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WO2010093595A1 - 2‑pyridones fongicides - Google Patents

2‑pyridones fongicides Download PDF

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Publication number
WO2010093595A1
WO2010093595A1 PCT/US2010/023548 US2010023548W WO2010093595A1 WO 2010093595 A1 WO2010093595 A1 WO 2010093595A1 US 2010023548 W US2010023548 W US 2010023548W WO 2010093595 A1 WO2010093595 A1 WO 2010093595A1
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Prior art keywords
compound
independently selected
alkyl
ring members
optionally substituted
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PCT/US2010/023548
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English (en)
Inventor
Thomas Paul Selby
Thomas Martin Stevenson
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E. I. Du Pont De Nemours And Company
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Publication of WO2010093595A1 publication Critical patent/WO2010093595A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain 2-pyridones, their //-oxides, salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formula 1 (including all geometric isomers, stereoisomers and atropisomers) //-oxides, and salts thereof:
  • Q is O or S
  • R 1 is H, cyano, hydroxy, amino, C ⁇ -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C ⁇ -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, cyclopropyl, halocyclopropyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, C 2 -C 4 alkylsulfmylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C 4 cyanoalkyl, Q-C 3 hydroxyalkyl, Q-C 3 alkoxy, Q-C 3 haloalkoxy, C ⁇ -C 3 alkylthio, C ⁇ -C 3 haloalkylthio, C 1 -C 3 alkylamino or C 2 -C
  • R 4 is H, halogen, cyano, hydroxy, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 2 alkenyl, C 2 haloalkenyl or C 2 alkynyl; each R 5 is independently halogen, cyano, hydroxy, amino, nitro, -CHO, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 6 dialkylaminocarbonyl, C 2 -C 6 alkylaminoalkoxy, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3
  • each R 7a is independently cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 haloalkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 6
  • this invention pertains to a compound of Formula 1 (including all stereoisomers such as enantiomers, diastereomers, atropisomers and geometric isomers), an iV-oxide, or a salt thereof.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising (a) a compound of Formula 1 (or an JV-oxide or salt thereof) wherein R 1 is cyano, hydroxy, amino, C 1 -C 4 alkyl,
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising (a) a mixture of a compound of Formula 1 (or an JV-oxide or salt thereof) wherein R 1 is cyano, hydroxy, amino, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, cyclopropyl, halocyclopropyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, C 2 -C 4 alkylsulf ⁇ nylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C 4 cyanoalkyl, C 1 -C 3 hydroxyalkyl, C 1 -C 3
  • This invention further relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of the invention (e.g., as a composition described herein).
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having,” “contains,” “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • 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 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.
  • 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.
  • plant includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds). Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.
  • seedling used either alone or in a combination of words means a young plant developing from the embryo of a seed"
  • the term “broadleaf ' used either alone or in words such as “broadleaf crop” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
  • alkylating agent refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom.
  • alkylating does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified, for example, for R 1 , R 3 and R 4 .
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain and branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, and the different butyl, pentyl and hexyl isomers.
  • Alkenyl includes straight-chain and branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain and branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, /-propyloxy, and the different butoxy, pentoxy and hexyloxy isomers.
  • alkylthio includes straight-chain and branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfmyl includes both enantiomers of an alkylsulf ⁇ nyl group.
  • Alkylamino includes an NH radical substituted with a straight-chain or branched alkyl group. Examples of “alkylamino” include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH. Examples of “dialkylamino” include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • dialkylaminocarbonyl examples include
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on another alkoxy moiety.
  • alkoxyalkoxy examples include CH 3 OCH 2 O, CH 3 CH 2 OCH 2 O and (CH 3 ) 2 CHOCH 2 O.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and
  • alkylsulfmylalkyl and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.
  • Alkylaminoalkyl denotes alkylamino substitution on alkyl.
  • alkylaminoalkyl include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 , CH 3 CH 2 CH 2 CH 2 NHCH 2 and CH 3 CH 2 NHCH 2 CH 2 .
  • dialkylaminoalkyl include ((CH 3 ) 2 CH) 2 NCH 2 , (CH 3 CH 2 CH 2 ) 2 NCH 2 and CH 3 CH 2 (CH 3 )NCH 2 CH 2 .
  • Alkylaminoalkoxy denotes alkylamino substitution on alkoxy. Examples of
  • alkylaminoalkoxy include CH 3 NHCH 2 CH 2 O, CH 3 NHCH 2 CH 2 CH 2 O and CH 3 CH(CH 3 )NHCH 2 CH 2 O.
  • Alkylcarbonylthio denotes a straight-chain or branched alkylcarbonyl attached to and linked through a sulfur atom.
  • alkylcarbonyloxy denotes a straight-chain or branched alkylcarbonyl bonded and linked through an oxygen atom.
  • Alkylsulfonylamino denotes an NH radical substituted with alkylsulfonyl.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 . “Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to a straight-chain or branched alkyl group.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- or 1,4-cyclohexadienyl.
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Alkylcycloalkylalkyl denotes an alkyl group substituted with alkylcycloalkyl.
  • alkylcycloalkylalkyl examples include methylcyclohexylmethyl and ethylcyclopropylmethyl.
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 6 carbon atom ring members.
  • cycloalkylcycloalkyl examples include cyclopropylcyclopropyl (such as lj'-bicyclopropyl-l-yl, 1 , l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as l,l'-bicyclohexyl-l-yl), and the different cis- and trans-cycloalkylcycloalkyl isomers, (such as (li?,25)-l,l'-bicyclopropyl-2- yl and (li?,2i?)-l,l'-bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as lj'-bicyclopropyl-l-yl, 1 , l'-bicyclopropyl-2-yl
  • Cycloalkylamino denotes an NH radical substituted with cycloalkyl.
  • Examples of “cycloalkylamino” include cyclopropylamino and cyclohexylamino.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkenyl is defined analogously to the term “haloalkyl”.
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, F 2 CHCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • haloalkylamino examples include CF 3 (CH 3 )CHNH, (CF 3 ) 2 CHNH and CH 2 ClCH 2 NH.
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • halocycloalkyl examples include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl.
  • halodialkyl either alone or in compound words such as “halodialkylamino" means at least one of the two alkyl groups is substituted with at least one halogen atom, and independently each halogenated alkyl group may be partially or fully substituted with halogen atoms which may be the same or different.
  • halodialkylamino include (BrCH 2 CH 2 ) 2 N and BrCH 2 CH 2 (ClCH 2 CH 2 )N.
  • “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 CH 2 .
  • the term “hydroxyhaloalkyl” denotes a haloalkyl group substituted with one hydroxy group and includes, for example, hexafluorohydoxypropyl.
  • “Hydroxycarbonylalkyl” denotes hydroxycarbonyl substitution on a straight-chain or branched alkyl. Examples of “hydroxycarbonylalkyl” include HOC(O)CH 2 CH(CH 3 ), HOC(O)CH 2 CH 2 and HOC(O)CH 2 .
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl. Naming of substituents in the present disclosure uses recognized terminology providing conciseness in precisely conveying to those skilled in the art the chemical structure. For sake of conciseness, locant descriptors may be omitted.
  • Cj-C The total number of carbon atoms in a substituent group is indicated by the "Cj-C;" prefix where i and j are numbers from 1 to 12.
  • C 1 -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • the number of optional substituents may be restricted by an expressed limitation.
  • the phrase “optionally substituted with up to 3 substituents independently selected from R 7 on carbon atom ring members” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • the phrase “optionally substituted with up to 5 substituents independently selected from R 7 on carbon atom ring members” means that 0, 1, 2, 3, 4 or 5 substituents can be present if the number of available connection points allows.
  • said substituents are independently selected from the group of defined substituents (e.g., (R 5 ) m wherein m is 1, 2, 3, 4 or 5 or (R v ) r in Exhibit 1 wherein r is 1, 2, 3, 4 or 5).
  • substituents e.g., (R 5 ) m wherein m is 1, 2, 3, 4 or 5 or (R v ) r in Exhibit 1 wherein r is 1, 2, 3, 4 or 5.
  • a "ring” or “ring system” as a component of Formula 1 is carbocyclic (e.g. phenyl) or heterocyclic (e.g. pyridinyl).
  • ring system denotes two or more connected rings.
  • bicyclic ring system denotes a ring system consisting of two rings sharing at least two common atoms.
  • a "fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them (e.g., a pair of R 5 substituents taken together to form a naphthalenyl ring system or a pair of R 7 and R 7a substituents taken together to form a heterocyclic ring system).
  • the term "spirocyclic ring system” denotes a ring system consisting of two rings connected at a single atom so the rings have a single atom in common.
  • aromatic indicates that each of the ring atoms of a fully unsaturated ring is essentially in the same plane and has a /?-orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with H ⁇ ckel's rule.
  • carbocyclic ring denotes a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • a carbocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring.
  • saturated carbocyclic ring refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms .
  • heterocyclic ring or “heterocycle” denote rings in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S). Typically a heterocyclic ring contains no more than 3 N atoms, no more than 2 O atoms and no more than 2 S atoms. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring. The term “fully unsaturated heterocyclic ring” includes both aromatic and nonaromatic heterocycles.
  • heterocyclic ring When a fully unsaturated heterocyclic ring satisfies H ⁇ ckel's rule, then said ring is also called a "heteroaromatic ring” or “aromatic heterocyclic ring".
  • the terms “heteroaromatic ring system” or “heteroaromatic bicyclic ring system” denote a ring system in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S) and at least one ring is aromatic. Unless otherwise indicated, heterocyclic rings and heteroaromatic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • R 2 and R 3 comprises a phenyl ring or a 6-membered heterocyclic ring
  • the ortho, meta and para positions of each ring is relative to the connection of the ring to the remainder of Formula 1.
  • R 2 and R 3 can independently be, inter alia, a phenyl ring optionally substituted with up to 5 substituents selected from a group of substituents as defined in the Summary of Invention.
  • phenyl optionally substituted with up to five substituents is the ring illustrated as U-I in Exhibit 1, wherein R v is selected from a group of substituents as defined in the Summary of the Invention for R 2 and R 3 (i.e. R 6 on the R 2 ring, and R 7 on the R 3 ring) and r is an integer from 0 to 5.
  • R 2 optional substituents include R 6 on carbon atom ring members and R 6 ⁇ on nitrogen atom ring members; and R 3 optional substituents include R 7 on carbon atom ring members and R 7a on nitrogen atom ring members).
  • substituents are optional, 0 to 5 substituents may be present, limited only by the number of available points of attachment.
  • the ring members selected from up to 2 O, up to 2 S and up to 3 N atoms are optional, provided at least one ring member is not carbon (e.g., N, O or S).
  • the nitrogen atom ring members may be oxidized as iV-oxides, because compounds relating to Formula 1 also include iV-oxide derivatives.
  • Examples of a 3-, A-, 5- or 6-membered fully unsaturated heterocyclic ring include the rings U-2 through U-29 as illustrated in Exhibit 1; and examples of a 3-, A-, 5- or 6-membered saturated or partially unsaturated heterocyclic ring include the rings G-I through G-45 as illustrated in Exhibit 2.
  • the variable R v is any substituent as defined in the Summary of the Invention for R 2 and R 3 (i.e.
  • R 2 optional substituents include R 6 on carbon atom ring members and R 6 ⁇ on nitrogen atom ring members; and R 3 optional substituents include R 7 on carbon atom ring members and R 7a on nitrogen atom ring members) and r is an integer from 0 to 5, limited by the number of available positions on each depicted ring.
  • R v groups are shown in the structures U-2 through U-29 and G-I through G-45, it is noted that they do not need to be present since they are optional substituents.
  • the nitrogen atoms that require substitution to fill their valence are substituted with H or R v .
  • (R v ) r can be attached to any available carbon or nitrogen atom of the depicted ring.
  • the depicted ring can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the depicted ring by replacement of a hydrogen atom.
  • the fused ring can be a 5-, 6- or 7-membered ring including as ring members the two atoms shared with the ring to which the substituents are attached.
  • the other 3 to 5 ring members of the fused ring are provided by the pair of R 5 substituents, the pair of R 6 and/or R 6a substituents or the pair of R 7 and/or R 7a substituents taken together.
  • These other ring members can include up to 5 carbon atoms (as allowed by the ring size) and optionally up to 4 heteroatoms selected from up to 2 O, up to 2 S and up to 3 N.
  • the fused ring is optionally substituted with up to 3 substituents as noted in the Summary of the Invention.
  • Exhibit 3 provides, as illustrative examples, rings formed by a pair of adjacent R 5 , R 6 , R 6a , R 7 or R 7a substituents taken together. As these rings are fused with a ring of Formula 1, a portion of the Formula 1 ring is shown and the dashed lines represent the ring bonds of the Formula 1 ring. In certain cases, as illustrated by T-3, T-5, T-8, T-I l, T-14 and T-16, the pattern of single and double bonds between ring members in the fused ring may affect the possible patterns of single and double bonds (according to valence bond theory) in the ring it is fused to in Formula 1, but each of the ring member atoms retains sp 2 hybridized orbitals (i.e.
  • the rings depicted can be fused to any two adjacent atoms of a ring of Formula 1, and furthermore can be fused in either of the two possible orientations.
  • the optional substituents (R v ) r are independently selected from the group consisting of C 1 -C 2 alkyl, halogen, cyano, nitro and C 1 -C 2 alkoxy on carbon ring members and from the group consisting of C 1 -C 2 alkyl, cyano and C 1 -C 2 alkoxy on nitrogen ring members.
  • r is an integer from 0 to 3, limited by the number of available positions on each T-ring.
  • R v When the attachment point between (R v ) r and the T-ring is illustrated as floating, R v may be bonded to any available T-ring carbon or nitrogen atom (as applicable).
  • r is nominally an integer from 0 to 3
  • some of the rings shown in Exhibit 3 have less than 3 available positions, and for these groups r is limited to the number of available positions.
  • “r" When “r" is 0 this means the ring is unsubstituted and hydrogen atoms are present at all available positions. If r is 0 and (R v ) r is shown attached to a particular atom, then hydrogen is attached to that atom.
  • the nitrogen atoms that require substitution to fill their valence are substituted with H or R v .
  • some of the rings shown in Exhibit 3 can form tautomers, and the particular tautomer depicted is representative of all the possible tautomers.
  • a pair of R 6 or R 7 substituents may also be taken together with the ring atom to which they are attached to form a 5-, 6- or 7-membered spirocyclic ring.
  • the spirocyclic ring includes as a ring member the atom shared with the ring to which the substituents are attached.
  • the other 4 to 6 ring members of the spirocyclic ring are provided by the pair of R 6 substituents or the pair of R 7 substituents taken together.
  • Exhibit 4 provides, as illustrative examples, rings formed by a pair of R 6 or R 7 substituents being taken together.
  • the dashed lines represent bonds in the ring to which the spirocyclic ring is attached.
  • the optional substituents (R v ) r are independently selected from the group consisting of C 1 -C 2 alkyl, halogen, cyano, nitro and C 1 -C 2 alkoxy on carbon ring members and from the group consisting of C 1 -C 2 alkyl, cyano and C 1 -C 2 alkoxy on nitrogen ring members.
  • r is an integer from 0 to 3, limited by the number of available positions on each J- ring.
  • R v may be bonded to any available J-ring carbon or nitrogen atom.
  • the optional substituents (R v ) r are independently selected from the group consisting of C 1 -C 2 alkyl, halogen, cyano, nitro and C 1 -C 2 alkoxy on carbon ring members and from the group consisting of C 1 -C 2 alkyl, cyano and C 1 -C 2 alkoxy on nitrogen ring members.
  • substituents (R v ) r are independently selected from the group consisting of C 1 -C 2 alkyl, halogen, cyano, nitro and C 1 -C 2 alkoxy on carbon ring members and from the group consisting of C 1 -C 2 alkyl, cyano and C 1 -C 2 alkoxy on nitrogen ring members.
  • Compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form TV-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • salts of the compounds of Formula 1 are useful for control of plant diseases caused by fungal plant pathogens (i.e. are agriculturally suitable).
  • the salts of the compounds of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium.
  • the present invention comprises compounds selected from Formula 1 (including all geometric isomers, stereoisomers and atropisomers), iV-oxides and agriculturally suitable salts thereof.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound represented by Formula 1.
  • Preparation and isolation of a particular polymorph of a compound represented by Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes //-oxides and salts thereof, and reference to "a compound of Formula 1" includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
  • Embodiment 1 A compound of Formula 1 wherein R 1 is hydrogen.
  • Embodiment 2. A compound of Formula 1 wherein R 1 is cyano, hydroxy, amino, C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 1 -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, cyclopropyl, halocyclopropyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, C 2 -C 4 alkylsulfinylalkyl, C 2 -C 4 alkylsulfonylalkyl, C 2 -C 4 cyanoalkyl, C 1 -C 3 hydroxyalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 1 -C 3
  • Embodiment 3 A compound of Embodiment 2 wherein R 1 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 4 cyanoalkyl or C 1 -C 3 alkoxy.
  • Embodiment 4 A compound of Embodiment 3 wherein R 1 is C 1 -C 4 alkyl.
  • Embodiment 4a A compound of Embodiment 4 wherein R 1 is methyl, ethyl, or n-propyl.
  • Embodiment 5 A compound of Embodiment 4 wherein R 1 is C 1 -C 2 alkyl.
  • Embodiment 5a A compound of Embodiment 4a or 5 wherein R 1 is methyl.
  • Embodiment 6 A compound of Formula 1 or any one of Embodiments 1 through 5 wherein Q is O.
  • Embodiment 7 A compound of Formula 1 or any one of Embodiments 1 through 6 wherein each W and Y is independently CH 2 , O, S, NR 8 or a direct bond.
  • Embodiment 7a A compound of Embodiment 7 wherein each R 8 is H.
  • Embodiment 8. A compound of Embodiment 7 wherein each W and Y is independently
  • Embodiment 9 A compound of Formula 1 or any one of Embodiments 1 through 8 wherein W is a direct bond.
  • Embodiment 9a A compound of Formula 1 or any one of Embodiments 1 through 8 wherein Y is a direct bond.
  • Embodiment 10. A compound of Formula 1 or any one of Embodiments 1 through 9a wherein W and Y are each a direct bond.
  • Embodiment 12a A compound of Embodiment 12 wherein R 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 6 ; or a pyridinyl or oxadiazolyl ring, the heterocyclic ring optionally substituted with up to 3 substituents independently selected from selected from R 6 on carbon atom ring members.
  • Embodiment 13 A compound of Embodiment 12 wherein R 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 6 .
  • Embodiment 14 A compound of Embodiment 13 wherein the R 6 substituents are at the 2-, 3- and/or 5-positions.
  • Embodiment 15 A compound of Embodiment 14 wherein R 2 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 6 .
  • Embodiment 16 A compound of Embodiment 15 wherein the R 6 substituents are at the
  • Embodiment 17 A compound of Embodiment 15 wherein the R 6 substituents are at the
  • Embodiment 18 A compound of Formula 1 or any one of Embodiments 1 through 17 wherein when R 2 is an optionally substituted phenyl or pyridinyl ring, then R 2 is a phenyl or pyridinyl ring substituted with 2 or 3 substituents independently selected from R 6 .
  • Embodiment 19 A compound of Formula 1 or any one of Embodiments 1 through 18 wherein when R 2 is an optionally substituted phenyl ring, then R 2 is a phenyl ring substituted with 2 or 3 substituents independently selected from R 6 .
  • Embodiment 20 A compound of Formula 1 or any one of Embodiments 1 through 19 wherein when R 2 is an optionally substituted phenyl ring, then R 2 is a phenyl ring substituted with 2 substituents independently selected from R 6 attached at the meta positions of the phenyl ring.
  • Embodiment 21 Embodiment 21.
  • Embodiment 22a A compound of Embodiment 22 wherein R 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 7 ; or a pyridinyl or oxadiazolyl ring, the heterocyclic ring optionally substituted with up to 3 substituents independently selected from selected from R 7 on carbon atom ring members; or when Y is a direct bond, then R 3 is also selected from halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • Embodiment 23 A compound of Embodiment 22 or 22a wherein R 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 7 ; or when Y is a direct bond, then R 3 is also selected from halogen, C 1 -C 6 alkyl,
  • Embodiment 23 a C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • Embodiment 23 a C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • R 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 7 ; or when Y is a direct bond, then R 3 is also selected from halogen, C 1 -C 4 alkyl, C 2 -C 3 alkenyl, Q-C 3 haloalkyl, cyclopropyl, C 2 -C 6 alkylcarbonyl, C 2 -C 3 alkoxy carbony 1 or C 1 -C 5 hydroxy alky 1.
  • Embodiment 24 A compound of Embodiment 23 or 23 a wherein R 3 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 7 ; or when Y is a direct bond, then R 3 is also selected from C 1 -C 4 alkyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • R 3 is also selected from C 1 -C 4 alkyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • R 3 is a phenyl ring optionally substituted with up to 1 substituent selected from R 7 ; or when Y is a direct bond, then R 3 is also selected from C 1 -C 4 alkyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl.
  • Embodiment 25 A compound of Embodiment 24 wherein R 3 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 7 ; or when Y is a direct bond, then R 3 is also selected from C 3 -C 4 alkyl and C 3 -C 4 hydroxyalkyl wherein the carbon atom chain of said alkyl or hydroxyalkyl is branched at the carbon atom connecting R 3 to the remainder of Formula 1.
  • Embodiment 26 A compound of Formula 1 or any one of Embodiments 1 through 25 wherein R 3 is an optionally substituted phenyl or heterocyclic ring.
  • Embodiment 27 A compound of Embodiment 26 wherein R 3 is an optionally substituted phenyl ring.
  • Embodiment 28 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein Y is a direct bond, and R 3 is other than an optionally substituted phenyl ring or heterocyclic ring.
  • Embodiment 29 A compound of Formula 1 or any one of Embodiments 1 through 28 wherein when R 3 is an optionally substituted phenyl ring, then R 3 is substituted with at least one R 7 substituent attached at an ortho position of the phenyl ring.
  • Embodiment 30 A compound of Formula 1 or any one of Embodiments 1 through 29 wherein when R 3 is an optionally substituted phenyl ring, then R 3 is a phenyl ring substituted with 1 to 2 substituent independently selected from R 7 .
  • Embodiment 31 A compound of Formula 1 or any one of Embodiments 1 through 30 wherein when R 3 is an optionally substituted phenyl ring, then R 3 is a phenyl ring substituted with 1 substituent selected from R 7 attached at an ortho or para position of the phenyl ring.
  • Embodiment 32 A compound of Formula 1 or any one of Embodiments 1 through 31 wherein R 4 is H, halogen, hydroxy or C 1 -C 2 alkyl.
  • Embodiment 33 A compound of Embodiment 32 wherein R 4 is H, halogen or hydroxy.
  • Embodiment 34 A compound of Embodiment 33 wherein R 4 is H.
  • Embodiment 35 A compound of Formula 1 or any one of Embodiments 1 through 34 wherein each R 5 , R 6 and R 7 is independently halogen, cyano, C 1 -C 6 alkyl,
  • Embodiment 36 A compound of Embodiments 35 wherein each R 5 , R 6 and R 7 is independently halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy.
  • Embodiment 37 A compound of Embodiment 36 wherein each R 5 , R 6 and R 7 is independently halogen, Q-C 3 alkyl or C 1 -C 3 alkoxy.
  • Embodiment 38 A compound of Embodiment 37 wherein each R 5 , R 6 and R 7 is independently halogen, methyl or methoxy.
  • Embodiment 39 A compound of Embodiment 38 wherein each R 5 is independently halogen or methoxy.
  • Embodiment 39a A compound of Embodiment 39 wherein each R 5 is methoxy.
  • Embodiment 40 A compound of Embodiment 38 wherein each R 6 is independently chloro or methoxy.
  • Embodiment 40a A compound of Embodiment 40 wherein each R 6 is methoxy.
  • Embodiment 41 A compound of Embodiment 38 wherein each R 7 is independently halogen.
  • Embodiment 41a A compound of Embodiment 41 wherein each R 7 is fluoro.
  • Embodiment 42 A compound of Formula 1 or any one of Embodiments 1 through 41a wherein each R 6a and R 7a is independently cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
  • C 1 -C 6 haloalkyl C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 1 -C 6 alkylthio or C 1 -C 6 haloalkylthio.
  • Embodiment 43 A compound of Embodiment 42 wherein each R 6a and R 7a is independently C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl or C 1 -C 6 alkoxy.
  • Embodiment 44 A compound of Embodiment 43 wherein each R 6a and R 7a is independently C 1 -C 2 alkyl.
  • Embodiment 45 A compound of Formula 1 or any one of Embodiments 1 through 44 wherein m is an integer selected from 1, 2 and 3.
  • Embodiment 46 A compound of Embodiment 45 wherein m is an integer selected from
  • Embodiment 47 A compound of Formula 1 or any one of Embodiments 1 through 46 wherein m is 3 and the R 5 substituents are attached at ortho and para positions of the phenyl ring.
  • Embodiment 48 A compound of Formula 1 or any one of Embodiments 1 through 47 wherein m is 2 and the R 5 substituents are attached the ortho positions of the phenyl ring.
  • Embodiments of this invention can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of
  • Embodiment A A compound of Formula 1 wherein Q is O;
  • R 1 is C 1 -C 4 alkyl, C 2 -C 4 alkenyl, C 1 -C 4 haloalkyl, C 2 -C 4 cyanoalkyl or C 1 -C 3 alkoxy;
  • Embodiment B A compound of Embodiment A wherein R 1 is C 1 -C 4 alkyl; each W and Y is independently CH 2 , O, S or a direct bond;
  • R 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 6 ; or a 5- or 6-membered heterocyclic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to
  • R 3 is also selected from halogen, cyano, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl;
  • R 4 is H, halogen, hydroxy or C 1 -C 2 alkyl; and each R 6a and R 7a is independently C 1 -C 6 alkyl,
  • Embodiment C A compound of Embodiment B wherein R 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 6 ; or a pyridinyl or oxadiazolyl ring, the heterocyclic ring optionally substituted with up to 3 substituents independently selected from selected from R 6 on carbon atom ring members;
  • R 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 7 ; or a pyridinyl or oxadiazolyl ring, the heterocyclic ring optionally substituted with up to 3 substituents independently selected from selected from R 7 on carbon atom ring members; or when Y is a direct bond, then R 3 is also selected from halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl and C 1 -C 6 hydroxyalkyl; and m is an integer selected from 1, 2 and 3.
  • Embodiment D A compound of Embodiment C wherein
  • R 1 is C 1 -C 2 alkyl; W and Y are each direct bond; R 2 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 6 ; R 3 is a phenyl ring optionally substituted with up to 3 substituents independently selected from R 7 ; or
  • R 3 is halogen, C 1 -C 4 alkyl, C 2 -C 3 alkenyl, C 1 -C 3 haloalkyl, cyclopropyl, C 2 -C 6 alkylcarbonyl, C 2 -C 3 alkoxycarbonyl or C 1 -C 6 hydroxyalkyl;
  • R 4 is H, halogen or hydroxy; and each R 5 , R 6 and R 7 is independently halogen, C 1 -C 6 alkyl, C 2 -C 6 alkenyl,
  • Embodiment E A compound of Embodiment D wherein R 1 is methyl;
  • R 2 is a phenyl ring optionally substituted with up to 2 substituents independently selected from R 6 ;
  • R 3 is a phenyl ring optionally substituted with up to 1 substituent selected from R 7 ;
  • R 3 is C 1 -C 4 alkyl, C 2 -C 6 alkoxycarbonyl or C 1 -C 6 hydroxyalkyl;
  • R 4 is H; each R 5 , R 6 and R 7 is independently halogen, C 1 -C 3 alkyl or C 1 -C 3 alkoxy; and
  • m is an integer selected from 2 and 3.
  • Embodiment G A compound of Embodiment F wherein each R 5 is independently halogen; and each R 6 is methoxy.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, iV-oxides, and salts thereof), and at least one other fungicide.
  • a compound of Formula 1 including all stereoisomers, iV-oxides, and salts thereof
  • at least one other fungicide are compositions comprising a compound corresponding to any of the compound embodiments described above.
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, iV-oxides, and salts thereof) (i.e. in a fungicidally effective amount), and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • a compound of Formula 1 including all stereoisomers, iV-oxides, and salts thereof
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1 (including all stereoisomers, TV-oxides, and salts thereof).
  • a compound of Formula 1 including all stereoisomers, TV-oxides, and salts thereof.
  • methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above.
  • the compounds are applied as compositions of this invention.
  • compounds of Formula 1 wherein R 1 is other than H can be prepared by reacting compounds of Formula Ia (Formula 1 wherein R 1 is H) with alkylating agents of Formula 2 (wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate) in the presence of an acid acceptor.
  • alkylating agents of Formula 2 wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate
  • Suitable acid acceptors for the reaction include inorganic bases such as alkali or alkaline earth metal (e.g., lithium, sodium, potassium and cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases such as triethylamine, iV,jV-diisopropylethylamine and 1,8-diaza- bicyclo[5.4.0]undec-7-ene.
  • inorganic bases such as alkali or alkaline earth metal (e.g., lithium, sodium, potassium and cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides
  • organic bases such as triethylamine, iV,jV-diisopropylethylamine and 1,8-diaza- bicyclo[5.4.0]undec-7-ene.
  • a wide variety of solvents are suitable for the method of Scheme 1 including, for example, tetrahydrofuran, dichloromethane, N, ⁇ /-dimethylformamide, NJV- dimethylacetamide, JV-methylpyrrolidinone, acetonitrile, lower alkanols, and acetone; and mixtures of the foregoing.
  • Typical reaction temperatures range from about -20 to 200 0 C, and more typically between about 0 and 50 0 C.
  • R is other than H (e.g., alkyl, alkenyl, alkynyl, or the like)
  • compounds of Formula 1 are prepared by contacted compounds of Formula 3 with ammonia or ammonium hydroxide (R 1 is H) or primary amines (R 1 is other than H) of Formula 4 as illustrated in Scheme 2.
  • This method is generally conducted in a liquid phase, usually comprising a solvent, such as lower alkanols, tetrahydrofuran, dichloromethane, N, ⁇ /-dimethylformamide, ⁇ iV-dimethylacetamide, JV-methylpyrrolidinone, water, and acetonitrile or a mixture of organic solvent with water, at a temperature between about -20 to 200 0 C, and typically between about of 50 to 140 0 C.
  • a solvent such as lower alkanols, tetrahydrofuran, dichloromethane, N, ⁇ /-dimethylformamide, ⁇ iV-dimethylacetamide, JV-methylpyrrolidinone, water, and acetonitrile or a mixture of organic solvent with water,
  • the starting 2-pyranones of Formula 3 can be prepared by reaction of acetylenes of Formula 5 with ketones of Formula 6 in the presence of a base.
  • Suitable bases for this method include inorganic bases such as alkali or alkaline earth metal (e.g., lithium, sodium, potassium and cesium) hydrides, hexamethyldisilazides, dialkylamides, alkoxides, carbonates, phosphates and hydroxides, and organic bases such as triethylamine, JV,jV-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene.
  • Particularly useful as a base is sodium methoxide.
  • reaction is carried out in a suitable solvent such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dimethoxyethane, ⁇ /, ⁇ /-dimethylformamide, JV,iV-dimethylacetamide, JV-methylpyrrolidinone, and acetonitrile; and mixtures thereof.
  • a suitable solvent such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dimethoxyethane, ⁇ /, ⁇ /-dimethylformamide, JV,iV-dimethylacetamide, JV-methylpyrrolidinone, and acetonitrile; and mixtures thereof.
  • a suitable solvent such as diethyl ether, tert-butyl methyl ether, tetrahydrofuran, dimethoxyethane, ⁇ /, ⁇ /-dimethylformamide, JV,iV-di
  • Acetylenes of Formula 5 are commercially available and can be synthesized by known methods; see, for example,ierivsky et al., Synthetic Communications 1994 24(1), 85-88; Hari et al, Tetrahedron Letters 2008 49(33), 4965-4967; Hari et al, Heterocycles 2007 74, 545-552; Zou et al., Tetrahedron Letters 2003 44(48), 8709-8711; and references cited therein.
  • Ketones of Formula 6 are commercially available and can be synthesized by known methods; see, for example, Neitzel et al, Journal of Organic Chemistry 2000, 65(20), 6458- 6461; PCT Patent Application Publication WO 89/00562; and references cited therein.
  • Example 1 Steps A through B illustrate the synthesis of a compound of Formula 6 wherein W is a direct bond and R 2 is 2,6-difluorophenyl.
  • the reaction is performed by contacting a compound of Formula 7 with an oxidizing agent such as an alkali metal hexacyanoferrate(II) (e.g., potassium hexacyanoferrate(II) or sodium hexacyanoferrate(II)) in the presence of an acid acceptor and solvent.
  • an oxidizing agent such as an alkali metal hexacyanoferrate(II) (e.g., potassium hexacyanoferrate(II) or sodium hexacyanoferrate(II)) in the presence of an acid acceptor and solvent.
  • Suitable acid acceptors for the present 5 method include inorganic bases such as alkali or alkaline earth metal (e.g., lithium, sodium, potassium and cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases such as triethylamine, JV,jV-diisopropylethylamine and 1,8-diazabicyclo [5.4.0]undec-7-ene.
  • An acid acceptor of particular note for the present method is sodium hydroxide.
  • solvents can be used to form the suitable solvent for this method
  • the method is most satisfactorily conducted using solvents in which the acid acceptor and oxidizing agent (e.g., alkali metal hexacyanoferrate(II)) are substantially soluble.
  • the acid acceptor and oxidizing agent e.g., alkali metal hexacyanoferrate(II)
  • water e.g., dimethyl sulfoxide/water.
  • the oxidizing agent used is an alkali metal hexacyanoferrate(II) typically the molar ratio relative to Formula 7 is from about 1.1 to about 20, and more typically from about 4 to about 8.
  • General procedures for oxidation of pyridinium salts are known in the art and can be readily adapted to prepare compounds of Formula 1. Particularly useful are Decker oxidative reaction conditions. For leading references see, for example, Weber et al., Chemische Berichte 1985, 118, 3429- 3437; Matsumura et al., Bulletin of the Chemical Society of Japan 1970, 43, 3540-3542; and Hollan et al., BiochemicalJournal 1948, 43, 423-426.
  • pyridinium salts of Formula 7 can be prepared by the reaction of pyridines of Formula 9 with alkylating agents of Formula 2 (wherein Lg is a leaving group such as Cl, Br, I or a sulfonate, for example, /?-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate).
  • alkylating agent is generally present in an excess, typically in the range of about 1.1 to 20 molar equivalents relative to the pyridine of Formula 9.
  • the reaction is carried out in a suitable solvent such as tetrahydrofuran, acetonitrile, acetone, diethyl ether, ⁇ f, ⁇ /-dimethylformamide, JV,iV-dimethylacetamide, alcohols (e.g., methanol, ethanol), and water.
  • a suitable solvent such as tetrahydrofuran, acetonitrile, acetone, diethyl ether, ⁇ f, ⁇ /-dimethylformamide, JV,iV-dimethylacetamide, alcohols (e.g., methanol, ethanol), and water.
  • the method is most satisfactorily conducted using solvents in which the pyridine of Formula 9 is preferably completely or at least substantially soluble and the pyridinium salt of Formula 7 typically has low solubility at ambient temperatures (e.g., about 15-40 0 C) in the volume of solvent used such as acetone.
  • the present method is typically conducted at a temperature between about -20 to 200 0 C, and more typically between about 0 to 100 0 C.
  • Alkylation of pyridines to form pyridinium salts is well known in the chemistry literature. For representative procedures see Matsumura et al., Bulletin of the Chemical Society of Japan 1970, 43, 3540-3542; and Hollan et al., BiochemicalJournal 1948, 43, 423-426.
  • halides of Formula 9 are commercial available and can also be prepared by known methods.
  • halides of Formula 9 i.e. when R 5 , R 6 , and/or R 7 is halogen
  • halides of Formula 9 can be contacted with organoboronic acids, organoboronic esters, organotrifluoroborates, organotin reagents, Grignard reagents or organozinc reagents in the presence of transition metal-catalyzed (e.g., palladium(II) acetate, palladium(II) chloride, tetrakis(triphenylphosphine)palladium(0), bis(triphenylphosphine)palladium(II) dichloride, dichloro[l,r-bis(diphenylphosphino)ferrocene]palladium(II), bis(triphenyl- phosphine)dichloronickel(II) and copper(I) salts).
  • transition metal-catalyzed e.g., palladium(II) acetate, palladium(II) chloride, tetrakis(triphenylphosphine)
  • the aryl or heteroaryl R 2 ring and/or R 3 ring may be more conveniently incorporated after forming the central 2-pyridone ring.
  • a variety of conditions published in the chemistry literature can be used for introduction of an aryl or heteroaryl ring onto a 2-pyridone ring including contacting halo-substituted 2-pyridones with organoboronic acids using metal-catalyzed cross-coupling reaction conditions (relevant references listed in preceding paragraph).
  • Step B Preparation of l-(2,6-difluorophenyl)-2-(3,5-dimethoxyphenyl)ethanone
  • Step C Preparation of 6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-4-phenyl-2H- pyran-2-one
  • Step D Preparation of 6-(2,6-difluorophenyl)-5-(3,5-dimethoxyphenyl)-4-(2-phenyl)- 1 -methyl-2( 1 H)-pyridinone
  • the resulting oil was purified by silica gel column chromatography (30% ethyl acetate in hexanes as eluant) to provided the title compound, a compound of the present invention, as a solid (150 mg), melting at 157-159 0 C.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is O.
  • the present disclosure also includes Tables IA through 64 A, each of which is constructed the same as Table 1 above except that the row heading in Table 1 (i.e. "R 2 is 3,5- di-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is O”) is replaced with the respective row heading shown below.
  • Table IA the row heading is "R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is O"
  • R 3 is as defined in Table 1 above.
  • Tables 2A through 64A are constructed similarly.
  • IA R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is O.
  • 2A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is O.
  • 3A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is O.
  • 4A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is O.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is O.
  • 6A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is O.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is O.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is O.
  • 9A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is O.
  • 1OA R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are each a direct bond; and Q is O.
  • HA R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are both a direct bond; and Q is O.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are each a direct bond; and Q is O.
  • 13A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are both a direct bond; and Q is O.
  • 14A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is O.
  • 15A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is O.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeO; W and Y are each a direct bond; and Q is O.
  • 17A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeO; W and Y are both a direct bond; and Q is O.
  • 18A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is O.
  • R 2 is 2-Cl, 5-Me-Ph; (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is O.
  • 2OA R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 3-MeO; W and Y are each a direct bond; and Q is O.
  • 21A R 2 is 2-Cl, 5-Me-Ph; (R 5 ) m is 2,6-di-F, 3-MeO; W and Y are each a direct bond; and Q is O.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is O.
  • 23A R 2 is 2-Cl, 3,5-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is O.
  • 24A R 2 is 2-Cl, 3,5-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is O.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is O.
  • 26A is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is O.
  • 27A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are both a direct bond; and Q is O.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are both a direct bond; and Q is O.
  • 29A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is O.
  • 3OA R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) ra is 2,6-di-F, 4-MeO; W and Y are both a direct bond; and Q is O.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph;
  • (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 3-MeO; W and Y are each a direct bond; and Q is O.
  • i 3A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is S.
  • i 5A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is S.
  • i 7A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is S.
  • i 9A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is S.
  • 41A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is S.
  • 42A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are each a direct bond; and Q is S.
  • 44A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are both a direct bond; and Q is S.
  • 45A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are each a direct bond; and Q is S.
  • 46A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are both a direct bond; and Q is S.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is S.
  • 48A R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is S.
  • 49A R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeO; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 5-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeO; W and Y are both a direct bond; and Q is S.
  • 5 IA R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is S.
  • 52A R 2 is 2-Cl, 5-Me-Ph; (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is S.
  • R 2 is 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 3-MeO; W and Y are each a direct bond; and Q is S.
  • 54A R 2 is 2-Cl, 5-Me-Ph; (R 5 ) m is 2,6-di-F, 3-MeO; W and Y are each a direct bond; and Q is S.
  • 55A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 3,5-MeO-Ph; (R 5 ) m is 4-F; W and Y are each a direct bond; and Q is S.
  • 57A R 2 is 2-Cl, 3,5-MeO-Ph; (R 5 ) m is 2,4-di-F; W and Y are each a direct bond; and Q is S.
  • 58A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F; W and Y are each a direct bond; and Q is S.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,4,6-tri-F; W and Y are each a direct bond; and Q is S.
  • 6OA R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 4-Cl; W and Y are both a direct bond; and Q is S.
  • 61A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 4-MeO; W and Y are both a direct bond; and Q is S.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,3,6-tri-F; W and Y are each a direct bond; and Q is S.
  • 63A R 2 is 2-Cl, 3,5-di-MeO-Ph; (R 5 ) m is 2,6-di-F, 4-MeO; W and Y are both a direct bond; and Q is S.
  • R 2 is 2-Cl, 3,5-di-MeO-Ph;
  • (R 5 ) m is 2,6-di-F, 4-MeNH(CH 2 ) 3 O; W and Y are each a direct bond; and Q is
  • W is O; and Y is a direct bond.
  • W is S; and Y is a direct bond.
  • R 1 is MeO
  • R 2 is 3,5-di-MeO-Ph
  • R 5a is H
  • W and Y are each a direct bond.
  • the present disclosure also includes Tables 3B through 19B, each of which is constructed the same as Table 3 above except that the row heading in Table 3 (i.e. "R 1 is MeO; R 2 is 3,5-di-MeO-Ph; R 5a is H; and W and Y are each a direct bond”) is replaced with the respective row heading shown below.
  • Table 3B the row heading is "R 1 is MeO; R 2 is 2-Cl, 5-MeO-Ph; R 5a is H; and W and Y are each a direct bond", and R 3 is as defined in Table 3 above.
  • Tables 3B through 19B are constructed similarly.
  • R 1 is MeO
  • R 2 is 2-Cl, 5-MeO-Ph
  • R 5a is H
  • W and Y are each a direct bond.
  • R 1 is MeO
  • R 2 is 3,5-di-MeO-Ph
  • R 5a is F
  • W and Y are each a direct bond.
  • R 1 is MeO
  • R 2 is 2-Cl, 5-MeO-Ph
  • R 5a is F
  • W and Y are each a direct bond.
  • R 1 is CN; R 2 is 3,5-di-MeO-Ph; R 5a is H; W and Y are each a direct bond.
  • R 1 is CN; R 2 is 2-Cl, 5-MeO-Ph; R 5a is H; W and Y are each a direct bond.
  • R 1 is CN; R 2 is 3,5-di-MeO-Ph; R 5a is F; W and Y are both a direct bond.
  • R 1 is CN; R 2 is 2-Cl, 5-MeO-Ph; R 5a is F; W and Y are both a direct bond.
  • R 1 is Et; R 2 is 3,5-di-MeO-Ph; R 5a is H; W and Y are both a direct bond.
  • R 1 is Et; R 2 is 2-Cl, 5-MeO-Ph; R 5a is H; W and Y are both a direct bond.
  • R 1 is Et; R 2 is 3,5-di-MeO-Ph; R 5a is F; W and Y are both a direct bond.
  • R 1 is Et; R 2 is 2-Cl, 5-MeO-Ph; R 5a is F; W and Y are both a direct bond.
  • R 1 is MeO
  • R 2 is 2-Cl, 3,5-di-MeO-Ph
  • R 5a is H
  • W and Y are each a direct bond.
  • R 1 is MeO
  • R 2 is 2-Cl, 3,5-di-MeO-Ph
  • R 5a is F
  • W and Y are each a direct bond.
  • R 1 is CN; R 2 is 2-Cl, 3,5-di-MeO-Ph; R 5a is H; W and Y are each a direct bond.
  • R 1 is CN; R 2 is 2-Cl, 3,5-di-MeO-Ph; R 5a is F; W and Y are both a direct bond.
  • R 1 is Et; R 2 is 2-Cl, 3,5-di-MeO-Ph; R 5a is H; W and Y are both a direct bond.
  • R 1 is Et
  • R 2 is 2-Cl
  • R 5a is F
  • W and Y are both a direct bond.
  • W and Y are each a direct bond. W and Y are each a direct bond.
  • a compound of Formula 1 of this invention (including //-oxides and salts thereof) will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include both liquid and solid compositions.
  • Liquid compositions include solutions (including emulsif ⁇ able concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion.
  • nonaqueous liquid compositions are emulsif ⁇ able concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • An emulsif ⁇ able granule combines the advantages of both an emulsif ⁇ able concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting. Liquid and solid formulations can be applied onto seeds of crops and other desirable vegetation as seed treatments before planting to protect developing roots and other subterranean plant parts and/or foliage through systemic uptake.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, ⁇ /,iV-dimethylalkanamides (e.g., ⁇ /, ⁇ /-dimethylformamide), limonene, dimethyl sulfoxide, JV-alkylpyrrolidones (e.g., JV-methylpyrrolidinone), ethylene glycol, Methylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 22 ), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants.
  • surfactants also known as “surface-active agents”
  • surface-active agents generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as JV-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as JV-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water.
  • Active ingredient slurries, with particle diameters of up to 2,000 ⁇ m can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ m.
  • Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 ⁇ m range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Pellets can be prepared as described in U.S. 4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493.
  • Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030.
  • Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 9 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 17 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • Compound 22 20.00% polyvinylpyrrolidone -vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%
  • Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application.
  • Aqueous compositions for direct applications to the plant or portion thereof typically at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.
  • the compounds of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.
  • the compounds and/or compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, turf, vegetable, field, cereal, and fruit crops.
  • pathogens include: Oomycetes, including Phytophthora diseases such as Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici, Pythium diseases such as Pythium aphanidermatum, and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora spp. (including Peronospora tabacina and Peronospora parasitica), Pseudoperonospora spp. (including Pseudoperonospora cubensis) and Bremia lactucae; Ascomycetes, including Alternaria diseases such as Alternaria solani and Alternaria brassicae, Guignardia diseases such as
  • Venturia diseases such as Venturia inaequalis
  • Septoria diseases such as Venturia inaequalis
  • Septoria nodorum and Septoria tritici powdery mildew diseases such as Erysiphe spp.
  • Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres, anthracnose diseases such as Glomerella or Colletotrichum spp.
  • Puccinia spp. such as Puccinia recondita, Puccinia striiformis, Puccinia hordei, Puccinia graminis and Puccinia arachidis
  • Rutstroemia floccosum also known as Sclerontina homoeocarpa
  • compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds can also be applied to seeds to protect the seeds and seedlings developing from the seeds.
  • the compounds can also be applied through irrigation water to treat plants.
  • Rates of application for these compounds can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • a fungicidally effective amount can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • One skilled in the art can easily determine through simple experimentation the fungicidally effective amount necessary for the desired level of plant disease control.
  • Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient.
  • Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.1 to about 1O g per kilogram of seed.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • fungicides insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners
  • growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus
  • the present invention also pertains to a composition
  • a composition comprising a compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • the other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent.
  • one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • compositions which in addition to the compound of Formula 1 include at least one fungicidal compound selected from the group consisting of the classes (1) methyl benzimidazole carbamate (MBC) fungicides; (2) dicarboximide fungicides; (3) demethylation inhibitor (DMI) fungicides; (4) phenylamide fungicides; (5) amine/morpholine fungicides; (6) phospholipid biosynthesis inhibitor fungicides; (7) carboxamide fungicides; (8) hydroxy(2-amino-)pyrimidine fungicides; (9) anilinopyrimidine fungicides; (10) //-phenyl carbamate fungicides; (11) quinone outside inhibitor (QoI) fungicides; (12) phenylpyrrole fungicides; (13) quinoline fungicides; (14) lipid peroxidation inhibitor fungicides; (15) melanin biosynthesis inhibitors-reductase (MBI-R) fungicides; (15)
  • Methyl benzimidazole carbamate (MBC) fungicides (Fungicide Resistance Action Committee (FRAC) code 1) inhibit mitosis by binding to ⁇ -tubulin during microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure.
  • Methyl benzimidazole carbamate fungicides include benzimidazole and thiophanate fungicides.
  • the benzimidazoles include benomyl, carbendazim, fuberidazole and thiabendazole.
  • the thiophanates include thiophanate and thiophanate-methy 1.
  • DMI Demethylation inhibitor
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.
  • the imidazoles include clotrimazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole.
  • the pyrimidines include fenarimol and nuarimol.
  • the piperazines include triforine.
  • the pyridines include pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
  • Phenylamide fungicides are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide.
  • Phenylamide fungicides include acylalanine, oxazolidinone and butyro lactone fungicides.
  • the acylalanines include benalaxyl, benalaxyl-M, furalaxyl, metalaxyl and metalaxyl- M/mefenoxam.
  • the oxazolidinones include oxadixyl.
  • the butyrolactones include ofurace.
  • Amine/morpholine fungicides include morpholine, piperidine and spiroketal-amine fungicides.
  • the morpholines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin and piperalin.
  • the spiroketal-amines include spiroxamine.
  • Phospholipid biosynthesis inhibitor fungicides (Fungicide Resistance Action Committee (FRAC) code 6) inhibit growth of fungi by affecting phospholipid biosynthesis.
  • Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides.
  • the phosphorothiolates include edifenphos, iprobenfos and pyrazophos.
  • the dithiolanes include isoprothiolane.
  • Carboxamide fungicides (Fungicide Resistance Action Committee (FRAC) code 7) inhibit Complex II (succinate dehydrogenase) fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase.
  • Carboxamide fungicides include benzamides, furan carboxamides, oxathiin carboxamides, thiazole carboxamides, pyrazole carboxamides and pyridine carboxamides.
  • the benzamides include benodanil, flutolanil and mepronil.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamides include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole carboxamides include furametpyr, penthiopyrad, bixafen, isopyrazam, ⁇ /-[2-(l l S,2i?)-[l,r-bicyclopropyl]-2-ylphenyl]-3- (difluoromethyl)-l -methyl- lH-pyrazole-4-carboxamide and penflufen (N-[2-(l,3-dimethyl- butyl)phenyl]-5-fluoro-l ,3-dimethyl-lH-pyrazole-4-carboxamide).
  • the pyridine carboxamides include boscalid.
  • ⁇ ydroxy(2-amino-)pyrimidine fungicides inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • Anilinopyrimidine fungicides (Fungicide Resistance Action Committee (FRAC) code 9) are proposed to inhibit biosynthesis of the amino acid methionine and to disrupt the secretion of hydrolytic enzymes that lyse plant cells during infection. Examples include cyprodinil, mepanipyrim and pyrimethanil.
  • FRAC Function III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the "quinone outside" (Q 0 ) site of the cytochrome bc ⁇ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone outside inhibitor fungicides also known as strobilurin fungicides
  • the methoxyacrylates include azoxystrobin, enestroburin (SYP-Z071), picoxystrobin and pyraoxystrobin (SYP-3343).
  • the methoxycarbamates include pyraclostrobin and pyrametostrobin (SYP-4155).
  • the oximinoacetates include kresoxim-methyl and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, metominostrobin, orysastrobin, ⁇ -[methoxyimino]-iV-methyl-2-[[[ 1 -[3-(trifluoromethyl)phenyl]ethoxy]imino]- methyljbenzeneacetamide and 2-[[[3-(2,6-dichlorophenyl)- 1 -methyl-2-propen- 1 -ylidene]- amino]oxy]methyl]- ⁇ -(methoxyimino)- ⁇ /-methylbenzeneacetamide.
  • the oxazolidinediones include famoxadone.
  • the dihydrodioxazines include fluoxastrobin.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Fenpiclonil and fludioxonil are examples of this fungicide class.
  • Quinoline fungicides (Fungicide Resistance Action Committee (FRAC) code 13) are proposed to inhibit signal transduction by affecting G-proteins in early cell signaling. They have been shown to interfere with germination and/or appressorium formation in fungi that cause powder mildew diseases. Quinoxyfen and tebufloquin are examples of this class of fungicide.
  • Lipid peroxidation inhibitor fungicides are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis.
  • Lipid peroxidation fungicides include aromatic carbon and 1,2,4-thiadiazole fungicides.
  • the aromatic carbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos- methyl.
  • the 1,2,4-thiadiazole fungicides include etridiazole.
  • MBI-R Melanin biosynthesis inhibitors-reductase fungicides
  • FRAC Field Action Committee
  • Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • Squalene- epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafine.
  • Examples include pencycuron.
  • Quinone inside inhibitor (QiI) fungicides (Fungicide Resistance Action Committee (FRAC) code 21) inhibit Complex III mitochondrial respiration in fungi by affecting ubiquinol reductase. Reduction of ubiquinol is blocked at the "quinone inside" (Qj) site of the cytochrome bc ⁇ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone inside inhibitor fungicides include cyanoimidazole and sulfamoyltriazole fungicides. The cyanoimidazoles include cyazofamid. The sulfamoyltriazoles include amisulbrom.
  • (2) "Benzamide fungicides" (Fungicide Resistance Action Committee (FRAC) code
  • microtubule assembly inhibit mitosis by binding to ⁇ -tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include zoxamide.
  • Examples include blasticidin-S.
  • Action Committee (FRAC) code 25) inhibit growth of fungi by affecting protein biosynthesis.
  • examples include streptomycin.
  • This class includes 2,6-dinitroanilines such as fluazinam, pyrimidonehydrazones such as ferimzone and dinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.
  • Carboxylic acid fungicides (Fungicide Resistance Action Committee (FRAC) code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • Heteroaromatic fungicides include isoxazole and isothiazolone fungicides.
  • the isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • Phosphonate fungicides include phosphorous acid and its various salts, including fosetyl-aluminum.
  • Thiophene-carboxamide fungicides (Fungicide Resistance Action Committee (FRAC) code 38) are proposed to affect ATP production. Examples include silthiofam.
  • Carboxylic acid amide (CAA) fungicides are proposed to inhibit phospholipid biosynthesis and cell wall deposition. Inhibition of these processes prevents growth and leads to death of the target fungus.
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph and flumorph.
  • the valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate and valiphenal.
  • the mandelic acid amides include mandipropamid, ⁇ /-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3- methoxyphenyl] ethyl]-3 -methyl-2- [(methylsulfonyl)amino]butanamide and N-[2- [4- [ [3 -(4- chlorophenyl)-2-propyn- 1 -yl]oxy] -3 -methoxyphenyl] ethyl] -3 -methyl-2- [(ethylsulfonyl)amino]butanamide.
  • Tetracycline antibiotic fungicides (Fungicide Resistance Action Committee (FRAC) code 41) inhibit growth of fungi by affecting complex 1 nicotinamide adenine dinucleotide (NADH) oxidoreductase. Examples include oxytetracycline.
  • Benzamide fungicides (Fungicide Resistance Action Committee (FRAC) code 43) inhibit growth of fungi by derealization of spectrin- like proteins.
  • Examples include acylpicolide fungicides such as fluopicolide and fluopyram.
  • Host plant defense induction fungicides include benzo-thiadiazole, benzisothiazole and thiadiazole-carboxamide fungicides.
  • the benzo-thiadiazoles include acibenzolar-S-methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole-carboxamides include tiadinil and isotianil.
  • Multi-site contact fungicides inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • This class of fungicides includes: (45.1) “copper fungicides" (Fungicide Resistance Action Committee (FRAC) code Ml)", (45.2) “sulfur fungicides” (Fungicide Resistance Action Committee (FRAC) code M2), (45.3) “dithiocarbamate fungicides” (Fungicide Resistance Action Committee (FRAC) code M3), (45.4) "phthalimide fungicides” (Fungicide Resistance Action Committee (FRAC) code M4), (45.5) "chloronitrile fungicides” (Fungicide Resistance Action Committee (FRAC) code M5), (45.6) “sulfamide fungicides” (Fungicide Resistance Action Committee (FRAC) code M6), (45.7) "guanidine fungicides” (Fungicide Resistance Action Committee (FRAC) code M7), (45.8) “triazine fungicides” (Fungicides)
  • Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur.
  • Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb and ziram.
  • Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol.
  • Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil.
  • Sulfamide fungicides include dichlofluanid and tolyfluanid.
  • Guanidine fungicides include dodine, guazatine, iminoctadine albesilate and iminoctadine triacetate.
  • Triazine fungicides include anilazine.
  • Quinone fungicides include dithianon.
  • Fungicides other than fungicides of classes (1) through (45) include certain fungicides whose mode of action may be unknown. These include: (46.1) “thiazole carboxamide fungicides” (Fungicide Resistance Action Committee (FRAC) code U5), (46.2) “phenyl-acetamide fungicides” (Fungicide Resistance Action Committee (FRAC) code U6), (46.3) “quinazolinone fungicides” (Fungicide Resistance Action Committee (FRAC) code U7), (46.4) "benzophenone fungicides” (Fungicide Resistance Action Committee (FRAC) code U8) and (46.5) "triazolopyrimidine fungicides”.
  • the thiazole carboxamides include ethaboxam.
  • the phenyl-acetamides include cyflufenamid and iV-[[(cyclopropylmethoxy)- amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]benzeneacetamide.
  • the quinazolinones include proquinazid.
  • the benzophenones include metrafenone.
  • the triazolopyrimidines include ametoctradin.
  • the (b46) class also includes bethoxazin, neo- asozin (ferric methanearsonate), pyrrolnitrin, quinomethionate, iV-[2-[4-[[3-(4-chloro- phenyl)-2-propyn- 1 -yl]oxy] -3 -methoxyphenyl] ethyl] -3 -methyl-2- [(methylsulfonyl)amino]- butanamide, ⁇ /-[2-[4-[[3-(4-chlorophenyl)-2-propyn- 1 -yl]oxy]-3-methoxyphenyl]ethyl]-3- methyl-2-[(ethylsulfonyl)amino]butanamide, 2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2- [3-(2-methoxyphenyl)-2-thiazolidinylidene
  • composition comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of the aforedescribed classes (1) through (46).
  • a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • a mixture i.e. composition
  • a composition comprising said mixture (in fungicidally effective amount) and further comprising at least one additional surfactant selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • insecticides such as abamectin, acephate, acetamiprid, acrinathrin, amidoflumet (S- 1955), avermectin, azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3-bromo- l-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-lH- pyrazole-5-carboxamide), cyflumetofen, cyfluthrin,
  • Bacillus thuringiensis subsp. kurstaki, and the encapsulated delta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII); entomopathogenic fungi, such as green muscardine fungus; and entomopathogenic virus including baculovirus, nucleopolyhedro virus (NPV) such as ⁇ zNPV, AfNPV; and granulosis virus (GV) such as CpGV.
  • NPV nucleopolyhedro virus
  • GV granulosis virus
  • Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins).
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1 :3000 and about 3000:1. Of note are weight ratios between about 1 :300 and about 300:1 (for example ratios between about 1 :30 and about 30:1).
  • weight ratios between about 1 :300 and about 300:1 for example ratios between about 1 :30 and about 30:1).
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of diseases controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • combinations of a compound of this invention with other biologically active (particularly fungicidal) compounds or agents can result in a greater-than-additive (i.e. synergistic) effect. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable.
  • synergism of fungicidal active ingredients occurs at application rates giving agronomically satisfactory levels of fungal control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
  • a combination of a compound of Formula 1 with at least one other fungicidal active ingredient is such a combination where the other fungicidal active ingredient has different site of action from the compound of Formula 1.
  • a combination with at least one other fungicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management.
  • a composition of the present invention can further comprise a biologically effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.
  • compositions which in addition to compound of Formula 1 include at least one compound selected from the group consisting of (1) alkylenebis(dithiocarbamate) fungicides; (2) cymoxanil; (3) phenylamide fungicides; (4) proquinazid (6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone); (5) chlorothalonil; (6) carboxamides acting at complex II of the fungal mitochondrial respiratory electron transfer site; (7) quinoxyfen; (8) metrafenone; (9) cyflufenamid; (10) cyprodinil; (11) copper compounds; (12) phthalimide fungicides; (13) fosetyl-aluminum; (14) benzimidazole fungicides; (15) cyazofamid; (16) fluazinam; (17) iprovalicarb; (18) propamocarb; (19) validomycin; (20) dichloroph
  • Sterol biosynthesis inhibitors control fungi by inhibiting enzymes in the sterol biosynthesis pathway.
  • Demethylase-inhibiting fungicides have a common site of action within the fungal sterol biosynthesis pathway, involving inhibition of demethylation at position 14 of lanosterol or 24-methylene dihydrolanosterol, which are precursors to sterols in fungi.
  • Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs.
  • the demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM).
  • DMI fungicides are divided between several chemical classes: azoles (including triazoles and imidazoles), pyrimidines, piperazines and pyridines.
  • the triazoles include azaconazole, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prothioconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole and uniconazole.
  • the imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole, oxpoconazole, prochloraz and triflumizole.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
  • bc ⁇ Complex Fungicides (group 28) have a fungicidal mode of action which inhibits the be i complex in the mitochondrial respiration chain.
  • the bc ⁇ complex is sometimes referred to by other names in the biochemical literature, including complex III of the electron transfer chain, and ubihydroquinone: cytochrome c oxidoreductase. This complex is uniquely identified by Enzyme Commission number EC 1.10.2.2.
  • the bc ⁇ complex is described in, for example, J. Biol. Chem. 1989, 264, 14543-48; Methods Enzymol. 1986, 126, 253-71; and references cited therein.
  • Strobilurin fungicides such as azoxystrobin, dimoxystrobin, enestroburin (SYP-Z071), fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin and trifloxystrobin are known to have this mode of action (H. Sauter et al., Angew. Chem. Int. Ed. 1999, 38, 1328-1349).
  • Other fungicidal compounds that inhibit the bc ⁇ complex in the mitochondrial respiration chain include famoxadone and fenamidone.
  • Alkylenebis(dithiocarbamate)s include compounds such as mancozeb, maneb, propineb and zineb.
  • Phenylamides (group (3)) include compounds such as metalaxyl, benalaxyl, furalaxyl and oxadixyl.
  • Carboxamides include compounds such as boscalid, carboxin, fenfuram, flutolanil, furametpyr, mepronil, oxycarboxin, thifluzamide, penthiopyrad and ⁇ /-[2-(l,3-dimethylbutyl)phenyl]-5-fluoro-l,3-dimethyl-lH- pyrazole-4-carboxamide (PCT Patent Publication WO 2003/010149), and are known to inhibit mitochondrial function by disrupting complex II (succinate dehydrogenase) in the respiratory electron transport chain.
  • complex II succinate dehydrogenase
  • Copper compounds include compounds such as copper oxychloride, copper sulfate and copper hydroxide, including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Phthalimides include compounds such as folpet and captan.
  • Benzimidazole fungicides include benomyl and carbendazim.
  • Dichlorophenyl dicarboximide fungicides include chlozolinate, dichlozoline, iprodione, isovaledione, myclozolin, procymidone and vinclozolin.
  • Non-DMI sterol biosynthesis inhibitors include morpholine and piperidine fungicides.
  • the morpho lines and piperidines are sterol biosynthesis inhibitors that have been shown to inhibit steps in the sterol biosynthesis pathway at a point later than the inhibitions achieved by the DMI sterol biosynthesis (group (27)).
  • the morpho lines include aldimorph, dodemorph, fenpropimorph, tridemorph and trimorphamide.
  • the piperidines include fenpropidin.
  • Preferred for better control of plant diseases caused by fungal plant pathogens are mixtures of a compound of this invention with a fungicide selected from the group: azoxystrobin, kresoxim-methyl, trifloxystrobin, pyraclostrobin, picoxystrobin, dimoxystrobin, metominostrobin/fenominostrobin, quinoxyfen, metrafenone, cyflufenamid, fenpropidine, fenpropimorph, cyproconazole, epoxiconazole, flusilazole, metconazole, propiconazole, proquinazid, prothioconazole, tebuconazole, triticonazole, famoxadone and penthiopyrad.
  • azoxystrobin kresoxim-methyl
  • trifloxystrobin e.g., pyraclostrobin
  • picoxystrobin dimoxystrobin
  • Specifically preferred mixtures are selected from the group: combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with azoxystrobin, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with kresoxim-methyl, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with trifloxystrobin, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with pyraclostrobin, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with picoxystrobin, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19, Compound 20, Compound 22, Compound 23, and Compound 27 with dimoxystrobin, combinations of Compound 6, Compound 9, Compound 13, Compound 17, Compound 19,
  • Tests A-F General protocol for preparing test suspensions for Tests A-F: The test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at the desired concentration (in ppm) in acetone and purified water (50/50 mix) containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-F. Spraying a 200 ppm test suspension to the point of run-off on the test plants was the equivalent of a rate of 500 g/ha. (An asterisk "*" next to the rating value indicates a 40 ppm test suspension.)
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20 0 C for 8 days, after which time visual disease ratings were made.
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20 0 C for 24 h, and then moved to a growth chamber at 20 0 C for 7 days, after which time visual disease ratings were made.
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Septoria tritici (the causal agent of wheat leaf blotch) and incubated in saturated atmosphere at 20 0 C for 48 h, and then moved to a growth chamber at 20 0 C for 19 days, after which time visual disease ratings were made.
  • Septoria tritici the causal agent of wheat leaf blotch
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Septoria nodorum
  • test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Alternaria solani (the causal agent of tomato early blight) and incubated in a saturated atmosphere at 27 0 C for
  • test suspension was sprayed to the point of run-off on tomato seedlings.
  • seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of tomato Botrytis) and incubated in saturated atmosphere at 20 0 C for 48 h, and then moved to a growth chamber at 24 0 C for 3 days, after which time visual disease ratings were made.
  • Botrytis cinerea the causal agent of tomato Botrytis
  • Results for Tests A-F are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). All results are for 200 ppm except where followed by "*", which indicates 40 ppm.
  • Test A Compound No. Test B Test C Test D Test E Test F
  • Test A Test B Test C Test D Test E Test F

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Abstract

La présente invention concerne des composés de formule 1, y compris tous leurs stéréo-isomères, N‑oxydes et sels, dans laquelle R1, R2, R3, R4, R5, Q, W, Y et m sont tels que définis dans la description. L'invention concerne également des compositions contenant les composés de formule 1 et des méthodes permettant de lutter contre des maladies végétales provoquées par un agent pathogène fongique comprenant l'application d'une quantité efficace d'un composé ou d'une composition de l'invention.
PCT/US2010/023548 2009-02-10 2010-02-09 2‑pyridones fongicides WO2010093595A1 (fr)

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Cited By (16)

* Cited by examiner, † Cited by third party
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US8334307B2 (en) 2010-06-01 2012-12-18 Biotheryx Inc. Hydroxypyridone derivatives, pharmaceutical compositions thereof, and their therapeutic use for treating proliferative diseases
WO2015195474A1 (fr) * 2014-06-18 2015-12-23 Biotheryx, Inc. Dérivés d'hydroxypyridone, compositions pharmaceutiques contenant lesdits dérivés, et leur utilisation thérapeutique pour traiter des maladies inflammatoires, neurodégénératives ou d'origine immunologique
WO2016052247A1 (fr) * 2014-10-03 2016-04-07 住友化学株式会社 Composé pyrimidinone
WO2017090654A1 (fr) * 2015-11-26 2017-06-01 住友化学株式会社 Composition antiparasitaire et son utilisation
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JPWO2018225829A1 (ja) * 2017-06-08 2020-04-09 三井化学アグロ株式会社 ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤
JP7118961B2 (ja) 2017-06-12 2022-08-16 三井化学アグロ株式会社 ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤
WO2018230516A1 (fr) * 2017-06-12 2018-12-20 三井化学アグロ株式会社 Composé de pyridone et agent antimicrobien l'utilisant comme ingrédient actif pour l'agriculture et l'horticulture
JPWO2018230516A1 (ja) * 2017-06-12 2020-04-16 三井化学アグロ株式会社 ピリドン化合物およびそれを有効成分とする農園芸用殺菌剤
WO2022221165A1 (fr) 2021-04-13 2022-10-20 Fmc Corporation Pyridones fongicides

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