WO2023158602A1 - Halométhylcétones, hydrates et éthers d'énol fongicides - Google Patents

Halométhylcétones, hydrates et éthers d'énol fongicides Download PDF

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Publication number
WO2023158602A1
WO2023158602A1 PCT/US2023/012882 US2023012882W WO2023158602A1 WO 2023158602 A1 WO2023158602 A1 WO 2023158602A1 US 2023012882 W US2023012882 W US 2023012882W WO 2023158602 A1 WO2023158602 A1 WO 2023158602A1
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alkyl
independently
methyl
optionally substituted
alkoxy
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PCT/US2023/012882
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English (en)
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Daniel AKWABOAH
Srinivas CHITTABOINA
Travis Chandler MCMAHON
Zhengao FENG
Hengbin Wang
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Fmc Corporation
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/04—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
    • C07D213/30—Oxygen atoms
    • 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
    • C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/22—Nitrogen and oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
    • C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
    • C07D261/06—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members
    • C07D261/08—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having two or more double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D419/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms
    • C07D419/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen, oxygen, and sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • each R 7 is independently F, Cl, I, Br, cyano, methyl, trifluoromethyl or methoxy; q is 0, 1, 2, 3 or 4;
  • L is (CR 8a R 8b ) n ; each R 8a and R 8b is independently H, halogen, cyano, hydroxy, nitro, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy; n is 0, 1, 2 or 3;
  • G is phenyl is substituted with 1 to 3 substituents independently selected from R 9 and optionally substituted with up to 3 substituents independently selected from R 10 ;
  • G is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up
  • compositions, mixture, process, method, article, or apparatus 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, method, article, or apparatus.
  • nonagronomic refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products stored product
  • agro-forestry and vegetation management e.g., public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • crop vigor refers to
  • 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).
  • alkylthioalkylthio examples include CH 3 SCH 2 S, CH 3 SCH 2 CH 2 S, CH 3 CH 2 SCH 2 S, CH 3 CH 2 CH 2 SCH 2 S and CH 3 CH 2 SCH 2 CH 2 S.
  • alkylsufonylalkylthio denotes alkylsufonyl substitution on alkylthio group.
  • alkylthioalkoxy denotes alkylthio substitution on an alkoxy group.
  • the terms “(alkenylthio)carbonyl” and “(alkynylthio)carbonyl” are likewise defined.
  • alkenyl(thiocarbonyl) and alkynyl(thiocarbonyl) are likewise defined.
  • dialkylamino examples include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • Alkylaminoalkyl denotes alkylamino substitution on alkyl.
  • alkylaminoalkyl examples 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 .
  • alkoxycarbonylalkoxy denotes a straight-chain or branched alkoxycarbonyl substitution on an alkoxy group.
  • alkenylcarbonylamino and “alkynylcarbonylamino” are likewise defined.
  • Alkylsulfonylamino denotes an NH radical substituted with alkylsulfonyl.
  • alkenylsulfonylamino and alkynylsulfonylamino are likewise defined.
  • alkylsulfonyloxy denotes an alkylsulfonyl group bonded to an oxygen atom.
  • alkenylaminosulfonyl and alkynylaminosulfonyl are likewise defined.
  • alkenylaminosulfonylamino and “alkynylaminosulfonylamino” are likewise defined.
  • alkoxyalkoxyalkyl examples include CH 3 OCH 2 OCH 2 , CH 3 OCH 2 OCH 2 CH 2 and CH 3 CH 2 OCH 2 OCH 2 .
  • alkenylcarbonyloxy and alkynylcarbonyloxy are likewise defined.
  • alkoxycarbonylalkyl denotes alkoxycarbonyl substitution on alkyl.
  • alkenylaminocarbonyloxy and “alkynylaminocarbonyloxy” are likewise defined.
  • 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.
  • 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.
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members.
  • cycloalkylcycloalkyl examples include cyclopropylcyclopropyl (such as 1,1'- bicyclopropyl-1-yl, 1,1'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as 1,1'-bicyclohexyl-1-yl), and the different cis- and trans-cycloalkylcycloalkyl isomers, (such as (1R,2S)-1,1'-bicyclopropyl-2-yl and (1R,2R)-1,1'-bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as 1,1'- bicyclopropyl-1-yl, 1,1'-bicyclopropyl-2-yl
  • cyclohexylcyclopentyl such as 4- cyclopen
  • cycloalkylaminoalkyl examples include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to a straight-chain or branched alkyl group.
  • Cycloalkylcarbonyloxy denotes cycloalkylcarbonyl attached to and linked through an oxygen atom.
  • haloalkyl or “alkyl substituted with halogen” include CF 3 , ClCH 2 , CF 3 CH 2 and CF 3 CCl2.
  • haloalkenyl or “haloalkynyl” “haloalkoxy”, “haloalkylsulfonyl”, “halocycloalkyl”, and the like, are defined analogously to the term “haloalkyl”.
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 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.
  • halocycloalkyl include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group.
  • Cyanoalkyl examples include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Cyanoalkoxy denotes an alkoxy group substituted with one cyano group. Examples of “cyanoalkoxy” include NCCH 2 O, NCCH 2 CH 2 O and CH 3 CH(CN)CH 2 O.
  • Cyanoalkylthio denotes an alkylthio group substituted with one cyano group. Examples of “cyanoalkylthio” include NCCH 2 S, NCCH 2 CH 2 S and CH 3 CH(CN)CH 2 S.
  • “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group.
  • hydroxyalkyl examples include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 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.
  • the term “halotrialkylsilyl” is likewise defined. Examples of “halotrialkylsilyl” include trifluormethylsilyl and trichloromethylsilyl.
  • Trialkylsilyloxy denotes a trialkylsilyl group attached to and linked through an oxygen atom, such as trimethylsilyloxy, triethylsilyloxy and tert-butyldimethylsilyloxy.
  • the total number of carbon atoms in a substituent group is indicated by the “C i -C j ” prefix where i and j are numbers from 1 to 15.
  • C 1 -C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C2 alkoxyalkyl designates CH 3 OCH 2
  • C3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C4 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 .
  • a molecular fragment i.e.
  • radical is denoted by a series of atom symbols (e.g., C, H, N, O and S) the implicit point or points of attachment will be easily recognized by those skilled in the art. In some instances herein, particularly when alternative points of attachment are possible, the point or points of attachment may be explicitly indicated by a hyphen (“-”).
  • hyphen (“-”).
  • unsubstituted” in connection with a group such as a ring or ring system means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1.
  • optionally substituted means that the number of substituents can be zero.
  • optionally substituted groups may be substituted with as many optional substituents as can be accommodated by replacing a hydrogen atom with a non-hydrogen substituent on any available carbon or nitrogen atom.
  • the number of optional substituents ranges from 1 to 3.
  • the term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.”
  • 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 10” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • variable group When a variable group is shown to be optionally attached to a position, for example (R 10 ) y in Exhibit A wherein x may be 0, then hydrogen may be at the position even if not recited in the definition of the variable group.
  • the dotted line in rings depicted in the present description e.g., the rings G-44, G-45, G-48 and G-49 shown in Exhibit A
  • the bond indicated can be a single bond or double bond.
  • 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.
  • a “ring” or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring system” denotes two or more connected rings.
  • 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).
  • the term “bicyclic ring system” denotes a ring system consisting of two rings sharing two or more common atoms. In a “fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them.
  • aromatic indicates that each of the ring atoms is essentially in the same plane and has a p-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 Hückel’s rule
  • carrier ring denotes a ring 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. When a fully unsaturated carbocyclic ring satisfies Hückel’s rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” 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. As used herein, the term “partially unsaturated ring” or “partially unsaturated heterocycle” refers to a ring which contains unsaturated ring atoms and one or more double bonds but is not aromatic.
  • heterocyclic ring or “heterocycle” denotes a ring wherein at least one of the atoms forming the ring backbone is other than carbon.
  • a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Hückel’s rule, then said ring is also called a “heteroaromatic ring” or aromatic heterocyclic ring.
  • saturated heterocyclic ring refers to a heterocyclic ring containing only single bonds between ring members.
  • heterocyclic rings and ring systems are attached to the remainder of Formula 1 through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.
  • Compounds of this invention can exist as one or more stereoisomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis- and trans-isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species.
  • Formula 1 compounds contain at least one double bond and the configuration of substituents about that double bond can be (Z) or (E) (cis or trans), or a mixture thereof.
  • a wavy bond e.g., as shown in the T-3 moiety in the Summary of the Invention indicates a single bond which is linked to an adjacent double bond wherein the geometry about the adjacent double bond is either (Z)-configuration (syn-isomer or cis-isomer) or (E)-configuration (anti-isomer or trans-isomer), or a mixture thereof.
  • This invention also includes compounds of Formula 1 wherein one stereoisomer is enriched relative to the other stereoisomer(s).
  • compounds of Formula 1 wherein T is T-3 and the substituents attached to the double bond in the T-3 moiety are in a predominately (Z)- configuration, or predominately an (E)-configuration.
  • the ratio of the (Z)- to (E)-isomers in any compounds of Formula 1, whether produced stereoselectivity or non-stereoselectivity, may take on a broad range of values.
  • compounds of Formula 1 may comprise from about 10 to 90 percent by weight of the (Z)-isomer to about 90 to 10 percent by weight of the (E)-isomer.
  • Formula 1 compounds may contain from about 15 to 85 percent by weight of the (Z)-isomer and about 85 to 15 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 25 to 75 percent by weight of the (Z)-isomer and about 75 to 25 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 35 to 65 percent by weight of the (Z)-isomer and about 65 to 35 percent by weight of the (E)-isomer; in another embodiment, the mixture contains about 45 to 55 percent by weight of the (Z)-isomer and about 55 to 45 percent by weight of the (E)-isomer.
  • compositions of this invention have at least a 50% enantiomeric excess; more preferably at least a 75% enantiomeric excess; still more preferably at least a 90% enantiomeric excess; and the most preferably at least a 94% enantiomeric excess of the more active isomer.
  • This invention comprises mixtures of conformational isomers.
  • this invention includes compounds that are enriched in one conformer relative to others.
  • This invention comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • 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 N-oxides.
  • nitrogen-containing heterocycles which can form N-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, N-oxides, and agriculturally suitable salts, and solvates 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 to the presence or absence of co-crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound represented by Formula 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.
  • crystallization using selected solvents and temperatures.
  • ketones of Formula 11 i.e. compounds of Formula 1 wherein T is T-1
  • ketones of Formula 12 may exist in equilibrium with their corresponding hydrates of Formula 12 (i.e. compounds of Formula 1 wherein T is T-2, and R 2a X and R 2b Y are both OH).
  • the equilibrium typically favors the hydrate form.
  • This invention comprises all ketonic and solvated forms of Formula 1 compounds, and mixtures thereof in all proportions. Unless otherwise indicated, reference to a compound by one tautomer description is to be considered to include all tautomers. Additionally, some of the unsaturated rings and ring systems depicted in Exhibit A can have an arrangement of single and double bonds between ring members different from that depicted. Such differing arrangements of bonds for a particular arrangement of ring atoms correspond to different tautomers. For these unsaturated rings and ring systems, the particular tautomer depicted is to be considered representative of all the tautomers possible for the arrangement of ring atoms shown. Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes stereoisomers, N-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 T is T-1.
  • Embodiment 2. A compound of Formula 1 wherein T is T-2 or T-3.
  • Embodiment 3. A compound of Embodiment 2 wherein T is T-2.
  • Embodiment 4. A compound of Embodiment 2 wherein T is T-3.
  • Embodiment 5. A compound of Formula 1 or any one of Embodiments 1 through 4 wherein R 1 is CF 3 .
  • Embodiment 7. A compound of Embodiment 6 wherein W is O.
  • Embodiment 8. A compound of Formula 1 or any one of Embodiments 1 through 5 wherein W is NR 3 .
  • Embodiment 11 A compound of Embodiment 10 wherein R 3 is H, cyano or OR 3a .
  • Embodiment 12. A compound of Formula 1 or any one of Embodiments 1 through 11 wherein R 3a is H, C 1 -C 2 alkyl, C 2 -C 3 alkylcarbonyl or C 2 -C 3 haloalkylcarbonyl.
  • Embodiment 13 A compound of Embodiment 12 wherein R 3a is H.
  • Embodiment 14 A compound of Formula 1 or any one of Embodiments 1 through 13 wherein when R 3b is separate (i.e.
  • R 3b is H, C 1 -C 3 alkyl, C 2 -C 3 alkylcarbonyl or C 2 -C 3 haloalkylcarbonyl.
  • Embodiment 15 A compound of Embodiment 14 wherein R 3b is H or methyl.
  • Embodiment 16 A compound of Formula 1 or any one of Embodiments 1 through 15 wherein when R 3c is separate (i.e. not taken together with R 3b to form a ring), then R 3c is H or C 1 -C 2 alkyl.
  • Embodiment 17 A compound of Embodiment 16 wherein R 3c is H or methyl.
  • Embodiment 19 A compound of Formula 1 or any one of Embodiments 1 through 17 wherein X is O, S, NH or NOH.
  • Embodiment 20 A compound of Embodiment 19 wherein X is O or NOH.
  • Embodiment 21 A compound of Embodiment 20 wherein X is O.
  • Embodiment 23 A compound of Formula 1 or any one of Embodiments 1 through 21 wherein Y is O, S, NH or NOH.
  • Embodiment 24 A compound of Formula 1 or any one of Embodiments 1 through 21 wherein Y is O, S, NH or NOH.
  • Embodiment 24 A compound of Formula 1 or any one of Embodiments 1 through 21 wherein Y is
  • Embodiment 23 wherein Y is O or NOH.
  • Embodiment 25 A compound of Embodiment 24 wherein Y is O.
  • Embodiment 26 A compound of Formula 1 or any one of Embodiments 1 through 25 wherein R 4a and R 4b are each independently H, hydroxy or C 1 -C 2 alkyl.
  • Embodiment 27 A compound of Embodiment 26 wherein R 4a and R 4b are each independently H, hydroxy or methyl.
  • Embodiment 28 A compound of Formula 1 or any one of Embodiments 1 through 27 wherein when R 2a and R 2b are separate (i.e.
  • R 2a and R 2b are each independently H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, C 3 -C 15 trialkylsilyl or C 3 -C 15 halotrialkylsilyl.
  • Embodiment 29 A compound of Embodiment 28 wherein R 2a and R 2b are each independently H, C 1 -C 3 alkyl, C 2 -C 3 alkenyl, trimethylsilyl or halotrimethylsilyl.
  • Embodiment 30 A compound of Embodiment 29 wherein R 2a and R 2b are each independently H, C 1 -C 2 alkyl, trimethylsilyl or halotrimethylsilyl.
  • Embodiment 31 A compound of Embodiment 30 wherein R 2a and R 2b are each independently H or C 1 -C 2 alkyl.
  • Embodiment 32 A compound of Embodiment 31 wherein R 2a and R 2b are each independently H or methyl.
  • Embodiment 33 A compound of Embodiment 32 wherein R 2a and R 2b are each H.
  • Embodiment 34 A compound of Formula 1 or any one of Embodiments 1 through 33 wherein when R 2a and R 2b are taken together to form a ring (i.e.
  • a compound of Embodiment 34 wherein R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5- to 6-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, wherein up to 1 carbon atom ring member is C( O), the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl, methoxy and halomethoxy on carbon atom ring members.
  • Embodiment 36 Embodiment 36.
  • Embodiment 38 A compound of Embodiment 37 wherein R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
  • Embodiment 39 A compound of Formula 1 or any one of Embodiments 1 through 38 wherein R 2c is C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkenyl, C 2 -C 3 haloalkenyl, C 2 -C 3 alkynyl or C 2 -C 3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SC ⁇ N and C 1 -C 2 alkoxy.
  • R 2c is C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkenyl, C 2 -C 3 haloalkenyl, C 2 -C 3 alkynyl or C 2 -C 3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SC ⁇ N and C 1 -C 2 alkoxy.
  • Embodiment 41 A compound of Embodiment 40 wherein R 2c is C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 2 -C 3 alkenyl, C 2 -C 3 haloalkenyl or C 2 -C 3 alkynyl.
  • Embodiment 42 A compound of Embodiment 41 wherein R 2c is C 1 -C 2 alkyl, C 2 -C 3 alkenyl or C 2 -C 3 alkynyl.
  • Embodiment 43 A compound of Embodiment 42 wherein R 2c is methyl or ethyl.
  • Embodiment 44 A compound of Embodiment 43 wherein R 2c is ethyl.
  • Embodiment 45. A compound of Formula 1 or any one of Embodiments 1 through 44 wherein R 2d is H, cyano, halogen or C 1 -C 2 alkyl.
  • Embodiment 46 A compound of Embodiment 45 wherein R 2d is H, cyano, Cl, F or methyl.
  • Embodiment 47 A compound of Embodiment 46 wherein R 2d is H or methyl.
  • Embodiment 48 A compound of Embodiment 47 wherein R 2d is H.
  • Embodiment 49 A compound of Formula 1 or any one of Embodiments 1 through 48 wherein A 1 is CH 2 , NH, O or S.
  • Embodiment 50 A compound of Formula 1 or any one of Embodiments 1 through 48 wherein A 1 is CR 5a R 5b , O or S.
  • Embodiment 51 A compound of Embodiment 50 wherein A 1 is CR 5a R 5b or O.
  • Embodiment 52 A compound of Embodiment 51 wherein A 1 is CR 5a R 5b .
  • Embodiment 53 A compound of Embodiment 53.
  • Embodiment 54 A compound of Formula 1 or any one of Embodiments 1 through 53 wherein A 1 is N(R 6 ).
  • Embodiment 55 A compound of Formula 1 or any one of Embodiments 1 through 54 wherein A 2 is a direct bond, CH 2 , NH, O or S.
  • Embodiment 56 A compound of Formula 1 or any one of Embodiments 1 through 54 wherein A 2 is a direct bond, CR 5a R 5b , O or S.
  • Embodiment 57 A compound of Embodiment 56 wherein A 2 is a direct bond, CR 5a R 5b or O.
  • Embodiment 58 A compound of Embodiment 56 wherein A 2 is a direct bond, CR 5a R 5b or O.
  • Embodiment 57 wherein A 2 is a direct bond, CH 2 or O.
  • Embodiment 58a A compound of Embodiment 58 wherein A 2 is a direct bond or CH 2 .
  • Embodiment 59 A compound of Embodiment 58 wherein A 2 is a direct bond or O.
  • Embodiment 60 A compound of Embodiment 59 wherein A 2 is a direct bond.
  • Embodiment 61. A compound of Formula 1 or any one of Embodiments 1 through 60 wherein A 2 is N(R 6 ).
  • Embodiment 62 A compound of Formula 1 or any one of Embodiments 1 through 60 wherein A 2 is N(R 6 ).
  • Embodiment 66. A compound of Formula 1 or any one of Embodiments 1 through 65 wherein when A is A 1 -A 2 , then A 1 -A 2 is selected from O, CH 2 , OCH 2 and CH 2 O.
  • Embodiment 70. A compound of Formula 1 or any one of Embodiments 1 through 69 wherein each R 5a and R 5b is independently H, cyano, hydroxy, Br, Cl, F or methyl.
  • Embodiment 71 A compound of Embodiment 70 wherein each R 5a and R 5b is independently H, cyano hydroxy or methyl.
  • Embodiment 74. A compound of Formula 1 or any one of Embodiments 1 through 73 wherein each R 6 is independently H, C 1 -C 2 alkyl or C 2 -C 3 alkylcarbonyl.
  • Embodiment 75. A compound of Embodiment 74 wherein each R 6 is each independently H or C 1 -C 2 alkyl.
  • Embodiment 76. A compound of Embodiment 75 wherein each R 6 is each H.
  • Embodiment 77. A compound of Formula 1 or any one of Embodiments 1 through 76 wherein J is J-1 through J-3, J-6 through J-10, J-14 or J-15.
  • Embodiment 77 wherein J is J-1 through J-3, J-6 through J-10 or J-14.
  • Embodiment 78 A compound of Embodiment 77a wherein J is J-1, J-2, J-3, J-6 or J-14.
  • Embodiment 79 A compound of Embodiment 78 wherein J is J-1, J-6 or J-14.
  • Embodiment 80 A compound of Embodiment 79 wherein J is J-1 or J-6.
  • Embodiment 81 A compound of Embodiment 79 wherein J is J-14.
  • Embodiment 82 A compound of Embodiment 80 wherein J is J-1.
  • Embodiment 83 A compound of Embodiment 80 wherein J is J-6.
  • Embodiment 84 A compound of Embodiment 84.
  • Embodiment 85. A compound of Embodiment 84 wherein each R 7 is independently F or Cl.
  • Embodiment 86. A compound of Embodiment 84 wherein each R 7 is independently F or methyl.
  • Embodiment 87. A compound of Embodiment 86 wherein each R 7 is F.
  • Embodiment 88. A compound of Formula 1 or any one of Embodiments 1 through 87 wherein q is 0, 1 or 2.
  • Embodiment 88a. A compound of Embodiment 88 wherein q is 1 or 2.
  • Embodiment 88b. A compound of Embodiment 88a wherein q is 2.
  • Embodiment 89 A compound of Embodiment 88 wherein q is 0 or 1.
  • Embodiment 90 A compound of Embodiment 89 wherein q is 1.
  • Embodiment 91 A compound of Embodiment 89 wherein q is 0.
  • Embodiment 92 A compound of Formula 1 or any one of Embodiments 1 through 91 wherein each R 8a and R 8b is independently H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy.
  • Embodiment 93 Embodiment 93.
  • Embodiment 92 wherein each R 8a and R 8b is independently H, halogen, C 1 -C 2 alkyl or C 1 -C 2 haloalkyl.
  • Embodiment 94 A compound of Embodiment 93 wherein each R 8a and R 8b is independently H, halogen or methyl.
  • Embodiment 95 A compound of Embodiment 94 wherein each R 8a and R 8b is independently H or methyl.
  • Embodiment 96 A compound of Embodiment 95 wherein each R 8a and R 8b is H.
  • Embodiment 97 A compound of Formula 1 or any one of Embodiments 1 through 96 wherein n is 0, 1 or 2.
  • Embodiment 97 wherein n is 1 or 2.
  • Embodiment 97b A compound of Embodiment 97a wherein n is 2.
  • Embodiment 98 A compound of Embodiment 97 wherein n is 0 or 1.
  • Embodiment 99 A compound of Embodiment 98 wherein n is 1.
  • Embodiment 100 A compound of Embodiment 98 wherein n is 0.
  • Embodiment 101 A compound of Formula 1 or any one of Embodiments 1 through 100 wherein L is a direct bond, CH 2 , CH(Me) or CH 2 CH 2 .
  • Embodiment 102 A compound of Embodiment 101 wherein L is a direct bond, CH 2 or CH 2 CH 2 .
  • Embodiment 103 A compound of Embodiment 102 wherein L is a direct bond or CH 2 .
  • Embodiment 104. A compound of Embodiment 103 wherein L is CH 2 .
  • Embodiment 105. A compound of Embodiment 103 wherein L is a direct bond.
  • Embodiment 106. A compound of Formula 1 or any one of Embodiments 1 through 105 wherein G is selected from G-1 through G-118 as shown in Exhibit A. Exhibit A
  • Embodiment 107 A compound of Embodiment 106 wherein G is G-1 through G-16, G-20, G-22 through G-30, G-36 through G-42, G-54 through G-60, G-85, G-86, G-108, G-110 or G-111.
  • Embodiment 107a A compound of Embodiment 107 wherein G is G-20.
  • Embodiment 107b A compound of Embodiment 106 wherein G is G-1, G-12, G-20, G-103 and G-104.
  • Embodiment 108 A compound of Embodiment 106 wherein G is G-1, G-12, G-20, G-103 and G-104.
  • Embodiment 109. A compound of Embodiment 108 wherein G is G-1 through G-13, G-22, G-24, G-25, G-26, G-28, G-29, G-41, G-42, G-54, G-57, G-58, G-59 or G-60.
  • Embodiment 109 wherein G is G-1, G-2, G-3, G-7, G-8, G-9, G-10, G-12, G-13, G-22, G-29, G-42, G-54 or G-58.
  • Embodiment 111 A compound of Embodiment 110 wherein G is G-1, G-3, G-12, G-13, G-22 or G-42.
  • Embodiment 112. A compound of Embodiment 111 wherein G is G-1, G-3, G-12 or G-13.
  • Embodiment 113 A compound of Embodiment 112 wherein G is G-1, G-12 or G-13.
  • Embodiment 114 A compound of Embodiment 112 wherein G is G-1.
  • Embodiment 115 A compound of Embodiment 112 wherein G is G-1.
  • Embodiment 115 A compound of Embodiment 112 wherein G is G-1, Embodiment 115.
  • Embodiment 112 wherein G is G-3.
  • Embodiment 116 A compound of Embodiment 112 wherein G is G-12.
  • Embodiment 117 A compound of Embodiment 112 wherein G is G-13.
  • Embodiment 118 A compound of Embodiment 114 wherein the 2-position of G-1 is connected to Z and the 4-position is connected to R 9 .
  • Embodiment 119 A compound of Embodiment 114 wherein the 2-position of G-1 is connected to Z and the 5-position is connected to R 9 .
  • Embodiment 120 A compound of Embodiment 115 wherein the 1-position of G-3 is connected to Z and the 4-position is connected to R 9 .
  • Embodiment 121 A compound of Embodiment 115 wherein the 1-position of G-3 is connected to Z and the 4-position is connected to R 9 .
  • Embodiment 122. A compound of Embodiment 116 wherein the 1-position of G-12 is connected to Z and the 3-position is connected to R 9 .
  • Embodiment 123. A compound of Embodiment 116 wherein the 1-position of G-12 is connected to Z, the 3-position is connected to R 9 and the 5-position is connected to R 10 .
  • Embodiment 124. A compound of Embodiment 116 wherein the 1-position of G-12 is connected to Z and the 5-position is connected to R 9 .
  • Embodiment 117 wherein the 1-position of G-13 is connected to Z and the 4-position is connected to R 9 .
  • Embodiment 126. A compound of Embodiment 117 wherein the 1-position of G-13 is connected to Z and the 5-position is connected to R 9 .
  • Embodiment 127. A compound of any one of Embodiments 106 through 126 wherein x is 1 or 2.
  • Embodiment 128. A compound of Embodiment 127 wherein x is 1.
  • Embodiment 129 A compound of Embodiment 127 wherein x is 2.
  • Embodiment 130. A compound of any one of Embodiments 106 through 129 wherein y is 0, 1 or 2.
  • Embodiment 130 wherein y is 0 or 1.
  • Embodiment 132 A compound of Embodiment 131 wherein y is 0.
  • Embodiment 133a A compound of Embodiment 130 wherein y is 0 or 1.
  • Embodiment 132 A compound of Embodiment 131 wherein y is 0.
  • Embodiment 133c Embodiment 133
  • Embodiment 135a A compound of Embodiment 134 wherein each R 9 is independently C 2 -C 4 alkoxy(thiocarbonyl).
  • Embodiment 134 wherein each R 9 is independently -(CR 11a R 11b )mR 9a .
  • Embodiment 135b A compound of Embodiment 135a wherein each R 9 is independently -CH 2 R 9a .
  • Embodiment 138 A compound of Formula 1 or any one of Embodiments 1 through 135 wherein each m is independently 1 or 2.
  • Embodiment 138a A compound of Formula 1 or any one of Embodiments 1 through 135 wherein each m is independently 1 or 2.
  • Embodiment 138 wherein each m is 1.
  • Embodiment 143 Embodiment 143.
  • Embodiment 143a Embodiment 143a.
  • Embodiment 143b Embodiment 143b.
  • Embodiment 144 Embodiment 144.
  • Embodiment 145 Embodiment 145.
  • Embodiment 147 is
  • Embodiment 147c is
  • each R 9a is independently C 2 -C 6 alkylcarbonyloxy or C 2 -C 6 alkoxycarbonyloxy.
  • Embodiment 151 Embodiment 151.
  • each R 10 is independently halogen or C 2 -C 3 alkoxycarbonyl.
  • Embodiment 158 A compound of Formula 1 or any one of Embodiments 1 through 157a wherein each R 11a and R 11b is independently H, halogen, cyano, C 1 -C 2 alkyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 haloalkylcarbonyl, C 2 -C 3 alkoxycarbonyl or C 2 -C 3 haloalkoxycarbonyl.
  • Embodiment 159 Embodiment 159.
  • Embodiment 160. A compound of Embodiment 159 wherein each R 11a and R 11b is independently H, methyl or C 2 -C 3 alkoxycarbonyl.
  • a compound of Embodiment 160 wherein each R 11a and R 11b is independently H, methyl or EtOC( O).
  • Embodiment 162 A compound of Embodiment 161 wherein each R 11a and R 11b is H. Embodiment 163. A compound of Formula 1 or any one of Embodiments 1 through 162 wherein each R 12a is independently C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy, C 4 -C 8 cycloalkylalkoxy or C 2 -C 6 alkoxyalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 3 substituents independently selected from halogen and methyl.
  • Embodiment 163a A compound of Embodiment 163 wherein each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 4 -C 8 cycloalkylalkoxy or C 2 -C 6 alkoxyalkoxy.
  • Embodiment 163b A compound of Embodiment 163 wherein each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 4 -C 8 cycloalkylalkoxy or C 2 -C 6 alkoxyalkoxy.
  • each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 4 -C 8 cycloalkylalkoxy or C 2 -C 6 alkoxyalkoxy.
  • Embodiment 163c A compound of Embodiment 163b wherein each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy or C 4 -C 8 cycloalkylalkoxy.
  • Embodiment 163d Embodiment 163d.
  • each R 12a is independently C 1 -C 3 haloalkoxy, C 2 -C 4 alkenyloxy or C 4 -C 5 cycloalkylalkoxy.
  • Embodiment 164 is independently C 1 -C 3 haloalkoxy, C 2 -C 4 alkenyloxy or C 4 -C 5 cycloalkylalkoxy.
  • each R 12a is independently C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy or C 4 -C 8 cycloalkylalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 3 substituents independently selected from halogen and methyl.
  • Embodiment 165 is independently C 1 -C 6 haloalkoxy, C 1 -C 6 hydroxyalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkyn
  • each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy or C 4 -C 8 cycloalkylalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 3 substituents independently selected from halogen and methyl.
  • Embodiment 166 is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 2 -C 6 haloalkynyloxy or C 4 -C 8 cycloalkylalkoxy; or pheny
  • each R 12a is independently C 1 -C 4 haloalkoxy, C 2 -C 4 cyanoalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 2 -C 4 alkynyloxy, C 2 -C 4 haloalkynyloxy or C 4 -C 6 cycloalkylalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 3 substituents independently selected from halogen and methyl.
  • Embodiment 167 Embodiment 167.
  • each R 12a is independently C 1 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 2 -C 4 alkynyloxy or C 4 -C 6 cycloalkylalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
  • Embodiment 168 is independently C 1 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 2 -C 4 alkynyloxy or C 4 -C 6 cycloalkylalkoxy; or phenyl-CH 2 O, each phenyl ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
  • each R 12a is independently C 1 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 4 -C 6 cycloalkylalkoxy or phenyl-CH 2 O.
  • Embodiment 170 Embodiment 170.
  • each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 4 -C 8 cycloalkylalkoxy or phenyl-CH 2 O.
  • Embodiment 170a A compound of Embodiment 170 wherein each R 12a is independently C 1 -C 6 haloalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy or C 4 -C 8 cycloalkylalkoxy.
  • Embodiment 171 A compound of Embodiment 170 wherein each R 12a is independently C 1 -C 3 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 4 -C 6 cycloalkylalkoxy or phenyl-CH 2 O.
  • Embodiment 172 A compound of Embodiment 171 wherein each R 12a is independently C 2 -C 4 alkenyloxy, C 2 -C 4 haloalkenyloxy, C 4 -C 5 cycloalkylalkoxy or phenyl-CH 2 O.
  • each R 12b is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 halocycloalkylalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 haloalkoxyalkyl, C 2 -
  • Embodiment 174 A compound of Embodiment 173 wherein each R 12b is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 haloalkoxyalkyl, C 2 -C 4 alkylaminoalkyl or C 3 -C 5 dialkylaminoalkyl.
  • each R 12b is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl or C 2 -C 4 alkoxyalkyl.
  • Embodiment 176 A compound of Embodiment 175 wherein each R 12b is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropylmethyl or C 2 -C 4 alkoxyalkyl.
  • Embodiment 177 is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropylmethyl or C 2 -C 4 alkoxyalkyl.
  • each R 12b is independently H, C 1 -C 2 alkyl or C 1 -C 2 haloalkyl.
  • Embodiment 178 A compound of Embodiment 177 wherein each R 12b is independently H or methyl.
  • Embodiment 180. A compound of Formula 1 or any one of Embodiments 1 through 179 wherein when each R 12c is separate (i.e.
  • each R 12c is independently H, cyano, hydroxy, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 1 -C 5 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 haloalkylcarbonyl, C 4 -C 7 cycloalkylcarbonyl, C 2 -C 5 alkoxycarbonyl, C 2 -C 5 alkylaminocarbonyl or C 3 -C 5 dialkylaminocarbonyl.
  • Embodiment 180a A compound of Embodiment 180 wherein each R 12c is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 1 -C 5 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl, C 2 -C 4 haloalkylcarbonyl, C 4 -C 7 cycloalkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 180b A compound of Embodiment 180 wherein each R 12c is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 1 -C 5 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alky
  • each R 12c is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl, C 4 -C 5 cycloalkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • each R 12c is independently C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl, C 4 -C 5 cycloalkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • each R 12c is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 5 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 183. A compound of Embodiment 182 wherein each R 12c is independently H, C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 183a is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 5 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • each R 12c is independently C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 5 alkoxycarbonyl.
  • Embodiment 183a A compound of Embodiment 183 wherein each R 12c is independently H or methyl.
  • Embodiment 185 A compound of Embodiment 184 wherein each R 12c is methoxy.
  • Embodiment 186 is
  • each R 12d is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkylalkyl
  • Embodiment 188 A compound of Embodiment 187 wherein each R 12d is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 haloalkoxyalkyl, C 2 -C 4 alkylaminoalkyl or C 3 -C 5 dialkylaminoalkyl.
  • Embodiment 189 A compound of Embodiment 187 wherein each R 12d is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 3 -C 5 cycloalkyl, C 4 -C
  • each R 12d is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl or C 2 -C 4 alkoxyalkyl.
  • Embodiment 190 A compound of Embodiment 189 wherein each R 12d is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropylmethyl or C 2 -C 4 alkoxyalkyl.
  • Embodiment 196 Embodiment 196.
  • each R 12e is independently NH 2 , C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 1 -C 6 hydroxyalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 cycloalkyl, C 2 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 haloalkoxyalkyl, C 3 -C 8 alkoxyalkoxyalkyl, C 2 -C 6 alkylaminoalkyl, C 3 -C 8 dialkylaminoalkyl,
  • Embodiment 199 A compound of Embodiment 198 wherein each R 12e is independently C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 1 -C 6 hydroxyalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 4 -C 6 cycloalkylalkoxy, C 2 -C 6 alkoxyalkyl or C 2 -C 6 haloalkoxyalkyl.
  • Embodiment 200 Embodiment 200.
  • each R 12e is independently C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 4 -C 5 cycloalkylalkoxy or C 2 -C 6 alkoxyalkyl.
  • each R 12e is independently C 2 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 4 -C 5 cycloalkylalkoxy or C 2 -C 6 alkoxyalkyl.
  • each R 12e is independently C 2 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkenyl, C 2 -C 4 alkoxy, C 1 -C 3 haloalkoxy or C 4 -C 5 cycloalkylalkoxy.
  • Embodiment 202 A compound of Embodiment 201 wherein each R 12e is independently C 2 -C 3 alkyl, C 2 -C 4 alkoxy, C 1 -C 3 haloalkoxy or C 4 -C 5 cycloalkylalkoxy.
  • Embodiment 202a is independently C 2 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkenyl, C 2 -C 4 alkoxy, C 1 -C 3 haloalkoxy or C 4 -C 5 cycloalkylalkoxy.
  • each R 12e is independently C 2 -C 3 alkoxy, C 1 -C 3 haloalkoxy or C 4 -C 5 cycloalkylalkoxy.
  • Embodiment 203 A compound of Embodiment 202 wherein each R 12e is independently C 2 -C 4 alkoxy or C 1 -C 3 haloalkoxy.
  • Embodiment 204 A compound of Embodiment 203 wherein each R 12e is ethoxy.
  • Embodiment 205 is
  • each R 12f is independently hydroxy or NR 20a R 20b ; or C 1 -C 6 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 5 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from cyano and halogen.
  • Embodiment 206 is independently hydroxy or NR 20a R 20b ; or C 1 -C 6 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 10 cycloalkylalkoxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 5 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from cyano and halogen.
  • each R 12f is independently C 1 -C 5 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 6 cycloalkylalkoxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 5 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • Embodiment 206a is independently C 1 -C 5 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 6 cycloalkylalkoxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 5 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 6 cycloalkylalkoxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 5 alkoxycarbonyloxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • Embodiment 206b A compound of Embodiment 206a wherein each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy, C 4 -C 6 cycloalkylalkoxy or C 2 -C 4 alkylcarbonyloxy.
  • Embodiment 206b A compound of Embodiment 206b.
  • each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy or C 4 -C 5 cycloalkylalkoxy.
  • Embodiment 207 A compound of Embodiment 206 wherein each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy or C 4 -C 6 cycloalkylalkoxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • Embodiment 208 is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy or C 4 -C 6 cycloalkylalkoxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy or cyclopropylmethoxy, each optionally substituted with up to 3 substituents independently selected from halogen.
  • Embodiment 209 A compound of Embodiment 208 wherein each R 12f is independently C 1 -C 4 alkoxy, C 2 -C 4 alkenyloxy or cyclopropylmethoxy.
  • Embodiment 209a A compound of Embodiment 209 wherein each R 12f is independently C 1 -C 4 alkoxy.
  • Embodiment 210 is independently C 1 -C 4 alkoxy.
  • each R 12f is independently C 3 -C 4 alkenyloxy.
  • Embodiment 211 A compound of Formula 1 or any one of Embodiments 1 through 210 wherein when each R 12i and R 12j is separate (i.e. not taken together to form a ring), then each R 12i and R 12j is independently H, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 2 -C 4 alkylcarbonyl.
  • Embodiment 212 A compound of Embodiment 211 wherein each R 12i and R 12j is independently H, methyl or C 2 -C 3 alkylcarbonyl.
  • each R 13 is independently halogen, cyano, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylthio, C 1 -C 4 alkylsufonyl or C 3 -C 6 cycloalkyl.
  • each R 13 is independently halogen, cyano, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylthio, C 1 -C 4 alkylsufonyl or C 3 -C 6 cycloalkyl.
  • each R 13 is independently halogen, cyano, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylthio or C 3 -C 5 cycloalkyl.
  • Embodiment 215. A compound of Embodiment 214 wherein each R 13 is independently halogen, cyano, C 1 -C 4 alkoxy, C 2 -C 4 alkoxycarbonyl, C 1 -C 4 alkylthio or C 3 -C 5 cycloalkyl.
  • Embodiment 216 Embodiment 216.
  • each R 13 is independently Br, Cl, F, cyano, methoxy, C 2 -C 4 alkoxycarbonyl, C 1 -C 2 alkylthio or cyclopropyl.
  • each R 14a is independently H, cyano, hydroxy, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C 5 alkoxycarbonyl or C 3 -C 5 dialkylaminocarbonyl.
  • Embodiment 220 Embodiment 220.
  • each R 14a is independently H, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C 5 alkoxycarbonyl or C 3 -C 5 dialkylaminocarbonyl.
  • each R 14a is independently H, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C 5 alkoxycarbonyl or C 3 -C 5 dialkylaminocarbonyl.
  • each R 14a is independently H, C 1 -C 2 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl or C 2 -C 4 alkoxycarbonyl.
  • Embodiment 222 A compound of Embodiment 198 wherein each R 14a is independently H or C 1 -C 2 alkyl.
  • Embodiment 223. A compound of Embodiment 222 wherein each R 14a is independently H or methyl.
  • Embodiment 224 A compound of Embodiment 223 wherein each R 14a is H.
  • Embodiment 225 is
  • each R 14b is independently H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 halocycloalkylalkyl, C 2 -C 6 halocycloalkylalkyl, C 2 -C 6
  • Embodiment 226 A compound of Embodiment 225 wherein each R 14b is independently H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 haloalkoxyalkyl, C 2 -C 4 alkylaminoalkyl or C 3 -C 5 dialkylaminoalkyl.
  • Embodiment 227 Embodiment 227.
  • each R 14b is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 3 -C 5 cycloalkyl, C 4 -C 6 cycloalkylalkyl or C 2 -C 4 alkoxyalkyl.
  • Embodiment 228 A compound of Embodiment 227 wherein each R 14b is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropylmethyl or C 2 -C 4 alkoxyalkyl.
  • each R 14b is independently H, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or cyclopropylmethyl.
  • Embodiment 300 A compound of Embodiment 229 wherein each R 14b is independently H, methyl or cyclopropylmethyl.
  • Embodiment 301 A compound of Embodiment 228 wherein each R 14b is independently H, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or cyclopropylmethyl.
  • Embodiment 306. A compound of Formula 1 or any one of Embodiments 1 through 305 wherein each R 16 is independently hydroxy, NR 20a R 20b , C 1 -C 2 alkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkylcarbonyloxy or C 2 -C 4 alkoxycarbonyloxy.
  • each R 19 is independently cyano, halogen, hydroxy, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 3 alkoxyalkoxy, C 1 -C 3 alkylthio, C 1 -C 3 alkylsulfinyl, C 1 -C 3 alkylsulfonyl, C 1 -C 3 haloalkylsulfonyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 haloalkylcarbonyl, C 2 -C 3 alkoxycarbonyl, C 2 -C 3 alkylaminocarbonyl or C 3 -C 5 dialkylaminocarbonyl.
  • Embodiment 315 A compound of Embodiment 314 wherein each R 19 is independently cyano, halogen, hydroxy, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 alkylsulfonyl, C 1 -C 2 haloalkylsulfonyl, C 2 -C 3 alkylcarbonyl, C 2 -C 3 haloalkylcarbonyl, C 2 -C 3 alkoxycarbonyl or C 2 -C 3 alkylaminocarbonyl.
  • Embodiment 316 A compound of Embodiment 315 wherein each R 19 is independently cyano, halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 2 -C 3 alkylcarbonyl, C 2 -C 3 haloalkylcarbonyl or C 2 -C 3 alkoxycarbonyl.
  • Embodiment 317 A compound of Embodiment 315 wherein each R 19 is independently cyano, halogen, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 2 alkoxy, C 1 -C 2 haloalkoxy, C 2 -C 3 alkylcarbonyl, C 2 -C 3 haloalkylcarbonyl or C 2
  • Embodiment 318. A compound of Embodiment 317 wherein each R 19 is independently cyano, halogen, cyclopropyl or methoxy.
  • Embodiment 319. A compound of Embodiment 318 wherein each R 19 is independently halogen.
  • Embodiment 325 Embodiment 325.
  • Embodiment 330. A compound of Embodiment 329 wherein each V is CH 2 .
  • Embodiment 331. A compound of Formula 1 or any one of Embodiments 1 through 330 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 ; or a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R 27 ; or a 3- to 6-membered nonaromatic heterocyclic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, wherein up to 2 ring members are
  • Embodiment 332 A compound of Embodiment 331 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 ; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thienyl, isoxazolinyl, piperidinyl, morpholinyl or piperazinyl, each optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 333 Embodiment 333.
  • Embodiment 335 Embodiment 335.
  • Embodiment 337. A compound of Formula 1 or any one of Embodiments 1 through 336 wherein when each R 20a is separate (i.e. not taken together with R 20b to form a ring), then each R 20a is independently H, methyl or methylcarbonyl.
  • each R 20b is independently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.
  • Embodiment 339 is independently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.
  • Embodiment 340 Embodiment 340.
  • Embodiment 341. A compound of Formula 1 or any one of Embodiments 1 through 247 wherein each R 21 and R 23 is independently H, cyano, halogen, methyl or methoxy.
  • each R 22 is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkylcarbonyl or C 2 -C 3 alkoxycarbonyl; or phenyl optionally substituted with up to 2 substituents independently selected halogen and methyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
  • Embodiment 344. A compound of Formula 1 or any one of Embodiments 1 through 343 wherein each R 24 is independently H, cyano or C 1 -C 2 alkyl.
  • Embodiment 345. A compound of Formula 1 or any one of Embodiments 1 through 344 wherein each R 25 and R 26 is independently H, cyano, hydroxy, C 1 -C 4 alkyl or C 1 -C 4 haloalkyl.
  • Embodiment 346. A compound of Embodiment 345 wherein each R 25 and R 26 is independently H, cyano, hydroxy or C 1 -C 2 alkyl.
  • Embodiment 347 A compound of Formula 1 or any one of Embodiments 1 through 346 wherein each R 27 is independently halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy.
  • Embodiment 348 A compound of Embodiment 347 wherein each R 27 is independently halogen, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or C 1 -C 2 alkoxy.
  • Embodiment 349. A compound of Embodiment 348 wherein each R 27 is independently halogen, methyl or methoxy.
  • Embodiment 350 A compound of Formula 1 or any one of Embodiments 1 through 346 wherein each R 27 is independently halogen, cyano, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl or C 1 -C 4 alkoxy.
  • Embodiment 348 A compound
  • a compound of Embodiment 351 wherein Z is a direct bond, O, NH or C( O).
  • Embodiment 354. A compound of Formula 1 or any one of Embodiments 1 through 353 wherein each R 28 is independently H or C 1 -C 3 alkyl.
  • Embodiment 355. A compound of Embodiment 354 wherein each R 28 is independently H or methyl.
  • Embodiment 356. A compound of Formula 1 or any one of Embodiments 1 through 355 wherein p is 0 or 2.
  • Embodiment 357. A compound of Embodiment 356 wherein p is 2.
  • 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 Formula 1.
  • embodiments of this invention including Embodiments 1-357 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention. Combinations of Embodiments 1-357 are illustrated by: Embodiment A.
  • Embodiment G A compound of Formula 1 wherein T is T-2 or T-3; R 1 is CF 3 ; X is O; Y is O; R 2a and R 2b are each H; or R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms; R 2c is methyl or ethyl; R 2d is H; A 1 is O; A 2 is a direct bond; each R 5a and R 5b is H; J is J-1, J-6 or J-14; each R 7 is F; q is 0, 1 or 2; each R 8a and R 8b is H; n is 1 or 2; G is selected from the group consisting of: wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring; x is 1; and y is 0 or 1; R 9 is
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of: O-ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1- yl]oxy]phenyl]methyl]-1H-pyrazole-4-carbothioate (Compound 7); (Z)-(1-(4-((2-ethoxy-3,3,3-trifluoroprop-1-en-1-yl)oxy)benzyl)-1H-pyrazol-4- yl)methyl methoxy(methyl)carbamate (Compound 18); [1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H- pyrazol-4-yl]methyl propanoate (Compound 21); [1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]
  • Embodiment BB A compound of Embodiment A wherein R 2a and R 2b are each independently H or methyl; or R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 2 substituents independently selected from halogen, methyl and halomethyl on a carbon atom ring member;
  • a 1 is O;
  • a 2 is a direct bond, CH 2 or O;
  • R 5a and R 5b are H; J is J-1, J-6 or J-14; q is 0; each R 8a and R 8b is independently H or methyl; n is 0 or 1; G is G-1, G-3, G-12 or G-13; x is 1 or 2; y is 0 or 1; each R 9 is independently -(CR 11a R 11b )mR 9
  • this invention also provides a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof), and at least one other fungicide.
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-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.
  • compositions comprising a compound corresponding to any of the compound embodiments described above.
  • This invention provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to a plant seed, a fungicidally effective amount of a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof).
  • a fungicidally effective amount of a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof.
  • methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments described above.
  • the compounds are applied as compositions of this invention.
  • One or more of the following methods and variations as described in Schemes 1-23 can be used to prepare the compounds of Formula 1.
  • Compounds of Formula 1 wherein G is a heterocyclic ring or ring system (e.g., pyrazole) linked to L via a nitrogen atom, and Z is a direct bond can be prepared by displacement of an appropriate leaving group La of compounds of Formula 2 with nitrogen-containing heterocycles of Formula 3 in the presence of a base, as depicted in Scheme 1.
  • Suitable bases include inorganic bases such as alkali or alkaline earth metal (e.g., lithium, sodium, potassium and cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides.
  • a variety of solvents are suitable for this method including, for example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, acetonitrile and acetone.
  • Particularly useful reaction conditions include using cesium carbonate or potassium carbonate as the base, and N,N-dimethylformamide or acetonitrile as the solvent at temperatures ranging between about 0 to 80 °C.
  • Suitable leaving groups in the compounds of Formula 2 include bromide, chlorine, iodide, mesylate (OS(O) 2 CH 3 ), triflate (OS(O) 2 CF 3 ), and the like.
  • Alkyl bromides can similarly be prepared using phosphorus tribromide or phosphorus oxybromide, or carbon tetrabromide or N-bromosuccinimide in the presence of triphenylphosphine (for conditions, see present Example 1, Step E and Example 4, Step C).
  • Sulfonates can be prepared by reaction of a compound of Formula 4 with a sulfonating agent such as methanesulfonyl chloride, typically in the presence of a base, under conditions well known to one skilled in the art of organic synthesis.
  • Scheme 2 General methods useful for preparing compounds of Formula 4 are well known in the literature.
  • compounds of Formula 1 wherein G is an N-linked heterocycle can be prepared by reaction of primary or secondary alcohols of Formula 6 with nitrogen-containing heterocycles of Formula 3 using Mitsunobu coupling reaction conditions, as shown in Scheme 4.
  • Mitsunobu reactions are typically run in tetrahydrofuran with triphenylphosphine and diisopropyl azodicarboxylate (DIAD) or diethyl azodicarboxylate (DEAD) at room temperature.
  • Diisopropyl azodicarboxylate DIAD
  • DEAD diethyl azodicarboxylate
  • Polymer supported triphenylphosphine can be used to ease purification.
  • the functional groups Y 1 and Y 2 are selected from, but not limited to, moieties such as aldehydes, ketones, esters, acids, amides, thioamides, nitriles, amines, alcohols, thiols, hydrazines, oximes, amidines, amide oximes, olefins, acetylenes, halides, alkyl halides, methanesulfonates, trifluoromethanesulfonates (triflate), boronic acids, boronates, and the like, which under the appropriate reaction conditions, will allow for the construction of the various G rings.
  • moieties such as aldehydes, ketones, esters, acids, amides, thioamides, nitriles, amines, alcohols, thiols, hydrazines, oximes, amidines, amide oximes, olefins, acetylenes, halides
  • reaction of a compound of Formula 7 where Y 1 is a chlorooxime moiety with a compound of Formula 8 where Y 2 is a vinyl or acetylene group in the presence of a base will give a compound of Formula 1 where G is an isoxazoline or isoxazole ring, respectively.
  • G is an isoxazoline or isoxazole ring
  • WO 2018/118781 Examples 1, 2 and 6
  • WO 2018/187553 Example 13
  • the synthetic literature describes many general methods for forming heterocyclic rings and ring systems, such as those illustrated in G-1 through G-118 of Embodiment 106; see, for example, Comprehensive Heterocyclic Chemistry, Volumes 4-6, A. R. Katritzky and C. W.
  • the ethyl ester of trifluoroacetic acid i.e. ethyl trifluoroacetate
  • trifluoroacetonitrile and various trifluoroacetate salts can also be used.
  • double addition on the trifluoroacetyl compound can occur.
  • Conducting the reaction at –65 °C, or more preferably at –78 °C, can reduce the occurrence of double addition adducts to trace amounts, particularly when using organometallic species of Formula 9 wherein M is Li or MgBr. Many other organometallic species yield similar results.
  • compounds of Formula 1a can be prepared via alkylation of ethyl 4,4,4- trifluoroacetoacetate (ETFAA) with compounds of Formula 10 wherein La is a leaving group such as halogen (e.g., Cl, Br) or sulfonate (e.g., mesylate), and the like, as illustrated in Scheme 7.
  • ETFAA is first treated with a base such as sodium hydride in a polar aprotic solvent such as tetrahydrofuran, tetrahydrofuran/hexamethylphosphoramide (HMPA) or acetone.
  • the reaction is run in the presence of a fluoride initiator such as tetrabutylammonium fluoride, and in an anhydrous solvent such as toluene or dichloromethane at about –78 °C (for reaction conditions see, for example, Angew. Chem., Int. Ed.1998, 37(6), 820-821).
  • Cesium fluoride can also be used as an initiator in a solvent such as 1,2-dimethoxyethane (glyme) at room temperature (for reaction conditions see, for example, J. Org. Chem.1999, 64, 2873).
  • Formula 1a wherein A is A 1 -A 2 - CR 5a R 5b ) wherein R 1 is CF 3 and at least one R 5a or R 5b is H can be prepared by reacting acid chlorides of Formula 12 with trifluoroacetic anhydride (TFAA) and pyridine in a solvent such as dichloromethane or toluene at temperatures between about 0 to 80 °C, followed by aqueous hydrolysis (for reaction conditions see, for example, Tetrahedron 1995, 51, 2573-2584).
  • TFAA trifluoroacetic anhydride
  • Compounds of Formula 12 can be prepared from compounds of Formula 11 by ester hydrolysis to the corresponding carboxylic acid and treatment with oxalyl chloride, as known to one skilled in the art.
  • Scheme 9 As shown in Scheme 10, compounds of Formula 1b (i.e. Formula 1 wherein T is T-2) wherein R 2a X and R 2b Y are OH can be prepared by reacting phenyl ketones of Formula 13 with trifluoroacetic esters (e.g., ethyl trifluoroacetate) in the presence of a base such as sodium hydride and in a solvent such as tetrahydrofuran, at a temperature between about 0 to 70 °C.
  • the target compounds of Formula 1b are typically isolated as their ketone hydrates (i.e. dihydroxy) upon aqueous hydrolysis.
  • Scheme 10 illustrates a specific example wherein a phenyl ketone of Formula 14 is reacted with ethyl trifluoroacetate in the presence of sodium hydride in tetrahydrofuran to provide a compound of Formula 5a (i.e. Formula 5 wherein A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 ).
  • A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 .
  • Step A illustrates the preparation of a compound of Formula 14.
  • Scheme 11 As shown in Scheme 12, compounds of Formula 1b (i.e. Formula 1 wherein T is T-2) wherein R 2a X and R 2b Y are OH can also be prepared by oxidation of alcohols of Formula 15 to the corresponding dihydroxy.
  • the oxidation reaction can be performed by a variety of means, such as by treatment of the alcohols of Formula 15 with manganese dioxide, Dess-Martin periodinane, pyridinium chlorochromate or pyridinium dichromate.
  • PCT publication WO 2020/056090 Example 6, Step F and Example 8, Step F).
  • ketones of Formula 1a may exist in equilibrium with their corresponding ketone hydrates (i.e. dihydroxy) of Formula 1b (i.e. Formula 1 wherein T is T-2) wherein R 2a X and R 2b Y are OH.
  • the predominance of Formula 1a or Formula 1b is dependent upon several factors, such as environment and structure. For example, in an aqueous environment ketones of Formula 1a can react with water to give ketone hydrates (also known as 1,1-geminal diols) of Formula 1b.
  • Conversion back to the keto-form can usually be achieved by treatment with a dehydrating agent such as magnesium sulfate or molecular sieves.
  • a dehydrating agent such as magnesium sulfate or molecular sieves.
  • the ketone moiety is in close proximity to an electron- withdrawing group, such as when R 1 is a trifluoromethyl group, the equilibrium typically favors the dihydrate form.
  • conversion back to the keto-form may require a strong dehydrating agent, such as phosphorus pentoxide (P 2 O 5 ).
  • P 2 O 5 phosphorus pentoxide
  • ketones of Formula 1a may also exist in equilibrium with their hemiketals, hemithioketals and hemiaminals of Formula 1b 1 (i.e. Formula 1b wherein R 2b Y is OH and R 2a is other than H) along with their ketals, thioketals aminals of Formula 1b wherein R 2a and R 2b are other than H.
  • Compounds of Formula 1b 1 can be prepared by reacting a compound of Formula 1a with a compound of formula R 2a X-H (e.g., alcohols for X being O, thiols for X being S or amines for X being NR 4a ), usually in the presence of a catalyst, such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF 3 ), (see, for example, Master Organic Chemistry (Online), On Acetals and Hemiacetals, May 28, 2010, www.masterorganic- chemistry.com/2010/201728/on-acetals-and-hemiacetals).
  • a catalyst such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF 3 )
  • compounds of Formula 1b1 can be treated with a compound of formula R 2b Y-H (e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR 4b ) under dehydrating conditions, or other means of water removal that will drive the equilibrium in the reaction to the right, to provide compounds of Formula 1b wherein R 2a and R 2b are other than H.
  • a compound of formula R 2b Y-H e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR 4b
  • ketones of Formula 1a can initially be treated with two equivalents (or an excess amount) of an alcohol, thiol or amine typically in the presence of a catalyst together with a dehydrating agent to provide compounds of Formula 1b directly (see, for example, the preparation of dimethylketals using methanol and trimethyl orthoformate in US 6,350,892).
  • Scheme 14 As shown in Scheme 15, cyclic ketals of Formula 1b 2 (i.e.
  • Formula 1b wherein X and Y are O, and R 2a and R 2b are taken together to form a 5- to 7-membered ring can be prepared by treating the corresponding ketones of Formula 1a with haloalcohols (e.g., 2-chloroethanol or 2- bromopropanol) in the presence of a base such as potassium carbonate or potassium tert-butoxide and in as solvent such as acetonitrile or N,N-dimethylformamide.
  • haloalcohols e.g., 2-chloroethanol or 2- bromopropanol
  • a base such as potassium carbonate or potassium tert-butoxide
  • solvent such as acetonitrile or N,N-dimethylformamide
  • Scheme 15 The method of Scheme 15 is also useful for preparing cyclic ketals starting from the corresponding ketone hydrate intermediate of Formula 5.
  • Scheme 16 illustrates a specific example wherein the ketone hydrate of Formula 5a (i.e. Formula 5 wherein A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 ) is reacted with 2-chloroethanol in the presence of potassium carbonate in acetonitrile to provide a compound of Formula 5b (i.e. Formula 5 wherein A is OCH 2 , X and Y are O, R 2a and R 2b are taken together to form a 5-membered ring and R 1 is CF 3 ).
  • the method of Scheme 16 is illustrated in present Example 1, Step C.
  • Formula 17 wherein R 5a and R 5b are H, X and Y are O and R 2a and R 2b are taken together to form a 5- membered ring
  • haloalcohols e.g., 2-chloroethanol or 3-bromopropanol
  • basic conditions e.g., potassium tert-butoxide in a solvent such as N,N-dimethylformamide or tetrahydrofuran
  • a variety of methods are disclosed in the chemical literature for the conversion of ketones to cyclic ketals and can be readily adapted to prepare compounds of Formula 19 (see, for example, G. Hilgetag and A.
  • a mesylate or tosylate group can be installed by treating the alcohol with methanesulfonyl chloride (mesyl chloride) or 4-toluenesulfonyl chloride (tosyl chloride) in the presence of a base such as triethylamine at a temperature between about 0 to 40 °C and in a solvent such as dichloromethane.
  • a triflate group can be installed by treating the alcohol with triflic anhydride (CF 3 SO 2 ) 2 O as illustrated in PCT publication WO 2020/056090 (Example 4, Step C).
  • Compounds of Formula 18 are known and can be prepared by methods known to one skilled in the art. Scheme 18 Compounds of Formula 1c (i.e.
  • Formula 1 wherein T is T-3 and X is O can be prepared by reacting a compound of Formula 1a (i.e. Formula 1 wherein T is T-1 and W is O) wherein A is A 1 -A 2 -CR 5a R 5b and at least one of R 5a and R 5b is H with a compound of Formula 21 in the presence of a base, as illustrated in Scheme 19.
  • Suitable bases include cesium or potassium carbonate in a solvent such as N,N-dimethylformamide or dimethyl sulfoxide at temperatures from about 20 to 80 °C.
  • the method of Scheme 19 results in a mixture of O-alkylated product (typically as a mixture of (E)- and (Z)-isomers), along with C-alkylated product. Purification can be achieved using standard techniques such as column chromatography (see Magnetic Resonance in Chemistry 1991, 29, 675-678). Compounds of Formula 21 are commercially available and can be easily synthesized by general methods known to one skilled in the art. Scheme 19 The method of Scheme 19 is also useful for preparing compounds of Formula 1c starting from the corresponding ketone hydrates.
  • Scheme 20 illustrates a specific example where a ketone hydrate of Formula 1b 4 (i.e.
  • Formula 1b wherein L is CH 2 , J is phenyl, A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 ) is reacted with iodoethane in the presence of cesium carbonate in dimethyl sulfoxide at a temperature between about 25 to 75 °C to provide a compound of Formula 1c 1 (i.e. Formula 1c wherein L is CH 2 , J is phenyl, A is O, R 2d is H, XR 2c is OCH 2 CH 3 and R 1 is CF 3 ).
  • PCT publication WO 2020/056090, Example 5 illustrates the method of Scheme 20.
  • Scheme 20 The method of Scheme 20 can also be performed starting from the corresponding ketone hydrate of Formula 5a (i.e. Formula 5 wherein A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 ), as shown in Scheme 21.
  • A is OCH 2
  • R 2a X and R 2b Y are OH and R 1 is CF 3
  • Scheme 21 One skilled in the art will recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. In particular, certain R 9 substituents attached to the G ring may be obtained via functional group interconversion reactions.
  • compounds of Formula 1d i.e.
  • Formula 1 wherein the G ring is substituted with R 9 , and R 9 is -(CR 11a R 11b )mR 9a and R 9a is alkylcarbonyloxy, alkenylcarbonyloxy, cycloalkylcarbonyloxy, alkoxycarbonyloxy, and the like) can be prepared by reacting a carboxylic acid of Formula 22 with an alcohol of Formula 23. The reaction proceeds via activation of the carboxylic acid of Formula 22 followed by coupling with the alcohol of Formula 23. Activation of the carboxylic acid takes place with the aid of a coupling reagent, or alternatively by conversion of the carboxylic acid to the acid halide.
  • compounds of Formulae 23 and 22 can be reacted in the presence of a carbodiimide coupling reagent, such as N,N'-dicyclehexylcarbodiimide (DCC), N-ethyl-N'-(3- dimethylaminopropyl)carbodiimide (EDC) or N,N'-diisopropylcarbodimide (DIC).
  • a carbodiimide coupling reagent such as N,N'-dicyclehexylcarbodiimide (DCC), N-ethyl-N'-(3- dimethylaminopropyl)carbodiimide (EDC) or N,N'-diisopropylcarbodimide (DIC).
  • DCC N,N'-dicyclehexylcarbodiimide
  • EDC N-ethyl-N'-(3- dimethylaminopropyl)carbodiimide
  • DIC N,N'-di
  • esters from carboxylic acids and alcohols include use of coupling reagents such as benzotriazol-1-yl-oxy-tris-pyrrolidinophosphonium hexafluorophosphate (PyBOP ®), O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate (HATU) and 2-(1H-benzotriazol-1-yl)-1,1,3,3-tetramethyluronium hexa- fluorophosphate (HBTU).
  • PyBOP ® benzotriazol-1-yl-oxy-tris-pyrrolidinophosphonium hexafluorophosphate
  • HATU O-(7-azabenzotriazol-1-yl)-N,N,N',N'-tetramethyluronium hexafluorophosphate
  • HBTU 2-(1H-benzotriazol
  • the reaction is typically run in a polar aprotic solvent such as N,N-dimethylformamide, tetrahydrofuran or dichloromethane and in the presence of a base such as pyridine, triethylamine or N,N-diisopropylethylamine.
  • a polar aprotic solvent such as N,N-dimethylformamide, tetrahydrofuran or dichloromethane
  • a base such as pyridine, triethylamine or N,N-diisopropylethylamine.
  • polymer-supported coupling reagents such as polymer bound dicyclohexyl carbodiimide (DCC).
  • a carboxylic acid of Formula 22 can be reacted with a halogenating reagent such as thionyl chloride, oxalyl chloride, phosphorus trichloride, phosphorus oxychloride or phosphorus pentachloride in a solvent such as dichloromethane or toluene and optionally in the presence of a catalytic amount of N,N-dimethylformamide to provide the corresponding acid chloride.
  • the coupling step typically includes a base such as triethylamine, N,N-diisopropylethylamine and pyridine (for reaction conditions see Example 4, Step F).
  • Step B Preparation of ethyl 4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)benzoate
  • ethyl 2,2,2-trifluoroacetate 31.8 g, 0.22 mol
  • sodium hydride 60% in oil, 8.94 g, 0.22 mol
  • the reaction mixture was cooled to 0 °C, and then ethyl 4-(2-oxo-2-phenylethoxy)benzoate (i.e. the product of Step A) (53 g, 0.19 mol) was added portionwise.
  • the reaction mixture was heated at 70 °C for 2.5 h, and then cooled to 0 °C and diluted with hydrochloric acid (1 N solution in water, 140 mL). After stirring for 15 minutes, saturated aqueous sodium bicarbonate solution (250 mL) was added, and the resulting mixture was extracted with ethyl acetate (2 x 380 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting solid was triturated with pentane (100 mL) to provide the title compound as an off-white solid (43 g).
  • Step B the product of Step B) (42 g, 0.14 mol) in N,N-dimethylformamide (80 mL) was added potassium carbonate (58.9 g, 0.43 mol). After 10 minutes, 2-chloroethanol (34.5 g, 0.43 mol) was added dropwise to the reaction mixture and stirring was continued for 16 h. The reaction mixture was cooled to 0 °C and ice-cold water (250 mL) was added. The resulting mixture was extracted with ethyl acetate (2 x 300 mL), and the combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step D Preparation of 4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]- benzenemethanol
  • ethyl 4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]benzoate i.e. the product of Step C) (25 g, 78.1 mmol) in tetrahydrofuran (120 mL) at 0 °C was added lithium aluminum hydride (2 M solution in tetrahydrofuran, 58.5 mL, 117 mmol).
  • the reaction mixture was allowed to warm to room temperature and stirred for 3 h, and then cooled to 0 °C and diluted with ethyl acetate (180 mL) and water (100 mL). The resulting mixture was filtered through a pad of Celite®, rinsing with ethyl acetate (100 mL). The organic layer was separated, dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting solid was triturated with petroleum ether to provide the title compound as an off-white solid (20 g).
  • Step E Preparation of 2-[[4-(bromomethyl)phenoxy]methyl]-2-(trifluoromethyl)-1,3- dioxolane To a mixture of 4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]benzenemethanol (i.e.
  • Step D the product of Step D) (36 g, 0.13 mol) in dichloromethane (300 mL) at 0 °C was added tetrabromomethane (47.1 g, 0.14 mol) and triphenylphosphine (37.3 g, 0.14 mol). The reaction mixture was allowed to warm to room temperature and stirred for 2 h, and then cooled to 0 °C, diluted with ice-cold water (80 mL) and extracted with dichloromethane (2 x 150 mL). The combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step F Preparation of ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]- phenyl]methyl]-1H-pyrazole-4-carboxylate
  • acetonitrile 220 mL
  • cesium carbonate 57.3 g, 0.18 mol
  • Step E the product of Step E) (30 g, 87.9 mmol) was added to the reaction mixture and stirring was continued for 7 h.
  • the reaction mixture was filtered through a frit funnel, rinsing with acetonitrile (50 mL), and the filtrate was concentrated under reduced pressure.
  • the resulting material was purified by silica gel chromatography (eluting with 15% ethyl acetate in petroleum ether) to provide the title compound as an off-white solid (26.2 g).
  • Step G Preparation of 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl]- methyl]-1H-pyrazole-4-methanol To a mixture of ethyl 1-[[4-[[2-(trifluoromethyl)-1,3-dioxolan-2-yl]methoxy]phenyl] ⁇ methyl]-1H-pyrazole-4-carboxylate (i.e.
  • Step F the product of Step F) (30 g, 74.9 mmol) in tetrahydrofuran (200 mL) at 0 °C was added dropwise lithium aluminum hydride (1 M solution in tetrahydrofuran, 112 mL, 112 mmol).
  • the reaction mixture was stirred at 0 °C for 2 h, and then diluted with ethyl acetate (300 mL) and water (200 mL).
  • the resulting mixture was filtered through a pad of Celite®, rinsing with ethyl acetate (50 mL). The organic layer was separated, dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • reaction mixture was stirred at 0 °C for 1 h, and then diluted with water (1.2 mL) and sodium hydroxide (10% aqueous solution, 2.4 mL), followed by more water (1.2 mL). After stirring for 15 minutes, the mixture was filtered through a pad of Celite® and the filtrate was concentrated under reduced pressure to provide the title compound as an oil (8 g).
  • Step B Preparation of 4-(chloromethyl)-1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen- 1-yl]oxy]phenyl]methyl]-1H-pyrazole
  • Step C Preparation of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]- methyl]-1H-pyrazole-4-acetonitrile To a mixture of 4-(chloromethyl)-1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1- yl]oxy]phenyl]methyl]-1H-pyrazole (i.e.
  • Step D Preparation of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]- methyl]-1H-pyrazole-4-acetic acid To a mixture of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]- 1H-pyrazole-4-acetonitrile (i.e.
  • Step C the product of Step C) (1.0 g, 2.9 mmol) in water (5 mL) was added acetic acid (5 mL, 2.9 mmol) and sulfuric acid (5 mL, 2.9 mmol). The reaction mixture was heated at 100 °C for 4 h, and then cooled to room temperature and diluted with water. The resulting mixture was extracted with ethyl acetate, and the combined organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure to provide the title compound as an oil (0.7 g).
  • Step E Preparation of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]- methyl]-N-methoxy-N-methyl-1H-pyrazole-4-acetamide To a mixture of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]- 1H-pyrazole-4-acetic acid (i.e.
  • Step D the product of Step D) (150 mg, 0.41 mmol) and N,O- dimethylhydroxylamine hydrochloride (27 mg, 0.45 mmol) in dichloromethane (10 mL) was added propanephosphonic acid anhydride (T3P) (50% in ethyl acetate, 0.18 mL, 0.61 mmol) and triethylamine (0.11 mL, 0.81 mmol).
  • T3P propanephosphonic acid anhydride
  • T3P propanephosphonic acid anhydride
  • the reaction mixture was stirred for 3 h, and then diluted with water and extracted with dichloromethane. The organic extract was dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • Step B Preparation of 4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]benzene- methanol
  • ethyl 4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]benzoate i.e. the product of Step A
  • tetrahydrofuran 202 mL
  • lithium aluminum hydride 2 M solution in tetrahydrofuran, 50.5 mL, 0.10 mol
  • Step B) the product of Step B) (9.3 g, 35.5 mmol) and triphenylphosphine (15.8 g, 60.3 mmol) in dichloromethane (236 mL) was cooled to 0 °C, and then N-bromosuccinimide (9.47 g, 53.2 mmol) was added portionwise over 5 minutes. After 30 minutes, saturated aqueous sodium bicarbonate solution was added to the reaction mixture, and the aqueous layer was separated and extracted with dichloromethane. The combined organics were washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate, filtered, and concentrated under reduced pressure.
  • Step D Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]- phenyl]methyl]-1H-pyrazole-4-carboxylate To a mixture of 1-(bromomethyl)-4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy] benzene (i.e.
  • Step C) the product of Step C) (6.98 g, 21.5 mmol) in N,N-dimethylformamide (85.9 mL) was added ethyl 1H-pyrazole-4-carboxylate (3.61 g, 25.8 mmol) followed by cesium carbonate (17.5 g, 53.7 mmol).
  • the reaction mixture was heated at 65 °C overnight, and then cooled to room temperature and diluted with water (100 mL) and ethyl acetate (200 mL). The aqueous layer was separated and extracted with ethyl acetate. The combined organics were washed with saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • Step E Preparation of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]- phenyl]methyl]-1H-pyrazole-4-methanol To a mixture of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]- phenyl]methyl]-1H-pyrazole-4-carboxylate (i.e.
  • Step D the product of Step D) (5.96 g, 15.5 mmol) in tetrahydrofuran (78 mL) at 0 °C was added dropwise lithium aluminum hydride (2 M in tetrahydrofuran, 15.5 mL, 31.0 mmol).
  • the reaction mixture was stirred for 1 h, and then water (1.2 mL) was slowly added, followed by sodium hydroxide (15% aqueous solution, 1.2 mL) and more water (3.6 mL).
  • the reaction mixture was allowed to warm to room temperature, stirred for 15 minutes, and then dried over magnesium sulfate, filtered and concentrated under reduce pressure.
  • Step F Preparation of [1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]- phenyl]methyl]-1H-pyrazol-4-yl]methyl propanoate To a mixture of 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]- 1H-pyrazole-4-methanol (i.e.
  • Step E the product of Step E) (0.15 g, 0.44 mmol) in dichloromethane (2.2 mL) at 0 °C was added pyridine (0.053 mL, 0.657 mmol) followed by propionyl chloride (0.057 mL, 0.657 mmol).
  • pyridine 0.053 mL, 0.657 mmol
  • propionyl chloride 0.057 mL, 0.657 mmol
  • reaction mixture was allowed to warm to room temperature and stirred for 1 h, and then cooled to –78 °C, and diethyl oxalate (1.4 mL, 10.2 mmol) was added. After 30 minutes, the reaction mixture was diluted with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 45 to 50% ethyl acetate in hexanes) to provide the title compound as an oil (0.3 g).
  • Step C Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1- yl]oxy]phenyl]methyl]- ⁇ -oxo-1H-pyrazole-4-acetate
  • 1-(chloromethyl)-4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy] benzene i.e. the product of Step B
  • benzene i.e. the product of Step B
  • ethyl 2-oxo-2-(1H-pyrazol-4-yl) acetate i.e.
  • Step A the product of Step A) (0.359 g, 2.14 mmol) in acetonitrile (10 mL) was added potassium carbonate (0.369 g, 2.67 mmol).
  • the reaction mixture was heated at 70 °C for 4 h, cooled to room temperature, and then diluted with water.
  • the resulting mixture was extracted with ethyl acetate, and the organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure.
  • the resulting material was purified by MPLC (eluting with 25-30% ethyl acetate in hexanes) to provide the title compound as an oil (0.5 g).
  • Step D Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1- yl]oxy]phenyl]methyl]- ⁇ -hydroxy-1H-pyrazole-4-acetate
  • Step C the product of Step C) (150 mg, 0.364 mmol) in methanol (10 mL) at 0 °C was added sodium borohydride (0.021 g, 0.546 mmol). After 3 h, the reaction mixture was diluted with saturated aqueous ammonium chloride solution and extracted with ethyl acetate. The organic extracts were dried over sodium sulfate, filtered and concentrated under reduced pressure. The resulting material was purified by MPLC (eluting with 50-55% ethyl acetate in hexanes) to provide the title compound as an oil (0.08 g).
  • Step E Preparation of ethyl ⁇ -(acetyloxy)-1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1- propen-1-yl]oxy]phenyl]methyl]-1H-pyrazole-4-acetate
  • ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]- methyl]- ⁇ -hydroxy-1H-pyrazole-4-acetate i.e.
  • reaction mixture was concentrated under reduce pressure.
  • the resulting mixture was diluted with water and saturated aqueous sodium bicarbonate solution, and then washed with ethyl acetate (3 x 5 mL).
  • the resulting aqueous layer was acidified with hydrochloric acid (1N) to a pH of about 2, and then extracted with ethyl acetate (3 x 10 mL).
  • the combined organic extracts were dried over sodium sulfate, filtered and concentrated to provide the title compound as a white solid (1.22 g).
  • Step B Preparation of ethyl 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]- phenyl]methyl]-N-(2-propen-1-yloxy)-1H-pyrazole-4-carboxamide
  • 1-[[4-[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]- 1H-pyrazole-4-carboxylic acid i.e.
  • Step B) the product of Step B) (1.30 g, 3.65 mmol) in N,N- dimethylformamide (10 mL) was added hydroxy-1H-benzotriazole (HOBT) (0.542 g, 4.01 mmol), 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) (0.77 g, 4.01 mmol), triethylamine (0.66 mL, 4.74 mmol) and O-2-propenylhydroxylamine (0.32 g, 4.38 mmol). The reaction mixture was stirred overnight, and then diluted with water (30 mL), and extracted with ethyl acetate (3 x 5 mL).
  • HOBT hydroxy-1H-benzotriazole
  • EDC 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride
  • EDC 1-(3-dimethylaminopropyl)
  • compositions comprising the compound with at least one additional fungicidal compound as described in the Summary of the Invention, 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.
  • a composition i.e. formulation
  • 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.
  • a compound of Formula 1, or mixture thereof can be formulated in a number of ways, including: (i) the compound of Formula 1 and optionally one or more other biologically active compounds or agents can be formulated separately and applied separately or applied simultaneously in an appropriate weight ratio, e.g., as a tank mix; or (ii) the compound of Formula 1 and optionally one or more other biologically active compounds or agents can be formulated together in the proper weight ratio.
  • Useful formulations include both liquid and solid compositions.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in-water emulsions, flowable concentrates 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, oil-in-water emulsion, flowable concentrate and suspo-emulsion.
  • the general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • the general types of solid 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 emulsifiable granule combines the advantages of both an emulsifiable 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, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. 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, N,N-dimethylalkanamides (e.g., N,N- dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N- methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene 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
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), 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. 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. When added to a liquid, surfactants (also known as “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.
  • surfactants can be classified as nonionic, anionic or cationic.
  • 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 oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide
  • 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 N-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 N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • 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.
  • 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. See Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp 147-48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, pp 8-57 and following, and WO 91/13546.
  • 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.
  • One embodiment of the present invention relates to a method for controlling fungal pathogens, comprising diluting the fungicidal composition of the present invention (a compound of Formula 1 formulated with surfactants, solid diluents and liquid diluents or a formulated mixture of a compound of Formula 1 and at least one other fungicide) with water, and optionally adding an adjuvant to form a diluted composition, and contacting the fungal pathogen or its environment with an effective amount of said diluted composition.
  • a spray composition formed by diluting with water a sufficient concentration of the present fungicidal composition can provide sufficient efficacy for controlling fungal pathogens
  • separately formulated adjuvant products can also be added to spray tank mixtures.
  • Adjuvants are commonly known as “spray adjuvants” or “tank-mix adjuvants”, and include any substance mixed in a spray tank to improve the performance of a pesticide or alter the physical properties of the spray mixture.
  • Adjuvants can be anionic or nonionic surfactants, emulsifying agents, petroleum-based crop oils, crop-derived seed oils, acidifiers, buffers, thickeners or defoaming agents.
  • Adjuvants are used to enhancing efficacy (e.g., biological availability, adhesion, penetration, uniformity of coverage and durability of protection), or minimizing or eliminating spray application problems associated with incompatibility, foaming, drift, evaporation, volatilization and degradation.
  • adjuvants are selected with regard to the properties of the active ingredient, formulation and target (e.g., crops, insect pests).
  • the amount of adjuvants added to spray mixtures is generally in the range of about 0.1 % to 2.5% by volume.
  • the application rates of adjuvants added to spray mixtures are typically between about 1 to 5 L per hectare.
  • Representative examples of spray adjuvants include: Adigor ® (Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet® (Helena Chemical Company) polyalkyleneoxide modified heptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83% paraffin based mineral oil.
  • compositions formulated for seed treatment generally comprise a film former or adhesive agent. Therefore typically a seed coating composition of the present invention comprises a biologically effective amount of a compound of Formula 1 and a film former or adhesive agent. Seeds can be coated by spraying a flowable suspension concentrate directly into a tumbling bed of seeds and then drying the seeds. Alternatively, other formulation types such as wetted powders, solutions, suspoemulsions, emulsifiable concentrates and emulsions in water can be sprayed on the seed. This process is particularly useful for applying film coatings on seeds.
  • a flowable suspension formulated for seed treatment typically comprises from about 0.5 to about 70% of the active ingredient, from about 0.5 to about 30% of a film-forming adhesive, from about 0.5 to about 20% of a dispersing agent, from 0 to about 5% of a thickener, from 0 to about 5% of a pigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0 to about 1% of a preservative, and from 0 to about 75% of a volatile liquid diluent.
  • 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 Ascomycota, Basidiomycota, Zygomycota phyla, and the fungal-like Oomycota class. 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 but are not limited to those listed in Table 1-1.
  • names for both the sexual/teleomorph/perfect stage as well as names for the asexual/anamorph/imperfect stage (in parentheses) are listed where known. Synonymous names for pathogens are indicated by an equal sign.
  • the sexual/teleomorph/perfect stage name Phaeosphaeria nodorum is followed by the corresponding asexual/anamorph/imperfect stage name Stagnospora nodorum and the synonymous older name Septoria nodorum.
  • compositions or combinations also have activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae, and other related species.
  • the compounds of the invention are useful for improving (i.e. increasing) the ratio of beneficial to harmful microorganisms in contact with crop plants or their propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or in the agronomic environment of the crop plants or their propagules.
  • Compounds of the invention are useful in treating all plants, plant parts and seeds.
  • Plant and seed varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods.
  • Genetically modified plants or seeds are those in which a heterologous gene (transgene) has been stably integrated into the plant's or seed’s genome.
  • a transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
  • Genetically modified plant cultivars which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics.
  • Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Treatment of genetically modified plants and seeds with compounds of the invention may result in super-additive or enhanced effects. For example, reduction in application rates, broadening of the activity spectrum, increased tolerance to biotic/abiotic stresses or enhanced storage stability may be greater than expected from just simple additive effects of the application of compounds of the invention on genetically modified plants and seeds.
  • Compounds of this invention are useful in seed treatments for protecting seeds from plant diseases.
  • treating a seed means contacting the seed with a biologically effective amount of a compound of this invention, which is typically formulated as a composition of the invention.
  • This seed treatment protects the seed from soil- borne disease pathogens and generally can also protect roots and other plant parts in contact with the soil of the seedling developing from the germinating seed.
  • the seed treatment may also provide protection of foliage by translocation of the compound of this invention or a second active ingredient within the developing plant.
  • Seed treatments can be applied to all types of seeds, including those from which plants genetically transformed to express specialized traits will germinate. Representative examples include those expressing proteins toxic to invertebrate pests, such as Bacillus thuringiensis toxin or those expressing herbicide resistance such as glyphosate acetyltransferase, which provides resistance to glyphosate. Seed treatments with compounds of this invention can also increase vigor of plants growing from the seed.
  • Compounds of this invention and their compositions, both alone and in combination with other fungicides, nematicides and insecticides, are particularly useful in seed treatment for crops including, but not limited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats, barley, rye and rice), potatoes, vegetables and oilseed rape.
  • the compounds of this invention are useful in treating postharvest diseases of fruits and vegetables caused by fungi, oomycetes and bacteria. These infections can occur before, during and after harvest.
  • infections can occur before harvest and then remain dormant until some point during ripening (e.g., host begins tissue changes in such a way that infection can progress or conditions become conducive for disease development); also infections can arise from surface wounds created by mechanical or insect injury.
  • the compounds of this invention can reduce losses (i.e. losses resulting from quantity and quality) due to postharvest diseases which may occur at any time from harvest to consumption.
  • Treatment of postharvest diseases with compounds of the invention can increase the period of time during which perishable edible plant parts (e.g., fruits, seeds, foliage, stems, bulbs, tubers) can be stored refrigerated or un-refrigerated after harvest, and remain edible and free from noticeable or harmful degradation or contamination by fungi or other microorganisms.
  • Treatment of edible plant parts before or after harvest with compounds of the invention can also decrease the formation of toxic metabolites of fungi or other microorganisms, for example, mycotoxins such as aflatoxins.
  • 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, fruits, 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. Control of postharvest pathogens which infect the produce before harvest is typically accomplished by field application of a compound of this invention, and in cases where infection occurs after harvest the compounds can be applied to the harvested crop as dips, sprays, fumigants, treated wraps and box liners.
  • the compounds can also be applied using an unmanned aerial vehicle (UAV) for the dispension of the compositions disclosed herein over a planted area.
  • UAV unmanned aerial vehicle
  • the planted area is a crop-containing area.
  • the crop is selected from a monocot or dicot.
  • the crop is selected form rice, corn, barley, sobean, wheat, vegetable, tobacco, tea tree, fruit tree and sugar cane.
  • the compositions disclosed herein are formulated for spraying at an ultra-low volume.
  • Products applied by drones may use water or oil as the spray carrier.
  • Typical spray volume (including product) used for drone applications globally is 5.0 liters/ha – 100 liters/ha (approximately 0.5-10 gpa).
  • Suitable rates of application for the compounds of this invention can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, the population structure of the pathogen to be controlled, 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, the population structure of the pathogen to be controlled, 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 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed.
  • One skilled in the art can easily determine through simple experimentation the application rates for the compounds of this invention, and compositions thereof, needed to provide the desired spectrum of plant protection and control of plant diseases and optionally other plant pests.
  • Compounds of the present invention may also be useful for increasing vigor of a crop plant. This method comprises contacting the crop plant (e.g., foliage, flowers, fruit or roots) or the seed from which the crop plant is grown with a compound of Formula 1 in amount sufficient to achieve the desired plant vigor effect (i.e. biologically effective amount). Typically the compound of Formula 1 is applied in a formulated composition.
  • the compound of Formula 1 is often applied directly to the crop plant or its seed, it can also be applied to the locus of the crop plant, i.e. the environment of the crop plant, particularly the portion of the environment in close enough proximity to allow the compound of Formula 1 to migrate to the crop plant.
  • the locus relevant to this method most commonly comprises the growth medium (i.e. medium providing nutrients to the plant), typically soil in which the plant is grown.
  • Treatment of a crop plant to increase vigor of the crop plant thus comprises contacting the crop plant, the seed from which the crop plant is grown or the locus of the crop plant with a biologically effective amount of a compound of Formula 1.
  • Increased crop vigor can result in one or more of the following observed effects: (a) optimal crop establishment as demonstrated by excellent seed germination, crop emergence and crop stand; (b) enhanced crop growth as demonstrated by rapid and robust leaf growth (e.g., measured by leaf area index), plant height, number of tillers (e.g., for rice), root mass and overall dry weight of vegetative mass of the crop; (c) improved crop yields, as demonstrated by time to flowering, duration of flowering, number of flowers, total biomass accumulation (i.e. yield quantity) and/or fruit or grain grade marketability of produce (i.e.
  • the compounds of the present invention may increase the vigor of treated plants compared to untreated plants by preventing and/or curing plant diseases caused by fungal plant pathogens in the environment of the plants. In the absence of such control of plant diseases, the diseases reduce plant vigor by consuming plant tissues or sap, or transmiting plant pathogens such as viruses. Even in the absence of fungal plant pathogens, the compounds of the invention may increase plant vigor by modifying metabolism of plants.
  • the vigor of a crop plant will be most significantly increased by treating the plant with a compound of the invention if the plant is grown in a nonideal environment, i.e. an environment comprising one or more aspects adverse to the plant achieving the full genetic potential it would exhibit in an ideal environment.
  • a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment comprising plant diseases caused by fungal plant pathogens.
  • a method for increasing vigor of a crop plant wherein the crop plant is grown in an environment not comprising plant diseases caused by fungal plant pathogens.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematicides, 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, nematicides, 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
  • 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.
  • one aspect of the present invention is a fungicidal composition comprising (i.e. a mixture or combination of) a compound of Formula 1, an N-oxide, or a salt thereof (i.e. component a), and at least one other fungicide (i.e. component b).
  • composition of the present invention can further comprise a fungicidally effective amount of at least one additional fungicidal active ingredient having a similar spectrum of control but a different site of action.
  • composition which in addition to the Formula 1 compound of component (a), includes as component (b) at least one fungicidal compound selected from the group consisting of the FRAC-defined mode of action (MOA) classes, including (A) nucleic acids metabolism, (B) cytoskeleton and motor protein, (C) respiration, (D) amino acids and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell wall, (P) host plant defense induction, (U) unknown mode of action, (M) chemicals with multi-site activity and (BM) biologicals with multiple modes of action.
  • MOA FRAC-defined mode of action
  • FRAC-recognized or proposed target sites of action along with their FRAC target site codes belonging to the above MOA classes are (A1) RNA polymerase I, (A2) adenosine deaminase, (A3) DNA/RNA synthesis (proposed), (A4) DNA topoisomerase type II (gyrase), (B1)-(B3) ß- tubulin assembly in mitosis, (B4) cell division (unknown site), (B5) delocalization of spectrin- like proteins, (B6) actin/myosin/fimbrin function, (C1) complex I NADH odxido-reductase, (C2) complex II: succinate dehydrogenase, (C3) complex III: cytochrome bc1 (ubiquinol oxidase) at Qo site, (C4) complex III: cytochrome bc1 (ubiquinone reductase) at Qi site, (C5) uncouplers of oxidative phospho
  • composition which in addition to the Formula 1 compound of component (a), includes as component (b) at least one fungicidal compound selected from the group consisting of the classes (b1) methyl benzimidazole carbamate (MBC) fungicides; (b2) dicarboximide fungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4) phenylamide (PA) fungicides; (b5) amine/morpholine fungicides; (b6) phospholipid biosynthesis inhibitor fungicides; (b7) succinate dehydrogenase inhibitor (SDHI) fungicides; (b8) hydroxy(2-amino-)pyrimidine fungicides; (b9) anilinopyrimidine (AP) fungicides; (b10) N-phenyl carbamate fungicides; (b11) quinone outside inhibitor (QoI) fungicides; (b12) phenylpyrrole (PP) fungicides; (b13
  • component (b) comprises at least one fungicidal compound from each of two different groups selected from (b1) through (b54).
  • groups (b1) through (b54) are as follows.
  • (b1) “Methyl benzimidazole carbamate (MBC) fungicides” (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-methyl.
  • FRAC code 2 “Dicarboximide fungicides” (FRAC code 2) inhibit a mitogen-activated protein (MAP)/histidine kinase in osmotic signal transduction. Examples include chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
  • DMI Demethylation inhibitor
  • FRAC code 3 Step 3
  • SBI Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, which plays a role in sterol production.
  • Sterols such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi.
  • DMI fungicides are divided between several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles and triazolinthiones.
  • the piperazines include triforine.
  • the pyridines include buthiobate, pyrifenox, pyrisoxazole and ( ⁇ S)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3- pyridinemethanol.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the imidazoles include econazole, imazalil, oxpoconazole, pefurazoate, prochloraz and triflumizole.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, ⁇ -(1-chlorocyclopropyl)- ⁇ -[2-(2,2- dichlorocyclopropy
  • the triazolinthiones include prothioconazole.
  • 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.
  • FRAC code 4 “Phenylamide fungicides” (FRAC code 4) 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 butyrolactone fungicides.
  • the acylalanines include benalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyl and metalaxyl-M (also known as 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.
  • FRAC code 6 “Phospholipid biosynthesis inhibitor fungicides” (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.
  • SDHI fungicides include phenylbenzamide, phenyloxoethylthiophene amide, pyridinylethylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, N-cyclopropyl-N-benzyl-pyrazole carboxamide, N-methoxy-(phenyl-ethyl)-pyrazole carboxamide, pyridine carboxamide and pyrazine carboxamide fungicides.
  • the phenylbenzamides include benodanil, flutolanil and mepronil.
  • the phenyloxoethylthiophene amides include isofetamid.
  • the pyridinylethylbenzamides include fluopyram.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamides include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole-4-carboxamides include benzovindiflupyr, bixafen, flubeneteram (provisional common name, Registry Number 1676101-39-5), fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne (provisional common name, Registry Number 1803108-03-3), sedaxane and N-[2-(2,4-dichlorophenyl)-2- methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.
  • the N- cyclopropyl-N-benzyl-pyrazole carboxamides include isoflucypram.
  • the N-methoxy-(phenyl- ethyl)-pyrazole carboxamides include pydiflumetofen.
  • the pyridine carboxamides include boscalid.
  • the pyrazine carboxamides include pyraziflumid. (b8) “Hydroxy-(2-amino-)pyrimidine fungicides” (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • fungicides (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 code 10 “N-Phenyl carbamate fungicides” (FRAC code 10) 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 diethofencarb.
  • Quinone outside inhibitor fungicides include methoxyacrylate, methoxyacetamide, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzylcarbamate fungicides.
  • the methoxyacrylates include azoxystrobin, coumoxystrobin, enoxastrobin (also known as enestroburin), flufenoxystrobin, picoxystrobin and pyraoxystrobin.
  • the methoxyacetamides include mandestrobin.
  • the methoxy- carbamates include pyraclostrobin, pyrametostrobin and triclopyricarb.
  • the oximinoacetates include kresoxim-methyl and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, fenaminstrobin, metominostrobin and orysastrobin.
  • the dihydrodioxazines include fluoxastrobin.
  • the oxazolidinediones include famoxadone.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • the quinazolinones include proquinazid.
  • “Lipid peroxidation inhibitor fungicides” FRAC code 14
  • FRAC code 14 “Lipid peroxidation inhibitor fungicides”
  • etridiazole Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis.
  • Cell peroxidation fungicides include aromatic hydrocarbon and 1,2,4-thiadiazole fungicides.
  • the aromatic hydrocarboncarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl.
  • the 1,2,4-thiadiazoles include etridiazole.
  • MBI-R Melanin biosynthesis inhibitors-reductase fungicides
  • FRAC code 16.1 inhibits the naphthal reduction step in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides.
  • the isobenzofuranones include fthalide.
  • the pyrroloquinolinones include pyroquilon.
  • the triazolobenzothiazoles include tricyclazole.
  • Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides (FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • MMI-P Melanin biosynthesis inhibitor-polyketide synthase
  • FRAC code 16.3 inhibit polyketide synthase in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethylcarbamate fungicides. The trifluoroethylcarbamates include tolprocarb.
  • SBBI Sterol Biosynthesis Inhibitor
  • Keto reductase inhibitor fungicides include hydroxyanilides and amino-pyrazolinones. Hydroxyanilides include fenhexamid. Amino-pyrazolinones include fenpyrazamine. Quinofumelin (provisional common name, Registry Number 861647-84-9) and ipflufenoquin (provisional common name, Registry Number 1314008-27-9) are also believed to be keto reductase inhibitor fungicides.
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafine.
  • Quinone inside inhibitor fungicides include cyanoimidazole, sulfamoyltriazole and picolinamide fungicides.
  • the cyanoimidazoles include cyazofamid.
  • the sulfamoyltriazoles include amisulbrom.
  • the picolinamides include fenpicoxamid (Registry Number 517875-34-2).
  • FRAC code 22 “Benzamide and thiazole carboxamide fungicides” (FRAC code 22) 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.
  • the benzamides include toluamides such as zoxamide.
  • the thiazole carboxamides include ethylaminothiazole carboxamides such as ethaboxam.
  • FRAC code 23 “Enopyranuronic acid antibiotic fungicides” (FRAC code 23) inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.
  • FRAC code 24 “Hexopyranosyl antibiotic fungicides” (FRAC code 24) inhibit growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.
  • Glucopyranosyl antibiotic: protein synthesis fungicides” (FRAC code 25) inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.
  • Glucopyranosyl antibiotic fungicides (FRAC code U18, previously FRAC code 26 reclassified to U18) are proposed to inhibit trehalase and inositol biosynthesis. Examples include validamycin.
  • b28) “Carbamate fungicides” (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Iodocarb, propamacarb and prothiocarb are examples of this fungicide class.
  • b31 “Carboxylic acid fungicides” (FRAC code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • FRAC code 32 “Heteroaromatic fungicides” (FRAC code 32) are proposed to affect DNA/ribonucleic acid (RNA) synthesis. Heteroaromatic fungicides include isoxazoles and isothiazolones. The isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • FRAC code P07 “Phosphonate fungicides” (FRAC code P07, previously FRAC code 33 reclassified to P07) include phosphorous acid and its various salts, including fosetyl-aluminum.
  • FRAC code 34 “Phthalamic acid fungicides” (FRAC code 34) include teclofthalam.
  • FRAC code 35 “Benzotriazine fungicides” (FRAC code 35) include triazoxide.
  • Benzene-sulfonamide fungicides” (FRAC code 36) include flusulfamide.
  • FRAC code 37 “Pyridazinone fungicides” (FRAC code 37) include diclomezine.
  • FRAC code 38 Thiophene-carboxamide fungicides
  • Examples include silthiofam.
  • FRAC code 39 “Complex I NADH oxidoreductase inhibitor fungicides” (FRAC code 39) inhibit electron transport in mitochondria and include pyrimidinamines such as diflumetorim, pyrazole- 5-carboxamides such as tolfenpyrad, and quinazoline such as fenazaquin.
  • CAA Carboxylic acid amide
  • FRAC code 40 inhibit cellulose synthase which 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, flumorph and pyrimorph.
  • the valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb and valifenalate (also known as valiphenal).
  • the mandelic acid amides include mandipropamid, N- [2-[4-[[3-(4-chlorophenyl)-2-propyn-1-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.
  • fungi “Tetracycline antibiotic fungicides” (FRAC code 41) inhibit growth of fungi by affecting protein synthesis. Examples include oxytetracycline.
  • FRAC code M12 “Thiocarbamate fungicides” (FRAC code M12, previously FRAC code 42 reclassified to M12) include methasulfocarb.
  • Benzamide fungicides (FRAC code 43) inhibit growth of fungi by delocalization of spectrin-like proteins. Examples include pyridinylmethyl benzamides such as fluopicolide and fluopimomide.
  • Microbial fungicides disrupt fungal pathogen cell membranes.
  • Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB1600, D747, TJ100 (also called strain 1 BE; known from EP2962568), and the fungicidal lipopeptides which they produce.
  • Plant extract fungicides include terpene hydrocarbons, terpene alcohols and terpen phenols such as the extract from Melaleuca alternifolia (tea tree) and plant oils (mixtures) such as eugenol, geraniol and thymol.
  • Cyanoacrylate fungicides FRAC code 47
  • Cyanoacrylates include fungicides such as phenamacril.
  • Polyene fungicides cause disruption of the fungal cell membrane by binding to ergosterol, the main sterol in the membrane.
  • Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone.
  • “Host plant defense induction fungicides” induce host plant defense mechanisms.
  • Host plant defense induction fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microbial (FRAC code P06) and phosphonate fungicides (FRAC code P07, see (b33) above).
  • the benzothiadiazoles include acibenzolar-S- methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole carboxamides include tiadinil and isotianil.
  • the polysaccharides include laminarin.
  • the plant extracts include extract from Reynoutria sachalinensis (giant knotweed).
  • the microbials include Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS117. (b52) “Multi-site activity fungicides” inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • Multi-site activity fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code M11) and thiocarbamate (FRAC code M12, see (b42) above) fungicides.
  • FRAC code M01 copper fungicides
  • FRAC code M02 sulfur fungicides
  • FRAC code M03 dithiocarbamate fungicides
  • FRAC code M04 phthalimide fungicide
  • 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 ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, 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. Multi-site contact guanidine fungicides include, guazatine, iminoctadine albesilate and iminoctadine triacetate. Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionate).
  • Maleimide fungicides include fluoroimide.
  • Biologicals with multiple modes of action include agents from biological origins showing multiple mechanisms of action without evidence of a dominating mode of action.
  • This class of fungicides includes polypeptide (lectin), phenol, sesquiterpene, tritepenoid and coumarin fungicides (FRAC code BM01) such as extract from the cotyledons of lupine plantlets. This class also includes momicrobial fungicides (FRAC code BM02, see (b44) above).
  • FRAC code BM02 see (b44) above.
  • b54 “Fungicides other than fungicides of component (a) and components (b1) through (b53)”; include certain fungicides whose mode of action may be unknown.
  • the phenyl-acetamides include cyflufenamid.
  • the guanidines include dodine.
  • the thiazolidines include flutianil.
  • the pyrimidinonehydrazones include ferimzone.
  • the 4-quinolylacetates include tebufloquin.
  • the tetrazolyloximes include picarbutrazox.
  • the (b54) class also includes bethoxazin, dichlobentiazox (provisional common name, Registry Number 957144-77-3), dipymetitrone (provisional common name, Registry Number 16114-35-5), flometoquin, neo-asozin (ferric methanearsonate), pyrrolnitrin, tolnifanide (Registry Number 304911-98-6), N'-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N- ethyl-N-methylmethanimidamide, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl N-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate.
  • Additional “Fungicides other than fungicides of classes (b1) through (b54)” whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b54.7) through (b54.12), as shown below.
  • Component (54.7) relates to (1S)-2,2-bis(4-fluorophenyl)-1-methylethyl N-[[3-(acetyloxy)- 4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name florylpicoxamid, Registry Number 1961312-55-9) which is believed to be a Quinone inside inhibitor (QiI) fungicide (FRAC code 21) inhibiting the Complex III mitochondrial respiration in fungi.
  • QiI Quinone inside inhibitor
  • FRAC code 21 inhibiting the Complex III mitochondrial respiration in fungi.
  • Component (54.8) relates to 1-[2-[[[[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy]methyl]-3- methylphenyl]-1,4-dihydro-4-methyl-5H-tetrazol-5-one (provisional common name metyltetraprole, Registry Number 1472649-01-6), which is believed to be a quinone outside inhibitor (QoI) fungicide (FRAC code 45) inhibiting the Complex III mitochondrial respiration in fungi, and is effective against QoI resistant strains.
  • QoI quinone outside inhibitor
  • Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl, Registry Number 1358061-55-8), which is believed to be promoter tubulin polymerization, resulting antifungal activity against fungal species belonging to the phyla Ascomycota and Basidiomycota.
  • Component (54.10) relates to (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (provisional common name aminopyrifen, Registry Number 1531626-08-0) which is believed to inhibit GWT-1 protein in glycosylphosphatidylinositol-anchor biosynthesis in Neurospora crassa.
  • Component (b54.11) relates a compound of Formula b54.11
  • R b1 and R b3 are each independently halogen; and R b2 is H, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 3 -C 6 cycloalkyl.
  • Examples of compounds of Formula b54.11 include (b54.11a) methyl N-[[5-[1-(2,6-difluoro-4- formylphenyl)-1H-pyrazol-3-yl]-2-methylphenyl] methyl]carbamate, (b54.11b) methyl N-[[5-[1- (4-cyclopropyl-2,6-dichlorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]methyl]carbamate, (b54.11c) methyl N-[[5-[1-(4-chloro-2,6-difluorophenyl)-1H-pyrazol-3-yl]-2-methylphenyl]- methyl]carbamate, (b54.11d) methyl N-[[5-[1-(4-cyclopropyl-2,6-difluorophenyl)-1H-pyrazol-3- yl]-2-methylphenyl]
  • Component (b54.12) relates to a compound of Formula b54.12 wherein R b4 is R b6 is C 2 -C 4 alkoxycarbonyl or C 2 -C 4 haloalkylaminocarbonyl; L is CH 2 or CH 2 O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12; R b5 is ; and R b7 is C 1 -C 3 alkyl, wherein the wavy bond indicates the adjacent double bond is either (Z)- or (E)-configuration, or a mixture thereof.
  • Examples of compounds of Formula b54.12 include (b54.12a) N-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide, (b54.12b) ethyl 1-[[4-[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]phenoxy]methyl]-1H-pyrazole-4-carboxylate, (b54.12c) ethyl 1-[[4-[[[(1Z)-2-ethoxy-3,3,3-trifluoro-1-propen-1-yl]oxy]phenyl]methyl]-1H- pyrazole-4-carboxylate and (b54.12d) ethyl 1-[[4-[[[2-(trifluoromethyl)-1,3-dioxolan-2- yl]methoxy
  • compositions comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of the aforedescribed classes (b1) through (b54), including (b54.7) through (b54.12).
  • 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 comprising a compound of Formula 1 and at least one fungicidal compound selected from the group of specific compounds listed above in connection with classes (b1) through (b54). Also of particular note is 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.
  • component (b) fungicides include acibenzolar-S-methyl, aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole, azoxystrobin, benalaxyl (including benalaxyl- M), benodanil, benomyl, benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr, bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S, boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil, chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, copper sulfate, coumoxystrobin, c
  • fungicidal composition comprising as component (a) a compound of Formula 1 (or an N-oxide or salt thereof) and as component (b) at least one fungicide selected from the preceding list.
  • component (a) a compound of Formula 1 (or an N-oxide or salt thereof)
  • component (b) at least one fungicide selected from the preceding list.
  • combinations of compounds of Formula 1 (or an N-oxide or salt thereof) i.e.
  • Component (a) in compositions) with aminopyrifen (Registry Number 1531626-08- 0), azoxystrobin, benzovindiflupyr, bixafen, captan, carpropamid, chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate, cymoxanil, cyproconazole, cyprodinil, dichlobentiazox (Registry Number 957144-77-3), diethofencarb, difenoconazole, dimethomorph, dipymetitrone, epoxiconazole, ethaboxam, fenarimol, fenhexamid, fluazinam, fludioxonil, fluindapyr, fluopyram, flusilazole, flutianil, flutriafol, fluxapyroxad, folpet, ipflufenoquin (Registry Number 1314008-27-9), i
  • Component (b) in compositons Generally preferred for better control of plant diseases caused by fungal plant pathogens (e.g., lower use rate or broader spectrum of plant pathogens controlled) or resistance management are mixtures of a compound of Formula 1, an N-oxide, or salt thereof, with a fungicidal compound selected from the group: amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, dimoxystrobin, fenpropimorph, florylpicoxamid, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, ipfentrifluconazole, iprodione, kresoxim-
  • invertebrate pest control compounds or agents such as abamectin, acephate, acetamiprid, acrinathrin, afidopyropen ([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b- decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1- b]pyrano[3,4-e]pyran-4-yl]methyl cyclopropanecarboxylate), amidoflumet (S-1955), avermectin, azadirachtin, azinphos-methyl, bif
  • 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 HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.
  • NPV nucleopolyhedro virus
  • GV granulosis virus
  • One embodiment of biological agents for mixing with compounds of this disclosure include entomopathogenic bacteria such as Bacillus thuringiensis, and the encapsulated delta-endotoxins of Bacillus thuringiensis such as MVP® and MVPII® bioinsecticides prepared by the CellCap® process (CellCap®, MVP® and MVPII® are trademarks of Mycogen Corporation, Indianapolis, Indiana, USA); entomopathogenic fungi such as green muscardine fungus; and entomopathogenic (both naturally occurring and genetically modified) viruses including baculovirus, nucleopolyhedro virus (NPV) such as Helicoverpa zea nucleopolyhedrovirus (HzNPV), Anagrapha falcifera nucleopolyhedrovirus (AfNPV); and granulosis virus (GV) such as Cydia pomonella granulosis virus (CpGV).
  • NPV nucleopolyhedr
  • compositions where in the weight ratio of component (a) to component (b) are from about 125:1 to about 1:125. With many fungicidal compounds of component (b), these compositions are particularly effective for controlling plant diseases caused by fungal plant pathogens. Of particular note are compositions wherein the weight ratio of component (a) to component (b) is from about 25:1 to about 1:25, or from about 5:1 to about 1:5.
  • weight ratio of component (a) to component (b) is from about 25:1 to about 1:25, or from about 5:1 to about 1:5.
  • One skilled in the art can easily determine through simple experimentation the weight ratios and application rates of fungicidal compounds necessary for the desired spectrum of fungicidal protection and control. It will be evident that including additional fungicidal compounds in component (b) may expand the spectrum of plant diseases controlled beyond the spectrum controlled by component (a) 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.
  • combinations of a compound of the invention with other biologically active compounds or agents can result in a less-than-additive (i.e. safening) effect on organisms beneficial to the agronomic environment.
  • a compound of the invention may safen a herbicide on crop plants or protect a beneficial insect species (e.g., insect predators, pollinators such as bees) from an insecticide.
  • Fungicides of note for formulation with compounds of Formula 1 to provide mixtures useful in seed treatment include but are not limited to amisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil, cyproconazole, difenoconazole, dimethomorph, florylpicoxamid, fluazinam, fludioxonil, flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, mefentrifluconazole, metconazole, myclobutanil, paclobutrazole, penflufen
  • Invertebrate pest control compounds or agents with which compounds of Formula 1 can be formulated to provide mixtures useful in seed treatment include but are not limited to abamectin, acetamiprid, acrinathrin, afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin, buprofezin, cadusafos, carbaryl, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin, cyantraniliprole, cyclaniliprole, cyfluthrin, beta-cyfluthrin, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, zeta- cypermethrin, cyroma
  • Compositions comprising compounds of Formula 1 useful for seed treatment can further comprise bacteria and fungi that have the ability to provide protection from the harmful effects of plant pathogenic fungi or bacteria and/or soil born animals such as nematodes.
  • Bacteria exhibiting nematicidal properties may include but are not limited to Bacillus firmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans.
  • a suitable Bacillus firmus strain is strain CNCM I- 1582 (GB-126) which is commercially available as BioNem TM .
  • a suitable Bacillus cereus strain is strain NCMM I-1592. Both Bacillus strains are disclosed in US 6,406,690.
  • Other suitable bacteria exhibiting nematicidal activity are B.
  • Bacteria exhibiting fungicidal properties may include but are not limited to B. pumilus strain GB34.
  • Fungal species exhibiting nematicidal properties may include but are not limited to Myrothecium verrucaria, Paecilomyces lilacinus and Purpureocillium lilacinum.
  • Seed treatments can also include one or more nematicidal agents of natural origin such as the elicitor protein called harpin which is isolated from certain bacterial plant pathogens such as Erwinia amylovora.
  • harpin which is isolated from certain bacterial plant pathogens such as Erwinia amylovora.
  • Harpin-N-Tek seed treatment technology available as N- Hibit TM Gold CST.
  • Seed treatments can also include one or more species of legume-root nodulating bacteria such as the microsymbiotic nitrogen-fixing bacteria Bradyrhizobium japonicum.
  • These inocculants can optionally include one or more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod) factors produced by rhizobia bacteria during the initiation of nodule formation on the roots of legumes.
  • LCOs lipo-chitooligosaccharides
  • Nod nodulation
  • the Optimize® brand seed treatment technology incorporates LCO Promoter Technology TM in combination with an inocculant.
  • Seed treatments can also include one or more isoflavones which can increase the level of root colonization by mycorrhizal fungi.
  • Mycorrhizal fungi improve plant growth by enhancing the root uptake of nutrients such as water, sulfates, nitrates, phosphates and metals.
  • isoflavones include, but are not limited to, genistein, biochanin A, formononetin, daidzein, glycitein, hesperetin, naringenin and pratensein.
  • Formononetin is available as an active ingredient in mycorrhizal inocculant products such as PHC Colonize® AG. Seed treatments can also include one or more plant activators that induce systemic acquired resistance in plants following contact by a pathogen.
  • TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens.
  • the pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Table A below for compound descriptions.
  • the abbreviation “Cmpd.” stands for “Compound”, and the abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.
  • 19 F NMR spectra are reported in ppm relative to trichlorofluoromethane in CDCl 3 solution unless indicated otherwise.
  • MS molecular weight of the highest isotopic abundance positively charged parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule having the highest isotopic abundance, or the highest isotopic abundance negatively charged ion (M–1) formed by loss of H+ (molecular weight of 1).
  • M+1 molecular weight of the highest isotopic abundance positively charged parent ion
  • M–1 molecular weight of the highest isotopic abundance negatively charged ion
  • test suspensions for Test A 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 by volume) containing 250 ppm of the surfactant PEG400 (polyhydric alcohol esters). The resulting test suspensions were then used in Test A. TEST A The test solution was sprayed to the point of run-off on soybean seedlings.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Sont divulgués des composés de formule I y compris tous les isomères et stéréoisomères, tautomères, N-oxydes géométriques et des sels de ceux-ci, G, Z, L, J, A et T étant tels que définis dans la description. Sont divulgués également des compositions contenant les composés de formule 1 et des procédés de lutte contre une maladie de plante provoquée par un pathogène fongique comprenant l'application d'une quantité efficace d'un composé ou d'une composition selon l'invention.
PCT/US2023/012882 2022-02-15 2023-02-13 Halométhylcétones, hydrates et éthers d'énol fongicides WO2023158602A1 (fr)

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