WO2021183707A2 - Halométhyl cétones et hydrates fongicides et leurs mélanges - Google Patents

Halométhyl cétones et hydrates fongicides et leurs mélanges Download PDF

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Publication number
WO2021183707A2
WO2021183707A2 PCT/US2021/021806 US2021021806W WO2021183707A2 WO 2021183707 A2 WO2021183707 A2 WO 2021183707A2 US 2021021806 W US2021021806 W US 2021021806W WO 2021183707 A2 WO2021183707 A2 WO 2021183707A2
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WO
WIPO (PCT)
Prior art keywords
fungicides
methyl
independently
composition
alkyl
Prior art date
Application number
PCT/US2021/021806
Other languages
English (en)
Other versions
WO2021183707A8 (fr
WO2021183707A3 (fr
Inventor
Robert James Pasteris
Travis Chandler MCMAHON
Hengbin Wang
Alvin Donald Crews, Jr.
Liana HIE
Earl William Reed
Srinivas CHITTABOINA
Ravisekhara P. Reddy
Srinivasa Rao Uppalapati
Yuzhong Chen
Byron VEGA-JIMENEZ
Original Assignee
Fmc Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to EP21766969.6A priority Critical patent/EP4117432A4/fr
Application filed by Fmc Corporation filed Critical Fmc Corporation
Priority to CN202180031728.9A priority patent/CN115460921A/zh
Priority to CA3174932A priority patent/CA3174932A1/fr
Priority to BR112022018107A priority patent/BR112022018107A2/pt
Priority to JP2022554496A priority patent/JP2023518172A/ja
Priority to AU2021233845A priority patent/AU2021233845A1/en
Priority to US17/910,079 priority patent/US20240122180A1/en
Priority to MX2022011299A priority patent/MX2022011299A/es
Priority to IL296160A priority patent/IL296160A/en
Publication of WO2021183707A2 publication Critical patent/WO2021183707A2/fr
Publication of WO2021183707A3 publication Critical patent/WO2021183707A3/fr
Priority to CONC2022/0014334A priority patent/CO2022014334A2/es
Publication of WO2021183707A8 publication Critical patent/WO2021183707A8/fr

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    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • A01N37/38—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system
    • A01N37/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids having at least one oxygen or sulfur atom attached to an aromatic ring system having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/24—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms
    • A01N43/26—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings
    • A01N43/28—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with two or more hetero atoms five-membered rings with two hetero atoms in positions 1,3
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • A01N43/44—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom three- or four-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
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-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
    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • 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
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • 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
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • 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
    • A01N47/14—Di-thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P3/00—Fungicides

Definitions

  • This invention relates to certain halomethyl ketone and hydrate derivatives, their A-oxidcs and salts, and to mixtures and compositions comprising such halomethyl ketone and hydrate derivatives and methods for using such derivatives and their mixtures and compositions as fungicides.
  • This invention relates to a fungicidal composition (i.e. combination, mixture) comprising
  • T is selected from the group consisting of: wherein the bond extending to the left is attached to A;
  • R 1 is CF 3 , CHF 2 , CC1 3 , CHC1 2 , CF 2 C1, CFC1 2 or CHFC1;
  • W is O, S or NR 3 ;
  • R 3a is H, benzyl, C 4 -C 4 alkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 4 haloalkylcarbonyl;
  • R 3b is H, C 4 -C 4 alkyl, C 2 -C 4 alkylcarbonyl or C 2 -C 4 haloalkylcarbonyl;
  • R 3C is H or C 4 -C 4 alkyl
  • R 3b and R 3c are taken together to form a 4- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups;
  • X is O, S or NR 5a ;
  • Y is O, S or NR 5b ;
  • R 5a and R 5b are each independently H, hydroxy or C 4 -C 4 alkyl
  • R 2a and R 2b are each independently H, C 4 -C 4 alkyl, C 2 -C 4 alkenyl, C 3 -C
  • R 2C is C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl or trifluoromethylsulfonyl, each optionally substituted with up 2 substituents independently selected from cyano, hydroxy, SCoN and C
  • R 2d is H, cyano, halogen or C1-C4 alkyl; each R 4a and R 4b is independently H or C4-C4 alkyl;
  • p is 2 or 3; when T is T-l or T-2, then A is A 1 -A 2 -CR 6a R 6b , wherein A 1 is connected to J, and CR 6a R 6b is connected to T; when T is T-3, then A is A ! -A 2 , wherein A 1
  • a 2 is a direct bond, CR 6e R 6f , N(R 7b ), O or S;
  • J is selected from the group consisting of:
  • each R 8 is independently F, Cl, I, Br, cyano, methyl, trifluoromethyl or methoxy; q is 0, 1, 2, 3 or 4;
  • L is (CR 9a R 9b ) n ; each R 9a and R 9b is independently H, halogen, cyano, hydroxy, nitro, C 1 -C3 alkyl, C 3 -C3 haloalkyl, C 3 -C3 alkoxy or C 3 -C3 haloalkoxy; haloalkyl; or
  • each R l la is independently halogen, hydroxy, cyano, amino, nitro, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl
  • E 2 is G-Z, wherein Z is attached to L;
  • G is phenyl optionally substituted with up to 3 substituents independently selected from R 13 ; or
  • G is a 5- to 6-membered heteroaromatic ring, each ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R 13 ; or
  • R 18a and R 18b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 methyl groups; each R 19 is independently amino, cyano, halogen, hydroxy, nitro, -SH, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C 4 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 2 -C 4 alkoxyalkoxy, C 1 -C 4 alkylthio, C 4 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 4 -C
  • each R 22 is independently H, C 3 -C5 alkyl, C 3 -C5 haloalkyl, C 2 -C5 alkenyl, C 2 -C5 haloalkenyl, C 2 -C5 alkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C 2 -C5 alkylcarbonyl or C 2 -C5 alkoxycarbonyl; or each R 22 is phenyl optionally substituted with up to 2 substituents independently selected halogen and C 3 -C3 alkyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up
  • This invention also relates to a composition
  • a composition comprising: (a) at least one compound selected from the compounds of Formula 1 described above, /V-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.
  • This invention also relates to a composition
  • a composition comprising one of the aforesaid compositions comprising component (a) and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention also 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 one of the aforesaid compositions.
  • the aforedescribed method can also be described as a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of one of the aforesaid compositions to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed).
  • This invention also relates to a compound of Formula 1 described above, a tautomer, an A-oxidc or salt thereof.
  • compositions comprising, “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’.
  • agronomic refers to the production of field crops such as for food and fiber and includes the growth of maize or corn, soybeans and other legumes, rice, cereal (e.g., wheat, oats, barley, rye and rice), leafy vegetables (e.g., lettuce, cabbage, and other cole crops), fruiting vegetables (e.g., tomatoes, pepper, eggplant, crucifers and cucurbits), potatoes, sweet potatoes, grapes, cotton, tree fruits (e.g., pome, stone and citrus), small fruit (e.g., berries and cherries) and other specialty crops (e.g., canola, sunflower and olives).
  • wheat e.g., wheat, oats, barley, rye and rice
  • leafy vegetables e.g., lettuce, cabbage, and other cole crops
  • fruiting vegetables e.g., tomatoes, pepper, eggplant, crucifers and cucurbits
  • potatoes e.g., sweet potatoes, grapes, cotton, tree fruits (e
  • nonagronomic refers to other than field crops, such as horticultural crops (e.g., greenhouse, nursery or ornamental plants not grown in a field), residential, agricultural, commercial and industrial structures, turf (e.g., sod farm, pasture, golf course, lawn, sports field, etc.), wood products, stored product, agro-forestry and vegetation management, public health (i.e. human) and animal health (e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife) applications.
  • horticultural crops e.g., greenhouse, nursery or ornamental plants not grown in a field
  • turf e.g., sod farm, pasture, golf course, lawn, sports field, etc.
  • wood products e.g., stored product, agro-forestry and vegetation management
  • public health i.e. human
  • animal health e.g., domesticated animals such as pets, livestock and poultry, undomesticated animals such as wildlife
  • crop vigor refers to rate of growth or biomass accumulation of a crop plant.
  • An “increase in vigor” refers to an increase in growth or biomass accumulation in a crop plant relative to an untreated control crop plant.
  • the term “crop yield” refers to the return on crop material, in terms of both quantity and quality, obtained after harvesting a crop plant.
  • An “increase in crop yield” refers to an increase in crop yield relative to an untreated control crop plant.
  • biologically effective amount refers to the amount of a biologically active compound (e.g., a compound of Formula 1 or a mixture with at least one other fungicidal compound) sufficient to produce the desired biological effect when applied to (i.e. contacted with) a fungus to be controlled or its environment, or to a plant, the seed from which the plant is grown, or the locus of the plant (e.g., growth medium) to protect the plant from injury by the fungal disease or for other desired effect (e.g., increasing plant vigor).
  • a biologically active compound e.g., a compound of Formula 1 or a mixture with at least one other fungicidal compound
  • plant includes members of Kingdom Plantae, particularly seed plants (Spermatopsida), at all life stages, including young plants (e.g., germinating seeds developing into seedlings) and mature, reproductive stages (e.g., plants producing flowers and seeds).
  • Portions of plants include geotropic members typically growing beneath the surface of the growing medium (e.g., soil), such as roots, tubers, bulbs and corms, and also members growing above the growing medium, such as foliage (including stems and leaves), flowers, fruits and seeds.
  • seedling used either alone or in a combination of words means a young plant developing from the embryo of a seed.
  • narrowleaf 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.
  • 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).
  • MO A mode of action
  • FRAC Fungicide Resistance Action Committee
  • FRAC-defined modes of actions include (A) nucleic acids metabolism, (B) cytoskeleton and motor protein, (C) respiration, (D) amino acids and protein synthesis, (E) signal transduction, (F) lipid synthesis or transport and membrane integrity or function, (G) sterol biosynthesis in membranes, (H) cell wall biosynthesis, (I) melanin synthesis in cell wall, (P) host plant defense induction, (U) unknown mode of action, (M) chemicals with multi-site activity and (BM) biologicals with multiple modes of action.
  • Each mode of action i.e.
  • letters A through BM) contain one or more subgroups (e.g., A includes subgroups Al, 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., Al, A2, A3 and A4 is assigned a FRAC code which is a number and/or letter.
  • the FRAC code for subgroup Al 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.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain and branched alkyl, such as, methyl, ethyl, n -propyl, /-propyl, and the different butyl, pentyl and hexyl isomers.
  • Alkenyl includes straight- chain and branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain and branched alkynes such as ethynyl, 1-propynyl, 2-propynyl, and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH2, CH2CH2, CH(CH3), CH2CH2CH2, CH2CH(CH3), and the different butylene isomers.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene examples include CH2CoC, CoCCH2, and the different butynylene, pentynylene or hexynylene isomers.
  • cycloalkylene denotes a cycloalkanediyl ring.
  • examples of “cycloalkylene” include cyclobutanediyl, cyclopentanediyl and cyclohexanediyl.
  • cycloalkenylene denotes a cycloalkenediyl ring containing one olefinic bond. Examples of “cycloalkenylene” include cyclopropenediyl and cyclopentenediyl.
  • Alkoxy includes, for example, methoxy, ethoxy, 77-propyloxy, /-propyloxy, and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkynyloxy includes straight-chain and branched alkynyl attached to and linked through an oxygen atom. Examples of “alkynyloxy” include HCoCCH 2 0 and CH 3 CoCCH 2 0.
  • alkylthio includes straight-chain and branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio and butylthio isomers.
  • Alkenylsulfinyl includes both enantiomers of an alkenylsulfinyl group.
  • Alkynylthio includes straight-chain and branched alkynyl attached to and linked through a sulfur atom. Examples of “alkynylthio” include HCoCCH 2 S and CH 3 CoCCH 2 S.
  • Alkynylsulfinyl includes both enantiomers of an alkynylsulfinyl group.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 ;
  • alkylsulfinylalkyl and alkylsulfonylalkyl include the corresponding sulfoxides and sulfones, respectively.
  • the terms “(alkenylthio)carbonyl” and “(alkynylthio)carbonyl” are likewise defined.
  • alkenyl(thiocarbonyl) and alkynyl(thiocarbonyl) are likewise defined.
  • alkenylamino(thiocarbonyl) and alkynylamino(thiocarbonyl) are likewise defined.
  • alkenylthio)carbonylamino and “(alkynylthio)carbonylamino” are likewise defined. Examples of
  • Alkylamino includes an NH radical substituted with a straight-chain or branched alkyl group.
  • alkylamino include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and
  • alky laminoalky G examples include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 ,
  • alkynyloxycarbonyl are likewise defined.
  • alkenylaminocarbonyl and “alkynylaminocarbonyl” are likewise defined.
  • alkenylcarbonylamino and alkynylcarbonylamino are likewise defined.
  • alkynylcarbonylamino include
  • alkenylaminocarbonylamino and “alkynylaminocarbonylamino” are likewise defined.
  • alkynylaminocarbonylamino examples include
  • Alkylsulfonylamino denotes an NH radical substituted with alkylsulfonyl.
  • alkenylsulfonylamino and “alkynylsulfonylamino” are likewise defined.
  • alkylsulfonyloxy denotes an alkylsulfonyl group bonded to an oxygen atom.
  • alkenylaminosulfonyl and “alkynylaminosulfonyl” are likewise defined.
  • alkynylaminosulfonyl include
  • alkenylaminosulfonylamino and
  • alky ny lamino sulfony lamino are likewise defined.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 0CH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on another alkoxy moiety.
  • Alkoxyalkoxyalkyl denotes alkoxyalkoxy substitution on alkyl.
  • alkoxyalkoxyalkyl include CH 3 OCH 2 OCH 2 , CH 3 OCH 2 OCH 2 CH 2 and CH 3 CH 2 OCH 2 OCH 2 .
  • alkenylcarbonyloxy and “alkynylcarbonyloxy” are likewise defined.
  • alkynylcarbonyloxy include
  • alkenylaminocarbonyloxy and “alkynylaminocarbonyloxy” are likewise defined.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • the term “cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to a straight-chain or branched alkyl group.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety and includes, for example, ethylcyclopropyl, z-propylcyclobutyl, methylcyclopentyl and methylcyclohexyl.
  • Alkylcycloalkylalkyl denotes alkylcycloalkyl substitution on alkyl. Examples of “alkylcycloalkylalkyl” include methylcyclohexylmethyl and ethylcycloproylmethyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- or 1,4-cyclohexadienyl.
  • cycloalky lcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members.
  • cycloalky lcycloalkyl examples include cyclopropylcyclopropyl (such as 1,1'- bicyclopropyl-l-yl, l,l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4- cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as I,G-bicyclohexyl-l-yl), and the different cis- and / ra nv - c y c 1 o a 1 k y 1 c y c 1 o a 1 k y 1 isomers, (such as ( 1 R.2S)- 1 , 1 '-bicyclopropyl-2-yl and ( IR,2R)- 1 , 1 '-bicyclopropyl-2-yl) .
  • cyclopropylcyclopropyl such as 1,1
  • cycloalkoxy denotes cycloalkyl attached to and linked through an oxygen atom including, for example, cyclopentyloxy and cyclohexyloxy.
  • cycloalkoxyalkyl denotes cycloalkoxy substitution on an alkyl moiety. Examples of “cycloalkoxyalkyl” include cyclopropyloxymethyl, cyclopentyloxyethyl, and other cycloalkoxy groups bonded to a straight-chain or branched alkyl moiety.
  • cycloalkylaminoalkyl denotes cycloalkylamino substitution on an alkyl group.
  • examples of “cycloalkylaminoalkyl” include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylamino moieties bonded to a straight-chain or branched alkyl group.
  • Cycloalkylcarbonyloxy denotes cycloalkylcarbonyl attached to and linked through an oxygen atom. Examples of “cycloalkylcarbonyloxy” include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include CF3, CICH2, CF3CH2 and CF3CCI2.
  • haloalkynyl examples include HOCCHC1, CF 3 CoC, CC1 3 CoC and FCH 2 CoCCH 2 .
  • haloalkoxy examples include CF 3 0, CC1 3 CH 2 0, F 2 CHCH2CH 2 0 and CF3CH2O.
  • halocycloalkyl examples include 2-chlorocyclopropyl, 2-fluorocyclobutyl, 3-bromocyclopentyl and 4-chorocyclohexyl.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 CH 2 .
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and / ⁇ ?/ 7-butyldi methyl si lyl.
  • the term “halotrialkylsilyl” is likewise defined. Examples of “halotrialkylsilyl” include trifluormethylsilyl and trichloromethylsilyl.
  • C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • a molecular fragment i.e. radical
  • 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
  • unsubstituted in connection with a group such as a ring or ring system means the group does not have any substituents other than its one or more attachments to the remainder of Formula 1.
  • optionally substituted means that the number of substituents can be zero. 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 13 ” means that 0, 1, 2 or 3 substituents can be present (if the number of potential connection points allows).
  • a range specified for the number of substituents e.g., x being an integer from 0 to 3 in Exhibit A
  • the number of positions available for substituents on a ring e.g., 1 position available for (R 13 ) x on G-7 in Exhibit A
  • the actual higher end of the range is recognized to be the number of available positions.
  • the dotted line in rings depicted in the present description (e.g., the rings G-44, G-45, G-48 and G-49 shown in Exhibit A) represents that the bond indicated can be a single bond or double bond.
  • a “ring” or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring system” denotes two or more connected rings.
  • the term “spirocyclic ring system” denotes a ring system consisting of two rings connected at a single atom (so the rings have a single atom in common).
  • the term “bicyclic ring system” denotes a ring system consisting of two rings sharing two or more common atoms. In a “fused bicyclic ring system” the common atoms are adjacent, and therefore the rings share two adjacent atoms and a bond connecting them.
  • aromatic indicates that each of the ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and that (4n + 2) p electrons, where n is a positive integer, are associated with the ring to comply with HiickeTs rule
  • carbocyclic ring denotes a ring wherein the atoms forming the ring backbone are selected only from carbon. Unless otherwise indicated, a carbocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated carbocyclic ring satisfies HiickeTs rule, then said ring is also called an “aromatic ring”. “Saturated carbocyclic” refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • the term “partially unsaturated ring” or “partially unsaturated heterocycle” refers to a ring which contains unsaturated ring atoms and one or more double bonds but is not aromatic.
  • the terms “heterocyclic ring” or “heterocycle” denotes a ring wherein at least one of the atoms forming the ring backbone is other than carbon.
  • a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies HiickeTs rule, then said ring is also called a “heteroaromatic ring” or aromatic heterocyclic ring.
  • “Saturated heterocyclic ring” refers to a heterocyclic ring containing only single bonds between ring members.
  • heterocyclic rings and ring systems are attached to the remainder of Formula 1 through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.
  • Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis- and /ran.s-isomcrs (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).
  • Compounds of this invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • T is T-3
  • Formula 1 compounds contain at least one double bond and the configuration of substituents about that double bond can be (Z) or (E) ( cis or trans), or a mixture thereof.
  • a wavy bond indicates a single bond which is linked to an adjacent double bond wherein the geometry about the adjacent double bond is either (Z)-configuration (svn-isomcr or cA-isomer) or (C)-con figuration (anti- isomer or trans- isomer), or a mixture thereof. That is, a wavy bond represents an unspecified (Z)- or ( E )- (cis- or trans-) isomer, or mixture thereof.
  • the compounds of the present invention can contain one or more chiral centers and therefore exist in enantiomeric and diastereomeric forms.
  • This invention also includes compounds of Formula 1 wherein one stereoisomer is enriched relative to the other stereoisomer(s).
  • compounds of Formula 1 wherein T is T-3 and the substituents attached to the double bond in the T-3 moiety are in a predominately (Z)- configuration, or predominately an (Tj-configuration.
  • the ratio of the (Z)- to ( ⁇ -isomers in any compounds of Formula 1, whether produced stereoselectivity or non-stereoselectivity, may take on a broad range of values.
  • compounds of Formula 1 may comprise from about 10 to 90 percent by weight of the (Z)- isomer to about 90 to 10 percent by weight of the (C)-isomcr.
  • Formula 1 compounds may contain from about 15 to 85 percent by weight of the (Z)- isomer and about 85 to 15 percent by weight of the ( ⁇ -isomer; in another embodiment, the mixture contains about 25 to 75 percent by weight of the (Z)- isomer and about 75 to 25 percent by weight of the (C)-isomcr; in another embodiment, the mixture contains about 35 to 65 percent by weight of the (Z)- isomer and about 65 to 35 percent by weight of the (C)-isomcr; in another embodiment, the mixture contains about 45 to 55 percent by weight of the (Z)- isomer and about 55 to 45 percent by weight of the (C)-isomcr.
  • this invention includes compounds that are enriched compared to the racemic mixture in an enantiomer of Formula 1. Also included are the essentially pure enantiomers of compounds of Formula 1. When enantiomerically enriched, one enantiomer is present in greater amounts than the other, and the extent of enrichment can be defined by an expression of enantiomeric excess (“ee”), which is defined as (2x-l) ⁇ 100%, where x is the mole fraction of the dominant enantiomer in the mixture (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).
  • ee enantiomeric excess
  • compositions of this invention have at least a 50% enantiomeric excess; more preferably at least a 75% enantiomeric excess; still more preferably at least a 90% enantiomeric excess; and the most preferably at least a 94% enantiomeric excess of the more active isomer.
  • enantiomerically pure embodiments of the more active isomer are enantiomerically pure embodiments of the more active isomer.
  • This invention comprises mixtures of conformational isomers.
  • this invention includes compounds that are enriched in one conformer relative to others.
  • This invention comprises all stereoisomers, conformational isomers and mixtures thereof in all proportions as well as isotopic forms such as deuterated compounds.
  • nitrogen containing heterocycles can form A-oxidcs 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 /V-oxides.
  • nitrogen-containing heterocycles which can form /V-oxides.
  • tertiary amines can form /V-oxides.
  • 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, V-oxides, and agriculturally suitable salts, and solvates thereof.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • 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
  • ketones of Formula l 1 i.e. compounds of Formula 1 wherein T is T-l
  • ketones of Formula l 2 may exist in equilibrium with their corresponding hydrates of Formula l 2 (i.e. compounds of Formula 1 wherein T is T-2, and R 2a X and R 2b Y are both OH).
  • the equilibrium typically favors the hydrate form.
  • This invention comprises all ketonic and solvated forms of Formula 1 compounds, and mixtures thereof in all proportions. Unless otherwise indicated, reference to a compound by one tautomer description is to be considered to include all tautomers.
  • some of the unsaturated rings and ring systems depicted in Exhibit A can have an arrangement of single and double bonds between ring members different from that depicted. Such differing arrangements of bonds for a particular arrangement of ring atoms correspond to different tautomers.
  • the particular tautomer depicted is to be considered representative of all the tautomers possible for the arrangement of ring atoms shown.
  • an aspect of the present invention is directed at a composition
  • a composition comprising (a) at least one compound selected from Formula 1, /V-oxides, and salts thereof, with (b) at least one additional fungicidal compound. More particularly, Component (b) is selected from the group consisting of
  • keto reductase inhibitor (bl7) keto reductase inhibitor (KRI) fungicides
  • OSBPI oxy sterol binding protein inhibitor
  • component (b54) fungicides other than fungicides of component (a) and components (bl) through (b53); and salts of compounds of (bl) through (b54).
  • component (b) comprises at least one fungicidal compound from each of two different groups selected from (bl) through (b54).
  • Methyl benzimidazole carbamate (MBC) fungicides (bl) (FRAC code 1) inhibit mitosis by binding to b-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.
  • “Dicarboximide fungicides (b2)” (FRAC code 2) inhibit a mitogen-activated protein (MAP)/histidine kinase in osmotic signal transduction.
  • MAP mitogen-activated protein
  • Examples include chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
  • DMI Demethylation inhibitor
  • fungicides (b3) FRAC code 3
  • SBI Sterol Biosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, which plays a role in sterol production.
  • Sterols such as ergosterol, are needed for membrane structure and function, making them essential for the development of functional cell walls. Therefore, exposure to these fungicides results in abnormal growth and eventually death of sensitive fungi.
  • DMI fungicides are divided between several chemical classes: piperazines, pyridines, pyrimidines, imidazoles, triazoles and triazolinthiones.
  • the piperazines include triforine.
  • the pyridines include buthiobate, pyrifenox, pyrisoxazole and (aS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3- pyridinemethanol.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the imidazoles include econazole, imazalil, oxpoconazole, pefurazoate, prochloraz and triflumizole.
  • the triazoles include azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, ipfentrifluconazole, mefentrifluconazole, metconazole, myclobutanil, penconazole, propiconazole, quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, uniconazole-P, a-(l-chlorocyclopropyl)-a-[2-(2,2- dichlorocyclopropy
  • the triazolinthiones include prothioconazole.
  • Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.
  • Phenylamide (PA) fungicides (b4) are specific inhibitors of RNA polymerase in Oomycete fungi. Sensitive fungi exposed to these fungicides show a reduced capacity to incorporate uridine into rRNA. Growth and development in sensitive fungi is prevented by exposure to this class of fungicide.
  • Phenylamide fungicides include acylalanine, oxazolidinone and butyrolactone fungicides.
  • the acylalanines include benalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyl and metalaxyl-M (also known as mefenoxam).
  • the oxazolidinones include oxadixyl.
  • the butyrolactones include ofurace.
  • Amine/morpholine fungicides (also known as non-DMI sterol biosynthesis inhibitors) 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 (b6) (FRAC code 6) inhibit growth of fungi by affecting phospholipid biosynthesis.
  • Phospholipid biosynthesis fungicides include phophorothiolate and dithiolane fungicides.
  • the phosphorothiolates include edifenphos, iprobenfos and pyrazophos.
  • the dithiolanes include isoprothiolane.
  • “Succinate dehydrogenase inhibitor (SDHI) fungicides (b7)” (FRAC code 7) inhibit complex II fungal respiration by disrupting a key enzyme in the Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibiting respiration prevents the fungus from making ATP, and thus inhibits growth and reproduction.
  • SDHI fungicides include phenylbenzamide, phenyloxoethylthiophene amide, pyridinylethylbenzamide, furan carboxamide, oxathiin carboxamide, thiazole carboxamide, pyrazole-4-carboxamide, /V-cyclopropyl-ZV-benzyl-pyrazole carboxamide, /V-methoxy-(phenyl-ethyl)-pyrazole carboxamide, pyridine carboxamide and pyrazine carboxamide fungicides.
  • the phenylbenzamides include benodanil, flutolanil and mepronil.
  • the phenyloxoethylthiophene amides include isofetamid.
  • the pyridinylethylbenzamide s include fluopyram.
  • the furan carboxamides include fenfuram.
  • the oxathiin carboxamides include carboxin and oxycarboxin.
  • the thiazole carboxamides include thifluzamide.
  • the pyrazole-4-carboxamides include benzovindiflupyr, bixafen, flubeneteram (provisional common name, Registry Number 1676101-39-5), fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne (provisional common name, Registry Number 1803108-03-3), sedaxane and /V-[2-(2,4-dichlorophenyl)-2- mcthoxy- 1 -mcthylcthylJ-3-(difluoiOmcthyl)- 1 -methyl- 1 //-pyrazolc-4-carboxamidc.
  • the N- cyc lopropy 1 - A- benzy 1 -py azo lc carboxamides include isoflucypram.
  • the A- mcthoxy-iphcnyl- ethyl)-pyrazole carboxamides include pydiflumetofen.
  • the pyridine carboxamides include boscalid.
  • the pyrazine carboxamides include pyraziflumid.
  • Haldroxy-(2-amino-)pyrimidine fungicides (b8) (FRAC code 8) inhibit nucleic acid synthesis by interfering with adenosine deaminase. Examples include bupirimate, dimethirimol and ethirimol.
  • AP fungicides
  • FRAC code 9 a nucleophilicity factor 9 fungicides
  • AP fungicides
  • Examples include cyprodinil, mepanipyrim and pyrimethanil.
  • A- Phenyl carbamate fungicides (blO)” (FRAC code 10) inhibit mitosis by binding to b- tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure. Examples include diethofencarb.
  • Quadrature outside inhibitor (Qol) fungicides (b 11 )” (FRAC code 11) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinone outside” (Qo) site of the cytochrome be ⁇ complex, which is located in the inner mitochondrial membrane of fungi. Inhibiting mitochondrial respiration prevents normal fungal growth and development.
  • Quinone outside inhibitor fungicides include methoxyacrylate, methoxyacetamide, methoxycarbamate, oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides (collectively also known as strobilurin fungicides), and oxazolidinedione, imidazolinone and benzy lcarbamate fungicides.
  • the methoxy acrylates include azoxystrobin, coumoxystrobin, enoxastrobin (also known as enestroburin), flufenoxystrobin, picoxystrobin and pyraoxystrobin.
  • the methoxyacetamides include mandestrobin.
  • the methoxy- carbamates include pyraclostrobin, pyrametostrobin and triclopyricarb.
  • the oximinoacetates include kresoxim-methyl and trifloxystrobin.
  • the oximinoacetamides include dimoxystrobin, fenaminstrobin, metominostrobin and orysastrobin.
  • the dihydrodioxazines include fluoxastrobin.
  • the oxazolidinediones include famoxadone.
  • the imidazolinones include fenamidone.
  • the benzylcarbamates include pyribencarb.
  • Phenylpyrrole (PP) fungicides (bl2) (FRAC code 12) inhibit a MAP/histidine kinase associated with osmotic signal transduction in fungi.
  • Fenpiclonil and fludioxonil are examples of this fungicide class.
  • Azanaphthalene fungicides (bl3) (FRAC code 13) are proposed to inhibit signal transduction by a mechanism which is as yet unknown. They have been shown to interfere with germination and/or appressorium formation in fungi that cause powdery mildew diseases.
  • Azanaphthalene fungicides include ary loxy quinolines and quinazolinones.
  • the aryloxyquinolines include quinoxyfen.
  • the quinazolinones include proquinazid.
  • Cell peroxidation inhibitor fungicides (bl4) 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.
  • Cell peroxidation fungicides include aromatic hydrocarbon and 1,2,4-thiadiazole fungicides.
  • the aromatic hydrocarboncarbon fungicides include biphenyl, chloroneb, dicloran, quintozene, tecnazene and tolclofos-methyl.
  • the 1,2,4-thiadiazoles include etridiazole.
  • Melanin biosynthesis inhibitor-reductase (MBI-R) fungicides (bl5)” (FRAC code 16.1) inhibit the naphthal reduction step in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-reductase fungicides include isobenzofuranone, pyrroloquinolinone and triazolobenzothiazole fungicides.
  • the isobenzofuranones include fthalide.
  • the pyrroloquinolinones include pyroquilon.
  • the triazolobenzothiazoles include tricyclazole.
  • Melanin biosynthesis inhibitor-dehydratase (MBI-D) fungicides (bl6a)” (FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-dehydratase fungicides include cyclopropanecarboxamide, carboxamide and propionamide fungicides.
  • the cyclopropanecarboxamides include carpropamid.
  • the carboxamides include diclocymet.
  • the propionamides include fenoxanil.
  • MBI-P Melanin biosynthesis inhibitor-polyketide synthase
  • bl6b fungicides
  • FRAC code 16.3 inhibit polyketide synthase in melanin biosynthesis.
  • Melanin is required for host plant infection by some fungi.
  • Melanin biosynthesis inhibitor-polyketide synthase fungicides include trifluoroethylcarbamate fungicides. The trifluoroethylcarbamates include tolprocarb.
  • Keto reductase inhibitor (KRI) fungicides (bl7) inhibit 3-keto reductase during C4-demethylation in sterol production.
  • Keto reductase inhibitor fungicides also known as Sterol Biosynthesis Inhibitors (SBI): Class III
  • SBI Sterol Biosynthesis Inhibitors
  • Hydroxyanilides include fenhexamid.
  • Amino-pyrazolinones include fenpyrazamine.
  • Quinofumelin provisional common name, Registry Number 861647-84-9
  • ipflufenoquin provisional common name, Registry Number 1314008-27-9
  • Squalene-epoxidase inhibitor fungicides (bl8)” (FRAC code 18) (SBI: Class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway.
  • 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.
  • Squalene-epoxidase inhibitor fungicides include thiocarbamate and allylamine fungicides.
  • the thiocarbamates include pyributicarb.
  • the allylamines include naftifine and terbinafine.
  • Polyoxin fungicides (bl9) (FRAC code 19) inhibit chitin synthase. Examples include polyoxin.
  • Phenylurea fungicides (b20) are proposed to affect cell division. Examples include pencycuron.
  • Quinone inside inhibitor (Qil) fungicides (b21) inhibit complex III mitochondrial respiration in fungi by affecting ubiquinone reductase. Reduction of ubiquinone is blocked at the “quinone inside” (Qi) site of the cytochrome be ⁇ 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, sulfamoyltriazole and picolinamide fungicides.
  • the cyanoimidazoles include cyazofamid.
  • the sulfamoyltriazoles include amisulbrom.
  • the picolinamides include fenpicoxamid (Registry Number 517875-34-2).
  • Benzamide and thiazole carboxamide fungicides inhibit mitosis by binding to b-tubulin and disrupting microtubule assembly. Inhibition of microtubule assembly can disrupt cell division, transport within the cell and cell structure.
  • the benzamides include toluamides such as zoxamide.
  • the thiazole carboxamides include ethylaminothiazole carboxamides such as ethaboxam.
  • Enopyranuronic acid antibiotic fungicides (b23)
  • FRAC code 23 inhibit growth of fungi by affecting protein biosynthesis. Examples include blasticidin-S.
  • Halopyranosyl antibiotic fungicides (b24)
  • FRAC code 24 inhibit growth of fungi by affecting protein biosynthesis. Examples include kasugamycin.
  • Glucopyranosyl antibiotic protein synthesis fungicides (b25)” (FRAC code 25) inhibit growth of fungi by affecting protein biosynthesis. Examples include streptomycin.
  • Glucopyranosyl antibiotic fungicides (b26) (FRAC code U18, previously FRAC code 26 reclassified to U18) are proposed to inhibit trehalase and inositol biosynthesis. Examples include validamycin.
  • “Cyanoacetamideoxime fungicides (b27)” include cymoxanil.
  • “Carbamate fungicides (b28)” (FRAC code 28) are considered multi-site inhibitors of fungal growth. They are proposed to interfere with the synthesis of fatty acids in cell membranes, which then disrupts cell membrane permeability. Iodocarb, propamacarb and prothiocarb are examples of this fungicide class.
  • Oxidative phosphorylation uncoupling fungicides (b29) (FRAC code 29) inhibit fungal respiration by uncoupling oxidative phosphorylation. Inhibiting respiration prevents normal fungal growth and development.
  • This class includes dinitrophenyl crotonates such as binapacryl, meptyldinocap and dinocap, and 2,6-dinitroanilines such as fluazinam.
  • Organic tin fungicides (b30) (FRAC code 30) inhibit adenosine triphosphate (ATP) synthase in oxidative phosphorylation pathway.
  • examples include fentin acetate, fentin chloride and fentin hydroxide.
  • Carboxylic acid fungicides (b31) inhibit growth of fungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II (gyrase). Examples include oxolinic acid.
  • Hetero aromatic fungicides (b32) are proposed to affect DNA/ribonucleic acid (RNA) synthesis.
  • Heteroaromatic fungicides include isoxazoles and isothiazolones.
  • the isoxazoles include hymexazole and the isothiazolones include octhilinone.
  • Phosphonate fungicides (b33) include phosphorous acid and its various salts, including fosetyl-aluminum.
  • Phthalamic acid fungicides (b34) include teclofthalam.
  • Benzotriazine fungicides (b35) include triazoxide.
  • Benzene-sulfonamide fungicides (b36) include flusulfamide.
  • “Pyridazinone fungicides (b37)” include diclomezine.
  • Thiophene-carboxamide fungicides (b38) are proposed to affect ATP production. Examples include silthiofam.
  • “Complex I NADH oxidoreductase inhibitor fungicides (b39)” inhibit electron transport in mitochondria and include pyrimidinamines such as diflumetorim, pyrazole- 5-carboxamides such as tolfenpyrad, and quinazoline such as fenazaquin.
  • Carboxylic acid amide (CAA) fungicides (b40) inhibit cellulose synthase which prevents growth and leads to death of the target fungus.
  • Carboxylic acid amide fungicides include cinnamic acid amide, valinamide carbamate and mandelic acid amide fungicides.
  • the cinnamic acid amides include dimethomorph, flumorph and pyrimorph.
  • the valinamide carbamates include benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb and valifenalate (also known as valiphenal).
  • the mandelic acid amides include mandipropamid, N- [2- [4- [ [3 -(4-chloropheny l)-2-propyn- 1 -yl] oxy ] -3 -methoxyphenyl] ethyl] -3 -methyl-2- [(methylsulfonyl)amino]butanamide and A-[2-[4-[[3-(4-chlorophenyl)-2-propyn-l-yl]oxy]-3- methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.
  • Tetracycline antibiotic fungicides (b41) (FRAC code 41) inhibit growth of fungi by affecting protein synthesis. Examples include oxy tetracycline.
  • Thiocarbamate fungicides (b42) include methasulfocarb.
  • Benzamide fungicides (b43) inhibit growth of fungi by delocalization of spectrin-like proteins.
  • examples include pyridinylmethyl benzamides such as fluopicolide and fluopimomide.
  • Microbial fungicides (b44) disrupt fungal pathogen cell membranes.
  • Microbial fungicides include Bacillus species such as Bacillus amyloliquefaciens strains AP-136, AP-188, AP-218, AP-219, AP-295, QST713, FZB24, F727, MB 1600, D747, TJ100 (also called strain 1 BE; known from EP2962568), and the fungicidal lipopeptides which they produce.
  • QoSI fungicides include triazolopyrimidylamines such as ametoctradin.
  • Plant extract fungicides (b46) (FRAC code 46) cause cell membrane disruption.
  • Plant extract fungicides include terpene hydrocarbons, terpene alcohols and terpen phenols such as the extract from Melaleuca alternifolia (tea tree) and plant oils (mixtures) such as eugenol, geraniol and thymol.
  • Cyanoacrylate fungicides (b47) (FRAC code 47) bind to the myosin motor domain and effect motor activity and actin assembly. Cyanoacrylates include fungicides such as phenamacril.
  • Polyene fungicides (b48) cause disruption of the fungal cell membrane by binding to ergosterol, the main sterol in the membrane. Examples include natamycin (pimaricin).
  • Oxysterol binding protein inhibitor (OSBPI) Fungicides (b49) (FRAC code 49) bind to the oxysterol-binding protein in oomycetes causing inhibition of zoospore release, zoospore motility and sporangia germination.
  • Oxysterol binding fungicides include piperdinylthiazoleisoxazolines such as oxathiapiprolin and fluoxapiprolin.
  • Aryl-phenyl-ketone fungicides (b50) (FRAC code 50, previously FRAC code U8 reclassified to 50) inhibit the growth of mycelium in fungi.
  • Aryl-phenyl ketone fungicides include benzophenones such as metrafenone, and benzoylpyridines such as pyriofenone.
  • “Host plant defense induction fungicides (b51)” induce host plant defense mechanisms.
  • Host plant defense induction fungicides include benzothiadiazole (FRAC code P01), benzisothiazole (FRAC code P02), thiadiazole carboxamide (FRAC code P03), polysaccharide (FRAC code P04), plant extract (FRAC code P05), microbial (FRAC code P06) and phosphonate fungicides (FRAC code P07, see (b33) above).
  • the benzothiadiazoles include acibenzolar-S- methyl.
  • the benzisothiazoles include probenazole.
  • the thiadiazole carboxamides include tiadinil and isotianil.
  • the polysaccharides include laminarin.
  • the plant extracts include extract from Reynoutria sachalinensis (giant knotweed).
  • the microbials include Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS 117.
  • Multi-site activity fungicides inhibit fungal growth through multiple sites of action and have contact/preventive activity.
  • Multi- site activity fungicides include copper fungicides (FRAC code M01), sulfur fungicides (FRAC code M02), dithiocarbamate fungicides (FRAC code M03), phthalimide fungicides (FRAC code M04), chloronitrile fungicides (FRAC code M05), sulfamide fungicides (FRAC code M06), multi-site contact guanidine fungicides (FRAC code M07), triazine fungicides (FRAC code M08), quinone fungicides (FRAC code M09), quinoxaline fungicides (FRAC code M10), maleimide fungicides (FRAC code Mil) and thiocarbamate (FRAC code M12, see (b42) above) fungicides.
  • Copper fungicides are inorganic compounds containing copper, typically in the copper(II) oxidation state; examples include copper oxychloride, copper sulfate and copper hydroxide (e.g., including compositions such as Bordeaux mixture (tribasic copper sulfate).
  • Sulfur fungicides are inorganic chemicals containing rings or chains of sulfur atoms; examples include elemental sulfur.
  • Dithiocarbamate fungicides contain a dithiocarbamate molecular moiety; examples include ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb and ziram.
  • Phthalimide fungicides contain a phthalimide molecular moiety; examples include folpet, captan and captafol. Chloronitrile fungicides contain an aromatic ring substituted with chloro and cyano; examples include chlorothalonil. Sulfamide fungicides include dichlofluanid and tolyfluanid. Multi-site contact guanidine fungicides include, guazatine, iminoctadine albesilate and iminoctadine triacetate. Triazine fungicides include anilazine. Quinone fungicides include dithianon. Quinoxaline fungicides include quinomethionate (also known as chinomethionate). Maleimide fungicides include fluoroimide.
  • Biologicals with multiple modes of action include agents from biological origins showing multiple mechanisms of action without evidence of a dominating mode of action.
  • This class of fungicides includes polypeptide (lectin), phenol, sesquiterpene, tritepenoid and coumarin fungicides (FRAC code BM01) such as extract from the cotyledons of lupine plantlets.
  • This class also includes momicrobial fungicides (FRAC code BM02, see (b44) above).
  • the phenyl-acetamides include cyflufenamid.
  • the guanidines include dodine.
  • the thiazolidines include flutianil.
  • the pyrimidinonehydrazones include ferimzone.
  • the 4-quinolylacetates include tebufloquin.
  • the tetrazolyloximes include picarbutrazox.
  • the (b54) class also includes bethoxazin, dichlobentiazox (provisional common name, Registry Number 957144-77-3), dipymetitrone (provisional common name, Registry Number 16114-35-5), flometoquin, neo-asozin (ferric methanearsonate), pyrrolnitrin, tolnifanide (Registry Number 304911-98-6), A-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]- V- ct h y 1 - A- met h y 1 met h an i m i da m i dc, 5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenyl A-[l-[[[[l-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]
  • Additional “Fungicides other than fungicides of classes (1) through (54)” whose mode of action may be unknown, or may not yet be classified include a fungicidal compound selected from components (b54.7) through (b54.13), as described below.
  • Component (54.7) relates to (lS)-2,2-bis(4-fluorophenyl)-l-methylethyl A-[[3-(acetyloxy)- 4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name florylpicoxamid, Registry Number 1961312-55-9) which is believed to be a Quinone inside inhibitor (Qil) fungicide (FRAC code 21) inhibiting the Complex III mitochondrial respiration in fungi.
  • Component (54.8) relates to 1 -[ 2-[ [ [ 1 -(4-chlorophcnyl)-l /7-pyrazol-3-yl]oxy]mcthyl]-3- mcthylphcnylj- 1 ,4-di hydro-4- mcthyl-5/7-tctrazol-5-onc (provisional common name metyltetraprole, Registry Number 1472649-01-6), which is believed to be a quinone outside inhibitor (Qol) fungicide (FRAC code 45) inhibiting the Complex III mitochondrial respiration in fungi, and is effective against Qol resistant strains.
  • Qol quinone outside inhibitor
  • Component (54.9) relates to 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5-phenylpyridazine (provisional common name pyridachlometyl, Registry Number 1358061-55-8), which is believed to be promoter tubulin polymerization, resulting antifungal activity against fungal species belonging to the phyla Ascomycota and Basidiomycota.
  • Component (54.10) relates to (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (provisional common name aminopyrifen, Registry Number 1531626-08-0) which is believed to inhibit GWT-1 protein in glycosylphosphatidylinositol-anchor biosynthesis in Neurospora crassa.
  • Component (b54.11) relates a compound of Formula b54.11 wherein
  • R bl and R b3 are each independently halogen
  • R b2 is H, halogen, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl or Cg-Cg cycloalkyl.
  • Examples of compounds of Formula b54.11 include (b54.11a) methyl /V-[[5-[l-(2,6-difluoro-4- formylphcnylj- 1 //-pyrazol-3-yl]-2-mcthy lphcnyl] methyl] carbamate, (b54.11b) methyl /V-[[5-[l- (4-cyclopiOpyl-2,6-dichloiOphcnyl)-l //-pyrazol-3-y lJ-2-mcthy lphcnyl J methyl Jcarbamatc,
  • Component (b54.12) relates a compound of Formula b54.12 b54.12 wherein R b4 is R b6 is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;
  • L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12;
  • R b5 is Examples of compounds of Formula b54.12 include (b54.12a) /V-(2,2,2-trifluoroethyl)-2-[[4-[5- (trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4-oxazolecarboxamide and (b54.12b) ethyl l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenoxy]methyl]-l -pyrazole-4- carboxylate.
  • Component (b54.13) relates a compound of Formula b54.13 wherein
  • R b7 , R b8 and R b9 are each independently H, halogen or cyano
  • R bl ° and R bl 1 are each independently H, halogen, C [ -C3 alkyl or C [ -C3 methoxy.
  • Examples of compounds of Formula b54.13 include (b54.13a) 4-( 2-ch loro-4- fluorophenyl )-/V-( 2- fluoro-4-methyl-6-nitrophenyl)-l, 3-dimethyl- l /-pyrazol-5-amine, (b54.13b) 4-(2-chloro-4- fluorophenyl)- V-(2-fluoro-6-nitrophenyl)-l, 3-dimethyl- l /-pyrazol-5-amine, (b54.13c) 3,5- difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l /-pyrazol-4-yl]-benzonitrile and (b54.13d) /V-(2-chloro-4
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes stereoisomers, /V-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 The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-l.
  • Embodiment 2 The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2.
  • Embodiment 3 The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-3.
  • Embodiment 3a The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, T is T-2 or T-3.
  • Embodiment 4 The composition comprising components (a) and (b) described in the Summary of the Invention wherein in Formula 1, R 1 is CF3.
  • Embodiment 5 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is O or S.
  • Embodiment 6 The composition of Embodiment 5 wherein W is O.
  • Embodiment 7 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 4 wherein in Formula 1, W is NR 3 .
  • Embodiment 9 The composition of Embodiment 8 wherein R 3 is H, cyano, C1-C2 alkyl or OR 3a .
  • Embodiment 10 The composition of Embodiment 9 wherein R 3 is H, cyano or OR 3a .
  • Embodiment 11 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 10 wherein in Formula 1, R 3a is H, C1-C2 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
  • Embodiment 12 The composition of Embodiment 11 wherein R 3a is H.
  • Embodiment 13 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 12 wherein in Formula 1, when R 3b is separate (i.e. not taken together with R 3c to form a ring), then R 3b is H, C1-C3 alkyl, C2-C3 alkylcarbonyl or C2-C3 haloalkylcarbonyl.
  • Embodiment 14 The composition of Embodiment 13 wherein R 3b is H or methyl.
  • Embodiment 15 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 14 wherein in Formula 1, when R 3c is separate (i.e. not taken together with R 3b to form a ring), then R 3C is H or C1-C2 alkyl.
  • Embodiment 16 The composition of Embodiment 15 wherein R 3c is H or methyl.
  • Embodiment 17 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O or NR 5a .
  • Embodiment 18 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 16 wherein in Formula 1, X is O, S, NH or NOH.
  • Embodiment 19 The composition of Embodiment 18 wherein X is O or NOH.
  • Embodiment 20 The composition of Embodiment 20 wherein X is O.
  • Embodiment 21 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O or NR 5b .
  • Embodiment 22 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 20 wherein in Formula 1, Y is O, S, NH or NOH.
  • Embodiment 23 The composition of Embodiment 22 wherein Y is O or NOH.
  • Embodiment 24 The composition of Embodiment 23 wherein Y is O.
  • Embodiment 25 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 24 wherein in Formula 1, R 5a and R 5b are each independently H, hydroxy or C1-C2 alkyl.
  • Embodiment 26 The composition of Embodiment 25 wherein R 5a and R 5b are each independently H, hydroxy or methyl.
  • Embodiment 27 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R 2a and R 2b are separate (i.e. not taken together to form a ring), then R 2a and R 2b are each independently H, C1-C3 alkyl, C2-C3 alkenyl, (CR 4a R 4b ) p -OH, (CR 4a R 4b ) p -Cl or (CR 4a R 4b ) p -Br.
  • Embodiment 27a Embodiment 27a.
  • composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 26 wherein in Formula 1, when R 2a and R 2b are separate (i.e. not taken together to form a ring), then R 2a and R 2b are each independently H, C1-C3 alkyl, C3-C35 trialkylsilyl or C3-C35 halotrialkylsilyl.
  • Embodiment 27b The composition of Embodiment 27a wherein R 2a and R 2b are each independently H, methyl, trimethylsilyl or halotrimethylsilyl.
  • Embodiment 27c The composition of Embodiment 27b wherein R 2a and R 2b are each independently H, methyl, trimethylsilyl or trifluoromethylsilyl
  • Embodiment 27d The composition of Embodiment 27c wherein R 2a and R 2b are each independently H, methy or trimethylsilyl.
  • Embodiment 27e The composition of Embodiment 27d wherein R 2a is H and R 2b is trimethylsilyl.
  • Embodiment 27f The composition of Embodiment 27d wherein R 2a is methyl and R 2b is trimethylsilyl.
  • Embodiment 28 The composition of Embodiment 27 wherein R 2a and R 2b are each independently H, C r C 3 alkyl, (CR 4a R 4b ) p -Cl or (CR 4a R 4b ) p -Br.
  • Embodiment 29 The composition of Embodiment 28 wherein R 2a and R 2b are each independently H, methyl, (CR 4a R 4b ) p -Cl or (CR 4a R 4b ) p -Br.
  • Embodiment 30 The composition of Embodiment 28 wherein R 2a and R 2b are each independently H or C3-C3 alkyl.
  • Embodiment 31 The composition of Embodiment 30 wherein R 2a and R 2b are each independently H or C3-C2 alkyl.
  • Embodiment 32 The composition of Embodiment 31 wherein R 2a and R 2b are each independently H or methyl.
  • Embodiment 33 The composition of Embodiment 32 wherein R 2a and R 2b are each H.
  • Embodiment 34 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 33 wherein in Formula 1, when R 2a and R 2b are separate (i.e. not taken together to form a ring), then one of R 2a and R 2b is (CR 4a R 4b ) p -OH, (CR 4a R 4b ) p -SH, (CR 4a R 4b ) p -Cl or (CR 4a R 4b ) p -Br, and the other is H.
  • Embodiment 35 The composition of Embodiment 34 wherein one of R 2a and R 2b is (CR 4a R 4b ) p -Cl or (CR 4a R 4b ) p -Br, and the other is H.
  • Embodiment 37 The composition of Embodiment 36 wherein R 2a and R 2b are each independently H or methyl; or R 2a and R 2b are taken together with the atoms X and
  • Embodiment 38 The composition of Embodiment 37 wherein R 2a and R 2b are each independently H or methyl; or R 2a and R 2b are taken together with the atoms X and
  • Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, cyano and methyl on carbon atom ring members.
  • Embodiment 39 The composition of Embodiment 38 wherein R 2a and R 2b are each H; or R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected methyl on a carbon atom ring member.
  • Embodiment 40 The composition of Embodiment 39 wherein R 2a and R 2b are each H; or R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
  • Embodiment 41 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 40 wherein in Formula 1, when R 2a and R 2b are taken together to form a ring (i.e.
  • Embodiment 42 The composition of Embodiment 41 wherein R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 2 substituents independently selected from halogen, cyano, methyl, halomethyl and methoxy on carbon atom ring members.
  • Embodiment 43 The composition of Embodiment 42 wherein R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member.
  • Embodiment 44 The composition of Embodiment 43 wherein R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
  • Embodiment 45 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 44 wherein in Formula 1, R 2c is C 1 -C3 alkyl, C 3 -C3 haloalkyl, C 2 -C3 alkenyl, C 2 -C3 haloalkenyl, C 2 -C3 alkynyl or C 2 -C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SCoN and C 3 -C 2 alkoxy.
  • R 2c is C 1 -C3 alkyl, C 3 -C3 haloalkyl, C 2 -C3 alkenyl, C 2 -C3 haloalkenyl, C 2 -C3 alkynyl or C 2 -C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano, hydroxy, SC
  • Embodiment 46 The composition of Embodiment 45 wherein R 2c is C 3 -C 2 alkyl, C 3 -C 2 haloalkyl, C 2 -C3 alkenyl, C 2 -C3 haloalkenyl, C 2 -C3 alkynyl or C 2 -C3 haloalkynyl, each optionally substituted with up 1 substituent selected from cyano and methoxy.
  • Embodiment 46a The composition of Embodiment 46 wherein R 2c is C 3 -C 2 alkyl, C 3 -C 2 haloalkyl, C 2 -C3 alkenyl, C 2 -C3 haloalkenyl or C 2 -C3 alkynyl.
  • Embodiment 47 The composition of Embodiment 46a wherein R 2c is C 3 -C 2 alkyl, C 2 -C3 alkenyl or C 2 -C3 alkynyl.
  • Embodiment 48 The composition of Embodiment 47 wherein R 2c is methyl or ethyl.
  • Embodiment 48a The composition of Embodiment 48 wherein R 2c is ethyl.
  • Embodiment 49 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 48a wherein in Formula 1, R 2d is H, cyano, halogen or C1-C2 alkyl.
  • Embodiment 49a The composition of Embodiment 49 wherein R 2d is H, cyano, Cl, F or methyl.
  • Embodiment 50 The composition of Embodiment 49a wherein R 2d is H or methyl.
  • Embodiment 51 The composition of Embodiment 50 wherein R 2d is H.
  • Embodiment 52 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 51 wherein in Formula 1, each R 4a and R 4b is independently H or C1-C2 alkyl.
  • Embodiment 53 The composition of Embodiment 52 wherein each R 4a and R 4b is independently H or methyl.
  • Embodiment 54 The composition of Embodiment 53 wherein each R 4a and R 4b is H.
  • Embodiment 55 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 2.
  • Embodiment 56 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 54 wherein in Formula 1, p is 3.
  • Embodiment 57 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 56 wherein in Formula 1, wherein A 1 is CR 6c R 6d , O or S.
  • Embodiment 58 The composition of Embodiment 57 wherein A 1 is CR 6c R 6d or O.
  • Embodiment 59 The composition of Embodiment 58 wherein A 1 is CR 6c R 6d .
  • Embodiment 60 The composition of Embodiment 58 wherein A 1 is O.
  • Embodiment 61 The composition comprising components (a) and (b) described in the
  • a 1 is CH2, NH, O or S.
  • Embodiment 62 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 61 wherein in Formula 1, A 1 is N(R 7a ).
  • Embodiment 63 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 63 wherein in Formula 1, A 2 is a direct bond, CR 6e R 6f , O or S.
  • Embodiment 64 The composition of Embodiment 63 wherein A 2 is a direct bond, CR 6e R 6f or O.
  • Embodiment 65 The composition of Embodiment 64 wherein A 2 is a direct bond or O.
  • Embodiment 66 The composition of Embodiment 65 wherein A 2 is a direct bond.
  • Embodiment 67 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A 2 is a direct bond, CH2, NH, O or S.
  • Embodiment 67a The composition of Embodiment 67 wherein A 2 is a direct bond, CH2 or
  • Embodiment 68 The composition of Embodiment 67a wherein A 2 is a direct bond or O.
  • Embodiment 69 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 62 wherein in Formula 1, A 2 is N(R 7b ).
  • Embodiment 70 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 69 wherein in Formula 1, when A is A 1 -A 2 -CR 6a R 6b , then A 1 -A 2 -CR 6a R 6b is selected from OCH 2 , OCH(Me), CH(OH)CH 2 , CH 2 CH 2 , SCH 2 , OCF 2 and CH 2 OCH 2 .
  • Embodiment 71 The composition of Embodiment 70 wherein A 1 -A 2 -CR 6a R 6b is selected from OCH 2 , OCH(Me) and CH 2 CH 2 .
  • Embodiment 72 The composition of Embodiment 71 wherein A 1 -A 2 -CR 6a R 6b is selected from OCH 2 and CH 2 CH 2 .
  • Embodiment 73 The composition of Embodiment 72 wherein A 1 -A 2 -CR 6a R 6b is OCtl ⁇ .
  • Embodiment 74 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 74 wherein in Formula 1, when A is A ⁇ A 2 , then A'-A 2 is selected from O, CH2, OCtl ⁇ and
  • Embodiment 75 The composition of Embodiment 74 wherein A'-A 2 is selected from O, CH 2 and CH 2 0.
  • Embodiment 76 The composition of Embodiment 75 wherein A'-A 2 is selected from O and Ctl ⁇ .
  • Embodiment 77 The composition of Embodiment 76 wherein A'-A 2 is O.
  • Embodiment 78 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 77 wherein in Formula 1, R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are each independently H, cyano, hydroxy, Br, Cl, F or methyl.
  • Embodiment 79 The composition of Embodiment 78 wherein R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are each independently H, cyano hydroxy or methyl.
  • Embodiment 80 The composition of Embodiment 79 wherein R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are each independently H or methyl.
  • Embodiment 8E The composition of Embodiment 80 wherein R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are each H.
  • Embodiment 82 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 81 wherein in Formula 1, R 7a and R 7b are each independently H, C1-C2 alkyl or C2-C3 alkylcarbonyl.
  • Embodiment 83 The composition of Embodiment 82 wherein R 7a and R 7b are each independently H or C1-C2 alkyl.
  • Embodiment 84 The composition of Embodiment 83 wherein R 7a and R 7b are each H.
  • Embodiment 85 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 84 wherein in Formula 1, when T is T-l or T-2, then A is A 1 -A 2 -CH2-
  • Embodiment 86 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 85 wherein in Formula 1, when T is T-l or T-2, then A is OCH 2 , SCH 2 , NHCH 2 , CH 2 CH 2 , OCH 2 CH 2 , SCH 2 CH 2 , NHCH 2 CH 2 , CH 2 OCH 2 , CH 2 SCH 2 or CH 2 NHCH 2 .
  • Embodiment 87 The composition of Embodiment 86 wherein when T is T-l or T-2, then A is OCH 2 , SCH 2 , CH 2 CH 2 , OCH 2 CH 2 , SCH 2 CH 2 , CH 2 OCH 2 or CH 2 SCH 2 .
  • Embodiment 88 The composition of Embodiment 87 wherein when T is T-l or T-2, then A is OCH 2 or CH 2 CH 2 .
  • Embodiment 89 The composition of Embodiment 88 wherein when T is T-l or T-2, then A is OCH 2 .
  • Embodiment 90 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 89 wherein in Formula 1, when T is T-3, then A is O, OCH 2 , SCH 2 , NHCH 2 , CH 2 , CH 2 CH 2 , CH 2 0, CH 2 S or CH 2 NH.
  • Embodiment 91 The composition of Embodiment 82 wherein when T is T-3, then A is O, CH 2 or OCH 2 .
  • Embodiment 92 The composition of Embodiment 91 wherein when T is T-3, then A is O or CH 2 .
  • Embodiment 93 The composition of Embodiment 92 wherein when T is T-3, then A is O.
  • Embodiment 94 The composition comprising components (a) and (b) described in the
  • J is J-l through J-3, J-6 through J- 10 or J- 14.
  • Embodiment 95 The composition of Embodiment 94 wherein J is J-l, J-2, J-3, J-6 or J- 14.
  • Embodiment 96 The composition of Embodiment 95 wherein J is J-l, J-6 or J- 14.
  • Embodiment 97 The composition of Embodiment 96 wherein J is J-l or J-6.
  • Embodiment 97a The composition of Embodiment 96 wherein J is J- 14.
  • Embodiment 98 The composition of Embodiment 97 wherein J is J-l.
  • Embodiment 99 The composition of Embodiment 97 wherein J is J-6.
  • Embodiment 100 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 99 wherein in Formula 1, each R 8 is independently F, Cl or methyl.
  • Embodiment 100a The composition of Embodiment 100 wherein each R 8 is independently F or Cl.
  • Embodiment 101 The composition of Embodiment 100 wherein each R 8 is independently F or methyl.
  • Embodiment 101a The composition of Embodiment 101 wherein each R 8 is F.
  • Embodiment 102 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 0 or 1.
  • Embodiment 102a The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 101a wherein in Formula 1, q is 3 or 4.
  • Embodiment 102b The composition of Embodiment 102a wherein in Formula 1, q is 4.
  • Embodiment 103 The composition of Embodiment 102 wherein q is 0.
  • Embodiment 103a The composition of Embodiment 102 wherein q is 1.
  • Embodiment 104 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 103a wherein in Formula 1, each R 9a and R 9b is independently H, halogen, C
  • Embodiment 105 The composition of Embodiment 104 wherein each R 9a and R 9b is independently H, halogen, Ci-C 2 alkyl or Ci-C 2 haloalkyl.
  • Embodiment 106 The composition of Embodiment 105 wherein each R 9a and R 9b is independently H, halogen or methyl.
  • Embodiment 107 The composition of Embodiment 106 wherein each R 9a and R 9b is independently H or methyl.
  • Embodiment 108 The composition of Embodiment 107 wherein each R 9a and R 9b is H.
  • Embodiment 109 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 108 wherein in Formula 1, n is 0, 1 or 2.
  • Embodiment 109a The composition of Embodiment 109 wherein n is 1 or 2.
  • Embodiment 110 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 109a wherein in Formula 1, n is 0 or 1.
  • Embodiment 111 The composition of Embodiments 109, 109a or 110 wherein n is 1.
  • Embodiment 112. The composition of Embodiments 109 or 110 wherein n is 0.
  • Embodiment 113 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 112 wherein in Formula 1, L is a direct bond, CH2, CH(Me) or CH2CH2.
  • Embodiment 113a The composition of Embodiment 113 wherein L is a direct bond, CH2 or CH 2 CH 2 .
  • Embodiment 114 The composition of Embodiment 113a wherein L is a direct bond or
  • Embodiment 115 The composition of Embodiment 114 wherein L is CH 2 .
  • Embodiment 115a The composition of Embodiment 114 wherein L is a direct bond.
  • Embodiment 116 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 115a wherein in Formula 1, E is E 1 .
  • Embodiment 116a The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 116 wherein in Formula 1, when L is a direct bond, then E is E 1 .
  • Embodiment 119 The composition of Embodiment 118 wherein E 1 is C ⁇ -C ⁇ alkoxy, C
  • Embodiment 120 The composition of Embodiment 119 wherein E 1 is C1-C3 alkoxy,
  • each carbon atom is optionally substituted with up to 1 substituent selected from R 10a and up to 3 substituents independently selected from R 10b .
  • Embodiment 120a The composition of Embodiment 120 wherein E 1 is C1-C3 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a .
  • Embodiment 121 The composition of Embodiment 120 wherein E 1 is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a and up to 3 substituents independently selected from R 10b .
  • Embodiment 121a The composition of Embodiment 120 wherein E 1 is C1-C2 alkoxy, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a .
  • Embodiment 121b The composition of Embodiment 121a wherein E 1 is methoxy optionally substituted with up to 1 substituent selected from R 10a .
  • Embodiment 121c The composition of Embodiment 121a wherein E 1 is methoxy substituted with 1 substituent selected from R 10a .
  • Embodiment 122 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 121c wherein in Formula 1, R 10a is phenyl optionally substituted with up to 3 substituents independently selected from R lla ; or a 5- to 6-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R lla on carbon atom ring members and R l lb on nitrogen atom ring members.
  • Embodiment 123 The composition of Embodiment 122 wherein R 10a is phenyl optionally substituted with up to 2 substituents independently selected from R l la ; or a 5- to 6- membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members and R llb on nitrogen atom ring members.
  • Embodiment 123a The composition of Embodiment 123 wherein R 10a is a 5-membered heterocyclic ring containing ring members selected from carbon atoms and 1 to 4 heteroatoms independently selected from up to 2 O and up to 3 N atoms, each ring optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members.
  • Embodiment 123b The composition of Embodiment 123a wherein R 10a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members.
  • Embodiment 123c The composition of Embodiment 123b wherein R 10a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members.
  • Embodiment 123d The composition of Embodiment 123c wherein R 10a is pyrazolyl optionally substituted with up to 1 substituent selected from R l la on a carbon atom ring member.
  • Embodiment 124 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 123c wherein in Formula 1, each R 10b is independently cyano, halogen, hydroxy, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, CyC ⁇ cycloalkyl, C 1 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 1 -C 4 alkylsulfonyl, C 4 -C 4 haloalkylsulfonyl, C 1 -C 4 alkylamino, C 2 -C 4 dialkylamino, C 2 -C 4 alkylcarbonyl or C 2 -C5 alkoxycarbonyl.
  • Embodiment 125 The composition of Embodiment 124 wherein each R 10b is independently halogen, hydroxy, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • Embodiment 125a The composition of Embodiment 125 wherein each R 10b is independently halogen, C 4 -C 2 alkyl, C 4 -C 2 haloalkyl, C 4 -C 2 alkoxy or C 2 -C 4 alkoxycarbonyl.
  • Embodiment 126 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 125a wherein in Formula 1, each R l la is independently halogen, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C % - C 4 alkenyl, C 2 -C 4 alkynyl, C 4 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C % - C 4 alkynyloxy, C 2 -C 4 alkoxyalkyl, alkylcarbonyloxy, C 1 -C 4 alkylsulfonyl,
  • Embodiment 127 The composition of Embodiment 126 wherein each R lla is independently halogen, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 1 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkylcarbonyl, C 2 - C, alkoxycarbonyl, C3-C 7 alkenyloxycarbonyl or C 2 -C6 alkylaminocarbonyl.
  • Embodiment 128 The composition of Embodiment 127 wherein each R lla is independently halogen, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkylcarbonyl, C 2 -C 4 alkoxycarbonyl or C3- C5 alkenyloxycarbonyl.
  • Embodiment 128a The composition of Embodiment 128 wherein each R l la is independently halogen, C 4 -C 2 alkyl, C 4 -C 2 haloalkyl, C 1 -C 2 alkoxy or C 2 -C3 alkoxycarbonyl.
  • Embodiment 128b The composition of Embodiment 128a wherein each R 1 la is independently methoxy carbonyl or ethoxycarbonyl.
  • Embodiment 128c The composition of Embodiment 128b wherein each R l la is ethoxycarbonyl.
  • Embodiment 129 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 128c wherein in Formula 1, each R l lb is independently C 1 -C 2 alkyl, C 1 -C 2 alkoxy, C 2 -C3 alkylcarbonyl or C 2 -C3 alkoxycarbonyl.
  • Embodiment 130 The composition of Embodiment 129 wherein each R llb is independently methyl, methoxy, methylcarbonyl or methoxycarbonyl.
  • Embodiment 13 E The composition of Embodiment 130 wherein each R llb is independently methyl or methoxy.
  • Embodiment 132 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 131 wherein in Formula 1, E is E 2 .
  • Embodiment 134 The composition of Embodiment 133 wherein G is selected from G-l through G-l 18 as shown in Exhibit A.
  • G-117 G-118 wherein the floating bond is connected to Z in Formula 1 through any available carbon or nitrogen atom of the depicted ring or ring system; and x is 0, 1, 2 or 3.
  • Embodiment 135. The composition of Embodiment 134 wherein G is G-l through G-16, G-20, G-22 through G-30, G-36 through G-42, G-54 through G-60, G-85, G-86, G- 108, G-110 or G-lll.
  • Embodiment 136 The composition of Embodiment 135 wherein G is G-l through G-16, G-22, G-24, G-25, G-26, G-28, G-29, G-30, G-36, G-37, G-38, G-41, G-42, G-54, G-57, G-58, G-59, G-60, G-85, G-86, G-108, G-110 or G-lll.
  • Embodiment 137 The composition of Embodiment 136 wherein G is G-l through G-13, G-22, G-24, G-25, G-26, G-28, G-29, G-41, G-42, G-54, G-57, G-58, G-59 or G-60.
  • Embodiment 138 The composition of Embodiment 137 wherein G is G-l, G-2, G-3, G-7, G-8, G-9, G-10, G-12, G-13, G-22, G-29, G-42, G-54 or G-58.
  • Embodiment 139 The composition of Embodiment 138 wherein G is G-l, G-3, G-12, G- 13, G-22 or G-42.
  • Embodiment 140 The composition of Embodiment 139 wherein G is G-l, G-3, G-12, G- 13 or G-22.
  • Embodiment 141 The composition of Embodiment 140 wherein G is G-l, G-3, G-12 or G-
  • Embodiment 142 The composition of Embodiment 141 wherein G is G-l or G-12.
  • Embodiment 143 The composition of Embodiment 142 wherein G is G-l.
  • Embodiment 144 The composition of Embodiment 142 wherein G is G-12.
  • Embodiment 145 The composition of Embodiment 140 wherein G is G-3.
  • Embodiment 146 The composition of Embodiment 140 wherein G is G-22.
  • Embodiment 147 The composition of Embodiment 143 wherein the 2-position of G-l is connected to Z and the 4-position is connected to R 13 .
  • Embodiment 148 The composition of Embodiment 143 wherein the 2-position of G-l is connected to Z and the 5-position is connected to R 13 .
  • Embodiment 149 The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 4-position is connected to R 13 .
  • Embodiment 150 The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3-position is connected to R 13 .
  • Embodiment 151 The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 3- and 5-positions are connected to R 13 .
  • Embodiment 152 The composition of Embodiment 144 wherein the 1-position of G-12 is connected to Z and the 5-position is connected to R 13 .
  • Embodiment 153 The composition of Embodiment 145 wherein the 1-position of G-3 is connected to Z and the 4-position is connected to R 13 .
  • Embodiment 154 The composition of Embodiment 146 wherein the 4-position of G-22 is connected to Z and the 2-position is connected to R 13 .
  • Embodiment 155 The composition of any one of Embodiments 147 through 154 wherein Z is a direct bond.
  • Embodiment 156 The composition of any one of Embodiments 147 through 155 wherein x is 1 and R 13 is methoxycarbonyl or ethoxycarbonyl.
  • Embodiment 157 The composition of any one of Embodiments 134 through 155 wherein x is 1 or 2.
  • Embodiment 158 The composition of Embodiment 157 wherein x is 1.
  • Embodiment 159 The composition of Embodiment 157 wherein x is 2.
  • Embodiment 160 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 134 through 155 wherein in Formula 1, x is 0.
  • Embodiment 166 The composition of Embodiment 165 wherein each R 13 is independently C2-C5 alkoxycarbonyl or C3-C5 alkenyloxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R 19 .
  • Embodiment 167 The composition of Embodiment 166 wherein each R 13 is independently C2-C5 alkoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R 19 .
  • Embodiment 168 The composition of Embodiment 167 wherein each R 13 is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 3 substituents independently selected from R 19 .
  • Embodiment 169 The composition of Embodiment 168 wherein each R 13 is independently methoxycarbonyl or ethoxycarbonyl, each optionally substituted with up to 1 substituent selected from R 19 .
  • Embodiment 170 The composition of Embodiment 169 wherein each R 13 is independently ethoxycarbonyl optionally substituted with up to 1 substituent selected from R 19 .
  • Embodiment 171 The composition of Embodiment 169 wherein each R 13 is independently methoxycarbonyl or ethoxycarbonyl.
  • Embodiment 172 The composition of Embodiment 171 wherein each R 13 is ethoxycarbonyl.
  • Embodiment 173 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 172 wherein in Formula 1, when each R 14a is separate (i.e. not taken together with R 14b to form a ring), then each R 14a is independently H, cyano, hydroxy, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.
  • Embodiment 174 The composition of Embodiment 173 wherein each R 14a is independently H, cyano, C 4 -C 4 alkyl, C 4 -C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl, C 2 -C5 alkoxycarbonyl or C3-C5 dialkylaminocarbonyl.
  • Embodiment 175. The composition of Embodiment 174 wherein each R 14a is independently H, C 4 -C 2 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 2 -C 4 alkylcarbonyl or C 2 -C 4 alkoxycarbonyl.
  • Embodiment 176 The composition of Embodiment 175 wherein each R 14a is independently H or C 4 -C 2 alkyl.
  • Embodiment 177 The composition of Embodiment 176 wherein each R 14a is independently H or methyl.
  • Embodiment 177a The composition of Embodiment 177 wherein each R 14a is H.
  • Embodiment 178 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 177a wherein in Formula 1, when each R 14b is separate (i.e. not taken together with R 14a to form a ring), then each R 14b is independently H, C
  • Embodiment 179 The composition of Embodiment 178 wherein each R 14b is independently H, C4-C4 alkyl, C4-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl, C2-C4 alkoxyalkyl, C2-C4 haloalkoxyalkyl, C2-C4 alkylaminoalkyl or C3-C5 dialkylaminoalkyl.
  • Embodiment 180 The composition of Embodiment 179 wherein each R 14b is independently H, C4-C3 alkyl, C4-C3 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C3-C5 cycloalkyl, C4-C6 cycloalkylalkyl or C2-C4 alkoxyalkyl.
  • Embodiment 181 The composition of Embodiment 180 wherein each R 14b is independently H, C4-C3 alkyl, C4-C3 haloalkyl, cyclopropylmethyl or C2-C4 alkoxyalkyl.
  • Embodiment 181a The composition of Embodiment 181 wherein each R 14b is independently H, C4-C2 alkyl, C4-C2 haloalkyl or cyclopropylmethyl.
  • Embodiment 181b The composition of Embodiment 181a wherein each R 14b is independently H, methyl or cyclopropylmethyl.
  • Embodiment 182 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 181b wherein in Formula 1, when R 14a and R 14b are taken together to form a 4- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
  • Embodiment 183 The composition of Embodiment 182 wherein R 14a and R 14b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
  • Embodiment 184 The composition of Embodiment 183 wherein R 14a and R 14b are taken together to form an azetidinyl or pyrrolidinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl.
  • Embodiment 185 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 184 wherein in Formula 1, each R 15 is independently H, cyano, halogen, methyl or methoxy.
  • Embodiment 186 The composition of Embodiment 185 wherein each R 15 is independently H or methyl.
  • Embodiment 187 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 186 wherein in Formula 1, each R 16 is independently hydroxy, NR 20a R 20b , C4-C2 alkoxy, C2-C4 alkenyloxy, C2-C4 alkylcarbonyloxy or C2-C4 alkoxycarbonyloxy.
  • Embodiment 188 The composition of Embodiment 187 wherein each R 16 is independently hydroxy, NR 20a R 20b or C4-C4 alkoxy.
  • Embodiment 189 The composition of Embodiment 188 wherein each R 16 is independently hydroxy, NR 20a R 20b or methoxy.
  • Embodiment 190 The composition of Embodiment 189 wherein each R 16 is hydroxy.
  • Embodiment 19 E The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 190 wherein in Formula 1, each R 17 is independently H or methyl.
  • Embodiment 192 The composition of Embodiment 191 wherein each R 17 is H.
  • Embodiment 193 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 192 wherein in Formula 1, when each R 18a and R 18b is separate (i.e. not taken together to form a ring), then each R 18a and R 18b is independently H, methyl or ethyl.
  • Embodiment 194 The composition of Embodiment 193 wherein each R 18a and R 18b is independently H or methyl.
  • Embodiment 195 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 194 wherein in Formula 1, when R 18a and R 18b are taken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.
  • Embodiment 196 The composition of Embodiment 195 wherein R 18a and R 18b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl, or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
  • Embodiment 197 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 196 wherein in Formula 1, each R 19 is independently cyano, halogen, hydroxy, C4-C3 alkyl, C
  • Embodiment 198 The composition of Embodiment 197 wherein each R 19 is independently cyano, halogen, hydroxy, C3-C2 alkyl, C3-C2 haloalkyl, C3-C6 cycloalkyl, C3-C2 alkoxy, C3-C2 haloalkoxy, C3-C2 alkylthio, C3-C2 alkylsulfonyl, C3-C2 haloalkylsulfonyl, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl, C2-C3 alkoxycarbonyl or C2-C3 alkylaminocarbonyl.
  • Embodiment 199 The composition of Embodiment 197 wherein each R 19 is independently cyano, halogen, C3-C2 alkyl, C3-C2 haloalkyl, C3-C6 cycloalkyl, C3-C2 alkoxy, C3-C2 haloalkoxy, C2-C3 alkylcarbonyl, C2-C3 haloalkylcarbonyl or C2-C3 alkoxycarbonyl.
  • Embodiment 200 The composition of Embodiment 199 wherein each R 19 is independently cyano, halogen, cyclopropyl, cyclobutyl, methoxy, halomethoxy or methoxycarbonyl.
  • Embodiment 200a The composition of Embodiment 200 wherein each R 19 is independently cyano, halogen, cyclopropyl or methoxy.
  • Embodiment 200b The composition of Embodiment 200a wherein each R 19 is independently cyano, Cl, F, cyclopropyl or methoxy.
  • Embodiment 204 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 203 wherein in Formula 1, each V is independently a direct bond; or C ⁇ -C ⁇ alkylene, C2-C6 alkenylene or CyC ⁇ alkynylene, each optionally substituted with up to 2 substituents independently selected from halogen, cyano, nitro, hydroxy, C3-C2 alkyl, C3-C2 haloalkyl, C3-C2 alkoxy and C3-C2 haloalkoxy.
  • Embodiment 205 The composition of Embodiment 204 wherein each V is independently a direct bond; or C3-C3 alkylene, each optionally substituted with up to 2 substituents independently selected from halogen, hydroxy, C3-C2 alkyl, C3-C2 alkoxy and C 1 -C 2 haloalkoxy.
  • Embodiment 206 The composition of Embodiment 205 wherein each V is independently a direct bond or C 1 -C3 alkylene.
  • Embodiment 207 The composition of Embodiment 206 wherein each V is independently a direct bond or CH 2 .
  • Embodiment 208 The composition of Embodiment 207 wherein each V is a direct bond.
  • Embodiment 209 The composition of Embodiment 207 wherein each V is independently C 1 -C 2 alkylene.
  • Embodiment 210 The composition of Embodiment 209 wherein each V is CH 2 .
  • Embodiment 212 The composition of Embodiment 210 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 ; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl, oxazolyl, isoxazolyl, thienyl, isoxazolinyl, piperidinyl, morpholinyl or piperazinyl, each optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 213 The composition of Embodiment 212 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 ; or pyridinyl, pyrazolyl, imidazolyl, triazolyl, thiazolyl or oxazolyl, each optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 214 The composition of Embodiment 213 wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 ; or pyridinyl or pyrazolyl, each optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 214a The composition of Embodiment 214 wherein each Q is independently phenyl or pyridinyl, each optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 214b The composition of Embodiment 214a wherein each Q is independently phenyl optionally substituted with up to 2 substituents independently selected from R 27 .
  • Embodiment 215. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 214b wherein in Formula 1, when each R 20a j s separate (i.e. not taken together with R 20b to form a ring), then each R 20a j s independently H, methyl or methylcarbonyl.
  • Embodiment 216 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 215 wherein in Formula 1, when each R 20b j s separate (i.e. not taken together with R 20a to form a ring), then each R 20b j s independently H, cyano, methyl, methylcarbonyl, methoxycarbonyl, methoxycarbonylmethyl, methylaminocarbonyl or dimethylaminocarbonyl.
  • Embodiment 217 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 216 wherein in Formula 1, when R 20a an d R 2 0 b arc taken together to form a 5- to 6-membered fully saturated heterocyclic ring, then said ring contains ring members, in addition to the connecting nitrogen atom, selected from carbon atoms and up to 1 heteroatom selected from up to 1 O, up to 1 S and up to 1 N atom, each ring optionally substituted with up to 2 methyl groups.
  • Embodiment 218 The composition of Embodiment 217 wherein R 20a an d R 2 0 b arc taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 methyl groups.
  • Embodiment 219. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 218 wherein in Formula 1, each R 21 and R 23 is independently H, cyano, halogen, methyl or methoxy.
  • Embodiment 220 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 219 wherein in Formula 1, each R 22 is independently H, C 1 -C3 alkyl, C 1 -C3 haloalkyl, C 2 -C3 alkylcarbonyl or C2-C3 alkoxycarbonyl; or phenyl optionally substituted with up to 2 substituents independently selected halogen and methyl; or a 5- to 6-membered fully saturated heterocyclic ring, each ring containing ring members selected from carbon atoms and up to 2 heteroatoms independently selected from up to 2 O, up to 2 S and up to 2 N atoms, each ring optionally substituted with up to 2 substituents independently selected from halogen and methyl.
  • Embodiment 22 The composition of Embodiment 220 wherein each R 22 is independently H or C1-C2 alkyl.
  • Embodiment 222 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 221 wherein in Formula 1, each R 24 is independently H, cyano or Ci-C 2 alkyl.
  • Embodiment 223 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 222 wherein in Formula 1, each R 25 and R 26 is independently H, cyano, hydroxy, C4-C4 alkyl or C r C 4 haloalkyl.
  • Embodiment 224 The composition of Embodiment 223 wherein each R 25 and R 26 is independently H, cyano, hydroxy or C4-C2 alkyl.
  • Embodiment 225 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 224 wherein in Formula 1, each R 27 is independently halogen, cyano, C4-C4 alkyl, C4-C4 haloalkyl or C4-C4 alkoxy.
  • Embodiment 226 The composition of Embodiment 225 wherein each R 27 is independently halogen, cyano, C4-C2 alkyl, C4-C2 haloalkyl or C4-C2 alkoxy.
  • Embodiment 227 The composition of Embodiment 226 wherein each R 27 is independently halogen, methyl or methoxy.
  • Embodiment 228 The composition of Embodiment 227 wherein each R 27 is independently halogen.
  • Embodiment 232 The composition of Embodiment 231 wherein Z is a direct bond.
  • Embodiment 233 The composition of Formula 1 or any one of Embodiments 1 through 232 wherein each R 28 is independently H or C
  • Embodiment 234. The composition of Embodiment 233 wherein each R 28 is independently
  • Embodiment 235 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 234 wherein in Formula 1, m is 0 or 2.
  • Embodiment 236 The composition of Embodiment 235 wherein m is 2.
  • Embodiment 237 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 236 wherein component (a) does not comprise an /V-oxide of a compound of Formula 1.
  • component (a) comprises a compound selected from the group consisting of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenyl]methyl]-l//-pyrazole-4-carboxylate (Compound 1); ethyl 1 - [ [4- [ [2-(trifluoro methyl)- 1 ,3 -dioxolan-2-yl] methoxy ]phenyl] methyl] - 1 /7-pyrazolc-4- carboxylate (Compound 32); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen- l-yl]oxy]phenyl]methyl]- l//-pyrazole-4- carboxylate (Compound 64); ethyl l-[[4-[[( lZ)-2-ethoxy-3, 3, 3-trifluoro-l -propen-
  • Embodiment 239. The composition of Embodiment 238 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127, 132, 162, 163, 171, 186, 218, 229, 263, 297, 330 and 331.
  • Embodiment 240 The composition of Embodiment 239 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 71, 126, 127,
  • Embodiment 241 The composition of Embodiment 240 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 127, 132, 162, 163, 171 and 263.
  • Embodiment 242. The composition of Embodiment 241 wherein component (a) comprises a compound selected from the group consisting of Compounds 32, 64, 126, 132, 163 and 263.
  • Embodiment 243 The composition of Embodiment 242 wherein component (a) comprises a compound selected from the group consisting of Compounds 32 and 64.
  • Embodiment 243a The composition of Embodiment 243 wherein component (a) is Compound 32.
  • Embodiment 243b The composition of Embodiment 243 wherein component (a) is Compound 64.
  • Embodiment 244 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2- yljmcthoxy] phenyl] methyl]- 1 //-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
  • Embodiment 245. The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 246 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l-yl]oxy]-3- fluorophcnyljmcthylj-l /7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
  • Embodiment 247 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[3-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 248 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnoxy] methyl]- 1 /7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
  • composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[2-[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljcthylj-l /7-pyrazolc-4-carboxylatc, its (£)-isomer or a mixture thereof.
  • Embodiment 250 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is phenylmethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 251 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is butyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 252 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is 3-chloropropyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnyljmcthylj-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 253 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is ethyl l-[[4-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yljoxyjphcnylmcthoxy] methyl]- 1 /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 254 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is methyl l-[[3-[[(lZ)-2-ethoxy-3,3,3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 255 The composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 243 wherein component (a) is propyl l-[[3-[[(lZ)-2 -ethoxy-3, 3, 3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 256 is propyl l-[[3-[[(lZ)-2 -ethoxy-3, 3, 3-trifluoro-l-propen-l- yl]oxy]phcnyl]mcthyl]-l /7-pyrazolc-4-carboxylatc, its ( ⁇ -isomer or a mixture thereof.
  • Embodiment 256 Embodiment 256.
  • Embodiment 257 The composition of Embodiments 238 through 256 wherein wherin component (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin, or trifloxystrobin.
  • Embodiment 258 The composition of Embodiment 257 wherein (b) comprises at least two fungicidal compounds, and when component (b) consists of a binary combination of two fungicidal compounds, wherein one of the fungicidal compounds is cyproconazole, difenconazole, epoxiconazole, flutriafol, prothioconazole or tebuconazole then the other fungicidal compound is other than azoxystrobin, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, isopyrazam, picoxystrobin, pyraclostrobin or trifloxystrobin.
  • Embodiments of this invention can be combined in any manner, and the descriptions of variables in the embodiments not only to the compositions comprising compounds of Formula 1 with at least one other fungicidal compound but also to compositions comprising compounds of Formula 1 with at least one invertebrate pest control compound or agent, and also to the compounds of Formula 1 and their compositions, and also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • embodiments of this invention including Embodiments 1-258 above as well as any other embodiments described herein, and any combination thereof, pertain to the methods of the present invention.
  • composition disclosed above comprising (a) at least one compound selected from the compounds of Formula 1 described above, /V-oxides, and salts thereof; and at least one invertebrate pest control compound or agent.
  • Combinations of Embodiments 1-258 are illustrated by:
  • Embodiment A The composition comprising components (a) and (b) described Summary of the
  • component (a) comprises a compound of Formula 1 or salt thereof, wherein in Formula 1,
  • R 1 is CF 3 , CC1 3 or CF 2 C1;
  • W is O
  • R 5a and R 5b are each independently H, hydroxy or methyl
  • R 2a and R 2b are each independently H or methyl
  • R 2C is C
  • R 2d is H or methyl
  • a 1 is CR 6c R 6d or O;
  • a 2 is a direct bond, CR 6e R 6f or O;
  • R 6a , R 6b , R 6c , R 6d , R 6e and R 6f are each independently H, cyano, hydroxy, Br, Cl, F or methyl;
  • J is J-l, J-6 or J- 14; each R 8 is independently F, Cl or methyl; each R 9a and R 9b is independently H, halogen or methyl; n is 0, 1 or 2;
  • E 1 is C ⁇ -C ⁇ alkoxy, C ⁇ -C ⁇ alkylsulfonyl, C 2 -C6 alkylcarbonyl or C 2 -C6 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a and up to 3 substituents independently selected from R 10b ;
  • G is selected from the group consisting of:
  • each R 14a is independently H, C [ -C 2 alkyl, C 2 -C4 alkenyl, C 2 -C4 alkynyl, C 2 -C4 alkylcarbonyl or C 2 -
  • R 14a and R 14b are taken together to form an azetidinyl, morpholinyl, pyrrolidinyl, piperidinyl, piperazinyl or thiomorpholinyl ring, each ring optionally substituted with up to 2 substituents independently selected from halogen or methyl; each R 19 is independently cyano, halogen, C [ -C 2 alkyl, C [ -C 2 haloalkyl, C3-C6 cycloalkyl, C [ -C 2 alkoxy, C
  • Embodiment AA The composition of Embodiment A wherein in Formula 1,
  • R 1 is CF 3 ;
  • X is O
  • Y is O
  • L is a direct bond or CH 2 ; and Z is a direct bond.
  • Embodiment AAA The composition of Embodiment A wherein in Formula 1,
  • R 1 is CF 3 ;
  • Z is a direct bond
  • Embodiment B The composition of Embodiment A wherein in Formula 1,
  • T is T-2 or T-3;
  • R 1 is CF 3 ;
  • X is O
  • Y is O
  • R 2a and R 2b are each independently H or methyl
  • R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms, the ring optionally substituted with up to 1 substituent selected from halogen, methyl and halomethyl on a carbon atom ring member;
  • R 2C is methyl or ethyl
  • R 2d is H
  • a 1 is O
  • a 2 is a direct bond or CH 2 ;
  • R 6a and R 6b are each independently H, cyano hydroxy or methyl
  • J is J-l or J-6; q is 0 or 1 ; each R 9a and R 9b is independently H or methyl;
  • E 1 is C
  • RlOa j s pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R l la on carbon atom ring members; each R 10b is independently halogen, C1-C2 alkyl, C1-C2 haloalkyl, C1-C2 alkoxy or C2-C4 alkoxycarbonyl;
  • Embodiment BB The composition of Embodiment B wherein in Formula 1,
  • L is a direct bond or CH2
  • G is G-l or G-12; and Z is a direct bond.
  • Embodiment BBB The composition of Embodiment B wherein in Formula 1,
  • Z is a direct bond
  • Embodiment C The composition of Embodiment B wherein in Formula 1,
  • R 2a and R 2b are each H; or
  • R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms;
  • a 2 is a direct bond;
  • R 6a and R 6b are each H;
  • R 8 is F or Cl
  • L is a direct bond, ⁇ 3 ⁇ 4 or CEECEE ;
  • E 1 is C r C 2 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a ;
  • R l ° a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members; each R l la is independently methoxycarbonyl or ethoxycarbonyl;
  • G is G-l and the 2-position of G-l is connected to Z and the 4-position is connected to R 13 ; or G is G-12 and the 1 -position of G-12 is connected to Z and the 4-position is connected to R 13 ; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R 13 ; x is 1;
  • R 14a is H
  • R 14b is H, methyl or cyclopropylmethyl
  • R 19 is cyano, halogen, cyclopropyl or methoxy
  • V is CH 2 ;
  • Q is phenyl optionally substituted with up to 2 substituents independently selected from R 27 ;
  • Embodiment CC The composition of Embodiment C wherein in Formula 1,
  • L is a direct bond or CH2
  • Z is a direct bond
  • Embodiment D The composition of Embodiment C wherein in Formula 1,
  • R 8 is F
  • L is a direct bond or CH2
  • E 1 is methoxy substituted with 1 substituent selected from R 10a ;
  • R l ° a is pyrazolyl optionally substituted with up to 1 substituent selected from R lla on a carbon atom ring member;
  • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R 13 ; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R 13 ; and
  • R 13 is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from Rl9;
  • R 19 is cyano, Cl, F, cyclopropyl or methoxy; and Z is a direct bond.
  • Embodiment DD The composition of Embodiment D wherein in Formula 1,
  • L is a direct bond or CH2, provided that when L is a direct bond, then E is E 1 , and when L is CH2, then E is E 2 .
  • Embodiment E The composition of Embodiment D wherein in Formula 1,
  • L is CH 2 ;
  • E is E 2 ;
  • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R 13 ;
  • R 13 is methoxycarbonyl or ethoxycarbonyl.
  • Embodiment EE The composition of Embodiment E wherein in Formula 1,
  • R 2a and R 2b are taken together with the atoms X and Y to which they are attached to form a 5-membered saturated ring containing ring members, in addition to the atoms X and Y, selected from carbon atoms.
  • Embodiment F The composition of any one of Embodiments A through EE wherein in Formula 1,
  • T T-2;
  • R 13 is ethoxycarbonyl
  • Embodiment G The composition of any one of Embodiments A through E wherein in Formula
  • T T-3;
  • R 13 is ethoxycarbonyl
  • Embodiment H The composition any one of Embodiments A through G wherein component (a) comprises a compound selected from the group consisting of: Compound 1, Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 221, Compound 229, Compound 231, Compound 262, Compound 263, Compound 265, Compound 297, Compound 330, Compound 331 and Compound 364.
  • component (a) comprises a compound selected from the group consisting of: Compound 1, Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 221, Compound 229, Compound 231, Compound 262, Compound 263, Compound 265, Compound 297, Compound 330, Compound 331 and Compound 364.
  • Embodiment I The composition of Embodiment H wherein component (a) comprises a compound selected from the group consisting of: Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 229, Compound 263, Compound 297, Compound 330 and Compound 331.
  • component (a) comprises a compound selected from the group consisting of: Compound 32, Compound 64, Compound 71, Compound 126, Compound 127, Compound 132, Compound 162, Compound 163, Compound 171, Compound 186, Compound 218, Compound 229, Compound 263, Compound 297, Compound 330 and Compound 331.
  • Embodiment J The composition of Embodiment I wherein component (a) comprises a Compound 32.
  • Embodiment K The composition of Embodiment I wherein component (a) comprises Compound 64.
  • Embodiment Bl The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl) methyl benzimidazole carbamate fungicides such as benomyl, carbendazim, fuberidazole thiabendazole, thiophanate and thiophanate-methyl.
  • component (b) includes at least one compound selected from (bl) methyl benzimidazole carbamate fungicides such as benomyl, carbendazim, fuberidazole thiabendazole, thiophanate and thiophanate-methyl.
  • Embodiment B2 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b2) dicarboximide fungicides such as chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
  • component (b) includes at least one compound selected from (b2) dicarboximide fungicides such as chlozolinate, dimethachlone, iprodione, procymidone and vinclozolin.
  • Embodiment B3 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b3) demethylation inhibitor fungicides such as triforine, buthiobate, pyrifenox, pyrisoxazole fenarimol, nuarimol, triarimol econazole, imazalil, oxpoconazole, pefurazoate, prochloraz, triflumizoleazaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole (including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazo
  • Embodiment B4 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b4) phenylamide fungicides such as metalaxyl, metalaxyl-M, benalaxyl, benalaxyl-M, furalaxyl, ofurace and oxadixyl.
  • phenylamide fungicides such as metalaxyl, metalaxyl-M, benalaxyl, benalaxyl-M, furalaxyl, ofurace and oxadixyl.
  • Embodiment B5. The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b5) amine/morpholine fungicides such as aldimorph, dodemorph, fenpropimorph, tridemorph, trimorphamide, fenpropidin, piperalin and spiroxamine.
  • component (b) includes at least one compound selected from (b5) amine/morpholine fungicides such as aldimorph, dodemorph, fenpropimorph, tridemorph, trimorphamide, fenpropidin, piperalin and spiroxamine.
  • Embodiment B6 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, iprobenfos, pyrazophos and isoprothiolane.
  • component (b) includes at least one compound selected from (b6) phospholipid biosynthesis inhibitor fungicides such as edifenphos, iprobenfos, pyrazophos and isoprothiolane.
  • Embodiment B7 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b7) succinate dehydrogenase inhibitor fungicides such as benodanil, flutolanil, mepronil, isofetamid, fluopyram, fenfuram, carboxin, oxycarboxin thifluzamide, benzovindiflupyr, bixafen, fluindapyr, fluxapyroxad, furametpyr, inpyrfluxam, isopyrazam, penflufen, penthiopyrad, pyrapropoyne, sedaxane, flubeneteram, isoflucypram, pydiflumetofen, boscalid and pyraziflumid.
  • succinate dehydrogenase inhibitor fungicides such as benodanil, flutolanil, me
  • Embodiment B8 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b8) hydroxy(2- amino-)pyrimidine fungicides such as bupirimate, dimethirimol and ethirimol.
  • Embodiment B9 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b9) anilinopyrimidine fungicides such as cyprodinil, mepanipyrim and pyrimethanil.
  • component (b) includes at least one compound selected from (b9) anilinopyrimidine fungicides such as cyprodinil, mepanipyrim and pyrimethanil.
  • Embodiment B10 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (blO) /V-phenyl carbamate fungicides such as diethofencarb.
  • Embodiment B 11 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl 1) fungicides quinone outside inhibitor fungicides such as azoxystrobin, coumoxystrobin, enoxastrobin, flufenoxystrobin, picoxystrobin, pyraoxystrobin, mandestrobin, pyraclostrobin, pyrametostrobin, triclopyricarb, kresoxim-methyl, trifloxystrobin, dimoxystrobin, fenaminstrobin, metominostrobin, orysastrobin, fluoxastrobin, famoxadone, fenamidone and pyribencarb.
  • fungicides quinone outside inhibitor fungicides such as azoxystrobin, coumoxystrobin, enoxastrobin, flufen
  • Embodiment B12 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl2) phenylpyrrole fungicides compound such as fenpiclonil and fludioxonil.
  • Embodiment B13 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl3) azanaphthalene fungicides such as quinoxyfen and proquinazid.
  • component (b) includes at least one compound selected from (bl3) azanaphthalene fungicides such as quinoxyfen and proquinazid.
  • Embodiment B14 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl4) cell peroxidation inhibitor fungicides such as biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl and etridiazole.
  • cell peroxidation inhibitor fungicides such as biphenyl, chloroneb, dicloran, quintozene, tecnazene, tolclofos-methyl and etridiazole.
  • Embodiment B15 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl5) melanin biosynthesis inhibitors -reductase fungicides such as fthalide, pyroquilon and tricyclazole.
  • component (b) includes at least one compound selected from (bl5) melanin biosynthesis inhibitors -reductase fungicides such as fthalide, pyroquilon and tricyclazole.
  • Embodiment B16a The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl6a) melanin biosynthesis inhibitors-dehydratase fungicides such as carpropamid, diclocymet, and fenoxanil.
  • component (b) includes at least one compound selected from (bl6a) melanin biosynthesis inhibitors-dehydratase fungicides such as carpropamid, diclocymet, and fenoxanil.
  • Embodiment B16b The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl6b) melanin biosynthesis inhibitor-polyketide synthase fungicides such as tolprocarb.
  • Embodiment B17 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl7) keto reductase inhibitor fungicides such as fenhexamid, fenpyrazamine, quinofumelin and ipflufenoquin.
  • component (b) includes at least one compound selected from (bl7) keto reductase inhibitor fungicides such as fenhexamid, fenpyrazamine, quinofumelin and ipflufenoquin.
  • Embodiment B18 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl8) squalene- epoxidase inhibitor fungicides such as pyributicarb, naftifine and terbinafine.
  • component (b) includes at least one compound selected from (bl8) squalene- epoxidase inhibitor fungicides such as pyributicarb, naftifine and terbinafine.
  • Embodiment B19 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (bl9) polyoxin fungicides such as polyoxin.
  • Embodiment B20 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 243 and A through K) wherein component (b) includes at least one compound selected from (b20) phenylurea fungicides such as pencycuron.
  • Embodiment B21 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b21) quinone inside inhibitor fungicides such as cyazofamid, amisulbrom and fenpicoxamid (Registry Number 517875-34-2).
  • component (b) includes at least one compound selected from (b21) quinone inside inhibitor fungicides such as cyazofamid, amisulbrom and fenpicoxamid (Registry Number 517875-34-2).
  • Embodiment B22 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b22) benzamide and thiazole carboxamide fungicides such as zoxamide and ethaboxam.
  • Embodiment B23 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b23) enopyranuronic acid antibiotic fungicides such as blasticidin-S.
  • Embodiment B24 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b24) hexopyranosyl antibiotic fungicides such as kasugamycin.
  • Embodiment B25 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b25) glucopyranosyl antibiotic: protein synthesis fungicides such as streptomycin.
  • Embodiment B26 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b26) glucopyranosyl antibiotic: trehalase and inositol biosynthesis fungicides such as validamycin.
  • Embodiment B27 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b27) cyanoacetylamideoxime fungicides such as cymoxanil.
  • Embodiment B28 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b28) carbamate fungicides such as propamacarb, prothiocarb and iodocarb.
  • component (b) includes at least one compound selected from (b28) carbamate fungicides such as propamacarb, prothiocarb and iodocarb.
  • Embodiment B29 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b29) oxidative phosphorylation uncoupling fungicides such as fluazinam, binapacryl, meptyldinocap and dinocap.
  • component (b) includes at least one compound selected from (b29) oxidative phosphorylation uncoupling fungicides such as fluazinam, binapacryl, meptyldinocap and dinocap.
  • Embodiment B30 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b30) organo tin fungicides such as fentin acetate, fentin chloride and fentin hydroxide.
  • organo tin fungicides such as fentin acetate, fentin chloride and fentin hydroxide.
  • Embodiment B31 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b31) carboxylic acid fungicides such as oxolinic acid.
  • Embodiment B32 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b32) heteroaromatic fungicides such as hymexazole and octhilinone.
  • component (b) includes at least one compound selected from (b32) heteroaromatic fungicides such as hymexazole and octhilinone.
  • Embodiment B33 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b33) phosphonate fungicides such as phosphorous acid and its various salts, including fosetyl-aluminum.
  • Embodiment B34 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b34) phthalamic acid fungicides such as teclofthalam.
  • Embodiment B35 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b35) benzotriazine fungicides such as triazoxide.
  • Embodiment B36 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b36) benzene- sulfonamide fungicides such as flusulfamide.
  • Embodiment B37 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b37) pyridazinone fungicides such as diclomezine.
  • Embodiment B38 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b38) thiophene- carboxamide fungicides such as silthiofam.
  • Embodiment B39 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b39) complex I NADH oxidoreductase inhibitor fungicides such as diflumetorim, tolfenpyrad and fenazaquin.
  • component (b) includes at least one compound selected from (b39) complex I NADH oxidoreductase inhibitor fungicides such as diflumetorim, tolfenpyrad and fenazaquin.
  • Embodiment B40 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b40) carboxylic acid amide fungicides such as dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate, mandipropamid, flumorph, dimethomorph, flumorph, pyrimorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, tolprocarb, valifenalate and mandipropamid.
  • carboxylic acid amide fungicides such as dimethomorph, benthiavalicarb, benthiavalicarb-isopropyl, iprovalicarb, valifenalate, mandipropamid.
  • Embodiment B41 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b41) tetracycline antibiotic fungicides such as oxy tetracycline.
  • Embodiment B42 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b42) thiocarbamate fungicides such as methasulfocarb.
  • Embodiment B43 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b43) benzamide fungicides such as fluopicolide and fluopimomide.
  • component (b) includes at least one compound selected from (b43) benzamide fungicides such as fluopicolide and fluopimomide.
  • Embodiment B44 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b44) microbial fungicides such as Bacillus amyloliquefaciens strains QST713, FZB24, MB 1600, D747, F727, TJ100 (also called strain 1 BE; known from EP2962568) and the fungicidal lipopeptides which they produce.
  • microbial fungicides such as Bacillus amyloliquefaciens strains QST713, FZB24, MB 1600, D747, F727, TJ100 (also called strain 1 BE; known from EP2962568) and the fungicidal lipopeptides which they produce.
  • Embodiment B45 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b45) quinone outside inhibitor, stigmatellin binding fungicides such as ametoctradin.
  • Embodiment B46 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b46) plant extract fungicides such as Melaleuca alternifolia, eugenol, geraniol and thymol.
  • component (b) includes at least one compound selected from (b46) plant extract fungicides such as Melaleuca alternifolia, eugenol, geraniol and thymol.
  • Embodiment B47 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b47) cyanoacrylate fungicides such as phenamacril.
  • Embodiment B48 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b48) polyene fungicides such as natamycin.
  • Embodiment B49 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b49) oxysterol binding protein inhibitor fungicides such as oxathiapiprolin and fluoxapiprolin.
  • component (b) includes at least one compound selected from (b49) oxysterol binding protein inhibitor fungicides such as oxathiapiprolin and fluoxapiprolin.
  • Embodiment B50 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b50) aryl-phenyl- ketone fungicides such as metrafenone and pyriofenone.
  • Embodiment B5E The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b51) host plant defense induction fungicides such as acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, extract from Reynoutria sachalinensis and Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS 117.
  • host plant defense induction fungicides such as acibenzolar-S-methyl, probenazole, tiadinil, isotianil, laminarin, extract from Reynoutria sachalinensis and Bacillus mycoides isolate J and cell walls of Saccharomyces cerevisiae strain LAS 117.
  • Embodiment B52 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b52) multi-site activity fungicides such as copper oxychloride, copper sulfate, copper hydroxide, Bordeaux composition (tribasic copper sulfide), elemental sulfur, ferbam, mancozeb, maneb, metiram, propineb, thiram, zinc thiazole, zineb, ziram, folpet, captan, captafol, chlorothalonil, dichlofluanid, tolyfluanid, guazatine, iminoctadine albesilate, iminoctadine triacetate, anilazine, dithianon, quinomethionate and fluoroimide.
  • multi-site activity fungicides such as copper oxychloride, copper sulfate
  • Embodiment B53 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b53) biological fungicides with multiple modes of action such as extract from the cotyledons of lupine plantlets.
  • Embodiment B54 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54) fungicides other than fungicides of component (a) and components (bl) through (b53), such as cyflufenamid, bethoxazin, neo-asozin, pyrrolnitrin, tebufloquin, dodine, flutianil, ferimzone, picarbutrazox, dichlobentiazox (Registry Number 957144-77-3), dipymetitrone (Registry Number 16114-35-5), flometoquin, tolnifanide (Registry Number 304911-98-6), /V-[4-[4- chloiO-3-(trinuoromcthyl)phcnoxyJ-2,5-dimcthylphc
  • Embodiment B55 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (lS)-2,2-bis(4-fluorophenyl)-l-methylethyl /V-[[3- (acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]-L-alaninate (provisional common name flory lpicoxamid) .
  • Embodiment B56 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes l-[2-[[[l-(4-chlorophenyl)-l -pyrazol-3-yl]oxy]methyl]- 3-mcthylphcnyl]-l ,4-dihydro-4-mcthyl-5/7-tctra/ol-5-onc (provisional common name mety ltetraprole) .
  • Embodiment B57 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes 3-chloro-4-(2,6-difluorophenyl)-6-methyl-5- phenylpyridazine (provisional common name pyridachlometyl).
  • Embodiment B58 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes (4-phenoxyphenyl)methyl 2-amino-6-methyl-pyridine-3- carboxylate (provisional common name aminopyrifen).
  • Embodiment B59 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.11) (i.e Formula b54.11) wherein
  • R bl ° and R bl 1 are each independently halogen
  • R 6 is H, halogen, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl or Cg-Cg cycloalkyl.
  • Embodiment B60 The composition of Embodiment B59 wherein component (b) includes at least one fungicidal compound selected from the group consisting of methyl A- [[5- [1 -(2,6- difluoro-4-formylphenyl)-l//-pyrazol-3-yl]-2-methylphenyl] methyl]carbamate, methyl N- [[5-[l-(4-cyclopropyl-2,6-dichlorophenyl)-l -pyrazol-3-yl]-2-methylphenyl]methyl]- carbamate, methyl A/-[[5-[l-(4-chloro-2,6-difluorophenyl)-l -pyrazol-3-yl]-2-methyl- phenyl]methyl]carbamate, methyl A/-[[5-[l-(4-cyclopropyl-2,6-difluorophenyl)-l -pyrazol- 3-yl]
  • Embodiment B61 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.12) (i.e Formula b54.12) b54.12 wherein R b4 is R b6 is C2-C4 alkoxycarbonyl or C2-C4 haloalkylaminocarbonyl;
  • L is CH2 or CH2O, wherein the atom to the right is connected to the phenyl ring in Formula b54.12;
  • R b5 is
  • Embodiment B62 The composition of Embodiment B61 wherein component (b) includes at least one fungicidal compound selected from the group consisting of N-( 2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide and ethyl l-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenoxy] methyl]- l /-pyrazole-4-carboxylate.
  • component (b) includes at least one fungicidal compound selected from the group consisting of N-( 2,2,2- trifluoroethyl)-2-[[4-[5-(trifluoromethyl)-l,2,4-oxadiazol-3-yl]phenyl]methyl]-4- oxazolecarboxamide and ethyl l-
  • Embodiment B63 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one compound selected from (b54.13) (i.e Formula b54.13) wherein
  • R b7 , R b8 and R b9 are each independently H, halogen or cyano; and R bl ° and R bl 1 are each independently H, halogen, C [ -C3 alkyl or C [ -C3 methoxy Embodiment B64.
  • component (b) includes at least one fungicidal compound selected from the group consisting of 4-(2-chloro-4- fl uo ro p h c n y 1 ) - A- (2 - fl u o ro - 4 - in c t h y 1 - 6 - n i t ro p h c n y 1 ) - 1 ,3-dimethyl- l /-pyrazol-5-amine, 4-(2- chloro-4-fluorophenyl)- V-(2-fluoro-6-nitrophenyl)-l, 3-dimethyl- l /-pyrazol-5-amine, 3,5- difluoro-4-[5-[(4-methoxy-2-nitrophenyl)amino]- 1,3-dimethyl- l -pyrazol-4-yl]- benzonitrile and A-(2-chloro-4- fl uo
  • Embodiment B65 The composition described in the Summary of the Invention (including but not limited to the composition of any one of Embodiments 1 through 258 and A through K) wherein component (b) includes at least one fungicidal compound (fungicide) selected from the group consisting of azoxystrobin, benzovindiflupyr, boscalid (nicobifen), bixafen, bromuconazole, carbendazim, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenbuconazole, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, hexaconazole, ipconazole kresoxim-methyl, manzate, metconazole, metomin
  • Embodiment B66 The composition of Embodiment B65 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyflufenamid, cyproconazole, difenoconazole, dimoxystrobin, epoxiconazole, famoxadone, fenpropidin, fenpropimorph, fluindapyr, flusilazole, flutriafol, fluxapyroxad, kresoxim-methyl, manzate, metconazole, metominostrobin, metrafenone, myclobutanil, penthiopyrad, picoxystrobin, propiconazole, proquinazid, prothioconazole, pydiflumetofen, pyraclostrobin, pyrametostrobin, pyraoxystrobin,
  • Embodiment B67 The composition of Embodiment B66 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, difenoconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin, methyl /V-[[5-[l-[2,6-difluoro-4-(l-methylethyl)phenyl]-l//- pyrazol-3 -yl] -2-methylphenyl]methyl] carbamate, methyl N- [ [5- [
  • Embodiment B68 The composition of Embodiment B67 wherein component (b) includes at least one compound selected from the group consisting of azoxystrobin, benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide, cyproconazole, epoxiconazole, fenpropidin, fenpropimorph, fluindapyr, flutriafol, fluxapyroxad, manzate, metominostrobin, picoxystrobin, prothioconazole, pydiflumetofen, pyraclostrobin, tebuconazole, trifloxystrobin.
  • azoxystrobin benzovindiflupyr, bixafen, chlorothalonil, copper hydroxide
  • cyproconazole epoxiconazole
  • fenpropidin fenpropimorph
  • fluindapyr flutriafol
  • fluxapyroxad man
  • component (a) comprises a compound of Formula 1 or a salt thereof.
  • compositions of the present invention comprising a fungicidally effective amount of a composition of Embodiments 1 through 258, A through K, and B1 through B68, and at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Embodiments of the invention further include methods for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition any one of Embodiments 1 through 258, A through K, and B1 through B68 (e.g., as a composition including formulation ingredients as described herein).
  • Embodiments of the invention also include methods for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of a composition of any one of Embodiments 1 through 258, A through K, and B 1 through B68 to the plant or plant seed.
  • Some embodiments of the invention involve control of a plant disease or protection from a plant disease that primarily afflicts plant foliage and/or applying the composition of the invention to plant foliage (i.e. plants instead of seeds).
  • the preferred methods of use include those involving the above preferred compositions; and the diseases controlled with particular effectiveness include plant diseases caused by fungal plant pathogens.
  • Combinations of fungicides used in accordance with this invention can facilitate disease control and retard resistance development.
  • Embodiment Cl A method for protecting a plant from a disease selected from rust, powdery mildew and Septoria diseases comprising applying to the plant a fungicidally effective amount of the composition comprising components (a) and (b) described in the Summary of the Invention or any one of Embodiments 1 through 258.
  • Embodiment C2 The method of Embodiment Cl wherein the disease is a rust disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b5) amine/morpholine fungicides, (b7) succinate dehydrogenase inhibitor fungicides, (b 11) quinone outside inhibitor (Qol) fungicides, (bl3) methyl benzimidazole carbamate fungicides and (b52) multi-site activity fungicides.
  • DMI demethylation inhibitor
  • b5 amine/morpholine fungicides
  • succinate dehydrogenase inhibitor fungicides succinate dehydrogenase inhibitor fungicides
  • Qol quinone outside inhibitor
  • bl3 methyl benzimidazole carbamate fungicides
  • multi-site activity fungicides multi-site activity fungicides.
  • Embodiment C3 The method of Embodiment C2 wherein component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (b7) succinate dehydrogenase inhibitor fungicides and (b 11 ) quinone outside inhibitor (Qol) fungicides.
  • DMI demethylation inhibitor
  • Qol quinone outside inhibitor
  • Embodiment C4 The method of Embodiment C3 wherein component (b) of the composition includes at least one fungicidal compound selected from the group consisting of azoxystrobin, cyproconazole, difenoconazole, epoxiconazole, fluindapyr, flutriafol, fluxapyroxad, picoxystrobin, prothioconazole, pyraclostrobin, tebuconazole and trifloxystrobin.
  • Embodiment C5 The method of Embodiments C2 through C4 wherein the disease is Asian soybean rust caused by Puccinia recondite.
  • Embodiment C6 The method of Embodiments C2 through C4 wherein the disease is wheat leaf rust caused by Phakopsora pachyrhizi.
  • Embodiment C7 The method of Embodiment Cl wherein the disease is a powdery mildew disease and component (b) of the composition includes at least one fungicidal compound selected from (b3) demethylation inhibitor (DMI) fungicides, (bl 1) quinine outside inhibitor (Qol) fungicides and (bl3) azanaphthalene fungicides.
  • DMI demethylation inhibitor
  • Qol quinine outside inhibitor
  • bl3 azanaphthalene fungicides.
  • Embodiment C8 The method of Embodiment C7 wherein the disease is wheat powdery mildew.
  • Embodiment C9 The method of Embodiment C7 wherein the disease is grape downy mildew.
  • Embodiment CIO The method of Embodiments C7 through C9 wherein component (b) includes at least one fungicidal compound selected from (b3) DMI fungicides.
  • Embodiment Cl 1. The method of Embodiment CIO wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole, epoxiconazole, prothioconazole and tebuconazole.
  • Embodiment C12 The method of Embodiment C 11 wherein component (b) includes at least one fungicidal compound selected from the group consisting of cyproconazole, difenoconazole and prothioconazole.
  • Embodiment C13 The method of Embodiments C8 through CIO wherein component (b) includes at least one fungicidal compound selected from (bl 1) Qol fungicides.
  • Embodiment C14 The method of Embodiment C 12 wherein component (b) includes at least one fungicidal compound selected from the group consisting of azoxystrobin, picoxystrobin and pyraclostrobin.
  • Embodiment C15 The method of Embodiment Cl wherein the disease is a Septoria disease and component (b) of the composition includes at least one fungicidal compound selected from the group consisting of epoxiconazole, metalaxyl (including metalaxyl-M), iprovalicarb and fenpropimorph.
  • fungicidal compound selected from the group consisting of epoxiconazole, metalaxyl (including metalaxyl-M), iprovalicarb and fenpropimorph.
  • Embodiment Cl 6 The method of Embodiment C 15 wherein the disease is wheat leaf blotch.
  • Embodiment C17 The method of any one of Embodiments Cl through C16 wherein components (a) and (b) are applied in synergistically effective amounts (and in a synergistic ratio relative to each other).
  • Embodiments Cl through C17 relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a fungicidal composition of the invention.
  • this invention also relates to a compound of Formula 1, or an A-oxidc or salt thereof. Also noted is that the embodiments of this invention, including Embodiments 1-258, relate also to compounds of Formula 1. Accordingly, combinations of Embodiments 1-258 are further illustrated by:
  • Embodiment Dl A compound of Formula 1, or an A-oxidc or salt thereof, wherein
  • T T-2;
  • R 1 is CF 3 ;
  • R 2a is H or methyl
  • R 2b is C3-C15 trialkylsilyl or C3-C35 halotrialkylsilyl
  • a 1 is O
  • a 2 is a direct bond or CH2;
  • R 6a and R 6b are each independently H, cyano hydroxy or methyl
  • J is J-l or J-6; q is 0 or 1 ;
  • L is a direct bond or CH2
  • E is E 1 or E 2 ;
  • E 1 is C3-C3 alkoxy, C2-C3 alkylcarbonyl or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a and up to 3 substituents independently selected from R 10b ;
  • Rl° a is pyrazolyl, imidazolyl or triazolyl, each optionally substituted with up to 2 substituents independently selected from R l la on carbon atom ring members; each R 10b is independently halogen, C3-C2 alkyl, C3-C2 haloalkyl, C3-C2 alkoxy or C2-C4 alkoxycarbonyl; each R l la is independently methoxycarbonyl or ethoxycarbonyl;
  • R 2a is H or methyl
  • R 2b is trimethylsilyl or halotrimethylsilyl
  • a 2 is a direct bond
  • R 6a and R 6b are each H;
  • R 8 is F or Cl
  • E 1 is C r C 2 alkoxy or C2-C3 alkoxycarbonyl, wherein each carbon atom is optionally substituted with up to 1 substituent selected from R 10a ;
  • R l ° a is pyrazolyl or imidazolyl, each optionally substituted with up to 2 substituents independently selected from R lla on carbon atom ring members; each R l la is independently methoxycarbonyl or ethoxycarbonyl;
  • G is G-l and the 2-position of G-l is connected to Z and the 4-position is connected to R 13 ; or G is G-12 and the 1 -position of G-12 is connected to Z and the 4-position is connected to R 13 ; or G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R 13 ; x is 1;
  • R 14a is H
  • R 14b is H, methyl or cyclopropylmethyl
  • R 19 is cyano, halogen, cyclopropyl or methoxy
  • V is CH 2 ;
  • Q is phenyl optionally substituted with up to 2 substituents independently selected from R 27 ;
  • Embodiment D3 A compound of Embodiment D2 wherein
  • R 2a is H or methyl
  • R 2b is trimethylsilyl
  • R 8 is F
  • E 1 is methoxy substituted with 1 substituent selected from R 10a ;
  • R l ° a is pyrazolyl optionally substituted with up to 1 substituent selected from R lla on a carbon atom ring member;
  • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R 13 ; or
  • G is G-12 and the 1-position of G-12 is connected to Z and the 3-position is connected to R 13 ;
  • R 13 is C2-C5 alkoxycarbonyl optionally substituted with up to 1 substituent selected from Rl9;
  • R 19 is cyano, Cl, F, cyclopropyl or methoxy
  • Z is a direct bond
  • Embodiment D3 A compound of Embodiment D3 wherein
  • R 2a is methyl
  • L is CH 2 ;
  • E is E 2 ;
  • G is G-12 and the 1-position of G-12 is connected to Z and the 4-position is connected to R 13 ;
  • R 13 is methoxycarbonyl or ethoxycarbonyl.
  • Additional embodiments include a fungicidal composition comprising: (1) a compound of any one of Embodiments D1 through D3; and (2) at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents. Additional embodiments also include a method for protecting a plant or plant seed from diseases caused by fungal pathogens comprising applying a fungicidally effective amount of the compound of any one of Embodiments D1 through D3 to the plant (or portion thereof) or plant seed (directly or through the environment (e.g., growing medium) of the plant or plant seed). Of note are embodiments relating to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, a fungicidally effective amount of a compound of any one of Embodiments D1 through D3.
  • This invention also provides a fungicidal composition
  • a fungicidal composition comprising a compound of Formula 1 (including all stereoisomers, /V-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, /V-oxides, and salts thereof
  • additional component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Compounds of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein R 1 is CF3 can be prepared by trifluoroacetylation of organometallic compounds of Formula 2.
  • the ethyl ester of trifluoroacetic acid i.e. ethyl trifluoroacetate
  • trifluoroacetonitrile and various trifluoroacetate salts can also be used.
  • double-addition on the trifluoroacetyl compound can occur.
  • M is, wherein R 1 is CF 3
  • Compounds of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein R 1 is CF3 can also be prepared via alkylation of ethyl 4,4,4-trifluoroacetoacetate (ETFAA) with compounds of Formula 3 wherein L a is a leaving group such as halogen (e.g., Cl, Br) or sulfonate (e.g., mesylate).
  • ETFAA is first treated with a base such as sodium hydride in a polar aprotic solvent such tetrahydrofuran (THF), THF/hexamethylphosphoramide (HMPA) or acetone.
  • THF tetrahydrofuran
  • HMPA hexamethylphosphoramide
  • the ETFAA anion then displaces the leaving group in compounds of Formula 3 to give an intermediate ester which undergoes hydrolysis and decarboxylation in the presence of lithium chloride (LiCl) and N, /V-dimethylformamide (DMF) to give the ketone compound of Formula la.
  • LiCl lithium chloride
  • DMF N, /V-dimethylformamide
  • L a is a leaving group such as Cl, Br or OMs
  • compounds of Formula la i.e. Formula 1 wherein T is T-l and W is O
  • R 1 is CF3
  • TMS-CF3 trifluoromethyltrimethylsilane
  • the reaction is run in the present of a fluoride initiator such as tetrabutylammonium fluoride, and in an anhydrous solvent such as toluene or dichloromethane at about -78 °C (for reaction conditions see, for example, Angew. Chem., Int. Ed. 1998, 37(6), 820-821).
  • Cesium fluoride can also be used as an initiator in a solvent such as 1,2-dimethoxy ethane (glyme) at room temperature (for reaction conditions see, for example, J. Org. Chem., 1999, 64, 2873).
  • a solvent such as 1,2-dimethoxy ethane (glyme) at room temperature (for reaction conditions see, for example, J. Org. Chem., 1999, 64, 2873).
  • the reaction proceeds through a trimethylsilicate intermediate, which is hydrolyzed with aqueous acid to give the desired trifluoromethyl ketone compound of Formula la.
  • Weinreb amides may also be used in place of the starting esters (see, for example, Chem. Commun. 2012, 48, 9610).
  • compounds of Formula la 1 (i.e. Formula la wherein A is Ai-A 2 - CR 6a R 6b ) wherein R 1 is CF3 and at least one R 6a or R 6b is H can be prepared by reacting acid chlorides of Formula 6 with trifluoroacetic anhydride (TFAA) and pyridine in a solvent such as dichloromethane or toluene at a temperature between about 0 to 80 °C followed by aqueous hydrolysis (for reaction conditions see, for example, Tetrahedron 1995, 51, 2573-2584).
  • TFAA trifluoroacetic anhydride
  • Compounds of Formula 6 can be prepared from compounds of Formula 5 by ester hydrolysis to the corresponding carboxylic acid and treatment with oxalyl chloride, as known to one skilled in the art.
  • R ba or R bb is H wherein R 1 is CF3 and at least one R ba or R 6b is H
  • compounds of Formula lb (i.e. Formula 1 wherein T is T-2) wherein R 2a X and R 2b Y are OH can be prepared by oxidation of alcohols of Formula 4 to the corresponding dihydroxy.
  • the oxidation reaction can be performed by a variety of means, such as by treatment of the alcohols of Formula 4 with manganese dioxide, Dess-Martin periodinane, pyridinium chlorochromate or pyridinium dichromate.
  • manganese dioxide Dess-Martin periodinane
  • pyridinium chlorochromate pyridinium dichromate
  • Scheme 6 illustrates a specific example of the general method of Scheme 5 for the preparation of a compound of Formula lb 1 (i.e. Formula lb wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2 and R 1 is CF3).
  • a compound of Formula 4a i.e. Formula 4 wherein L is CH2, J is phenyl (i.e. J-l), A is OCH2 and R 1 is CF 3
  • an oxidizing reagent such as Dess-Martin periodinane in a solvent such as dichloromethane at a temperature between about 0 to 80 °C.
  • Step C illustrates the method of Scheme 6.
  • M is, e.g., Li, Na, K, Cs or MgBr As shown in Scheme 8, compounds of Formula 4b (i.e. Formula 4 wherein A is
  • OCR 6a R 6b can be prepared by reacting a compound of Formula 7 with an epoxide of Formula 8.
  • the reaction is typically carried out in a solvent such as acetonitrile with a catalytic amount of a base such as cesium or potassium carbonate at a temperature between about 20 to 80 °C; or in a solvent such as dichloromethane with a catalytic amount of a Fewis acid such as boron trifluoride etherate at a temperature between about 0 to 40 °C.
  • Step E illustrates the method of Scheme 8.
  • One skilled in the art will recognize that the method of Scheme 8 can also be performed when A is SCR 6a R 6b or N(R ⁇ a )CR 6a R 6b , thus providing other compounds of Formula 4b.
  • Scheme 9 illustrates a specific example of the general method of Scheme 8 for the preparation of a compound of Formula 4b 1 (i.e. Formula 4b wherein L is CH 2 , J is phenyl (i.e. J-l), R 6a and R 6b are H and R 1 is CF 3 )
  • a compound of Formula 7a i.e. Formula 7 wherein L is CH 2 and J is phenyl (i.e. J-l)
  • 2-(trifluoromethyl)oxirane i.e. Formula 8a
  • Step B illustrates the method of Scheme 9.
  • W is O
  • Formula lb i.e. Formula 1 wherein T is T-2
  • R 2a X and R 2b Y are OH.
  • the predominance of Formula la or Formula lb is dependent upon several factors, such as environment and structure. For example, in an aqueous environment ketones of Formula la can react with water to give ketone hydrates (also known as 1,1-geminal diols) of Formula lb. Conversion back to the keto-form can usually be achieved by treatment with a dehydrating agent such as magnesium sulfate or molecular sieves.
  • a dehydrating agent such as magnesium sulfate or molecular sieves.
  • ketones of Formula la may also exist in equilibrium with their hemiketals, hemithioketals and hemiaminals of Formula lb 2 (i.e. Formula lb wherein R 2b Y is OH and R 2a is other than H) along with their ketals, thioketals aminals of Formula lb wherein R 2a and R 2b are other than H.
  • Compounds of Formula lb 2 can be prepared by reacting a compound of Formula la with a compound of formula R 2a X-H (e.g., alcohols for X being O, thiols for X being S or amines for X being NR 5a ), usually in the presence of an catalysis, such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF3), (see, for example, Master Organic Chemistry (Online), On Acetals and Hemiacetals, May 28, 2010, www.masterorganic- chemistry.com/2010/201728/on-acetals-and-hemiacetals).
  • a compound of formula R 2a X-H e.g., alcohols for X being O, thiols for X being S or amines for X being NR 5a
  • an catalysis such as a Bronsted (i.e. protic) acid or Lewis acid (e.g. BF3)
  • compounds of Formula lb 2 can be treated with a compound of formula R 2b Y-H (e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR 5b ) under dehydrating conditions, or other means of water removal that will drive the equilibrium in the reaction to the right, to provide compounds of Formula lb wherein R 2a and R 2b are other than H.
  • R 2b Y-H e.g., alcohols for Y being O, thiols for Y being S or amines for Y being NR 5b
  • ketones of Formula la can initially be treated with two equivalents (or an excess amount) of an alcohol, thiol or amine typically in the presence of a catalysis together with a dehydrating agent to provide compounds of Formula lb directly (see, for example, the preparation of the dimethylketals using methanol and trimethyl orthoformate in US 6,350,892).
  • cyclic ketals of Formula lb 3 (i.e. Formula lb wherein X and Y are O, and R 2a and R 2b are taken together to form a 5- to 7-membered ring) can be prepared by treating the corresponding ketones of Formula la with haloalcohols (e.g., 2-chloroethanol or 2- bromopropanol) in the presence of a base such as potassium carbonate or potassium ieri-butoxide and in as solvent such as acetonitrile or/V,/V-dimethylformamide (DMF).
  • haloalcohols e.g., 2-chloroethanol or 2- bromopropanol
  • a base such as potassium carbonate or potassium ieri-butoxide
  • solvent such as acetonitrile or/V,/V-dimethylformamide (DMF).
  • Scheme 12 illustrates a specific example where a ketone hydrate of Formula lb 4 (i.e. Formula lb wherein L is CH 2 , J is phenyl (i.e. J-l), A is OCH 2 , R 2a X and R 2b Y are OH and R 1 is CF 3 ) is reacted with 2-chloroethanol in the presence of potassium carbonate in acetonitrile at a temperature between about 25 to 70 °C to provide a compound of Formula lb 5 (i.e. Formula lb wherein L is CH 2 , J is phenyl (i.e. J-l), A is OCH 2 , X and Y are O, R 2a and R 2b are taken together to form a 5-membered ring and R 1 is CF 3 ).
  • Present Example 2 illustrates the method of Scheme 13.
  • Compounds of Formula 10 can be prepared using commercial precursors and known methods. For example, as shown in Scheme 15, compounds of Formula 10a (i.e. Formula 10 wherein R 6a and R 6b are H, X and Y are O and R 2a and R 2b are taken together to form a 5- membered ring) can be prepared reacting compounds of Formula 11 with haloalcohols (e.g., 2- chloroethanol or 3-bromopropanol) under basic conditions (e.g., potassium ieri-butoxide in a solvent such as A, A-di methyl formamidc or tetrahydrofuran) to provide compounds of Formula 12.
  • haloalcohols e.g., 2- chloroethanol or 3-bromopropanol
  • basic conditions e.g., potassium ieri-butoxide in a solvent such as A, A-di methyl formamidc or tetrahydrofuran
  • a mesylate or tosylate group can be installed by treating the alcohol with methanesulfonyl chloride (mesyl chloride) or 4-toluenesulfonyl chloride (tosyl chloride) in the presence of a base such as triethylamine at a temperature between about 0 to 40 °C and in a solvent such as dichloromethane.
  • a triflate group can be installed by treating the alcohol with triflic anhydride (CFgSC ⁇ O as illustrated in Example 4, Step C.
  • Compounds of Formula 11 are known and can be prepared by methods known to one skilled in the art.
  • Compounds of Formula lc (i.e. Formula 1 wherein T is T-3 and X is O) can be prepared by reacting a compound of Formula la (i.e. Formula 1 wherein T is T-l and W is O) wherein at least one of R 6a and R 6b is H with a compound of Formula 14 in the presence of a base, as illustrated in Scheme 16.
  • Suitable bases include cesium or potassium carbonate in a solvent such as A,A-di methyl formamidc (DMF) or dimethyl sulfoxide at temperatures from about 20 to 80 °C.
  • the method of Scheme 16 results in a mixture of O-alkylated product (typically as a mixture of ( E )- and (Z)-isomers), along with C-alkylated product.
  • Purification can be achieved using standard techniques such as column chromatography (see Magnetic Resonance in Chemistry 1991, 29, 675-678).
  • Compounds of Formula 14 are commercially available and can be easily synthesized by general methods known to one skilled in the art.
  • Scheme 16 wherein at least one L& is a leaving group such as of R 6a and R 6b is H Cl, Br, I, OMs, OTs or OTf
  • the method of Scheme 16 is also useful for preparing compounds of Formula lc stating from the corresponding ketone hydrate.
  • Scheme 17 illustrates a specific example where a ketone hydrate of Formula lb 4 (i.e. Formula lb wherein L is CH 2 , J is phenyl (i.e.
  • Compounds of Formula 1 wherein T is T-l and W is S can be prepared from the corresponding compounds wherein W is O by treatment with phosphorus pentasulfide or 2,4- bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2, 4-disulfide (Lawesson’s reagent) in solvents such as toluene, xylene or tetrahydrofuran.
  • solvents such as toluene, xylene or tetrahydrofuran.
  • E-L- moieties present in the compounds of Formula 1 and the intermediate compounds of Formulae 2 through 7 and 9 are common organic functional groups whose methods of preparation have been documented in the literature.
  • these well-known chemistry classes esters, amides, sulfonamides, sulfones, ethers, carbamates, ureas, heterocycles
  • can be readily prepared by a variety of methods see, for example, WO 2018/080859, WO 2018/118781, WO 2018/187553 and WO 2019/010192).
  • Step A Preparation of ethyl l-[(4-hydroxyphenyl)methyl]-l//-pyrazole-4-carboxylate
  • Step B Preparation of ethyl l-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate
  • Step C Preparation of ethyl 1 - [[4-(3, 3, 3-trifluoro-2, 2-dihydiOxypropoxy)phcny 1] methyl J-
  • Step A Preparation of methyl 2-(trifluoromethyl)-l,3-dioxolane-2-carboxylate
  • Step B Preparation of 2-(trifluoromethyl)- 1 ,3-dioxolane-2-methanol
  • Step C Preparation of [2-(trifluoromethyl)-l,3-dioxolan-2-yl]methyl 1,1,1-trifluoro- methanesulfonate
  • Step D Preparation of ethyl l-[[4-[[2-(trifluoromethyl)-l,3-dioxolan-2-yl]methoxy]- phenyl] methyl] - 1 /7-pyrazolc-4-carboxylatc
  • the filtrate was concentrated under reduced pressure to provide the title compound, a compound of the present invention, as a white solid (0.80 g).
  • a portion of the solid was further purified by silica gel chromatography (eluting with a gradient of 0 to 50% ethyl acetate in hexanes) to provide a solid melting at 59- 60 °C.
  • a nuclear Overhauser effect (NOE) was observed between the trifluoromethyl moiety and the vinyl proton indicating a c/.s-con figuration.
  • Step C Preparation of ethyl 1 -[[3-(accty loxy)phcnylJ methyl J-l /7-pyrazolc-4-carboxy late
  • Step D Preparation of ethyl l-[(3-hydroxyphenyl)methyl]-17/-pyrazole-4-carboxylate
  • Step E Preparation of ethyl l-[[3-(3,3,3-trifluoro-2-hydroxypropoxy)phenyl]methyl]-177- pyrazole-4-carboxylate
  • Step F Preparation of ethyl 1 - [[3-(3, 3, 3-trifluoiO-2,2-dihydiOxypiOpoxy)phcnyl] methyl J-
  • Step A Preparation of ethyl 1 -(hydroxymethyl)- 1 //-pyrazolc-4-carboxylatc
  • Step B Preparation of ethyl 1 -(chloromcthyl)- 1 //-pyrazolc-4-carboxylatc
  • Step C Preparation of ethyl 1 -[(4-mcthoxyphcnoxy)mcthylJ- 1 A-pyrazolc-4-carboxylatc
  • Step D Preparation of ethyl 1 -[(4-hydiOxyphenoxy)methylJ- 1 A-pyrazole-4-carboxy late
  • Step E Preparation of ethyl l-[[4-(3,3,3-trifluoro-2-hydroxypropoxy)phenoxy]methyl]-
  • Step L Preparation of ethyl l-[[4-(3,3,3-trifluoro-2,2-dihydroxypropoxy)phenoxy]- mcthylj- 1 //-pyrazolc-4-carboxylatc

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  • Life Sciences & Earth Sciences (AREA)
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  • Agronomy & Crop Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Mycology (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne une composition fongicide contenant (a) au moins un composé choisi parmi les composés de formule 1, y compris toutes les formes géométriques et les stéréoisomères, les tautomères, les A-oxydes et leurs sels, dans laquelle E, L, J, A et T sont tels que définis dans la description et (b) au moins un composé fongicide supplémentaire. L'invention concerne également un procédé de lutte contre les maladies des plantes provoquées par des agents pathogènes fongiques des plantes, lequel procédé consiste à appliquer, sur la plante, sur une partie de celle-ci ou sur ses semences, une quantité efficace d'un point de vue fongicide d'un composé de formule 1, d'un A-oxyde ou d'un sel de celui-ci (par exemple sous la forme d'un composant de la composition susmentionnée). L'invention concerne également une composition comprenant: (a) au moins un composé choisi parmi les composés de formule 1 décrits ci-dessus, leurs A-oxydes et leurs sels et (b) au moins un composé ou un agent de lutte contre les invertébrés nuisibles.
PCT/US2021/021806 2020-03-11 2021-03-11 Halométhyl cétones et hydrates fongicides et leurs mélanges WO2021183707A2 (fr)

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AU2021233845A AU2021233845A1 (en) 2020-03-11 2021-03-11 Fungicidal halomethyl ketones and hydrates and their mixtures
CN202180031728.9A CN115460921A (zh) 2020-03-11 2021-03-11 杀真菌的卤代甲基酮和水合物及其混合物
CA3174932A CA3174932A1 (fr) 2020-03-11 2021-03-11 Halomethyl cetones et hydrates fongicides et leurs melanges
BR112022018107A BR112022018107A2 (pt) 2020-03-11 2021-03-11 Halometilcetonas e hidratos fungicidas e misturas dos mesmos
JP2022554496A JP2023518172A (ja) 2020-03-11 2021-03-11 殺菌性ハロメチルケトン及び水和物並びにその混合物
EP21766969.6A EP4117432A4 (fr) 2020-03-11 2021-03-11 Halométhyl cétones et hydrates fongicides et leurs mélanges
US17/910,079 US20240122180A1 (en) 2020-03-18 2021-03-11 Fungicidal halomethyl ketones and hydrates and their mixtures
MX2022011299A MX2022011299A (es) 2020-03-11 2021-03-11 Halometil cetonas e hidratos fungicidas y sus mezclas.
IL296160A IL296160A (en) 2020-03-11 2021-03-11 Halomethyl ketones fungicides and their hydrates and mixtures
CONC2022/0014334A CO2022014334A2 (es) 2020-03-11 2022-10-07 Halometil cetonas e hidratos fungicidas y sus mezclas

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023046861A1 (fr) 2021-09-22 2023-03-30 Syngenta Crop Protection Ag Compositions fongicides
WO2023158602A1 (fr) 2022-02-15 2023-08-24 Fmc Corporation Halométhylcétones, hydrates et éthers d'énol fongicides
WO2024013106A1 (fr) 2022-07-11 2024-01-18 Syngenta Crop Protection Ag Compositions fongicides

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US6414179B1 (en) * 2000-02-18 2002-07-02 Bristol-Myers Squibb Company Alpha-and beta-substituted trifluoromethyl ketones as phospholipase inhibitors
TWI504350B (zh) * 2010-09-01 2015-10-21 Du Pont 殺真菌吡唑及其混合物
CN102924201B (zh) * 2012-10-24 2015-02-25 大连理工大学 一种制备全氟烷基烷基酮化合物的方法
TW201418223A (zh) * 2012-10-25 2014-05-16 Du Pont 經取代之甲苯基殺真菌劑
US10674727B2 (en) * 2015-11-19 2020-06-09 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US20190345150A1 (en) * 2016-04-12 2019-11-14 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
BR112019006490B1 (pt) * 2016-10-24 2023-11-28 Fmc Corporation Composto, composições fungicidas e métodos para o controle das doenças dos vegetais
AU2019337618A1 (en) * 2018-09-14 2021-04-01 Fmc Corporation Fungicidal halomethyl ketones and hydrates

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023046861A1 (fr) 2021-09-22 2023-03-30 Syngenta Crop Protection Ag Compositions fongicides
WO2023158602A1 (fr) 2022-02-15 2023-08-24 Fmc Corporation Halométhylcétones, hydrates et éthers d'énol fongicides
WO2024013106A1 (fr) 2022-07-11 2024-01-18 Syngenta Crop Protection Ag Compositions fongicides

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BR112022018107A2 (pt) 2022-11-08
EP4117432A4 (fr) 2024-03-27
CA3174932A1 (fr) 2021-09-16
EP4117432A2 (fr) 2023-01-18
UY39123A (es) 2021-10-29
TW202200013A (zh) 2022-01-01
CN115460921A (zh) 2022-12-09
WO2021183707A8 (fr) 2022-11-03
WO2021183707A3 (fr) 2021-11-11
CO2022014334A2 (es) 2022-10-31

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