(0) and CF3CF2S(0). Non limiting examples of "haloalkylsulfonyl" include CF3S(0)2, CC13S(0)2, CF3CH2S(0)2 and CF3CF2S(0)2.
The term "alkylthioalkyl" denotes alkylthio substitution on alkyl. Non limiting examples of "alkylthioalkyl" include -CH2SCH2, -CH2SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. The term "alkylthioalkoxy" denotes alkylthio substitution on alkoxy. The term "cycloalkylalkylamino" denotes cycloalkyl substitution on alkyl amino.
The terms alkoxyalkoxyalkyl, alkylaminoalkyl, dialkylaminoalkyl, cycloalkylaminoalkyl, cycloalkylaminocarbonyl and the like, are defined analogously to "alkylthioalkyl" or cycloalkylalkylamino .
The term "alkoxycarbonyl" is an alkoxy group bonded to a skeleton via a carbonyl group (-CO-). This definition also applies to alkoxycarbonyl as a part of a composite substituent, for example cycloalkylalkoxycarbonyl and the like, unless specifically defined elsewhere.
The term "alkoxycarbonylalkylamino" denotes alkoxy carbonyl substitution on alkyl amino.
The term "alkylcarbonylalkylamino" denotes alkyl carbonyl substitution on alkyl amino.
The terms alkylthioalkoxycarbonyl, cycloalky lalkylaminoalkyl and the like are defined analogously. Non limiting examples of "alkylsulfinyl" include but are not limited to methylsulphinyl, ethylsulphinyl, propylsulphinyl, 1-methylethylsulphinyl, butylsulphinyl, 1-methylpropylsulphinyl, 2- methylpropylsulphinyl, 1,1-dimethylethylsulphinyl, pentylsulphinyl, 1-methylbutylsulphinyl, 2- methylbutylsulphinyl, 3-methylbutylsulphinyl, 2,2-dimethylpropylsulphinyl, 1-ethylpropylsulphinyl, hexylsulphinyl, 1,1-dimethylpropylsulphinyl, 1,2-dimethylpropylsulphinyl, 1-methylpentylsulphinyl, 2-methylpentylsulphinyl, 3-methylpentylsulphinyl, 4-methylpentylsulphinyl, 1,1- dimethylbutylsulphinyl, 1,2-dimethylbutylsulphinyl, 1,3-dimethylbutylsulphinyl, 2,2- dimethylbutylsulphinyl, 2,3-dimethylbutylsulphinyl, 3,3-dimethylbutylsulphinyl, 1- ethylbutylsulphinyl, 2-ethylbutylsulphinyl, 1,1,2-trimethylpropylsulphinyl, 1,2,2- trimethylpropylsulphinyl, 1 -ethyl- 1-methylpropylsulphinyl and 1 -ethyl-2 -methylpropylsulphinyl and the different isomers. The term "arylsulfinyl" includes Ar-S(O), wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphinyl as a part of a composite substituent, for example haloalkylsulphinyl etc., unless specifically defined elsewhere.
Non limiting examples of "alkylsulfonyl" include but are not limited to methylsulphonyl, ethylsulphonyl, propylsulphonyl, 1-methylethylsulphonyl, butylsulphonyl, 1-methylpropylsulphonyl, 2-methylpropylsulphonyl, 1,1-dimethylethylsulphonyl, pentylsulphonyl, 1-methylbutylsulphonyl, 2- methylbutylsulphonyl, 3-methylbutylsulphonyl, 2,2-dimethylpropylsulphonyl, 1- ethylpropylsulphonyl, hexylsulphonyl, 1,1-dimethylpropylsulphonyl, 1,2-dimethylpropylsulphonyl, 1- methylpentylsulphonyl, 2-methylpentylsulphonyl, 3-methylpentylsulphonyl, 4- methylpentylsulphonyl, 1,1-dimethylbutylsulphonyl, 1,2-dimethylbutylsulphonyl, 1,3- dimethylbutylsulphonyl, 2,2-dimethylbutylsulphonyl, 2,3-dimethylbutylsulphonyl, 3,3- dimethylbutylsulphonyl, 1-ethylbutylsulphonyl, 2-ethylbutylsulphonyl, 1,1,2- trimethylpropylsulphonyl, 1,2,2-trimethylpropylsulphonyl, 1 -ethyl- 1-methylpropylsulphonyl and 1- ethyl-2-methylpropylsulphonyl and the different isomers. The term "arylsulfonyl" includes Ar-S(0)2, wherein Ar can be any carbocyle or heterocylcle. This definition also applies to alkylsulphonyl as a part of a composite substituent, for example alkylsulphonylalkyl etc., unless defined elsewhere.
The terms "alkylamino", "dialkylamino", and the like, are defined analogously to the above examples. The term "ring" or "ring system" as a component of formula I is carbocyclyl or heterocyclyl. The term "ring system" denotes one or more rings.
The term "bicyclic ring or ring system" denotes a ring system consisting of two or more common atom.
The term "aromatic" indicates that the Hueckel rule is satisfied and the term "non-aromatic" indicates that the Hueckel rule is not satisfied.
The terms "carbocycle" or "carbocyclic" or "carbocyclyl" include "aromatic carbocyclic ring system" and "nonaromatic carbocylic ring system" or polycyclic or bicyclic (spiro, fused, bridged, nonfused) ring compounds in which the ring may be aromatic or non-aromatic (where aromatic indicates that the Huckel rule is satisfied and non-aromatic indicates that the Huckel rule is not satisfied).
Non limiting examples of non-aromatic carbocyclic ring system are cyclopropyl, cyclobutyl, cyclopentyl, norbomyl and the like.
Non limiting examples of aromatic carbocyclic ring system are phenyl, naphthyl and the like.
The term "aryl" as used herein is a group that contains any carbon-based aromatic group including, but not limited to phenyl, naphthalene, biphenyl, anthracene, and the like. The aryl group can be substituted or unsubstituted. In addition, the aryl group can be a single ring structure or comprise multiple ring structures that are either fused ring structures or attached via one or more bridging groups such as a carbon-carbon bond.
The term "aralkyl" refers to aryl hydrocarbon radicals including an alkyl portion as defined above. Non limiting examples include benzyl, phenylethyl, and 6-napthylhexyl. As used herein, the term "aralkenyl" refers to aryl hydrocarbon radicals including an alkenyl portion, as defined above, and an aryl portion, as defined above. Non limiting examples include styryl, 3 -(benzyl) prop-2 -enyl, and 6- napthy lhex-2 -eny 1.
The term "hetero" in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
The term "heterocycle" or "heterocyclyl" includes "aromatic heterocycle" or "heteroaryl ring system" and "nonaromatic heterocycle ring system" or polycyclic or bicyclic (spiro, fused, bridged, non-fused) ring compounds in which ring may be aromatic or non-aromatic, wherein the heterocycle ring contains at least one heteroatom selected from N, O, S(0)o-2, and or C ring member of the heterocycle may be replaced by C(=0), C(=S), C(=CR*R*) and C=NR*, * indicates integers. The term "non-aromatic heterocycle" or "non-aromatic heterocyclic" means three- to fifteen- membered, preferably three- to twelve-membered, saturated or partially unsaturated heterocycle containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur: mono, bi- or tricyclic heterocycles which contain, in addition to carbon ring members, one to three nitrogen atoms and/or one oxygen or sulphur atom or one or two oxygen and/or sulphur atoms; if the ring contains more than one oxygen atom, they are not directly adjacent; for example (but not limited to) oxiranyl, aziridinyl, oxetanyl, azetidinyl, thietanyl, 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2- tetrahydrothienyl, 3-tetrahydrothienyl, 1-pyrrolidinyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 1- pyrazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5- oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 1-imidazolidinyl, 2-imidazolidinyl, 4- imidazolidinyl, l,2,4-oxadiazolidin-3-yl, l,2,4-oxadiazolidin-5-yl, l,2,4-thiadiazolidin-3-yl, 1,2,4- thiadiazolidin-5-yl, 1,2,4-triazolidin-l-yl, l,2,4-triazolidin-3-yl, l,3,4-oxadiazolidin-2-yl, 1,3,4- thiadiazolidin-2-yl, 1,3,4-triazolidin-l-yl, l,3,4-triazolidin-2-yl, 2,3-dihydrofm-2-yl, 2,3-dihydrofur- 3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4- dihydrothien-2-yl, 2,4-dihydrothien-3-yl, pyrrolinyl, 2-pyrrolin-2-yl, 2-pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3- isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2- isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin-3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4- isothiazolin-4-yl, 2-isothiazolin-5-yl, 3-isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-l-yl,
2.3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl,
3.4-dihydropyrazol-l-yl, 3 ,4-dihydropyrazol-3 -yl, 3 ,4-dihydropyrazol-4-yl, 3 ,4-dihydropyrazol-5-yl,
4.5-dihydropyrazol-l-yl, 4,5-dihydropyrazol-3-yl, 4,5-dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol-3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4- dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4- dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, piperidinyl, 2-piperidinyl, 3- piperidinyl, 4-piperidinyl, pyrazynyl, morpholinyl, thiomorphlinyl, l,3-dioxan-5-yl, 2- tetrahydropyranyl, 4-tetrahydropyranyl, 2-tetrahydrothienyl, 3-hexahydropyridazinyl, 4- hexahydropyridazinyl, 2-hexahydropyrimidinyl, 4-hexahydropyrimidinyl, 5-hexahydropyrimidinyl, 2- piperazinyl, l,3,5-hexahydrotriazin-2-yl, l,2,4-hexahydrotriazin-3-yl, cycloserines. This definition also applies to heterocyclyl as a part of a composite substituent, for example heterocyclylalkyl etc., unless specifically defined elsewhere.
The term "heteroaryl" means 5 or 6-membered, fully unsaturated monocyclic ring system containing one to four heteroatoms from the group of oxygen, nitrogen and sulphur; if the ring contains more than one oxygen atom, they are not directly adjacent; 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom: 5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms and one sulphur or oxygen atom as ring members, for example (but not limited thereto) furyl, thienyl, pyrrolyl, isoxazolyl, isothiazolyl, pyrazolyl, oxazolyl, thiazolyl, imidazolyl, 1,2,4-oxadiazolyl, 1,2,4-thiadiazolyl, 1,2,4-triazolyl, 1,3,4-oxadiazolyl, 1,3,4-thiadiazolyl, 1,3,4-triazolyl, tetrazolyl; nitrogen-bonded 5-membered heteroaryl containing one to four nitrogen atoms, orbenzofused nitrogen-bonded 5-membered heteroaryl containing one to three nitrogen atoms:
5-membered heteroaryl groups which, in addition to carbon atoms, may contain one to four nitrogen atoms or one to three nitrogen atoms as ring members and in which two adjacent carbon ring members or one nitrogen and one adjacent carbon ring member may be bridged by a buta-1, 3 -diene-1, 4-diyl group in which one or two carbon atoms may be replaced by nitrogen atoms, where these rings are attached to the skeleton via one of the nitrogen ring members, for example (but not limited to) 1- pyrrolyl, 1-pyrazolyl, 1,2,4-triazolyl, 1-imidazolyl, 1,2,3-triazolyl and 1,3,4-triazolyl.
6-membered heteroaryl which contains one to four nitrogen atoms: 6-membered heteroaryl groups which, in addition to carbon atoms, may contain, respectively, one to three and one to four nitrogen atoms as ring members, for example (but not limited thereto) 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3- pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, l,3,5-triazin-2- yl, l,2,4-triazin-3-yl and l,2,4,5-tetrazin-3-yl; benzofused 5-membered heteroaryl containing one to three nitrogen atoms or one nitrogen atom and one oxygen or sulphur atom: for example (but not limited to) indol-l-yl, indol-2-yl, indol-3-yl, indol-4-yl, indol-5-yl, indol-6-yl, indol-7-yl, benzimidazol-l-yl, benzimidazol-2-yl, benzimidazol-4-yl, benzimidazol-5-yl, indazol-l-yl, indazol-3- yl, indazol-4-yl, indazol-5-yl, indazol-6-yl, indazol-7-yl, indazol-2-yl, l-benzofuran-2-yl, 1- benzofuran-3-yl, l-benzofuran-4-yl, l-benzofuran-5-yl, 1-benzofuran- 6-yl, l-benzofuran-7-yl, 1- benzothiophen-2-yl, l-benzothiophen-3-yl, l-benzothiophen-4-yl, 1- benzothiophen-5-yl, 1- benzothiophen-6-yl, l-benzothiophen-7-yl, l,3-benzothiazol-2-yl, 1,3- benzothiazol-4-yl, 1,3- benzothiazol-5-yl, l,3-benzothiazol-6-yl, l,3-benzothiazol-7-yl, l,3-benzoxazol-2-yl, l,3-benzoxazol-4- yl, l,3-benzoxazol-5-yl, l,3-benzoxazol-6-yl and l,3-benzoxazol-7-yl; benzofused 6-membered heteroaryl which contains one to three nitrogen atoms: for example (but not limited to) quinolin-2-yl, quinolin-3-yl, quinolin-4-yl, quinolin-5-yl, quinolin-6-yl, quinolin-7-yl, quinolin-8-yl, isoquinolin-1- yl, isoquinolin-3-yl, isoquinolin-4-yl, isoquinolin-5-yl, isoquinolin-6-yl, isoquinolin-7-yl and isoquinolin-8-yl.
Non limiting examples of fused 6-5-membered heteroaryl include Indolizinyl; pyrazolo[l,5- ajpyridinyl; imidazo[l,2-a]pyridinyl; pyrrolo[l,2-a]pyrimidinyl; pyrazolo[l,5-a]pyrimidinyl; imidazo[l,2-a]pyrimidinyl; pyrrolo[l,2-a]pyrazinyl; pyrazolo[l,5-a]pyrazinyl; imidazo[l,2- ajpyrazinyl and the like. This definition also applies to heteroaryl as a part of a composite substituent, for example heteroarylalkyl etc., unless specifically defined elsewhere.
The term "Trialkylsilyl" includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom such as trimethylsilyl, triethylsilyl and t-butyl-dimethylsilyl.
The term "Halotrialkylsilyl" denotes at least one of the three alkyl radicals is partially or fully substituted with halogen atoms which may be the same or different. The term "Alkoxytrialkylsilyl" denotes at least one of the three alkyl radicals is substituted with one or more alkoxy radicals which may be the same or different. The term "Trialkylsilyloxy" denotes a trialkylsilyl moiety attached through oxygen.
Non limiting examples of "alkylcarbonyl" include C(0)CH3, C/O/CThCFbCTh and C(0)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=0), CH3CH20C(=0), CEECEECEEOC^O), (CH3)2CH0C(=0) and the different butoxy or pentoxycarbonyl isomers. Examples of "alkylaminocarbonyl" include CH3NHC(=0), CH3CH2NHC(=0), CH3CH2CH2NHC(=0), (CH3)2CHNHC(=0) and the different butylamino -or pentylaminocarbonyl isomers. Non limiting examples of "dialkylaminocarbonyl" include (CH3)2NC(=0), (CH3CH2)2NC(=0),
CH3CH2(CH3)NC(=0), CH3CH2CH2(CH3)NC(=0) and (CH3)2CHN(CH3)C(=0). Non limiting examples of "alkoxyalkylcarbonyl" include CH30CH2C(=0), CH30CH2CH2C(=0),
CH3CH20CH2C(=0), CH3CH2CH2CH20CH2C(=0) and CH3CH20CH2CH2C(=0). Non limiting examples of "alkylthioalkylcarbonyl" include CH3SCH2C(=0), CH3SCH2CH2C(=0), CH3CH2SCH2C(=0), CH3CH2CH2CH2SCH2C(=0) and CH3CH2SCH2CH2C(=0). The terms haloalkylsufonylaminocarbonyl, alkylsulfonylaminocarbonyl, alkylthioalkoxycarbonyl, alkoxycarbonylalkyl amino and the like are defined analogously.
Non limiting examples of "alkylaminoalkylcarbonyl" include CH3NHCH2C(=0), CH3NHCH2CH2C(=0), CH3CH2NHCH2C(=0), CH3CH2CH2CH2NHCH2C(=0) and CH3CH2NHCH2CH2C(=0).
The term "amide" means A-R'C=ONR"-B, wherein R' and R" indicates substituents and A and B indicate any group.
The term "thioamide" means A-R'C=SNR"-B, wherein R' and R" indicates substituents and A and B indicate any group.
The total number of carbon atoms in a substituent group is indicated by the "G- " prefix where i and j are numbers from 1 to 21. For example, Ci-C3 alkoxy designates methoxy through propoxy. In the above recitations, when a compound of formula (I) is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a compound is substituted with a substituent bearing a subscript indicates that the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e. g. (R)i-j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R1 or R2, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
In an embodiment, the present invention provides a compound of general formula (I),
Figure imgf000015_0001
The definition of each component of formula (I) is provided herein below in detail.
R1 and R2 are independently selected from the group consisting of cyano, nitro, Ci-G, -alkyl. C2- G, -alkenyl. G-G,-alkynyk G-G-haloalkyk G-G,-haloalkcnvl. G-G.-haloalkvnvl. OR7, C(=0)R7, C(=0)0R7, C(=0)N(R7)2, S(0)„R7, S(0)„R7-C(=0)R7, C(=0)R7-S(0)„R7, Ci-C6- alkyl-S(0)nR7, Ci-C6-alkyl-C(=0)-R7, C(R')=N(R"), Ci-Cio-aryl and C3-Cio-heterocyclyl; wherein said aryl or heterocyclyl group may be optionally substituted with one or more group selected from the group consisting of halogen, nitro, cyano, G-G, -alkyl. G-G-alkcnyk C2-C8- alkynyl, G-G,-haloalkyk C2-Cs-haloalkenyl, G-G,-alkoxy. C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, G-G-haloalkoxy. C2-Cs-haloalkenyloxy, C2-C8-haloalkynyloxy, G-G-alkylthio. C2-C8- alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-Cio-cycloalkyl, C4-Cio-cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C3-Cio-cycloalkylthio, C4- Cio-cycloalkenylthio, C3-Cio-cycloalkyl-Ci-C6-alkyl, C3-Cio-cycloalkyl-Ci-C6-alkyloxy, C3-C10- cycloalkyl-Ci-Ce-alkylthio, OR7, N(R7)2, C(=0)R7, C(=0)0R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl-C(=0)-R7, C(R')=N(R"), C7-Ci9-aralkyl, Ci-Cio aryl and C3-Cio-heterocyclyl.
Particularly, R1 and R2 are independently selected from the group consisting of cyano, C 1 -G,- alkyl, C2-C6-alkynyl, C(=0)N(R7)2, OR7, C(=0)R7, C(=0)0R7, S(0)„R7, C6-Cio-aryl and C3-C10- heterocyclyl; wherein said aryl or heterocyclyl group may be optionally substituted with one or more group selected from the group consisting of halogen, nitro, cyano, G-G, -alkyl. C2-C8- alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. C2-C8-haloalkenyl, G-G,-alkoxy. C2-Cs-alkenyloxy, C2- Cs-alkynyloxy, Ci-Ci-haloalkoxy, C2-Cs-haloalkenyloxy, C2-C8-haloalkynyloxy, Ci-C6-alkylthio, C2-C8-alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-C10- cycloalkyl, C4-Cio-cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C3-C10- cycloalkylthio, C4-Cio-cycloalkenylthio, C ¾ - C m -eye 1 o a 1 kyl - C i - G,- a 1 k 1. C ¾ - C m -eye 1 o a 1 kyl - C i - G, - alkyloxy, C3-Cio-cycloalkyl-Ci-C6-alkylthio, OR7, N(R7)2, C(=0)R7, C(=0)0R7, S(0)„R7, Ci-Gs- alkyl-S(0)„R7, Ci-C8-alkyl-C(=0)-R7, C(R')=N(R"), C7-Ci9-aralkyl, C6-Cio aryl and C3-C10- heterocyclyl.
More particularly, R1 is selected from the group consisting of cyano, nitro, G-G, -alkyl. C 1 -G,- alkynyl, C(=0)N(R7)2, C(=0)R7, C(=0)0R7, S(0)„R7, S(0)„R7-C(=0)R7, C(=0)R7-S(0)„R7 and C(R')=N(R").
More particularly, R2 is selected from the group consisting of S(0)o-iR7, G,-Gn-aryl and C3-C10- heterocyclyl; said G,- Go -aryl. C3-Cio-heterocyclyl group may be optionally substituted with at least one group selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G,- alkyl, C2-Cs-alkenyl, G-Cs-alkynyl, G-G,-haloalkyl. G-Cs-haloalkenyl, Ci-G^-alkoxy. C2-Cs- alkenyloxy, C2-Cs-alkynyloxy, Ci-Ci-haloalkoxy, C2-Cs-haloalkenyloxy, C2-C8-haloalkynyloxy, Ci-C6-alkylthio, G-G-alkenylthio, G-Cs-alkynylthio, Ci-Crrhaloalkylthio. C2-Cs- haloalkenylthio, C3-Cio-cycloalkyl, Ci-Go-cycloalkenyl, OR7, C(=0)0R7 and S(0)nR7.
Alternatively, R1 and R2 together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7-membered ring, which for its part may be optionally substituted by one or more R5 or R5a.
Particularly, R1 and R2 together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), may form a 5-membered ring selected from the group consisting of
Figure imgf000016_0001
R' is selected from the group consisting of hydrogen, halogen, G-G.-alkyl and G¾-G,- cycloalkyl. R" is selected from the group consisting of hydrogen, N(R')2, G-G, -alkyl. G-G-haloalkyl and C3-C8-cycloalkyl, each group of R'' is optionally substituted by one or more groups selected from the group consisting of halogen, cyano, R', OR', SR', N(R')2, Si(R')3, COOR', CON(R')2 and C -Ci2-aryl which is optionally substituted by one or more group R'.
R7 is selected from the group consisting of hydrogen, Ci-G, -alkyl. G-G-alkcnvl. C2-Cs- alkynyl, Ci-Ci-haloalkyl, G-Cs-haloalkenyl, C3-Cio-cycloalkyl, G-Go-cycloalkyl-G- Ci-alkyl, C3-Cio-halocycloalkyl, amino, mono-(Ci-C6-alkyl)amino, di-(Ci-C6- alkyl)amino, G-G' -aralkyk Ci- o aryl and C3-Cio-heterocyclyl.
Each group of R1, R2, R7 may optionally be substituted with one or more groups selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, Ci-G, -alkyl. C i -G,- haloalkyl, G-C6-cycloalkyl, Ci-Ci-alkoxy, Ci-Ci-haloalkoxy and Ci-C6-alkyl-amino.
R3 and R4 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 15- membered ring, which for its part may be optionally substituted by one or more R5 or R5a; with the proviso that when R1 and R2 represent cyano simultaneously, R3 and R4 will not form a pyrazine ring.
Particularly, R3 and R4 together with the atom to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5, 6 or 10-membered heterocyclic ring, which for its part may be optionally substituted by one or more R5 or R5a; with the proviso that when R1 and R2 represent cyano simultaneously, R3 and R4 will not form a pyrazine ring.
More particularly, R3 and R4 together with the atoms to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5, 6 or 10 membered ring selected from the group consisting of
Figure imgf000017_0001
Most particularly, R3 and R4 together with the atoms to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5 or 6 membered ring selected from the group consisting of
Figure imgf000018_0001
R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-C8- alkenyl, C2-Cs-alkynyl, G-G,-haloalkyl. C2-Cs-haloalkenyl, Ci-Ci-alkoxy, C2-Cs-alkenyloxy, C2- Cs-alkynyloxy, G-G,-haloalkoxy. C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, G-G,- alkylthio, C2-C8-alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, G- Cio-cycloalkyl, G-Cio-cycloalkenyl, G-Cio-cycloalkyloxy, G-Go-cycloalkenyloxy, C3-G0- cycloalkylthio, G-Cio-cycloalkenylthio, C3-Cio-cycloalkyl-Ci-C6-alkyl, C3-Go-cycloalkyl-G- Ce-alkyloxy, Cs-Go-cycloalkyl-Ci-Ce-alkylthio, OR7, C(=0)R7, C(=0)0R7, S(0)„R7, Ci-C8- alkyl-S(0)„R7, Ci-C8-alkyl-C(=0)-R7, C(R')=N(R"), C7-Ci9-aralkyl, Ce-Go-aryl, C3-C10- heterocyclyl; each group of R5 may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2.
Particularly, R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C 1 -G,- alkyl, C2-Cs-alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. Ci-Ci-alkoxy, G-G,-alkylthio. C3-G0- cycloalkyl, G-Go-cycloalkyl-G-Ce-alkyl, OR7, C(=0)0R7, Ci-C8-alkyl-(C=0)-R7, C7-C19- aralkyl, G,-Gn-aryl. C3-Go-heterocyclyl; said aryl or heterocyclyl group may optionally be substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, C 1 -G -alkyl and C 1 -G,- alkoxy.
More particularly, R5 is selected from the group consisting of cyano, nitro, C(=0)R7, C(=0)0R7, S(0)nR7, G-C8-alkyl-S(0)nR7, G-C8-alkyl-C(=0)-R7 and C(R')=N(R''); each group of R5 may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2.
R5a is selected from the group consisting of hydrogen, cyano, G-G, -alkyl. C2-C8 -alkenyl, C2-C8- alkynyl, G-Grhaloalkyl. C2-C8-haloalkenyl, Ci-Ci-alkoxy, C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, Ci-G-haloalkoxy. C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, C3-Cio-cycloalkyl, G-C10- cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C3-Cio-cycloalkyl-G-C6-alkyl, C3- Cio-cycloalkyl-Ci-Ce-alkyloxy, OR7, C(=0)R7, C(=0)OR7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci- C8-alkyl-(C=0)-R7, C(R')=N(R"), C7-Cie-aralkyl, G-Gn-aryl. C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR'', SR'', N(R")2, Si(R'')3, COOR", cyano and CON(R")2.
Particularly, R5a is selected from the group consisting of hydrogen, G-G, -alkyl. C2-Cs-alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. C2-C8-haloalkenyl, G-G,-alkoxy. C2-Cs-alkenyloxy, C2-C8- alkynyloxy, G-G,-haloalkoxy. C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, C3-Cio-cycloalkyl, C4-Cio-cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C 3 - C m -eye 1 o a 1 kyl - C 1 - C - alkyl, Cs-Cio-cycloalkyl-Ci-Ce-alkyloxy, C(=0)R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl- (C=0)-R7, C7-Ci9-aralkyl, G.-Gn-aryl. C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R")3, COOR'', cyano and CON(R")2.
Alternatively, two R5 substituents together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7-membered ring, which for its part may be substituted by one or more R6.
Particularly, two R5 substituents together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 5 to 6 membered ring, which for its part may be optionally substituted by one or more R6.
R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-C8- alkenyl, C2-Cs-alkynyl, G-G,-haloalkyl. C2-Cs-haloalkenyl, C2-C8-haloalkynyl, G,-G, -cycloalkyl. C(=0)R", C(=0)OR", OR'', N(R")2 and S(0)„R".
n and m represents integers wherein n= 0-2 and m= 0-2.
and/or N or S-oxides or agriculturally acceptable salts thereof.
In more preferred embodiment, the compound of general formula (I) is selected from 2-(5-methyl-4,6- dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, 2-(4,6-dioxo-5,6-dihydro- 4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, diethyl 2-(5-methyl-4,6-dioxo-5,6-dihydro-4H- [l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, diethyl 2-(4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5- c]pyrrol-2-ylidene)malonate, ethyl 2-cyano-2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5- c]pyrrol-2-ylidene)acetate, ethyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, methyl 2-cyano-2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2- ylidene)acetate, ethyl 2-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-cyanoacetate, 5-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-3-methylthiazolidine-2,4-dione, 2-(cyano(lH-imidazol-l-yl)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-([l,3]dithiolo[4,5-b]pyrido[2,3-e]pyrazin-2- ylidene)malononitrile, 2-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(lH-imidazol-l-yl)acetonitrile, ethyl 2-cyano-2-(4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, 2-(3-methyl- 2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 5-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-3-methyl-2-thioxothiazolidin-4-one, ethyl 2-([l,3]dithiolo[4,5-b]quinoxalin-2- ylidene)-2-cyanoacetate, methyl 2-([l,3]dithiolo[4,5-b]quinoxalin-2-ylidene)-2-cyanoacetate, 2-(2,4- dioxo-3-(prop-2-yn-l-yl)thiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 5- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-(prop-2-yn-l-yl)thiazolidine-2,4-dione, methyl 2-cyano-2- (4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, methyl 2-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-2-cyanoacetate, diethyl 2-(5-(4-fluorophenyl)-4,6-dioxo-5,6-dihydro-4H-
[1.3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, diethyl 2-([l,3]dithiolo[4,5-b]pyrazin-2- ylidene)malonate, diethyl 2-([l,3]dithiolo[4,5-b]quinoxalin-2-ylidene)malonate, 2-(3 -ally 1-2,4- dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(2,4-dioxo-3- propylthiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3 -benzyl-2, 4- dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-(cyclopropylmethyl)- 2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3 -ethyl-2, 4- dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 5-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-3-allylthiazolidine-2,4-dione, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- propylthiazolidine-2,4-dione, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-benzylthiazolidine-2,4- dione, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-(cyclopropylmethyl)thiazolidine-2,4-dione, 5- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-ethylthiazolidine-2,4-dione, 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetamide, 2-cyano-2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-
[1.3]dithiolo[4,5-c]pyrrol-2-ylidene)acetamide, 2-(3-allyl-4-oxo-2-thioxothiazolidin-5-ylidene)-
[1.3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(4-oxo-3-propyl-2-thioxothiazolidin-5-ylidene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(3-benzyl-4-oxo-2-thioxothiazolidin-5-ylidene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(3-cyclopropyl-4-oxo-2-thioxothiazolidin-5- ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile 2-(cyano(thiophen-2-yl)methylene)- [1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano( lH-pyrazol- 1 -yl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(phenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-((4-chlorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(cyano(4-fluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3-fluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- ((6-chloropyridin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 5- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-allyl-2-thioxothiazolidin-4-one, 5-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-3-propyl-2-thioxothiazolidin-4-one, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- benzyl-2-thioxothiazolidin-4-one, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-cyclopropyl-2- thioxothiazolidin-4-one, 2-(l,3-dimethyl-5-oxo-l,5-dihydro-4H-pyrazol-4-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(l-methyl-5-oxo-3-(trifluoromethyl)-l,5-dihydro-4H-pyrazol-4- ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((4-chloro-2- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloro-2- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(pyridin-3- yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-(trifluoromethyl)-lH- pyrazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-(prop-2-yn-l- yloxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-
(difluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,6- difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-chloro-4- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-fluoro-4- methylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-fluoro-3-
(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- (trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5- methyl-2-oxopyridin-l(2H)-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(l,3- dimethyl-2,5-dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3- methyl-2,5-dioxo-l-(prop-2-yn-l-yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-methyl-4-oxo-2-thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(2,5-dioxo-l,3-di(prop-2-yn-l-yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5, 6 -dicarbonitrile, 2-(3-allyl-2,5-dioxo-l-(prop-2-yn-l-yl)imidazolidin-4-ylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-(cyclopropylmethyl)-2,5-dioxo-l-(prop-2-yn-l- yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2-oxo-3-
(trifluoromethyl)pyridin-l(2H)-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(thiazol-2-ylthio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(3-(trifluoromethyl)phenyl)acetate, 2-((2- chlorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(m- tolyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5-fluoro-2- methylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(3,4-difluorophenyl)acetate, 2-(l-cyanoethylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(l-cyano-2-(4-fluorophenyl)-2-oxoethylidene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(methylthio)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(2-(4-chlorophenyl)-l-cyano-2-oxoethylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4,5-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-ethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, methyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-(l,3- dimethyl-5 -oxo -2-thioxoimidazolidin-4-y lidene)- [ 1,3] dithiolo [4, 5 -b] pyrazine-5 ,6 -dicarbonitrile, 2-(3- (3-methylbut-2-en-l-yl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-(2-methoxyethyl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(3-cyclopropyl-5-oxoisoxazol-4(5H)-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-methyl-5-oxoisoxazol-4(5H)-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(2,5-dimethylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3,4-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(2,3- difluorophenyl)acetamide, 2-(cyano(3,4,5-trimethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(3-
(trifluoromethyl)phenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N- (4-(trifluoromethyl)phenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)- N-(4-fluorophenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N- methylacetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(5-fluoro-2- methylphenyl)acetamide, 2-(cyano(2-fluoro-4-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(cyano(3-(trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(3-allyl-l-methyl-2,5-dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, tert-butyl 5-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2,4- dioxothiazolidine-3-carboxylate, 2-(2-(methylthio)-4-oxothiazol-5(4H)-ylidene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(cyano(2,3,6-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(cyano(2,4,6-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(cyano(2-fluoro-6-(trifluoromethyl)phenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3,5-bis(trifluoromethyl)phenyl)(cyano)methylene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,4,5-trifluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,3,4-trifluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,3-difluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)-N,N-dimethylacetamide, 2-(l-cyano-2-morpholino-2-oxoethylidene)-[l,3]dithiolo[4,5- b] pyrazine-5, 6 -dicarbonitrile, 2-(cyano(3,5-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(cyano(2,5-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3-fluoro-5-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(cyano(2,4-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-cyano-N,N-dimethylacetamide, 2- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-morpholino-3-oxopropanenitrile, propyl 2-cyano-2-(5,6- dicyano-[ l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, isopropyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, benzyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, allyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 2-(3-(2-morpholino-2-oxoethyl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5, 6 -dicarbonitrile, 2-(2,4-dioxo-3-(2-oxo-2-thiomorpholinoethyl)thiazolidin-5-ylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, tert-butyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, 2-(3-(4-methoxybenzyl)-2,4-dioxothiazolidin-5-ylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-methoxyethyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, prop-2-yn-l-yl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, cyclopropylmethyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, p-tolyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, 4-methoxyphenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3-methylbut-2-en-l-yl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, o-tolyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2- fluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, m-tolyl 2-cyano- 2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-(trifluoromethyl)phenyl 2-cyano-2- (5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, phenyl 2-cyano-2-(5,6-dicyano- [l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-chlorophenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-(trifluoromethoxy)phenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-chloroallyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, isopentyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3,4-difluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3-chlorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-fluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3- methoxyphenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-
(trifluoromethoxy)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3- (dimethylamino)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4- bromophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((2-chloro-6- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-
(trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- fluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- (trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3- chlorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- methoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4- dimethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3 -methyl-2, 4- dioxooxazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 4-(dimethylamino)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-bromophenyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3 -fluorophenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-(trifluoromethyl)benzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-fluoro-4-(trifluoromethyl)benzyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-chloro-2-fluoro-5-(trifluoromethyl)benzyl 2- cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,4-trifluorobenzyl 2-cyano-2- (5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,5-trifluorobenzyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,4,5-trifluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,6-trifluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,6-difluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3,5-difluorobenzyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((3-bromophenyl)(cyano)methylene)-
[1.3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(3-methoxyphenyl)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(4-methoxyphenyl)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-((2-bromophenyl)(cyano)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-((4-bromophenyl)(cyano)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(perfluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 4-(trifluoromethoxy)benzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3 -chloro-5-fluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-ethoxyphenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-(tert-butyl)phenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-ethoxyphenyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((4-chlorothiazol-2-yl)(cyano)methylene)-
[1.3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(thiazol-2-yl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(naphthalen-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- cyanophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-cyano-l-methyl- 5-(methylthio)-lH-pyrazol-3-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((6- chloropyridazin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(phenylthio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano((2- fluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-cyano-5- (ethylthio) - 1 -methyl- 1 H-py razol-3 -yl)methylene)- [ 1,3] dithiolo [4,5 -b]pyrazine-5 ,6 -dicarbonitrile, 2- (cyano((2,4-difluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(2-(methylthio)pyrimidin-4-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano((4-fluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano((2,6-difluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(6-methylpyridazin-3-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(3,5-dichloropyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3- chloro-5-(trifluoromethyl)pyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(2-nitrophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(2-(difluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano((4-fluorophenyl)sulfonyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(5-(trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(4-cyanophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,4- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((2-chloro-5- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-chloro-2,6- difluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile 2-((3-chloro-5- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5- nitropyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloropyrimidin-2- yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-bromo-5-
(trifluoromethyl)pyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- ((3-chloro-5-nitropyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(pyrazin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloropyridin- 2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-
(trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((4- chloropyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5- bromopyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (methylsulfonyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,5- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((2-chloro-4- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,6- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 3-(cyano(5,6- dicyano-[ l,3]dithiolo[4,5-b]pyrazin-2-ylidene)methyl)benzoate, methyl 4-(cyano(5,6-dicyano- [1.3]dithiolo[4,5-b]pyrazin-2-ylidene)methyl)benzoate, 2-((4-(tert-butyl)phenyl)(cyano)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-ethynylphenyl)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile or 2-(cyano(6-(trifluoromethyl)pyridin-2- y l)methy lene)- [ 1 , 3 ] dithiolo [4, 5 -b] pyrazine-5 ,6-dicarbonitrile.
The compounds of the present disclosure may be used 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. The person skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other isomer(s) or when separated from the other isomer(s). Additionally, the person skilled in the art knows processes or methods or technology to separate, enrich, and/or to selectively prepare said isomers.
It can be advantageous to isolate or synthesize in each case the biologically more effective isomer, for example specific enantiomers or diastereomers, or isomeric mixture, for example enantiomeric mixtures or diastereomeric mixtures, if the individual components have a different biological activity. The compounds of formula (I) and, where appropriate, the tautomers thereof, in each case in free form or in salt form, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
Any of the compounds according to the invention can also exist in one or more geometric isomer forms depending on the number of double bonds in the compound. The invention thus relates equally to all geometric isomers and to all possible mixtures, in all proportions. The geometric isomers can be separated according to general methods, which are known per se by a person ordinary skilled in the art.
Any of the compounds according to the invention, can also exist in one or more amorphic or isomorphic or polymorphic forms, depending on their preparation, purification storage and various other influencing factors. The invention thus relates all the possible amorphic, isomorphic and polymorphic forms, in all proportions. The amorphic, isomorphic and polymorphic forms can be prepared and/or separated and/or purified according to general methods, which are known per se by a person ordinary skilled in the art.
In one embodiment, the present invention provides use of compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, for controlling or preventing agricultural crops and/or horticultural crops against phytopathogenic fungi, bacteria, insects, nematodes or mites.
In preferred embodiment, the present invention provides use of compound of general formula (I), bi- oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, for controlling or preventing against phytopatho genic fungi of agricultural crops and/or horticultural crops.
The compounds according to the invention can be used for controlling undesired phytopathogenic microorganisms preferably fungal pathogens which occur in particular on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forests, or on organs, such as fruits, flowers, foliage, stalks, tubers, seeds or roots, of such plants, and in some cases even plant organs which are formed at a later point in time remain protected against these microorganisms.
The compounds of the formula (I) can possess potent microbicidal activity and can be used for the control of unwanted microorganisms, such as fungi, and bacteria, in agricultural or horticultural crop protection and in the protection of such materials.
The compounds of the formula (I) possess very good fungicidal properties and can be used in crop protection, for example for control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.
The compounds of the formula (I) can be used as bactericides in crop protection, for example, for control of Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and Streptomycetaceae.
The compounds of the formula (I) can be used for curative or protective control of phytopathogenic fungi. The invention therefore also relates to curative and protective methods for controlling phytopathogenic fungi by the use of the inventive active ingredients or compositions, which are applied to the seeds, to plants or plant parts, to fruit or to the soil in which the respective plants grow. The compounds of the formula (I) can be used for controlling or preventing against phytopathogenic fungi, bacteria, of agricultural crops and or horticultural crops.
The compounds of the formula (I) can be used in crop protection, wherein the agricultural crops are cereals, corn, rice, soybean and other leguminous plants, fruits and fruit trees, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and other vegetables, and ornamentals.
Furthermore, the present invention provides a process for preparing compounds of the formula (I).
In one embodiment, the present invention provides a composition for controlling or preventing phytopathogenic microorganisms, comprising a compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salts thereof and one or more inert carriers.
In another embodiment, the composition may additionally comprises one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
The concentration of the compound of general formula (I) ranges from 1 to 90% by weight with respect to the total weight of the composition, preferably from 5 to 50% by weight with respect to the total weight of the composition.
Furthermore, the present invention provides an agrochemical composition, comprising at least one compound of formula (I) and/or N-oxide or S-oxide or an agriculturally acceptable salt thereof.
In one embodiment, the present invention provides a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein said compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof, is applied to the plants, to parts thereof or a locus thereof.
In another embodiment, the present invention provides a method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and or horticultural crops, wherein the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof is applied to the seeds of plants.
In yet another embodiment, the present invention provides a method for controlling or preventing phytopathogenic microorganisms in agricultural crops and/or horticultural crops using the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof, which comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 1 g to 5 kg per hectare of agricultural or horticultural crops.
Furthermore, the present invention provides a method for combating harmful fungi, comprising treating, plants, the soil, seeds or the materials to be protected against fungal attack with an effective amount of at least one compound of formula (I) or with a composition.
In one embodiment, the present invention provides a seed comprising compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salt or composition or combination thereof, wherein the amount of the compound of general formula (I), or an N-oxide or S-oxide or an agriculturally acceptable salt thereof, is from 0.1 g to 10 kg per 100 kg of seed.
The compound of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The compounds of formula (I) and compositions thereof, respectively, are particularly suitable for controlling the following plant diseases:
Albugo spp.(white mst) on ornamentals, vegetables (e. g. A Candida) and sunflowers (e. g. A tragopogonis); Alternaria spp.(Altemaria leaf spot) on vegetables, rape (A brassicola or brassi cae), sugar beets (A tenuis ), fruits, rice, soybeans, potatoes (e. g. .1 solani or .1 alternata), tomatoes (e. g. A solani or A alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A tritici (anthracnose) on wheat and A hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e.g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on com, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e.g. strawberries), vegetables (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. zeaemaydis), rice, sugar beets (e.g. C. beticola), sugar cane, vegetables, coffee, soybeans (e.g. C. sojina or C. kikuchil) and rice; Cladosporium spp. on tomatoes (e.g. C. fulvum: leaf mold) and cereals, e.g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e.g. C. sativus, anamorph: B. sorokiniana) and rice (e.g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum (teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypit), corn (e.g. C. gramini cola: Anthracnose stalk rot), fruits, potatoes (e. g. C. coccodes: black dot), vegetables like beans (e.g. C. lindemuthianum) and soybeans (e.g. C. truncatum or C. gloeosporioides) ; Corticium spp., e.g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and ornamentals; Cycloconium spp., e.g. C. oleaginum on olive trees; Cylindrocarpon spp. (e.g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria 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. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum) , Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (E. pyn), soft fruits (E. veneta: anthracnose) and vines (E.ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (E. betae), vegetables (e. g. E. pist), such as cucurbits (e.g. E. cichoracearum), cabbages, rape (e.g. E. cruciferarum) ; Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e.g. E. turcicum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e.g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme) and F. tucumaniae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e.g. wheat or barley) and corn; Gib berella spp. on cereals (e. g. G. zeae) and rice (e.g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining com plex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e.g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoft) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena( bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; 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), rape (e. g. P. parasitica), onions (e.g. P. destructor), tobacco (P. tabacina) and soybeans (e.g. P. manshurica) ; Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e.g. on vines (e.g. P. tracheiphila and P. tetraspora) and soybeans (e.g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e.g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e.g. P. capsid), soybeans (e. g. P. megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad leaved trees (e.g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e.g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosa ceous plants, hop, pome and soft fruits, e.g. P. leucotricha on apples; Polymyxa spp., e.g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby trans mitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yallundae) on cereals, e.g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e.g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or, rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e.g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e.g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum) ; Ramu/aria spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soy beans (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) no dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tucken) on vines; Setospaeria spp. (leaf blight) on com (e.g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on com, (e.g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (po tato wart disease); Taphrina spp., e.g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fmits, vegetables, soybeans and cotton, e.g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incamata (grey snow mold) on barley or wheat; Urocystis spp., e.g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e.g. U. appendiculatus, syn. E. phaseofl) and sugar beets (e.g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), com (e. g. U. maydis: com smut) and sugar cane; Venturia spp. (scab) on apples (e.g. V inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fmits and ornamentals, vines, soft fmits, vegetables and field crops, e.g. V dahliae on strawberries, rape, potatoes and tomatoes.
In one embodiment, the present invention provides use of compounds of formula (I) and compositions thereof, for controlling and/or preventing plant diseases caused by pathogens such as: Pyricularia oryzae, Rhizoctonia solani, Botrytis cinerea, Alternaria solani, Colletotrichum capsici, Septoria lycopersici, Fusarium culmorum, Phakopsora pachyrhizi, Sphaerotheca fuliginea, Pseudoperonospora cubensis, Puccinia triticina, Septoria tritici, Phytopthora infestans, Plasmopara viticola, Uncinula necator.
In another embodiment, the present invention provides a method for combating phytopathogenic fungi, comprising treating plants, soil, seeds or materials to be protected against fungal attack with an effective amount of the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof as disclosed in the present invention.
The compounds of formula (I) and compositions thereof, respectively, are also suitable for controlling harmful fungi in the protection of stored products or harvest and in the protection of materials.
The term "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. As to the protection of wood and other materials, the particular attention is paid to the following harmful fungi: Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes such as Coni ophora spp., Corio/us spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Ser pula spp. and Tyromyces spp., Deuteromycetes such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria spp., Paecilomyces spp. and Zygomycetes such as Mucor spp., and in addition in the protection of stored products and harvest the following yeast fungi are worthy of note: Candida spp. and Saccharomyces cerevisae.
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.
According to the present invention, 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, can be protected in the freshly harvested state or in processed form, such as pre-dried, moistened, comminuted, ground, pressed or roasted, which process is also known as post-harvest treatment. Also falling under the definition of stored products is 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 combinations according the present invention can prevent disadvantageous effects such as decay, discoloration or mold. Preferably "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) and compositions 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 compounds of formula (I) and compositions thereof, respectively.
The term "plant health" is to be understood to denote a condition of the plant and/or its products which is determined by several indicators alone or in combination with each other such as yield (e. g. increased biomass and/or increased content of valuable ingredients), plant vigor (e.g. improved plant growth and/or greener leaves ("greening effect")), quality (e. g. improved content or composition of certain ingredients) and tolerance to abiotic and/or biotic stress. The above identified indicators for the health condition of a plant may be interdependent or may result from each other.
The term "seed" embraces seeds and plant propagules of all kinds including but not limited to hue seeds, seed pieces, suckers, corns, bulbs, fruits, tubers, grains, rhizomes, cuttings, cut shoots and the like and means in a preferred embodiment true seeds.
The present invention also comprises seeds coated or treated with or containing a compound of formula I. The term "coated or treated with and/or containing" generally signifies that the active ingredient is for the most part on the surface of the seed at the time of application, although a greater or lesser part of the ingredient may penetrate into the seed material, depending on the method of application. When the said seed product is (re)planted, it may absorb the active ingredient. In an embodiment, the present invention makes available a plant propagation material adhered thereto with a compound of formula (I). Further, it is hereby made available, a composition comprising a plant propagation material treated with a compound of formula (I).
Seed treatment comprises all suitable seed treatment techniques known in the art, such as seed dressing, seed coating, seed dusting, seed soaking and seed pelleting. The seed treatment application of the compound formula I, which is a preferred application method, can be carried out by any known methods, such as spraying or by dusting the seeds before sowing or during the sowing/planting of the seeds.
Suitable target plants are, in particular, cereals, such as wheat, barley, rye, oats, rice, maize or sorghum; beet, such as sugar or fodder beet; fruit, for example pome fruit, stone fruit or soft fmit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas or soya; oil plants, such as oilseed rape, mustard, poppies, olives, sunflowers, coconut, castor, cocoa or ground nuts; cucurbits, such as pumpkins, cucumbers or melons; fibre plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or bell peppers; Lauraceae, such as avocado, Cinnamonium or camphor; and also tobacco, nuts, coffee, eggplants, sugarcane, tea, pepper, grapevines, hops, the plantain family, latex plants and ornamentals (such as flowers, and lawn grass or turf). In an embodiment, the plant is selected from cereals, com, soybean, rice, sugarcane, vegetables and oil plants.
The term "plant" is to be understood as including also plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus and also plants which have been selected or hybridised to preserve and/or attain a desired trait, such as insect, fungi and /or nematode resistance. Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins from Bacillus cereus or Bacillus popilliae; or insecticidal proteins from Bacillus thuringiensis, such as 8-endotoxins, e.g. CrylAb, Cry 1 Ac, Cry IF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), e.g. Vipl, Vip2, Vip3 or Vip3A; or insecticidal proteins of bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins; toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins, barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosomeinactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA-reductase, ion channel blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase, diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and glucanases. In the context of the present invention there are to be understood by 8-endotoxins, for example CrylAb, CrylAc, CrylF, CrylFa2, Cry2Ab, Cry3A, Cry3Bbl or Cry9C, or vegetative insecticidal proteins (Vip), for example Vipl, Vip2, Vip3 or Vip3A, expressly also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced recombinant by a new combination of different domains of those proteins (see, for example, WO 02/15701). Truncated toxins, for example a truncated CrylAb, are known. In the case of modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In such amino acid replacements, preferably non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of Cry3A055, a cathepsin- G-recognition sequence is inserted into a Cry3A toxin (see WO 03/018810). Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, EP-A-451 878 and WO 03/052073. The processes for the preparation of such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0 367474, EP-A-0 401 979 and WO 90/13651. The toxin contained in the transgenic plants imparts to the plants tolerance to harmful insects. Such insects can occur in any taxonomic group of insects, but are especially commonly found in the beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera). Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylAb toxin); YieldGard Rootworm® (maize variety that expresses a Cry3Bbl toxin); YieldGard Plus® (maize variety that expresses a CrylAb and a Cry3Bbl toxin); Starlink® (maize variety that expresses a Cry9C toxin); Herculexl® (maize variety that expresses a Cry lFa2 toxin and the enzyme phosphinothricine N-acetyltransferase(PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylAc toxin); Bollgard I® (cotton variety that expresses a CrylAc toxin); Bollgard II® (cotton variety that expresses a CrylAc and a Cry2Ab toxin); VipCot® (cotton variety that expresses a Vip3A and a CrylAb toxin); Newleaf® (potato variety that expresses a Cry3A toxin); NatureGard®, 25Agrisure® GT Advantage (GA21 glyphosate-tolerant trait), Agrisure® CB Advantage (Bil l corn borer (CB) trait) and Protecta®. Further examples of such transgenic plants are: i) Bill Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which has been rendered resistant to attack by the European com borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a truncated CrylAb toxin. Bil l maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; ii)Btl76 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which have been rendered resistant to attack by the European com borer (Ostrinia nubi/alis and Sesamia nonagrioides) by transgenic expression of a CrylAb toxin. Btl76 maize also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate ammonium; iii) MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified Cry3A toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-G-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810; iv)MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a Cry3Bbl toxin and has resistance to certain Coleoptera insects; v) IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/ES/96/02; vi) 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160 Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the expression of the protein CrylF for achieving resistance to certain Lepidoptera insects and of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium; vii) NK603 x MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150
Brussels, Belgium, registration number C/GB/02/M3/03 consists of conventionally breed hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810. NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylAb toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include the European com borer.
The compounds of formula (I) can be present in different crystal modifications 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 form of compositions by treating the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms to be protected from fungal attack with a fungicidally effective amount of the active substances. The application can be carried out both before and after the infection of the plants, plant propagation materials, such as seeds, soil, surfaces, materials or rooms by the fungi.
Plant propagation materials may be treated with compounds of formula (I) as such or a composition comprising at least one compound of formula (I) 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) according to the invention.
An agrochemical composition comprises a fungicidally effective amount of a compound of formula (I). The term "effective amount" denotes an amount of the composition or of the compounds 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 compounds of formula (I), their oxides and salts can be converted into customary types of agrochemical compositions, e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e. g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 61h Ed. May 2008, Croplife International.
The compositions are prepared in a known manner, such as described by Mollet and Grube- mann, Formulation technology, Wiley VCH, Weinheim, 2001; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F lnforma, 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. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma- butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methyl pyrrolidone, fatty acid dimethyl amides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; 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.l : 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. Examples of sulfonates are alkylaryl sulfonates, diphenyl sulfonates, alpha-olefin sulfonates, lignin sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl and tridecylbenzenes, sulfonates of naphthalenes and alkyl naphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-substituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-substituted fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides. Examples of polymeric surfactants are homo- 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. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of 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, minerals or vegetable oils, and other auxiliaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F lnforma UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic 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 antifoaming agents are silicones, long chain alcohols, and salts of fatty acids. Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin, azo and phthalocyanine colorants).
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. alcohols) ad 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
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 dispersion. iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound of formula (I) and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in water-insoluble organic solvent (e. g. aromatic hydro carbon) ad 100 wt%. Dilution with water gives an emulsion.
iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound of formula (I) and 1-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into water ad 100 wt% by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound of formula (I) are comminuted with addition of 2- 10 wt% dispersants and wetting agents (e. g. sodium lignosulfonate and alcohol ethoxylate), 0.1-2 wt% thickener (e.g. xanthan gum) and water ad 100 wt% to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e. g. polyvinyl alcohol) is added.
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound of formula (I) are ground finely with addition of dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) ad 100 wt% and prepared as water- dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound 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.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound of formula (I) are comminuted with addition of 3- 10 wt% dispersants (e.g. sodium lignosulfonate), 1-5 wt% thickener (e.g. carboxymethyl cellulose) and water ad 100 wt% to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound of formula (I) are added to 5-30 wt% organic solvent blend (e. g. fatty acid dimethyl amide and cyclohexanone), 10-25 wt% surfactant blend (e. g. alcohol ethoxylate and arylphenol ethoxylate), and water ad 100 %. This mixture is stirred for 1 h to produce spontane ously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound of formula (I), 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15wt% acrylic monomers (e.g. methylmethacrylate, methacrylic acid and a di- or tri-acrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization results in the formation of poly(meth)acrylate microcapsules. Alternatively, 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). The addition of a polyamine (e.g. hexamethylenediamine) results in the formation of polyurea microcapsules. The monomers amount to 1- 10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1-10 wt% of a compound of formula (I) is ground finely and mixed intimately with solid carrier (e.g. finely divided kaolin) ad 100 wt%.
xii) Granules (GR, FG)
0.5-30 wt% of a compound of formula (I) is ground finely and associated with solid carrier (e. g. silicate) ad 100 wt%. Granulation is achieved by extrusion, spray -drying or fluidized bed.
xiii) Ultra-low volume liquids (UL)
1-50 wt% of a compound of formula (I) are dissolved in organic solvent (e.g. aromatic hydrocarbon) ad 100 wt%.
The 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 substance.
The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
For the purposes of treatment of plant propagation materials, particularly seeds, solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC), and gels (GF) are usually employed. The com positions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready -to-use preparations. Application can be carried out before or during sowing. Methods for applying compound of formula (I) and compositions thereof, respectively, onto plant propagation material, especially seeds, include dressing, coating, pelleting, dusting, and soaking as well as in-furrow application methods. Preferably, compound of formula (I) or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting. When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, and in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e.g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seeds) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and further pesticides (e. g. herbicides, insecticides, fungicides, growth regulators, safeners, biopesticides) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1: 100 to 100: 1, preferably 1: 10 to 10: 1.
A pesticide is generally a chemical or biological agent (such as pesticidal active ingredient, compound, composition, vims, 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. The term pesticides 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 of against certain pests; safeners that reduce unwanted herbicidal action of pesticides on crop plants; and plant growth promoters that affect plant physiology to increase plant growth, biomass, yield or any other quality parameter of the harvestable goods of a crop plant.
Biopesticides have been defined as a form of pesticides based on micro-organisms (bacteria, fungi, viruses, nematodes, etc.) or natural products (compounds, such as metabolites, proteins, or extracts from biological or other natural sources) (U.S. Environmental Protection Agency: http://www.epa.gov/pesticides/biopesticides/). Biopesticides are typically created by growing and concentrating naturally occurring organisms and/or their metabolites including bacteria and other microbes, fungi, viruses, nematodes, proteins, etc. They are often considered to be important components of integrated pest management (IPM) programs.
Biopesticides fall into two major classes, microbial and biochemical pesticides:
1. Microbial pesticides consist of bacteria, fungi or viruses (and often include the metabolites that bacteria and fungi produce) entomopathogenic nematodes are also classed as microbial pesticides, even though they are multicellular.
2. Biochemical pesticides are naturally occurring substances that control pests or provide other crop protection uses as defined below, but are relatively non-toxic to mammals
The user applies the composition according to the invention usually from a pre dosage device, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
The present invention further relates to a composition for controlling unwanted microorganisms comprising at least one of the compounds of the formula (I) and one or more inert carrier. The inert carrier further comprises agriculturally suitable auxiliaries, solvents, diluents, surfactants and/or extenders and the like.
The present invention further relates to a composition for controlling unwanted microorganisms, comprising at least one of the compounds of the formula (I) and/or one or more active compatible compound selected from fungicides, bactericides, acaricides, insecticides, nematicides, herbicides, biopesticides, plant growth regulators, antibiotics, fertilizers and/or mixtures thereof.
Generally, a compound of the present invention is used in the form of a composition (e.g. formulation) containing a carrier. A compound of the invention and compositions thereof can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra-low volume (ulv) liquid, ultra-low volume (ulv) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder.
A formulation typically comprises a liquid or solid carrier and optionally one or more customary formulation auxiliaries, which may be solid or liquid auxiliaries, for example unepoxidized or epoxidized vegetable oils (for example epoxidized coconut oil, rapeseed oil or soya oil), antifoams, for example silicone oil, preservatives, clays, inorganic compounds, viscosity regulators, surfactant, binders and/or tackifiers. The composition may also further comprise a fertilizer, a micronutrient donor or other preparations which influence the growth of plants as well as comprising a combination containing the compound of the invention with one or more other biologically active agents, such as bactericides, fungicides, nematicides, plant activators, acaricides, and insecticides. Accordingly, the present invention also makes available a composition comprising a compound of the invention and an agronomical carrier and optionally one or more customary formulation auxiliaries.
The compositions are prepared in a manner known per se, in the absence of auxiliaries for example by grinding, screening and/or compressing a solid compound of the present invention and in the presence of at least one auxiliary for example by intimately mixing and/or grinding the compound of the present invention with the auxiliary (auxiliaries). In the case of solid compounds of the invention, the grinding/milling of the compounds is to ensure specific particle size. These processes for the preparation of the compositions and the use of the compounds of the invention for the preparation of these compositions are also a subject of the invention.
As a rule, the compositions comprise 0.1 to 99%, especially 0.1 to 95%, of compound according to the present invention and 1 to 99.9%, especially 5 to 99.9%, of at least one solid or liquid carrier, it being possible as a rule for 0 to 25%, especially 0.1 to 20%, of the composition to be surfactants (% in each case meaning percent by weight). Whereas concentrated compositions tend to be preferred for commercial goods, the end consumer as a rule uses dilute compositions which have substantially lower concentrations of active ingredient.
Examples of foliar formulation types for pre-mix compositions are:
Figure imgf000044_0001
Whereas, examples of seed treatment formulation types for pre-mix compositions are:
Figure imgf000044_0002
Examples of formulation types suitable for tank-mix compositions are solutions, dilute emulsions, suspensions, or a mixture thereof, and dusts.
As with the nature of the formulations, the methods of application, such as foliar, drench, spraying, atomizing, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
The tank-mix compositions are generally prepared by diluting with a solvent (for example, water) the one or more pre-mix compositions containing different pesticides, and optionally further auxiliaries. Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers.
Generally, a tank-mix formulation for foliar or soil application comprises 0.1 to 20%, especially 0.1 to 15 %, of the desired ingredients, and 99.9 to 80 %, especially 99.9 to 85 %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 20 %, especially 0.1 to 15 %, based on the tank-mix formulation. Typically, a pre-mix formulation for foliar application comprises 0.1 to 99.9 %, especially 1 to 95%, of the desired ingredients, and 99.9 to 0.1 %, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre-mix formulation.
Normally, a tank-mix formulation for seed treatment application comprises 0.25 to 80%, especially 1 to 75 %, of the desired ingredients, and 99.75 to 20 %, especially 99 to 25 %, of a solid or liquid auxiliaries (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 40 %, especially 0.5 to 30 %, based on the tank-mix formulation.
Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 %, especially 1 to 95 %, of the desired ingredients, and 99.5 to 0.1 %, especially 99 to 5 %, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 %, especially 0.5 to 40 %, based on the pre-mix formulation whereas commercial products will preferably be formulated as concentrates (e.g., pre-mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition). Preferred seed treatment pre-mix formulations are aqueous suspension concentrates. The formulation can be applied to the seeds using conventional treating techniques and machines, such as fluidized bed techniques, the roller mill method, rotostatic seed treaters, and dram coaters. Other methods, such as spouted beds may also be useful. The seeds may be pre sized before coating. After coating, the seeds are typically dried and then transferred to a sizing machine for sizing. Such procedures are known in the art. The compounds of the present invention are particularly suited for use in soil and seed treatment applications.
In general, the pre-mix compositions of the invention contain 0.5 to 99.9 especially 1 to 95, advantageously 1 to 50 %, by mass of the desired ingredients, and 99.5 to 0.1, especially 99 to 5%, by mass of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries (or adjuvant) can be a surfactant in an amount of 0 to 50, especially 0.5 to 40 %, by mass based on the mass of the pre-mix formulation.
A compound of the formula (I) in a preferred embodiment, independent of any other embodiments, is in the form of a plant propagation material treating (or protecting) composition, wherein said plant propagation material protecting composition may comprises additionally a colouring agent. The plant propagation material protecting composition or mixture may also comprise at least one polymer from water-soluble and water-dispersible film-forming polymers that improve the adherence of the active ingredients to the treated plant propagation material, which polymer generally has an average molecular weight of at least 10,000 to about 100,000.
Examples of application methods for the compounds of the invention and compositions thereof, that is the methods of controlling pests in the agriculture, are spraying, atomizing, dusting, brushing on, dressing, scattering or pouring which are to be selected to suit the intended aims of the prevailing circumstances.
One method of application in agriculture is application to the foliage of the plants (foliar application), it being possible to select frequency and rate of application to match the danger of infestation with the pest or fungi in question. Alternatively, the active ingredient can reach the plants via the root system (systemic action), by applying the compound to the locus of the plants, for example by application of a liquid composition of the compound into the soil (by drenching), or by applying a solid form of the compound in the form of granules to the soil (soil application). In the case of paddy rice plants, such granules can be metered into the flooded paddy-field. The application of the compounds of the present invention to the soil is a preferred application method.
Typical rates of application per hectare are generally 1 to 5000 g of active ingredient per hectare.
The compounds of the invention and compositions thereof are also suitable for the protection of plant propagation material, for example seeds, such as fruit, tubers or kernels, or nursery plants, against pests of the above mentioned type. The propagation material can be treated with the compound prior to planting, for example seeds can be treated prior to sowing. Alternatively, the compound can be applied to seed kernels (coating), either by soaking the kernels in a liquid composition or by applying a layer of a solid composition. It is also possible to apply the compositions when the propagation material is planted to the site of application, for example into the seed furrow during drilling. These treatment methods for plant propagation material and the plant propagation material thus treated are further subjects of the invention. Typical treatment rates would depend on the plant and pest/fungi to be controlled and are generally between 1 to 200 grams per 100 kg of seeds, preferably between 5 to 150 grams per 100 kg of seeds, such as between 10 to 100 grams per 100 kg of seeds. The application of the compounds of the present invention to seeds is a preferred application method.
The activity of the compositions according to the invention can be broadened considerably, and adapted to prevailing circumstances, by adding, for example, one or more insecticidally, acaricidally, nematicidally and/or fungicidally active agents. The combinations compounds of formula (I) with other insecticidally, acaricidally, nematicidally and/or fungicidally active agents may also have further surprising advantages which can also be described, in a wider sense, improved properties, for example, better tolerance by plants, reduced phytotoxicity, pests or fungi can be controlled in their different development stages or better behaviour during their production, for example during grinding or mixing, during their storage or during their use.
The following list of pesticides together with which the compounds according to the invention can be used, is intended to illustrate the possible combinations by way of example.
The following combination of the compounds of formula (I) with other active compounds is an adjuvant selected from the group of substances consisting of all named mixing partners of the classes (A) to (O) as described below can, if their functional groups enable this, optionally form salts with suitable bases or acids appear as stereoisomers, even if not specifically mentioned in each case, or as polymorphs. They are also understood as being included herein. These examples are:
A) Inhibitors of the ergosterol biosynthesis, for example (A01) aldimorph, (A02) azaconazole, (A03) bitertanol, (A04) bromuconazole, (A05) cyproconazole, (A06) diclobutrazole, (A07) difenoconazole, (A08) diniconazole, (A09) diniconazole-M, (A10) dodemorph, (Al l) dodemorph acetate, (A12) epoxiconazole, (A13) etaconazole, (A14) fenarimol, (A15) fenbuconazole, (A16) fenhexamid, (A17) fenpropidin, (A18) fenpropimorph, (A19) fluquinconazole, (A20) llurprimidol, (A21) flusilazole, (A22) llutriafol, (A23) furconazole, (A24) furconazole-cis, (A25) hexaconazole, (A26) imazalil, (A27) imazalil sulfate, (A28) imibenconazole, (A29) ipconazole, (A30) metconazole, (A31) myclobutanil, (A32) naftifine, (A33) nuarimol, (A34) oxpoconazole, (A35) paclobutrazol, (A36) pefiirazoate, (A37) penconazole, (A38) piperalin, (A39) prochloraz, (A40) propiconazole, (A41) prothioconazole, (A42) pyributicarb, (A43) pyrifenox, (A44) quinconazole, (A45) simeconazole, (A46) spiroxamine, (A47) tebuconazole, (A48) terbinafine, (A49) tetraconazole, (A50) triadimefon, (A51) triadimenol, (A52) t ride morph. (A53) triflumizole, (A54) triforine, (A55) triticonazole, (A56) uniconazole, (A57) uniconazole-p, (A58) viniconazole, (A59) voriconazole, (A60) l-(4- chlorophenyl)-2-(lH-l,2,4-triazol-l-yl)cycloheptanol, (A61) methyl l-(2,2-dimethyl-2,3-dihydro-lH- inden-l-yl)-lH-imidazole-5-carboxylate, (A62) N'-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl) propoxy]phenyl}-N-ethyl-N-methylimidoformamide, (A63) N-ethyl-N-methyl-N'-{2-methyl-5- (trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl} imidoformamide, (A64) 0-[l-(4- methoxyphenoxy)-3,3-dimethylbutan-2-yl]-lH-imidazole-l-carbothioate, (A65) pyrisoxazole, (A66) 2-{ [3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-l,2,4-triazole-3- thione, (A67) l-{ [3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-lH-l,2,4-triazol-5- yl thiocyanate, (A68) 5-(allylsulfanyl)-l-{ [3-(2-chlorophenyl)-2-(2,4-difhiorophenyl)oxiran-2- yl]methyl}-lH-l, 2, 4-triazole, (A69) 2-[l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4- yl]-2, 4-dihydro-3H-l, 2, 4-triazole-3 -thione, (A70) 2-{ [rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl) oxiran-2-yl]methyl}-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A71) 2-{ [rel(2R,3R)-3- (2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A72) l-{ [rel(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-lH-l,2,4-triazol- 5-yl thiocyanate, (A73) l-{ [rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2- yl]methyl}-lH-l,2,4-triazol-5-yl thiocyanate, (A74) 5-(allylsulfanyl)-l-{ [rel(2R,3S)-3-(2- chlorophenyl)-2-(2,4-difluorophenyl)oxiran-2-yl]methyl}-lH-l, 2, 4-triazole, (A75) 5-(allylsulfanyl)-
1-{ [rel(2R,3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl) oxiran-2-yl]methyl}-lH-l, 2, 4-triazole,
(A76) 2-[(2S,4S,5S)-l-(2,4- dichlorophenyl) -5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-
1.2.4-triazole-3 -thione, (A77) 2-[(2R,4S,5 S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6- trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A78) 2-[(2R,4R,5R)-l-(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A79)
2-[(2S,4R,5R)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4- triazole-3 -thione, (A80) 2-[(2S,4S,5R)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-
2.4-dihydro-3H-l,2,4-triazole-3-thione, (A81) 2-[(2R,4S,5R)-l-(2,4-dichlorophenyl)-5-hydroxy- 2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A82) 2-[(2R,4R,5S)-l-(2,4- dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4-triazole-3-thione, (A83) 2-[(2S,4R,5S)-l-(2,4-dichlorophenyl)-5-hydroxy-2,6,6-trimethylheptan-4-yl]-2,4-dihydro-3H-l,2,4- triazole-3 -thione, (A84) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-l-(lH-l,2,4-triazol-l- yl)propan-2-ol, (A85) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-l-(lH- 1,2,4-triazol-l- yl)butan-2-ol, (A86) 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-l-(lH-l,2,4-triazol-l- yl)pentan-2-ol, (A87) 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-l-(lH-l,2,4-triazol-l-yl)butan-2-ol, (A88) 2-[2-chloro-4-(2,4-dichlorophenoxy)phenyl]-l-(lH-l,2,4-triazol-l-yl)propan-2-ol, (A89) (2R)- 2-(l-chlorocyclopropyl)-4-[(lR)-2,2-dichlorocyclopropyl]-l-(lH-l,2,4-triazol-l-yl)butan-2-ol, (A90) (2R)-2-( 1 -chlorocyclopropyl)-4-[( 1 S)-2,2-dichlorocyclopropyl] - 1 -( 1H- 1 ,2,4-triazol- 1 -yl)butan-2-ol, (A91) (2S)-2-(l-chlorocyclopropyl)-4-[(lS)-2,2-dichlorocyclopropyl]-l-(lH-l,2,4-triazol-l-yl)butan- 2-ol, (A92) (2S)-2-(l-chlorocyclopropyl)-4-[(lR)-2,2-dichlorocyclopropyl]-l-(lH-l,2,4-triazol-l- yl)butan-2-ol, (A93) (lS,2R,5R)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-l-(lH-l,2,4-triazol- l-ylmethyl)cyclopentanol, (A94) (lR,2S,5S)-5-(4-chlorobenzyl)-2-(chloromethyl)-2-methyl-l-(lH- l,2,4-triazol-l-ylmethyl)cyclopentanol, (A95) 5-(4-chlorobenzyl)-2- (chloromethyl)-2-methyl-l-(lH-
1.2.4-triazol-l-ylmethyl)cyclopentanol, Other Sterol biosynthesis inhibitors: (A96) chlorphenomizole, (A97) mefentrifluconazole.
B) Inhibitors of the respiratory chain at complex I or II, for example (B01) bixafen, (B02) boscalid, (B03) carboxin, (B04) cypropamide, (B05) diflumetorim, (B06) fenfuram, (B07) fluopyram, (B08) flutolanil, (B09) fluxapyroxad, (B 10) furametpyr, (B l l) furmecyclox, (B12) isopyrazam (mixture of syn-epimeric racemate 1RS,4SR,9RS and anti-epimeric racemate 1RS,4SR,9SR), (B 13) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (B 14) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (B 15) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (B 16) isopyrazam (syn-epimeric racemate 1RS,4SR,9RS), (B 17) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (B 18) isopyrazam (syn- epimeric enantiomer 1S,4R,9S), (B 19) mepronil, (B20) oxycarboxin, (B21) penflufen, (B22) penthiopyrad, (B23) pydiflumetofen, (B24) sedaxane, (B25) thilluzamide, (B26) l-methyl-N-[2- (l,l,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-lH-pyrazole-4-carboxamide, (B27) 3-
(difluoro methyl)- 1 -methyl-N-[2-( 1 , 1 ,2,2-tetrafluoroethoxy)phenyl] - lH-pyrazole-4 -carboxamide,
(B28) 3 -(difluoromethyl)-N-[4-fluoro-2-( 1 , 1 ,2,3 ,3 ,3 -hexafluoropropoxy)phenyl] - 1 -methyl-lH- pyrazole-4-carboxamide, (B29) N-[l-(2,4-dichlorophenyl)-l-methoxypropan-2-yl]-3-
(difluoromethyl)-l -methyl- lH-pyrazole-4-carboxamide, (B30) 5,8-dilluoro-N-[2-(2-fluoro-4-{ [4-
(trifluoromethyl)pyridin-2-yl]oxy}pyhenyl)ethyl]quinazolin-4-amine, (B31) benzovindiflupyr, (B32) N-[( 1 S,4R)-9-(dichloromethylene)- 1 ,2,3 ,4-tetrahydro- 1 ,4-methanonaphthalen-5-yl] -3 - (difluoromethyl)-l -methyl- lH-pyrazole-4-carboxamide, (B33) N-[(lR,4S)-9-(dichloromethylene)-
1.2.3.4-tetrahydro- 1 ,4-methanonaphthalen-5-yl] -3 -(difluoromethyl)- 1 -methyl- lH-pyrazole-4- carboxamide, (B34) 3-(difluoromethyl)-l-methyl-N-(l, 1,3 -trimethyl-2, 3-dihydro- lH-inden-4-yl)-lH- pyrazole-4-carboxamide, (B35) 1.3.5-trimcthyl-N-( 1. 1.3-trimcthyl-2.3-dihydro- 1 H-indcn-4-yl)- 1 H- pyrazole-4-carboxamide, (B36) 1 -methy 1-3 -(tri duo romcthyl)-N-( 1. 1.3-trimcthyl-2.3-dihydro- 1 H- inden-4-yl)-lH-pyrazole-4-carboxamide, (B37) l-methyl-3-(trifluoromethyl)-N-[(3R)-l,l,3-trimethyl-
2.3 -dihydro- lH-inden-4-yl] - lH-pyrazole-4-carboxamide, (B38) 1 -methyl-3 -(trifluoromethyl)-N-
[(3 S)-l, l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazole-4-carboxamide, (B39) 3-
(difluoro methyl)- 1 -methyl-N-[(3 S)- 1 , 1,3 -trimethyl-2,3 -dihydro- lH-inden-4-yl] - lH-pyrazole-4- carboxamide, (B40) 3-(dinuoromcthyl)- 1 -mcthyl-N-|(3R)- 1. 1.3 -tri methy 1-2.3 -dihvdro- 1 H-indcn-4- yl]-lH-pyrazole-4-carboxamide, (B41) l,3,5-trimethyl-N-[(3R)-l, l,3-trimethyl-2,3-dihydro-lH- inden-4-yl]-lH-pyrazole-4-carboxamide, (B42) l,3,5-trimethyl-N-[(3S)-l, l,3- trimethyl-2, 3 -dihydro- lH-inden-4-yl]-lH-pyrazole-4-carboxamide, (B43) benodanil, (B44) 2-chloro-N-(l, l,3-trimethyl-2,3- dihydro-lH-inden-4-yl)pyridine-3 -carboxamide, (B45) Isofetamid, (B46) l-methyl-3- (trifluoromethyl)-N-[2'-(trilluoromethyl)biphenyl-2-yl]-lH-pyrazole-4-carboxamide, (B47) N-(4'- chlorobiphenyl-2-yl)-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide, (B48) N-(2',4'- dichlorobiphenyl-2-yl)-3-(difluoromethyl)-l-methyl-lH-pyrazole-4-carboxamide, (B49) 3-
(difluoro methyl)- 1 -methy 1 -N-[4'-(trifluoromethyl)biphenyl-2-yl] - lH-pyrazole-4-carboxamide, (B 50) N-(2',5 '-difluorobiphenyl-2-yl)-l-methyl-3-(trifluoromethyl)-lH-pyrazole-4-carboxamide, (B51) 3- (difluoro methyl)- 1 -methyl-N-[4'-(prop- 1 -yn- 1 -yl)biphenyl-2-yl] - lH-pyrazole-4-carboxamide, (B52) 5-fluoro-l ,3 -dimethyl-N-[4'-(prop- 1 -yn- 1 -yl)biphenyl-2-yl] - lH-pyrazole-4-carboxamide, (B53 ) 2- chloro-N-[4'-(prop-l-yn-l-yl)biphenyl-2-yl]nicotinamide, (B54) 3-(difluoromethyl)-N- [4'-(3,3- dimethylbut-l-yn-l-yl)biphenyl-2-yl]-l-methyl-lH-pyrazole-4-carboxamide, (B55) N-[4'-(3,3- dimethylbut-l-yn-l-yl)biphenyl-2- yl]-5-fluoro-l,3-dimethyl-lH-pyrazole-4-carboxamide, (B56) 3- (difluoromethyl)-N-(4'-ethynylbiphenyl-2-yl)-l-methyl-lH-pyrazole-4-carboxamide, (B57) N-(4‘- ethynylbiphenyl-2-yl)-5-fluoro-l,3-dimethyl-lH-pyrazole-4-carboxamide, (B58) 2-chloro-N-(4'- ethynylbiphenyl-2-yl)nicotinamide, (B59) 2-chloro-N-[4'-(3,3-dimethylbut-l-yn-l-yl)biphenyl-2- y 1] nicotinamide, (B60) 4-(difluoro methy 1) -2 -methy 1-N - [4’ -(trifluoro methy l)biphenyl-2-y 1] -1,3- thiazole-5-carboxamide, (B61) 5-lluoro-N-[4'-(3-hydroxy-3-methylbut-l-yn-l-yl)biphenyl-2-yl]-l,3- dimethyl- lH-pyrazole-4-carboxamide, (B62) 2-chloro-N-[4'-(3 -hydroxy-3 -methylbut-1 -yn- 1 - yl)biphenyl-2-yl]nicotinamide, (B63) 3-(difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-l-yn-l- yl)biphenyl-2-yl]-l-methyl-lH-pyrazole-4-carboxamide, (B64) 5-fluoro-N-[4'-(3-methoxy-3- methylbut-l-yn-l-yl)biphenyl-2-yl]-l,3-dimethyl-lH-pyrazole-4-carboxamide, (B65) 2-chloro-N-[4'- (3 -methoxy-3 -methy lbut- 1 -y n- 1 -yl)bipheny 1-2 -yl] nicotinamide, (B66) 1,3 -dimethy l-N-( 1,1,3- trimethyl-2,3-dihydro-lH-inden-4-yl)-lH-pyrazole-4-carboxamide, (B67) l,3-dimethyl-N-[(3R)-
1.1.3 -trimethyl-2,3 -dihydro- lH-inden-4-yl] - lH-pyrazole-4-carboxamide, (B68) 1 ,3 -dimethyl-N-
[(3 S)-l, l,3-trimethyl-2,3-dihydro-lH-inden-4-yl]-lH-pyrazole-4-carboxamide, (B69) 3- (difluoromethyl)-N-methoxy-l-methyl-N-[l-(2,4,6-trichlorophenyl)propan-2-yl]-lH-pyrazole-4- carboxamide, (B70) 3 -(difluoromethyl)-N-(7-fluoro- 1 , 1 ,3 -trimethyl -2,3 -dihydro- lH-inden-4-yl)- 1 - methyl- lH-pyrazole-4-carboxamide, (B71) 3 -(difluoromethyl)-N-[(3 ,R)-7-fluoro- 1 , 1 ,3 -trimethyl-2,3 - dihydro- lH-inden-4-yl] - 1 -methyl- lH-pyrazole-4-carboxamide, (B72) 3 -(difluoromethy l)-N-[(3 S)-7- fluoro- 1 , 1 ,3 -trimethyl-2,3 -dihydro-lH-inden-4-yl] - 1 -methyl- lH-pyrazole-4-carboxamide.
C) Inhibitors of the respiratory chain at complex III, for example (C01) ametoctradin, (C02) amisulbrom, (C03) azoxystrobin, (C04) cyazofamid, (C05) coumethoxystrobin, (C06) coumoxystrobin, (C07) dimoxystrobin, (C08) enoxastrobin, (C09) famoxadone, (CIO) fenamidone, (Cl l) fenaminstrobin, (C12) flufenoxystrobin, (C13) fluoxastrobin, (C14) kresoxim-methyl, (C15) metominostrobin, (C16) mandestrobin, (C17) orysastrobin, (C18) picoxystrobin, (C19) pyraclostrobin, (C20) pyrametostrobin, (C21) pyraoxystrobin, (C22) pyribencarb, (C23) triclopyricarb, (C24) trifloxystrobin, (C25) (2E)-2-(2-{ [6-(3-chloro-2-methylphenoxy)-5- fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylacetamide, (C26) (2E)-2-
(methoxyimino)-N-methyl-2-(2-{ [({(lE)-l-[3-(trifluoromethyl)phenyl]ethylidene}
amino)oxy] methyl} phenyl) acetamide, (C27) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({ l-[3- (trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}acetamide, (C28) (2E)-2-{2-[({ [(lE)-l-(3-
{ [(E)-l-lluoro-2-phenylvinyl]oxy} phenyl)ethylidene] amino}oxy)methyl]phenyl}-2-
(methoxyimino)-N-methylacetamide, (C29) Fenaminostrobin, (C30) 5-methoxy-2-methyl-4-(2- { [({(lE)-l-[3-(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H- 1,2,4- triazol-3-one, (C31) methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl} sulfanyl)methyl] phenyl } -3 -methoxy aery late, (C32) N-(3 -ethyl-3 ,5 , 5 -trimethylcy clohexy l)-3 - formamido-2-hydroxybenzamide, (C33) 2-{2-[(2, 5-dimethylphenoxy)methyl]phenyl}-2 -methoxy -N- methylacetamide, (C34) 2-{2-[(2, 5-dimethylphenoxy)methyl]phenyl}-2 -methoxy -N- methylacetamide, (C35) (2E,3Z)-5-{ [l-(4-chlorophenyl)-lH-pyrazol-3-yl]oxy}-2-(methoxyimino)- N, 3 -dimethy lpent-3 -enamide .
D) Inhibitors of the mitosis and cell division, for example (D01) benomyl, (D02) carbendazim, (D03) chlorfenazole, (D04) diethofencarb, (D05) ethaboxam, (D06) fluopicolide, (D07) fiiberidazole, (D08) pencycuron, (D09) thiabendazole, (D10) thiophanate-methyl, (D l l) thiophanate, (D 12) zoxamide, (D13) 5-chloro-7-(4-methylpiperidin-l-yl)-6-(2,4,6-trifluorophenyl)[l,2,4]triazolo[l,5-a]pyrimidine, (D14) 3-chloro-5-(6-chloropyridin-3-yl)-6-methyl-4-(2,4,6- trifluorophenyl) pyridazine, (D15) 3- chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenyl-pyridazine , (D16) 3-chloro-6-methyl-5-phenyl-
4-(2,4,6-trifluorophenyl)pyridazine, (D17) N-ethyl-2-[(3-thynyl-8-methyl-6-quinolyl)oxy]butanamide , (D18) N-ethyl-2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-acetamide , (D19) 2-
[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)butanamide, (D20) 2-[(3-ethynyl-8-methyl-6- quinolyl)oxy]-N-(2-fluoroethyl)-2 -methoxy -acetamide, (D21) 2-[(3-ethynyl-8-methyl-6- quinolyl)oxy]-N-propyl-butanamide, (D22) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methoxy-N- propyl-acetamide, (D23) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-2-methylsulfanyl-N-propyl- acetamide, (D24) 2-[(3-ethynyl-8-methyl-6-quinolyl)oxy]-N-(2-fluoroethyl)-2-methylsulfanyl- acetamide, (D25) 4-(2-bromo-4-fluoro-phenyl)-N-(2-chloro-6-fluoro-phenyl)-2,5-dimethyl- pyrazol-3 -amine, (D26) Aminopyrazole.
E) Compounds capable to have a multisite action, for example (E01) bordeaux mixture, (E02) captafol, (E03) captan, (E04) chlorothalonil, (E05) copper hydroxide, (E06) copper naphthenate, (E07) copper oxide, (E08) copper oxychloride, (E09) copper(2+) sulfate, (E10) dichlofluanid, (El l) dithianon, (E12) dodine, (E13) dodine free base, (E14) ferbam, (E15) fluorofolpet, (E16) folpet, (E17) guazatine, (E18) guazatine acetate, (E19) iminoctadine, (E20) iminoctadine albesilate, (E21) iminoctadine triacetate, (E22) mancopper, (E23) mancozeb, (E24) maneb, (E25) metiram, (E26) metiram zinc, (E27) oxine- copper, (E28) propamidine, (E29) propineb, (E30) sulfur and sulfur preparations including calcium polysulfide, (E31) thiram, (E32) tolylfluanid, (E33) zineb, (E34) ziram, (E35) anilazine, (E36) dipymetitrone.
F) Compounds capable to induce a host defence, for example (F01) acibenzolar-S -methyl, (F02) isotianil, (F03) probenazole, (F04) tiadinil, (F05) laminarin, (F06) 4-cyclopropyl-N-(2,4- dimethoxyphenyl)thiadiazole-5 -carboxamide .
G) Inhibitors of the amino acid and/or protein biosynthesis, for example (G01) andoprim, (G02) blasticidin-S, (G03) cyprodinil, (G04) kasugamycin, (G05) kasugamycin hydrochloride hydrate, (G06) mepanipyrim, (G07) pyrimethanil, (G08) 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihy droisoquinolin- 1 -y l)quinoline, (G09)oxytetracy cline, (G 10) streptomycin.
H) Inhibitors of the ATP production, for example (H01) fentin acetate, (H02) fentin chloride, (H03) fentinhydroxide, (H04) silthiofam.
I) Inhibitors of the cell wall synthesis, for example (101) benthiavalicarb, (102) dimethomorph, (103) flumorph, (104) iprovalicarb, (105) mandipropamid, (106) polyoxins, (107) polyoxorim, (108) validamycin A, (109) valifenalate, (110) polyoxin B, (Il l) (2E)-3-(4-tert-butylphenyl)-3-(2- chloropyridin-4-yl)- l-(morpholin-4-yl)prop-2-en- 1 -one, (112) (2Z)-3 -(4-tert-butylphenyl)-3 -(2- chloropyridin-4-yl)-l-(morpholin-4-yl)prop-2-en-l-one.
J) Inhibitors of the lipid and membrane synthesis, for example (JO 1) biphenyl, (J02) chloroneb, (J03) dicloran, (J04) edifenphos, (J05) etridiazole, (J06) iodocarb, (J07) iprobenfos, (J08) isoprothiolane, (J09) propamocarb, (J10) propamocarb hydrochloride, (J 11) prothiocarb, (J12) pyrazophos, (J13) quintozene, (J14) tecnazene, (J15) toclofos-methyl.
K) Inhibitors of the melanin biosynthesis, for example (KOI) carpropamid, (K02) diclocymet, (K03) fenoxanil, (K04) phthalide, (K05) pyroquilon, (K06) tolprocarb, (K07)tricyclazole.
L) Inhibitors of the nucleic acid synthesis, for example (L01) benalaxyl, (L02) benalaxyl-M (kiralaxyl), (L03) bupirimate, (L04) clozylacon, (L05) dimethirimol, (L06) ethirimol, (L07) furalaxyl, (L08) hymexazol, (L09) metalaxyl, (L10) metalaxyl-M (mefenoxam), (LI 1) ofurace, (L12) oxadixyl, (L13) oxolinic acid, (L14)octhilinone.
M) Inhibitors of the signal transduction, for example (M01) chlozolinate, (M02) fenpiclonil, (M03) fludioxonil, (M04) iprodione, (M05) procymidone, (M06) quinoxyfen, (M07) vinclozolin, (M08) proquinazid.
N) Compounds capable to act as an uncoupler, for example (N01) binapacryl, (N02) dinocap, (N03) ferimzone, (N04) fluazinam, (N05) meptyldinocap.
O) Further compounds, for example (O01) benthiazole, (002) bethoxazin, (003) capsimycin, (004) carvone, (005) chinomethionat, (006) pyriofenone (chlazafenone), (007) cufraneb, (008) cyflufenamid, (009) cymoxanil, (OIO) cyprosulfamide, (Oi l) dazomet, (012) debacarb, (013) dichlorophen, (014) dichlobentiazox, (015) diclomezine, (016) difenzoquat, (017) difenzoquat metilsulfate, (018) diphenylamine, (019) ecomate, (020) fenpyrazamine, (021) fenhexamine, (022) flumetover, (023) fluoroimide, (024) flusulfamide, (025) flutianil, (026) fosetyl-aluminium, (027) fosetyl-calcium, (028) fosetyl-sodium, (029) hexachlorobenzene, (030) immamycin, (031) isothianil, (032) methasulfocarb, (033) methyl isothiocyanate, (034) metrafenone, (035) mildiomycin, (036) natamycin, (037) nickel dimethyldithiocarbamate, (038) nitrothal-isopropyl, (039) oxamocarb, (040) oxyfenthiin, (041) pentachlorophenol and salts, (042) phenothrin, (043) picarbutrazox (044) phosphorous acid and its salts, (045) propamocarb-fosetylate, (046) propanosine-sodium, (047) pyrimorph, (048) pyraziflumid (049) pyrrolnitrine, (050) tebufloquin, (051) tecloftalam, (052) tolnifanide, (053) triazoxide, (054) trichlamide, (055) zarilamid, (056) (3S,6S,7R,8R)-8-benzyl-3-[({3-[(isobutyryloxy)methoxy]-4-methoxypyridin-2-yl}carbonyl)amino]- 6-methyl-4,9-dioxo-l,5-dioxonan-7-yl 2-methylpropanoate, (057) l-(4-{4-[(5R)-5-(2,6- difluorophenyl)-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5-methyl-3- (trifluoromethyl)-lH-pyrazol-l-yl]ethanone, (058) l-(4-{4-[(5S)-5-(2,6-difluorophenyl)-4,5-dihydro-
1.2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)-2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]ethanone, (059) dichlobentiazox, (060) l-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl-lH- imidazole-l-carboxylate, (061) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine, (062) 2,3-dibutyl-6- chlorothieno[2,3-d]pyrimidin-4(3H)-one, (063) 2,6-dimethyl-lH,5H-[l,4]dithiino[2,3-c:5,6- c']dipyrrole-l,3,5,7(2H,6H)-tetrone, (064) 2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]-l-(4-{4- [(5R)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]-l,3-thiazol-2-yl}piperidin-l-yl)ethanone, (065) 2-[5- methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]-l-(4-{4-[(5S)-5-phenyl-4,5-dihydro-l,2-oxazol-3-yl]-
1.3-thiazol-2-yl}piperidin-l-yl)ethanone, (066) 2-[5-methyl-3-(trifluoromethyl)-lH-pyrazol-]-yl]-l- (4-[4-(5-phenyl-4,5-dihydro-l,2-oxazol-3-yl)-l,3- thiazol-2-yl]piperidin-l-yl}ethanone, (067) 2- butoxy-6-iodo-3-propyl-4H-chromen-4-one, (068) 2-chloro-5-[2-chloro-l-(2,6-dilluoro-4- methoxyphenyl)-4-methyl-lH-imidazol-5-yl]pyridine, (069) 2-phenylphenol and salts, (070) 3- (4,4,5- trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-l-yl)quinoline, (071) 3,4,5-trichloropyridine- 2,6-dicarbonitrile, (072) 3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (073) 4-(4-chlorophenyl)-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine, (074) 3-chloro-4-(2,6- difluorophenyl)-6-methyl-5-phenylpyridazine, (075) 5-amino-l,3,4-thiadiazole-2-thiol, (076) 5- chloro-N‘-phenyl-N'-(prop-2-yn-l-yl)thiophene-2-sulfonohydrazide, (077) 5-fluoro-2-[(4- fluorobenzyl)oxy]pyrimidin-4-amine, (078) 5-fluoro-2-[(4-methylbenzyl)oxy]pyrimidin-4-amine, (079) 5-methyl-6-octyl[l,2,4]triazolo[l,5-a]pyrimidin-7-amine, (080) ethyl (2Z)-3 -amino-2 -cyano-3- phenylacrylate, (081) N'-(4-{[3-(4-chlorobenzyl)-l,2,4-thiadiazol-5-yl]oxy}-2,5-dimethylphenyl)-N- ethyl-N-methylimidoformamide, (082) N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-l- yloxy)phenyl]propanamide, (083) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-l- yloxy)phenyl]propanamide, (084) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4- dichloronicotinamide, (085) N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinamide, (086) N-[l-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodonicotinamide, (087) N-{(E)-
[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide, (088) N-{(Z)-[(cyclopropylmethoxy)imino] [6-(difluoromethoxy)-2,3-difluorophenyl] methyl}-2- phenylacetamide, (089) N'-{4-[(3-tert-butyl-4-cyano-l,2-thiazol-5-yl)oxy]-2-chloro-5- methylphenyl}-N-ethyl-N-methylimidoformamide, (090) N-methyl-2-(l-{ [5-methyl-3-
(trifluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-N-(l,2,3,4-tetrahydronaphthalen-l-yl)-l,3- thiazole-4-carboxamide, (091) N-methyl-2-(l-{[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-N-[(lR)-l,2,3,4-tetrahydronaphthalen-l-yl]-l,3-thiazole-4-carboxamide, (092) N-methyl-2-(l-{[5-methyl-3-(trifluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-N-[(lS)- 1,2, 3, 4- tetrahydronaphthalen-l-yl]-l,3-thiazole-4-carboxamide, (093) pentyl (6-[({[(l-methyl-lH- tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl} carbamate, (094) phenazine-1- carboxylic acid, (095) quinolin-8-ol, (096) quinolin-8-ol sulfate (2:1), (097) tert-butyl (6-[({[(l- methyl-lH-tetrazol-5-yl)(phenyl) methylene]amino}oxy)methyl]pyridin-2-yl} carbamate, (098) (5- bromo-2-methoxy-4-methylpyridin-3-yl)(2,3,4-trimethoxy-6-methylphenyl) methanone, (099) N-[2- (4-{[3-(4-chlorophenyl)prop-2-yn-l-yl]oxy}-3-methoxyphenyl)thyl]-N2-(methylsulfonyl)valinamide, (OIOO) 4-oxo-4-[(2-phenylethyl)amino]butanoic acid, (OlOl) but-3-yn-l-yl (6-[({[(Z)-(l-methyl-lH- tetrazol-5-yl)(phenyl)methylene]amino}oxy)methyl]pyridin-2-yl} carbamate, (0102) 4-amino-5- fluoropyrimidin-2-ol (tautomeric form: 4-amino-5-fluoropyrimidin-2(lH)-one), (0103) propyl 3,4,5- trihydroxybenzoate, (0104) [3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-l,2-oxazol-4- yl](pyridin-3-yl)methanol, (0105) (S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-l,2- oxazol-4-yl](pyridin-3-yl)methanol, (0106) (R)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)- l,2-oxazol-4-yl](pyridin-3-yl)methanol, (0107) 2-fluoro-6-(trifluoromethyl)-N-(l, l,3-trimethyl-2,3- dihydro-lH-inden-4-yl)benzamide, (0108) 2-(6-benzylpyridin-2-yl)quinazoline, (0109) 2-[6-(3- fluoro-4-methoxyphenyl)-5-methylpyridin-2-yl]quinazoline, (0110) 3-(4,4-difluoro-3,3-dimethyl-3,4- dihydroisoquinolin-l-yl)quinoline, (0111) Abscisic acid, (0112) N'-[5-bromo-6-(2,3-dihydro-lH- inden-2-yloxy)-2-methylpyridin-3-yl]-N-ethyl-N-methylimidoformamide, (0113) N'-{5-bromo-6-[l- (3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (0114) N'-{5- bromo-6-[(lR)-l-(3,5-difluorophenyl)ethoxy]-2-methylpyridin-3-yl}-N-ethyl-N- methylimidofonnamide, (0115) N'-{5-bromo-6-[(lS)-l-(3,5-difluorophenyl)ethoxy]-2- methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (0116) N'-{5-bromo-6-[(cis-4- isopropylcyclohexyl)oxy] -2-methylpyridin-3-yl}-N-ethyl-N-methylimidoformamide, (0117) N'-{5- bromo-6-[(trans-4-isopropylcyclohexyl)oxy]-2-methylpyridin-3-yl}-N-ethyl-N- methylimidofonnamide, (0118) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-l- methyl-lH-pyrazole-4-carboxamide, (0119) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3- (difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0120) N-(2-tert-butylbenzyl)-N- cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0121) N-(5-chloro- 2-ethylbenzyl)-N-cyclopropyl-3 -(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide,
(0122) N-(5-chloro-2-isopropylbenzyl)-N-cyclopropyl-3 -(difluoromethyl)-5 -fluoro- 1 -methyl-lH- pyrazole-4-carboxamide, (0123) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5- fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0124) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N- (5-fluoro-2-isopropylbenzyl)-l-methyl-lH-pyrazole-4-carboxamide, (0125) N-cyclopropyl-N-(2- cyclopropyl-5-fluorobenzyl)-3-(dilluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4 -carboxamide,
(0126) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropy-3 -(difluoromethyl)-5 -fluoro- 1 -methyl-lH- pyrazole-4-carboxamide, (0127) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6- isopropylbenzyl)- 1 -methyl- lH-pyrazole-4-carboxamide, (0128) N-cyclopropyl-3 -(difluoromethyl)- N-(2-ethyl-5-methylbenzyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0129) N-cyclopropyl-3- (difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-l-methyl-lH-pyrazole-4 -carboxamide, (0130) N-cycIopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-l-methyl-lH- pyrazole-4-carboxamide, (0131) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)- 5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0132) N-[5-chloro-2-(trifluoromethyl)benzyl]-N- cy clopropyl-3 -(difluoro methyl) -5 -fluoro- 1 -methyl- 1 H-pyrazole-4-carboxamide, (0133) N- cyclopropyl-3-(difluoromethyl)-5-fluoro-l-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-lH- pyrazole-4-carboxamide, (0134) N-[2-chloro-6-(trifluoromethyl)benzyl] -N-cyclopropyl-3 -
(difluoromethyl)-5-fluoro-l-methyl-lH-pyrazole-4-carboxamide, (0135) N-[3-chloro-2-fluoro-6- (trifluoromethyl)benzyl] -N-cyclopropyl-3 -(difluoromethyl)-5-fluoro- 1 -methyl- lH-pyrazole-4- carboxamide, (0136) N-cyclopropyl-3-(difluoromethyl)-N-(2 -ethyl-4, 5-dimethylbenzyl)-5-fluoro-l- methyl-lH-pyrazole-4-carboxamide, (0137) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2- isopropylbenzyl)-l -methyl- lH-pyrazole-4-carbothioamide, (0138) N'-(2,5-dimethyl-4- phenoxyphenyl)-N-ethyl-N-methylimidoformamide, (0139) N'-{ 4-[(4,5-dichloro- 1 ,3 -thiazol-2- yl)oxy]-2,5-dimethylphenyl}-N-ethyl-N-methylimidoformamide, (0140) N-(4-chloro-2,6- difluorophenyl)-4-(2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazo 1-5-amine, (0141) 9-fluoro-2,2- dimethyl-5-(quinolin-3-yl)-2,3-dihydro-l,4-benzoxazepine, (0142) 2-{2-fluoro-6-[(8-fluoro-2- methylquinolin-3-yl)oxy]phenyl}propan-2-ol, (0143) 2-{2-[(7,8-difluoro-2-methylquinolin-3- yl)oxy]-6-fluorophenyl}propan-2-ol, (0144) 4-(2-chloro-4-fluorophenyl)-N-(2 -fluorophenyl)-!, 3- dimethyl-lH-pyrazol-5-amine, (0145) 4-(2-chloro-4-fluorophenyl)-N-(2,6-difluorophenyl)-l,3- dimethyl-lH-pyrazol-5-amine, (0146) 4-(2-chloro-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-l,3- dimethyl-lH-pyrazol-5-amine, (0147) 4-(2-bromo-4-fluorophenyl)-N-(2-chloro-6-fluorophenyl)-l,3- dimethyl-lH-pyrazol-5-amine, (0148) N-(2-bromo-6-fluorophenyl)-4-(2-chloro-4-fluorophenyl)-l,3- dimethyl-lH-pyrazol-5-amine, (0149) 4-(2-bromo-4-fluorophenyl)-N-(2-bromophenyl)-l,3-dimethyl- lH-pyrazol-5 -amine, (0150) 4-(2-bromo-4-fluorophenyl)-N-(2-bromo-6-fluorophenyl)-l,3-dimethyl- lH-pyrazol-5 -amine, (0151) 4-(2-bromo-4-fluorophenyl)-N-(2-chlorophenyl)-l,3-dimethyl-lH- pyrazol-5-amine, (0152) N-(2-bromophenyl)-4-(2-chloro-4-fluorophenyl)-l,3-dimethyl-lH-pyrazol- 5-amine, (0153) 4-(2-chloro-4-fluorophenyl)-N-(2-chlorophenyl)-l,3-dimethyl-lH-pyrazol-5-amine, (0154) 4-(2-bromo-4-fluorophenyl)-N-(2,6-difluorophenyl)- 1 ,3 -dimethyl- lH-pyrazol-5-amine, (0155) 4-(2-bromo-4-fluorophenyl)-N-(2 -fluorophenyl)-!, 3 -dimethyl- lH-pyrazol-5 -amine, (0156) N'-(4-{3-[(difluoromethyl)sulfanyl]phenoxy}-2,5-dimethylphenyl)-N-ethyl-N- methylimidoformamide, (0157) N’ -(2,5-dimethyl-4-{ 3 -[( 1 , 1 ,2,2-tetrafluoroethyl)sulfanyl] phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (0158) N‘ -(2, 5-dimethyl -4-{3-[(2, 2,2- trifluoroethyl)sulfanyl]phenoxy}phenyl)-N-ethyl-N-methylimidoformamide, (0159) N‘-(2,5- dimethyl-4-{ 3 -[(2,2,3 ,3 -tetrafluoropropyl)sulfanyl]phenoxy }phenyl)-N-ethyl-N- methylimidoformamide, (0160) N'-(2,5-dimethyl-4-{3-[(pentafluoroethyl)sulfanyl]phenoxy}phenyl)- N-ethyl-N-methylimidoformamide, (0161) N'-(4-{[3-(difluoromethoxy)phenyl]sulfanyl}-2,5- dimethylphenyl)-N-ethyl-N-methylimidoformamide, (0162) N'-(2,5-dimethyl-4-{ [3-(l, 1,2,2- tetrafluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (0163) N'-(2,5- dimethyl-4-{[3-(2,2,2-trifluoroethoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N-methylimidoformamide, (0164) N'-(2,5-dimethyl-4-{[3-(2,2,3,3-tetrafluoropropoxy)phenyl]sulfanyl}phenyl)-N-ethyl-N- methylimidoformamide, (0165) N'-(2,5-dimethyl-4-{[3-(pentafluoroethoxy)phenyl]sulfanyl}phenyl)- N-ethyl-N-methylimidofomiamide, (0166) 2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{5- [2 -(prop-2 -yn-l-yloxy)phenyl]-4,5-dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0167) 2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{5-[2-fluoro-6-(prop-2-yn-l- yloxy)phenyl]-4,5-dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0168) 2-[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{5-[2-chloro-6-(prop-2-yn-l-yloxy)phenyl]-4,5- dihydro-1, 2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0169) 2-{3-[2-(l-{ [3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol- 5-yl}phenyl methanesulfonate, (0170) 2-{3-[2-(l-{ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl
methanesulfonate, (0171) 2-[3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5S)-5-[2-(prop-2- yn-l-yloxy)phenyl]-4,5-dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0172) 2- [3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5R)-5-[2 -(prop-2 -yn-l-yloxy)phenyl]-4, 5- dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0173) 2-[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5S)-5-[2-fluoro-6-(prop-2-yn-l-yloxy)phenyl]-4,5- dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0174) 2-[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5R)-5-[2-fluoro-6-(prop-2-yn-l-yloxy)phenyl]-4,5- dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0175) 2-[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5S)-5-[2-chloro-6-(prop-2-yn-l-yloxy)phenyl]-4,5- dihydro-l,2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0176) 2-[3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]-l-[4-(4-{(5R)-5-[2-chloro-6-(prop-2-yn-l-yloxy)phenyl]-4,5- dihydro-1, 2-oxazol-3-yl}-l,3-thiazol-2-yl)piperidin-l-yl]ethanone, (0177) 2-{(5S)-3-[2-(l-{ [3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol- 5-yl}phenyl methanesulfonate, (0178) 2-{(5R)-3-[2-(l-{ [3,5-bis(difluoromethyl)-lH-pyrazol-l- yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-5-yl}phenyl methanesulfonate, (0179) 2-{(5S)-3-[2-(l-{ [3,5-bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-
4-yl]-4,5-dihydro-l,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate, (0180) 2-{(5R)-3-[2-(l-{ [3,5- bis(difluoromethyl)-lH-pyrazol-l-yl]acetyl}piperidin-4-yl)-l,3-thiazol-4-yl]-4,5-dihydro-l,2-oxazol-
5-yl}-3-chlorophenyl methanesulfonate, (0181) (3S,6S,7R,8R)-8-benzyl-3-{3-
[(isobutyryloxy)methoxy]-4-methoxypicolinamido} -6-methyl-4,9-dioxo-l,5-dioxonan-7-yl isobutyrate, (0182) N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine, (0183)N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N- ethyl-N-methylformamidine, (0184)N'-[4-[[3-[(4-chlorophenyl)methyl]-l,2,4-thiadiazol-5-yl]oxy]- 2, 5-dimethyl -phenyl]-N-ethyl-N-methyl-formamidine, (0185) N'-(5-bromo-6-indan-2-yloxy-2- methyl-3-pyridyl)-N-ethyl-N-methyl-formamidine, (0186) N'-[5-bromo-6-[l-(3,5- difluorophenyl)ethoxy]-2 methyl-3 -pyridyl]-N-ethyl-N-methyl-formamidine, (0187) N'-[5- bromo-6-(4-isopropylcyclohexoxy)-2 -methyl-3 -pyridyl] -N-ethyl-N-methyl-formamidine, (0188) N'- [5 -bromo-2-methyl-6-( 1 -phenylethoxy)-3 -pyridyl] -N-ethyl-N-methylformamidine, (0189) N'-
(2 -methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)phenyl)-N-ethyl-N -methyl formamidine, (0190) N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, (0191) (N-ethyl-N'-(4-(2-fluorophenoxy)-2,5-dimethylphenyl)-N- methylformimidamide , (0192) N'-(2-chloro-4-(2-fluorophenoxy)-5-methylphenyl)-N-ethyl-N- methylformimidamide, (0193) 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan- 2-ol, (0194) 2-[2-fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]-phen-yl]propan-2-ol, (0195) quinofumelin, (0196) 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-l,4-benzoxazepine, (0197) 2-
(6-benzyl-2-pyridyl)quinazoline, (0198)2-[6-(3-fluoro-4-methoxy-phenyl)-5-methyl-2- pyridyl]quinazoline, (0199) fluopimomide, (0200) florylpicoxamid.
P) Growth regulators, for example abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine. brassinolide, butralin, chlormequat, chlormequat chloride, choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, llurprimidol, lluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3 -acetic acid , maleic hydrazide, mefluidide, mepiquat, mepiquat chloride, naphthaleneacetic acid, N-6-benzyladenine, paclobutrazol, prohexadione, prohexadione-calcium, prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri-iodobenzoic acid , trinexapacethyl and uniconazole.
The active substances referred above, their preparation and their activity e.g. against harmful fungi is known (cf: http://www.alanwood.net/pesticides/); these substances are commercially available. The compounds described by IUPAC nomenclature, their preparation and their pesticidal activity are also known (cf. Can. J. Plant Sci. 48(6), 587-94, 1968; EP-A 141317; EP-A 152031; EP-A 226917; EP-A 243 970; EP-A 256503; EP-A 428941; EP-A 532022; EP-A 1028125; EP-A1035122; EP-A 1201648; EP-A 1122244, JP 2002316902; DE 19650197; DE 10021412; DE 102005009458; US 3,296,272; US 3,325,503; WO 98/46608; WO 99/14187; WO 99/24413; WO 99/27783; WO 00/29404; WO
00/46148; WO 00/65913; WO 01/54501; WO 01/56358; WO 02/22583; WO 02/40431; WO
03/10149; WO 03/11853; WO 03/14103; WO 03/16286; WO 03/53145; WO 03/61388; WO
03/66609; WO 03/74491; WO 04/49804; WO 04/83193; WO 05/120234; WO 05/123689; WO
05/123690; WO 05/63721; WO 05/87772; WO 05/87773; WO 06/15866; WO 06/87325; WO 06/87343; WO 07/82098; WO 07 /90624, WO 10/139271, WO 11 /028657, WO 12/168188, WO 07 /006670, WO 11/77514; WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/24010, WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833, CN 1907024, CN 1456054, CN 103387541, CN 1309897, WO 12/84812, CN 1907024, WO 09094442, WO 14/60177, WO 13/116251, WO 08/013622, , WO 94/01546, EP 2865265, WO 07/129454, WO 12/165511, WO 11/081174, WO 13/47441).
As described above the compound of formula (I) can be mixed with one or more active compatible compound selected from insecticides/acaricides/nematicides class, which are specified herein by their common names that are known and described, for example in The Pesticide Manual 17th Ed. , or can be searched in the internet (e.g. under www.alanwood.net/pesticides) . (1) Acetylcholinesterase (AChE) inhibitors such as carbamates, for example alanycarb, aldicarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, triazamate, trimethacarb, XMC and xylylcarb or organophosphates, such as acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S -methyl, diazinon, dichlorvos / DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O-(methoxyaminothio-phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, triclorfon and vamidothion.
(2) GABA-gated chloride channel antagonists, such as cyclodiene organochlorines, for example chlordane and endosulfan or phenylpyrazoles (fiproles), for example ethiprole and fipronil.
(3) Sodium channel modulators/voltage-dependent sodium channel blockers, such as pyrethroids, for example acrinathrin, allethrin, d -cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta- cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin |( 1 R)-/r< v-isomcrs|. deltamethrin, empenthrin [(EZ)-(lR)-isomers], esfenvalerate, etofenprox, fenpropathrin, fenvalerate, fluey thrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, kadethrin, momfluorothrin, permethrin, phenothrin |( 1 R)-/r< v-isomcr). prallethrin, pyrethrins (pyrethmm), resmethrin, silafluofen, tefluthrin, tetramethrin, tetramethrin [(1R) -isomers)], tralomethrin and transfluthrin or DDT or methoxychlor.
(4) Nicotinic acetylcholine receptor (nAChR) competitive modulators, such as neonicotinoids, for example acetamiprid, clothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam or nicotine or sulfoxaflor or flupyradifurone.
(5) Nicotinic acetylcholine receptor (nAChR) allosteric modulators, such as spinosyns, for example spinetoram and spinosad.
(6) Glutamate-gated chloride channel (GluCl) allosteric modulators, such as avermectins / milbemycins, for example abamectin, emamectin benzoate, lepimectin and milbemectin.
(7) Juvenile hormone mimics such as juvenile hormone analogues, for example hydroprene, kinoprene and methoprene or fenoxycarb or pyriproxyfen. (8) Active compounds with unknown or non-specific mechanisms of action, such as alkyl halides for example as methyl bromide and other alkyl halides or chloropicrin or fluorides or borates or tartar emetic or methyl isocyanate generators.
(9) Chordotonal organ TRPV channel modulators such as pyridine azomethine derivatives, for example pymetrozine and pyrifluquinazon or flonicamid.
(10) Mite growth inhibitors, for example clofentezine, hexythiazox and diflovidazin or etoxazole.
(11) Microbial disruptors of insect gut midgut, for example Bacillus thuringiensis subspecies israelensis, Bacillus thuringiensis subspecies aizawai, Bacillus thuringiensis subspecies kurstaki, Bacillus thuringiensis subspecies tenebrionis and Bacillus sphaericus and BT crop proteins: CrylAb, CrylAc, CrylFa, CrylA 105, Cry2Ab, Vip3a, mCry3A, Cry3Ab, Cry3Bb, Cry34Abl / Cry35Abl.
(12) Inhibitors of mitochondrial ATP synthase such as organotin miticides, for example azocyclotin, cyhexatin and fenbutatin oxide or diafenthiuron or propargite or tetradifon.
(13) Uncouplers of oxidative phosphorylation acting via disruption of the proton gradient, for example chlorfenapyr, DNOC and sulfluramid.
(14) Nicotinic acetylcholine receptor (nAChR) channel blockers, such as bensultap, cartap- hydrochloride, thiocyclam and thiosultap-sodium.
(15) Inhibitors of chitin biosynthesis, type 0, such as bistrifluoron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron and trillumuron.
(16) Inhibitors of chitin biosynthesis, type 1, such as buprofezin.
(17) Molting disruptors (particularly in Dipteran), such as cyromazine.
(18) Ecdysone receptor agonists, such as chromafenozide, halofenozide, methoxyfenozide and tebufenozide.
(19) Octopamine receptor agonists, such as amitraz.
(20) Mitochondrial complex III electron transport inhibitors such as hydramethylnon or acequinocyl or fluacrypyrim or bifenazate.
(21) Mitochondrial complex I electron transport inhibitors, for example, METI acaricides and insecticides, for example fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad and tolfenpyrad or rotenone (Derris).
(22) Voltage-dependent sodium channel blockers such as indoxacarb or metaflumizone.
(23) Inhibitors of acetyl CoA carboxylase, such as tetronic and tetramic acid derivatives, for example spirodiclofen, spiromesifen and spirotetramat.
(24) Mitochondrial complex IV electron transport inhibitors, such as phosphides, for example aluminum phosphide, calcium phosphide, zinc phosphide and phosphine or cyanides. (25) Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen and cyflumetofen or carboxanilides.
(26) Ryanodine receptor modulators such as diamides, for example chlorantraniliprole, cyantraniliprole, flubendiamide, tetraniliprole, (R)-3-chloro-N-l-{2-methyl-4-[l,2,2,2-tetrafluoro-l- (trifluoromethyl)ethyl]phenyl}-N2-(l-methyl-2-methylsulfonylethyl)phthalamide, (S)-3-chloro-Nl- {2-methyl-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]phenyl}-N2-(l-methyl-2- methylsulfonylethyl)phthalamide, methyl-2-[3,5-dibromo-2-({[3-bromo-l-(3-chloropyridin-2-yl)-lH- pyrazol-5-yl]carbonyl}amino)benzoyl]-l,2-dimethylhydrazinecarboxylate, N-[4,6-dichloro-2-
[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5- (trifluoromethyl)pyrazole-3-carboxamide, N-[4-chloro-2-[(diethyl-lambda-4- sulfanylidene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide, N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6-methyl-phenyl]-2- (3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide, N-[4,6-dichloro-2-[(di-2-propyl- lambda-4-su lfanylidene)carbamoyl]phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide, N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2- pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide, N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4-chloro- 6-methylphenyl]-3-bromo-l-(3-chloro-2-pyrid inyl)-lH-pyrazole-5-carboxamide;3-chloro-l-(3- chloro-2-pyridinyl)-N-[2,4-dichloro-6-[[(l-cyano-l-methylethyl)amino]carbonyl]phenyl]-lH- pyrazole-5 -carboxamide, 3-bromo-N-[2,4-dich loro-6-(methylcarbamoyl)phenyl]-l-(3,5-dichloro-2- pyridyl)-lH-pyrazole-5-carboxamide, N-[4-chloro-2-[[(l,l-dimethylethyl)amino]carbonyl]-6- methylphenyl] -1 -(3 -chloro-2-pyridinyl)-3 -(fluoromethoxy)- 1 H-pyrazole-5-carboxamide and cyhalodiamide.
(27) Chordotonal organ modulators on undefined target site such as flonicamid.
Further active ingredients with unknown or indeterminate mode of action, such as afidopyropen, afoxolaner, azadirachtin, benclothiaz, benzoximate, bifenazate, broflanilide, bromopropylate, chinomethionat, cryolite, cyclaniliprole, cycloxaprid, cyhalodiamide, dicloromezotiaz, dicofol, diflovidazin, flometoquin, fluazaindolizine, lluensulfone, flufenerim, llufenoxystrobin, llufiprole, fluhexafon, fluopyram, flmalaner, fluxametamide, fufenozide, guadipyr, heptafluthrin, imidaclothiz, iprodione, lotilaner, meperfluthrin, paichongding, pyflubumide, pyridalyl, pyrifluquinazon, pyriminostrobin, sarolaner, tetramethylfluthrin, tetrachlorantraniliprole, tioxazafen, triflumezopyrim and iodomethane; furthermore, preparations based on Bacillus firmus (1-1582, BioNeem, Votivo), and the following known active compounds: l-{2-fluoro-4-methyl-5-[(2,2,2- trifluoroethyl)sulfinyl]phenyl}-3-(trifluoromethyl)-lH-l,2,4-triazol-5-amine (known from W02006043635), { r-[(2E)-3-(4-chlorophenyl)prop-2-ene-l-yl]-5-fluorospiro[indole-3,4'-piperidine]- l(2H)-yl}(2-chloropyridin-4-yl)methanone (known from W02003106457), 2-chloro-N-[2-{l-[(2E)- 3-(4-chlorophenyl)prop-2-en-l-yl]piperidin-4-yl}-4-(trifluoromethyl)phenyl]isonicotinamide (known from W02006003494), 3-(2,5-dimethylphenyl)-4-hydroxy-8-methoxy-l,8-diazaspiro[4.5]dec-3-en-2- one (known from W02009049851), 3-(2,5-dimethylphenyl)-8-methoxy-2-oxo-l,8- diazaspiro[4.5]dec-3-en-4-yl ethyl carbonate (known from W02009049851), 4-(but-2-in-l-yloxy)-6- (3,5-dimethylpiperidin-l-yl)-5-fluoropyrimidine (known from W02004099160), 4-(but-2-in-l- yloxy)-6-(3-chlorophenyl)pyrimidine (known from W02003076415), PF1364 (CAS-Reg.No. 1204776-60-2), [methyl-2-[2-({ [3-bromo-l-(3-chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)- 5-chloro-3 -methylbenzoyl] -2-methylhydrazincarboxylate, methyl-2-[2-({ [3 -bromo- 1 -(3 - chloropyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2- ethylhydrazincarboxylate, methyl-2-[2-({ [3-bromo-l-(3-chloro-pyridin-2-yl)-lH-pyrazol-5- yl]carbonyl}amino)-5-cyano-3-methylbenzoyl]-2-methylhydrazincarboxylate and methyl-2-[3,5- dibromo-2-({ [3-bromo-l-(3-chloro-pyridin-2-yl)-lH-pyrazol-5-yl]carbonyl}amino)benzoyl]-2- ethylhydrazincarboxylate (known from W02005085216)], N-[2-(5-amino-l,3,4-thiadiazol-2-yl)-4- chloro-6-methylphenyl] -3 -bromo- 1 -(3 -chloropyridin-2-yl)- lH-pyrazole-5 -carboxamide (known from CN102057925), 4-[5-(3,5-dichlorophenyl)-5-(triiluoromethyl)-4,5-dihydro-l,2-oxazol-3-yl]-2- methyl-N-(l-oxidothietan-3-yl)benzamide (known from W02009080250), N-[(2E)-l-[(6- chloropyridine-3-yl)methyl]pyridin-2(lH)-ylidene]-2,2,2-trifluoroacetamide (known from
WO2012029672), l-[(2-chloro-l,3-thiazol-5-yl)methyl]-4-oxo-3-phenyl-4H-pyrido[l,2-a]pyrimidin- l-ium-2-olate (known from W02009099929), l-[(6-chloropyridin-3-yl)methyl]-4-oxo-3-phenyl-4H- pyrido[l,2-a]pyrimidin-l-ium-2-olate (known from W02009099929), 4-(3-{2,6-dichloro-4-[(3,3- dichloroprop-2-en- 1 -yl)oxy]phenoxy }propoxy)-2-methoxy-6-(trifluoromethyl)pyrimidine (known from CN101337940), N-[2-(ter/-butylcarbamoyl)-4-chloro-6-methylphenyl]-l-(3-chloropyridin-2-yl)- 3-(fluoromethoxy)-lH-pyrazole-5-carboxamide (known from WO2008134969), butyl-[2-(2,4- dichlorophenyl)-3-oxo-4-oxaspiro[4.5]dec-l-en-l-yl]carbonate (disclosed in CN102060818), 3(E)-3- [ 1 -[(6-chloro-3 -pyridyl)methyl] -2-pyridyliden] -1,1,1 -triiluoropropan-2-one (known from
WO2013144213), N-(methylsulfonyl)-6-[2-(pyridin-3-yl)-l,3-thiazol-5-yl]pyridine-2 -carboxamide (known from WO2012000896), N-[3-(benzylcarbamoyl)-4-chlorophenyl]-l-methyl-3- (pentafluoroethyl)-4-(trifluoromethyl)-lH-pyrazole-5-carboxamide (known from W02010051926). Other active compounds of unknown or uncertain mode of action: l l-(4-chloro-2,6-dimethylphenyl)- 12-hydroxy-l,4-dioxa-9-azadispiro[4.2.4.2]-tetradec-l l-en-10-one, 3-(4' -fluoro-2,4- dimethylbiphenyl-3-yl)-4-hydroxy-8-oxa-l-azaspiro[4.5]dec-3-en-2-one, l-[2-fluoro-4-methyl-5- [(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-l H-l,2,4-triazole-5-amine, Bacillus firmus;(E/Z)- N-[l-[ (6-ch loro-3 -pyridyl) methyl] -2 -pyridylidene ]-2,2,2-trilluoro-acetamide; (E/Z)- N-[l-[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; (E/Z)-2,2,2- trifluoro-N-[l-[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; (E/Z)-N-[l-[(6-bromo-3- pyridyl)methyl] -2-pyridylidene] -2,2,2-trifluoroacetamide; (/·. Z)-N-| 1 -| 1 -(6-chloro-3 -pyridyl)ethyl] -2- pyridylidene] -2,2,2-trifluoroacetamide; (E/Z)-N-[ 1 -[(6-chloro-3 -pyridyl)methyl] -2-pyridylidene] -2,2- difluoro-acetamide; (/·. Z)-2-chloro-N-| l-[ ( 6-chloro-3-pyridyl) methyl] -2-pyridylidene] -2,2- difluoro-acetamide; (E/Z)-N-[l-[(2-chloropyrimidin-5-yl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide; (E/Z)-N-[ 1 -[(6-chloro-3 -pyridyl)methyl] -2-pyridylidene] -2,2,3 ,3 ,3 -pentafluoro- propanamide); N-[l-[ (6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-thioacetamide; N- [ 1 -[(6-chloro-3 -pyridyl)methyl] -2-pyridylidene] -2,2,2-trifluoro-N'-isopropyl-acetamidine;
fluazaindolizine; 4-[5 -(3 ,5-dichlorophenyl)-5 -(trifluoromethyl)-4H-isoxazol-3 -yl] -2 -methyl -N-( 1- oxothietan-3-yl)benzamide; fluxametamide; 5-[3-[2,6-dichloro-4-(3,3- dichloroallyloxy)phenoxy]propoxy]-lH-pyrazole; 3-(benzoylmethylamino)-N-[2-bromo-4-
[ 1 ,2,2,3 ,3 ,3 -hexafluoro- 1 -(trifluoromethyl)propyl] -6-(trifluoromethyl)phenyl] -2-fluoro-benzamide; 3 - (benzoylmethylamino)-2-fluoro-N-[2-iodo-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]-6- (trifluoromethyl)phenyl]-benzamide; N-[3-[[[2-iodo-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]- 6-(trifhioromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; N-[3-[[[2-bromo-4-[l,2,2,2- tetrafluoro-l-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]-2-fluorophenyl]-4- fluoro-N-methylbenzamide; 4-fluoro-N-[2-fluoro-3-[[[2-iodo-4-[l,2,2,2-tetrafhioro-l-
(trifluoromethyl)ethyl] -6-(trifluoromethyl)phenyl] amino]carbonyl]phenyl] -N-methyl-benzamide; 3 - fluoroN-[2-fluoro-3-[[[2-iodo-4-[l,2,2,2-tetrafluoro-l-(trifhioromethyl)ethyl]- 6(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-N-methyl-benzamide; 2-chloro-N-[3-[[[2-iodo-4- [l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl]-6-(trifluoromethyl)phenyl]amino]carbonyl]phenyl]-3- pyridinecarboxamide; 4-cyano-N-[2-cyano-5-[[2,6-dibromo-4-[l,2,2,3,3,3-hexafluoro-l-
(trifluoromethyl) propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide;4-cyano-3-[(4-cyano-2- methyl-benzoyl)amino]-N-[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l-(trifluoromethyl) propyl]phenyl]- 2-fluoro-benzamide; N-[5-[[2-chloro-6-cyano-4-[l,2,2,3,3,3-hexafluoro-l-
(trifluoromethyl)propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; N-[5-[[2- bromo-6-chloro-4-[2,2,2-trifluoro-l-hydroxy-l-(trifluoromethyl)ethyl]phenyl]carbamoyl]-2-cyano- phenyl]-4-cyano-2-methyl-benzamide;N-[5-[[2-bromo-6-chloro-4-[l,2,2,3,3,3-hexafluoro-l- (trifluoromethyl) propyl]phenyl]carbamoyl]-2-cyano-phenyl]-4-cyano-2-methyl-benzamide; 4-cyano- N-[2-cyano-5-[[2,6-dichloro-4-[l,2,2,3,3,3-hexafluoro-l-
(trifluoromethyl)propyl]phenyl]carbamoyl]phenyl]-2-methyl-benzamide; 4-cyano-N-[2-cyano-5- [[2,6-dichloro-4-[l,2,2,2-tetrafluoro-l-(trifluoromethyl)ethyl] phenyl] carbamoyl] phenyl] -2 -methyl- benzamide; N-[5-[[2-bromo-6-chloro-4-[ 1, 2, 2, 2-tetrafluoro-l-(trifluoromethyl)ethyl] phenyl]carbamoyl]-2-cyan o-phenyl]-4-cya no-2-methyl-benzamide; 2-(l,3-dioxan-2-yl)-6-[2-(3- pyridinyl)-5-thiazolyl]-pyridine; 2-[6-[2-(5-fluoro-3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; 2-[6-[2-(3-pyridinyl)-5-thiazolyl]-2-pyridinyl]-pyrimidine; N-methylsulfonyl-6-[2-(3-pyridyl)thiazol- 5-yl]pyridine-2 -carboxamide; N-methylsLilfonyl-6-[2-(3-pyridyl)thiazol-5-yl]pyridine-2- carboxamide; N-ethyl-N-[4-methyl-2-(3-pyridyl)thiazol-5-yl]-3-methylthio-propan amide; N-methyl- N-[ 4-methyl-2-( 3-pyridyl)thiazol-5-yl]-3-methylthio-propanamide; N,N-2-dimethyl-N-[4-methyl-2- (3-pyridyl)thiazol-5-yl]-3-methylthiopropanamide; N-ethyl-2-methyl-N-[4-methyl-2-(3- pyridyl)thiazol-5-yl]-3-methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-2- methyl-3-methylthio-propanamide; N-[ 4-chloro-2-(3-pyridyl )thiazol-5-yl]-N ,2-dimethyl-3- methylthio-propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-methyl-3-methylthio- propanamide; N-[4-chloro-2-(3-pyridyl)thiazol-5-yl]-N-ethyl-3-methylthio-propanamide; l-[(6- chloro-3-pyridinyl)methyl]-l,2,3,5,6,7-hexahydro-5-methoxy-7-methyl-8-nitro-imidazo[l,2- a]pyridine; l-[(6-chloropyridin-3-yl)methyl]-7-methyl-8-nitro-l,2,3,5,6,7-hexahydroimidazo[l,2- a]pyridin-5-ol; l-isopropyl-N,5-dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; 1-(1,2- dimethylpropyl)-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N,N-5-dimethyl-N- pyridazin-4-yl-l -(2,2,2-trifluoro- 1 -methyl-ethyl)pyrazole-4-carboxamide; 1 -[ 1 -( 1- cyanocyclopropyl)ethyl]-N-ethyl-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N -ethyl-1 -(2- fluoro-l-methyl-propyl)-5-methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; l-(l,2-dimethylpropyl)- N, 5 -dimethy 1-N -py ridazin-4-yl-py razole-4-carboxamide ; 1-[1-(1 -cy anocy clopropy l)ethy 1] -N, 5 - dimethyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; N-methyl-l-(2-fluoro-l-methyl-propyl]-5- methyl-N-pyridazin-4-yl-pyrazole-4-carboxamide; l-(4,4-difluorocyclohexyl)-N-ethyl-5-methyl-N- pyridazin-4-yl-pyrazole-4-carboxamide; l-(4,4-dilluorocyclohexyl)-N,5-dimethyl-N-pyridazin-4-yl- pyrazole-4-carboxamide; N-( l-methylethyl)-2-(3-pyridinyl)-2 H-indazole-4-carboxamide; N- cyclopropyl-2-(3-pyridinyl)-2H-indazole-4-carboxamide; N-cyclohexyl-2-(3-pyridinyl)-2H-indazole- 4-carboxamide; 2-(3-pyridinyl)-N-(2,2,2-trifluoroethyl)-2H-indazole-4-carboxamide; 2-(3-pyridinyl)- N-[(tetrahydro-2-furanyl)methyl]-2H-indazole-5-carboxamide; methyl 2-[[2-(3-pyridinyl)-2H- indazol-5-yl] carbonyl] hydrazinecarboxy late; N-[(2,2-difluorocyclopropyl)methyl]-2-(3-pyridinyl)- 2H-indazole-5-carboxamide; N-(2,2-difluoropropyl)-2-(3-pyridinyl)-2H-indazole-5-carboxamide; 2- (3 -pyridinyl)N-(2-pyrimidinylmethyl )-2H-indazole-5-carboxamide; N-[(5-methyl-2- pyrazinyl)methyl]-2-( 3-pyridinyl)-2H-indazole-5-carboxamide, N-[3-chloro-l-(3-pyridyl) pyrazol-4- yl]N-ethyl-3-(3, 3 ,3-trifluoropropylsulfanyl) propanamide; N-[3-ch loro-l-( 3-pyridyl) pyrazol-4-yl]- N-ethyl-3 -(3 ,3 ,3 -trifluoropropylsulfinyl)propanamide; N-[3 -chloro- 1 -(3 -pyridyl)pyrazol-4-yl] -3 -[(2,2- difluorocy clopropy l)methylsulfanyl] -N-ethyl-propanamide; N-[3 -chloro- 1 -(3 -pyridyl)pyrazol-4-yl] -3- [(2,2-dilluorocyclopropyl) methylsulfinyl] -N-ethyl-propanamide; sarolaner, lotilaner, isocycloseram. The mass ratio of any two ingredients in each combination is selected as to give the desired effect. In general, the mass ratio would vary depending on the specific ingredient and how many ingredients are present in the combination. Generally, the mass ratio between any two ingredients in any combination of the present invention, independently of one another, is from 100: 1 to 1 : 100, including from 99: 1, 98:2, 97:3, 96:4, 95:5, 94:6, 93:7, 92:8, 91:9, 90: 10, 89: 11, 88: 12, 87: 13, 86: 14, 85: 15, 84: 16, 83: 17, 82: 18, 81: 19, 80:20, 79:21, 78:22, 77:23, 76:24, 75:25, 74:26, 73:27, 72:28,
71:29, 70:30, 69:31, 68:32, 67:33, 66:34, 65:45, 64:46, 63:47, 62:48, 61:49, 60:40, 59:41, 58:42,
57:43, 56:44, 55:45, 54:46, 53:47, 52:48, 51:49, 50:50, 49:51, 48:52, 47:53, 46:54, 45:55, 44:56,
43:57, 42:58, 41:59, 40:60, 39:61, 38:62, 37:63, 36:64, 35:65, 34:66, 33:67, 32:68, 31:69, 30:70,
29:71, 28:72, 27:73, 26:74, 25:75, 24:76, 23:77, 22:78, 21:79, 20:80, 19:81, 18:82, 17:83, 16:84,
15:85, 14:86, 13:87, 12:88, 11:89, 10:90, 9:91, 8:92, 7:93, 6:94, 5:95, 4:96, 3:97, 2:98, to 1 :99.
The combination of the present invention (i.e. those comprising a compound of the present invention and one more other biological active agent) may be applied simultaneously or sequentially.
In the event, the ingredients of a combination are applied sequentially (i.e., one after the other), the ingredients are applied sequentially within a reasonable period of each other to attain the biological performance, such as within a few horns or days. The order of applying the ingredients in the combination, i.e., whether the compounds of formula (I) should be applied first or not is not essential for working the present invention.
In the event ingredients of the combinations are applied simultaneously in the present invention, they may be applied as a composition containing the combination, in which case (A) the compound of formula (I) and the one or more other ingredients in the combinations can be obtained from separate formulation sources and mixed together (known as a tank-mix, ready -to-apply, spray broth, or slurry), or (B) the compound of formula (I) and the one or more other ingredients can be obtained as single formulation mixture source (known as a pre-mix, ready-mix, concentrate, or formulated product).
In an embodiment, independent of other embodiments, a compound according to the present invention is applied as a combination. Accordingly, the present invention also provides a composition comprising a compound according the invention as herein described and one or more other biological active agents, and optionally one or more customary formulation auxiliaries; which may be in the form of a tank-mix or pre-mix composition.
The mixtures of active substances according to the present invention are suitable as fungicides, as are the compounds of formula I. They are distinguished by an outstanding effectiveness against a broad spectrum of phytopathogenic fungi, especially from the classes of the Ascomycetes, Basidiomycetes, Deuteromycetes and Peronosporomycetes (syn. Oomycetes). In addition, it is referred to the explanations regarding the fungicidal activity of the compounds and the compositions containing compounds of formula (I), respectively.
There are large number of suitable known standard methods, such as alkylation, halogenation, acylation, amidation, oximation, oxidation and reduction. The choice of the preparation methods which are suitable are depending on the properties (reactivity) of the substituents in the intermediates. These reactions can be conveniently performed in a solvent. These reactions can be conveniently performed at various temperatures. These reactions can be conveniently performed in an inert atmosphere. The reactants can be reacted in the presence of a base. Examples of suitable bases are alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal hydrides, alkali metal or alkaline earth metal amides, alkali metal or alkaline earth metal alkoxides, alkali metal or alkaline earth metal acetates, alkali metal or alkaline earth metal carbonates, alkali metal or alkaline earth metal dialkylamides or alkali metal or alkaline earth metal alkylsilylamides, alkylamines, alkylenediamines, free or N-alkylated saturated or unsaturated cycloalkylamines, basic heterocycles, ammonium hydroxides and carbocyclic amines. Examples which may be mentioned are sodium hydroxide, sodium hydride, sodium amide, sodium methoxide, sodium acetate, sodium carbonate, potassium tert-butoxide, potassium hydroxide, potassium carbonate, potassium hydride, lithium diisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, Y. Y-dictbvlanilinc. pyridine, 4-( Y, Y-dimcthylamino)pyridinc. quinuclidine, N-methylmorpholine, benzyltrimethylammonium hydroxide and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction according to scheme-1 is preferably carried out in a solvent selected from standard solvents which are inert under the prevailing reaction conditions. Preference is given to aliphatic, alicyclic or aromatic hydrocarbons, such as, petroleum ether, hexane, toluene; halogenated hydrocarbons, such as, chlorobenzene, dichloromethane, chloroform, carbon tetrachloride or dichloroethane ; ethers, such as, diethyl ether, diisopropyl ether, methyl /-butyl ether (MTBE), dioxane, tetrahydrofuran or 1,2-dimethoxy ethane; nitriles, such as, acetonitrile or propionitrile, or; amides, such as, Y, Y-d i m c t h v 1 fo rm a m i dc (DMF), Y, Y-d i m c t h v 1 ac c t a m i dc . Y- m c t h v 1 fo r ma n i 1 i dc . N- methylpyrrolidone (NMP) or hexamethylenephosphoric triamide; esters, such as, for example, methyl acetate or ethyl acetate; sulfoxides, such as, dimethyl sulfoxide (DMSO); sulfones, such as, sulfolane; alcohols, such as, methanol, ethanol, nor isopropanol, 1,1-, iso-, sec- or tert-butanol, ethanediol, propane- 1,2-diol, ethoxy ethanol, methoxyethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether or mixtures of these.
The reactants can be reacted with each other as such, i.e. without adding a solvent or diluent. The reaction is advantageously carried out in a temperature range from approximately -80 °C to approximately +140 °C, preferably from approximately -30 °C to approximately +100 °C, in many cases in the range between ambient temperature and approximately +80 °C.
A compound of formula (I) can be converted in a manner known per se into another compound of formula (I) by replacing one or more substituents of the starting compound of formula (I) in the customary manner by (an)other substituent(s) according to the invention. Depending on the choice of the reaction conditions and starting materials which are suitable in each case, it is possible, for example, in one reaction step only to replace one substituent by another substituent according to the invention, or a plurality of substituents can be replaced by other substituents according to the invention in the same reaction step. Salts of compounds of formula (I) can be prepared in a manner known per se. Thus, for example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or with a suitable ion exchange reagent. A salt is chosen depending on its tolerances for compound's use, such as agricultural or physiological tolerance. Salts of compounds of formula (I) can be converted in the customary manner into the free compounds of formula (I), acid addition salts, for example, by treatment with a suitable basic compound or with a suitable ion exchanger reagent and salts with bases, for example, by treatment with a suitable acid or with a suitable ion exchange reagent. Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I), acid addition salts, for example, into other acid addition salts, for example by treatment of a salt of inorganic acid such as hydrochloride with a suitable metal salt such as a sodium, barium or silver, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt which forms, for example silver chloride, is insoluble and thus precipitates from the reaction mixture.
The compounds of the present invention as defined by general formula (I) and/or in table 1 may be prepared, in known manner, in a variety of ways as described in schemes 1.
The invention is now illustrated in further details by the following examples, without imposing any limitation thereto.
CHEMISTRY EXAMPLES:
Scheme 1:
Figure imgf000066_0001
General Procedure: 1
To a stirred solution of compound 1 in a solvent, base was added at 0 °C. The reaction mixture was allowed to stir at 25 °C. To this reaction mixture, carbon disulfide was added at 0 °C and allowed to stir at 25 °C. Substituted dihalo compound 2 was added to the reaction mixture and allowed to stir at 25 °C. After completion of the reaction, water was added to the reaction mixture and product was extracted with an organic solvent. The combined organic phases were washed with brine, dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography to obtain title compound-I.
General Procedure: 2
To a stirred solution of compound 1 in a solvent, base was added at 0 °C. The reaction mixture was allowed to stir at 25 °C. To this reaction mixture, carbon disulfide was added at 0 °C and allowed to stir at 25 °C. Substituted dihalo compound 2 was added to the reaction mixture and allowed to stir at 25 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain title compound-I.
Example 1: 2-(Cyano(lH-imidazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred solution of 2-(lH-imidazol-l-yl)acetonitrile (400 mg, 3.73 mmol) in dimethylsulfoxide (5 mL), potassium hydroxide (461 mg, 8.22 mmol) was added at 0 °C and stirred for 30 min at 25 °C. To this reaction mixture, carbon disulfide (0.29 mL, 4.85 mmol) was added and stirred for another 15 min. 5,6-Dichloropyrazine-2,3-dicarbonitrile (743 mg, 3.73 mmol) was added portion- wise to the reaction mixture and allowed to stir for 2 h at 25 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 40% ethyl acetate in hexane) to obtain 2-(cyano(lH-imidazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (350 mg, 1.31 mmol, 30% yield).
Example 2: 2-(l-Cyano-2-(4-fluorophenyl)-2-oxoethylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred suspension of sodium hydride (60% in mineral oil, 270 mg, 6.74 mmol) in tetrahydrofuran (10 mL), a solution of 4-fluorobenzoylacetonitrile (500 mg, 3.06 mmol) in L',L - dimethylformamide (5 mL) was added and stirred for 2 h at 0 °C. To this reaction mixture, carbon disulfide (0.20 mL, 3.37 mmol) was added and allowed to stir for 2 h at 25 °C. 5, 6- Dichloropyrazine-2,3-dicarbonitrile (610 mg, 3.06 mmol) was added portion-wise to the reaction mixture and allowed to stir for 2 h at 25 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (100 mL). Ethyl acetate layer was washed with brine (100 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 30% ethyl acetate in hexane) to obtain 2-(l-cyano-2- (4-fluorophenyl)-2-oxoethylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (130 mg, 0.36 mmol, 12% yield).
Example 3: Methyl-2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate:
To a stirred solution of 5,6-dichloropyrazine-2,3-dicarbonitrile (500 mg, 2.51 mmol) in dimethylsulfoxide (10 mL), potassium 2-cyano-3-methoxy-3-oxoprop-l-ene-l,l-bis(thiolate) (632 mg, 2.51 mmol) was added at 0 °C. The reaction mixture was allowed to stir at 25 °C for 16 h. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain methyl-2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate (315 mg, 1.04 mmol, 42% yield).
Example 4: 2-(3-Methyl-5-oxoisoxazol-4(5H)-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred solution of 3-methylisoxazol-5(4H)-one (300 mg, 3.03 mmol) in dimethylsulfoxide (10 mL), potassium hydroxide (374 mg, 6.66 mmol) and carbon disulfide (0.22 mL, 3.63 mmol) were added successively at 0 °C. The reaction mixture was allowed to stir at 25 °C for 1 h. To this reaction mixture, 5,6-dichloropyrazine-2,3-dicarbonitrile (602 mg, 3.03 mmol) was added and stirred for 16 h at 25 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2-(3-methyl-5-oxoisoxazol-4(5H)-ylidene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (270 mg, 0.9 mmol, 30% yield).
Example 5: 2-(l,3-Dimethyl-5-oxo-l,5-dihydro-4H-pyrazol-4-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile:
To a stirred solution of 2,5-dimethyl-2,4-dihydro-3H-pyrazol-3-one (300 mg, 2.68 mmol) in dimethylsulfoxide (8 mL), potassium hydroxide (330 mg, 5.89 mmol) and carbon disulfide (0.19 mL, 3.21 mmol) were added portion-wise at 0 °C. The reaction mixture was allowed to stir at 25 °C for 1 h. 5,6-Dichloropyrazine-2,3-dicarbonitrile (532 mg, 2.68 mmol) was added and the reaction mixture was stirred for 16 h at 25 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2-(l,3-dimethyl-5-oxo- l,5-dihydro-4H-pyrazol-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (220 mg, 0.7 mmol, 26% yield).
Example 6: 2-(Cyano(m-tolyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile: To a stirred suspension of sodium hydride (60% in mineral oil, 335 mg, 8.39 mmol) in tetrahydrofuran (10 mL), a solution of 2-(m-tolyl)acetonitrile (500 mg, 3.81 mmol) in L',L - dimethylformamide (5 mL) was added and stirred for 2 h at 0 °C. To this reaction mixture, carbon disulfide (0.25 mL, 4.19 mmol) was added and allowed to stir for 2 h at 25 °C. 5,6- Dichloropyrazine-2,3-dicarbonitrile (758 mg, 3.81 mmol) was added portion- wise to the reaction mixture and allowed to stir for 2 h at 25 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (100 mL). Ethyl acetate layer was washed with brine (100 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 10% ethyl acetate in hexane) to obtain 2-(cyano(m- tolyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (270 mg, 0.81 mmol, 21% yield).
Example 7: 2-(3-Methyl-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred solution of 3-methylthiazolidine-2,4-dione (400 mg, 3.05 mmol) in L',L - dimethylformamide (10 mL), potassium hydroxide (376 mg, 6.71 mmol) and carbon disulfide (0.22 mL, 3.66 mmol) were added successively at 0 °C. The reaction mixture was allowed to stir at 25 °C for 1 h. 5,6-Dichloropyrazine-2,3-dicarbonitrile (607 mg, 3.05 mmol) was added and the reaction mixture was stirred for 16 h at 25 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2 -(3 -methyl-2, 4- dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (265 mg, 0.79 mmol, 26% yield).
Example 8: 2-(l,3-Dimethyl-2,5-dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred solution of l,3-dimethylimidazolidine-2,4-dione (200 mg, 1.56 mmol) in dimethylsulfoxide (6 mL), potassium hydroxide (193 mg, 3.43 mmol) and carbon disulfide (0.11 mL, 1.87 mmol) were added portion-wise at 0 °C. The reaction mixture was allowed to stir at 25 °C for lh. 5,6-Dichloropyrazine-2,3-dicarbonitrile (311 mg, 1.56 mmol) was added and the reaction mixture was stirred for 16 h at 25 °C. After completion of the reaction water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2-(l,3-dimethyl-2,5- dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (350 mg, 1.06 mmol, 68% yield). Example 9: 2-(5-Methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2- ylidene)malononitrile:
To a stirred solution of 3,4-dichloro-l-methyl-lH-pyrrole-2,5-dione (0.5 g, 2.78 mmol) in L',L - dimethylformamide (2.5 mL), a solution of potassium 2,2-dicyanoethene-l,l-bis(thiolate) (0.67 g, 3.06 mmol) in water (2.5 mL) was added at 0 °C and the reaction mixture was stirred for 16 h at 25 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5- c]pyrrol-2-ylidene)malononitrile (518 mg, 2.08 mmol, 75% yield).
Example 10: 2-(Cyano(thiazol-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile:
To a stirred suspension of sodium hydride (60% in mineral oil, 283 mg, 7.09 mmol) in tetrahydrofuran (10 mL), a solution of 2-(thiazol-2-yl) acetonitrile (400 mg, 3.22 mmol) in L',L - dimethylformamide (5 mL) was added and stirred for 1 h at 0 °C. To this reaction mixture, carbon disulfide (0.21 mL, 3.54 mmol) was added and stirred for 1 h at 0 °C. 5,6-Dichloropyrazine-2,3- dicarbonitrile (641 mg, 3.22 mmol) was added and the reaction mixture was stirred for 1 h at 0 °C. After completion of the reaction, water was added to the reaction mixture. The precipitated solid was collected by filtration to obtain 2-(cyano(thiazol-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile (450 mg, 1.38 mmol, 43% yield).
Example 11: 2-(Cyano((4-fluorophenyl)sulfonyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred solution of 2-((4-fluorophenyl)sulfonyl)acetonitrile (0.170 g, 0.85 mmol) in L', U- dimethylformamide (3.0 mL), sodium hydride (60% in mineral oil, 68 mg, 1.79 mmol) and carbon disulphide (0.06 mL, 1.02 mmol) were added successively and stirred for 10 min at 0 °C. To this reaction mixture, 5,6-dichloropyrazine-2,3-dicarbonitrile (0.17 g, 0.85 mmol) was added portion-wise and stirred for 1 h at 0 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 30% ethyl acetate in hexane) to obtain 2-(cyano((4- fluorophenyl)sulfonyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (200 mg, 0.5 mmol, 58% yield).
Example 12: 2-((6-Chloropyridazin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile: To a stirred solution of 2-(6-chloropyridazin-3-yl)acetonitrile (0.2 g, 1.30 mmol) in L',L - dimethylformamide (4.0 mL), sodium hydride (60% in mineral oil, 0.11 g, 2.73 mmol) and carbon disulfide (0.1 mL, 1.56 mmol) were added successively and stirred for 10 min at 0 °C. To this reaction mixture, 5,6-dichloropyrazine-2,3-dicarbonitrile (0.26 g, 1.30 mmol) was added portion-wise and stirred for 1 h at 0 °C. Water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 30% ethyl acetate in hexane) to obtain 2-((6-chloropyridazin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile (100 mg, 0.28 mmol, 22% yield).
Example 13: 2-((5-Chloropyrimidin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile:
To a stirred suspension of sodium hydride (60% in mineral oil, 229 mg, 5.73 mmol) in tetrahydrofuran (10 mL), a solution of 2-(5-chloropyrimidin-2-yl)acetonitrile (400 mg, 2.60 mmol) in \, \ -d i me t hv 1 fo rma m i dc (5 mL) was added and stirred for 1 h at 0 °C. To this reaction mixture, carbon disulfide (0.17 mL, 2.87 mmol) was added and stirred for 1 h at 0 °C. 5,6-Dichloropyrazine- 2,3-dicarbonitrile (518 mg, 2.60 mmol) was added portion-wise to the reaction mixture and stirred for 1 h at 0 °C. Water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain crude product. The crude product was then purified by column chromatography on silica gel (eluent-hexane to 30% ethyl acetate in hexane) to obtain 2-((5-chloropyrimidin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile (250 mg, 0.70 mmol, 27% yield).
Example 14: 2-(Cyano(pyrazin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile:
To a stirred suspension of sodium hydride (60% in mineral oil, 185 mg, 4.62 mmol) in tetrahydrofuran (10 mL), a solution of 2-(pyrazin-2-yl)acetonitrile (250 mg, 2.10 mmol) in L',L - dimethylformamide (5 mL) was added and stirred for 1 h at 0 °C. To this reaction mixture, carbon disulfide (0.14 mL, 2.31 mmol) was added and stirred for lh at 0 °C. 5,6-Dichloropyrazine-2,3- dicarbonitrile (418 mg, 2.10 mmol) was added portion-wise to the reaction mixture and stirred for 1 h at 0 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain crude product. The crude product was then purified by column chromatography on silica gel (eluent- hexane to 30% ethyl acetate in hexane) to obtain 2-(cyano(pyrazin-2-yl)methylene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile (110 mg, 0.34 mmol, 16% yield).
Example 15: 2-Cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate:
To a stirred suspension of sodium hydride (60% in mineral oil, 191 mg, 4.78 mmol) in tetrahydrofuran (10 mL), a solution of phenyl 2-cyanoacetate (350 mg, 2.17 mmol) in L',L - dimethylformamide (5 mL) was added and stirred for 2 h at 0 °C. To this reaction mixture, carbon disulfide (0.14 mL, 2.39 mmol) was added and stirred for 2 h at 25 °C. 5,6-Dichloropyrazine-2,3- dicarbonitrile (432 mg, 2.17 mmol) was added portion-wise to the reaction mixture and stirred for 1 h at 0 °C. After completion of the reaction, water was added to the reaction mixture and the product was extracted twice with ethyl acetate (50 mL). Ethyl acetate layer was washed with brine (50 mL), dried over anhydrous sodium sulphate, filtered and evaporated under reduced pressure to obtain a crude product. The crude product was then purified by column chromatography on silica gel (eluent- hexane to 30% ethyl acetate in hexane) to obtain phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate (300 mg, 0.83 mmol, 38% yield).
The following table- 1 illustrates in a non-limiting manner examples of compounds according to the invention. In the following examples, M+l (or M-l) means the molecular ion peak, plus or minus 1 a.m.u. (atomic mass unit) respectively, as observed in mass spectroscopy ¾-NMR data of selected examples are written in the form of 'H-NMR-pcak lists. To each signal peaks the d-value in ppm and the no of proton in round brackets are listed.
For calibrating chemical shift for H spectra, we used tetramethylsilane and/or the chemical shift of the respective solvent, especially in the case of spectra measured in DMSO. Therefore in NMR peak lists, tetramethylsilane peak can occur, but not necessarily.
Table 1: NMR and LCMS data of compounds of formula (I)
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
* Compound names generated using Chemdraw Professional 17.1
As described herein the compounds of general formula (I) shown fungicidal activity which is exerted with respect to numerous phytopathogenic fungi which attack on important agricultural crops. Compounds of the present invention were assessed for biological activity against one or more of the following pathogens: Biological Test Examples for fungal pathogens
Example 1: Pyricularia oryzae (Rice blast):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into Petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 6 10 12 13 14 18 25
35 66 68 70 73 74 77 78 79 81 82 83 84 85 87 90 91 92 94 98 99 100 107 111 112 113 116 117 119 122 130 131 132 133 134 137 138 140 143 145 146 147 149 150 151 152 153 154 155 157 158 164 165 173 177 180 182 189 190 202 203 204 206 208 209 210 214 215 221 222 225 226
227 228 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 2: Rhizoctonia solani (Rice sheath blight/Potato black scurf):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into Petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 14 18 25 39
44 45 75 82 83 85 87 92 94 107 112 117
119 125 130 131 134 138 146 147 152 153 154 173
176 177 189 206 207 208 209 222 225 227 228 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 3: Botrytis cinerea (Gray mold):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into Petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 22 °C temperature and 90% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 12 14 18 25
65 67 68 70 73 74 75 77 79 81 82 85
87 91 92 94 96 98 107 108 111 113 117 119
130 131 154 177 189 203 206 207 208 209 214 215
221 223 225 226 228 at 300 ppm gave more than 70% in these tests when compared to the untreated check which showed extensive disease development.
Example 4: Alternaria solani (early blight of tomato/potato):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into Petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 13 14 18 20
25 28 35 36 39 41 44 45 46 47 63 66
73 74 75 77 79 81 82 83 85 87 91 92
93 94 95 98 101 102 103 107 108 109 111 112
113 115 116 117 118 119 122 125 127 128 130 131
134 136 137 138 140 141 142 143 145 146 147 148
149 151 152 153 154 155 156 158 161 162 166 169
170 171 172 173 174 175 176 177 178 180 181 189
202 203 204 206 208 209 210 221 222 226 228 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 5: Colletotrichum capsid (anthracnose):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Potato Dextrose Agar medium just prior to dispensing it into Petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 12 13 18 25
44 45 46 47 48 53 54 55 75 78 79 81
82 83 85 86 87 91 92 93 94 98 102 103
107 108 109 110 111 112 113 116 117 118 119 122 125 130 131 133 134 137 138 140 142 143 145 146 147 148 149 151 152 153 154 155 156 158 172 173 175 176 177 180 182 188 189 193 197 198 202 203 204 206 207 208 209 210 215 221 222 223 224 225 226 227 228 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 6: Septoria ly coper sid (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 compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 70% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 18 25 35 44
45 47 48 53 54 55 56 57 66 73 74 111
113 117 119 125 130 131 132 133 134 140 143 146
147 154 177 189 204 206 208 209 221 225 228 at 300 ppm gave more than 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 7: Fusarium culmorum (Foot rot of cereals):
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 compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with 5 mm size mycelial disc taken form periphery of actively growing virulent culture plate. Plates were incubated in growth chambers at 25 °C temperature and 60% relative humidity for seven days and radial growth was measured. Compounds 6 10 11 18 25 35 44
45 47 48 57 66 75 79 82 83 189 204 206
208 209 225 228 at 300 ppm gave 70% control in these tests when compared to the untreated check which showed extensive disease development.
Example 8: Phytophthora infestans (Late blight of potato & tomato):
Compounds were dissolved in 0.3% dimethyl sulfoxide and then added to Rye Agar medium just prior to dispensing it into petri dishes. 5 mL medium with compound in the desired concentration was dispensed into 60 mm sterile petri-plates. After solidification each plate was seeded with a 5 mm size mycelial disc taken from the periphery of actively growing virulent culture plates. Plates were incubated in growth chambers at 18 °C temperature and 95% relative humidity for seven days and radial growth was measured. Compounds 6 8 10 15 16 17 21 22
23 24 25 33 41 43 71 74 75 90 92 96
101 104 105 106 108 109 111 112 113 114 115 117
118 119 120 121 122 125 129 130 131 132 133 134
135 135 136 137 138 139 141 142 144 150 151 152
153 154 156 157 158 159 160 161 162 164 165 168
169 172 173 174 175 178 180 187 188 190 191 192
193 195 196 197 199 200 201 202 203 204 205 206
207 208 209 210 211 212 216 220 225 226 227 229 at 300 ppm gave 70% control in these tests when compared to the untreated check which showed extensive disease development.
Having described the invention with reference to certain preferred aspects, other aspects will become apparent to one skilled in the art from consideration of the specification. It will be apparent to those skilled in the art that many modifications, both to materials and methods, may be practiced without departing from the scope of the invention.

Claims

CLAIMS:
1. A compound of general formula (I),
Figure imgf000091_0001
wherein,
R1 and R2 are independently selected from the group consisting of cyano, nitro, Ci-G, -alkyl. C2- G, -alkenyl. G-G,-alkynyk G-G,-haloalkyk Ci-Ci-haloalkenyl, Ci-Ci-haloalkynyl, OR7, C(=0)R7, C(=0)0R7, C(=0)N(R7)2, S(0)„R7, S(0)„R7-C(=0)R7, C(=0)R7-S(0)„R7, Ci-C6- alkyl-S(0)nR7, Ci-C6-alkyl-C(=0)-R7, C(R')=N(R"), Ci-Cio-aryl and C3-Cio-heterocyclyl; wherein said aryl or heterocyclyl group is optionally substituted with one or more group selected from the group consisting of halogen, nitro, cyano, G-G, -alkyl. G-G-alkcnyl. C2-C8- alkynyl, G-G,-haloalkyk C2-Cs-haloalkenyl, Ci-Ci-alkoxy, C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, Ci-G-haloalkoxy. C2-Cs-haloalkenyloxy, C2-C8-haloalkynyloxy, Ci-G-alkylthio. C2-C8- alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-Cio-cycloalkyl, C4-Cio-cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C3-Cio-cycloalkylthio, C4- Cio-cycloalkenylthio, C3-Cio-cycloalkyl-Ci-C6-alkyl, C3-Cio-cycloalkyl-Ci-C6-alkyloxy, C3-C10- cycloalkyl-Ci-Ce-alkylthio, OR7, N(R7)2, C(=0)R7, C(=0)0R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl-C(=0)-R7, C(R')=N(R"), C7-Ci9-aralkyl, Ci-Cio aryl and C3-Cio-heterocyclyl;
R' is selected from the group consisting of hydrogen, halogen, G-G, -alkyl and G -G,- cycloalkyl;
R" is selected from the group consisting of hydrogen, N(R')2, G-G, -alkyl. G-G,-haloalkyl and C3-Cs-cycloalkyl, each group of R" is optionally substituted by one or more groups selected from the group consisting of halogen, cyano, R', OR', SR', N(R')2, Si(R')3, COOR', CON(R')2 and C^-G 2-aryl which is optionally substituted by one or more group R';
R7 is selected from the group consisting of hydrogen, G-G, -alkyl. C2-Cs-alkenyl, C2-C8- alkynyl, G-G,-haloalkyk C2-Cs-haloalkenyl, C3-Cio-cycloalkyl, C,-C m-cy cloalky l-C 1 -Ck,- alkyl, C3-Cio-halocycloalkyl, amino, mono-(Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino, C7-Ci9-aralkyl, G,-Cm aryl and C3-Cio-heterocyclyl; each group of R1, R2, R7 may optionally be substituted with one or more groups selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, G-G, -alkyl. G-G,-haloalkyl. C3-C10- cycloalkyl, Ci-Ci-alkoxy and Ci-Ci-haloalkoxy and Ci-Ci-alkyl-amino; or
R1 and R2 together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7- membered ring, which for its part is optionally substituted by one or more R5 or R5a;
R3 and R4 together with the atom to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 12- membered ring, which for its part is optionally substituted by one or more R5 or R5a; with the proviso that when R1 and R2 represent cyano simultaneously, R3 and R4 will not form a pyrazine ring;
R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, Ci-G, -alkyl. G-G- alkenyl, G-G-alkynyl, G-G-haloalkyl. G-G-haloalkenyl, G-G,-alkoxy. G-G-alkenyloxy, G- G-alkynyloxy, G-G,-haloalkoxy. C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, G-G,-alkylthio. C2-C8-alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-G0- cycloalkyl, G-Go-cycloalkenyl, G-Cio-cycloalkyloxy, G-Cio-cycloalkenyloxy, C3-G0- cycloalkylthio, G-Cio-cycloalkenylthio, G-Go-cycloalkyl-G-G-alkyl, G-Go-cycloalkyl-G-G- alkyloxy, C3-Cio-cycloalkyl-Ci-G-alkylthio, OR7, C(=0)R7, C(=0)OR7, S(0)nR7, G-G-alkyl- S(0)nR7, Ci-G-alkyl-(C=0)-R7, C(R')=N(R"), G-Ge-aralkyl, G-Cio-aryl, C3-Cio-heterocyclyl; each group of R5 may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R'')3, COOR", cyano and CON(R")2;
R5a is selected from the group consisting of hydrogen, cyano, G-G, -alkyl. G-G -alkenyl, G-G- alkynyl, G-G-haloalkyl, G-G-haloalkenyl, G-G-alkoxy, G-G-alkenyloxy, G-G-alkynyloxy, G-G-haloalkoxy, C2-G-haloalkenyloxy, G-G-haloalkynyloxy, C3-Cio-cycloalkyl, C4-G0- cycloalkenyl, G-Cio-cycloalkyloxy, G-Cio-cycloalkenyloxy, C3-Cio-cycloalkyl-Ci-G-alkyl, G- Go-cycloalkyl-G-G-alkyloxy, OR7, C(=0)R7, C(=0)0R7, S(0)„R7, G-G-alkyl-S(0)„R7, G- G-alkyl-(C=0)-R7, C(R')=N(R"), G-Ge-aralkyl, G-Go-aryl, C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2;
or
two R5 substituents together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7-membered ring, which for its part is optionally substituted by one or more R6;
R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl.
G-G-alkenyl, G-G-alkynyl, G-G-haloalkyl, G-G-haloalkenyl, G-G-haloalkynyl, G- -cycloalkyl, C(=0)R", C(=0)OR", OR'', N(R")2 and S(0)„R'';
n and m represents integers wherein n= 0-2 and m= 0-2; and/or N or S-oxides or agriculturally acceptable salts thereof.
2. The compound as claimed in claim 1, wherein
R1 and R2 are independently selected from the group consisting of cyano, G-G, -alkyl. G-G,- alkynyl, C(=0)N(R7)2, OR7, C(=0)R7, C(=0)OR7, S(0)„R7, G-G n-ary 1 and G-Go-heterocyclyl; wherein said aryl or heterocyclyl group is optionally substituted with one or more group selected from the group consisting of halogen, nitro, cyano, G-G, -alkyl. C2-Cs-alkenyl, G-G-alkynyl. G- G,-haloalkyk C2-C8-haloalkenyl, Ci-Ci-alkoxy, G-Cs-alkenyloxy, G-Cs-alkynyloxy, G-G,- haloalkoxy, C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, G-G,-alkyithio. C2-C8-alkenylthio, G- Cs-alkynylthio, G-G,-haloalkyithio. C2-C8-haloalkenylthio, G-Cio-cycloalkyl, G-Go- cycloalkenyl, G-Cio-cycloalkyloxy, G-Cio-cycloalkenyloxy, C3-Cio-cycloalkylthio, G-Go- cycloalkenylthio, G-Go-cycloalkyl-G-C6-alkyl, G-Go-cycloalkyl-G-C6-alkyloxy, G-Go- cycloalkyl-Ci-Ce-alkylthio, OR7, N(R7)2, C(=0)R7, C(=0)0R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, G-C8-alkyl-C(=0)-R7, C(R')=N(R"), G-Ge-aralkyl, G-Go aryl and G-Go-heterocyclyl;
R' is selected from the group consisting of hydrogen, halogen, G-G, -alkyl and G¾-G,- cycloalkyl;
R'' is selected from the group consisting of hydrogen, NR'2, straight chain or branched chain G-G, -alkyl. G-G,-haloalkyi and Ci-G-cycloalkyk each group of R'' is optionally substituted by one or more groups selected from the group consisting of halogen, R', OR', SR', N(R'2), Si(R')3, COOR', cyano, CON(R')2 and G^-G 2-aryl which is optionally substituted by one or more group R';
R7 is selected from the group consisting of hydrogen, G-G, -alkyl. C2-Cs-alkenyl, G-Cs-alkynyl, G-G,-haloalkyk C2-C8-haloalkenyl, G-Cio-cycloalkyl, G-Gn-cycloalkyi-C 1 - G, -alkyl. G-C 1 r halocycloalkyl, amino, mono-(G-C6-alkyl)amino, di-(G-C6-alkyl)amino, G-Ge-aralkyl, C6-G0 aryl and G-Go-heterocyclyl; each group of R1, R2, R7 may optionally be substituted with one or more groups selected from the group consisting of hydrogen, halogen, hydroxyl, cyano, nitro, amino, G-Ci-alkyl, Ci-Ci-haloalkyl, G-Go-cycloalkyl, G-Ci-alkoxy and G-Ci-haloalkoxy and G-G, -alkyl-amino:
R3 and R4 together with the atom to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5, 6 or 10-membered heterocyclic ring, which for its part is optionally substituted by one or more R5 or R5a; with the proviso that when R1 and R2 represent cyano simultaneously, R3 and R4 will not form a pyrazine ring;
R5 is selected from the group consisting of cyano, nitro, C(=0)R7, C(=0)OR7, S(0)nR7, G-Cs- alkyl-S(0)nR7, G-C8-alkyl-C(=0)-R7 and C(R')=N(R"); each group of R5 may optionally be substituted by one or more groups selected from the group consisting of halogen, R". OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2;
R5a is selected from the group consisting of hydrogen, Ci-G, -alkyl. C2-C8-alkenyl, C2-C8-alkynyl, Ci-Ci-haloalkyl, C2-C8-haloalkenyl, Ci-Ci-alkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy, -C6- haloalkoxy, C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, C3-Cio-cycloalkyl, G-Go- cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, G-Go-cycloalkyl-G-G-alkyl, G- Go-cycloalkyl-G-G-alkyloxy, C(=0)R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl-(C=0)-R7, G-Ci9-aralkyl, G,-Gn-aryl. G-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2;
or two R5 substituents together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 5 to 6 membered ring, which for its part is optionally substituted by one or more R6;
R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-C8-alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. C2-C8-haloalkenyl, C2-C8-haloalkynyl, G- -cycloalkyl, C(=0)R'', C(=0)OR'', OR'', N(R")2 and S(0)„R'';
n and m represents integers wherein n= 0-2 and m= 0-2.
3. The compound as claimed in claim 1, wherein
R1 and R2 together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7- membered ring, which for its part is optionally substituted by one or more R5 or R5a;
R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. G-G- alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. C2-C8-haloalkenyl, G-G,-alkoxy. C2-C8-alkenyloxy, G- C8-alkynyloxy, G-G-haloalkoxy. C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, G-G,-alkylthio. C2-C8-alkenylthio, C2-C8-alkynylthio, G-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-G0- cycloalkyl, G-Cio-cycloalkenyl, G-Cio-cycloalkyloxy, G-Cio-cycloalkenyloxy, G-C10- cycloalkylthio, G-Cio-cycloalkenylthio, G-Go-cycloalkyl-G-G-alkyl, G-Go-cycloalkyl-G- G-alkyloxy, G-Go-cycloalkyl-G-G-alkylthio, OR7, C(=0)R7, C(=0)OR7, S(0)„R7, G-G- alkyl-S(0)„R7, Ci-C8-alkyl-C(=0)-R7, C(R')=N(R"), G-Gs-aralkyl, G-Go-aryl and C3-G0- heterocyclyl; each group of R5 may optionally be substituted by one or more groups selected from the group consisting of halogen, R'', OR'', SR'', N(R")2, Si(R'')3, COOR'', cyano and CON(R")2; R5a is selected from the group consisting of hydrogen, Ci-G, -alkyl. C2-C8-alkenyl, C2-C8-alkynyl, G-G-haloalkyl. C2-C8-haloalkenyl, G-G,-alkoxy. C2-C8-alkenyloxy, C2-C8-alkynyloxy, C i -G,- haloalkoxy, C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, C3-Cio-cycloalkyl, C4-C10- cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C 3 - C m -eye 1 o a 1 kyl - C 1 - G, - a 1 k 1. C3- Cio-cycloalkyl-Ci-Ce-alkyloxy, C(=0)R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl-(C=0)-R7, G-G -aralkyl. G^-Cm-aryl. C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR", SR", N(R")2, Si(R")3, COOR", cyano and CON(R")2;
or two R5 substituents together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), S(0)m and Si(R')2, may form a 3- to 7-membered ring, which for its part is optionally substituted by one or more R6;
R6 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl.
C2-C8-alkenyl, C2-C8-alkynyl, G-G,-haloalkyl. C2-C8-haloalkenyl, C2-C8-haloalkynyl, C3- Ci -cycloalkyl, C(=0)R", C(=0)0R", OR", N(R")2 and S(0)„R";
n and m represents integers wherein n= 0-2 and m= 0-2.
4. The compound as claimed in claim 1, wherein
R1 and R2 together with the atoms to which they are attached or together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), C(=S), may form a 5-membered ring selected from the group consisting of
Figure imgf000095_0001
R3 and R4 together with the atoms to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5, 6 or 10 membered ring selected from the group consisting of
Figure imgf000096_0001
R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-C8- alkenyl, C2-Cs-alkynyl, Ci-G,-haloalkyl. Ci-Ci-alkoxy, C 1 - Cr, -a 1 ky 11 h i o . C3-Cio-cycloalkyl, C3- Cio-cycloalkyl-Ci-Ce-alkyl, OR7, C(=0)0R7, Ci-C8-alkyl-(C=0)-R7, C7-Ci9-aralkyl, C6-Cio-aryl, C3-Cio-heterocyclyl; said aryl or heterocyclyl group may optionally be substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, Ci-Ci -alkyl and C 1 -G,- alkoxy;
R5a is selected from the group consisting of hydrogen, G-G, -alkyl. C2-Cs-alkenyl, G-G-alkynyl. G-G-haloalkyl. C2-Cs-haloalkenyl, G-G,-alkoxy. C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, C 1 -G,- haloalkoxy, C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, C3-Cio-cycloalkyl, C4-C10- cycloalkenyl, C3-Cio-cycloalkyloxy, C4-Cio-cycloalkenyloxy, C 3 - C m -eye 1 o a 1 kyl - C 1 -Cr.-al k 1. C3- Cio-cycloalkyl-Ci-Ce-alkyloxy, C(=0)R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, Ci-C8-alkyl-(C=0)-R7, C7-Cis-aralkyl, G, -Go-aryl. C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR", SR", N(R")2, Si(R")3, COOR", cyano and CON(R")2;
R7 is selected from the consisting of hydrogen, G-G, -alkyl. G-G,-haloalkyk C3-Cio-cycloalkyl, C3-Cio-halocycloalkyl, amino, mono-(Ci-C6-alkyl)amino, di-(Ci-C6-alkyl)amino, C7-Cis-aralkyl, Ci-Cio aryl and C3-Cio-heterocyclyl;
each group of R1 , R2 and R7 are may optionally be substituted with one or more groups selected from the group consisting of halogen, hydroxyl, cyano, nitro, amino, G-G, -alkyl. C 1 -G,- haloalkyl, G-G,-alkox and Ci-G,-haloalko\y.
5. The compound as claimed in claim 1, wherein
R1 is selected from the group consisting of cyano, nitro, G-G, -alkyl alkynyl, C(=0)N(R7)2, C(=0)R7, C(=0)OR7, S(0)„R7, S(0)„R7-C(=0)R7, C(=0)R7-S(0)„R7 and C(R')=N(R");
R2 is selected from the group consisting of S(0)o-iR7, G,-G n-ary 1 and C3-Cio-heterocyclyl; said G,- Cio-aryl, C3-Cio-heterocyclyl is optionally substituted with at least one group selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-Cs-alkenyl, C2-Cs-alkynyl, G-G,-haloalkyl. C2-Cs-haloalkenyl, Ci-G,-alkoxy. C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, C 1 -G,- haloalkoxy, C2-C8-haloalkenyloxy, C2-C8-haloalkynyloxy, Ci-Cn-alkylthio. C2-C8-alkenylthio, C2-C8-alkynylthio, Ci-G,-haloalkylthio. C2-C8-haloalkenylthio, C3-Cio-cycloalkyl, G-C n cy cl oalkcnyl. OR7, C(=0)0R7 and S(0)nR7; R3 and R4 together with the atoms to which they are attached together with further atoms selected from the group consisting of C, N, O, S and optionally including 1 to 3 ring members selected from the group consisting of C(=0), may form a 5, 6 or 10 membered ring selected from the group consisting of
Figure imgf000097_0001
R5 is selected from the group consisting of hydrogen, halogen, cyano, nitro, G-G, -alkyl. C2-C8- alkenyl, C2-Cs-alkynyl, G-G,-haloalkyl. Ci-Ci-alkoxy, G-G, -alkyl thio. G-Cio-cycloalkyl, C3-G0- cycloalkyl-G-C6-alkyl, OR7, C(=0)0R7, Ci-C8-alkyl-C(=0)-R7, C7-Ci9-aralkyl, Ci-Go-aryl and C3-Cio-heterocyclyl; said aryl or heterocyclyl group may optionally be substituted by one or more groups selected from the group consisting of halogen, cyano, nitro, G-G, -alkyl and C 1 -G,- alkoxy;
R5a is selected from the group consisting of hydrogen, G-G, -alkyl. C2-Cs-alkenyl, C2-Cs-alkynyl, G-G,-haloalkyl. C2-Cs-haloalkenyl, G-G,-alko\y. C2-Cs-alkenyloxy, C2-Cs-alkynyloxy, C 1 -G,- haloalkoxy, C2-Cs-haloalkenyloxy, C2-C8-haloalkynyloxy, G-Go-cycloalkyl, G-Go- cycloalkenyl, G-Cio-cycloalkyloxy, G-Cio-cycloalkenyloxy, C ¾ - C m -eye 1 o a 1 kyl - C 1 - G, - a 1 k 1. G- Cio-cycloalkyl-Ci-Ce-alkyloxy, C(=0)R7, S(0)„R7, Ci-C8-alkyl-S(0)„R7, G-C8-alkyl-(C=0)-R7, CT-Ci- -aralkyl. G,-Cm-aryl. C3-Cio-heterocyclyl; each group of R5a may optionally be substituted by one or more groups selected from the group consisting of halogen, R", OR", SR", N(R")2, Si(R")3, COOR", cyano and CON(R")2;
n represents integer wherein n= 0-2.
6. The compound as claimed in claim 1, wherein said compound of general formula (I) is selected from 2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, 2- (4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malononitrile, diethyl 2-(5-methyl-
4.6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, diethyl 2-(4,6-dioxo-5,6- dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, ethyl 2-cyano-2-(5-methyl-4,6-dioxo-5,6- dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, ethyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, methyl 2-cyano-2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-
[1.3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- methylthiazolidine-2,4-dione, 2-(cyano(lH-imidazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-
5.6-dicarbonitrile, 2-([l,3]dithiolo[4,5-b]pyrido[2,3-e]pyrazin-2-ylidene)malononitrile, 2-
([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(lH-imidazol-l-yl)acetonitrile, ethyl 2-cyano-2-(4,6-dioxo-
5.6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, 2-(3-methyl-2,4-dioxothiazolidin-5- ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- methyl-2-thioxothiazolidin-4-one, methyl 2-([l,3]dithiolo[4,5-b]quinoxalin-2-ylidene)-2- cyanoacetate, 2-(2,4-dioxo-3-(prop-2-yn-l-yl)thiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-(prop-2-yn-l-yl)thiazolidine-2,4-dione, methyl 2-cyano-2-(4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetate, methyl 2- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-cyanoacetate, diethyl 2-(5-(4-fluorophenyl)-4,6-dioxo-5,6- dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)malonate, diethyl 2-([l,3]dithiolo[4,5-b]quinoxalin- 2-ylidene)malonate, 2-(3-allyl-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(2,4-dioxo-3-propylthiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-benzyl-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3 -(cyclopropylmethyl)-2,4-dioxothiazolidin-5 -ylidene)-[ 1 ,3] dithiolo [4,5-b]pyrazine-
5.6-dicarbonitrile, 2-(3-ethyl-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-allylthiazolidine-2,4-dione, 5-
([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-propylthiazolidine-2,4-dione, 5-([l,3]dithiolo[4,5-b]pyrazin- 2-ylidene)-3-benzylthiazolidine-2,4-dione, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-
(cyclopropylmethyl)thiazolidine-2,4-dione, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- ethylthiazolidine-2,4-dione, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetamide, 2-cyano-2-(5-methyl-4,6-dioxo-5,6-dihydro-4H-[l,3]dithiolo[4,5-c]pyrrol-2-ylidene)acetamide, 2-(3- allyl-4-oxo-2-thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(4-oxo-3- propyl-2-thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-benzyl-4- oxo-2 -thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-cyclopropyl- 4-oxo-2-thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(thiophen-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(lH- pyrazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(phenyl)methylene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((4-chlorophenyl)(cyano)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-fluorophenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-fluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-((6-chloropyridin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-allyl-2-thioxothiazolidin-4-one, 5-
([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-propyl-2-thioxothiazolidin-4-one, 5-([l,3]dithiolo[4,5- b]pyrazin-2-ylidene)-3-benzyl-2-thioxothiazolidin-4-one, 5-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3- cyclopropyl-2-thioxothiazolidin-4-one, 2-( l,3-dimethyl-5-oxo-l,5-dihydro-4H-pyrazol-4-ylidene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(l-methyl-5-oxo-3-(trifluoromethyl)-l, 5-dihydro- 4H-pyrazol-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((4-chloro-2- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloro-2- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(pyridin-3- yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-(trifluoromethyl)-lH- pyrazol-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-(prop-2-yn-l- yloxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-
(difluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,6- difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-chloro-4- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-fluoro-4- methylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-fluoro-3-
(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- (trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5- methyl-2-oxopyridin-l(2H)-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(l,3- dimethyl-2,5-dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3- methyl-2,5-dioxo-l-(prop-2-yn-l-yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-methyl-4-oxo-2-thioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(2,5-dioxo-l,3-di(prop-2-yn-l-yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(3-allyl-2,5-dioxo-l-(prop-2-yn-l-yl)imidazolidin-4-ylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-(cyclopropylmethyl)-2,5-dioxo-l-(prop-2-yn-l- yl)imidazolidin-4-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2-oxo-3-
(trifluoromethyl)pyridin-l(2H)-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(thiazol-2-ylthio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(3-(trifluoromethyl)phenyl)acetate, 2-((2- chlorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(m- tolyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5-fluoro-2- methylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-(3,4-difluorophenyl)acetate, 2-(l-cyanoethylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(l-cyano-2-(4-fluorophenyl)-2-oxoethylidene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(methylthio)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(2-(4-chlorophenyl)-l-cyano-2-oxoethylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4,5-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-ethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, methyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-(l,3- dimethyl-5 -oxo -2-thioxoimidazolidin-4-y lidene)- [ 1,3] dithiolo [4, 5 -b] pyrazine-5 ,6 -dicarbonitrile, 2-(3 - (3-methylbut-2-en-l-yl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-(2-methoxyethyl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(3-cyclopropyl-5-oxoisoxazol-4(5H)-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(3-methyl-5-oxoisoxazol-4(5H)-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(2,5-dimethylphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3,4-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(2,3- difluorophenyl)acetamide, 2-(cyano(3,4,5-trimethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(3-
(trifluoromethyl)phenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N- (4-(trifluoromethyl)phenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)- N-(4-fluorophenyl)acetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N- methylacetamide, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-N-(5-fluoro-2- methylphenyl)acetamide, 2-(cyano(2-fluoro-4-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-(trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(3-allyl-l-methyl-2,5-dioxoimidazolidin-4-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, tert-butyl 5-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2,4- dioxothiazolidine-3-carboxylate, 2-(2-(methylthio)-4-oxothiazol-5(4H)-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,3,6-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,4,6-trifluorophenyl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2-fluoro-6-(trifluoromethyl)phenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3,5-bis(trifluoromethyl)phenyl)(cyano)methylene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,4,5-trifluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,3,4-trifluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,3-difluorophenyl)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)-N,N-dimethylacetamide, 2-(l-cyano-2-morpholino-2-oxoethylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,5-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(cyano(2,5-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(3-fluoro-5-(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine- 5,6-dicarbonitrile, 2-(cyano(2,4-difluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-2-cyano-N,N-dimethylacetamide, 2- ([l,3]dithiolo[4,5-b]pyrazin-2-ylidene)-3-morpholino-3-oxopropanenitrile, propyl 2-cyano-2-(5,6- dicyano-[ l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, isopropyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, benzyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, allyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 2-(3-(2-morpholino-2-oxoethyl)-2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(2,4-dioxo-3-(2-oxo-2-thiomorpholinoethyl)thiazolidin-5-ylidene)- [l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, tert-butyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, 2-(3-(4-methoxybenzyl)-2,4-dioxothiazolidin-5-ylidene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-methoxyethyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, prop-2-yn-l-yl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, cyclopropylmethyl 2-cyano-2-(5,6-dicyano- [l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, p-tolyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, 4-methoxyphenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3-methylbut-2-en-l-yl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, o-tolyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2- fluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, m-tolyl 2-cyano- 2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-(trifluoromethyl)phenyl 2-cyano-2- (5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, phenyl 2-cyano-2-(5,6-dicyano- [l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-chlorophenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-(trifluoromethoxy)phenyl 2-cyano-2-(5,6-dicyano- [l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-chloroallyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5- b]pyrazin-2-ylidene)acetate, isopentyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3,4-difluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2- ylidene)acetate, 3-chlorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-fluorophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3- methoxyphenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-
(trifluoromethoxy)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3- (dimethylamino)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4- bromophenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((2-chloro-6- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-
(trifluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- fluorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2-
(trifluoromethyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3- chlorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- methoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4- dimethoxyphenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(3-methyl-2,4- dioxooxazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 4-(dimethylamino)phenyl 2-cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-bromophenyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3 -fluorophenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-(trifluoromethyl)benzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-fluoro-4-(trifluoromethyl)benzyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-chloro-2-fluoro-5-(trifluoromethyl)benzyl 2- cyano-2-(5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,4-trifluorobenzyl 2-cyano-2- (5,6-dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,5-trifluorobenzyl 2-cyano-2-(5,6- dicyano-[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,4,5-trifluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,3,6-trifluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2,6-difluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3,5-difluorobenzyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((3-bromophenyl)(cyano)methylene)-
[1.3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(3-methoxyphenyl)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(4-methoxyphenyl)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-((2-bromophenyl)(cyano)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-((4-bromophenyl)(cyano)methylene)-
[1,3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(perfluorophenyl)methylene)-
[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 4-(trifluoromethoxy)benzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3 -chloro-5-fluorobenzyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 3-ethoxyphenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-(tert-butyl)phenyl 2-cyano-2-(5,6-dicyano-
[l,3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 4-ethoxyphenyl 2-cyano-2-(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)acetate, 2-((4-chlorothiazol-2-yl)(cyano)methylene)-
[1.3] dithiolo [4,5 -b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(thiazol-2-yl)methylene)-[l,3]dithiolo[4,5- b]pyrazine-5,6-dicarbonitrile, 2-(2,4-dioxothiazolidin-5-ylidene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(naphthalen-l-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3,4- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2- cyanophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-cyano-l-methyl- 5-(methylthio)-lH-pyrazol-3-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((6- chloropyridazin-3-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(phenylthio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano((2- fluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5 ,6-dicarbonitrile, 2-(cyano(4-cyano-5- (ethylthio)-l-methyl-lH-pyrazol-3-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano((2,4-difluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(2-(methylthio)pyrimidin-4-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano((4-fluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano((2,6-difluorophenyl)thio)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(6-methylpyridazin-3-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(3,5-dichloropyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3- chloro-5-(trifluoromethyl)pyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6- dicarbonitrile, 2-(cyano(2-nitrophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(2-(difluoromethoxy)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano((4-fluorophenyl)sulfonyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-
(cyano(5-(trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(4-cyanophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,4- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((2-chloro-5- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-chloro-2,6- difluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-chloro-5- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(5- nitropyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloropyrimidin-2- yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((3-bromo-5-
(trifluoromethyl)pyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- ((3-chloro-5-nitropyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2- (cyano(pyrazin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5-chloropyridin- 2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(3-
(trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (trifluoromethyl)pyridin-2-yl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((4- chloropyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((5- bromopyridin-2-yl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4- (methylsulfonyl)phenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,5- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-((2-chloro-4- fluorophenyl)(cyano)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(2,6- dichlorophenyl)methylene)-[l,3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, methyl 3-(cyano(5,6- dicyano-[ l,3]dithiolo[4,5-b]pyrazin-2-ylidene)methyl)benzoate, methyl 4-(cyano(5,6-dicyano-
[1.3]dithiolo[4,5-b]pyrazin-2-ylidene)methyl)benzoate, 2-((4-(tert-butyl)phenyl)(cyano)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile, 2-(cyano(4-ethynylphenyl)methylene)-
[1.3]dithiolo[4,5-b]pyrazine-5,6-dicarbonitrile or 2-(cyano(6-(trifluoromethyl)pyridin-2- y l)methy lene)- [ 1,3] dithiolo [4, 5 -b] pyrazine-5 ,6-dicarbonitrile.
7. A composition for controlling or preventing phytopathogenic microorganisms, comprising a compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salts thereof as claimed in claim 1 and one or more inert carriers.
8. The composition as claimed in claim 7, wherein said composition may additionally comprises one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
9. The composition as claimed in claims 7 or 8, wherein the concentration of the compound of general formula (I) ranges from 10 to 90% by weight with respect to the total weight of the composition, preferably from 30 to 70% by weight with respect to the total weight of the composition.
10. A combination comprising the compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salts thereof as claimed in claim 1 and one or more active compatible compound selected from fungicides, insecticides, nematicides, acaricides, biopesticides, herbicides, plant growth regulators, antibiotics, nutrients or fertilizers.
11. Use of compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof as claimed in claim 1 or 7 or 10, for controlling or preventing agricultural crops and or horticultural crops against phytopathogenic fungi.
12. The use of the compound of general formula (I) as claimed in claim 11, wherein the agricultural crops are cereals, com, rice, soybean and other leguminous plants, fruits and fruit trees, nuts and nut trees, citrus and citrus trees, any horticultural plants, cucurbitaceae, oleaginous plants, tobacco, coffee, tea, cacao, sugar beet, sugar cane, cotton, potato, tomato, onions, peppers and other vegetables, and ornamentals.
13. A seed comprising compound of general formula (I), N-oxide or S-oxide or agriculturally acceptable salt thereof as claimed in claim 1, wherein the amount of the compound of general formula (I), or an N-oxide or S-oxide or an agriculturally acceptable salt thereof, is from 0.1 g to 10 kg per 100 kg of seed.
14. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein said compound of general formula (I), N-oxide, S-oxide, agriculturally acceptable salt, composition or combination thereof as claimed in claim 1 or 7 or 10, is applied to the plants, to parts thereof or a locus thereof.
15. A method for controlling or preventing infestation of useful plants by phytopathogenic microorganisms in agricultural crops and/or horticultural crops, wherein the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof as claimed in claim 1 or 7 or 10, is applied to the seeds of plants.
16. A method for controlling or preventing phytopathogenic microorganisms in agricultural crops and/or horticultural crops using the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof as claimed in claim 1 or 7 or 10, which comprises a step of applying an effective dosage of the compound or the composition or the combination, in amounts ranging from 50 g to 5 kg per hectare of agricultural and/or horticultural crops.
17. A method for combating phytopathogenic fungi, comprising treating plants, soil, seeds or materials to be protected with the compound of general formula (I), N-oxide, S-oxides, agriculturally acceptable salt, composition or combination thereof as claimed in claim 1 or 7 or 10.
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