WO2017105999A1 - Dérivés de n-[[5-[[[1-(phényl)éthylidène]amino]oxy]phényl]-méthyl]carbamate et composés associés utilisés comme fongicides pour lutter contre les maladies des plantes - Google Patents

Dérivés de n-[[5-[[[1-(phényl)éthylidène]amino]oxy]phényl]-méthyl]carbamate et composés associés utilisés comme fongicides pour lutter contre les maladies des plantes Download PDF

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WO2017105999A1
WO2017105999A1 PCT/US2016/065567 US2016065567W WO2017105999A1 WO 2017105999 A1 WO2017105999 A1 WO 2017105999A1 US 2016065567 W US2016065567 W US 2016065567W WO 2017105999 A1 WO2017105999 A1 WO 2017105999A1
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methyl
compound
fungicides
alkyl
phenyl
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PCT/US2016/065567
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English (en)
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Kimberly Katherine Marcus
Andrew Edmund Taggi
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E I Du Pont De Nemours And Company
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound 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
    • C07D213/53—Nitrogen atoms

Definitions

  • This invention relates to certain substituted benzenes, their N-oxides, salts and compositions, and methods of their use as fungicides.
  • This invention is directed to compounds of Formula 1 (including all stereoisomers),
  • Z is a radical selected from the group consisting of
  • a 1 and A 2 are each independently O, NR 7a or S;
  • W is O or S
  • Q is CR 6a R 6b , O or NR 7b ;
  • R 1 is H, halogen, cyano, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3
  • R 2 is halogen, cyano, C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, C 3 -C 6 cycloalkyl, C 3 -C 15 trialkylsilyl or C 3 -C 15 halotrialkylsilyl;
  • R 3 is selected from the group consisting of G, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 a lkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 2 -C 8 a lkylcarbonyl, C 2 -C 8 alkoxycarbonyl, C 2 -C 8 alkylaminocarbonyl, C 3 -C 8 d ialkylaminocarbonyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, C 3 -C 6 cycloalkoxy, C 3 -C 6 halocycloalkoxy, C 2 -C 8 alkylcarbonyloxy, C 4 -C 8 cycloalkylcarbonyloxy, C 1 -C 6 alkylthio, C 3 -C 6 cycl
  • R 3 is selected from the group consisting of C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6
  • a lkoxyalkyl C 2 -C 6 alkylthioalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkoxy, C 1 -C 6 a lkylthio, C 1 -C 6 alkylsulfinyl and C 1 -C 6 alkylsulfonyl, each group substituted w ith 1 or 2 substituents independently selected from R 8a on carbon atom group members;
  • G is phenyl, benzoyl, phenoxy, phenylsulfonyl or naphthalenyl, each ring or ring
  • R 4 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 1 -C 6 a lkoxy, C 1 -C 6 haloalkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 haloalkoxyalkyl, C 1 -C 6 a lkylthio or C 1 -C 6 haloalkylthio; or phenyl, benzyl or phenoxy, each ring o ptionally substituted with up to 3 substituents independently selected from R 10 ;
  • R5 is H, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 3 alkoxy or C 1 -C 4
  • R5 is H, C 1 -C 4 alkyl, C 1 -C 4 h aloalkyl or C 3 -C 6 cycloalkyl;
  • R 6a is H, halogen, cyano, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6
  • R 6b is H, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy or C 2 -C 6 alkoxyalkyl; or R 6a and R 6b are taken together with the carbon atom to which they are attached to form a 3- to 6-membered saturated carbocyclic ring optionally substituted with up to 2 substituents independently selected from halogen and methyl;
  • R7a and R7b is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3
  • ialkylaminocarbonyl C 4 -C 10 cycloalkylaminocarbonyl, C 1 -C 6 alkoxy, C 1 -C 6 h aloalkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 6 h aloalkynyloxy, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, C 4 -C 10
  • each J is independently phenyl or naphthalenyl, each optionally substituted with up to 5 substituents independently selected R 13 ; or a 5- to 7-membered heteroaromatic ring or an 8- to 11-membered fused heterobicyclic ring system, each ring or ring system 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 or ring system optionally substituted with up to 5 substituents i ndependently selected from R 13 ;
  • e ach R9 is independently H, cyano, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl;
  • e ach R10 is independently cyano, halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3
  • R11 is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl or C 3 -C 8 cycloalkyl;
  • e ach R12 is independently H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 2 -C 3 alkylcarbonyl or C 2 -C 3 haloalkylcarbonyl;
  • R13 is independently halogen, cyano, nitro, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 a lkenyl, C 2 -C 6 haloalkenyl C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, C4 C6 alkylcycloalkyl, C1 C6 alkoxy, C1 C6 haloalkoxy, C1 C6 a lkylthio or C 1 -C 6 haloalkylthio; and
  • m 0 or 1.
  • this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising (a) a compound of the invention (i.e. in a fungicidally effective amount); and (b) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also relates to a fungicidal composition
  • a fungicidal composition comprising (a) a compound of the invention; and (b) at least one other fungicide (e.g., at least one other fungicide having a different site of action).
  • This invention further relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of the invention (e.g., as a composition described herein).
  • This invention also relates to a composition
  • a composition comprising a compound of Formula 1, an N-oxide, or a salt thereof, and at least one invertebrate pest control compound or agent.
  • compositions As used herein, the terms“comprises,”“comprising,”“includes,”“including,”“has,” “having,”“contains,”“containing,”“characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition, mixture, process, 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.
  • transitional phrase“consisting essentially of” is used to define a composition, method or apparatus that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term“consisting essentially of” occupies a middle ground between “comprising” and“consisting of”. Where applicants have defined an invention or a portion thereof with an open ended term such as“comprising,” it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms “consisting essentially of” or“consisting of.”
  • “or” refers to an inclusive or and not to an exclusive or.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • indefinite articles“a” and“an” preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore“a” or“an” should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
  • “plant” includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds).
  • Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.
  • seedling means a young plant developing from the embryo of a seed.
  • the term“broadleaf” used either alone or in words such as “broadleaf crop” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
  • the terms“fungal pathogen” and“fungal plant pathogen” include pathogens in the Ascomycota, Basidiomycota and Zygomycota phyla, and the fungal-like Oomycota class that are the causal agents of a broad spectrum of plant diseases of economic importance, affecting ornamental, turf, vegetable, field, cereal and fruit crops.
  • “protecting a plant from disease” or“control of a plant disease” includes preventative action (interruption of the fungal cycle of infection, colonization, symptom development and spore production) and/or curative action (inhibition of colonization of plant host tissues).
  • mode of action is as define by the Fungicide Resistance Action Committee (FRAC), and is used to distinguish fungicides according to their biochemical mode of action in the biosynthetic pathways of plant pathogens.
  • FRAC-defined modes of actions include (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (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, (NC) not classified and (M) multi-site contact activity.
  • A nucleic acid synthesis
  • B mitosis and cell division
  • C respiration
  • D amino acid and protein synthesis
  • E signal transduction
  • F lipid synthesis and membrane integrity
  • G sterol biosynthesis in membranes
  • H cell wall biosynthesis
  • I melanin synthesis in
  • Each mode of action (i.e. letters A through M) contain one or more subgroups (e.g., A includes subgroups A1, A2, A3 and A4) based either on individual validated target sites of action, or in cases where the precise target site is unknown, based on cross resistance profiles within a group or in relation to other groups.
  • Each of these subgroups (e.g., A1, A2, A3 and A4) is asigned a FRAC code (a number and/or letter).
  • the FRAC code for subgroup A1 is 4. Additional information on target sites and FRAC codes can be obtained from publicly available databases maintained, for example, by FRAC.
  • cross resistance refers to the phenomenon that occurs when a pathogen develops resistance to one fungicide and simultaneously becomes resistant to one or more other fungicides. These other fungicides are typically, but not always, in the same chemical class or have the same target site of action, or can be detoxified by the same mechanism.
  • a molecular fragment i.e. radical
  • a series of atom symbols e.g., C, H, N, O and S
  • the point or points of attachment may be explicitly indicated by a hyphen (“-”).
  • - hyphen
  • “-SCN” indicates that the point of attachment is the sulfur atom (i.e. thiocyanato, not isothiocyanato).
  • alkylating agent refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom.
  • a leaving group such as halide or sulfonate
  • the term“alkylating” does not limit the carbon-containing radical to alkyl; the carbon-containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified, for example, for R 5 .
  • alkyl used either alone or in compound words such as“alkylthio” or“haloalkyl” includes straight-chain or branched alkyl such as methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl also includes moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylamino includes an NH radical substituted with straight-chain or branched alkyl.
  • alkylamino include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH and (CH 3 ) 2 CHNH.
  • dialkylamino examples include (CH3)2N, (CH3CH2)2N and CH3CH2(CH3)N.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, i-propyloxy and the different butyl, pentyl and hexyloxy isomers.“Alkoxyalkyl” denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 . “Alkenyloxy” includes straight-chain or branched alkenyl attached to and linked through an oxygen atom.
  • Alkynyloxy includes straight-chain or branched alkynyl attached to and linked through an oxygen atom. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and CH 3 C ⁇ CCH 2 CH 2 O.
  • Alkoxyalkoxy denotes alkoxy substitution on another alkoxy moiety. Examples of “alkoxyalkoxy” include CH 3 OCH 2 O, CH 3 OCH 2 CH 2 CH 2 O and CH 3 CH 2 OCH 2 O.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propyl, butyl, pentyl and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • cycloalkyl denotes a saturated carbocyclic ring consisting of between 3 to 6 carbon atoms linked to one another by single bonds.
  • examples of“cycloalkyl” include cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, i-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl.
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • cycloalkylthio denotes cycloalkyl attached to and linked through a sulfur atom such as cyclopropylthio and cyclopentylthio; “cycloalkylsulfonyl” includes the corresponding sulfones.
  • Cycloalkylalkoxy denotes cycloalkyl substitution on an alkoxy group. Examples of cycloalkylalkoxy include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. “Cycloalkylamino” denotes an NH radical substituted with cycloalkyl.
  • “cycloalkylamino” examples include cyclopropylamino and cyclohexylamino.
  • “Cycloalkylcarbonyloxy” denotes cycloalkylcarbonyl attached to and linked through an oxygen atom.
  • cycloalkylcarbonyloxy examples include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy.
  • halogen either alone or in compound words such as“halomethyl” or “haloalkyl”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as“haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of“haloalkyl” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, F 2 CHCH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • halocycloalkyl examples include chlorocyclopropyl, fluorocyclobutyl and chlorocyclohexyl.
  • 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.
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the prefix “C i -C j ” where i and j are numbers from 1 to 10.
  • C 1 -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH 3 CH 2 OCH 2 CH 2 .
  • the term“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.
  • T he term“optionally substituted” means that the number of substituents can be zero. Unless otherwise indicated, 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. Commonly, the number of optional substituents (when present) 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).
  • the phrase“optionally substituted with up to 5 substituents independently selected from R 8b ” means that 0, 1, 2, 3, 4 or 5 substituents can be present if the number of available connection points allows.
  • 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“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 of a fully unsaturated ring are essentially in the same plane and have 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.
  • “carbocyclic ring” or“carbocycle” denote a ring wherein the atoms forming the ring backbone are selected only from carbon. When a fully unsaturated carbocyclic ring satisfies Hückel’s rule, then said ring is also called an“aromatic carbocyclic ring”.
  • saturated carbocyclic ring refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • heterocyclic ring denotes a ring or ring system in which at least one atom forming the ring backbone is not carbon (e.g., N, O or S).
  • a heterocyclic ring contains no more than 3 N atoms, no more than 2 O atoms and no more than 2 S atoms.
  • a heterocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring.
  • heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • R 4 or J comprises a phenyl or 6-membered heterocyclic ring (e.g., pyridinyl), the ortho, meta and para positions of each ring are relative to the connection of the ring to the remainder of Formula 1.
  • R 4 or J comprises a phenyl ring attached through the linker CH 2 (i.e. benzyl) to the remainder of Formula 1, the ortho, meta and para positions of the phenyl ring are relative to the connection of the ring to the linker CH 2 .
  • the nitrogen atom ring members may be oxidized as N-oxides, because compounds relating to Formula 1 also include N-oxide derivatives.
  • the R 8b substituents are optional, thus 0 to 5 substituents may be present, limited only by the number of available points of attachment on G.
  • R 3 is (inter alia) selected from the group consisting of C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C 1 -C 6 alkoxy, C 2 -C 6 alkoxyalkoxy, C 1 -C 6 alkylthio, C 1 -C 6 alkylsulfinyl and C 1 -C 6 alkylsulfonyl, each group substituted with 1 or 2 substituents independently selected from R 8a on carbon atom group members.
  • each group e.g., C 1 -C 6 alkyl
  • each group must have at least one, and no more than two, substituents selected from R 8a .
  • R 3 is denoted as a series of atoms (e.g., CH 3 CH 2 , CH 3 OCH 2 or CH 3 OCH 2 O)
  • the atom on the right side is connected to the reaminder of Formula 1; and unless otherwise indicated, an R 8a substituent(s) can be attached to any available carbon atom by replacement of a hydrogen on said carbon atom.
  • R3 is defined as“CH 3 CH 2 ” which is substituted with one R 8a , then this includes both R 8a CH2CH a
  • 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.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. For a comprehensive discussion of all aspects of stereoisomerism, see Ernest L. Eliel and Samuel H. Wilen, Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.
  • 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.
  • 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.
  • 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. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • beneficial effects e.g., suitability for preparation of useful formulations, improved biological performance
  • 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 Z is Z-1.
  • Embodiment 2 A compound of Formula 1 wherein Z is Z-2.
  • E mbodiment 3 A compound of Formula 1 or Embodiments 1 and 2 wherein A 1 and A 2 a re each independently O or NR 7a .
  • E mbodiment 4 A compound of Embodiment 3 wherein A 1 is O and A 2 is NR 7a .
  • Embodiment 4a A compound of Embodiment 4 wherein A 1 is O.
  • E mbodiment 4b A compound of Embodiment 4 wherein A 2 is NR 7a .
  • Embodiment 5 A compound of Formula 1 or any one of Embodiments 1 through 4b wherein W is O.
  • Embodiment 6 A compound of Formula 1 or any one of Embodiments 1 through 5 w herein Q is CR 6a R 6b .
  • Embodiment 7 A compound of Formula 1 or any one of Embodiments 1 through 5 wherein Q is O.
  • Embodiment 8 A compound of Formula 1 or any one of Embodiments 1 through 5 w herein Q is NR 7b .
  • Embodiment 9 A compound of Formula 1 or any one of Embodiments 1 through 8 w herein R1 is halogen, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy.
  • E mbodiment 10 A compound of Embodiment 9 wherein R1 is halogen, cyano, C 1 -C 2 a lkyl or C 1 -C 2 haloalkyl.
  • Embodiment 11 A compound of Embodiment 10 wherein R is F, Cl, Br, cyano, methyl or trifluoromethyl.
  • Embodiment 12 A compound of Embodiment 11 wherein R 1 is Cl, F or methyl.
  • Embodiment 12a A compound of Embodiment 11 wherein R 1 is Cl or methyl.
  • E mbodiment 14 A compound of Embodiment 12a wherein R 1 is methyl.
  • Embodiment 15 A compound of Formula 1 or any one of Embodiments 1 through 14 w herein R 2 is halogen, cyano, methyl or trifluoromethyl.
  • E mbodiment 16 A compound of Embodiment 15 wherein R 2 is halogen or methyl.
  • Embodiment 17 A compound of Embodiment 16 wherein R 2 is Cl or methyl.
  • R3 is selected from the group consisting of G, C 1 -C 4 alkyl, C 1 -C 4 h aloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 4 alkoxy and C 1 -C 4 haloalkoxy; or C 1 -C 4 a lkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 4 alkoxy, C 2 -C 4 alkoxyalkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkylsulfinyl and C 1 -C 4 alkylsulfonyl, each group substituted with 1 substituent selected from R 8a on a carbon atom group member.
  • E mbodiment 19 A compound of Embodiment 18 wherein R 3 is selected from the group c onsisting of G; or C 1 -C 2 alkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl, C 1 -C 2 a lkoxy, C 2 -C 4 alkoxyalkoxy, C 1 -C 2 alkylthio, C 1 -C 2 alkylsulfinyl and C 1 -C 2 alkylsulfonyl, each group substituted with 1 substituent selected from R 8a on a carbon atom group member.
  • E mbodiment 21 A compound of Embodiment 20 wherein R 3 is selected from the group c onsisting of G; or CH 3 , CH 3 CH 2 , CH 3 OCH 2 , CH 3 O and CH 3 OCH 2 O, each s ubstituted with 1 substituent selected from R 8a .
  • E mbodiment 22 A compound of Embodiment 21 wherein R 3 is selected from the group consisting of G, R 8a CH2, R 8a CH 8a
  • G is phenyl or phenoxy, each ring optionally substituted with up to 3 s ubsti
  • Embodiment 26 A compound of Embodiment 25 wherein G is phenyl optionally s ubstituted with up to 3 substituents independently selected from R 8b ; or a 5- to 6-membered heterocyclic ring or an 8- to 11-membered fused heterobicyclic ring system, each ring or ring system 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 or ring system optionally substituted with up to 3 s ubstituents independently selected from R 8b .
  • Embodiment 27 A compound of Embodiment 26 wherein G is phenyl, pyrazolyl, triazolyl, pyridinyl, pyrimidinyl, 2,3-dihydrobenzofuranyl, 1,3-benzodioxolyl, 3,4-dihydro-2H-1-benzopyranyl or 2,3-dihydro-1,4-benzodioxinyl, each ring or ring system optionally substituted with up to 3 substituents independently s elected from R 8b .
  • Embodiment 28 A compound of Embodiment 27 wherein G is phenyl, pyrazolyl, triazolyl, pyridinyl or pyrimidinyl, each ring optionally substituted with up to 3 s ubstituents independently selected from R 8b .
  • Embodiment 28a A compound of Embodiment 28 wherein G is phenyl or pyridinyl, each ring optionally substituted with up to 3 substituents independently selected f rom R 8b .
  • Embodiment 28b A compound of Embodiment 28a wherein G is phenyl or pyridinyl, each ring optionally substituted with up to 2 substituents independently selected f rom R 8b .
  • Embodiment 29 A compound of Formula 1 or any one of Embodiments 1 through 24 wherein G is one of G-1 through G-20 depicted in Exhibit 1;
  • R 8c is selected from H and R 8b ; and k is 0 to 3.
  • Embodiment 30 A compound of Embodiment 29 wherein k is 0, 1 or 2.
  • Embodiment 30a A compound of Embodiment 29 wherein k is 1 or 2.
  • Embodiment 31 A compound of Embodiment 29 wherein G is G-8, G-11, G-12, G-15, G-18 or G-20.
  • Embodiment 32 A compound of Embodiment 31 wherein G is G-8, G-11 or G-12.
  • Embodiment 32a A compound of Embodiment 31 wherein G is G-8 or G-12.
  • Embodiment 33 A compound of Embodiment 32a wherein G is G-8.
  • Embodiment 34 A compound of Embodiment 32a wherein G is G-12.
  • Embodiment 35 A compound of Formula 1 or any one of Embodiments 1 through 34 w herein R4 is H, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, C 2 -C 3 alkoxyalkyl, C 2 -C 3 haloalkoxyalkyl, C 1 -C 3 alkylthio or C 1 -C 3 haloalkylthio; or phenyl, benzyl or phenoxy, each ring optionally s ubstituted with up to 3 substituents independently selected from R 10 .
  • E mbodiment 36 A compound of Embodiment 35 wherein R 4 is H, methyl, ethyl, trifluoromethyl, cyclopropyl or methoxy; or phenyl, benzyl or phenoxy, each ring optionally substituted with up to 2 substituents independently selected from R 10 .
  • E mbodiment 36a A compound of Embodiment 36 wherein R 4 is H, methyl, ethyl or trifluoromethyl.
  • E mbodiment 37 A compound of Embodiment 36a wherein R 4 is methyl.
  • Embodiment 38 A compound of Formula 1 or any one of Embodiments 1 through 37 w herein R5 is C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or cyclopropyl.
  • E mbodiment 39 A compound of Embodiment 38 wherein R 5 is methyl, ethyl or trifluoromethyl.
  • E mbodiment 40 A compound of Embodiment 39 wherein R 5 is methyl.
  • Embodiment 41 A compound of Formula 1 or any one of Embodiments 1 through 40 w herein when R 6a is separate (i.e. not taken together with R 6b ), then R 6a is H, h alogen, cyano, C 1 -C 2 alkyl or C 1 -C 2 haloalkyl.
  • E mbodiment 42 A compound of Embodiment 41 wherein R 6a is H, F, cyano or methyl.
  • Embodiment 43 A compound of Embodiment 42 wherein R 6a is H.
  • Embodiment 44 A compound of Formula 1 or any one of Embodiments 1 through 43 w herein when R 6b is separate (i.e. not taken together with R 6a ), then R 6b is H, h alogen, C 1 -C 2 alkyl or C 1 -C 2 haloalkyl.
  • E mbodiment 45 A compound of Embodiment 44 wherein R 6b is H, F or methyl.
  • Embodiment 46. A compound of Embodiment 45 wherein R 6b is H.
  • Embodiment 47 A compound of Formula 1 or any one of Embodiments 1 through 46 w herein each R 7a and R 7b is independently H, methyl, halomethyl or methylcarbonyl.
  • E mbodiment 49 A compound of Embodiment 48 wherein each R 7a and R 7b is H.
  • Embodiment 50 A compound of Formula 1 or any one of Embodiments 1 through 49 wherein each R 8a and R 8b is independently J, halogen, C 1 -C 6 alkyl, C 1 -C 6 h aloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy.
  • E mbodiment 51 A compound of Embodiment 50 wherein each R 8a is J.
  • Embodiment 52 A compound of Embodiment 50 wherein each R is independently h alogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy.
  • each R 8b is independently halogen, methyl, halomethyl, cyclopropyl, methoxy or halomethoxy.
  • E mbodiment 53a A compound of Embodiment 53 wherein each R 8b is independently halogen, methyl or methoxy.
  • Embodiment 54 A compound of Formula 1 or any one of Embodiments 1 through 51 wherein each J is independently phenyl optionally substituted with up to 3 s ubstituents independently selected from R 13 ; or a 5- to 6-membered heteroaromatic ring or an 8- to 11-membered fused heterobicyclic ring system, each ring or ring system 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 or ring system optionally substituted with up to 3 s ubstituents independently selected from R 13 .
  • Embodiment 55 A compound of Embodiment 54 wherein each J is independently phenyl, pyrazolyl, triazolyl, pyridinyl, pyrimidinyl, 2,3-dihydrobenzofuranyl, 1,3-benzodioxolyl, 3,4-dihydro-2H-1-benzopyran or 2,3-dihydro-1,4- benzodioxinyl, each ring or ring system optionally substituted with up to 3 s ubstituents independently selected from R 13 .
  • Embodiment 56 A compound of Embodiment 55 wherein each J is independently phenyl, pyrazolyl, triazolyl, pyridinyl or pyrimidinyl, each ring optionally s ubstituted with up to 3 substituents independently selected from R 13 .
  • Embodiment 56a A compound of Embodiment 56 wherein each J is independently phenyl or pyridinyl, each ring optionally substituted with up to 2 substituents i ndependently selected from R 13 .
  • Embodiment 57 A compound of Formula 1 or any one of Embodiments 1 through 56a w herein each R 10 is independently halogen, methyl, halomethyl or methoxy.
  • Embodiment 59 A compound of Formula 1 or any one of Embodiments 1 through 58 w herein each R 12 is independently H, methyl or methylcarbonyl.
  • Embodiment 60 A compound of Formula 1 or any one of Embodiments 1 through 59 w herein each R13 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy.
  • E mbodiment 61 A compound of Embodiment 60 wherein each R 13 is independently halogen, methyl, ethyl, trifluoromethyl or methoxy.
  • Embodiment 62 A compound of Formula 1 or any one of Embodiments 1 through 61 wherein m is 0.
  • 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 1-62 above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment A A compound of Formula 1 wherein
  • Z is Z-1;
  • a 1 and A 2 are each independently O or NR 7a ;
  • W is O
  • R 1 is halogen, cyano, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 1 -C 2 haloalkoxy;
  • G is one of G-1 through G-20 (depicted in Exhibit 1); wherein the bond shown projecting to the left is bonded to Formula 1;
  • R 8c is selected from H and R 8b ;
  • k 0 to 3;
  • R 4 is H, methyl, ethyl, trifluoromethyl, cyclopropyl or methoxy; or phenyl, benzyl or phenoxy, each ring optionally substituted with up to 2 s ubstituents independently selected from R 10 ;
  • R 5 is C 1 -C 2 alkyl, C 1 -C 2 haloalkyl or cyclopropyl;
  • R 6a is H, F, cyano or methyl
  • R 6b is H, F or methyl
  • R 7a and R 7b is independently H, methyl, halomethyl or methylcarbonyl; each R 8a and R 8b is independently J, halogen, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy or C 1 -C 6 haloalkoxy; each J is independently phenyl, pyrazolyl, triazolyl, pyridinyl or pyrimidinyl, each ring optionally substituted with up to 3 substituents independently s elected from R 13 ;
  • R 10 is independently halogen, methyl, halomethyl or methoxy
  • R13 is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropyl, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy; and m is 0.
  • Embodiment B A compound of Embodiment A wherein
  • Q is CR 6a R 6b ;
  • a 1 is O
  • a 2 is NR 7a ;
  • R 1 is F, Cl, Br, cyano, methyl or trifluoromethyl
  • R 3 is selecte from the group consisting of G, R 8a CH2, R 8a CH2CH2,
  • G is G-8, G-11, G-12, G-15, G-18 or G-20;
  • k 0, 1 or 2;
  • R 4 is H, methyl, ethyl or trifluoromethyl
  • R 5 is methyl, ethyl or trifluoromethyl
  • R 6a and R 6b are each H;
  • R 7a is H or methyl
  • R 8a is J
  • e ach R8b is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl,
  • J is phenyl or pyridinyl, each ring optionally substituted with up to 2
  • Embodiment C A compound of Embodiment B wherein
  • R 1 is Cl, F or methyl
  • R 3 is selected from the group consisting of G, R 8a CH2, R 8a CH2CH2 and R 8a CH2O;
  • G is G-8, G-11 or G-12;
  • R 5 is methyl
  • R 7a is H
  • R 8b is independently halogen, methyl, halomethyl, cyclopropyl, methoxy or halomethoxy.
  • Embodiment D A compound of Embodiment C wherein
  • R 3 is selected from the group consisting of G and R 8a CH2;
  • G is G-8 or G-12
  • R 4 is methyl
  • e ach R 8b is independently halogen, methyl or methoxy.
  • Embodiment E A compound of Embodiment D wherein
  • R 1 is Cl or methyl
  • R 3 is G
  • G is G-8.
  • Embodiment F A compound of Formula 1 wherein
  • Z is Z-1;
  • a 1 is O
  • a 2 is NR 7a ;
  • W is O
  • Q is CR 6a R 6b ;
  • R 1 is F, Cl, Br, cyano, methyl or trifluoromethyl
  • R 3 is G or R 8a CH2
  • G is one of G is G-8, G-11, G-12, G-15, G-18 or G-20 (depicted in Exhibit 1); wherein the bond shown projecting to the left is bonded to Formula 1; R 8c is H;
  • k 0, 1 or 2;
  • R 4 is H, methyl, ethyl or trifluoromethyl
  • R 5 is methyl, ethyl or trifluoromethyl
  • R 6a is H, F, cyano or methyl
  • R 6b is H, F or methyl
  • R 7a is H or methyl
  • R 8a is J
  • e ach R8b is independently halogen, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, cyclopropy, C 1 -C 3 alkoxy or C 1 -C 3 haloalkoxy;
  • J is phenyl or pyridinyl, each ring optionally substituted with up to 2
  • each R 13 is independently halogen, methyl, ethyl, trifluoromethyl or methoxy;
  • Embodiment G A compound of Embodiment F wherein
  • R 3 is G
  • G is G-8, G-11 or G-12;
  • R 4 is methyl
  • R 5 is methyl
  • R 6a and R 6b are H;
  • R 7a is H
  • R 8b is independently halogen, methyl, halomethyl, cyclopropyl, methoxy or halomethoxy.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof), and at least one other fungicide.
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof
  • at least one other fungicide are compositions comprising a compound corresponding to any of the compound embodiments described above.
  • This invention provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, 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.
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention provides a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed, a fungicidally effective amount of a compound of Formula 1 (including all stereoisomers, N-oxides, and salts thereof).
  • a compound of Formula 1 including all stereoisomers, N-oxides, and salts thereof.
  • embodiments of such methods are methods comprising applying a fungicidally effective amount of a compound corresponding to any of the compound embodiments describe above.
  • the compounds are applied as compositions of this invention.
  • compounds of Formula 1 can be prepared from boronic acids o f Formula 2, or derivatives thereof, (e.g., Formula 2 wherein M is B(OH) 2 or B(OC(CH 3 ) 2 C(CH 3 ) 2 O)) and oximes of Formula 3 using copper(II)-mediated coupling conditions, such as the Chan-Lam reaction or known modifications thereof.
  • Typical reaction conditions involve the presence of a suitable base such as pyridine or triethylamine, a copper(II) salt catalyst such as copper(II) acetate and an aprotic solvent like dichloromethane 1,2-dichloroethane or chloroform, at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture, in the presence of oxygen or ambient atmospheric air.
  • a suitable base such as pyridine or triethylamine
  • a copper(II) salt catalyst such as copper(II) acetate and an aprotic solvent like dichloromethane 1,2-dichloroethane or chloroform
  • oximes of Formula 3 can be prepared by the reaction of a ldehydes or ketones of Formula 4, wherein R 3 and R 4 are, for example, H, alkyl or aryl groups, with hydroxylamine or a hydroxylamine salt (e.g., hydroxylamine hydrochloride) in a suitable solvent (e.g., ethanol, methanol or water) at a temperature generally ranging from room temperature to the reflux temperature of the reaction mixture.
  • a base is needed to liberate hydroxylamine from its salt.
  • Suitable bases include, but are not limited to, sodium hydroxide, sodium bicarbonate, sodium acetate, pyridine or sodium carbonate. In some cases, pyridine is used as both base and solvent in this reaction.
  • compounds of Formula 2a i.e. Formula 2 wherein M is B(OC(CH 3 ) 2 C(CH 3 ) 2 O)
  • M is B(OC(CH 3 ) 2 C(CH 3 ) 2 O
  • compounds of Formula 2a can be prepared by reaction of the corresponding iodide or bromide of Formula 5 with bis(pinacolato)diboron (i.e. Formula 6) using well-known Pd- catalyzed cross-coupling conditions, such as Miyaura boraylation reaction or related procedures.
  • Typical Miyaura conditions involving the use of a suitable Pd-catalyst (e.g., PdCl 2 (diphenylphosphinoferrocene)), a base (e.g., potassium acetate) and a polar solvent such as N,N-dimethylformamide or dimethylsulfoxide, at a temperature ranging from about 50 to 120 ⁇ C.
  • Pd-catalyst e.g., PdCl 2 (diphenylphosphinoferrocene)
  • a base e.g., potassium acetate
  • a polar solvent such as N,N-dimethylformamide or dimethylsulfoxide
  • the boronic acids of Formula 2b can be obtained from the boronates of Formula 2a, as shown in Scheme 3.
  • a variety of methods reported in the chemical literature can be used to convert the boronic esters of Formula 2a to the acids of Formula 2b, including oxidative cleavage with sodium periodate (NaIO 4 ) in aqueous tetrahydrofuran or aqueous acetone in the presence of ammonium acetate at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture;
  • Example 1, Step E illustrates this method.
  • a compound of Formula 5a i.e. Formula 5 wherein Z is Z-2, Q i s CR 6a R 6b and W is O
  • a compound of Formula 5b i.e. Formula 5 wherein Z is Z-2, Q is CR 6a R 6b , W is O and R 5 is H
  • Lg is a leaving group such as halide (e.g., Cl, Br, I) or sulfonate (e.g., mesylate, triflate, p-toluenesulfonate), and the like.
  • Reactions of this type are typically carried out in a solvent such as N,N-dimethylformamide, acetonitrile or water, in the presence of a base such as potassium carbonate, sodium carbonate or sodium hydroxide, at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture.
  • a base such as potassium carbonate, sodium carbonate or sodium hydroxide
  • compounds of Formula 5b can be prepared from isocyanates of Formula 8 by reaction with trimethylsilylazide (also known as azidotrimethylsilane) or sodium azide, in a solvent such as N,N-dimethylformamide, tetrahydrofuran or toluene at a temperature ranging from about 0 °C to the reflux temperature of the reaction mixture.
  • a solvent such as N,N-dimethylformamide, tetrahydrofuran or toluene
  • a Lewis acid such as aluminum trichloride or boron trifluoride.
  • compounds of Formula 8 can be prepared from compounds of F ormula 9 wherein X 2 is chlorine or bromine by reaction with a cyanate reagent such as silver cyanate, potassium cyanate or tetraethylammonium cyanate in a solvent such as tetrahydrofuran, toluene, dichloromethane, diethylether, N,N-dimethylformamide or acetone at a temperature ranging from about room temperature to the reflux temperature of the reaction mixture.
  • a cyanate reagent such as silver cyanate, potassium cyanate or tetraethylammonium cyanate
  • a solvent such as tetrahydrofuran, toluene, dichloromethane, diethylether, N,N-dimethylformamide or acetone
  • compounds of Formula 8 can be prepared from amines of Formula 10 by treatment with a reagent such as phosgene, diphosgene or triphosgene in the presence of a base such as triethylamine, sodium hydrogencarbonate or pyridine in a solvent such as dichloromethane, ethyl acetate, toluene or tetrahydrofuran at a temperature ranging from about 0 °C to the reflux temperature of the reaction mixture.
  • a reagent such as phosgene, diphosgene or triphosgene
  • a base such as triethylamine, sodium hydrogencarbonate or pyridine
  • a solvent such as dichloromethane, ethyl acetate, toluene or tetrahydrofuran
  • C ompounds of Formula 9a can be prepared from carboxylic acid derivatives of Formula 11 via a two-step synthesis as shown in Scheme 7. Reduction of carboxylic acids of Formula 11 using a reducing agent such lithium aluminum hydride or a borane/tetrahydrofuran complex in an aprotic solvent such as tetrahydrofuran or diethyl ether at a temperature between about room temperature and the reflux temperature of the reaction mixture provides benzylic alcohols of Formula 12.
  • a reducing agent such lithium aluminum hydride or a borane/tetrahydrofuran complex
  • an aprotic solvent such as tetrahydrofuran or diethyl ether
  • benzylic alcohols of Formula 12 can be converted to benzyl halides of Formula 9a by treatment with a reagent such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus tribromide or hydrogen bromide.
  • a reagent such as thionyl chloride, phosphorus pentachloride, phosphorus trichloride, phosphorus oxychloride, phosphorus tribromide or hydrogen bromide.
  • a mines of Formula 10a (i.e. Formula 10 wherein R 6a and R 6b are H) can be prepared by reduction of the corresponding nitriles of Formula 13, as depicted in Scheme 8. Reductions of this type can be carried out using a reducing agent such as lithium aluminum hydride, Raney nickel or sodium borohydride in the presence of nickel(II) chloride in a solvent such as methanol, ethanol or tetrahydrofuran at a temperature ranging from about 0 °C to the reflux temperature of the reaction mixture.
  • a reducing agent such as lithium aluminum hydride, Raney nickel or sodium borohydride
  • nickel(II) chloride in a solvent such as methanol, ethanol or tetrahydrofuran at a temperature ranging from about 0 °C to the reflux temperature of the reaction mixture.
  • This type of transformation is well documented in the literature; see, for example, J. Org. Chem. 2009, 74, 1964-1970; Org. Lett.
  • X1 is Br or I wherein X 1 is Br or I
  • compounds of Formula 5c i.e. Formula 5 wherein Z is Z-1, A 1 is O, A 2 is N, R 7b is H and W is O
  • a base such as triethylamine or pyridine
  • the reaction can be carried out without solvent other than the compounds of Formulae 14, 15 and the base or in an aprotic solvent such as dichloromethane, chloroform, diethyl ether or tetrahydrofuran at a temperature ranging from about 0 to 50 °C.
  • Acid chlorides of Formula 15 are commercially available and can be prepared by methods known in the literature; for a general synthesis of compounds of Formula 15, see Advanced Organic Synthesis, 4 th Edition, Wiley & Sons 1992, 437, and references cited therein.
  • Compounds of Formula 14 are known or can easily be synthesized by general methods known to one skilled in the art.
  • compounds of Formula 14a i.e. Formula 14 wherein Q is O
  • compounds of Formula 14a can be prepared from fluorobenzene derivatives of Formula 16 as shown in Scheme 10.
  • the reaction of a compound of Formula 16 with acetohydroximate of Formula 17 is typically carried out in a polar aprotic solvent such as N,N-dimethylformamide in the presence of a suitable base such as potassium tert-butoxide or sodium hydride at a temperature ranging from about -10 to 120 °C.
  • the resulting compound of Formula 18 can then be deprotected using a strong acid such as perchloric acid at a temperature ranging from about -10 to about 40 °C to give a compound of Formula 14a (for a reference see Organic Preparations and Procedures International 1997, 29(5), 594-600).
  • a strong acid such as perchloric acid at a temperature ranging from about -10 to about 40 °C to give a compound of Formula 14a (for a reference see Organic Preparations and Procedures International 1997, 29(5), 594-600).
  • Compounds of Formula 1 may also be prepared by condensation of amines of Formula 19 with aldehydes or ketones of Formula 20.
  • the reaction is typically carried out in a polar solvent such as methanol or dichloromethane in the presence of a base such as sodium acetate or an acid such as hydrochloric acid at a temperature ranging from room temperature to the reflux temperature of the reaction mixture.
  • a polar solvent such as methanol or dichloromethane
  • a base such as sodium acetate or an acid such as hydrochloric acid
  • aryl halides of Formula 21 may be coupled with acetohydroximate of Formula 16 in the presence of palladium catalysts to form compounds of Formula 22.
  • Typical reaction conditions for this transformation include a palladium catalyst (e.g., allyl-PdCl) 2 , phosphine l igand (e.g., t-BuBrettPhos or t-BuXPhos), Cs 2 CO 3 as a base, and toluene as solvent at elevated temperature (e.g., 65 °C).
  • Acid hydrolysis of compounds of Formula 22 using aqueous hydrochloric acid in dioxane at a temperature ranging between 0 °C and room temperature provides amines of Formula 19.
  • Compounds of Formula 1, or intermediates for their preparation may contain aromatic nitro groups, which can be reduced to amino groups, and then converted via reactions well known in the art (e.g., Sandmeyer reaction) to various halides.
  • aromatic amines anilines
  • diazonium salts phenols
  • aromatic halides such as bromides or iodides prepared via the Sandmeyer reaction can react with alcohols under copper-catalyzed conditions, such as the Ullmann reaction or known modifications thereof, to provide compounds of Formula 1 that contain alkoxy substituents.
  • halogen groups such as fluorine or chlorine
  • alcohols under basic conditions to provide compounds of Formula 1 containing the corresponding alkoxy substituents.
  • Step A Preparation of 1-(6-methoxy-3-pyridinyl)ethanone oxime
  • the resulting aqueous mixture was treated with concentrated hydrochloric acid and then filtered.
  • the filtrate was washed with diethyl ether (3 x), and then basified by adding aqueous sodium hydroxide (50% solution in water).
  • the resulting mixture was diluted with dichloromethane and filtered through a pad of Celite® (diatomaceous earth) on a sintered glass frit funnel, rinsing with dichloromethane.
  • the filtrate was extracted with dichloromethane (3 x), and the combined organic layers were dried over magnesium sulfate and filtered.
  • the filtrate was concentrated under reduced pressure to provide the title compound as an oil (8.37 g), which was used without further purification.
  • Step C Preparation of methyl N-[(5-bromo-2-methylphenyl)methyl]carbamate
  • 5-bromo-2-methylbenzenemethanamine i.e. the product of Step B
  • ethyl acetate 100 mL
  • water 20 mL
  • potassium carbonate 8.11 g, 58.7 mmol
  • the reaction mixture was cooled to 0 °C, and then methyl chloroformate (3.6 mL, 46 mmol) was added dropwise.
  • the reaction mixture was allowed to warm to ambient temperature and stirred for 1.5 h.
  • the reaction mixture was separated, and the aqueous layer was extracted with ethyl acetate (2 x). The combined organic layers were washed with water (4 x), dried over magnesium sulfate, filtered and concentrated in under reduced pressure. The resulting material was purified by silica gel column chromatography (10 to 50% gradient of ethyl acetate in hexanes as eluant) to provide the title compound as an off-white solid (9.20 g).
  • Step D Preparation of methyl N-[[2-methyl-5-(4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl)phenyl]methyl]carbamate
  • the reaction mixture was purged with nitrogen for an additional 10 minutes, and then heated at 90 °C under a nitrogen atmosphere overnight.
  • the reaction mixture was cooled to ambient temperature, diluted with diethyl ether and water, and filtered.
  • the filtrate was separated and the organic layer was washed with water (6 x), dried over magnesium sulfate, filtered and concentrated under reduced pressure.
  • the resulting material was purified by silica gel column chromatography (5 to 40% gradient of ethyl acetate in hexanes as eluant) to provide the title compound as a white solid (4.10 g).
  • Step E Preparation of methyl N-[(5-borono-2-methylphenyl)methyl]carbamate
  • a mixture of methyl N-[[2-methyl-5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- yl)phenyl]methyl]carbamate i.e. the product of Step D
  • acetone 50 mL
  • 1 M aqueous ammonium acetate solution (30 mL, 29 mmol
  • sodium periodate 4.32 g, 20.2 mmol
  • reaction mixture was filtered, and the filtrate was diluted with ethyl acetate, washed with saturated aqueous sodium chloride solution (4 x), dried over magnesium sulfate and concentrated under reduce pressure to provide the title compound as a white solid (0.9 g).
  • Step F Preparation of methyl N-[[5-[[(E)-[1-(6-methoxy-3- pyridinyl)ethylidene]amino]oxy]-2-methylphenyl]methyl]carbamate
  • N-[(5-borono-2-methylphenyl)methyl]carbamate i.e. the product of Step E)
  • 1,2-dichloroethane 14 mL
  • Step A the product of Step A) (150 mg, 0.904 mmol), pyridine (220 ⁇ L, 2.71 mmol), 4 ⁇ molecular sieves (0.55 g) and copper(II) acetate (33 mg, 0.18 mmol).
  • the reaction mixture was stirred and ambient temperature for 36 h while exposed to air.
  • the reaction mixture was diluted with ethyl acetate and water, and the layers were separated.
  • the organic layer was washed with water and 1 N sodium hydroxide (4 x), dried over magnesium sulfate and concentrated under reduced pressure.
  • the resulting material was purified by silica gel column chromatography (10 to 50% gradient of ethyl acetate in hexanes as eluant) to provide the title compound, a compound of the present invention, as an off-white solid (97 mg).
  • i means iso
  • c means cyclo
  • n means normal
  • s means secondary
  • Me means methyl
  • Bu means butyl
  • Pr means propyl
  • MeO means methoxy
  • CN means cyano
  • Ph means phenyl.
  • a compound of Formula 1 of this invention (including N-oxides and salts thereof) will generally be used as a fungicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier.
  • 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.
  • 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.
  • 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 C 6 –C 22 ), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants.
  • surfactants also known as“surface-active agents”
  • surface-active agents generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as 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. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 ⁇ m range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • Pellets can be prepared as described in U.S.4,172,714.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S.4,144,050, U.S.3,920,442 and DE 3,246,493.
  • Tablets can be prepared as taught in U.S.5,180,587, U.S.5,232,701 and U.S. 5,208,030.
  • Films can be prepared as taught in GB 2,095,558 and U.S.3,299,566.
  • 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.
  • 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
  • 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.
  • additional 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 2.5% to 0.1 % 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. Various coating machines and processes are available to one skilled in the art. Suitable processes include those listed in P. Kosters et al., Seed Treatment: Progress and Prospects, 1994 BCPC Mongraph No.57, and references listed therein.
  • Compound 27 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
  • Compound 22 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No.25–50 sieves)
  • Compound 17 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
  • Compound 9 20.00% polyvinylpyrrolidone-vinyl acetate copolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00% polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol (POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water 65.75%
  • Compound 3 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 water 58.7%
  • Compound 27 10.0% imidacloprid 5.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0% water 53.7%
  • Water-soluble and water-dispersible formulations are typically diluted with water to form aqueous compositions before application.
  • Aqueous compositions for direct applications to the plant or portion thereof typically contain at least about 1 ppm or more (e.g., from 1 ppm to 100 ppm) of the compound(s) of this invention.
  • 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 Oomycata 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.
  • 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.
  • 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 (transgenic 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. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Table 2-1. Additional information for the genetic modifications listed in Table 2-1 can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.
  • Treatment of genetically modified plants and seeds with compounds of the invention may result in super-additive or synergistic 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.
  • 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.
  • 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 and bacteria. These infections can occur before, during and after harvest. For example, 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); 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.
  • Rates of application for these compounds can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • a fungicidally effective amount can be influenced by factors such as the plant diseases to be controlled, the plant species to be protected, ambient moisture and temperature and should be determined under actual use conditions.
  • One skilled in the art can easily determine through simple experimentation the fungicidally effective amount necessary for the desired level of plant disease control.
  • Foliage can normally be protected when treated at a rate of from less than about 1 g/ha to about 5,000 g/ha of active ingredient.
  • Seed and seedlings can normally be protected when seed is treated at a rate of from about 0.001 g (more typically about 0.1 g) to about 10 g per kilogram of seed.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including fungicides, insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • fungicides insecticides, nematocides, bactericides, acaricides, herbicides, herbicide safeners
  • growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus
  • the present invention also pertains to a composition
  • a composition comprising a compound of Formula 1 (in a fungicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • the other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent.
  • one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • one aspect of the present invention is a fungicidal composition
  • 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).
  • a combination where the other fungicidal active ingredient has different site of action from the compound of Formula 1.
  • a combination with at least one other fungicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management.
  • a composition of the present invention can further comprise a 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 (A) nucleic acid synthesis, (B) mitosis and cell division, (C) respiration, (D) amino acid and protein synthesis, (E) signal transduction, (F) lipid synthesis and membrane integrity, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis in membranes, (I) melanin synthesis in cell wall, (P) host plant defense induction, multi-site contact activity and unknown mode 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, (B1-B3) ß- tubulin assembly in mitosis, (B4) cell division (proposed), (B5) delocalization of spectrin- like proteins, (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 phosphorylation, (C6) inhibitors of oxidative phosphorylation, ATP synthase, (
  • 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 fungicides; (b5) amine/morpholine fungicides; (b6) phospholipid biosynthesis inhibitor fungicides; (b7) succinate dehydrogenase inhibitor fungicides; (b8) hydroxy(2- amino-)pyrimidine fungicides; (b9) anilinopyrimidine fungicides; (b10) N-phenyl carbamate fungicides; (b11) quinone outside inhibitor (QoI) fungicides; (b12) phenylpyrrole fungicides; (b13) azanaphthalene fungicides; (b1) methyl
  • (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.
  • b2“Dicarboximide fungicides” (FRAC code 2) inhibit a MAP/histidine kinase in osmotic signal transduction.
  • Examples include chlozolinate, iprodione, procymidone and vinclozolin.
  • DMI Demethylation inhibitor
  • FRAC code 3 Step 3
  • 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: azoles (including triazoles and imidazoles), pyrimidines, piperazines, pyridines and triazolinthiones.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, , quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, ⁇ -(1- chlorocyclopropyl)- ⁇ -[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole
  • the imidazoles include econazole, imazalil, oxpoconazole, prochloraz, pefurazoate and triflumizole.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate, pyrifenox, pyrisoxazole (3-[(3R)-5-(4-chlorophenyl)-2,3- dimethyl-3-isoxazolidinyl]pyridine, mixture of 3R,5R- and 3R,5S-isomers) and ( ⁇ S)-[3-(4- chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol.
  • the triazolinthiones include prothioconazole and 2-[2-(1-chlorocyclopropyl)-4-(2,2- dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione.
  • Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205–258.
  • Phenylamide fungicides 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.
  • Phospholipid biosynthesis inhibitor fungicides include phophorothiolate and dithiolane fungicides.
  • the phosphorothiolates include edifenphos, iprobenfos and pyrazophos.
  • the dithiolanes include isoprothiolane.
  • SDHI fungicides include phenylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, pyridine carboxamide,, phenyl oxoethyl thiophene amides and pyridinylethyl benzamides
  • the benzamides include benodanil, flutolanil and mepronil.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamides include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole-4-carboxamides include benzovindiflupyr (N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4- methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide), bixafen, fluxapyroxad (3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluoro[1,1′-biphenyl]-2- yl)-1H-pyrazole-4-carboxamide), furametpyr, isopyrazam (3-(difluoromethyl)-1- methyl-N- [1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4- carboxamide), penflufen (N-[2-(1,3-dimethylbutyl)phenyl
  • the pyridine carboxamides include boscalid.
  • the phenyl oxoethyl thiophene amides include isofetamid (N-[1,1-dimethyl-2-[2- methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide).
  • the pyridinylethyl benzamides include fluopyram.
  • FRAC code 8 “Hydroxy-(2-amino-)pyrimidine fungicides” (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • (b10)“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, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzylcarbamate fungicides.
  • the methoxyacrylates include azoxystrobin, coumoxystrobin (methyl ( ⁇ E)-2-[[(3-butyl-4-methyl-2-oxo-2H-1- benzopyran-7-yl)oxy]methyl]- ⁇ -(methoxymethylene)benzeneacetate), enoxastrobin (methyl ( ⁇ E)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]- ⁇ - (methoxymethylene)benzeneaceate) (also known as enestroburin), flufenoxystrobin (methyl ( ⁇ E)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]- ⁇ - (methoxymethylene)benzeneacetate), picoxystrobin, and pyraoxystrobin (methyl ( ⁇ E)-2- [[[3-(4-chlorophenyl)-1-methyl-1H-
  • the methoxycarbamates include pyraclostrobin ,pyrametostrobin (methyl N-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazol-5- yl)oxy]methyl]phenyl]-N-methoxycarbamate) and triclopyricarb (methyl N-methoxy-N-[2- [[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate).
  • the oximinoacetates include kresoxim-methyl, and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, fenaminstrobin (( ⁇ E)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propen-1- ylidene]amino]oxy]methyl]- ⁇ -(methoxyimino)-N-methylbenzeneacetamide),
  • the dihydrodioxazines include fluoxastrobin.
  • the oxazolidinediones include famoxadone.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Class (b11) also includes mandestrobin (2-[(2,5-dimethylphenoxy)methyl]- ⁇ -methoxy-N-benzeneacetamide).
  • Azanaphthalene fungicides include aryloxyquinolines and quinazolinones.
  • the aryloxyquinolines include quinoxyfen.
  • the quinazolinones include proquinazid.
  • Lipid peroxidation inhibitor fungicides are proposed to inhibit lipid peroxidation which affects membrane synthesis in fungi. Members of this class, such as etridiazole, may also affect other biological processes such as respiration and melanin biosynthesis.
  • Lipid peroxidation fungicides include aromatic 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.
  • MMI-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 inhibitors-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 in required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitors-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • SBI Sterol Biosynthesis Inhibitor
  • Class III fungicides include hydroxyanilide fungicides and amino-pyrazolinone fungicides. Hydroxyanilides include fenhexamid. Amino-pyrazolinones include fenpyrazamine (S-2- propen-1-yl 5-amino-2,3-dihydro-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-1H-pyrazole- 1-carbothioate).
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafine.
  • Quinone inside inhibitor (QiI) fungicides inhibit Complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone is blocked at the“quinone inside” (Q i ) site of the cytochrome bc 1 complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone inside inhibitor fungicides include cyanoimidazole and sulfamoyltriazole fungicides.
  • the cyanoimidazoles include cyazofamid.
  • the sulfamoyltriazoles include amisulbrom.
  • Benzamide and thiazole carboxamide fungicides 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 zoxamide.
  • the thiazole carboxamides include ethaboxam.
  • Glucopyranosyl antibiotic protein synthesis fungicides
  • FRAC code 25 Glucopyranosyl antibiotic: protein synthesis fungicides
  • 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. Propamacarb, iodocarb, and prothiocarb are examples of this fungicide class.
  • b30 “Organo tin fungicides” (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in oxidative phosphorylation pathway.
  • Examples include fentin acetate, fentin chloride and fentin hydroxide.
  • FRAC code 31 “Carboxylic acid fungicides” (FRAC code 31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • Heteroaromatic fungicides include isoxazoles and isothiazolones.
  • the isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • Carboxylic acid amide (CAA) fungicides inhibit cellulose synthase which prevents growth and leads to death of the target fungus.
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide and other carbamate, and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph, flumorph and pyrimorph (3-(2-chloro-4-pyridinyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4- morpholinyl)-2-propene-1-one).
  • valinamide and other carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb (2,2,2-trifluoroethyl N- [(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate) and valifenalate (methyl N-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)- ⁇ -alaninate) (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.
  • Benzamide fungicides inhibit growth of fungi by delocalization of spectrin-like proteins.
  • Examples include pyridinylmethyl benzamide fungicides such as fluopicolide (now FRAC code 7, pyridinylethyl benzamides).
  • Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains QST 713, FZB24, MB1600, D747 and the fungicidal lipopeptides which they produce.
  • Q x I fungicides include triazolopyrimidylamines such as ametoctradin (5- ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine).
  • Plant extract fungicides include terpene hydrocarbons and terpene alcohols such as the extract from Melaleuca alternifolia (tea tree).
  • Host plant defense induction fungicides FRAC code P
  • Host plant defense induction fungicides include benzothiadiazoles, benzisothiazole and thiadiazole-carboxamide fungicides.
  • the benzothiadiazoles include acibenzolar-S-methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole- carboxamides include tiadinil and isotianil.
  • (b48)“Multi-site contact fungicides” inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • This class of fungicides includes: (b48.1) “copper fungicides” (FRAC code M1)”, (b48.2)“sulfur fungicides” (FRAC code M2), (b48.3)“dithiocarbamate fungicides” (FRAC code M3), (b48.4)“phthalimide fungicides” (FRAC code M4), (b48.5)“chloronitrile fungicides” (FRAC code M5), (b48.6)“sulfamide fungicides” (FRAC code M6), (b48.7) multi-site contact“guanidine fungicides” (FRAC code M7), (b48.8)“triazine fungicides” (FRAC code M8), (b48.9)“quinone fungicides” (FRAC code M9), (b48.10)“quinoxaline
  • “Sulfur fungicides” are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur.
  • “Dithiocarbamate fungicides” contain a dithiocarbamate molecular moiety; examples include mancozeb, metiram, propineb, ferbam, maneb, thiram, zineb and ziram.
  • “Phthalimide fungicides” contain a phthalimide molecular moiety; examples include folpet, captan and captafol.
  • “Chloronitrile fungicides” contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil.
  • “Sulfamide fungicides” include dichlofluanid and tolyfluanid. 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.
  • (b49)“Fungicides other than fungicides of classes (b1) through (b48)” include certain fungicides whose mode of action may be unknown. These include: (b49.1),“phenyl- acetamide fungicides” (FRAC code U6), , (b49.2)“ aryl-phenyl-ketone fungicides” (FRAC code U8), (b49.3)“guanidine fungicides” (FRAC code U12), (b49.4)“thiazolidine fungicides” (FRAC code U13), (b49.5)“pyrimidinone-hydrazone fungicides” (FRAC code U14) and (b49.6) compounds that bind to oxysterol-binding protein as described in PCT Patent Publication WO 2013/009971.
  • the phenyl-acetamides include cyflufenamid and N- [[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]- benzeneacetamide.
  • the aryl-phenyl ketones include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone (5-chloro-2-methoxy-4-methyl-3-pyridinyl)(2,3,4- trimethoxy-6-methylphenyl)methanone).
  • the quanidines include dodine.
  • the thiazolidines include flutianil ((2Z) 2 [[2 fluoro 5 (trifluoromethyl)phenyl]thio] 2 [3 (2 methoxyphenyl) 2-thiazolidinylidene]acetonitrile).
  • the pyrimidinonehydrazones include ferimzone.
  • the (b49.6) class includes oxathiapiprolin (1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3- isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1- yl]ethanone) and its R-enantiomer which is 1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro- 3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]- ethanone (Registry Number 1003319-79-6).
  • the (b49) class also includes bethoxazin, flometoquin (2-ethyl-3,7-dimethyl-6-[4- (trifluoromethoxy)phenoxy]-4-quinolinyl methyl carbonate), fluoroimide, neo-asozin (ferric methanearsonate), picarbutrazox (1,1-dimethylethyl N-[6-[[[[((Z)-1-methyl-1H-tetrazol- 5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate), pyrrolnitrin, quinomethionate, tebufloquin (6-(1,1-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate), tolnifanide (N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesul
  • Additional“Fungicides other than fungicides of classes (1) through (46)” whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b49.7) through (b49.12), as shown below.
  • Component (b49.7) relates to a compound of Formula b49.7
  • Examples of a compound of Formula b49.7 include (b49.7a) (2-chloro-6-fluorophenyl)- methyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazole- carboxylate (Registry Number 1299409-40-7) and (b49.7b) (1R)-1,2,3,4-tetrahydro- 1-naphthalenyl 2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]- 4-thiazolecarboxylate (Registry Number 1299409-42-9).
  • Methods for preparing compounds of Formula b46.2 are described in PCT Patent Publications WO 2009/132785 and WO 2011/051243.
  • Component (b49.8) relates to a compound of Formula b49.8
  • R b2 is CH 3 , CF 3 or CHF 2 ;
  • R b3 is CH 3 , CF 3 or CHF 2 ;
  • R b4 is halogen or cyano; and
  • n is 0, 1, 2 or 3.
  • Examples of a compound of Formula b49.8 include (b49.8a) 1-[4-[4-[5-[(2,6- difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl- 3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone. Methods for preparing compounds of Formula b49.8 are described in PCT Patent Application PCT/US11/64324.
  • Component (b4799) relates to a compound of Formula b49.9
  • Rb5 is -CH 2 OC(O)CH(CH 3 ) 2 , -C(O)CH 3 , -CH 2 OC(O)CH 3 ,
  • Examples of a compound of Formula b49.9 include (b49.9a) [[4-methoxy-2- [[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5- dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl 2-methylpropanoate (Registry Number 517875-34-2), (b49.9b) (3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]- carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl 2-methyl- propanoate (Registry Number 234112-93-7), (b49.9c) (3S,6S,7R,8R)
  • Component (b49.10) relates to a compound of Formula b49.10
  • R b6 is H or F
  • R b7 is -CF 2 CHFCF 3 or -CF 2 CF 2 H.
  • Examples of a compound of Formula b49.10 are (b49.10a) 3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoro- propoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide (Registry Number 1172611-40-3) and (b49.10b) 3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H- pyrazole-4-carboxamide (Registry Number 923953-98-4).
  • Compounds of Formula 49.10 can be prepared by methods described in PCT Patent Publication WO 2007/017450.
  • Component b49.11 relates a compound of Formula b49.11
  • R b8 is halogen, C 1 -C 4 alkoxy or C 2 -C 4 alkynyl
  • R b9 is H, halogen or C 1 -C 4 alkyl
  • R b10 is C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 –-C 12 alkoxy, C 2 -C 12 alkoxyalkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 4 -C 12 alkoxyalkenyl, C 4 -C 12 alkoxyalkynyl, C 1 -C 12 alkylthio or C 2 -C 12 alkylthioalkyl;
  • R b11 is methyl or–Y b13 -R b12 ;
  • R b12 is C1-C2 alkyl
  • Y b13 is CH2, O or S.
  • Examples of compounds of Formula b49.11 include (b49.11a) 2-[(3-bromo-6- quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide, (b49.11b) 2-[(3- ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)- acetamide, (b49.11c) N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2- (methylthio)acetamide, (b49.11d) 2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl- 2-propyn-1-yl)-2-(methylthio)acetamide and (b49.
  • Component 49.12 relates to N'-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5- yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide, which is believed to inhibit C24-methyl transferase involved in the biosynthesis of sterols.
  • a mixture comprising a compound of Formula 1 and at least one fungicidal compound selected from the group consisting of the aforedescribed classes (1) through (49).
  • 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 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 (1) through (49).
  • 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
  • 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, bifenthrin, bifenazate, buprofezin, carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, cyantraniliprole (3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6- [(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide), cyclaniliprole (3-bromo-N- [2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2- pyr
  • 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
  • Compounds of this invention and compositions thereof can be applied to plants genetically transformed to express proteins toxic to invertebrate pests (such as Bacillus thuringiensis delta-endotoxins).
  • proteins toxic to invertebrate pests such as Bacillus thuringiensis delta-endotoxins.
  • the effect of the exogenously applied fungicidal compounds of this invention may be synergistic with the expressed toxin proteins.
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1:3000 and about 3000:1. Of note are weight ratios between about 1:300 and about 300:1 (for example ratios between about 1:30 and about 30:1).
  • weight ratios between about 1:300 and about 300:1 for example ratios between about 1:30 and about 30:1.
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of diseases controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • combinations of a compound of this invention with other biologically active (particularly fungicidal) compounds or agents (i.e. active ingredients) 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, fluazinam, fludioxonil, flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin, flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam, metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin, prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole, thiabendazole, thiophanate-methyl, thiram, trifloxystrobin and
  • 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, cyrom
  • 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 elicitor protein
  • An example is the 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.
  • a plant activator which induces such protective mechanisms is acibenzolar-S-methyl.
  • the numerical value reported in the column“AP + (M+1)” is the molecular weight of the observed molecular ion formed by addition of H + (molecular weight of 1) to the molecule having the greatest isotopic abundance (i.e. M);
  • the numerical v alue reported in the column“AP - (M-1)” is the molecular weight of the observed molecular ion formed by loss of H + (molecular weight of 1) from the molecule having the greatest isotopic abundance (i.e. M).
  • the presence of molecular ions containing one or more higher a tomic weight isotopes of lower abundance is not reported.
  • the reported M+1 and M-1 peaks were observed by mass spectrometry using atmospheric pressure c hemical ionization (AP + ).
  • a 1 H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (dd)-doublet of doublets, (m)-multiplet, (br s)-broad singlet, (br d)-broad doublet and (br m)-broad multiplet.
  • test suspensions for Tests A-F 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 PEG 400 (polyhydric alcohol esters). The resulting test suspensions were then used in Tests A-F.
  • PEG 400 polyhydric alcohol esters
  • test suspension was sprayed to the point of run-off on tomato seedlings.
  • seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of tomato Botrytis) and incubated in saturated atmosphere at 20 °C for 48 h, and then moved to a growth chamber at 27 °C for 3 days, after which time disease ratings were visually made.
  • Botrytis cinerea the causal agent of tomato Botrytis
  • test suspension was sprayed to the point of run-off on tomato seedlings.
  • seedlings were inoculated with a spore suspension of Alternaria solani (the causal agent of early blight on tomatoes) and incubated in saturated atmosphere at 27 °C for 48 h, and then moved to a growth chamber at 20 °C for 3 days, after which time disease ratings were visually made.
  • Alternaria solani the causal agent of early blight on tomatoes
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Septoria nodorum (the causal agent of wheat glume blotch) and incubated in a saturated atmosphere at 20 °C for 48 h, and then moved to a growth chamber at 20 °C for 6 days, after which time disease ratings were visually made.
  • Septoria nodorum the causal agent of wheat glume blotch
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Zymoseptoria tritici (the causal agent of wheat leaf blotch) and incubated in a saturated atmosphere at 24 °C for 48 h, and then moved to a growth chamber at 20 °C for 17 days, after which time disease ratings were visually made.
  • Zymoseptoria tritici the causal agent of wheat leaf blotch
  • test suspension was sprayed to the point of run-off on wheat seedlings.
  • seedlings were inoculated with a spore suspension of Puccinia recondita f. sp. tritici (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20 °C for 24 h, and then moved to a growth chamber at 20 °C for 6 days, after which time disease ratings were visually made.
  • test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f. sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20 °C for 8 days, after which time disease ratings were visually made.
  • Results for Tests A-F are given in Table A.
  • a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls).
  • a dash (–) indicates no test results. All results are for 200 ppm except when an asterisk“*” is next to the rating value, which indicates a 50 ppm test suspension was used, or a double asterisk“**”, which indicates a 10 ppm test suspension was used.

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Abstract

L'invention concerne des composés de formule I, y compris les isomères géométriques et les stéréoisomères, les N-oxydes et leurs sels, (Formule 1) où Z, Q, R1, R2, R3, R4 et m sont tels que définis dans la description. L'invention concerne également des compositions contenant les composés de formule I et des procédés permettant de lutter contre les maladies des plantes causées par un agent pathogène fongique, lesdits procédés consistant à appliquer une quantité efficace d'un composé ou d'une composition selon l'invention.
PCT/US2016/065567 2015-12-18 2016-12-08 Dérivés de n-[[5-[[[1-(phényl)éthylidène]amino]oxy]phényl]-méthyl]carbamate et composés associés utilisés comme fongicides pour lutter contre les maladies des plantes WO2017105999A1 (fr)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015157005A1 (fr) * 2014-04-10 2015-10-15 E I Du Pont De Nemours And Company Mélanges fongicides de dérivés de tolyle

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015157005A1 (fr) * 2014-04-10 2015-10-15 E I Du Pont De Nemours And Company Mélanges fongicides de dérivés de tolyle

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