WO2015108779A1 - Pyrimidinyloxy benzene derivatives as herbicides - Google Patents

Pyrimidinyloxy benzene derivatives as herbicides Download PDF

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Publication number
WO2015108779A1
WO2015108779A1 PCT/US2015/010823 US2015010823W WO2015108779A1 WO 2015108779 A1 WO2015108779 A1 WO 2015108779A1 US 2015010823 W US2015010823 W US 2015010823W WO 2015108779 A1 WO2015108779 A1 WO 2015108779A1
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WO
WIPO (PCT)
Prior art keywords
compound
alkyl
haloalkyl
ome
independently
Prior art date
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PCT/US2015/010823
Other languages
French (fr)
Inventor
Nicholas Ryan DEPREZ
Ravisekhara P. Reddy
Paula Louise Sharpe
Thomas Martin Stevenson
Original Assignee
E. I. Du Pont De Nemours And Company
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Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=52462412&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2015108779(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority to ES15703143T priority Critical patent/ES2719410T3/en
Priority to MX2016009163A priority patent/MX2016009163A/en
Priority to KR1020167021834A priority patent/KR102381581B1/en
Priority to PE2021000675A priority patent/PE20211544A1/en
Priority to BR112016016443A priority patent/BR112016016443B8/en
Priority to EA201691439A priority patent/EA030009B1/en
Priority to PL15703143T priority patent/PL3094631T3/en
Priority to MYPI2016702111A priority patent/MY184202A/en
Priority to AU2015206757A priority patent/AU2015206757A1/en
Priority to CA2934891A priority patent/CA2934891C/en
Priority to JP2016546934A priority patent/JP6541667B2/en
Priority to UAA201608862A priority patent/UA124329C2/en
Priority to SI201530679T priority patent/SI3094631T1/en
Priority to MDA20160095A priority patent/MD4807C1/en
Application filed by E. I. Du Pont De Nemours And Company filed Critical E. I. Du Pont De Nemours And Company
Priority to US15/111,047 priority patent/US10131652B2/en
Priority to DK15703143.6T priority patent/DK3094631T3/en
Priority to CN201580004764.0A priority patent/CN105916849B/en
Priority to KR1020217030673A priority patent/KR102381584B1/en
Priority to SG11201604813YA priority patent/SG11201604813YA/en
Priority to EP15703143.6A priority patent/EP3094631B1/en
Publication of WO2015108779A1 publication Critical patent/WO2015108779A1/en
Priority to IL246373A priority patent/IL246373B/en
Priority to US16/191,905 priority patent/US10654840B2/en
Priority to AU2019226283A priority patent/AU2019226283B2/en
Priority to US15/931,090 priority patent/US11447476B2/en
Priority to AU2021232774A priority patent/AU2021232774B2/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/08—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing solids as carriers or diluents
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
    • 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
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/32—Ingredients for reducing the noxious effect of the active substances to organisms other than pests, e.g. toxicity reducing compositions, self-destructing compositions
    • 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
    • A01N43/48—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
    • 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
    • A01N43/72—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
    • A01N43/72—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
    • A01N43/88—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 six-membered rings with three ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/32—One oxygen, sulfur or nitrogen atom
    • C07D239/34—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • This invention relates to certain pyrimidinyloxy benzene derivatives, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.
  • the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
  • JP 61236766 A discloses certain carbon-linked pyrimidinyloxy benzene derivitaves as herbicides.
  • WO 94/17059 discloses certain carbon linked pyrimidinyloxy benzene derivative as herbicides.
  • This invention is directed to compounds of Formula 1 (including all stereoisomers),
  • Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
  • Z is O or S;
  • alkoxyhaloalkyl C2-C6 alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, Ci -C4 hydroxyalkyl, C2-C4 alkylthioalkyl, SO n R 1A , Si(CH 3 ) 3 or B(-OC(R 1B ) 2 C(R 1B ) 2 0-); or a phenyl ring optionally substituted with up to 5 substituents independently selected from R 1C ; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R 1C on carbon atom ring members and R 1D on nitrogen atom ring members;
  • R 2 is halogen, cyano, nitro, C1 -C4 alkoxy, C 1 -C4 alkyl, C2-Cg alkenyl, C2-Cg alkynyl,
  • n 0, 1, 2 or 3;
  • each n is independently 0, 1 or 2;
  • each R 1A , R 2A and R 3E is independently C r C 4 alkyl, C r C 4 haloalkyl, C r C 4
  • each R 1B is independently H or Ci -C4 alkyl
  • each R 1C is independently hydroxy, halogen, cyano, nitro, C ⁇ -Cg alkyl, C ⁇ -Cg
  • haloalkyl C ⁇ -Cg alkoxy or C ⁇ -Cg haloalkoxy
  • each R 1D is independently cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy or C2
  • each R 3A is independently Ci -C4 alkyl or Ci -C4 haloalkyl
  • each R 3B is independently H, Ci -C4 alkyl or Ci -C4 haloalkyl;
  • each R 3C is independently H or Ci -C4 alkyl
  • each R 3D is independently H, amino, Ci -C4 alkyl or Ci -C4 alkylamino;
  • each R F is independently hydroxy, halogen, cyano, nitro, C ⁇ -Cg alkyl, C ⁇ -Cg
  • each R G is independently cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy or C2
  • this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof.
  • This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).
  • This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) through (b 16); and salts of compounds of (bl) through (bl6).
  • 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 or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • seedling used either alone or in a combination of words means a young plant developing from the embryo of a seed.
  • the term “broadleaf used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
  • the term “alkylating agent” refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term “alkylating” does not limit the carbon-containing radical to alkyl; the carbon- containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for Q, R 1 and R 3 .
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 0, CH 3 C ⁇ CCH 2 0 and CH 3 C ⁇ CCH 2 CH 2 0.
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl” denotes alkylthio substitution on alkyl.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • 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 .
  • Alkylamino dialkylamino
  • dialkylamino are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • 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.
  • haloalkyl or “alkyl substituted with halogen” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkoxy is defined analogously to the term “haloalkyl”.
  • haloalkoxy include CF 3 0-, CC1 3 CH 2 0-, HCF 2 CH 2 CH 2 0- and CF 3 CH 2 0-.
  • 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 -.
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1 , said substituents (when they exceed 1) are independently selected from the group of defined substituents, (e.g., (R ⁇ ) n , n is 0, 1 , 2 or 3). Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the integers between i and j inclusive.
  • variable group When a variable group is shown to be optionally attached to a position, (for example (R ⁇ ) n attached to Q wherein n may be 0, then hydrogen may be at the position even if not recited in the variable group definition.
  • hydrogen atoms When one or more positions on a group are said to be "not substituted” or “unsubstituted”, then hydrogen atoms are attached to take up any free valency.
  • a "ring” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring member” refers to an atom or heteroatom forming the backbone of a ring. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic ring".
  • saturated carbocyclic refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • heterocyclic ring denote a ring in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Huckel's rule, then said ring is also called a “heteroaromatic ring” or “aromatic heterocyclic ring”. Unless otherwise indicated, heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • Aromatic indicates that each of the ring atoms is essentially in the same plane and has a / ⁇ -orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with Huckel's rule.
  • optionally substituted in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated.
  • optionally substituted is used interchangeably with the phrase “substituted or unsubstituted” or with the term “(un)substituted.” Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
  • Q When Q is a 5- or 6-membered (nitrogen-containing) heterocyclic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described.
  • Q can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention.
  • An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-l in Exhibit 1, wherein R v is R 1 as defined in the Summary of the Invention for Q and r is an integer (from 0 to 4).
  • Q can be (among others) 5- or 6-membered aromatic heterocyclic ring, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention.
  • Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for Q (i.e. R 1 ) and r is an integer from 0 to 4, limited by the number of available positions on each U group.
  • U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups r is limited to the integers 0 or 1 , and r being 0 means that the U group is unsubstituted and a hydrogen is present at the position indicated by (R v ) r .
  • R v groups are shown in the structures U-l through U-61, it is noted that they do not need to be present since they are optional substituents. Note that when R v is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or R v . Note that when the attachment point between (R v ) r and the U group is illustrated as floating, (R v ) r can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. Note that some U groups can only be substituted with less than 4 R v groups (e.g., U-2 through U-47 and U-52 through U-61).
  • Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
  • Noncrystalline 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 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
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides.
  • nitrogen-containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • the salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
  • Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):
  • Embodiment 1 A com ound of Formula 1 wherein Q is selected from
  • Embodiment 2 A compound of Embodiment 1 wherein Q is selected from Q-l
  • Embodiment 3 A compound of Embodiment 2 wherein Q is selected from Q-7
  • Embodiment 4 A compound of Embodiment 3 wherein Q is selected from Q-16 and Q-18.
  • Embodiment 5 A compound of Embodiment 4 wherein Q is Q-16.
  • Embodiment 6 A compound of Embodiment 4 wherein Q is Q-18.
  • Embodiment 7 A compound of Embodiment 1 wherein Q is selected from Q-43
  • Embodiment 8 A compound of Embodiment 7 wherein Q is selected from Q-43, Q-
  • Embodiment 9 A compound of Embodiment 8 wherein Q is selected from Q-43, Q- 44 and Q-45.
  • Embodiment 10 A compound of Embodiment 9 wherein Q is Q-43.
  • Embodiment 1 A compound of Embodiment 10 wherein Q is Q-45.
  • Embodiment 12 A compound of Formula 1 or any one of Embodiments 1 through 1 1 either alone or in combination, wherein Z is O.
  • Embodiment 13 A compound of Formula 1 or any one of Embodiments 1 through 12 either alone or in combination, wherein each R 1 is independently halogen, cyano,
  • Embodiment 14 A compound of Embodiment 13 wherein each R 1 is independently halogen, cyano, CHO, C j -C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C j -C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C 4 haloalkynyl, C ⁇ -C 4 alkoxy, C3-C 4 alkenyloxy, C3-C 4 alkynyloxy, C ⁇ -C 4 haloalkoxy, C3-C 4 haloalkenyloxy, C3-C 4 haloalkynyloxy,
  • Embodiment 15 A compound of Embodiment 14 wherein each R 1 is independently halogen, cyano, C j -C 4 alkyl, C j -C 4 haloalkyl, C j -C 4 alkoxy, C j -C 4 haloalkoxy or SO n R 1A .
  • Embodiment 16 A compound of Embodiment 15 wherein each R 1 is independently halogen, C ⁇ -C 4 alkyl, C ⁇ -C 4 haloalkyl or C ⁇ -C 4 haloalkoxy.
  • Embodiment 17 A compound of Embodiment 16 wherein each R 1 is independently halogen, C 1 -C4 haloalkyl or C1 -C4 haloalkoxy.
  • Embodiment 18 A compound of Embodiment 17 wherein each R 1 is independently halogen or Ci -C4 haloalkyl.
  • Embodiment 19 A compound of Embodiment 18 wherein each R 1 is independently F,
  • Embodiment 20 A compound of Formula 1 or any one of Embodiments 1 through 19 either alone or in combination, wherein r is 0, 1 or 2.
  • Embodiment 20a A compound of Embodiment 20 wherein r is 1.
  • Embodiment 21 A compound of Formula 1 or any one of Embodiments 1 through 19 either alone or in combination, wherein s is 1.
  • Embodiment 21a A compound of Formula 1 or any one of Embodiments 1 through
  • Embodiment 21b A compound of Formula 1 or any one of Embodiments 1 through
  • Embodiment 22 A compound of Formula 1 or any one of Embodiments 1 through
  • R 2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl.
  • Embodiment 23 A compound of Embodiment 22 wherein R 2 is halogen or Ci -C4 alkyl.
  • Embodiment 24 A compound of Embodiment 23 wherein R 2 is halogen or CH3.
  • Embodiment 25 A compound of Embodiment 24 wherein R 2 is halogen.
  • Embodiment 26 A compound of Embodiment 25 wherein R 2 is F, CI or Br.
  • Embodiment 27 A compound of Formula 1 or any one of Embodiments 1 through 26 either alone or in combination, wherein m is 0, 1 or 2.
  • Embodiment 28 A compound of Embodiment 27 wherein m is 0 or 1.
  • Embodiment 29 A compound of Embodiment 28 wherein m is 1.
  • Embodiment 30 A compound of Embodiment 27 wherein m is 0 (i.e. the 3-, 4-, 5- and 6-positions are unsubtituted by R 3 ).
  • Embodiment 31 A compound of Formula 1 or any one of Embodiments 1 through 30 either alone or in combination, wherein each R 3 is independently halogen, cyano, CHO, C r C 4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C r C 4 haloalkyl, C 2 -C 4 haloalkenyl, C 2 -C4 haloalkynyl, C 3 -C6 cycloalkyl, C 3 -C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C 2 -Cg alkylcarbonyl, C 2 -Cg haloalkylcarbonyl, C 2 -Cg alkoxycarbonyl, C1 -C4 alkoxy, C 3 -C4 alkenyloxy, C 3 -C4 alkynyloxy, C1 -C4 haloalkoxy, C 3 -
  • Embodiment 32 A compound of Embodiment 31 wherein each R 3 is independently halogen, cyano, CHO, C 1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C 1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-C6 cyanoalkyl, SO n R 3E ; or a 5- or 6-membered
  • heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R 3F on carbon atom ring members and R 3G on nitrogen atom ring members.
  • Embodiment 33 A compound of Embodiment 32 wherein each R 3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, Ci -C4 haloalkyl, C2-C6 alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C 1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl.
  • Embodiment 34 A compound of Embodiment 33 wherein each R 3 is independently halogen, cyano, Ci -C4 alkyl or Ci -C4 haloalkyl.
  • Embodiment 35 A compound of Embodiment 34 wherein each R 3 is independently halogen or cyano.
  • Embodiment 36 A compound of Embodiment 35 wherein each R 3 is independently halogen.
  • Embodiment 37 A compound of Formula 1 or any one of Embodiments 1 through 36 either alone or in combination, wherein R 3 is attached to the remainder of Formula 1 at the 3 -position.
  • Embodiment 38 A compound of Formula 1 or any one of Embodiments 1 through 37 either alone or in combination, wherein each R 1A is independently Ci -C4 alkyl or C 1 -C4 haloalkyl.
  • Embodiment 39 A compound of Embodiment 38 wherein each R 1A is independently C 1 -C4 haloalkyl.
  • Embodiment 40 A compound of Formula 1 or any one of Embodiments 1 through 39 either alone or in combination, wherein each R 3E is independently Ci -C4 alkyl.
  • Embodiment 41 A compound of Formula 1 or any one of Embodiments 1 through 40 either alone or in combination, wherein each R 3A is independently C i -C4 alkyl.
  • Embodiment 42 A compound of Formula 1 or any one of Embodiments 1 through 41 either alone or in combination, wherein each R 3B is independently H or Ci -C4 alkyl.
  • Embodiment 43 A compound of Formula 1 or any one of Embodiments 1 through 42 either alone or in combination, wherein each R 3C is independently H or Ci -C4 alkyl.
  • Embodiment 44 A compound of Formula 1 or any one of Embodiments 1 through 43 either alone or in combination, wherein each R 3D is independently H or C 1-C4 alkyl.
  • Embodiment 45 A compound of Formula 1 or any one of Embodiments 1 through 44 either alone or in combination, wherein each n is independently 0 or 2.
  • Embodiment 46 A compound of Embodiment 45 wherein n is 2.
  • Embodiment 47 A compound of Embodiment 45 wherein n is 0.
  • Embodiment 48 A compound of Formula 1 or any one of Embodiments 1 through 47 either alone or in combination, provided that i) when Q is 5-chloro-2-pyridinyl; Z is O; and R3 is 4 chloro, then R2 is other than CI or Br; ii) when Q is 4-CF3-2- pyrimidinyl; Z is O; and m is 0, then R2 is other than CI or Br; and iii) when Q is 6-CF3-2-pyridinyl; Z is O; and m is 0, then R2 is other than Br.
  • Embodiment IP A compound of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides as described in the Summary of the Invention.
  • Embodiment 2P A compound of Embodiment 1 wherein Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, and optionally substituted with 1 to 3 R 1 .
  • Embodiment 3P A com ound of Embodiment 2 wherein Q is selected from
  • r 0, 1, 2 or 3;
  • s is 0 or 1.
  • Embodiment 4P A compound of any one of Embodiments 1 through 3 wherein Q is a
  • 5- membered aromatic heterocylic ring bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R 1 , and is selected from Q-1 through Q-41.
  • Embodiment 5P A compound of Embodiment 4 wherein Q is selected from Q-7
  • Embodiment 6P A compound of Embodiment 5 wherein Q is selected from Q-9, Q- 11, Q-12, Q-16, Q-18, Q-22, Q-23, Q-24 and Q-25.
  • Embodiment 7P A compound of Embodiment 6 wherein Q is selected from Q-11, Q- 18 and Q-22.
  • Embodiment 8P A compound of any one of Embodiments 1 through 3 wherein Q is
  • 6- membered aromatic heterocylic ring bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R 1 , and is selected from Q-42 through Q-54.
  • Embodiment 9P A compound of Embodiment 8 wherein Q is selected from Q-42, Q-
  • Embodiment 10P A compound of Embodiment 9 wherein Q is selected from Q-42, Q- 43, Q-47 and Q-48.
  • Embodiment 1 IP A compound of Embodiment 10 wherein Q is selected from Q-42, Q-47 and Q-48.
  • Embodiment 12P A compound of Embodiment 1 1 wherein Q is selected from Q-42.
  • Embodiment 13P A com ound of Embodiment 12 wherein Q is
  • Embodiment 14P A compound of any one of Embodiments 1 through 3 wherein Q is selected from Q-7 through Q-24, Q-42, Q-43, Q-44, Q-47, Q-48 and Q-49.
  • Embodiment 15P A compound of Embodiment 14 wherein Q is selected from Q-9, Q-l l , Q-12, Q-16, Q-18, Q-22, Q-23, Q-24, Q-25, Q-42, Q-43, Q-47 and Q-48.
  • Embodiment 16P A compound of Embodiment 1 wherein Q is phenyl substituted with 1 to 3 Rl .
  • Embodiment 17P A compound of Embodiment 16 whererin Q is phenyl substituted with 1 to 2 R! .
  • Embodiment 18P A compound of Embodiment 17 wherein Q is phenyl substituted with 1 R 1 at the 3- or 4-positions (i.e. meta or para to the attachment of phenyl to the remainder of Formula 1).
  • Embodiment 19P A compound of Embodiment 1 wherein when Q is phenyl
  • Embodiment 20P A compound of Embodiment 1 wherein when Q is phenyl
  • Embodiment 2 IP.
  • Embodiment 22P A compound of any one of Embodiments 1 through 21 wherein R 1 is halogen, cyano, CHO, -C4 alkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl or SO n R 1A .
  • Embodiment 23P A compound of Embodiment 22 wherein R 1 is halogen, cyano, -C4 alkyl, C1-C4 alkoxy, -C4 haloalkyl, -C4 haloalkoxy, or SCF 3 .
  • Embodiment 24P A compound of Embodiment 23 wherein R 1 is halogen, y-C ⁇ alkyl or C1-C4 haloalkyl or y-C ⁇ haloalkoxy.
  • Embodiment 25P A compound of Embodiment 24 wherein R 1 is halogen y-C ⁇
  • Embodiment 26P A compound of Embodiment 25 wherein R 1 is CI, Br, CF 3 or OCF 3 .
  • Embodiment 27P A compound of any one of Embodiments 1 through 22 wherein each n is independently 0, 1 or 2.
  • Embodiment 28P A compound of Embodiment 27 wherein each n is independently 0.
  • Embodiment 29P A compound of Embodiment 28 wherein each n is independently 2.
  • Embodiment 30P A compound of any one of Embodiments 1 through 29 wherein R 2 is halogen, C1 -C4 alkyl or C 1 -C4 haloalkyl.
  • Embodiment 3 IP A compound of Embodiment 30 wherein R 2 is halogen or C1 -C4 alkyl.
  • Embodiment 32P A compound of Embodiment 31 wherein R 2 is halogen or CH3.
  • Embodiment 33P A compound of Embodiment 32 wherein R 2 is halogen.
  • Embodiment 34P A compound of Embodiment 33 wherein R 2 is F, CI or Br.
  • Embodiment 35P A compound of any one of Embodiments 1 through 34 wherein m is 0, 1 or 2.
  • Embodiment 36P A compound of Embodiment 35 wherein m is 0 or 1.
  • Embodiment 37P A compound of Embodiment 36 wherein m is 1.
  • Embodiment 38P A compound of Embodiment 37 wherein m is 0 (i.e. the 3-, 4-, 5- and 6-positions of the benzene ring are unsubtituted by R 3 ).
  • Embodiment 40P A compound of Embodiment 39 wherein each R 3 is independently halogen, cyano, amino, C1 -C4 alkyl, C 2 -C4 alkenyl, C 2 -C4 alkynyl, C 1 -C4 alkoxy, C 2 -C4 alkoxycarbonyl, C 2 -C4 alkylcarbonyloxy, C 2 -C4 alkoxyalkyl or C1 -C4 haloalkyl.
  • Embodiment 41P A compound of Embodiment 40 wherein each R 3 is independently halogen, cyano, amino or C 1 -C4 alkyl.
  • Embodiment 42P A compound of Embodiment 41 wherein each R 3 is independently cyano.
  • Embodiment 43P A compound of any one of Embodiments 1 through 37 or 39
  • each R 3 is attached to the remainder of Formula 1 at the 3-, 4- or 6-position.
  • Embodiment 44P A compound of Embodiments 43 wherein each R 3 is attached to the remainder of Formula 1 at the 3- or 4-position.
  • Embodiment 45P A compound of Embodiment 44 wherein R 3 is attached to the
  • Embodiment 46P A compound of any one of Embodiments 1 through 22 or 27 or 29 through 45 wherein R 1A is Ci -C4 alkyl or Ci -C4 haloalkyl.
  • Embodiment 47P A compound of Embodiment 46 wherein R 1A is Ci -C4 haloalkyl.
  • Embodiment 48P A compound of any one of Embodiments 1 through 37 or 39
  • R 3E is Ci -C4 alkyl
  • Embodiment 49P A compound of any one of Embodiments 1 through 37 or 39
  • R 3A is C 1 -C4 alkyl.
  • Embodiment 50P A compound of any one of Embodiments 1 through 37 or 39
  • R 3B is H or Ci -C4 alkyl.
  • Embodiment 5 IP.
  • a compound of any one of Embodiments 1 through 37 or 39 is a compound of any one of Embodiments 1 through 37 or 39.
  • R 3C is H or Ci -C4 alkyl.
  • Embodiment 52P A compound of any one of Embodiments 1 through 37 or 39
  • R 3D is H or Ci -C4 alkyl.
  • Embodiment 53P A compound of any one of Embodiments 1 through 52 wherein Z is
  • Embodiment 54P A compound of any one of Embodiments 1 through 53 wherein
  • R 3 is positioned at the 3-, 5- or 6-positions (i.e. the 3-, 5- and 6- positions of the benzene ring).
  • Embodiment 55P A compound of any one of Embodiments 1 through 53 wherein
  • R 3 is other than CI at the 4-position.
  • Embodiments of this invention can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the a compound of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • embodiments of this invention including Embodiments 1-48 and 1P-55P above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
  • Embodiment AAA A compound of Formula 1 wherein
  • Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
  • Z is O or S
  • n 0, 1, 2 or 3;
  • each R 1A , R 2A and R 3E is independently C r C 4 alkyl, C r C 4 haloalkyl, C r C 4
  • R 3A is C1-C4 alkyl or C r C 4 haloalkyl
  • R 3B is H, C r C 4 alkyl or C r C 4 haloalkyl
  • R C is independently H or Ci -C4 alkyl
  • R D is independently H or C 1 -C4 alkyl
  • n 0, 1, or 2;
  • the compound of Formula 1 is other than 5-chloro-2-[(4'-methyl[l,l'- biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-74-0), 5-chloro-2-[(4'- chloro[l,r-biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-72-8), 5-chloro-2- [(3 * -chloro[l,r-biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-76-2) and 5-chloro-2-[[3'-(trifluoromethyl)[ 1 , 1 '-biphenyl]2-yl]oxy]-pyrimidine (CAS # 107492-75-1); and provided i) when Q is 5-chloro-2-pyridinyl; Z is O; and R 3 is 4-chloro, then R 2 is other than CI or Br; ii) when Q is 4-CF3-2-pyrimidinyl; Z
  • Embodiment AA A compound of Embodiment AAA or a compound of Formula 1 as described in the Summary of the Invention wherein
  • Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
  • Z is O or S;
  • alkoxyhaloalkyl C2 ⁇ Cg alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-Cg cyanoalkyl, C2-Cg cyanoalkoxy, Ci -C4 hydroxyalkyl, C2-C4 alkylthioalkyl, SO n R 1A , Si(CH 3 ) 3 or B(-OC(R 1B ) 2 C(R 1B ) 2 0-); or a phenyl ring optionally substituted with up to 5 substituents independently selected from R 1C ; or a 5- or
  • 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R 1C on carbon atom ring members and R 1D on nitrogen atom ring members;
  • R 2 is halogen, cyano, nitro, C1 -C4 alkoxy, C 1 -C4 alkyl, C2-Cg alkenyl, C2-Cg alkynyl,
  • n 0, 1, 2 or 3;
  • each n is independently 0, 1 or 2;
  • each R 1A , R 2A and R 3E is independently C r C 4 alkyl, C r C 4 haloalkyl, C r C 4
  • each R 1B is independently H or Ci -C4 alkyl
  • each R 1C is independently hydroxy, halogen, cyano, nitro, C ⁇ -Cg alkyl, C ⁇ -Cg
  • each R 1D is independently cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy or C2-
  • each R 3A is independently Ci -C4 alkyl or Ci -C4 haloalkyl
  • each R 3B is independently H, Ci -C4 alkyl or Ci -C4 haloalkyl;
  • each R 3C is independently H or Ci -C4 alkyl
  • each R 3D is independently H, amino, Ci -C4 alkyl or Ci -C4 alkylamino;
  • each R F is independently hydroxy, halogen, cyano, nitro, C ⁇ -Cg alkyl, C ⁇ -Cg
  • each R G is independently cyano, C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C ⁇ -Cg alkoxy or C2- Cg alkylcarbonyl;
  • Embodiment A A compound of Embodiment AA wherein
  • Q is selected from Q-l through Q-55 wherein r is 0, 1, 2 or 3; and s is 0 or 1;
  • each R 1 is independently halogen, cyano, SF 5 , CHO, Ci -C4 alkyl, C2-C4 alkenyl,
  • R 3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, i -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg cycloalkyl,
  • Z is O
  • n 0, 1 or 2.
  • Embodiment B A compound of Embodiment A wherein
  • each R 1 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C1 -C4 hydroxyalkyl, C 2 -C 4 alkylthioalkyl or SO n R 1A ;
  • R 2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl
  • each R 3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-Cg
  • haloalkylcarbonyl C2-C6 alkoxycarbonyl, Ci -C4 alkoxy, Ci -C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, SO n R 3E ; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R 3F on carbon atom ring members and R 3G on nitrogen atom ring members; and
  • m 0 or 1.
  • Embodiment C 1. A compound of Embodiment B wherein
  • Q is selected from Q-7 through Q-24;
  • each R 1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
  • R 2 is halogen or Ci -C4 alkyl
  • each R 3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl,
  • C1 -C4 haloalkyl C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl;
  • each R 1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
  • Embodiment C A compound of Embodiment B wherein
  • Q is selected from Q-43, Q-44, Q-45, Q-48, Q-49 and Q-50;
  • each R 1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
  • R 2 is halogen or Ci -C4 alkyl
  • each R 3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl,
  • C1 -C4 haloalkyl C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl;
  • each R 1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
  • Embodiment D A compound of Embodiment C 1 wherein
  • Q is selected from Q-16 and Q-18;
  • each R 1 is independently halogen, Ci -C4 alkyl, Ci -C4 haloalkyl or Ci -C4 haloalkoxy;
  • R 2 is halogen or CH 3 ; and each R 3 is independently halogen, cyano, Ci -C4 alkyl or C i -C4 haloalkyl.
  • Embodiment D2 A compound of Embodiment C2 wherein
  • Q is selected from Q-43, Q-44 and Q-45;
  • each R 1 is independently halogen, Ci -C4 alkyl, C i -C4 haloalkyl or Ci -C4 haloalkoxy;
  • R 2 is halogen or CH 3 ;
  • each R 3 is independently halogen, cyano, Ci -C4 alkyl or C i -C4 haloalkyl.
  • Specific embodiments include compounds of Formula 1 selected from the group consisting of:
  • Embodiment Ap A compound of the Summary of the Invention wherein
  • Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, and optionally substituted with 1 to 3 R 1 ; or
  • Q is phenyl substituted with 1 to 3 R 1 ;
  • R 1 is halogen, cyano, CHO, C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkyl, Ci -C4 haloalkoxy, C 2 - C 4 alkoxyalkyl, C 2 -C 4 alkylthioalkyl or SO n R 1A ;
  • each n is independently 0, 1 or 2
  • R 2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl
  • n 0, 1 or 2;
  • each R 3 is attached to the remainder of Formula 1 at the 3-, 4- or 6-position;
  • R 1A is C1-C4 alkyl or C r C 4 haloalkyl
  • R 3E is C r C 4 alkyl
  • R 3A is C1-C4 alkyl
  • R 3B is H or C r C 4 alkyl
  • R 3C is H or C r C 4 alkyl
  • R 3D is H or C r C 4 alkyl.
  • Embodiment Bp A compound of Embodiment A wherein
  • Q is selected from Q-l through Q-54 (i.e. as described in Embodiment 3);
  • Z is O
  • R 1 is halogen, cyano, C 1 -C4 alkyl, C1 -C4 alkoxy, C 1 -C4 haloalkyl, C1 -C4 haloalkoxy, or SCF 3 ;
  • R 2 is halogen or Ci -C4 alkyl
  • n 0 or 1 ;
  • each R 3 is independently halogen, cyano, amino, Ci -C4 alkyl, C 2 -C4 alkenyl, C 2 -C4 alkynyl, C 1 -C4 alkoxy, C 2 -C4 alkoxycarbonyl, C 2 -C4 alkylcarbonyloxy, C 2 -C4 alkoxyalkyl or Ci -C4 haloalkyl; and
  • each R 3 is attached to the remainder of Formula 1 at the 3- or 4-position.
  • Embodiment Cp A compound of Embodiment B wherein Q is a 5-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R 1 , and is selected from Q-l through Q-41;
  • R 1 is halogen C1-C4 haloalkyl or C1-C4 haloalkoxy
  • R 2 is halogen or CH 3 ;
  • each R 3 is independently halogen, cyano, amino or C1-C4 alkyl.
  • Embodiment Dp A compound of Embodiment C wherein
  • R 1 is halogen C1-C4 haloalkyl or C1-C4 haloalkoxy
  • R 2 is halogen or CH 3 ;
  • each R 3 is independently halogen, cyano, amino or C1-C4 alkyl.
  • Embodiment Ep A compound of Embodiment D wherein
  • Q is selected from Q-42, Q-43, Q-44, Q-47, Q-48 and Q-49;
  • R 1 is CI, Br, CF 3 or OCF 3 ;
  • R 2 is halogen
  • each R 3 is independently cyano.
  • Specific embodiments include a compound of Formula 1 selected from the group consisting of:
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
  • the compounds of the invention e.g., as a composition described herein.
  • embodiments relating to methods of use are those involving the compounds of embodiments described above.
  • Compounds of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.
  • herbicidal compositions of the present invention comprising the compounds of embodiments described above.
  • This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics and (b5) 5 -enol-pyruvylshikimate-3 -phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (blO) auxin transport inhibitors, (bl 1) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl-pyruv
  • Photosystem II inhibitors are chemical compounds that bind to the D-l protein at the Qfl-binding niche and thus block electron transport from to QB in the chloroplast thylakoid membranes.
  • the electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction.
  • the QB-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate.
  • binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil
  • binding site B binds the phenylureas such as diuron
  • binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate.
  • photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazon, bromacil, bromofenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumyluron, cyanazine, daimuron, desmedipham, desmetryn, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn,
  • AHAS inhibitors are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for protein synthesis and cell growth.
  • AHAS acetohydroxy acid synthase
  • ALS acetolactate synthase
  • AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron- sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-
  • prosulfuron pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-l,3,5-triazin-2-yl)carbonyl]-6- fluorophenyl] -1,1 -difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl and tritosulfuron.
  • triafamone N-[2-[(4,6-dimethoxy-l,3,5-triazin-2-yl)carbonyl]-6- fluoropheny
  • ACCase inhibitors are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back.
  • ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.
  • auxin is a plant hormone that regulates growth in many plant tissues.
  • auxin mimics are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species.
  • auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl- 4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clacyfos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro- 3-methoxyphenyl)-2-pyridinecarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro- 6-(4-chloro-2-
  • EEPSP (5 -enol-pyruvylshikimate-3 -phosphate) synthase inhibitors) are chemical compounds that inhibit the enzyme, 5 -enol-pyruvylshikimate-3 -phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine.
  • EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points.
  • Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group.
  • Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).
  • Photosystem I electron diverters are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles "leak", leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.
  • PPO inhibitors are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out.
  • PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl
  • GS (glutamine synthase) inhibitors are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes.
  • the GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((25)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.
  • VLCFA very long chain fatty acid
  • elongase inhibitors are herbicides having a wide variety of chemical structures, which inhibit the elongase.
  • Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs.
  • very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains.
  • Such herbicides include acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro- 5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(l- naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxy
  • auxin transport inhibitors are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein.
  • auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(l-naphthyl)phthalamic acid and 2-[(l-naphthalenylamino)carbonyl]benzoic acid).
  • PDS phytoene desaturase inhibitors
  • bl l are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step.
  • PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone norflurzon and picolinafen.
  • HPPD (4-hydroxyphenyl-pyruvate dioxygenase) inhibitors are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase.
  • HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3 -[ [2-[(2-methoxyethoxy)methyl] -6-(trifluoromethyl)-3 - pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro- 4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-l,3-cyclohexanedione),
  • HST homogentisate solenesyltransererase inhibitors
  • HST inhibitors include haloxydine, pyriclor, 3-(2- chloro-3 ,6-difluorophenyl)-4-hydroxy- 1 -methyl- 1 ,5 -naphthyridin-2( lH)-one, 7-(3 ,5 - dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-3 ⁇ 4]pyrazin-6(5H)-one and 4- (2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.
  • HST inhibitors also include com ounds of Formulae A and B.
  • R dl is H, CI or CF 3 ;
  • R d2 is H, CI or Br;
  • R d3 is H or CI;
  • R d4 is H, CI or CF 3 ;
  • R d5 is CH 3 , CH 2 CH 3 or CH 2 CHF 2 ;
  • R el is H, F, CI, CH 3 or CH 2 CH 3 ;
  • R e2 is H or CF 3 ;
  • R e3 is H, CH 3 or CH 2 CH 3 ;
  • R e4 is H, F or Br;
  • R e5 is CI, CH 3 , CF 3 , OCF 3 or CH 2 CH 3 ;
  • R e6 is H, CH 3 , CH 2 CHF 2 or C ⁇ CH;
  • R e7 is
  • Cellulose biosynthesis inhibitors inhibit the biosynthesis of cellulose in certain plants. They are most effective when using a pre-aplication or early post-application on young or rapidly growing plants.
  • cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N 2 -[(li?,25)-2,3-dihydro-2,6-dimethyl-lH- inden-l-yl]-6-(l-fluoroethyl)-l ,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
  • herbicides include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl) organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors.
  • mitotic disruptors e.g., flamprop-M-methyl and flamprop-M-isopropyl
  • organic arsenicals e.g., DSMA, and MSMA
  • 7,8-dihydropteroate synthase inhibitors e.g., chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors.
  • Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (bl) through (bl4) or act through a combination of modes of action listed above.
  • herbicides examples include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, cyclopyrimorate (6-chloro-3-(2- cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone ( 1 -(2,4-dichlorophenyl)-N-(2,4-dif uorophenyl)- 1 ,5-dihydro-N-( 1 - methylethyl)-5-oxo-4H-l ,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclo
  • herbicide safeners are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation.
  • herbicide safeners include but are not limited to benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N- (aminocarbonyl)-2-fluor
  • the compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-9 can be used to prepare the compounds of Formula 1.
  • the definitions of Q, R 1 , R 2 and R 3 in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention unless otherwise noted.
  • Compounds of Formulae 1A-1C, 2A-2F, 4A and 8A are various subsets of the compounds of Formula 1, 2 4 and 8 and all substituents for Formulae 1A-1C, 2A-2F, 4A and 8A are as defined above for Formula 1 unless otherwise noted.
  • a compound of Formula 1 can be prepared by nucleophilic substitution by heating a compound of Formula 2 in a suitable solvent, such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide in the presence of a base such as potassium or cesium carbonate, at temperatures ranging from 50 to 110 °C, with a compound of Formula 3 (where LG is halogen or S02Me). The reaction is typically conducted at temperatures ranging from 50 to 110 °C.
  • LG is halogen or SO2CH3
  • boron compounds of Formula 5 or tin compounds of Formula 6 can be coupled with intermediates of Formula 4 under Suzuki or Stille conditions to give compounds of Formula 1.
  • Suzuki couplings typically are conducted in the presence of Pd(0) or Pd(II) salts, a suitable ligand, and a base.
  • Suitable bases for this transformation include potassium carbonate or cesium carbonate, while Pd(II) salts such as Pd(OAc) 2 or PdCl 2 can be used in conjunction with ligands such as triphenylphosphine or l,l'-bis(diphenylphosphino)ferrocene (dppf).
  • reaction can be run in a solvent such as dioxane, 1 ,2-dimethoxyethane or toluene at a temperature ranging from ambient to reflux.
  • a solvent such as dioxane, 1 ,2-dimethoxyethane or toluene
  • R C , - C 4 alkyl
  • Suitable methoxy i.e. when R A is CH 3
  • deprotecting reagents such as BBr 3 , AICI3 and HBr in acetic acid can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature of from -80 to 120 °C.
  • solvents such as toluene, dichloromethane and dichloroethane at a temperature of from -80 to 120 °C.
  • Suitable acetoxy i.e.
  • deprotecting agents include potassium carbonate in methanol or ammonium acetate in aqueous methanol at room temperature can be used as discussed in Das, et al, Tetrahedron 2003, 59, 1049-1054 and methods cited therein.
  • a compound of Formula 2B can be combined with Amberlyst 15® in methanol (as discussed in Das, et al. Tet. Lett. 2003, 44, 5465-5468) or combined with sodium acetate in ethanol (as discussed in Narender, T., et al. Synthetic Communications 2009, 39(11), 1949-1956) to obtain a compound of Formula 2C.
  • An intermediate of Formula 2B can be prepared as shown in Scheme 4 from an intermediate of Formula 7 by a variety of methods known to one skilled in the art.
  • Compounds of Formula 2B can be accessed by coupling precursors of Formula 7 wherein J is Br, CI, I or trifluoromethanesulfonate with boronate or trialkyltin group-containing heterocycles (i.e compounds of Formula 5 or Formula 6 using the Suzuki conditions or the Stille conditions of Scheme 2).
  • compounds of Formula 7 wherein J is a boronate or trialkyltin group may be coupled with halogen-substituted heterocycles Q-X using the methods shown in Scheme 2 to afford compounds of Formula 2B.
  • J in Formula 7 is an alkene, alkyne, oxime, nitrile or ketone
  • various heterocycles can be prepared using methods described in Katritsky, Advances in Heterocyclic Chemistry, Vol. 1-104, Elsevier.
  • the desired product can be isolated using routing separation techniques known in the art.
  • a compound of Formula 4A can be prepared by coupling of phenols of Formula 9 with a compound of Formula 3 under the nucleophilic substitution conditions described in Scheme 1.
  • a compound of Formula IB (i.e. a compound of Formula 1 where Z is O; and m is 1 at the 3-position) can be prepared by "C-H activation" of a compound of Formula 1A (a compound of Formula 1 wherein Z is O; and m is 0).
  • paladium(II) acetate along with either an N-halosuccinimide, PhI(OAc)2, N-fluoropyridinium tetrafluoroborate, or a lower alkyl boronic acid can be used to introduce the R 3 variable as I, Br, CI, -OAc, F, and lower alkyl substituents respectively.
  • chemistry based on "C-H activation” can be used to prepare a compound of Formulae 2F (i.e. a compound of Formula 2A wherein Z is S) as shown in Scheme 8.
  • a compound of Formula 8 can first be converted to a compound of Formula 8A (i.e. a compound of Formula 6 wherin the ortho "H” is X; and X is Br or I) by utilizing a stepwise introduction of substituents using "C-H activation”.
  • Iodides and bromides of Formula 8A can then be further functionalized by copper mediated cross-coupling with thiourea as described in Qi, Junsheng, Chin. J. Chem.
  • R J is other than H
  • X is Br or I
  • a one-pot deprotection of a compound of Formula 11 is readily achieved using 10% aqueous sodium hydroxide or methanolic potassium hydroxide to afford the corresponding aryl thiol.
  • Subsequent reaction with a compound of Formula 3 at or slightly above room temperature provides the product 1C (i.e. a compound of Formula 1 wherein Z is S).
  • Methods for Newman-Kwart rearrangements are found in Lloyd- Jones, Guy C, Synthesis 2008, 661-689.
  • Step A Synthesis of 5-chloro-2-[2-[5-[[[(l,l- dimethylethyl)diphenylsilyl]oxy]methyl]-3-isoxazolyl]phenoxy]pyrimidine To a solution of 3-(2-methoxyphenyl)-5-isoxazolemethanol (prepared as described in
  • Step B Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5-isoxazolemethanol
  • Step A Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5- isoxazolecarboxaldehyde
  • reaction mixture was allowed to cool to ambient temperature and quenched with a saturated solution of sodium bicarbonate.
  • the phases were separated and the aqueous layer was again washed with dichloromethane.
  • the combined organic phases were dried with MgSC ⁇ , concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the title product (0.395 g).
  • Step B Synthesis of 5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]- pyrimidine
  • Step A Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione
  • l-(2-fluoro-6-methoxyphenyl)ethanone 2.6 g, 15.5 mmol
  • difluoroacetic acid ethyl ester 3.0 mmol
  • sodium hydride 1.2 g, 31.0 mmol
  • Step B Synthesis of 3-difluoromethyl-5-(2-fluoro-6-methoxyphenyl)isoxazole
  • Step A Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione
  • Step B Synthesis of 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)-4H-isoxazol- 5-ol
  • Step C Synthesis of 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)isoxazole
  • Step D Synthesis of 2-[5-(difluoromethyl)-3-isoxazolyl]-3-fluorophenol
  • Step E Synthesis of 5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]-3- fluorophenoxy]pyrimidine
  • the mixture was then cooled, diluted with diethyl ether and water, filtered thru a celite pad and rinsed with ethyl acetate and water.
  • the phases were separated and the aqueous phase was extracted twice with diethyl ether.
  • the combined organic phases were washed twice with water and saturated aqueous sodium chloride, dried over magnesium sulfate, and concentrated to provide 0.2 lg crude product.
  • the crude product was purified with a 12 g Teledyne Isco silica gel column eluting with 10 to 30% EtOAc-Hexanes gradient to provide the title compound, a compound of the present invention as a solid (0.23 g).
  • the reaction was cooled, diluted with dichloromethane and filtered thru a celite pad, rinsing with dichloromethane and then de-ionized water.
  • the phases were separated.
  • the aqueous phase was extracted twice with dichloromethane.
  • the combined organic phases were washed with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated to give a solid.
  • a solid was filtered from hexanes to give 34 mg.
  • a second crop was obtained from the filtrate from hexanes to yield 506 mg of a light orange- brown solid of the title compound.
  • the mixture was filtered thru a celite pad, rinsed with toluene and then ethyl acetate.
  • the filtrate was washed twice with saturated aqueous sodium hydrogencarbonate, saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated to a crude product.
  • the crude product was purified with a 12 g Teledyne Isco silica gel column eluting with 10 to 30% EtOAc-Hexanes gradient to provide the title compound, a compound of the present invention as a solid (40 mg).
  • Step C Synthesis of 5-bromo-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]- pyrimidine
  • Step B Synthesis of 5-chloro-2-[2-[5-(trifluoromethyl)-3-isoxazolyl]-3- fluorophenoxy]pyrimidine
  • step A (i.e. the product of step A) (606 mg, 2.29 mmol) in dimethylsulfoxide (15 mL) was added 5- chloro-2-methylsulfonyl-pyrimidine (527mg, 2.74mmol) followed by cesium carbonate (l . lg, 3.43mmol) and the reaction stirred for 18 h.
  • the reaction was partitioned between water and ethyl acetate, the phases were separated and the aqueous layer was again washed with ethyl acetate.
  • Step A Synthesis of 2-(trifluoromethyl)-4H- 1 -benzopyran-4-one
  • Step C Synthesis of 5-chloro-2-[2-[3-(trifluoromethyl)-5-isoxazolyl)phenoxy]- pyrimidine
  • Step A Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione
  • Step B Synthesis of 3-(difluoromethyl)-5-(2-fluoro-6-methoxyphenyl)isoxazole
  • Step D Synthesis of 5-bromo-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3- fluorophenoxy]pyrimidine
  • Isoxazol-4-yl 4-CHF 2 -oxazol-2-yl 3-F-isoxazol-4-yl 4-CHO-oxazol-2-yl 3 -Cl-isoxazol-4-yl 4-CN-oxazol-2-yl 3-Br-isoxazol-4-yl 4-OMe-oxazol-2-yl 3-I-isoxazol-4-yl 4- OCF 3 -oxazol-2-yl 3-Me-isoxazol-4-yl 4- Ph-oxazol-2-yl 3 -Et-isoxazol-4-yl Thiazol-2-yl 3 -CF3 -isoxazol-4-yl 5- F-thiazol-2-yl -CHF2-isoxazol-4-yl 5-Cl-thiazol-2-yl 3-CHO-isoxazol-4-yl 5-Br-thiazol-2-yl 3 -CN-isoxazol
  • Isothiazol-4-yl 4-CF 3 -thiazol-2-yl 3 -F-isothiazol-4-yl 4-CHF 2 -thiazol-2-yl 3-Cl-isothiazol-4-yl 4-CHO-thiazol-2-yl 3 -Br-isothiazol-4-yl 4-CN-t azol-2-yl 3 -I-isothiazol-4-yl 4-OMe-thiazol-2-yl 3 -Me-isothiazol-4-yl 4-OCF 3 -thiazol-2-yl 3-Et-isothiazol-4-yl 4-Ph-thiazol-2-yl 3 -CF3 -isothiazol-4-yl Oxazol-5-yl -CHF 2 -isothiazol-4-yl 2-F-oxazol-5-yl 2-Cl-oxazol-5-yl
  • the present disclosure also includes Tables 2 through 1584.
  • the remainder of Table 2 is constructed in the same way, and hence the remainder of Tables through 1584 is constructed the same way.

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Abstract

Disclosed are compounds of Formula (1), including all stereoisomers, N-oxides, and salts thereof, wherein Q, Z, R2, R3 and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (1) and methods for controlling undesired vegetation comprising contacting the undesired vegetation or its environment with an effective amount of a compound or a composition of the invention.

Description

TITLE
PYRIMIDINYLOXY BENZENE DERIVATIVES AS HERBICIDES
FIELD OF THE INVENTION
This invention relates to certain pyrimidinyloxy benzene derivatives, their N-oxides, salts and compositions, and methods of their use for controlling undesirable vegetation.
BACKGROUND OF THE INVENTION
The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
JP 61236766 A (Sumitomo, 1986) discloses certain carbon-linked pyrimidinyloxy benzene derivitaves as herbicides. WO 94/17059 (Nippon Soda, 1994) discloses certain carbon linked pyrimidinyloxy benzene derivative as herbicides.
SUMMARY OF THE INVENTION
This invention is directed to compounds of Formula 1 (including all stereoisomers),
(N-oxides, and salts thereof), agricultural compositions containing them and their use as herbicides:
Figure imgf000002_0001
Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
Formula 1 through a carbon atom, and optionally substituted with 1 to 4 R1; Z is O or S;
each R1 is independently halogen, cyano, nitro, SF5, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-Cg alkylcycloalkyl, C4-Cg cycloalkylalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C2~Cg alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6
alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, Ci -C4 hydroxyalkyl, C2-C4 alkylthioalkyl, SOnR1A, Si(CH3)3 or B(-OC(R1B)2C(R1B)20-); or a phenyl ring optionally substituted with up to 5 substituents independently selected from R1C; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R1C on carbon atom ring members and R1D on nitrogen atom ring members;
R2 is halogen, cyano, nitro, C1 -C4 alkoxy, C 1 -C4 alkyl, C2-Cg alkenyl, C2-Cg alkynyl,
SOnR2A, C1-C4 haloalkyl or C3-C6 cycloalkyl;
each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-Cg alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1 -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 alkoxyhaloalkyl, C2-C6 alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C2-C6 cyanoalkoxy, C2-C4 alkylthioalkyl, Si(CH3)3, C≡CSi(CH3)3, C(=0)N(R3A)(R3B), C(=NOR3C)H, C(=NR3D)H, SOnR E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R F on carbon atom ring members and R3G on nitrogen atom ring members; or pyrimidinyloxy;
m is 0, 1, 2 or 3;
each n is independently 0, 1 or 2;
each R1A, R2A and R3E is independently CrC4 alkyl, CrC4 haloalkyl, CrC4
alkylamino or C2-C6 dialkylamino; each R1B is independently H or Ci -C4 alkyl;
each R1C is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy;
each R1D is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2
Cg alkylcarbonyl;
each R3A is independently Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3B is independently H, Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3C is independently H or Ci -C4 alkyl;
each R3D is independently H, amino, Ci -C4 alkyl or Ci -C4 alkylamino;
each R F is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy; and
each R G is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2
Cg alkylcarbonyl;
More particularly, this invention pertains to a compound of Formula 1 (including all stereoisomers), an N-oxide or a salt thereof. This invention also relates to a herbicidal composition comprising a compound of the invention (i.e. in a herbicidally effective amount) and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).
This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) through (b 16); and salts of compounds of (bl) through (bl6).
DETAILS OF THE INVENTION
As used herein, the terms "comprises," "comprising," "includes," "including," "has," "having," "contains", "containing," "characterized by" or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated. For example, a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
The transitional phrase "consisting of excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase "consisting of appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. The transitional phrase "consisting essentially of is used to define a composition, process or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention. The term "consisting essentially of occupies a middle ground between "comprising" and "consisting of.
Where applicants have defined an invention or a portion thereof with an open-ended term such as "comprising," it should be readily understood that (unless otherwise stated) the description should be interpreted to also describe such an invention using the terms "consisting essentially of or "consisting of."
Further, unless expressly stated to the contrary, "or" refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
Also, the indefinite articles "a" and "an" preceding an element or component of the invention are intended to be nonrestrictive regarding the number of instances (i.e. occurrences) of the element or component. Therefore "a" or "an" should be read to include one or at least one, and the singular word form of the element or component also includes the plural unless the number is obviously meant to be singular.
As referred to herein, the term "seedling", used either alone or in a combination of words means a young plant developing from the embryo of a seed.
As referred to herein, the term "broadleaf used either alone or in words such as "broadleaf weed" means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons. As used herein, the term "alkylating agent" refers to a chemical compound in which a carbon-containing radical is bound through a carbon atom to a leaving group such as halide or sulfonate, which is displaceable by bonding of a nucleophile to said carbon atom. Unless otherwise indicated, the term "alkylating" does not limit the carbon-containing radical to alkyl; the carbon- containing radicals in alkylating agents include the variety of carbon-bound substituent radicals specified for Q, R1 and R3.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkenyloxy" includes straight-chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH20, (CH3)2C=CHCH20, (CH3)CH=CHCH20, (CH3)CH=C(CH3)CH20 and
CH2=CHCH2CH20. "Alkynyloxy" includes straight-chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH20, CH3C≡CCH20 and CH3C≡CCH2CH20. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy. "Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. "Alkylamino", "dialkylamino", and the like, are defined analogously to the above examples.
"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. The term "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 F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkoxy", and the like, is defined analogously to the term "haloalkyl". Examples of "haloalkoxy" include CF30-, CC13CH20-, HCF2CH2CH20- and CF3CH20-. "Alkylcarbonyl" denotes a straight-chain or branched alkyl moieties bonded to a C(=0) moiety. Examples of "alkylcarbonyl" include CH3C(=0)-, CH3CH2CH2C(=0)- and (CH3)2CHC(=0)-. Examples of "alkoxycarbonyl" include CH3OC(=0)-, CH3CH2OC(=0)-, CH3CH2CH2OC(=0)-, (CH3)2CHOC(=0)- and the different butoxy- or pentoxycarbonyl isomers.
The total number of carbon atoms in a substituent group is indicated by the "C -Cj" prefix where i and j are numbers from 1 to 6. For example, C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl; C2 alkoxyalkyl designates CH3OCH2-; C3 alkoxyalkyl designates, for example, CH3CH(OCH3)-, CH3OCH2CH2- or CH3CH2OCH2-; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2- and CH3CH2OCH2CH2-. When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1 , said substituents (when they exceed 1) are independently selected from the group of defined substituents, (e.g., (R^)n, n is 0, 1 , 2 or 3). Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the integers between i and j inclusive. When a group contains a substituent which can be hydrogen, for example (when m = 0), then when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a variable group is shown to be optionally attached to a position, (for example (R^)n attached to Q wherein n may be 0, then hydrogen may be at the position even if not recited in the variable group definition. When one or more positions on a group are said to be "not substituted" or "unsubstituted", then hydrogen atoms are attached to take up any free valency.
Unless otherwise indicated, a "ring" as a component of Formula 1 (e.g., substituent Q) is carbocyclic or heterocyclic. The term "ring member" refers to an atom or heteroatom forming the backbone of a ring. When a fully unsaturated carbocyclic ring satisfies Huckel's rule, then said ring is also called an "aromatic ring". "Saturated carbocyclic" refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
The terms "heterocyclic ring", "heterocycle" denote a ring in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur. Typically a heterocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. Unless otherwise indicated, a heterocyclic ring can be a saturated, partially unsaturated, or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Huckel's rule, then said ring is also called a "heteroaromatic ring" or "aromatic heterocyclic ring". Unless otherwise indicated, heterocyclic rings can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
"Aromatic" indicates that each of the ring atoms is essentially in the same plane and has a /^-orbital perpendicular to the ring plane, and that (4n + 2) π electrons, where n is a positive integer, are associated with the ring to comply with Huckel's rule.
The term "optionally substituted" in connection with the heterocyclic rings refers to groups which are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the biological activity possessed by the unsubstituted analog. As used herein, the following definitions shall apply unless otherwise indicated. The term "optionally substituted" is used interchangeably with the phrase "substituted or unsubstituted" or with the term "(un)substituted." Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other. When Q is a 5- or 6-membered (nitrogen-containing) heterocyclic ring, it may be attached to the remainder of Formula 1 though any available carbon or nitrogen ring atom, unless otherwise described. As noted above, Q can be (among others) phenyl optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. An example of phenyl optionally substituted with one to five substituents is the ring illustrated as U-l in Exhibit 1, wherein Rv is R1 as defined in the Summary of the Invention for Q and r is an integer (from 0 to 4).
As noted above, Q can be (among others) 5- or 6-membered aromatic heterocyclic ring, which may be saturated or unsaturated, optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention. Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from one or more substituents include the rings U-2 through U-61 illustrated in Exhibit 1 wherein Rv is any substituent as defined in the Summary of the Invention for Q (i.e. R1) and r is an integer from 0 to 4, limited by the number of available positions on each U group. As U-29, U-30, U-36, U-37, U-38, U-39, U-40, U-41, U-42 and U-43 have only one available position, for these U groups r is limited to the integers 0 or 1 , and r being 0 means that the U group is unsubstituted and a hydrogen is present at the position indicated by (Rv)r.
Exhibit 1
Figure imgf000008_0001
U-2 U-3 U-4 U-5
Figure imgf000008_0002
U-7 U-8 U-9 U-10 U-l l
Figure imgf000008_0003
U-12 U-13 U-14 U-16 U-17
Figure imgf000009_0001
U-18 U-20 U-21 U-22
Figure imgf000009_0002
U-23 U-24 U-26 U-27 U-28
Figure imgf000009_0003
U-29 U-30 U-32 U-33 U-34
Figure imgf000009_0004
-42 -43 -45 -46
Figure imgf000009_0005
Figure imgf000010_0001
U-58 U-59 U-60 U-61
Although Rv groups are shown in the structures U-l through U-61, it is noted that they do not need to be present since they are optional substituents. Note that when Rv is H when attached to an atom, this is the same as if said atom is unsubstituted. The nitrogen atoms that require substitution to fill their valence are substituted with H or Rv. Note that when the attachment point between (Rv)r and the U group is illustrated as floating, (Rv)r can be attached to any available carbon atom or nitrogen atom of the U group. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. Note that some U groups can only be substituted with less than 4 Rv groups (e.g., U-2 through U-47 and U-52 through U-61).
A wide variety of synthetic methods are known in the art to enable preparation of aromatic and nonaromatic heterocyclic rings and ring systems; for extensive reviews see the eight volume set of Comprehensive Heterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief, Pergamon Press, Oxford, 1984 and the twelve volume set of Comprehensive Heterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V. Scriven editors-in-chief, Pergamon Press, Oxford, 1996.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. Stereoisomers are isomers of identical constitution but differing in the arrangement of their atoms in space and include enantiomers, diastereomers, cis-trans isomers (also known as geometric isomers) and atropisomers. Atropisomers result from restricted rotation about single bonds where the rotational barrier is high enough to permit isolation of the isomeric species. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
Compounds of Formula 1 typically exist in more than one form, and Formula 1 thus include all crystalline and non-crystalline forms of the compounds they represent. Noncrystalline 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). The term "polymorph" refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability. One skilled in the art will appreciate that a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1. Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures. For a comprehensive discussion of polymorphism see R. Hilfiker, Ed., Polymorphism in the Pharmaceutical Industry, Wiley- VCH, Weinheim, 2006.
One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
One skilled in the art recognizes that because in the environment and under physiological conditions salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms. Thus a wide variety of salts of a compound of Formula 1 are useful for control of undesired vegetation (i.e. are agriculturally suitable). The salts of a compound 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. When a compound of Formula 1 contains an acidic moiety such as a carboxylic acid or phenol, salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):
Embodiment 1. A com ound of Formula 1 wherein Q is selected from
Figure imgf000012_0001
Q-l Q-2 Q-3 Q-4 Q-5
Figure imgf000012_0002
Q-16 Q-17 Q-18 Q-19 Q-20
Figure imgf000013_0001
wherein r is 0, 1 , 2 or 3; and s is 0 or 1.
Embodiment 2. A compound of Embodiment 1 wherein Q is selected from Q-l
through Q-42.
Embodiment 3. A compound of Embodiment 2 wherein Q is selected from Q-7
through Q-24.
Embodiment 4. A compound of Embodiment 3 wherein Q is selected from Q-16 and Q-18.
Embodiment 5. A compound of Embodiment 4 wherein Q is Q-16.
Embodiment 6. A compound of Embodiment 4 wherein Q is Q-18.
Embodiment 7. A compound of Embodiment 1 wherein Q is selected from Q-43
through Q-55.
Embodiment 8. A compound of Embodiment 7 wherein Q is selected from Q-43, Q-
44, Q-45, Q-48, Q-49 and Q-50.
Embodiment 9. A compound of Embodiment 8 wherein Q is selected from Q-43, Q- 44 and Q-45.
Embodiment 10. A compound of Embodiment 9 wherein Q is Q-43.
Embodiment 1 1. A compound of Embodiment 10 wherein Q is Q-45.
Embodiment 12. A compound of Formula 1 or any one of Embodiments 1 through 1 1 either alone or in combination, wherein Z is O.
Embodiment 13. A compound of Formula 1 or any one of Embodiments 1 through 12 either alone or in combination, wherein each R1 is independently halogen, cyano,
SF5, CHO, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl,
C2-Cg alkoxycarbonyl, Cj-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C - C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy,
Figure imgf000014_0001
alkoxyalkyl,
Figure imgf000014_0002
hydroxyalkyl, C2-
C4 alkylthioalkyl or SOnR1A.
Embodiment 14. A compound of Embodiment 13 wherein each R1 is independently halogen, cyano, CHO, Cj-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, Cj-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C}-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C}-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy,
Figure imgf000014_0003
hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A.
Embodiment 15. A compound of Embodiment 14 wherein each R1 is independently halogen, cyano, Cj-C4 alkyl, Cj-C4 haloalkyl, Cj-C4 alkoxy, Cj-C4 haloalkoxy or SOnR1A.
Embodiment 16. A compound of Embodiment 15 wherein each R1 is independently halogen, C^-C4 alkyl, C^-C4 haloalkyl or C^-C4 haloalkoxy. Embodiment 17. A compound of Embodiment 16 wherein each R1 is independently halogen, C 1 -C4 haloalkyl or C1 -C4 haloalkoxy.
Embodiment 18. A compound of Embodiment 17 wherein each R1 is independently halogen or Ci -C4 haloalkyl.
Embodiment 19. A compound of Embodiment 18 wherein each R1 is independently F,
CI, Br, CF3, CHF2 or CH2F.
Embodiment 20. A compound of Formula 1 or any one of Embodiments 1 through 19 either alone or in combination, wherein r is 0, 1 or 2.
Embodiment 20a. A compound of Embodiment 20 wherein r is 1.
Embodiment 21. A compound of Formula 1 or any one of Embodiments 1 through 19 either alone or in combination, wherein s is 1.
Embodiment 21a. A compound of Formula 1 or any one of Embodiments 1 through
20a either alone or in combination, wherein when Q is Q-16 and r is 1 then R1 is attached at the 5 position of the Q-16 ring.
Embodiment 21b. A compound of Formula 1 or any one of Embodiments 1 through
20a either alone or in combination, wherein when Q is Q-18 and r is 1 then R1 is attached at the 3 position of the Q-18 ring.
Embodiment 22. A compound of Formula 1 or any one of Embodiments 1 through
21b either alone or in combination, wherein R2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl.
Embodiment 23. A compound of Embodiment 22 wherein R2 is halogen or Ci -C4 alkyl.
Embodiment 24. A compound of Embodiment 23 wherein R2 is halogen or CH3.
Embodiment 25. A compound of Embodiment 24 wherein R2 is halogen.
Embodiment 26. A compound of Embodiment 25 wherein R2 is F, CI or Br.
Embodiment 27. A compound of Formula 1 or any one of Embodiments 1 through 26 either alone or in combination, wherein m is 0, 1 or 2.
Embodiment 28. A compound of Embodiment 27 wherein m is 0 or 1.
Embodiment 29. A compound of Embodiment 28 wherein m is 1.
Embodiment 30. A compound of Embodiment 27 wherein m is 0 (i.e. the 3-, 4-, 5- and 6-positions are unsubtituted by R3).
Embodiment 31. A compound of Formula 1 or any one of Embodiments 1 through 30 either alone or in combination, wherein each R3 is independently halogen, cyano, CHO, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1 -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C(=0)N(R3A)(R3B), C(=NOR3C)H, SOnR3E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members.
Embodiment 32. A compound of Embodiment 31 wherein each R3 is independently halogen, cyano, CHO, C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1 -C4 alkoxy, C1 -C4 haloalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-C6 cyanoalkyl, SOnR3E; or a 5- or 6-membered
heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members.
Embodiment 33. A compound of Embodiment 32 wherein each R3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, Ci -C4 haloalkyl, C2-C6 alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C1 -C4 alkoxy, C1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl.
Embodiment 34. A compound of Embodiment 33 wherein each R3 is independently halogen, cyano, Ci -C4 alkyl or Ci -C4 haloalkyl.
Embodiment 35. A compound of Embodiment 34 wherein each R3 is independently halogen or cyano.
Embodiment 36. A compound of Embodiment 35 wherein each R3 is independently halogen.
Embodiment 37. A compound of Formula 1 or any one of Embodiments 1 through 36 either alone or in combination, wherein R3 is attached to the remainder of Formula 1 at the 3 -position.
Embodiment 38. A compound of Formula 1 or any one of Embodiments 1 through 37 either alone or in combination, wherein each R1A is independently Ci -C4 alkyl or C1 -C4 haloalkyl.
Embodiment 39. A compound of Embodiment 38 wherein each R1A is independently C1 -C4 haloalkyl. Embodiment 40. A compound of Formula 1 or any one of Embodiments 1 through 39 either alone or in combination, wherein each R3E is independently Ci -C4 alkyl. Embodiment 41. A compound of Formula 1 or any one of Embodiments 1 through 40 either alone or in combination, wherein each R3A is independently C i -C4 alkyl. Embodiment 42. A compound of Formula 1 or any one of Embodiments 1 through 41 either alone or in combination, wherein each R3B is independently H or Ci -C4 alkyl.
Embodiment 43. A compound of Formula 1 or any one of Embodiments 1 through 42 either alone or in combination, wherein each R3C is independently H or Ci -C4 alkyl.
Embodiment 44. A compound of Formula 1 or any one of Embodiments 1 through 43 either alone or in combination, wherein each R3D is independently H or C 1-C4 alkyl.
Embodiment 45. A compound of Formula 1 or any one of Embodiments 1 through 44 either alone or in combination, wherein each n is independently 0 or 2.
Embodiment 46. A compound of Embodiment 45 wherein n is 2.
Embodiment 47. A compound of Embodiment 45 wherein n is 0.
Embodiment 48. A compound of Formula 1 or any one of Embodiments 1 through 47 either alone or in combination, provided that i) when Q is 5-chloro-2-pyridinyl; Z is O; and R3 is 4 chloro, then R2 is other than CI or Br; ii) when Q is 4-CF3-2- pyrimidinyl; Z is O; and m is 0, then R2 is other than CI or Br; and iii) when Q is 6-CF3-2-pyridinyl; Z is O; and m is 0, then R2 is other than Br.
Embodiments of the present invention as described in the Summary of the Invention and Embodiment AAA also include the following:
Embodiment IP. A compound of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides as described in the Summary of the Invention.
Embodiment 2P. A compound of Embodiment 1 wherein Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, and optionally substituted with 1 to 3 R1.
Embodiment 3P. A com ound of Embodiment 2 wherein Q is selected from
Figure imgf000017_0001
Q-1 Q-2 Q-3 Q-4 Q-5
Figure imgf000018_0001
Figure imgf000019_0001
Q-41 Q-43 Q-45
Figure imgf000019_0002
r is 0, 1, 2 or 3; and
s is 0 or 1.
Embodiment 4P. A compound of any one of Embodiments 1 through 3 wherein Q is a
5- membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R1, and is selected from Q-1 through Q-41.
Embodiment 5P. A compound of Embodiment 4 wherein Q is selected from Q-7
through Q-24.
Embodiment 6P. A compound of Embodiment 5 wherein Q is selected from Q-9, Q- 11, Q-12, Q-16, Q-18, Q-22, Q-23, Q-24 and Q-25.
Embodiment 7P. A compound of Embodiment 6 wherein Q is selected from Q-11, Q- 18 and Q-22.
Embodiment 8P. A compound of any one of Embodiments 1 through 3 wherein Q is
6- membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R1, and is selected from Q-42 through Q-54.
Embodiment 9P. A compound of Embodiment 8 wherein Q is selected from Q-42, Q-
43, Q-44, Q-47, Q-48 and Q-49.
Embodiment 10P. A compound of Embodiment 9 wherein Q is selected from Q-42, Q- 43, Q-47 and Q-48. Embodiment 1 IP. A compound of Embodiment 10 wherein Q is selected from Q-42, Q-47 and Q-48.
Embodiment 12P. A compound of Embodiment 1 1 wherein Q is selected from Q-42. Embodiment 13P. A com ound of Embodiment 12 wherein Q is
Figure imgf000020_0001
Embodiment 14P. A compound of any one of Embodiments 1 through 3 wherein Q is selected from Q-7 through Q-24, Q-42, Q-43, Q-44, Q-47, Q-48 and Q-49.
Embodiment 15P. A compound of Embodiment 14 wherein Q is selected from Q-9, Q-l l , Q-12, Q-16, Q-18, Q-22, Q-23, Q-24, Q-25, Q-42, Q-43, Q-47 and Q-48.
Embodiment 16P. A compound of Embodiment 1 wherein Q is phenyl substituted with 1 to 3 Rl .
Embodiment 17P. A compound of Embodiment 16 whererin Q is phenyl substituted with 1 to 2 R! .
Embodiment 18P. A compound of Embodiment 17 wherein Q is phenyl substituted with 1 R1 at the 3- or 4-positions (i.e. meta or para to the attachment of phenyl to the remainder of Formula 1).
Embodiment 19P. A compound of Embodiment 1 wherein when Q is phenyl
substituted with 1 to 3 R1, m is 1 , 2 or 3.
Embodiment 20P. A compound of Embodiment 1 wherein when Q is phenyl
substituted with 1 to 3 R1, m is 1 or 2.
Embodiment 2 IP. A compound of Embodiment 1 wherein Q is other than phenyl
substituted with 1 to 4 R1.
Embodiment 22P. A compound of any one of Embodiments 1 through 21 wherein R1 is halogen, cyano, CHO, -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1-C4 haloalkyl, C1-C4 haloalkoxy, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl or SOnR1A.
Embodiment 23P. A compound of Embodiment 22 wherein R1 is halogen, cyano, -C4 alkyl, C1-C4 alkoxy, -C4 haloalkyl, -C4 haloalkoxy, or SCF3.
Embodiment 24P. A compound of Embodiment 23 wherein R1 is halogen, y-C^ alkyl or C1-C4 haloalkyl or y-C^ haloalkoxy.
Embodiment 25P. A compound of Embodiment 24 wherein R1 is halogen y-C^
haloalkyl or y-C^ haloalkoxy.
Embodiment 26P. A compound of Embodiment 25 wherein R1 is CI, Br, CF3 or OCF3. Embodiment 27P. A compound of any one of Embodiments 1 through 22 wherein each n is independently 0, 1 or 2.
Embodiment 28P. A compound of Embodiment 27 wherein each n is independently 0. Embodiment 29P. A compound of Embodiment 28 wherein each n is independently 2. Embodiment 30P. A compound of any one of Embodiments 1 through 29 wherein R2 is halogen, C1 -C4 alkyl or C 1 -C4 haloalkyl.
Embodiment 3 IP. A compound of Embodiment 30 wherein R2 is halogen or C1 -C4 alkyl.
Embodiment 32P. A compound of Embodiment 31 wherein R2 is halogen or CH3. Embodiment 33P. A compound of Embodiment 32 wherein R2 is halogen.
Embodiment 34P. A compound of Embodiment 33 wherein R2 is F, CI or Br.
Embodiment 35P. A compound of any one of Embodiments 1 through 34 wherein m is 0, 1 or 2.
Embodiment 36P. A compound of Embodiment 35 wherein m is 0 or 1.
Embodiment 37P. A compound of Embodiment 36 wherein m is 1.
Embodiment 38P. A compound of Embodiment 37 wherein m is 0 (i.e. the 3-, 4-, 5- and 6-positions of the benzene ring are unsubtituted by R3).
Embodiment 39P. A compound of any one of Embodiments 1 through 37 wherein each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C(=0)N(R3A)(R3B), C(=NOR3C)H,
C(=N)(R3D)H, CrC4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl, C 1 -C4 haloalkyl, CrC4 haloalkoxy, SOnR3E or C3-C6 cycloalkyl.
Embodiment 40P. A compound of Embodiment 39 wherein each R3 is independently halogen, cyano, amino, C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 alkoxy, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl or C1 -C4 haloalkyl.
Embodiment 41P. A compound of Embodiment 40 wherein each R3 is independently halogen, cyano, amino or C 1 -C4 alkyl.
Embodiment 42P. A compound of Embodiment 41 wherein each R3 is independently cyano.
Embodiment 43P. A compound of any one of Embodiments 1 through 37 or 39
through 42 wherein each R3 is attached to the remainder of Formula 1 at the 3-, 4- or 6-position.
Embodiment 44P. A compound of Embodiments 43 wherein each R3 is attached to the remainder of Formula 1 at the 3- or 4-position.
Embodiment 45P. A compound of Embodiment 44 wherein R3 is attached to the
remainder of Formula 1 at the 3 -position. Embodiment 46P. A compound of any one of Embodiments 1 through 22 or 27 or 29 through 45 wherein R1A is Ci -C4 alkyl or Ci -C4 haloalkyl.
Embodiment 47P. A compound of Embodiment 46 wherein R1A is Ci -C4 haloalkyl. Embodiment 48P. A compound of any one of Embodiments 1 through 37 or 39
wherein R3E is Ci -C4 alkyl.
Embodiment 49P. A compound of any one of Embodiments 1 through 37 or 39
wherein R3A is C 1 -C4 alkyl.
Embodiment 50P. A compound of any one of Embodiments 1 through 37 or 39
wherein R3B is H or Ci -C4 alkyl.
Embodiment 5 IP. A compound of any one of Embodiments 1 through 37 or 39
wherein R3C is H or Ci -C4 alkyl.
Embodiment 52P. A compound of any one of Embodiments 1 through 37 or 39
wherein R3D is H or Ci -C4 alkyl.
Embodiment 53P. A compound of any one of Embodiments 1 through 52 wherein Z is
O.
Embodiment 54P. A compound of any one of Embodiments 1 through 53 wherein
when m is 1, R3 is positioned at the 3-, 5- or 6-positions (i.e. the 3-, 5- and 6- positions of the benzene ring).
Embodiment 55P. A compound of any one of Embodiments 1 through 53 wherein
when m is 1, R3 is other than CI at the 4-position.
Embodiments of this invention, including Embodiments 1-48 and 1P-55P above as well as any other embodiments described herein, can be combined in any manner, and the descriptions of variables in the embodiments pertain not only to the a compound of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. In addition, embodiments of this invention, including Embodiments 1-48 and 1P-55P above as well as any other embodiments described herein, and any combination thereof, pertain to the compositions and methods of the present invention.
Embodiment AAA. A compound of Formula 1 wherein
Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
Formula 1 through a carbon atom, and optionally substituted with 1 to 4 R1; or Q is phenyl substituted with 1 to 4 R1;
Z is O or S;
R1 is halogen, cyano, CHO, C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkyl, Ci -C4 haloalkoxy, C2- C4 alkoxyalkyl, C2-C4 alkylthioalkyl, SOnR1A, C2-Cg dialkylamino, C1 -C4 cyanoalkyl, C 1 -C4 hydroxyalkyl, CH(=NOH) or C3-C6 cycloalkyl; or unsubstituted phenyl; or unsubstituted pyridyl; R2 is halogen, cyano, nitro, C1 -C4 alkoxy, C 1 -C4 alkyl, C2-Cg alkenyl, C2-Cg alkynyl, SOnR2A or C1-C4 haloalkyl;
each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C(=0)N(R3A)(R3B), C(=NOR3C)H, C(=N)(R3D)H, CrC4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl, C 1 -C4 haloalkyl, Ci -C4 haloalkoxy, SOnR E or C3-C6 cycloalkyl; or phenyl optionally substituted with cyano, halogen or Ci -C4 alkyl;
m is 0, 1, 2 or 3;
each R1A, R2A and R3E is independently CrC4 alkyl, CrC4 haloalkyl, CrC4
alkylamino or
Figure imgf000023_0001
dialkylamino;
R3A is C1-C4 alkyl or CrC4 haloalkyl;
R3B is H, CrC4 alkyl or CrC4 haloalkyl;
R C is independently H or Ci -C4 alkyl;
R D is independently H or C 1 -C4 alkyl; and
n is 0, 1, or 2;
provided the compound of Formula 1 is other than 5-chloro-2-[(4'-methyl[l,l'- biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-74-0), 5-chloro-2-[(4'- chloro[l,r-biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-72-8), 5-chloro-2- [(3*-chloro[l,r-biphenyl]2-yl)oxy]-pyrimidine (CAS # 107492-76-2) and 5-chloro-2-[[3'-(trifluoromethyl)[ 1 , 1 '-biphenyl]2-yl]oxy]-pyrimidine (CAS # 107492-75-1); and provided i) when Q is 5-chloro-2-pyridinyl; Z is O; and R3 is 4-chloro, then R2 is other than CI or Br; ii) when Q is 4-CF3-2-pyrimidinyl; Z is O; and m is 0, then R2 is other than CI or Br; and iii) when Q is 6-CF3-2- pyridinyl; Z is O; and m is 0, then R2 is other than Br.
Embodiment AA. A compound of Embodiment AAA or a compound of Formula 1 as described in the Summary of the Invention wherein
Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
Formula 1 through a carbon atom, and optionally substituted with 1 to 4 R1; Z is O or S;
each R1 is independently halogen, cyano, nitro, SF5, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C2-Cg alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-Cg
alkoxyhaloalkyl, C2~Cg alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-Cg cyanoalkyl, C2-Cg cyanoalkoxy, Ci -C4 hydroxyalkyl, C2-C4 alkylthioalkyl, SOnR1A, Si(CH3)3 or B(-OC(R1B)2C(R1B)20-); or a phenyl ring optionally substituted with up to 5 substituents independently selected from R1C; or a 5- or
6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R1C on carbon atom ring members and R1D on nitrogen atom ring members;
R2 is halogen, cyano, nitro, C1 -C4 alkoxy, C 1 -C4 alkyl, C2-Cg alkenyl, C2-Cg alkynyl,
SOnR2A, C1-C4 haloalkyl or C3-C6 cycloalkyl;
each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C4-C8 cycloalkylalkyl, C2~Cg alkylcarbonyl, C2~Cg haloalkylcarbonyl, C2~Cg alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1 -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C2~Cg alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-Cg cyanoalkyl, C2-Cg cyanoalkoxy, C2-C4 alkylthioalkyl, Si(CH3)3, C≡CSi(CH3)3, C(=0)N(R3A)(R3B), C(=NOR3C)H, C(=NR3D)H, SOnR E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R F on carbon atom ring members and R3G on nitrogen atom ring members; or pyrimidinyloxy;
m is 0, 1, 2 or 3;
each n is independently 0, 1 or 2;
each R1A, R2A and R3E is independently CrC4 alkyl, CrC4 haloalkyl, CrC4
alkylamino or C2-C6 dialkylamino;
each R1B is independently H or Ci -C4 alkyl;
each R1C is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy; each R1D is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2-
Cg alkylcarbonyl;
each R3A is independently Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3B is independently H, Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3C is independently H or Ci -C4 alkyl;
each R3D is independently H, amino, Ci -C4 alkyl or Ci -C4 alkylamino;
each R F is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy; and
each R G is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2- Cg alkylcarbonyl;
Embodiment A. A compound of Embodiment AA wherein
Q is selected from Q-l through Q-55 wherein r is 0, 1, 2 or 3; and s is 0 or 1;
each R1 is independently halogen, cyano, SF5, CHO, Ci -C4 alkyl, C2-C4 alkenyl,
C2-C4 alkynyl, Ci -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2~Cg alkylcarbonyl, C2~Cg haloalkylcarbonyl, C2~Cg alkoxycarbonyl, C1 -C4 alkoxy,
C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-Cg cyanoalkyl, C1 -C4 hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A;
R3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, i -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg cycloalkyl,
C3-Cg halocycloalkyl, C4-C8 alkylcycloalkyl, C2~Cg alkylcarbonyl, C2~Cg haloalkylcarbonyl, C2~Cg alkoxycarbonyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3- C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4
haloalkynyloxy, C3~Cg cycloalkoxy, C3~Cg halocycloalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-Cg cyanoalkyl,
C(=0)N(R3A)(R3B), C(=NOR3C)H, SOnR3E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members;
Z is O; and
m is 0, 1 or 2.
Embodiment B. A compound of Embodiment A wherein
each R1 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C1 -C4 hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A;
R2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-Cg alkylcarbonyl, C2-Cg
haloalkylcarbonyl, C2-C6 alkoxycarbonyl, Ci -C4 alkoxy, Ci -C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, SOnR3E; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members; and
m is 0 or 1.
Embodiment C 1. A compound of Embodiment B wherein
Q is selected from Q-7 through Q-24;
each R1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
CrC4 haloalkoxy or SOnR1A;
R2 is halogen or Ci -C4 alkyl;
each R3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl,
C1 -C4 haloalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and
each R1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
Embodiment C2. A compound of Embodiment B wherein
Q is selected from Q-43, Q-44, Q-45, Q-48, Q-49 and Q-50;
each R1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
CrC4 haloalkoxy or SOnR1A;
R2 is halogen or Ci -C4 alkyl;
each R3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl,
C1 -C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and
each R1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
Embodiment D 1. A compound of Embodiment C 1 wherein
Q is selected from Q-16 and Q-18;
each R1 is independently halogen, Ci -C4 alkyl, Ci -C4 haloalkyl or Ci -C4 haloalkoxy; R2 is halogen or CH3; and each R3 is independently halogen, cyano, Ci -C4 alkyl or C i -C4 haloalkyl.
Embodiment D2. A compound of Embodiment C2 wherein
Q is selected from Q-43, Q-44 and Q-45;
each R1 is independently halogen, Ci -C4 alkyl, C i -C4 haloalkyl or Ci -C4 haloalkoxy; R2 is halogen or CH3; and
each R3 is independently halogen, cyano, Ci -C4 alkyl or C i -C4 haloalkyl.
Specific embodiments include compounds of Formula 1 selected from the group consisting of:
5-chloro-2-[2-(5-chloro-2-pyridinyl)phenoxy]pyrimidine (Compound 1),
5-chloro-2-[2-[5-(fluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine (Compound 32),
2-[2-(3-bromo-5-isoxazolyl)phenoxy]-5-chloropyrimidine (Compound 12),
5-chloro-2-[2-[5-(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine (Compound 27),
5-chloro-2-[3-chloro-2-(5-chloro-2-pyridinyl)phenoxy]pyrimidine (Compound 23),
4- [2-[(5-bromo-2-pyrimidinyl)oxy]phenyl]-2-(trifluoromethyl)pyrimidine
(Compound 21),
2- [2-(2-bromo-5 -thiazolyl)phenoxy] -5 -(trifluoromethyl)pyrimidine (Compound 15),
5- chloro-2-[4-methyl-2-[2-(trifluoromethyl)-4-pyridinyl]phenoxy]pyrimidine
(Compound 24),
5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine (Compound 35),
5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine (Compound 53),
5 -chloro-2-[2- [5 -(difluoromethyl)-3 -isoxazolyl] -3 -fluorophenoxy]pyrimidine
(Compound 55),
5-bromo-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine (Compound
62) ,
5-chloro-2-[2-[3-(trifluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine (Compound
63) ,
5 -chloro-2-[2- [3 -(difluoromethyl)-5 -isoxazolyl] -3 -fluorophenoxy]pyrimidine
(Compound 144),
5 -bromo-2- [2- [3 -(difluoromethyl)-5 -isoxazolyl]-3 -fluorophenoxy]pyrimidine
(Compound 145),
5 -chloro-2-[2-[5 -(trifluoromethyl)-3 -isoxazolyl] -3 -fluorophenoxy]pyrimi dine
(Compound 168) and 5-chloro-2-[2-[5-(trifluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine (Compound 200).
Embodiments of the present invention as described in the Summary of the Invention and Embodiment AAA also include the following:
Embodiment Ap. A compound of the Summary of the Invention wherein
Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, and optionally substituted with 1 to 3 R1; or
Q is phenyl substituted with 1 to 3 R1;
R1 is halogen, cyano, CHO, C1 -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkyl, Ci -C4 haloalkoxy, C2- C4 alkoxyalkyl, C2-C4 alkylthioalkyl or SOnR1A;
each n is independently 0, 1 or 2
R2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl;
m is 0, 1 or 2;
each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C(=0)N(R3A)(R3B), C(=NOR3C)H, C(=N)(R3D)H, CrC4 alkoxy, C2-C4 cyanoalkoxy, C2-C4 alkylcarbonyl, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl, C 1 -C4 haloalkyl, CrC4 haloalkoxy, SOnR3E or C3-C6 cycloalkyl;
each R3 is attached to the remainder of Formula 1 at the 3-, 4- or 6-position;
R1A is C1-C4 alkyl or CrC4 haloalkyl;
R3E is CrC4 alkyl;
R3A is C1-C4 alkyl;
R3B is H or CrC4 alkyl;
R3C is H or CrC4 alkyl; and
R3D is H or CrC4 alkyl.
Embodiment Bp. A compound of Embodiment A wherein
Q is selected from Q-l through Q-54 (i.e. as described in Embodiment 3);
Z is O;
R1 is halogen, cyano, C 1 -C4 alkyl, C1 -C4 alkoxy, C 1 -C4 haloalkyl, C1 -C4 haloalkoxy, or SCF3;
R2 is halogen or Ci -C4 alkyl;
m is 0 or 1 ;
each R3 is independently halogen, cyano, amino, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 alkoxy, C2-C4 alkoxycarbonyl, C2-C4 alkylcarbonyloxy, C2-C4 alkoxyalkyl or Ci -C4 haloalkyl; and
each R3 is attached to the remainder of Formula 1 at the 3- or 4-position.
Embodiment Cp. A compound of Embodiment B wherein Q is a 5-membered aromatic heterocylic ring, bound to the remainder of Formula 1 through a carbon atom, optionally substituted with R1, and is selected from Q-l through Q-41;
R1 is halogen C1-C4 haloalkyl or C1-C4 haloalkoxy;
R2 is halogen or CH3; and
each R3 is independently halogen, cyano, amino or C1-C4 alkyl.
Embodiment Dp. A compound of Embodiment C wherein
Q is 6-membered aromatic heterocylic ring, bound to the remainder of Formula 1
through a carbon atom, optionally substituted with R1, and is selected from Q-42 through Q-54;
R1 is halogen C1-C4 haloalkyl or C1-C4 haloalkoxy;
R2 is halogen or CH3; and
each R3 is independently halogen, cyano, amino or C1-C4 alkyl.
Embodiment Ep. A compound of Embodiment D wherein
Q is selected from Q-42, Q-43, Q-44, Q-47, Q-48 and Q-49;
R1 is CI, Br, CF3 or OCF3;
R2 is halogen; and
each R3 is independently cyano.
Specific embodiments include a compound of Formula 1 selected from the group consisting of:
5 -chloro-2- [2-(5 -chloro-2-pyridinyl)phenoxy]pyrimidine (Compound 1 );
5-chloro-2-[2-[5-(fluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine (Compound 32); 2-[2-(3-bromo-5-isoxazolyl)phenoxy]-5-chloropyrimidine (Compound 12);
5 -chloro-2- [[4'-(trifluoromethoxy) [1,1 '-biphenyl] -2-yl]oxy]pyrimidine (Compound 42);
5 -chloro-2- [2- [5 -(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine (Compound 27); 5 -chloro-2- [3 -chloro-2-(5 -chloro-2 -pyridinyl)phenoxy]pyrimidine (Compound 23); 4- [2- [(5 -bromo-2-pyrimidinyl)oxy]phenyl] -2-(trifluoromethyl)pyrimidine (Compound
21);
2-[2-(2-bromo-5-thiazolyl)phenoxy]-5-(trifluoromethyl)pyrimidine (Compound 15); and
5 -chloro-2- [4-methyl-2- [2-(trifluoromethyl)-4-pyridinyl]phenoxy]pyrimidine
(Compound 24).
This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). Of note as embodiments relating to methods of use are those involving the compounds of embodiments described above. Compounds of the invention are particularly useful for selective control of weeds in crops such as wheat, barley, maize, soybean, sunflower, cotton, oilseed rape and rice, and specialty crops such as sugarcane, citrus, fruit and nut crops.
Also noteworthy as embodiments are herbicidal compositions of the present invention comprising the compounds of embodiments described above.
This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics and (b5) 5 -enol-pyruvylshikimate-3 -phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (blO) auxin transport inhibitors, (bl 1) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl-pyruvate dioxygenase (HPPD) inhibitors, (bl3) homogentisate solenesyltransererase (HST) inhibitors, (bl4) cellulose biosynthesis inhibitors, (bl5) other herbicides including mitotic disruptors, organic arsenicals, asulam, bromobutide, cinmethylin, cumyluron, dazomet, difenzoquat, dymron, etobenzanid, flurenol, fosamine, fosamine-ammonium, metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid and pyributicarb, and (bl6) herbicide safeners; and salts of compounds of (bl) through (bl6).
"Photosystem II inhibitors" (bl) are chemical compounds that bind to the D-l protein at the Qfl-binding niche and thus block electron transport from to QB in the chloroplast thylakoid membranes. The electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction. The QB-binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate. Examples of photosystem II inhibitors include ametryn, amicarbazone, atrazine, bentazon, bromacil, bromofenoxim, bromoxynil, chlorbromuron, chloridazon, chlorotoluron, chloroxuron, cumyluron, cyanazine, daimuron, desmedipham, desmetryn, dimefuron, dimethametryn, diuron, ethidimuron, fenuron, fluometuron, hexazinone, ioxynil, isoproturon, isouron, lenacil, linuron, metamitron, methabenzthiazuron, metobromuron, metoxuron, metribuzin, monolinuron, neburon, pentanochlor, phenmedipham, prometon, prometryn, propanil, propazine, pyridafol, pyridate, siduron, simazine, simetryn, tebuthiuron, terbacil, terbumeton, terbuthylazine, terbutryn and trietazine.
"AHAS inhibitors" (b2) are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for protein synthesis and cell growth. Examples of AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, bispyribac-sodium, cloransulam-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, diclosulam, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, florasulam, flucarbazone-sodium, flumetsulam, flupyrsulfuron-methyl, flupyrsulfuron- sodium, foramsulfuron, halosulfuron-methyl, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazethapyr, imazosulfuron, iodosulfuron-methyl (including sodium salt), iofensulfuron (2-iodo-N-[[(4-methoxy-6-methyl-l ,3,5-triazin-2- yl)amino]carbonyl]benzenesulfonamide), mesosulfuron-methyl, metazosulfuron (3-chloro-4- (5,6-dihydro-5-methyl-l,4,2-dioxazin-3-yl)-N-[[(4,6-dimethoxy-2- pyrimidinyl)amino]carbonyl]- 1 -methyl- lH-pyrazole-5-sulfonamide), metosulam, metsulfuron-methyl, nicosulfuron, oxasulfuron, penoxsulam, primisulfuron-methyl, propoxycarbazone-sodium, propyrisulfuron (2-chloro-N-[[(4,6-dimethoxy-2- pyrimidinyl)amino] carbonyl] -6-propylimidazo [ 1 ,2-¾]pyridazine-3 -sulfonamide),
prosulfuron, pyrazosulfuron-ethyl, pyribenzoxim, pyriftalid, pyriminobac-methyl, pyrithiobac-sodium, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thiencarbazone, thifensulfuron-methyl, triafamone (N-[2-[(4,6-dimethoxy-l,3,5-triazin-2-yl)carbonyl]-6- fluorophenyl] -1,1 -difluoro-N-methylmethanesulfonamide), triasulfuron, tribenuron-methyl, trifloxysulfuron (including sodium salt), triflusulfuron-methyl and tritosulfuron.
"ACCase inhibitors" (b3) are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back. Examples of ACCase inhibitors include alloxydim, butroxydim, clethodim, clodinafop, cycloxydim, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, pinoxaden, profoxydim, propaquizafop, quizalofop, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl and fenoxaprop-P-ethyl.
Auxin is a plant hormone that regulates growth in many plant tissues. "Auxin mimics" (b4) are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species. Examples of auxin mimics include aminocyclopyrachlor (6-amino-5-chloro-2-cyclopropyl- 4-pyrimidinecarboxylic acid) and its methyl and ethyl esters and its sodium and potassium salts, aminopyralid, benazolin-ethyl, chloramben, clacyfos, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro-6-(4-chloro-2-fluoro- 3-methoxyphenyl)-2-pyridinecarboxylic acid), halauxifen-methyl (methyl 4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylate), MCPA, MCPB, mecoprop, picloram, quinclorac, quinmerac, 2,3,6-TBA, triclopyr, and methyl 4-amino-3-chloro-6-(4- chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate.
"EPSP (5 -enol-pyruvylshikimate-3 -phosphate) synthase inhibitors" (b5) are chemical compounds that inhibit the enzyme, 5 -enol-pyruvylshikimate-3 -phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine. EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points. Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group. Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).
"Photosystem I electron diverters" (b6) are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles "leak", leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include diquat and paraquat.
"PPO inhibitors" (b7) are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out. Examples of PPO inhibitors include acifluorfen-sodium, azafenidin, benzfendizone, bifenox, butafenacil, carfentrazone, carfentrazone-ethyl, chlomethoxyfen, cinidon-ethyl, fluazolate, flufenpyr-ethyl, flumiclorac-pentyl, flumioxazin, fluoroglycofen-ethyl, fluthiacet-methyl, fomesafen, halosafen, lactofen, oxadiargyl, oxadiazon, oxyfluorfen, pentoxazone, profluazol, pyraclonil, pyraflufen-ethyl, saflufenacil, sulfentrazone, thidiazimin, tiafenacil (methyl N-[2- [[2-chloro-5-[3 ,6-dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)- 1 (2H)-pyrimidinyl]-4- fluorophenyl]thio]-l-oxopropyl]-P-alaninate) and 3-[7-fluoro-3,4-dihydro-3-oxo-4-(2- propyn- 1 -yl)-2H- 1 ,4-benzoxazin-6-yl] dihydro- 1 ,5 -dimethyl-6-thioxo- 1 ,3 ,5 -triazine- 2,4(lH,3H)-dione.
"GS (glutamine synthase) inhibitors" (b8) are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes. The GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P ((25)-2-amino-4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.
"VLCFA (very long chain fatty acid) elongase inhibitors" (b9) are herbicides having a wide variety of chemical structures, which inhibit the elongase. Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs. In plants, very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains. Such herbicides include acetochlor, alachlor, anilofos, butachlor, cafenstrole, dimethachlor, dimethenamid, diphenamid, fenoxasulfone (3-[[(2,5-dichloro-4-ethoxyphenyl)methyl]sulfonyl]-4,5-dihydro- 5,5-dimethylisoxazole), fentrazamide, flufenacet, indanofan, mefenacet, metazachlor, metolachlor, naproanilide, napropamide, napropamide-M ((2R)-N,N-diethyl-2-(l- naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.
"Auxin transport inhibitors" (blO) are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein. Examples of auxin transport inhibitors include diflufenzopyr, naptalam (also known as N-(l-naphthyl)phthalamic acid and 2-[(l-naphthalenylamino)carbonyl]benzoic acid).
"PDS (phytoene desaturase inhibitors) (bl l) are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step. Examples of PDS inhibitors include beflubutamid, diflufenican, fluridone, flurochloridone, flurtamone norflurzon and picolinafen.
"HPPD (4-hydroxyphenyl-pyruvate dioxygenase) inhibitors" (bl2) are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase. Examples of HPPD inhibitors include benzobicyclon, benzofenap, bicyclopyrone (4-hydroxy-3 -[ [2-[(2-methoxyethoxy)methyl] -6-(trifluoromethyl)-3 - pyridinyl]carbonyl]bicyclo[3.2.1]oct-3-en-2-one), fenquinotrione (2-[[8-chloro-3,4-dihydro- 4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]carbonyl]-l,3-cyclohexanedione),
isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrione, tefuryltrione, tembotrione, topramezone, 5-chloro-3-[(2-hydroxy-6-oxo-l- cyclohexen-l-yl)carbonyl]-l-(4-methoxyphenyl)-2(lH)-quinoxalinone, 4-(2,6-diethyl-4- methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone, 4-(4-fluorophenyl)-6-[(2- hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-methyl-l,2,4-triazine-3,5(2H,4H)-dione, 5- [(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2-(3-methoxyphenyl)-3-(3-methoxypropyl)- 4(3H)-pyrimidinone, 2-methyl-N-(4-methyl- 1 ,2,5-oxadiazol-3-yl)-3-(methylsulfmyl)-4- (trifluoromethyl)benzamide and 2-methyl-3-(methylsulfonyl)-N-(l -methyl- lH-tetrazol-5-yl)- 4-(trifluoromethyl)benzamide. HST (homogentisate solenesyltransererase) inhibitors (bl3) disrupt a plant's ability to convert homogentisate to 2-methyl-6-solanyl-l ,4-benzoquinone, thereby disrupting carotenoid biosynthesis. Examples of HST inhibitors include haloxydine, pyriclor, 3-(2- chloro-3 ,6-difluorophenyl)-4-hydroxy- 1 -methyl- 1 ,5 -naphthyridin-2( lH)-one, 7-(3 ,5 - dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-¾]pyrazin-6(5H)-one and 4- (2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.
HST inhibitors also include com ounds of Formulae A and B.
Figure imgf000034_0001
B
wherein Rdl is H, CI or CF3; Rd2 is H, CI or Br; Rd3 is H or CI; Rd4 is H, CI or CF3; Rd5 is CH3, CH2CH3 or CH2CHF2; and Rd6 is OH, or -OC(=0)-z-Pr; and Rel is H, F, CI, CH3 or CH2CH3; Re2 is H or CF3; Re3 is H, CH3 or CH2CH3; Re4 is H, F or Br; Re5 is CI, CH3, CF3, OCF3 or CH2CH3; Re6 is H, CH3, CH2CHF2 or C≡CH; Re7 is
OH, -OC(=0)Et, -OC(=0)-z-Pr or -OC(=0)-t-Bu; and Ae8 is N or CH.
Cellulose biosynthesis inhibitors (bl4) inhibit the biosynthesis of cellulose in certain plants. They are most effective when using a pre-aplication or early post-application on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N2-[(li?,25)-2,3-dihydro-2,6-dimethyl-lH- inden-l-yl]-6-(l-fluoroethyl)-l ,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
Other herbicides (bl5) include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl) organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors. Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (bl) through (bl4) or act through a combination of modes of action listed above. Examples of other herbicides include aclonifen, asulam, amitrole, bromobutide, cinmethylin, clomazone, cumyluron, cyclopyrimorate (6-chloro-3-(2- cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), daimuron, difenzoquat, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone ( 1 -(2,4-dichlorophenyl)-N-(2,4-dif uorophenyl)- 1 ,5-dihydro-N-( 1 - methylethyl)-5-oxo-4H-l ,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb and 5-[[(2,6-difluorophenyl)methoxy]methyl]- 4,5-dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole.
"Herbicide safeners" (bl6) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops. These compounds protect crops from injury by herbicides but typically do not prevent the herbicide from controlling undesired vegetation. Examples of herbicide safeners include but are not limited to benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, dicyclonon, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-diethyl, mephenate, methoxyphenone, naphthalic anhydride, oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide and N- (aminocarbonyl)-2-fluorobenzenesulfonamide, l-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), 4-(dichloroacetyl)-l-oxa- 4-azospiro[4.5]decane (MON 4660).
The compounds of Formula 1 can be prepared by general methods known in the art of synthetic organic chemistry. One or more of the following methods and variations as described in Schemes 1-9 can be used to prepare the compounds of Formula 1. The definitions of Q, R1, R2 and R3 in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention unless otherwise noted. Compounds of Formulae 1A-1C, 2A-2F, 4A and 8A are various subsets of the compounds of Formula 1, 2 4 and 8 and all substituents for Formulae 1A-1C, 2A-2F, 4A and 8A are as defined above for Formula 1 unless otherwise noted.
One or more of the following methods and variations as described in Schemes 1-9 can be used to prepare the compounds of Formula 1. The definitions of Q, R1, R2 and R3 in the compounds of Formulae 1-11 below are as defined above in the Summary of the Invention unless otherwise noted.
As shown in Scheme 1 a compound of Formula 1 can be prepared by nucleophilic substitution by heating a compound of Formula 2 in a suitable solvent, such as acetonitrile, tetrahydrofuran or N,N-dimethylformamide in the presence of a base such as potassium or cesium carbonate, at temperatures ranging from 50 to 110 °C, with a compound of Formula 3 (where LG is halogen or S02Me). The reaction is typically conducted at temperatures ranging from 50 to 110 °C. Scheme 1
Figure imgf000036_0001
LG is halogen or SO2CH3
Alternatively, as shown in Scheme 2, boron compounds of Formula 5 or tin compounds of Formula 6 can be coupled with intermediates of Formula 4 under Suzuki or Stille conditions to give compounds of Formula 1. Suzuki couplings typically are conducted in the presence of Pd(0) or Pd(II) salts, a suitable ligand, and a base. Suitable bases for this transformation include potassium carbonate or cesium carbonate, while Pd(II) salts such as Pd(OAc)2 or PdCl2 can be used in conjunction with ligands such as triphenylphosphine or l,l'-bis(diphenylphosphino)ferrocene (dppf). Conditions for Suzuki couplings are well documented in the literature (see for example Angewandte Chemie International Edition 2006, 45, 3484 and Tetrahedron Letters 2002, 55(14), 2885). Boron intermediates of Formula 5 are commercially available or can be prepared from the corresponding halides or trifluoromethanesulfonates by methods known in the literature (see for example PCT Patent Publication WO 2007/043278, US Pat. No. 8,080,566, Organic Letters 2011, 75(6), 1366 and Organic Letters 2012, 14(2), 600). Stille couplings typically can be conducted in the presence of Pd(0) or a Pd(II) salt, a ligand and a Cu(I) salt such as copper(I) iodide. The reaction can be run in a solvent such as dioxane, 1 ,2-dimethoxyethane or toluene at a temperature ranging from ambient to reflux. For conditions and reagents employed in Stille couplings see Chemical Reviews 2007, 107(1), 133-173.
Scheme 2
,B(OR)2
palladium catalyst,
Figure imgf000037_0001
R = C , - C4 alkyl
As shown in Scheme 3, a compound of Formula 2C (i.e. a compound of Formula 2 where Z is O) can be prepared by deprotection of a compound of Formula 2B (i.e. a compound of Formula 2A wherein Z is O; and R^ is CH3 or -C(=0)CH3) with a suitable deprotecting agent. Suitable methoxy (i.e. when RA is CH3) deprotecting reagents such as BBr3, AICI3 and HBr in acetic acid can be used in the presence of solvents such as toluene, dichloromethane and dichloroethane at a temperature of from -80 to 120 °C. Suitable acetoxy (i.e. when RA is -C(=0)CH3) deprotecting agents include potassium carbonate in methanol or ammonium acetate in aqueous methanol at room temperature can be used as discussed in Das, et al, Tetrahedron 2003, 59, 1049-1054 and methods cited therein. Alternatively, a compound of Formula 2B can be combined with Amberlyst 15® in methanol (as discussed in Das, et al. Tet. Lett. 2003, 44, 5465-5468) or combined with sodium acetate in ethanol (as discussed in Narender, T., et al. Synthetic Communications 2009, 39(11), 1949-1956) to obtain a compound of Formula 2C. Other useful phenolic protecting groups suitable for use in preparing a compound of Formula 2C can be found in Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, New Jersey, 1991.
Scheme 3
Figure imgf000037_0002
2B
RA = CH3 or -C(=0)CH3 2C An intermediate of Formula 2B can be prepared as shown in Scheme 4 from an intermediate of Formula 7 by a variety of methods known to one skilled in the art. Compounds of Formula 2B can be accessed by coupling precursors of Formula 7 wherein J is Br, CI, I or trifluoromethanesulfonate with boronate or trialkyltin group-containing heterocycles (i.e compounds of Formula 5 or Formula 6 using the Suzuki conditions or the Stille conditions of Scheme 2). Alternatively, compounds of Formula 7 wherein J is a boronate or trialkyltin group may be coupled with halogen-substituted heterocycles Q-X using the methods shown in Scheme 2 to afford compounds of Formula 2B. The skilled chemist will realize that with the prudent choice of groups X and J in reactions involving compounds of Formula 7 and Q-X can synthesize the intermediate 2B utilizing various cross coupling procedures such as Kumada coupling, Hiyama coupling or Negishi coupling described in "Metal-Catalyzed Cross-Coupling Reactions", Eds. A. de Meijere and F. Diederich, Wiley- VCH, Weinheim, 2004, vols 1 and 2.
When J in Formula 7 is an alkene, alkyne, oxime, nitrile or ketone, various heterocycles can be prepared using methods described in Katritsky, Advances in Heterocyclic Chemistry, Vol. 1-104, Elsevier. In cases where regioisomeric mixtures are produced, the desired product can be isolated using routing separation techniques known in the art.
Scheme 4
Figure imgf000038_0001
7 2B
RA is CH3 or -C(=0)CH3
As shown in Scheme 5, a compound of Formula 4A can be prepared by coupling of phenols of Formula 9 with a compound of Formula 3 under the nucleophilic substitution conditions described in Scheme 1.
5
Figure imgf000038_0002
4A
or OS02CF3
As shown in Scheme 6, a compound of Formula IB, (i.e. a compound of Formula 1 where Z is O; and m is 1 at the 3-position) can be prepared by "C-H activation" of a compound of Formula 1A (a compound of Formula 1 wherein Z is O; and m is 0). For example, paladium(II) acetate along with either an N-halosuccinimide, PhI(OAc)2, N-fluoropyridinium tetrafluoroborate, or a lower alkyl boronic acid can be used to introduce the R3 variable as I, Br, CI, -OAc, F, and lower alkyl substituents respectively. These methods are detailed in reviews of selective activation of C-H bonds in Chemical Reviews 2010, 110, 575-1211 and references cited therein. Methods for "C-H activation" can also be found in Wencel-Delord et al, Nature Chemistry 2013, 5, 369-375 and a series of reviews of "C-H activation" in Accounts of Chemical Research 2012, 45, 777-958 and references cited therein. Iodides and bromides of Formula IB can then be further functionalized by various cross coupling procedures described in "Metal-Catalyzed Cross-Coupling Reactions", Eds A. de Meijere and F. Diederich, Wiley- VCH, Weinheim, 2004, vols 1 and 2.
heme 6
Figure imgf000039_0001
Chemistry based on "C-H activation" can also be used to prepare a compound of Formula 2D (i.e. a compound of Formula 2 wherein Z is O; R is -C(0)CH3; and m is 1 at the 3 -position) as shown in Scheme 7 utilizing palladium(II) acetate and (diacetoxyiodo)benzene as described above for Scheme 6. A compound of Formula 2D can subsequently be converted via methods disclosed in Schemes 1 and 6 to provide a compound of Formula 1.
Scheme 7
Figure imgf000039_0002
Similarly, chemistry based on "C-H activation" can be used to prepare a compound of Formulae 2F (i.e. a compound of Formula 2A wherein Z is S) as shown in Scheme 8. A compound of Formula 8 can first be converted to a compound of Formula 8A (i.e. a compound of Formula 6 wherin the ortho "H" is X; and X is Br or I) by utilizing a stepwise introduction of substituents using "C-H activation". Iodides and bromides of Formula 8A can then be further functionalized by copper mediated cross-coupling with thiourea as described in Qi, Junsheng, Chin. J. Chem. 2010, 28, 1441-1443 to provide the aryl thiol after acidic deprotection. Palladium catalyzed cross-coupling reactions of aryl halides can give protected thiols that can, in turn, be deprotected under either acidic conditions or basic conditions (e.g. cesium fluoride) to provide a compound of Formula 2F. These conditions are discussed in Organ, Michael G., Angew. Chem. Int. Ed. 2012, 51, 3314-3322 and the references cited therein. Also, relevant conditions can be found in Takashiro Itoh, J. Org. Chem. 2006, 71, 2203-2206. A compound of Formula 2F can then be converted via methods disclosed in Schemes 1 and 7 to provide a compound of Formula 1.
Scheme 8
C-H activation
(stepwise when
RJ is other than H)
Figure imgf000040_0001
X is Br or I
8 8A 2F
In Scheme 9, the phenol, 2E is reacted with N,N-dimethyl thiocarbamoyl chloride in N,N-dimethylformamide in the presence of a strong tertiary amine base such as l,4-diazabicyclo[2.2.2]octane or N-methylmorpholine for acidic phenols (for less-acidic phenols, prior deprotonation with sodium hydride may be advantageous) to form the O-aryl N,N-dimethylthiocarbamate of Formula 10. Newman-Kwart rearrangement of a compound of Formula 10 at temperatures ranging from 200 to 300 °C provides the intermediate S-aryl dimethylthiocarbamate of Formula 11. A one-pot deprotection of a compound of Formula 11 is readily achieved using 10% aqueous sodium hydroxide or methanolic potassium hydroxide to afford the corresponding aryl thiol. Subsequent reaction with a compound of Formula 3 at or slightly above room temperature provides the product 1C (i.e. a compound of Formula 1 wherein Z is S). Methods for Newman-Kwart rearrangements are found in Lloyd- Jones, Guy C, Synthesis 2008, 661-689. Scheme 9
Figure imgf000041_0001
It is recognized by one skilled in the art that various functional groups can be converted into others to provide different a compound of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward fashion, see Larock, R. C, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley- VCH, New York, 1999. For example, intermediates for the preparation of a compound of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted via reactions well known in the art such as the Sandmeyer reaction, to various halides, providing a compound of Formula 1. The above reactions can also in many cases be performed in alternate order
It is recognized that some reagents and reaction conditions described above for preparing a compound of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 4th ed.; Wiley: Hoboken, New Jersey, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of a compound of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular presented to prepare a compound of Formula 1.
One skilled in the art will also recognize that a compound of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ^H NMR spectra are reported in ppm downfield from tetramethylsilane in CDCI3; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets, "dt" means doublet of triplets, and "bs" means broad singlet.
It is recognized by one skilled in the art that various functional groups can be converted into others to provide different compounds of Formula 1. For a valuable resource that illustrates the interconversion of functional groups in a simple and straightforward fashion, see Larock, R. C, Comprehensive Organic Transformations: A Guide to Functional Group Preparations, 2nd Ed., Wiley- VCH, New York, 1999. For example, intermediates for the preparation of compounds of Formula 1 may contain aromatic nitro groups, which can be reduced to amino groups, and then be converted via reactions well known in the art such as the Sandmeyer reaction, to various halides, providing compounds of Formula 1. The above reactions can also in many cases be performed in alternate order
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula 1 may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 1. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular presented to prepare the compounds of Formula 1.
One skilled in the art will also recognize that compounds of Formula 1 and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Steps in the following Examples illustrate a procedure for each step in an overall synthetic transformation, and the starting material for each step may not have necessarily been prepared by a particular preparative run whose procedure is described in other Examples or Steps. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. ¾ NMR spectra are reported in ppm downfield from tetramethylsilane at 500 MHz in CDCI3 unless otherwise indicated; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets and "dt" means doublet of triplets.
SYNTHESIS EXAMPLE 1
Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5-isoxazolemethanol
(Compound 31)
Step A: Synthesis of 5-chloro-2-[2-[5-[[[(l,l- dimethylethyl)diphenylsilyl]oxy]methyl]-3-isoxazolyl]phenoxy]pyrimidine To a solution of 3-(2-methoxyphenyl)-5-isoxazolemethanol (prepared as described in
Bioorganic Med. Chem. 2004, 12, 3965 (0.500 mg, 0.243 mmol) in tetrahydrofuran (25 mL) was added t-butyldiphenylsilyl chloride (0.804 mg, 2.92 mmol) followed by imidazole (0.199 mg, 2.92 mmol). After 2 h the solvent was removed under vacuum. Purification using chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the intermediate 5-[[[(l,l-dimethylethyl)diphenylsilyl]oxy]methyl]-3-(2- methoxyphenyl)isoxazole and the material was taken on without further purification.
To a solution of 5-[[[(l,l-dimethylethyl)diphenylsilyl]oxy]methyl]-3-(2- methoxyphenyl)isoxazole (3.10 g, 0.699 mmol) in dichloromethane (35 mL) at 0 °C was added a 1.0 M solution of boron tribromide (34.9 mL) and the reaction was stirred at this temperature for 1 h. The reaction was quenched with a saturated solution of sodium bicarbonate. The phases were separated, and the aqueous layer was washed with additional dichloromethane. The combined organic phases were combined, dried with MgS04 and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes afforded 2-[5-[[[(l,l- dimethylethyl)diphenylsilyl]oxy]methyl]-3-isoxazolyl]phenol which was taken taken to the next step withot further purification. To a solution of 2-[5-[[[(l,l-dimethylethyl)diphenylsilyl]oxy]methyl]-3- isoxazolyl]phenol (2.78 g, 6.47 mmol) in acetonitrile (60 mL) was added 2,5-dichloropyrimidine (1.15 g, 7.70 mmol) and potassium carbonate (2.24 g, 16.2 mmol) and the reaction was heated to 80 °C for 6 h. The reaction mixture was allowed to warm to room temperature and the solvent was removed under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes afforded the title product (2.27 g).
!H NMR δ 8.41 (s, 2H), 8.00-7.97 (m, 1H), 7.67-7.61 (m, 4H), 7.56-7.50 (m, 1H), 7.47- 7.36 (m, 7H), 7.28-7.26 (m, 1H), 6.56 (t, 1H), 1.05 (s, 9H). MS (AP+) = 542.
Step B: Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5-isoxazolemethanol
To a solution of 5-chloro-2-[5-[[[(l,l-dimethylethyl)diphenylsilyl]oxy]methyl]-3- isoxazolyl]phenoxy]pyrimidine (i.e. the product from Step A) (2.27 g, 4.19 mmol) in tetrahydrofuran (15 mL) was added acetic acid (0.50 mL) followed by a solution of 75% tetrabutylammonium fluoride in water (2.9 mL) and the reaction was allowed to stir for 2 h. The reaction was quenched with a saturated solution of sodium bicarbonate and the phases were partitioned and the aqueous phase was further washed with ethyl acetate. The combined organic phases were combined, dried over MgS04 and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes afforded the title product, a compound of the present invention (1.21 g).
!H NMR δ 8.45 (s, 2H), 7.99-7.95 (m, 1H), 7.56-7.52 (m, 1H), 7.42-7.38 (m, 1H), 7.28- 7.25 (m, 1H), 6.64-6.61 (m, 1H), 4.77-4.73 (m, 2H).
SYNTHESIS EXAMPLE 2
Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5-isoxazolecarboxaldehyde
(Compound 33)
Step A: Synthesis of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5- isoxazolecarboxaldehyde
Pyridinium chlorochromate (263 mg, 1.22 mmol) and silica gel (200 mg) were combined and mixed as solids. This mixture was then added to a stirring solution of 3-[2- [(5-chloro-2-pyrimidinyl)oxy]phenyl]-5-isoxazolemethanol (i.e. the product obtained in Step A of Example 1) (309 mg, 1.02 mmol) in dichloromethane (5.0 mL) and the reaction was allowed to stir for 18 h. The solution was filtered to remove the silica gel and the organic phase was washed with a 1 M hydrochloric acid solution. The organic phase was dried with MgSC"4 and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afforded the title product, a compound of the present invention (0.307 g) .
!H NMR δ 9.95 (s, 1H), 8.46 (s, 2H), 8.06-8.01 (m, 1H), 7.61-7.56 (m, 1H), 7.47-7.41 (m, 1H), 7.38 (s, 1H), 7.32-7.29 (m, 1H). MS (AP+) = 302. SYNTHESIS EXAMPLE 3
Synthesis of 5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine
(Compound 35)
Step A Synthesis of 5-chloro-2-[2-[5-(difluoromethyl)-3- isoxazolyl]phenoxy]pyrimidine
To a stirred solution of 3-[2-[(5-chloro-2-pyrimidinyl)oxy]phenyl]-5- isoxazolecarboxaldehyde (i.e. the product from Step A of Example 2) (100 mg, 0.332 mmol) in dichloromethane (3.0 mL) at -78 °C was added Deoxo-Fluor® (161 mg, 0.729 mmol) and the reaction was allowed to return to ambient temperature. Upon consumption of the starting material as evidenced by thin-layer chromatography, the solvent was removed under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afforded the title product, a compound of the present invention (36.3 mg). !H NMR δ 8.46 (s, 2H), 8.01-7.96 (m, 1H), 7.59-7.54 (m, 1H), 7.44-7.38 (m, 1H), 7.31- 7.27 (m, 1H), 6.98-6.96 (s, 1H), 6.83-6.60 (m, 1H). MS (EST ) = 324.
SYNTHESIS EXAMPLE 4
Synthesis of 2-[2-(3-bromo-5-isoxazolyl)phenoxy]-5-chloropyrimidine (Compound 12) Step A: Synthesis of 3-bromo-5-(2-methoxyphenyl)isoxazole
To a solution of l-ethynyl-2-methoxybenzene (0.78 g, 5.92 mmol) in dichloromethane (10 mL) was added dibromoformaldoxime (1.00 g, 4.93 mmol). The mixture was cooled to 0 °C and potassium bicarbonate (1.48 g, 14.8 mmol) was added, followed by heating to 40 °C for 18 h. Water was added to the reaction mixture, the phases separated, and the aqueous layer was again washed with dichloromethane. The combined organic phases were dried over MgS04, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the title product, a compound of the present invention (1.04 g).
!H NMR δ 7.94 (dd, 1H), 7.47-7.42 (m, 1H), 7.09 (dd, 1H), 7.02 (dd, 1H), 6.85 (s, 1H), 3.97 (s, 3H). MS (AP+) = 254.
Step B: Synthesis of 2-(3-bromo-5-isoxazolyl)phenol
To a solution of 3-bromo-5-(2-methoxyphenyl)isoxazole (i.e. the product from Step A) (0.50 g, 1.97 mmol) in dichloromethane (20mL) was added a 1 M solution of boron tribromide in dichloromethane (9.86 mmol) at -78 °C and the solution was allowed to warm to room temperature and stir for 18 h. Dichloroethane (20 mL) was added, and reaction mixture was concentrated to remove the excess dichloromethane. Boron tribromide in dichloromethane (9.86 mmol) was again added and the reaction was heated to 80 °C until completion as evidenced by thin-layer chromatography. The reaction mixture was allowed to cool to ambient temperature and quenched with a saturated solution of sodium bicarbonate. The phases were separated and the aqueous layer was again washed with dichloromethane. The combined organic phases were dried with MgSC^, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the title product (0.395 g).
!H NMR δ 7.76 (dd, 1H), 7.39-7.33 (m, 1H), 7.09-7.02 (m, 1H), 6.96-6.93 (m, 1H), 6.02 (s, 1H). MS (AP -) = 238.
Step C: 2-[2-(3-bromo-5-isoxazolyl)phenoxy]-5-chloropyrimidine
To a solution of 2-(3-bromo-5-isoxazolyl)phenol (i.e. the product from Step B) (100 mg, 0.417 mmol) in acetonitrile (5 mL) was added 2,5-dichloropyrimidine (75.0 mg, 0.503 mmol) and potassium carbonate (288 mg, 2.08mmol) then the solution was stirred at ambient temperature for 18 h. The reaction was then heated at 40 °C for 2 h followed by 80 °C for two hours. The solution was then cooled to ambient temperature, water was added, the phases were separated and the aqueous layer was again washed with dichloromethane. The combined organic phases were dried over MgS04, concentrated under vacuum, and purified by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes to afford the title product, a compound of the present invention (122 mg). !H NMR δ 8.49 (s, 2H), 8.03 (dd, 1H), 7.58-7.53 (m, 1H), 7.43 (dt, 1H), 7.29 (dd, 1H), 6.74 (s, 1H). MS (AP+) = 352.
SYNTHESIS EXAMPLE 5
Synthesis of 5 -chloro-2- [2- [4-(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine
(Compound 25)
Step A: Synthesis of 2-[4-(trifluoromethyl)-2-pyridinyl]phenol
2-Chloro-4-trifluoromethylpyridine (1.0 g, 5.5 mmol) and 2-(4,4,5,5-tetramethyl- l ,3,2-dioxaborolan-2-yl)phenol (1.57 g, 7.16 mmol) were combined in dimethoxy ethane (18 mL) and water (1.8 mL). To this mixture were added sodium carbonate (2.28 g, 16.5 mmol) and tetrakis(triphenylphosphine)palladium(0) (0.32 g, 0.27 mmol). The reaction was heated at 90 °C for 2.5 h and allowed to stir at 23 °C for 18 h. The mixture was diluted with water (20 mL) and dichloromethane (20 mL) and the layers separated. The aqueous layer was washed with dichloromethane (10 mL). The combined dichloromethane layers were washed with saturated aqueous sodium chloride solution (10 mL) and dried over sodium sulfate. After filtration the organic layer was evaporated and the solid thus obtained was triturated with hexanes (20 mL). The filtrate was concentrated to provide 1.18 g of the title compound as a yellow solid which was used in Step B without further purification.
!H NMR δ 13.61 (s, 1H), 8.72 (d, 1H), 8.12 (s, 1H), 7.83 (d, 1H), 7.47 (m, 1H), 7.36 (s, 1H), 7.06 (d, 1H), 6.96 (t, 1H). Step B Synthesis of 5-chloro-2-[2-[4-(trifluoromethyl)-2- pyridinyl]phenoxy]pyrimidine
2-[4-(Trifiuoromethyl)-2-pyridinyl]phenol (i.e. the product from Step A) (0.20 g, 0.84 mmol) and 2,5-dichloropyrimidine (0.14 g, 0.92 mmol) were dissolved in acetonitrile (2 mL) and treated with powdered potassium carbonate (0.34 g, 2.5 mmol). The mixture was heated to 80 °C for 18 h. After cooling, the reaction mixture was diluted with water (10 mL) and ethyl acetate (10 mL) and the layers separated. The aqueous layer was washed with ethyl acetate (10 mL). The combined ethyl acetate solution was washed with saturated aqueous sodium chloride solution (10 mL) and dried over MgS04. The filtrate was evaporated under reduced pressure and subjected to chromatography through 12 g silica gel eluting with 10 to 20% ethyl acetate in hexanes. Appropriate fractions were pooled and evaporated to provide the title compound, a compound of the present invention (0.2 g) as a clear oil.
!H NMR δ 8.75 (d, 1H), 8.39 (s, 2H), 7.91 (s, 1H), 7.88 (m, 1H), 7.54 (m, 1H), 7.44 (m, 1H), 7.37 (d, 1H), 7.28 (m, 1H).
SYNTHESIS EXAMPLE 6
Synthesis of 5-chloro-2-[4-methyl-2-[6-(trifiuoromethyl)-3-pyridinyl]phenoxy]pyrimidine
(Compound 22)
Step A: Synthesis of 2-(2-bromo-4-methylphenoxy)-5-chloropyrimidine
2-Bromo-4-methylphenol (280 mg, 1.5 mmol) and 2,5-dichloropyrimidine (246 mg, 1.65 mmol) were combined in 6 mL of acetonitrile under a nitrogen atmosphere. Powdered potassium carbonate (455 mg, 3.3 mmol) was added and the resulting mixture was heated at reflux for 6 h. The reaction mixture was cooled and diluted with de-ionized water and ethyl acetate. The aqueous layer was separated and extracted twice with ethyl acetate. The combined organic layers were washed with brine, dried over MgS04, filtered and concentrated under reduced pressure. The resulting residue was purified by medium pressure liquid chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes to yield the title compound (270 mg).
¾ NMR δ 8.48 (s, 2H), 7.47 (d, 1H), 7.18 (m, 1H), 7.11 (m, 1H), 2.37 (s, 3H).
Step B Synthesis of 5-chloro-2-[4-methyl-2-[6-(trifluoromethyl)-3- pyridinyl]phenoxy]pyrimidine
A mixture of 2-(2-bromo-4-methylphenoxy)-5-chloropyrimidine (i.e. the product of Step A; 190 mg, 0.63 mmol), 5-[6-(trifluoromethyl)-3-pyridinyl]-boronic acid (133 mg, 0.70 mmol), sodium carbonate (0.6 mL of 2 M aqueous solution, 1.26 mmol) and tetrakis(triphenylphosphine)palladium(0) (73 mg, 0.06 mmol) in toluene (9 mL) and ethanol (1 mL) was heated at 90 °C for 2 h. The reaction mixture was then concentrated under reduced pressure, and the residue was purified by medium pressure liquid chromatography on silica gel eluted with 0 to 10% ethyl acetate in hexanes to yield the title compound, a compound of the present invention (190 mg).
¾ NMR δ 8.77 (d, 1H), 8.36 (s, 2H), 8.02 (m, 1H), 7.64 (d, 1H), 7.31 (m, 2H), 7.15 (d, 1H), 2.45 (s, 3H).
SYNTHESIS EXAMPLE 7
Synthesis of 5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine
(Compound 53)
Step A: Synthesis of 2-(3-difluoromethyl-5-isoxazolyl)phenol
To a solution of 25% sodium methoxide in methanol (5 mL) and tetrahydrofuran (10 mL), acetophenone (1 g, 7.3 mmol) and difluoroacetate (1 g, 8.1 mmol) in tetrahydrofuran (2 mL) was added and heated at 60 °C for 5 h. The reaction was cooled to room temperature and treated with 36% aq hydrochloric acid (4 mL) and stirred at 60 °C for 2 h. The reaction was quenched by adding water (15 mL) and the organic solvent was removed under vacuum. The precipitated product 2-difluoromethyl-4-chromenone (1.4 g) was filtered and dissolved in ethanol (5 mL). To this solution, hydroxylamine acetate (22 mmol) in water (5 mL) was added and the mixture was heated at 60 °C for 3 h. After cooling the reaction to ambient temperature 4,4-difluoro-l-(2-hydroxyphenyl)-butane-l,3-dione 3-oxime was precipitated with the addition of water (20 mL). This product was collected by filtration and suspended in acetic acid (5 mL) and 36% aqueous hydrochloric acid (1.8 mL) at room temperature and stirred at 80 °C for 15 min to obtain the titile compound as a beige solid (800 mg).
!H NMR δ 7.82 (m,l H), 7.36 (s, 1 H), 7.07 (m, 1 H), 6.95 (m, 2H), 6.82 (t, 1H), 6.05 (s, 1H). MS (ESI+) = 212
Step B: Synthesis of 5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]- pyrimidine
To a solution of 2-(3-difluoromethyl-5-isoxazolyl)phenol (i.e. the product from Step
A) (2.1 g, 9.71 mmol) in anhydrous N,N-dimethylformamide (8 mL) was added 2,5- dichloropyrimidine (1.5 g, 10.2 mmol) and potassium carbonate (2.9 g, 21.3 mmol). The reaction was heated at 90 °C for 1 h. The solution was cooled to ambient temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 10% ethyl acetate in hexanes afforded the title compound, a compound of the present invention, as a solid (2.2 g).
!H NMR δ 8.49 (s, 2H), 8.06 (m, 1H), 7.57 (m, 1H), 7.44 (m, 1H), 7.31 (m, 1H), 6.88 (s, 1H), 6.74 (t, 1H). MS (ESI+) = 324 SYNTHESIS EXAMPLE 8
Synthesis of 5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3-fluorophenoxy]pyrimidine
(Compound 144)
Step A: Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione To a solution of l-(2-fluoro-6-methoxyphenyl)ethanone (2.6 g, 15.5 mmol) and difluoroacetic acid ethyl ester (3.9 mL, 31.0 mmol) in anhydrous N,N-dimethylformamide at 0 °C was added sodium hydride (1.2 g, 31.0 mmol). The reaction mixture was heated at 80 °C for 1 h. The reaction was then cooled to 0 °C, diluted with ethyl acetate and acidified with 1 N aqueous hydrochloric acid. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined and dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound (2.5 g). !H NMR δ 7.39 (m, 1H), 6.77 (m, 2H), 6.24 (s, 1H), 6.01 (t, 1 H), 3.87 (s, 3 H). MS (ESI+) = 247
Step B: Synthesis of 3-difluoromethyl-5-(2-fluoro-6-methoxyphenyl)isoxazole
A solution of 4,4-difluoro- l-(2-fluoro-6-methoxyphenyl)butane-l,3-dione (i.e. the product from Step A) (2.5 g, 10 mmol) and hydroxylamine hydrochloride (2.1 g, 30 mmol) in ethanol (25 mL) was stirred at 80 °C. After 1 h the solvent was removed under vacuum.
The resulting residue was diluted with water and extracted with dichloromethane. The organic phase was dried with magnesium sulfate and concentrated under vacuum.
Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound (1.5 g).
!H NMR δ 7.41 (m, 1 H), 6.69 - 6.98 (m, 4H), 3.93 (s, 3 H). MS (ESI+) = 244
Step C: Synthesis of 2-(3-difluoromethyl-5-isoxazolyl)-3-fluorophenol
To a solution of 3-difluoromethyl-5-(2-fluoro-6-methoxyphenyl)isoxazole (i.e. the product from Step B) (1.5 g, 6.2 mmol.) in dichloromethane (10 mL) at 0 °C was added a 1.0 M solution of boron tribromide in dichloromethane (31 mL, 31 mmol). The reaction mixture was warmed to ambient temperature and stirred for 6 h. The reaction was cooled to 0 °C and slowly quenched with a saturated aqueous solution of sodium bicarbonate. The biphasic mixture was stirred at room temperature for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried and concentrated under vacuum. The crude residue was purified by chromatography on silica gel, eluting with 0 to 10%> ethyl acetate in hexanes, to afford the title compound (980 mg). !H NMR δ 7.33 (m, 1 H), 6.66 - 6.99 (m, 4 H). MS (ESI+) = 230 Step D: Synthesis of 5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3- fluorophenoxy]pyrimidine
To a solution of 2-(3-difluoromethyl-5-isoxazolyl)-3-fluorophenol (i.e. the product from Step C) (120 mg, 0.5 mmol) in anhydrous N,N-dimethylformamide (2 mL) was added 2,5-dichloropyrimidine (85 mg, 0.57 mmol) and potassium carbonate (244 mg, 1.04 mmol). The reaction was heated at 80 °C for 4 h. The mixture was cooled to ambient temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound, a compound of the present invention, as a solid (110 mg).
!H NMR δ 8.46 (s, 2H), 7.56 (m, 1H), 7.21 (m, 1H), 7.13 (m, 1H), 6.87 (m, 1 H), 6.74 (t, 1 H). MS (ESI+) = 342
SYNTHESIS EXAMPLE 9
Synthesis of 5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]-3-fluorophenoxy]pyrimidine
(Compound 55)
Step A: Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione
A solution of 2-fluoro-6-methoxyacetophenone (6.83 g, 40.6 mmol) and ethyl difluoroacetate (7.45g, 60 mmol) in tetrahydrofuran (35 mL) was added dropwise to a solution of tetrahydrofuran (20 mL) and 25% sodium methoxide (10.2g, 47.2 mmol) over 15 minutes. The reaction was complete in 3h as determined by high pressure liquid chromatography. The reaction was partially concentrated under vacuum to remove most of the tetrahydrofuran and methanol, and then diluted with toluene and water. The aqueous phase was acidified with 37% hydrochloric acid (5g), followed by extraction with toluene. The combined organic phases were concentrated under vacuum to provide title compound (7.98 g).
!H NMR δ 7.39 (td, 1 H) 6.72 - 6.81 (m, 2 H) 6.25 (d, 1 H) 5.87 - 6.14 (m, 1 H) 3.88 (s, 3 H).
Step B: Synthesis of 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)-4H-isoxazol- 5-ol
To a solution of 4,4-difluoro- l-(2-fluoro-6-methoxyphenyl)butane-l,3-dione (i.e. the product from Step A) (7.98 g, 32.4 mmol) in 35 mL methanol at room temperature was added a 50% hydroxylamine solution (2.78g, 42.1 mmol) and IN sodium hydroxide solution (1.50 mL, 1.50 mmol) followed by heating to 65 °C for 2h. The reaction was cooled to room temperature and diluted with water and toluene. The phases were separated and the organic phase was concentrated under vacuum to provide the title compound (7.99 g). in NMR δ 7.36 (td, 1 H) 6.73 - 6.82 (m, 2 H) 5.79 - 6.05 (m, 1 H) 3.88 (s, 3 H) 3.67 - 3.73 (m, 1 H) 3.47 - 3.51 (m, 1 H) 3.34 - 3.42 (m, 1 H).
Step C: Synthesis of 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)isoxazole
To toluene (80 mL) was added 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)-4H- isoxazol-5-ol (i.e. the product from Step B) (7.99 g, 30.6 mmol) followed by /?-toluenesulfonic acid monohydrate (0.700 g, 3.68 mmol). The mixture was heated to a vigorous reflux (107 - 111 °C) for two hours at which point high pressure liquid chromatography determined the reaction was complete. The cooled reaction mixture was washed with a saturated sodium bicarbonate solution, followed by water. The organic phase was concentrated under vacuum to provide the title compound (7.44 g).
in NMR δ 7.40 (td, 1 H) 6.69 - 6.94 (m, 4 H) 3.88 (s, 3 H).
Step D: Synthesis of 2-[5-(difluoromethyl)-3-isoxazolyl]-3-fluorophenol
To a solution of 5-(difluoromethyl)-3-(2-fluoro-6-methoxyphenyl)isoxazole (i.e. the product from Step C) (3.72 g, 15.3 mmol) in dichloromethane (15 mL) at 3 °C was added a 1M solution of boron tribromide in dichloromethane (18.0 mL, 18 mmol) over 5 min. The reaction was then allowed to warm to room temperature. After 90 minutes it was determined the reaction was complete using high pressure liquid chromatography and the reaction was treated with a 10% aqueous solution of potassium bicarbonate (10 mL). The phases were separated and the organic phase was concentrated under vacuum. The resulting brown solid was triturated with a water/methanol solution (~2/l) providing the title compound (3.34 g). !H NMR δ 9.63 - 9.75 (m, 1 H) 7.33 (td, 1 H) 7.21 (ddd, 1 H) 6.71 - 6.96 (m, 3 H).
Step E: Synthesis of 5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]-3- fluorophenoxy]pyrimidine
To a solution of 2-[5-(difluoromethyl)-3-isoxazolyl]-3-fluorophenol (i.e. the product from Step D) (1.61 g, 7.02 mmol) and 5-methyl-2-methylsulfonylpyrimidine (1.49 g, 7.72 mmol) in N,N-dimethylformamide (9 mL) was added potassium carbonate (4.24 g, 17.5 mmol) and the reaction was allowed to stir at room temperature for 24 h. The reaction was diluted with water and toluene, the phases were separated and the organic solvent was removed under vacuum. To the resulting oil was added 8 mL of methanol and a tan slurry formed, after further dilution with a methanol/water solution (20 mL), the precipitate was filtered providing the title compound, a compound of the present invention (2.24g).
!H NMR δ 8.45 (s, 2 H) 7.54 (td, 1 H) 7.19 (ddd, 1 H) 7.14 (dt, 1 H) 6.88 (dt, 1 H) 6.61 - 6.85 (m, 1 H). SYNTHESIS EXAMPLE 10
Preparation of 5 -chloro-2- [3 -cyano-2- [4-(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine
(Compound 158)
A solution of 5-chloro-2-[2-[4-(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine (i.e. the product of example 5, step B) (0.30 g, 0.853 mmoles) in 4.27 mL of N,N- dimethylformamide under a nitrogen atmosphere was treated with copper(II) bromide (0.19 g, 0.853 mmoles), palladium(II) acetate (9 mg, 0.0426 mmoles) and potassium ferricyanide (0.06 g, 0.17 mmoles). The mixture was heated at 130°C for 18 hours. The mixture was then cooled, diluted with diethyl ether and water, filtered thru a celite pad and rinsed with ethyl acetate and water. The phases were separated and the aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed twice with water and saturated aqueous sodium chloride, dried over magnesium sulfate, and concentrated to provide 0.2 lg crude product. The crude product was purified with a 12 g Teledyne Isco silica gel column eluting with 10 to 30% EtOAc-Hexanes gradient to provide the title compound, a compound of the present invention as a solid (0.23 g).
!H NMR δ 8.86 (d, 1H), 8.40 (s, 2H), 7.78 (d&s, 2H), 7.62 (t, 1H), 7.52 (d, 1H), 7.50 (d, 1H).
SYNTHESIS EXAMPLE 11
Synthesis of 5-chloro-2-[2-[5-(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine (Compound
27)
Step A: Synthesis of 2-[5-(trifluoromethyl)-2-pyridinyl]phenol
2-Chloro-5-(trifluoromethyl)pyridine (1.0 g, 5.50 mmoles) and 2-(4,4,5,5-tetramethyl- l,3,2-dioxaborolan-2-yl)phenol (1.57 g, 7.16 mmoles) were combined in 16 mL of 1,2- dimethoxyethane and 1.8 mL of de-ionized water under a nitrogen atmosphere. Solid sodium carbonate (2.28g, 16.5 mmoles) and then tetrakis(triphenylphosphine) palladium (0) (0.32g, 0.27 mmoles) were added. The reaction was heated at reflux approximately ninety minutes. The reaction was cooled, diluted with dichloromethane and filtered thru a celite pad, rinsing with dichloromethane and then de-ionized water. The phases were separated. The aqueous phase was extracted twice with dichloromethane. The combined organic phases were washed with saturated aqueous sodium chloride, dried over magnesium sulfate, filtered and concentrated to give a solid. A solid was filtered from hexanes to give 34 mg. A second crop was obtained from the filtrate from hexanes to yield 506 mg of a light orange- brown solid of the title compound.
!H NMR δ 8.81 (s, 1H), 8.04 (m, 2H), 7.83 (d, 1H), 7.38 (t, 1H), 7.07 (d, 1H), 6.98 (t, 1H). Step B: Synthesis of 5-chloro-2-[2-[5-(trifluoromethyl)-2-pyridinyl]phenoxy]- pyrimidine
A mixture of 2-[5-(trifluoromethyl)-2-pyridinyl]phenol (i.e. the product of step A) (0.20 g, 0.836 mmoles) and 2,5-dichloropyrimidine (0.14 g, 0.919 mmoles) in 2.0 mL of Ν,Ν-dimethylformamide was stirred under a nitrogen atmosphere. Powdered potassium carbonate (0.35 g, 2.51 mmoles) was added and the mixture was heated at 80 °C overnight. The reaction was cooled before diluting with de-ionized water and diethyl ether. The phases were separated. The aqueous phase was extracted twice with diethyl ether. The combined organic phases were washed three times with de-ionized water, dried over sodium sulfate, filtered and concentrated to 0.37 g of solid. A solid was filtered from hexanes and some diethyl ether to give 103 mg of the title compound, a compound of the present invention. !H NMR δ 8.84 (s, 1H), 8.40 (s, 2H), 7.92(d, 1H), 7.87 (s&d, 2H), 7.54 (t, 1H), 7.45 (t, 1H), 7.27 (d,lH).
SYNTHESIS EXAMPLE 12
Preparation of 5-chloro-2-[2-[5-(trifluoromethyl)-2-pyridinyl]-3-chlorophenoxy]pyrimidine
(Compound 160)
5-Chloro-2-[2-[5-(trifluoromethyl)-2-pyridinyl]phenoxy]-pyrimidine (i.e. the product of example 11, step B) (0.14 g, 0.398 mmoles) was dissolved in 2 mL of acetic acid. Palladium acetate (0.01 g, 0.039 mmoles) and N-chlorosuccinimide (0.11 g, 0.796 mmoles) were added and the mixture was heated at 100 °C for three hours. The mixture was cooled to room temperature overnight and then diluted with toluene and ethyl acetate. The mixture was filtered thru a celite pad, rinsed with toluene and then ethyl acetate. The filtrate was washed twice with saturated aqueous sodium hydrogencarbonate, saturated aqueous sodium chloride, dried over magnesium sulfate and concentrated to a crude product. The crude product was purified with a 12 g Teledyne Isco silica gel column eluting with 10 to 30% EtOAc-Hexanes gradient to provide the title compound, a compound of the present invention as a solid (40 mg).
!H NMR δ 8.82 (s, 1H), 8.41 (s, 2H), 7.93 (d, 1H), 7.52 (d, 1H), 7.47 (m, 2H), 7.19 (m, 1H).
SYNTHESIS EXAMPLE 13
Synthesis of 5-bromo-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine
(Compound 62)
Step A: Synthesis of 5-(difluoromethyl)-3-(2-methoxyphenyl)isoxazole
To a solution of acetophenone (3.0 g, 20 mmol) in methanol (15 mL) was added a 30% sodium methoxide in methanol solution (5.0 mL) and the reaction stirred for five minutes. Next ethyl difluoroacetate (2.97 g, 24 mmol) was added and the reaction was heated to reflux for 18 h. The reaction was allowed to cool to room temperature and the solvent was removed under vacuum. To the residue was added 1M hydrochloric acid and ethyl acetate, the phases were separated, the organic phase was dried using magnesium sulfate and the solvent was removed under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes afforded the desired product which was taken on directly. A solution of 4,4-difluoro-l-(2-methoxyphenyl)butane-l,3-dione from the previous step in ethanol (30 mL) was added dropwise to a solution of hydroxylamine hydrochloride (1.4 g, 20 mmol) in 1M sodium hydroxide (21 mL). The reaction was then heated to reflux for 2 h, followed by cooling to room temperature. The product was precipitated from solution by the addition of water and collected via vacuum filtration to afford the desired product which was taken on directly (AP+ 244, 1H NMR δ ppm 7.79 (d, 1 H) 7.38 - 7.46 (m, 1 H) 6.93 - 7.04 (m, 2 H) 5.76 - 6.04 (m, 1 H) 3.88 (s, 3 H) 3.67 - 3.80 (m, 1 H) 3.49 - 3.55 (m, 1 H)). Next, a solution of 5-(difluoromethyl)-3-(2-methoxyphenyl)-4H-isoxazol-5-ol from the previous step was taken up in trifluoroacetic acid (20 mL) and heated to 70 °C for 18 h. The reaction was cooled to room temperature and the solvent was removed under vacuum. The resulting residue was dissolved in dichloromethane and washed with a saturated solution of sodium bicarbonate. The phases were separated, the organic phase was dried using magnesium sulfate and the solvent was removed under vacuum. Purification by chromatography on silica gel eluting with 0 to 100% ethyl acetate in hexanes afforded the title compound (2.0 g, AP+ = 226).
lH NMR δ 7.91 (dd, 1 H) 7.42 - 7.50 (m, 1 H) 6.98 - 7.12 (m, 3 H) 6.66 - 6.93 (m, 1 H) 3.92 (s, 3 H).
Step B: Synthesis of 2-[5-(difluoromethyl)-3-isoxazolyl]phenol
To a solution of 5-(difluoromethyl)-3-(2-methoxyphenyl)isoxazole (i.e. the product of step A) (2.01 g, 8.92 mmol) in dichloromethane (50 mL) at 0 °C was added a 1M solution of boron tribromide in dichloromethane (13.3 mL, 13.3 mmol) and the reaction was allowed to warm to room temperature over three hours. The solvent was removed under vacuum and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes to afford the title compound (1.66g, AP- = 210).
!H NMR δ 9.14 (s, 1 H) 7.51 (dd, 1 H) 7.39 (ddd, 1 H) 7.11 (dd, 1 H) 6.97 - 7.04 (m, 2 H) 6.70 - 6.95 (m, 1 H).
Step C: Synthesis of 5-bromo-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]- pyrimidine
To a solution of 2-[5-(difluoromethyl)-3-isoxazolyl]phenol (i.e. the product of step B) (427 mg, 2.01 mmol) and 5-bromo-2-chloro-pyrimidine (468 mg, 2.42 mmol) in acetonitrile (10 mL) was added potassium carbonate (695 mg, 5.03 mmol) and the reaction was heated to 80 °C for 18 h. The solvent was removed under vacuum and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes to afford the title compound, a compound of the present invention, as a solid (555 mg, mp = 88.9-92.8 °C). in NMR δ 8.53 (s, 2 H) 7.98 (dd, 1 H) 7.53 - 7.60 (m, 1 H) 7.41 (td, 1 H) 7.28 (dd, 1 H) 6.97 (t, 1 H) 6.59 - 6.84 (m, 1 H).
SYNTHESIS EXAMPLE 14
Synthesis of 5-chloro-2-[2-[5-(trifluoromethyl)-3-isoxazolyl]-3-fluorophenoxy]pyrimidine
(Compound 168)
Step A: Synthesis of 5-(difluoromethyl)-3-(2-methoxyphenyl)-4H-isoxazol-5-ol
To a solution of 2-fluoro-6-methoxyacetophenone (1.0 g, 5.9 mmol) in tetrahydrofuran (2 mL) was added a 30% sodium methoxide in methanol solution (1.4 mL). To this mixture was added dropwise a solution of ethyl trifluoroacetate (0.805 g, 6.49 mmol) in tetrahydrofuran (1 mL) and the reaction stirred at room temperature for 2 h. To the reaction was added 1M hydrochloric acid solution and ethyl acetate, the phases were separated and the aqueous phase was again washed with ethyl acetate. The combined organic phases were dried with magnesium sulfate and concentrated under vacuum to provide the desired product (AP- = 263) which was taken onto the next step directly. Next, to a solution of 4,4,4- trifluoro-l-(2-fluoro-6-methoxyphenyl)butane-l,3-dione (from the previous step) in ethanol (14 mL) was added 1M sodium hydroxide solution (7 mL) followed by hydroxylamine hydrochloride (410 mg, 5.9 mmol) and the reaction stirred overnight at room temperature. The solvent was removed under vacuum and the residue was purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes and 0 to 20% methanol in dichlromethane to afford the product (AP+ = 280, 1Η NMR δ ppm 7.37 (td, 1 Η) 6.74 - 6.83 (m, 2 Η) 3.89 (s, 3 Η) 3.79 (d, 1 Η) 3.50 (dd, 1 Η)) which was taken onto the next step directly To a solution of 3-(2-fluoro-6-methoxy-phenyl)-5-(trifluoromethyl)-4H-isoxazol-5- ol (from the previous step) in dichloromethane (20 mL) at 0 °C was added a 1M solution of boron tribromide in dichloromethane (11.8 mL, 11.8 mmol) and the reaction was allowed to warm to room temperature over 2 h. The solvent was removed under vacuum. The residue was dissolved in dichloromethane and washed with a saturated solution of sodium bicarbonate, the aqueous phase was washed with dichloromethane. The combined organic phases were dried with magnesium sulfate, concentrated under vacuum and purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate in hexanes, providing the title compound (606 mg, AP- = 264).
in NMR δ 9.86 (s, 1 H) 7.32 (td, 1 H) 6.84 - 6.90 (m, 1 H) 6.68 (ddd, 1 H) 3.86 - 3.94 (m, 1 H) 3.75 (dd, 1 H) 3.56 (s, 1 H).
Step B: Synthesis of 5-chloro-2-[2-[5-(trifluoromethyl)-3-isoxazolyl]-3- fluorophenoxy]pyrimidine
To a solution of 3-(2-fluoro-6-hydroxyphenyl)-5-(trifluoromethyl)-4H-isoxazol-5-ol
(i.e. the product of step A) (606 mg, 2.29 mmol) in dimethylsulfoxide (15 mL) was added 5- chloro-2-methylsulfonyl-pyrimidine (527mg, 2.74mmol) followed by cesium carbonate (l . lg, 3.43mmol) and the reaction stirred for 18 h. The reaction was partitioned between water and ethyl acetate, the phases were separated and the aqueous layer was again washed with ethyl acetate. The combined organic phases were dried with magnesium sulfate and concentrated under vacuum. The residue was purified by chromatography on silica gel, eluting with 0 to 100% ethyl acetate, to afford the title compound, a compound of the present invention, (198mg, AP+ = 360).
!H NMR δ 8.46 (s, 2 H) 7.56 (td, 1 H) 7.21 (ddd, 1 H) 7.15 (dt, 1 H) 7.02 (dd, 1 H).
SYNTHESIS EXAMPLE 15
Synthesis of 5-chloro-2-[2-[3-(trifluoromethyl)-5-isoxazolyl)phenoxy]pyrimidine
(Compound 63)
Step A: Synthesis of 2-(trifluoromethyl)-4H- 1 -benzopyran-4-one
2-Hydroxyacetophenone (10 g, 66.7 mmol) was dissolved in trifluoroacetic anhydride (19 ml, 133.3 mmol) and pyridine (10.8 mL, 133.3 mmol). The reaction mixture was heated at 70 °C and stirred for 12 h. After cooling the reaction mixture was diluted with 1 M hydrochloric acid and methylene chloride and washed with water. The organic phase was dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 5% ethyl acetate in hexanes afforded the title compound (10.5 g) as a pale yellow solid.
!H NMR δ 8.21 (m, 1 H), 7.76 (m, 1H), 7.77 (d, 1H), 7.46 (m, 1H), 6.73 (s, 1H). MS (ESI+) = 215
Step B: Synthesis of 2-[3-(trifluoromethyl)-5-isoxazolyl]phenol
To a solution of 2-(trifluoromethyl)-4H-l-benzopyran-4-one (i.e. the product of step A) (10.5 g, 48.8 mmol) in ethanol (50 mL), hydroxylamine acetate (146 mmol) in water (50 mL) was added. The mixture was heated at 60 °C for 4 h. After cooling the reaction to ambient temperature 4,4,4-trifluoro-l-(2-hydroxyphenyl)-butane-l,3-dione 3-oxime was precipitated with the addition of water (200 mL).
in NMR δ 9.30 (s, 1H), 7.37 (m, 1H), 7.19 (m, 1H), 7.06 (m, 1H), 6.94 (m, 1H), 3.87 (d, 1H), 3.69 (d, 1H).
This product was collected by filtration and suspended in acetic acid (30 mL) and 36 % aqueous hydrochloric acid (10.8 mL) at room temperature. The mixture was stirred at 80 °C for 30 min to afford the title compound as a white solid (4.6 g).
!H NMR δ 7.88 (m, 1H), 7.37 (m, 1H), 7.08 (m, 1H), 7.01 (s, 1H), 6.95 (m, 1H). MS (ESI+) = 230
Step C: Synthesis of 5-chloro-2-[2-[3-(trifluoromethyl)-5-isoxazolyl)phenoxy]- pyrimidine
To a solution of 2-[3-(trifluoromethyl)-5-isoxazolyl]phenol (i.e. the product of step B) (2.2 g, 9.4 mmol) in anhydrous N,N-dimethylformamide (10 mL) was added 2,5- dichloropyrimidine (1.5 g, 10.3 mmol) and potassium carbonate (2.9 g, 20.6 mmol). The reaction was heated at 80 °C for 2 h. The solution was cooled to ambient temperature and diluted with water. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 5% ethyl acetate in hexanes afforded the title compound, a compound of the present invention, as a solid (2.1 g).
!H NMR δ 8.49 (s, 2H), 8.08 (m, 1H), 7.58 (m, 1H), 7.45 (m, 1H), 7.32 (m, 1H), 6.91 (s, 1H). MS (ESI+) = 342. Melting Point: 114-115 °C
SYNTHESIS EXAMPLE 16
Synthesis of 5-bromo-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3-fluorophenoxy]pyrimidine
(Compound 145)
Step A: Synthesis of 4,4-difluoro- 1 -(2-fluoro-6-methoxyphenyl)butane- 1 ,3-dione
To a solution of l-(2-fluoro-6-methoxyphenyl)ethanone (2.6 g, 15.5 mmol) and difluoroacetic acid ethyl ester (3.9 mL, 31.0 mmol) in anhydrous N,N-dimethylformamide at 0 °C was added sodium hydride (1.2 g, 31.0 mmol). The reaction mixture was heated at 80 °C for 1 h. The reaction was then cooled down to 0 °C, diluted with ethyl acetate and acidified with 1 N aqueous hydrochloric acid. The phases were separated and the aqueous phase was washed with additional ethyl acetate. The organic phases were combined and dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound (2.5 g).
!H NMR δ 7.39 (m, 1H), 6.77 (m, 2H), 6.24 (s, 1H), 6.01 (t, 1 H), 3.87 (s, 3 H). MS (ESI+) = 247
Step B: Synthesis of 3-(difluoromethyl)-5-(2-fluoro-6-methoxyphenyl)isoxazole
A solution of 4,4-difluoro- l-(2-fluoro-6-methoxyphenyl)butane-l,3-dione (i.e. the product of step A) (2.5 g, 10 mmol) and hydroxylamine hydrochloride (2.1 g, 30 mmol) in ethanol (25 mL) was stirred at 80 °C. After 1 h the solvent was removed under vacuum.
The resulting residue was diluted with water and extracted with dichloromethane. The organic phase was dried with magnesium sulfate and concentrated under vacuum.
Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound (1.5 g).
!H NMR δ 7.41 (m, 1 H), 6.69 - 6.98 (m, 4H), 3.93 (s, 3 H). MS (ESI+) = 244
Step C: Synthesis of 2-[3-(difluoromethyl)-5-isoxazolyl]-3-fluorophenol
To a solution of 3-(difluoromethyl)-5-(2-fluoro-6-methoxyphenyl)isoxazole (i.e. the product of step B) (1.5 g, 6.2 mmol.) in dichloromethane (10 mL) at 0 °C was added a 1.0 M solution of boron tribromide in dichloromethane (31 mL, 31 mmol). The reaction mixture was warmed to ambient temperature and stirred for 6 h. The reaction was cooled to 0 °C and slowly treated with a saturated aqueous solution of sodium bicarbonate. The biphasic mixture was stirred at room temperature for 1 h. The phases were separated and the aqueous phase was extracted with dichloromethane. The combined organic phases were dried and concentrated under vacuum. The crude residue was purified by chromatography on silica gel, eluting with 0 to 10% ethyl acetate in hexanes, to afford the title compound (980 mg). !H NMR δ 7.33 (m, 1 H), 6.66 - 6.99 (m, 4 H). MS (ESI+) = 230
Step D: Synthesis of 5-bromo-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3- fluorophenoxy]pyrimidine
To a solution of 2-[3-(difluoromethyl)-5-isoxazolyl]-3-fluorophenol (i.e. the product of step C) (229 mg, 1 mmol) in anhydrous N,N-dimethylformamide (2.5 mL) was added 5- bromo-2-chloropyrimidine (212 mg, 1.1 mmol) and potassium carbonate (304 mg, 2.2 mmol). The reaction was heated at 80 °C for 1 h. The solution was cooled to ambient temperature and diluted with water. The phases were separated and the aqueous layer was washed with additional ethyl acetate. The organic phases were combined, dried with magnesium sulfate and concentrated under vacuum. Purification by chromatography on silica gel eluting with 0 to 15% ethyl acetate in hexanes afforded the title compound, a compound of the present invention, as a solid (320 mg).
!H NMR δ 8.54 (s, 2H), 7.54 (m, 1H), 7.20 (m, 1H), 7.13 (m, 1H), 6.86 (m, 1 H), 6.75 (t, 1 H). MS (ESI+) = 387
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 1584 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Bu means butyl, z'-Pr means isopropyl, Bu means butyl, c-Pr cyclopropyl, c-Bu means cyclobutyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, NHMe methylamino, -CN means cyano, Py means pyridinyl, -NO2 means nitro, tzl meand triazol, pzl means pyrazol, izl means imidazole, odzl means oxadiazol, tdzl means thiadiazol and SC^Me means methylsulfonyl.
Table 1
Figure imgf000058_0001
R2 = CI; Z = O; and R3
and is:
4-I-isothiazol-5-yl 4 -Me - isothiazol- 5 -y 1 4-Et-isothiazol-5-yl 4-CF3-isothiazol-5-yl 4-CHF2-isothiazol-5-yl 4-CHO-isothiazol-5-yl 4-CN-isothiazol-5-yl 4-OMe-isothiazol-5-yl
4- OCF3-isothiazol-5-yl
4 - Ph- isothiazol- 5 -yl Isothiazol-3-yl
5- F-isothiazol-3-yl 5-Cl-isothiazol-3-yl 5-Br-isothiazol-3-yl
5-I-isothiazol-3-yl 5 -Me - isothiazol- 3 -yl 5-Et-isothiazol-3-yl 5 -CF 3 -isothiazol- 3 -yl 5 -CHF2 -isothiazol-3 -yl
5- CHO-isothiazol-3-yl 5-CN-isothiazol-3-yl
5-CH2CN-isothiazol-3-yl 5-OMe-isothiazol-3-yl 5-OCF3-isothiazol-3-yl 5 -Ph-isothiazol-3 -yl 4-F-isothiazol-3-yl 4-Cl-isothiazol-3-yl 4-Br- isothiazol-3 -yl 4-I-isothiazol-3-yl 4-Me-isothiazol-3-yl 4-Et-isothiazol-3-yl 4-CF3 -isothiazol-3 -yl 4-CHF2-isothiazol-3-yl 4-CHO-isothiazol-3-yl 4-CN-isothiazol-3 -yl
Figure imgf000059_0001
4-OMe-isothiazol-3-yl -OCF3 -isothiazol-3 -yl 4-Et-oxazol-2-yl
4- Ph-isothiazol-3-yl 4-CF3-oxazol-2-yl
Isoxazol-4-yl 4-CHF2-oxazol-2-yl 3-F-isoxazol-4-yl 4-CHO-oxazol-2-yl 3 -Cl-isoxazol-4-yl 4-CN-oxazol-2-yl 3-Br-isoxazol-4-yl 4-OMe-oxazol-2-yl 3-I-isoxazol-4-yl 4- OCF3-oxazol-2-yl 3-Me-isoxazol-4-yl 4- Ph-oxazol-2-yl 3 -Et-isoxazol-4-yl Thiazol-2-yl 3 -CF3 -isoxazol-4-yl 5- F-thiazol-2-yl -CHF2-isoxazol-4-yl 5-Cl-thiazol-2-yl 3-CHO-isoxazol-4-yl 5-Br-thiazol-2-yl 3 -CN-isoxazol-4-yl 5-I-thiazol-2-yl 3-OMe-isoxazol-4-yl 5-Me-thiazol-2-yl -OCF3 -isoxazol-4-yl 5-Et-thiazol-2-yl 3 -Ph-isoxazol-4-yl 5-CF3-thiazol-2-yl 5-F-isoxazol-4-yl 5- CHF2-thiazol-2-yl 5-Cl-isoxazol-4-yl 5-CHO-thiazol-2-yl 5-Br-isoxazol-4-yl 5-CN-thiazol-2-yl 5-I-isoxazol-4-yl 5-CH2CN-thiazol-2-yl
5- Me-isoxazol-4-yl 5-OMe-thiazol-2-yl 5-Et-isoxazol-4-yl 5-OCF3-thiazol-2-yl
5-CF3-isoxazol-4-yl 5-Ph-thiazol-2-yl 5-CHF2-isoxazol-4-yl 4-F-thiazol-2-yl 5-CHO-isoxazol-4-yl 4-Cl-thiazol-2-yl 5-CN-isoxazol-4-yl 4-Br-thiazol-2-yl 5-OMe-isoxazol-4-yl 4-I-thiazol-2-yl 5-OCF3-isoxazol-4-yl 4-Me-thiazol-2-yl 5-Ph-isoxazol-4-yl 4-Et-thiazol-2-yl
Isothiazol-4-yl 4-CF3-thiazol-2-yl 3 -F-isothiazol-4-yl 4-CHF2-thiazol-2-yl 3-Cl-isothiazol-4-yl 4-CHO-thiazol-2-yl 3 -Br-isothiazol-4-yl 4-CN-t azol-2-yl 3 -I-isothiazol-4-yl 4-OMe-thiazol-2-yl 3 -Me-isothiazol-4-yl 4-OCF3-thiazol-2-yl 3-Et-isothiazol-4-yl 4-Ph-thiazol-2-yl 3 -CF3 -isothiazol-4-yl Oxazol-5-yl -CHF2-isothiazol-4-yl 2-F-oxazol-5-yl
Figure imgf000060_0001
2-Cl-oxazol-5-yl
2-Br-oxazol-5-yl
2-Me-oxazol-5-yl
-CF3-oxazol-5-yl
-CHF2-oxazol-5-yl 2-CN-oxazol-5-yl
-OMe-oxazol-5-yl-OCF3-oxazol-5-yl 2-Ph-oxazol-5-yl
4-F-oxazol-5-yl
4-Cl-oxazol-5-yl
4-Br-oxazol-5-yl
4-Me-oxazol-5-yl
-CF3-oxazol-5-yl
-CHF2-oxazol-5-yl 4-CN-oxazol-5-yl
-OMe-oxazol-5-yl-OCF3-oxazol-5-yl 4-Ph-oxazol-5-yl
Thiazol-5-yl
2-F-thiazol-5-yl
2-Cl-thiazol-5-yl
2-Br-thiazol-5-yl
2-Me-thiazol-5-yl
2-CF3-thiazol-5-yl-CHF2-thiazol-5-yl 2-CN-thiazol-5-yl
-OMe-thiazol-5-yl-OCF3-thiazol-5-yl 2-Ph-thiazol-5-yl
4-F-thiazol-5-yl
4-Cl-thiazol-5-yl
4-Br-thiazol-5-yl
4-Me-thiazol-5-yl
4-CF3-thiazol-5-yl-CHF2-thiazol-5-yl 4-CN-thiazol-5-yl -OMe-thiazol-5-yl
Figure imgf000061_0001
-OCF3-l-Me-l#-izl-4-yl 5-OCF3-l-Me-l -pzl-4-yl 2-Ph-l-Me-l#-izl-4-yl 5-Ph-l-Me-l /-pzl-4-yl 5-F-l-Me-l#-izl-4-yl l /-pzl-5-yl 5-Cl-l-Me-l//-izl-4-yl l-Me-l /-pzl-5-yl 5-Br-l-Me-li/-izl-4-yl 3-F-l-Me-ltf-pzl-5-yl l,5-di-Me-l//-izl-4-yl 3-Cl-l-Me-l /-pzl-5-yl 5-CF3-l-Me-l /-izl-4-yl 3-Br-l-Me-l /-pzl-5-yl-CHF2-l-Me-l /-izl-4-yl 1.3- di-Me-l /-pzl-5-yl 5-CN-l-Me-l#-izl-4-yl 3-CF3-l-Me-l#-pzl-5-yl -OMe-l-Me-l//-izl-4-yl 3 -CHF2- 1 -Me- l /-pzl-5-yl-OCF3 - 1 -Me- l/f-izl-4-yl 3-CN-l-Me-l /-pzl-5-yl 5-Ph-l-Me-l/-izl-4-yl 3- OMe-l-Me-l /-pzl-5-yl l /-izl-5-yl 3 -OCF3 - 1 -Me- l#-pzl-5-yl l-Me-l /-izl-5-yl 3- Ph-l-Me-l//-pzl-5-yl 2-F-l-Me-l /-izl-5-yl 4- F-l-Me-l /-pzl-5-yl 2-Cl-l-Me-l/-izl-5-yl 4-Cl-l-Me-l /-pzl-5-yl 2-Br-l-Me-l#-izl-5-yl 4-Br-l-Me-l /-pzl-5-yl l,2-di-Me-l /-izl-5-yl 1.4- di-Me-l /-pzl-5-yl 2-CF3-l-Me-l -izl-5-yl 4- CF3-l-Me-l /-pzl-5-yl-CHF2-l-Me-l /-izl-5-yl 4-CHF2- 1 -Me- ltf-pzl-5-yl 2-CN-l-Me-l -izl-5-yl 4-CN-l-Me-l /-pzl-5-yl -OMe-l-Me-li-izl-5-yl 4-OMe-l-Me-l//-pzl-5-yl-OCF3-l-Me-l//-izl-5-yl 4-OCF3 - 1 -Me- l /-pzl-5-yl 2-Ph-l-Me-l/-izl-5-yl 4-Ph-l-Me-l#-pzl-5-yl 4-F-l-Me-li-izl-5-yl Thiophene-2-yl 4-Cl-l-Me-l /-izl-5-yl Thiophene-3-yl 4-Br-l-Me-l/-izl-5-yl Furan-2-yl l,4-di-Me-l/-izl-5-yl Furan-3-yl 4-CF3-l-Me-l /-izl-5-yl l /-pyrrol-2-yl-CHF2-l-Me-ltf-izl-5-yl l-Me-l /-pyrrol-2-yl 4-CN-l-Me-l/-izl-5-yl l /-pyrrol-3-yl -OMe-l-Me-l /-izl-5-yl 1- Me-l /-pyrrol-3-yl-OCF3-l-Me-l//-izl-5-yl [l,3,4]odzl-2-yl 4-Ph-l-Me-l /-izl-5-yl 2- F-[l,3,4]odzl-5-yl l /-pzl-3-yl 2-Cl-[l,3,4]odzl-5-yl l-Me-li -pzl-3-yl 2-Br-[l,3,4]odzl-5-yl 4-F-l-Me-l /-pzl-3-yl 2-Me-[l,3,4]odzl-5-yl 4-Cl-l-Me-l#-pzl-3-yl 2-CF3-[l,3,4]odzl-5-yl
Figure imgf000062_0001
2-CHF2-[l,3,4]odzl-5-yl 5-Br-[l,2,4]odzl-3-yl 2-CN-[l,3,4]odzl-5-yl 5-Me-[l,2,4]odzl-3-yl 2-OMe-[l,3,4]odzl-5-yl 5-CF3-[l,2,4]odzl-3-yl 2-OCF3-[l,3,4]odzl-5-yl 5-CHF2-[l,2,4]odzl-3-yl [l,3,4]tdzl-2-yl 5-CN-[l,2,4]odzl-3-yl 2-F-[l,3,4]tdzl-5-yl 5-OMe-[l,2,4]odzl-3-yl 2-Cl-[l,3,4]tdzl-5-yl 5-OCF3-[l,2,4]odzl-3-yl 2-Br-[l,3,4]tdzl-5-yl 5-Ph-[l,2,4]odzl-3-yl 2-Me-[l,3,4]tdzl-5-yl [l,2,4]tdzl-5-yl 2-CF3-[l,3,4]tdzl-5-yl 3-F-[l,2,4]tdzl-5-yl 2-CHF2-[l ,3,4]tdzl-5-yl 3-Cl-[l,2,4]tdzl-5-yl 2-CN-[l,3,4]tdzl-5-yl 3-Br-[l,2,4]tdzl-5-yl 2-OMe-[l,3,4]tdzl-5-yl 3-Me-[l,2,4]tdzl-5-yl 2-OCF3-[l,3,4]tdzl-5-yl 3-CF3-[l,2,4]tdzl-5-yl
4//-[l,2,4]tzl-3-yl 3-CHF2-[l,2,4]tdzl-5-yl 4-Me-4#-[l,2,4]tzl-3-yl 3-CN-[l,2,4]tdzl-5-yl 3-F-4-Me-4#-[l,2,4]tzl-5-yl 3- OMe-[l,2,4]tdzl-5-yl -Cl-4-Me-4tf-[l,2,4]tzl-5-yl 3- OCF3-[l,2,4]tdzl-5-yl -Br-4-Me-4#-[l,2,4]tzl-5-yl 3- Ph-[l,2,4]tdzl-5-yl
3.4- di-Me-4#-[l,2,4]tzl-5-yl [l,2,4]tdzl-3-yl -CF3-4-Me-4#-[l,2,4]tzl-5- 5-F-[l,2,4]tdzl-3-yl yi 5-Cl-[l ,2,4]tdzl-3-yl-CHF2-4-Me-4#-[l ,2,4]tzl-5- 5-Br-[l,2,4]tdzl-3-yl yi 5-Me-[l,2,4]tdzl-3-yl-CN-4-Me-4#-[ l,2,4]tzl-5-yl 5-CF3-[l,2,4]tdzl-3-yl-OMe-4-Me-4i/-[l ,2,4]tzl-5- 5-CHF2-[l,2,4]tdzl-3-yl yi 5-CN-[l,2,4]tdzl-3-yl-OCF3-4-Me-4#-[ l,2,4]tzl-5- 5-OMe-[l,2,4]tdzl-3-yl yi 5-OCF3-[l,2,4]tdzl-3-yl -Ph-4-Me-4#-[l,2,4]tzl-5-yl 5-Ph-[l,2,4]tdzl-3-yl l#-[l,2,4]tzl-3-yl [l,2,3]odzl-5-yl l-Me-l#-[l,2,4]tzl-3-yl 4- F-[l,2,3]odzl-5-yl 5-F-l -Me-l#-[l ,2,4]tzl-3-yl 4-Cl-[l,2,3]odzl-5-yl 5-Cl-l-Me-l /-[l,2,4]tzl-3-yl 4-Br-[l,2,3]odzl-5-yl 5-Br-l-Me-l /-[l,2,4]tzl-3-yl 4-Me-[l,2,3]odzl-5-yl
1.5- di-Me-l#-[ l,2,4]tzl-3-yl 4- CF3-[l,2,3]odzl-5-yl 5-CF3- 1 -Me- lH-[ 1 ,2,4]tzl-3- 4- CHF2-[l,2,3]odzl-5-yl yi 4-CN-[l,2,3]odzl-5-yl
Figure imgf000063_0001
-OMe-[l,2,3]odzl-5-yl 4-CN-l#-[l,2,3]tzl-5-yl- OCF3-[l,2,3]odzl-5-yl 4-OMe-li/-[l,2,3]tzl-5-yl
4- Ph-[l,2,3]odzl-5-yl 4-OCF3-l#-[l,2,3]tzl-5-yl
[l,2,3]odzl-4-yl 4-Ph-l#-[l,2,3]tzl-5-yl
5- F-[l,2,3]odzl-4-yl 5-F-pyridin-2-yl 5-Cl-[l,2,3]odzl-4-yl 5-Cl-pyridin-2-yl 5-Br-[l,2,3]odzl-4-yl 5-Br-pyridin-2-yl 5-Me-[l,2,3]odzl-4-yl 5-I-pyridin-2-yl 5-CF3-[l,2,3]odzl-4-yl 5-Me-pyridin-2-yl- CHF2-[l,2,3]odzl-4-yl 5-Et-pyridin-2-yl 5-CN-[l,2,3]odzl-4-yl 5-CF3-pyridin-2-yl -OMe-[l,2,3]odzl-4-yl 5-CHF2-pyridin-2-yl-OCF3-[l,2,3]odzl-4-yl 5-CHO-pyridin-2-yl 5-Ph-[l,2,3]odzl-4-yl 5-CN-pyridin-2-yl
[l,2,3]tdzl-5-yl 5-OMe-pyridin-2-yl 4-F-[l,2,3]tdzl-5-yl 5- OCF3-pyridin-2-yl 4-Cl-[l,2,3]tdzl-5-yl 5 -N(Me)2-pyridin-2-yl 4-Br-[l,2,3]tdzl-5-yl 5- Ph-pyridin-2-yl 4-Me-[l,2,3]tdzl-5-yl 3,5-di-Cl-pyridin-2-yl 4-CF3-[l,2,3]tdzl-5-yl 3-Me-5-Cl-pyridin-2-yl -CHF2-[l,2,3]tdzl-5-yl 3-CN-5-Cl-pyridin-2-yl 4-CN-[l,2,3]tdzl-5-yl 6- F-pyridin-2-yl 4-OMe-[l,2,3]tdzl-5-yl 6-Cl-pyridin-2-yl - OCF3-[l,2,3]tdzl-5-yl 6-Br-pyridin-2-yl
4- Ph-[l,2,3]tdzl-5-yl 6-I-pyridin-2-yl [l,2,3]tdzl-4-yl 6-Me-pyridin-2-yl
5- F-[l,2,3]tdzl-4-yl 6-Et-pyridin-2-yl 5-Cl-[l,2,3]tdzl-4-yl 6-CF3 -pyridin-2-yl 5-Br-[l,2,3]tdzl-4-yl 6- CHF2-pyridin-2-yl 5-Me-[l,2,3]tdzl-4-yl 6-CHO-pyridin-2-yl 5-CF3-[l,2,3]tdzl-4-yl 6-CN-pyridin-2-yl - CHF2-[l,2,3]tdzl-4-yl 6-OMe-pyridin-2-yl 5-CN-[l,2,3]tdzl-4-yl 6-OCF3 -pyridin-2-yl
5-OMe-[l,2,3]tdzl-4-yl 6-N(Me)2-pyridin-2-yl 5-OCF3-[l,2,3]tdzl-4-yl 6-Ph-pyridin-2-yl 5-Ph-[l,2,3]tdzl-4-yl 3-F-pyridin-2-yl
3 -[l,2,4]tzl-3-yl 3-Cl-pyridin-2-yl 5-F-3//-[l,2,4]tzl-3-yl
Figure imgf000064_0001
3-Br-pyridin-2-yl 3-I-pyridin-2-yl 5 -F-pyridazin-2 -yl 3 -Me-pyridin-2 -yl 5-Cl-pyridazin-2-yl 3 -Et-pyridin-2-yl 5-Br-pyridazin-2-yl 3-CF3-pyridin-2-yl 5-I-pyridazin-2-yl -CHF2-pyridin-2-yl 5-Me-pyridazin-2-yl 3-CHO-pyridin-2-yl 5 -Et-pyridazin-2-yl 3-CN-pyridin-2-yl 5 -CF3 -pyridazin-2 -yl 3-OMe-pyridin-2-yl 5 -CHF2-pyridazin-2 -yl 3 -OCF3 -pyridin-2 -yl 5-CHO-pyridazin-2-yl -N(Me)2-pyridin-2-yl 5 -CN-pyridazin- 2 -yl
3-Ph-pyridin-2-yl 5-OMe-pyridazin-2-yl,6-di-Cl-pyridin-2-yl 5-OCF3-pyridazin-2-yl 6-F-pyridin-3-yl 5-N(Me)2-pyridazin-2-yl 6-Cl-pyridin-3-yl 5 -Ph-pyridazin- 2 -yl 6-Br-pyridin-3-yl 5-F-pyrimidin-4-yl 6-I-pyridin-3-yl 5-Cl-pyrimidin-4-yl 6-Me-pyridin-3 -yl 5-Br-pyrimidin-4-yl 6-Et-pyridin-3-yl 5-I-pyrimidin-4-yl 6-CF3 -pyridin-3 -yl 5-Me-pyrimidin-4-yl 6-CHF2-pyridin-3 -yl 5-Et-pyrimidin-4-yl 6-CHO-pyridin-3-yl 5-CF3-pyrimidin-4-yl 6-C -pyridin-3 -yl 5-CHF2-pyrimidin-4-yl 6-OMe -pyridin-3 -yl 5 -CHO-pyrimidin-4-yl 6-OCF3 -pyridin-3 -yl 5-CN-pyrimidin-4-yl-N(Me)2-pyridin-3-yl 5-OMe-pyrimidin-4-yl
6-Ph-pyridin-3 -yl 5-OCF3-pyrimidin-4-yl ,6-di-Cl-pyridin-3-yl 5-N(Me)2-pyrimidin-4-yl-CN-6-Cl-pyridin-3-yl 5-Ph-pyrimidin-4-yl 3-F-pyridin-4-yl 2-F-pyrimidin-5-yl 3-Cl-pyridin-4-yl 2-Cl-pyrimidin-5-yl 3 -Br-pyridin-4-yl 2-Br-pyrimidin-5-yl 3-I-pyridin-4-yl 2 -I-pyrimidin-5 -yl 3 -Me-pyridin-4-yl 2 -Me-pyrimidin-5 -yl 3-Et-pyridin-4-yl 2-Et-pyrimidin-5-yl 3 -CF3 -pyridin-4-yl 2 -CF3 -pyrimidin-5 -yl 3-CHF2-pyridin-4-yl 2-CHF2-pyrimidin-5-yl 3-CHO-pyridin-4-yl 2-CHO-pyrimidin-5-yl 3 -CN-pyridin-4-yl 2 -CN-pyrimidin- 5 -yl
Figure imgf000065_0001
2 -OMe -pyrimidin- 5 -yl 6-CN-[l,2,4]triazin-3-yl
2- OCF3-pyrimidin-5-yl 4-Cl-[l,3,5]triazin-2-yl 2-N(Me)2-pyrimidin-5-yl 4-CF3 -phenyl
2 -Ph-pyrimidin- 5 -yl 4-OCF3 -phenyl 3 -Cl-pyrazin-2-yl 3 -OCF3 -phenyl 3 -CN-pyrazin-2-yl 3,5-di-OCF3-phenyl
3 -OMe-pyrazin-2-yl 3,5-di-Cl-phenyl
3- Cl-[l,2,4]triazin-6-yl
3-CN-[l,2,4]triazin-6-yl
Figure imgf000066_0001
The present disclosure also includes Tables 2 through 1584. Each Table is constructed in the the same manner as Table 1 above, except that the row heading in Table 1 (i.e. "R2 = CI; Z = O; and R3 = H (m = 0)") is replaced with the respective row heading shown below. For example, the first entry in Table 2 is a compound of Formula 1 wherein R1 is H, R2 is CI, Z is O, R3 is H (m = 0), and Q is isoxazol-5-yl (i.e. unsubstituted isoxazole attached to the remainder of Formula 1 at the 5 -position). The remainder of Table 2 is constructed in the same way, and hence the remainder of Tables through 1584 is constructed the same way.
Table Header Row Table Header Row
2 R2 = F, Z = O, R3 = H (m = 0) 23 R2 = F, Z = 0, R3 = 3-Ph
3 R2 = F, Z = O, R3 = 3-F 24 R2 = F, Z = S, R3 = 3-F
4 R2 = F, Z = O, R3 = 3-Cl 25 R2 = F, Z = S, R3 = 3 -CI
5 R2 = F, Z = O, R3 = 3-Br 26 R2 = F, Z = S, R3 = 3-Br
6 R2 = F, Z = 0, R3 = 3-I 27 R2 = F, Z = S, R3 = 3-1
7 R2 = F, Z = 0, R3 = 3-CN 28 R2 = F, Z = S, R3 = 3-CN
8 R2 = F, Z = O, R3 = 3-N02 29 R2 = F, Z = S, R3 = 3-N02
9 R2 = F, Z = O, R3 = 3-OMe 30 R2 = F, Z = S, R3 = 3-OMe
10 R2 = F, Z = 0, R3 = 3-OCF3 31 R2 = F, Z = S, R3 = 3-OCF3
11 R2 = F, Z = O, R3 = 3-CF3 32 R2 = F, Z = S, R3 = 3-CF3
12 R2 = F, Z = 0, R3 = 3-CHF2 33 R2 = F, Z = S, R3 = 3-CHF2
13 R2 = F, Z = 0, R3 = 3-CH2F 34 R2 = F, Z = S, R3 = 3-CH2F
14 R2 = F, Z = 0, R3 = 3-CHO 35 R2 = F, Z = S, R3 = 3-CHO
15 R2 = F, Z = O, R3 = 3-Me 36 R2 = F, Z = S, R3 = 3-Me
16 R2 = F, Z = O, R3 = 3-Et 37 R2 = F, Z = S, R3 = 3-Et
17 R2 = F, Z = O, R3 = 3-Ethynyl 38 R2 = F, Z = S, R3 = 3-Ethynyl
18 R2 = F, Z = O, R3 = 3-Ethenyl 39 R2 = F, Z = S, R3 = 3-Ethenyl
19 R2 = F, Z = O, R3 = 3-S02Me 40 R2 = F, Z = S, R3 = 3-S02Me
20 R2 = F, Z = O, R3 = 3-OAc 41 R2 = F, Z = S, R3 = 3-OAc
21 R2 = F, Z = O, R3 = 3-c-Pr 42 R2 = F, Z = S, R3 = 3-c-Pr
22 R2 = F, Z = O, R3 = 3-z-Pr 43 R2 = F, Z = S, R3 = 3-z-Pr
Figure imgf000066_0002
Table Header Row Table Header Row
44 R2 = F, Z = S, R3 = 3-Ph 81 R2 = F, Z = O, R3 = 5-Ethenyl
45 R2 = F, Z = O, R3 = 4-F 82 R2 = F, Z = O, R3 = 5-S02Me
46 R2 = F, Z = O, R3 = 4-Cl 83 R2 = F, Z = O, R3 = 5-OAc
47 R2 = F, Z = O, R3 = 4-Br 84 R2 = F, Z = O, R3 = 5-c-Pr
48 R2 = F, Z = O, R3 = 4-1 85 R2 = F, Z = O, R3 = 5- -Pr
49 R2 = F, Z = O, R3 = 4-CN 86 R2 = F, Z = O, R3 = 5-Ph
50 R2 = F, Z = O, R3 = 4-N02 87 R2 = F, Z = O, R3 = 6-F
51 R2 = F, Z = O, R3 = 4-OMe 88 R2 = F, Z = O, R3 = 6-Cl
52 R2 = F, Z = O, R3 = 4-OCF3 89 R2 = F, Z = O, R3 = 6-Br
53 R2 = F, Z = O, R3 = 4-CF3 90 R2 = F, Z = O, R3 = 6-1
54 R2 = F, Z = O, R3 = 4-CHF2 91 R2 = F, Z = O, R3 = 6-CN
55 R2 = F, Z = O, R3 = 4-CH2F 92 R2 = F, Z = O, R3 = 6-N02
56 R2 = F, Z = O, R3 = 4-CHO 93 R2 = F, Z = O, R3 = 6-OMe
57 R2 = F, Z = O, R3 = 4-Me 94 R2 = F, Z = O, R3 = 6-OCF3
58 R2 = F, Z = O, R3 = 4-Et 95 R2 = F, Z = O, R3 = 6-CF3
59 R2 = F, Z = O, R3 = 4-Ethynyl 96 R2 = F, Z = O, R3 = 6-CHF2
60 R2 = F, Z = O, R3 = 4-Ethenyl 97 R2 = F, Z = O, R3 = 6-CH2F
61 R2 = F, Z = O, R3 = 4-S02Me 98 R2 = F, Z = O, R3 = 6-CHO
62 R2 = F, Z = O, R3 = 4-OAc 99 R2 = F, Z = O, R3 = 6-Me
63 R2 = F, Z = O, R3 = 4-c-Pr 100 R2 = F, Z = O, R3 = 6-Et
64 R2 = F, Z = O, R3 = 4-z-Pr 101 R2 = F, Z = O, R3 = 6-Ethynyl
65 R2 = F, Z = O, R3 = 4-Ph 102 R2 = F, Z = O, R3 = 6-Ethenyl
66 R2 = F, Z = O, R3 = 5-F 103 R2 = F, Z = O, R3 = 6-S02Me
67 R2 = F, Z = O, R3 = 5-Cl 104 R2 = F, Z = O, R3 = 6-OAc
68 R2 = F, Z = O, R3 = 5-Br 105 R2 = F, Z = O, R3 = 6-c-Pr
69 R2 = F, Z = O, R3 = 5-1 106 R2 = F, Z = O, R3 = 6-z-Pr
70 R2 = F, Z = O, R3 = 5-CN 107 R2 = F, Z = O, R3 = 6-Ph
71 R2 = F, Z = O, R3 = 5-N02 108 R2 = F, Z = O, R3 = 3,4-di-F
72 R2 = F, Z = O, R3 = 5-OMe 109 R2 = F, Z = O, R3 = 3,5-di-F
73 R2 = F, Z = O, R3 = 5-OCF3 110 R2 = F, Z = O, R3 = 3,6-di-F
74 R2 = F, Z = O, R3 = 5-CF3 111 R2 = F, Z = O, R3 = 4,5-di-F
75 R2 = F, Z = O, R3 = 5-CHF2 112 R2 = F, Z = O, R3 = 3,4-di-Cl
76 R2 = F, Z = O, R3 = 5-CH2F 113 R2 = F, Z = O, R3 = 3,5-di-Cl
77 R2 = F, Z = O, R3 = 5-CHO 114 R2 = F, Z = O, R3 = 3,6-di-Cl
78 R2 = F, Z = O, R3 =5-Me 115 R2 = F, Z = O, R3 = 4,5-di-Cl
79 R2 = F, Z = O, R3 = 5-Et 1 16 R2 = F, Z = O, R3 = 3,4-di-Br
80 R2 = F, Z = O, R3 = 5-Ethynyl 1 17 R2 = F, Z = O, R3 = 3,5-di-Br
Figure imgf000067_0001
Table Header Row Table Header Row
118 R2 = F, Z = O, R3 = 3,6-di-Br 155 R2 = Br, Z = O, R3 = 3-CF3
119 R2 = F, Z = O, R3 = 4,5-di-Br 156 R2 = Br, Z = O, R3 = 3-CHF2
120 R2 = F, Z = O, R3 = 3,4-di-CN 157 R2 = Br, Z = O, R3 = 3-CH2F
121 R2 = F, Z = O, R3 = 3,5-di-CN 158 R2 = Br, Z = O, R3 = 3-CHO
122 R2 = F, Z = O, R3 = 3,6-di-CN 159 R2 = Br, Z = O, R3 = 3-Me
123 R2 = F, Z = O, R3 = 4,5-di-CN 160 R2 = Br, Z = O, R3 = 3-Et
124 R2 = F, Z = O, R3 = 3,4-di-Me 161 R2 = Br, Z = O, R3 = 3-Ethynyl
125 R2 = F, Z = O, R3 = 3,5-di-Me 162 R2 = Br, Z = O, R3 = 3-Ethenyl
126 R2 = F, Z = O, R3 = 3,6-di-Me 163 R2 = Br, Z = O, R3 = 3-S02Me
127 R2 = F, Z = O, R3 = 4,5-di-Me 164 R2 = Br, Z = O, R3 = 3-OAc
128 R2 = F, Z = O, R3 = 3,4-di-OMe 165 R2 = Br, Z = O, R3 = 3-c-Pr
129 R2 = F, Z = O, R3 = 3,5-di-OMe 166 R2 = Br, Z = O, R3 = 3-z-Pr
130 R2 = F, Z = O, R3 = 3,6-di-OMe 167 R2 = Br, Z = O, R3 = 3-Ph
131 R2 = F, Z = O, R3 = 4,5-di-OMe 168 R2 = Br, Z = S, R3 = 3-F
132 R2 = F, Z = O, R3 = 3,4-di-CF3 169 R2 = Br, Z = S, R3 = 3 -CI
133 R2 = F, Z = O, R3 = 3,5-di-CF3 170 R2 = Br, Z = S, R3 = 3-Br
134 R2 = F, Z = O, R3 = 3,6-di-CF3 171 R2 = Br, Z = S, R3 = 3-1
135 R2 = F, Z = O, R3 = 4,5-di-CF3 172 R2 = Br, Z = S, R3 = 3-CN
136 R2 = F, Z = O, R3 = 3-CN, 4-Me 173 R2 = Br, Z = S, R3 = 3-N02
137 R2 = F, Z = O, R3 = 3-CN, 4-F 174 R2 = Br, Z = S, R3 = 3-OMe
138 R2 = F, Z = O, R3 = 3-CN, 4-Br 175 R2 = Br, Z = S, R3 = 3-OCF3
139 R2 = F, Z = O, R3 = 3-CN, 4-OMe 176 R2 = Br, Z = S, R3 = 3-CF3
140 R2 = F, Z = O, R3 = 3-CN, 4-CF3 177 R2 = Br, Z = S, R3 = 3-CHF2
141 R2 = F, Z = O, R3 = 3-CN, 6-Me 178 R2 = Br, Z = S, R3 = 3-CH2F
142 R2 = F, Z = O, R3 = 3-CN, 6-F 179 R2 = Br, Z = S, R3 = 3-CHO
143 R2 = F, Z = O, R3 = 3-CN, 6-Br 180 R2 = Br, Z = S, R3 = 3-Me
144 R2 = F, Z = O, R3 = 3-CN, 6-OMe 181 R2 = Br, Z = S, R3 = 3-Et
145 R2 = F, Z = O, R3 = 3-CN, 6-CF3 182 R2 = Br, Z = S, R3 = 3-Ethynyl
146 R2 = Br, Z = O, R3 = H (m = 0) 183 R2 = Br, Z = S, R3 = 3-Ethenyl
147 R2 = Br, Z = O, R3 = 3-F 184 R2 = Br, Z = S, R3 = 3-S02Me
148 R2 = Br, Z = O, R3 = 3 -CI 185 R2 = Br, Z = S, R3 = 3-OAc
149 R2 = Br, Z = O, R3 = 3-Br 186 R2 = Br, Z = S, R3 = 3-c-Pr
150 R2 = Br, Z = O, R3 = 3-1 187 R2 = Br, Z = S, R3 = 3-z-Pr
151 R2 = Br, Z = O, R3 = 3-CN 188 R2 = Br, Z = S, R3 = 3-Ph
152 R2 = Br, Z = O, R3 = 3-N02 189 R2 = Br, Z = O, R3 = 4-F
153 R2 = Br, Z = O, R3 = 3-OMe 190 R2 = Br, Z = O, R3 = 4-Cl
154 R2 = Br, Z = O, R3 = 3-OCF3 191 R2 = Br, Z = O, R3 = 4-Br
Figure imgf000068_0001
Table Header Row Table Header Row
192 R2 = Br, Z = O, R3 = 4-1 229 R2 = Br, Z = O, R3 = 5-z-Pr
193 R2 = Br, Z = O, R3 = 4-CN 230 R2 = Br, Z = O, R3 = 5-Ph
194 R2 = Br, Z = O, R3 = 4-N02 231 R2 = Br, Z = O, R3 = 6-F
195 R2 = Br, Z = O, R3 = 4-OMe 232 R2 = Br, Z = O, R3 = 6-Cl
196 R2 = Br, Z = O, R3 = 4-OCF3 233 R2 = Br, Z = O, R3 = 6-Br
197 R2 = Br, Z = O, R3 = 4-CF3 234 R2 = Br, Z = O, R3 = 6-1
198 R2 = Br, Z = O, R3 = 4-CHF2 235 R2 = Br, Z = O, R3 = 6-CN
199 R2 = Br, Z = O, R3 = 4-CH2F 236 R2 = Br, Z = O, R3 = 6-N02
200 R2 = Br, Z = O, R3 = 4-CHO 237 R2 = Br, Z = O, R3 = 6-OMe
201 R2 = Br, Z = O, R3 = 4-Me 238 R2 = Br, Z = O, R3 = 6-OCF3
202 R2 = Br, Z = O, R3 = 4-Et 239 R2 = Br, Z = O, R3 = 6-CF3
203 R2 = Br, Z = O, R3 = 4-Ethynyl 240 R2 = Br, Z = O, R3 = 6-CHF2
204 R2 = Br, Z = O, R3 = 4-Ethenyl 241 R2 = Br, Z = O, R3 = 6-CH2F
205 R2 = Br, Z = O, R3 = 4-S02Me 242 R2 = Br, Z = O, R3 = 6-CHO
206 R2 = Br, Z = O, R3 = 4-OAc 243 R2 = Br, Z = O, R3 = 6-Me
207 R2 = Br, Z = O, R3 = 4-c-Pr 244 R2 = Br, Z = O, R3 = 6-Et
208 R2 = Br, Z = O, R3 = 4-z-Pr 245 R2 = Br, Z = O, R3 = 6-Ethynyl
209 R2 = Br, Z = O, R3 = 4-Ph 246 R2 = Br, Z = O, R3 = 6-Ethenyl
210 R2 = Br, Z = O, R3 = 5-F 247 R2 = Br, Z = O, R3 = 6-S02Me
211 R2 = Br, Z = O, R3 = 5-Cl 248 R2 = Br, Z = O, R3 = 6-OAc
212 R2 = Br, Z = O, R3 = 5-Br 249 R2 = Br, Z = O, R3 = 6-c-Pr
213 R2 = Br, Z = O, R3 = 5-1 250 R2 = Br, Z = O, R3 = 6-z-Pr
214 R2 = Br, Z = O, R3 = 5-CN 251 R2 = Br, Z = O, R3 = 6-Ph
215 R2 = Br, Z = O, R3 = 5-N02 252 R2 = Br, Z = O, R3 = 3,4-di-F
216 R2 = Br, Z = O, R3 = 5-OMe 253 R2 = Br, Z = O, R3 = 3,5-di-F
217 R2 = Br, Z = O, R3 = 5-OCF3 254 R2 = Br, Z = O, R3 = 3,6-di-F
218 R2 = Br, Z = O, R3 = 5-CF3 255 R2 = Br, Z = O, R3 = 4,5-di-F
219 R2 = Br, Z = O, R3 = 5-CHF2 256 R2 = Br, Z = O, R3 = 3,4-di-Cl
220 R2 = Br, Z = O, R3 = 5-CH2F 257 R2 = Br, Z = O, R3 = 3,5-di-Cl
221 R2 = Br, Z = O, R3 = 5-CHO 258 R2 = Br, Z = O, R3 = 3,6-di-Cl
222 R2 = Br, Z = O, R3 =5-Me 259 R2 = Br, Z = O, R3 = 4,5-di-Cl
223 R2 = Br, Z = O, R3 = 5-Et 260 R2 = Br, Z = O, R3 = 3,4-di-Br
224 R2 = Br, Z = O, R3 = 5-Ethynyl 261 R2 = Br, Z = O, R3 = 3,5-di-Br
225 R2 = Br, Z = O, R3 = 5-Ethenyl 262 R2 = Br, Z = O, R3 = 3,6-di-Br
226 R2 = Br, Z = O, R3 = 5-S02Me 263 R2 = Br, Z = O, R3 = 4,5-di-Br
227 R2 = Br, Z = O, R3 = 5-OAc 264 R2 = Br, Z = O, R3 = 3,4-di-CN
228 R2 = Br, Z = O, R3 = 5-c-Pr 265 R2 = Br, Z = O, R3 = 3,5-di-CN
Figure imgf000069_0001
Table Header Row Table Header Row
266 R2 = Br, Z = O, R3 = 3,6-di-CN 303 R2 = CI, Z = O, R3 = 3-Me
267 R2 = Br, Z = O, R3 = 4,5-di-CN 304 R2 = CI, Z = O, R3 = 3-Et
268 R2 = Br, Z = O, R3 = 3,4-di-Me 305 R2 = CI, Z = O, R3 = 3-Ethynyl
269 R2 = Br, Z = O, R3 = 3,5-di-Me 306 R2 = CI, Z = O, R3 = 3-Ethenyl
270 R2 = Br, Z = O, R3 = 3,6-di-Me 307 R2 = CI, Z = O, R3 = 3-S02Me
271 R2 = Br, Z = O, R3 = 4,5-di-Me 308 R2 = CI, Z = O, R3 = 3-OAc
272 R2 = Br, Z = O, R3 = 3,4-di-OMe 309 R2 = CI, Z = O, R3 = 3-c-Pr
273 R2 = Br, Z = O, R3 = 3,5-di-OMe 310 R2 = C1, Z = 0, R3 = 3-z-Pr
274 R2 = Br, Z = O, R3 = 3,6-di-OMe 311 R2 = CI, Z = O, R3 = 3-Ph
275 R2 = Br, Z = O, R3 = 4,5-di-OMe 312 R2 = CI, Z = S, R3 = 3-F
276 R2 = Br, Z = O, R3 = 3,4-di-CF3 313 R2 = CI, Z = S, R3 = 3 -CI
277 R2 = Br, Z = O, R3 = 3,5-di-CF3 314 R2 = CI, Z = S, R3 = 3-Br
278 R2 = Br, Z = O, R3 = 3,6-di-CF3 315 R2 = CI, Z = S, R3 = 3-1
279 R2 = Br, Z = O, R3 = 4,5-di-CF3 316 R2 = CI, Z = S, R3 = 3-CN
280 R2 = Br, Z = O, R3 = 3-CN, 4-Me 317 R2 = CI, Z = S, R3 = 3-N02
281 R2 = Br, Z = O, R3 = 3-CN, 4-F 318 R2 = CI, Z = S, R3 = 3-OMe
282 R2 = Br, Z = O, R3 = 3-CN, 4-Br 319 R2 = CI, Z = S, R3 = 3-OCF3
283 R2 = Br, Z = O, R3 = 3-CN, 4-OMe 320 R2 = CI, Z = S, R3 = 3-CF3
284 R2 = Br, Z = O, R3 = 3-CN, 4-CF3 321 R2 = CI, Z = S, R3 = 3-CHF2
285 R2 = Br, Z = O, R3 = 3-CN, 6-Me 322 R2 = CI, Z = S, R3 = 3-CH2F
286 R2 = Br, Z = O, R3 = 3-CN, 6-F 323 R2 = CI, Z = S, R3 = 3-CHO
287 R2 = Br, Z = O, R3 = 3-CN, 6-Br 324 R2 = CI, Z = S, R3 = 3-Me
288 R2 = Br, Z = O, R3 = 3-CN, 6-OMe 325 R2 = CI, Z = S, R3 = 3-Et
289 R2 = Br, Z = O, R3 = 3-CN, 6-CF3 326 R2 = CI, Z = S, R3 = 3-Ethynyl
290 R2 = CI, Z = O, R3 = H (m = 0) 327 R2 = CI, Z = S, R3 = 3-Ethenyl
291 R2 = CI, Z = O, R3 = 3-F 328 R2 = CI, Z = S, R3 = 3-S02Me
292 R2 = CI, Z = O, R3 = 3-Cl 329 R2 = CI, Z = S, R3 = 3-OAc
293 R2 = CI, Z = O, R3 = 3-Br 330 R2 = CI, Z = S, R3 = 3-c-Pr
294 R2 = CI, Z = O, R3 = 3-1 331 R2 = CI, Z = S, R3 = 3-z-Pr
295 R2 = CI, Z = O, R3 = 3-CN 332 R2 = CI, Z = S, R3 = 3-Ph
296 R2 = CI, Z = O, R3 = 3-N02 333 R2 = CI, Z = O, R3 = 4-F
297 R2 = CI, Z = O, R3 = 3-OMe 334 R2 = CI, Z = O, R3 = 4-Cl
298 R2 = CI, Z = O, R3 = 3-OCF3 335 R2 = CI, Z = O, R3 = 4-Br
299 R2 = CI, Z = O, R3 = 3-CF3 336 R2 = CI, Z = O, R3 = 4-1
300 R2 = CI, Z = O, R3 = 3-CHF2 337 R2 = CI, Z = O, R3 = 4-CN
301 R2 = CI, Z = O, R3 = 3-CH2F 338 R2 = CI, Z = O, R3 = 4-N02
302 R2 = CI, Z = O, R3 = 3-CHO
Figure imgf000070_0001
339 R2 = CI, Z = O, R3 = 4-OMe Table Header Row Table Header Row
340 R2 = CI, Z = O, R3 = 4-OCF3 377 R2 = CI, Z = O, R3 = 6-Br
341 R2 = CI, Z = O, R3 = 4-CF3 378 R2 = CI, Z = O, R3 = 6-1
342 R2 = CI, Z = O, R3 = 4-CHF2 379 R2 = CI, Z = O, R3 = 6-CN
343 R2 = CI, Z = O, R3 = 4-CH2F 380 R2 = CI, Z = O, R3 = 6-N02
344 R2 = CI, Z = O, R3 = 4-CHO 381 R2 = CI, Z = O, R3 = 6-OMe
345 R2 = CI, Z = O, R3 = 4-Me 382 R2 = CI, Z = O, R3 = 6-OCF3
346 R2 = CI, Z = O, R3 = 4-Et 383 R2 = CI, Z = O, R3 = 6-CF3
347 R2 = CI, Z = O, R3 = 4-Ethynyl 384 R2 = CI, Z = O, R3 = 6-CHF2
348 R2 = CI, Z = O, R3 = 4-Ethenyl 385 R2 = CI, Z = O, R3 = 6-CH2F
349 R2 = CI, Z = O, R3 = 4-S02Me 386 R2 = CI, Z = O, R3 = 6-CHO
350 R2 = CI, Z = O, R3 = 4-OAc 387 R2 = CI, Z = O, R3 = 6-Me
351 R2 = CI, Z = O, R3 = 4-c-Pr 388 R2 = CI, Z = O, R3 = 6-Et
352 R2 = CI, Z = O, R3 = 4-z-Pr 389 R2 = CI, Z = O, R3 = 6-Ethynyl
353 R2 = CI, Z = O, R3 = 4-Ph 390 R2 = CI, Z = O, R3 = 6-Ethenyl
354 R2 = CI, Z = O, R3 = 5-F 391 R2 = CI, Z = O, R3 = 6-S02Me
355 R2 = CI, Z = O, R3 = 5-Cl 392 R2 = CI, Z = O, R3 = 6-OAc
356 R2 = CI, Z = O, R3 = 5-Br 393 R2 = CI, Z = O, R3 = 6-c-Pr
357 R2 = CI, Z = O, R3 = 5-1 394 R2 = CI, Z = O, R3 = 6-z-Pr
358 R2 = CI, Z = O, R3 = 5-CN 395 R2 = CI, Z = O, R3 = 6-Ph
359 R2 = CI, Z = O, R3 = 5-N02 396 R2 = CI, Z = O, R3 = 3,4-di-F
360 R2 = CI, Z = O, R3 = 5-OMe 397 R2 = CI, Z = O, R3 = 3,5-di-F
361 R2 = CI, Z = O, R3 = 5-OCF3 398 R2 = CI, Z = O, R3 = 3,6-di-F
362 R2 = CI, Z = O, R3 = 5-CF3 399 R2 = CI, Z = O, R3 = 4,5-di-F
363 R2 = CI, Z = O, R3 = 5-CHF2 400 R2 = CI, Z = O, R3 = 3,4-di-Cl
364 R2 = CI, Z = O, R3 = 5-CH2F 401 R2 = CI, Z = O, R3 = 3,5-di-Cl
365 R2 = CI, Z = O, R3 = 5-CHO 402 R2 = CI, Z = O, R3 = 3,6-di-Cl
366 R2 = CI, Z = O, R3 =5-Me 403 R2 = CI, Z = O, R3 = 4,5-di-Cl
367 R2 = CI, Z = O, R3 = 5-Et 404 R2 = CI, Z = O, R3 = 3,4-di-Br
368 R2 = CI, Z = O, R3 = 5-Ethynyl 405 R2 = CI, Z = O, R3 = 3,5-di-Br
369 R2 = CI, Z = O, R3 = 5-Ethenyl 406 R2 = CI, Z = O, R3 = 3,6-di-Br
370 R2 = CI, Z = O, R3 = 5-S02Me 407 R2 = CI, Z = O, R3 = 4,5-di-Br
371 R2 = CI, Z = O, R3 = 5-OAc 408 R2 = CI, Z = O, R3 = 3,4-di-CN
372 R2 = CI, Z = O, R3 = 5-c-Pr 409 R2 = CI, Z = O, R3 = 3,5-di-CN
373 R2 = CI, Z = O, R3 = 5-z-Pr 410 R2 = CI, Z = O, R3 = 3,6-di-CN
374 R2 = CI, Z = O, R3 = 5-Ph 411 R2 = CI, Z = O, R3 = 4,5-di-CN
375 R2 = CI, Z = O, R3 = 6-F 412 R2 = CI, Z = O, R3 = 3,4-di-Me
376 R2 = CI, Z = O, R3 = 6-Cl 413
Figure imgf000071_0001
R2 = CI, Z = O, R3 = 3,5-di-Me Table Header Row Table Header Row
414 R2 = CI, Z = O, R3 = 3,6-di-Me 451 R2 = I, Z = O, R3 = 3-S02Me
415 R2 = CI, Z = O, R3 = 4,5-di-Me 452 R2 = I, Z = 0, R3 = 3-OAc
416 R2 = CI, Z = O, R3 = 3,4-di-OMe 453 R2 = I, Z = O, R3 = 3-c-Pr
417 R2 = CI, Z = O, R3 = 3,5-di-OMe 454 R2 = I, Z = 0, R3 = 3-z-Pr
418 R2 = CI, Z = O, R3 = 3,6-di-OMe 455 R2 = I, Z = O, R3 = 3-Ph
419 R2 = CI, Z = O, R3 = 4,5-di-OMe 456 R2 = I, Z = S, R3 = 3-F
420 R2 = CI, Z = O, R3 = 3,4-di-CF3 457 R2 = I, Z = S, R3 = 3-Cl
421 R2 = CI, Z = O, R3 = 3,5-di-CF3 458 R2 = I, Z = S, R3 = 3-Br
422 R2 = CI, Z = O, R3 = 3,6-di-CF3 459 R2 = I, Z = S, R3 = 3-1
423 R2 = CI, Z = O, R3 = 4,5-di-CF3 460 R2 = I, Z = S, R3 = 3-CN
424 R2 = CI, Z = O, R3 = 3-CN, 4-Me 461 R2 = I, Z = S, R3 = 3-N02
425 R2 = CI, Z = O, R3 = 3-CN, 4-F 462 R2 = I, Z = S, R3 = 3-OMe
426 R2 = CI, Z = O, R3 = 3-CN, 4-Br 463 R2 = I, Z = S, R3 = 3-OCF3
427 R2 = CI, Z = O, R3 = 3-CN, 4-OMe 464 R2 = I, Z = S, R3 = 3-CF3
428 R2 = CI, Z = O, R3 = 3-CN, 4-CF3 465 R2 = I, Z = S, R3 = 3-CHF2
429 R2 = CI, Z = O, R3 = 3-CN, 6-Me 466 R2 = I, Z = S, R3 = 3-CH2F
430 R2 = CI, Z = O, R3 = 3-CN, 6-F 467 R2 = I, Z = S, R3 = 3-CHO
431 R2 = CI, Z = O, R3 = 3-CN, 6-Br 468 R2 = I, Z = S, R3 = 3-Me
432 R2 = CI, Z = O, R3 = 3-CN, 6-OMe 469 R2 = I, Z = S, R3 = 3-Et
433 R2 = CI, Z = O, R3 = 3-CN, 6-CF3 470 R2 = I, Z = S, R3 = 3-Ethynyl
434 R2 = I, Z = O, R3 = H (m = 0) 471 R2 = I, Z = S, R3 = 3-Ethenyl
435 R2 = I, Z = O, R3 = 3-F 472 R2 = I, Z = S, R3 = 3-S02Me
436 R2 = I, Z = O, R3 = 3 -CI 473 R2 = I, Z = S, R3 = 3-OAc
437 R2 = I, Z = O, R3 = 3-Br 474 R2 = I, Z = S, R3 = 3-c-Pr
438 R2 = I, Z = O, R3 = 3-1 475 R2 = I, Z = S, R3 = 3-z-Pr
439 R2 = I, Z = 0, R3 = 3-CN 476 R2 = I, Z = S, R3 = 3-Ph
440 R2 = I, Z = O, R3 = 3-N02 477 R2 = I, Z = O, R3 = 4-F
441 R2 = I, Z = O, R3 = 3-OMe 478 R2 = I, Z = O, R3 = 4-Cl
442 R2 = I, Z = O, R3 = 3-OCF3 479 R2 = I, Z = O, R3 = 4-Br
443 R2 = I, Z = O, R3 = 3-CF3 480 R2 = I, Z = O, R3 = 4-1
444 R2 = I, Z = O, R3 = 3-CHF2 481 R2 = I, Z = O, R3 = 4-CN
445 R2 = I, Z = O, R3 = 3-CH2F 482 R2 = I, Z = O, R3 = 4-N02
446 R2 = I, Z = O, R3 = 3-CHO 483 R2 = I, Z = O, R3 = 4-OMe
447 R2 = I, Z = O, R3 = 3-Me 484 R2 = I, Z = O, R3 = 4-OCF3
448 R2 = I, Z = O, R3 = 3-Et 485 R2 = I, Z = O, R3 = 4-CF3
449 R2 = I, Z = O, R3 = 3-Ethynyl 486 R2 = I, Z = O, R3 = 4-CHF2
450 R2 = I, Z = O, R3 = 3-Ethenyl
Figure imgf000072_0001
487 R2 = I, Z = O, R3 = 4-CH2F Table Header Row Table Header Row
488 R2 = I, Z = O, R3 = 4-CHO 525 R2 = I, Z = O, R3 = 6-OMe
489 R2 = I, Z = O, R3 = 4-Me 526 R2 = I, Z = O, R3 = 6-OCF3
490 R2 = I, Z = O, R3 = 4-Et 527 R2 = I, Z = O, R3 = 6-CF3
491 R2 = I, Z = O, R3 = 4-Ethynyl 528 R2 = I, Z = O, R3 = 6-CHF2
492 R2 = I, Z = O, R3 = 4-Ethenyl 529 R2 = I, Z = O, R3 = 6-CH2F
493 R2 = I, Z = O, R3 = 4-S02Me 530 R2 = I, Z = O, R3 = 6-CHO
494 R2 = I, Z = O, R3 = 4-OAc 531 R2 = I, Z = O, R3 = 6-Me
495 R2 = I, Z = O, R3 = 4-c-Pr 532 R2 = I, Z = O, R3 = 6-Et
496 R2 = I, Z = O, R3 = 4-z-Pr 533 R2 = I, Z = O, R3 = 6-Ethynyl
497 R2 = I, Z = O, R3 = 4-Ph 534 R2 = I, Z = O, R3 = 6-Ethenyl
498 R2 = I, Z = O, R3 = 5-F 535 R2 = I, Z = O, R3 = 6-S02Me
499 R2 = I, Z = O, R3 = 5-Cl 536 R2 = I, Z = O, R3 = 6-OAc
500 R2 = I, Z = O, R3 = 5-Br 537 R2 = I, Z = O, R3 = 6-c-Pr
501 R2 = I, Z = O, R3 = 5-1 538 R2 = I, Z = O, R3 = 6-z-Pr
502 R2 = I, Z = O, R3 = 5-CN 539 R2 = I, Z = O, R3 = 6-Ph
503 R2 = I, Z = O, R3 = 5-N02 540 R2 = I, Z = 0, R3 = 3,4-di-F
504 R2 = I, Z = O, R3 = 5-OMe 541 R2 = I, Z = 0, R3 = 3,5-di-F
505 R2 = I, Z = O, R3 = 5-OCF3 542 R2 = I, Z = 0, R3 = 3,6-di-F
506 R2 = I, Z = O, R3 = 5-CF3 543 R2 = I, Z = O, R3 = 4,5-di-F
507 R2 = I, Z = O, R3 = 5-CHF2 544 R2 = I, Z = O, R3 = 3,4-di-Cl
508 R2 = I, Z = O, R3 = 5-CH2F 545 R2 = I, Z = O, R3 = 3,5-di-Cl
509 R2 = I, Z = O, R3 = 5-CHO 546 R2 = I, Z = O, R3 = 3,6-di-Cl
510 R2 = I, Z = O, R3 =5-Me 547 R2 = I, Z = O, R3 = 4,5-di-Cl
51 1 R2 = I, Z = O, R3 = 5-Et 548 R2 = I, Z = O, R3 = 3,4-di-Br
512 R2 = I, Z = O, R3 = 5-Ethynyl 549 R2 = I, Z = O, R3 = 3,5-di-Br
513 R2 = I, Z = O, R3 = 5-Ethenyl 550 R2 = I, Z = O, R3 = 3,6-di-Br
514 R2 = I, Z = O, R3 = 5-S02Me 551 R2 = I, Z = O, R3 = 4,5-di-Br
515 R2 = I, Z = O, R3 = 5-OAc 552 R2 = I, Z = O, R3 = 3,4-di-CN
516 R2 = I, Z = O, R3 = 5-c-Pr 553 R2 = I, Z = O, R3 = 3,5-di-CN
517 R2 = I, Z = O, R3 = 5-z-Pr 554 R2 = I, Z = O, R3 = 3,6-di-CN
518 R2 = I, Z = O, R3 = 5-Ph 555 R2 = I, Z = O, R3 = 4,5-di-CN
519 R2 = I, Z = O, R3 = 6-F 556 R2 = I, Z = O, R3 = 3,4-di-Me
520 R2 = I, Z = O, R3 = 6-Cl 557 R2 = I, Z = O, R3 = 3,5-di-Me
521 R2 = I, Z = O, R3 = 6-Br 558 R2 = I, Z = O, R3 = 3,6-di-Me
522 R2 = I, Z = O, R3 = 6-1 559 R2 = I, Z = O, R3 = 4,5-di-Me
523 R2 = I, Z = O, R3 = 6-CN 560 R2 = I, Z = O, R3 = 3,4-di-OMe
524 R2 = I, Z = O, R3 = 6-N02 561 R2 = I, Z = O, R3 = 3,5-di-OMe Table Header Row Table Header Row
562 R2 = I, Z = O, R3 = 3,6-di-OMe 599 R2 = Me, Z = O, R3 = 3-Ph
563 R2 = I, Z = O, R3 = 4,5-di-OMe 600 R2 = Me, Z = S, R3 = 3-F
564 R2 = I, Z = O, R3 = 3,4-di-CF3 601 R2 = Me, Z = S, R3 = 3 -CI
565 R2 = I, Z = O, R3 = 3,5-di-CF3 602 R2 = Me, Z = S, R3 = 3-Br
566 R2 = I, Z = O, R3 = 3,6-di-CF3 603 R2 = Me, Z = S, R3 = 3-1
567 R2 = I, Z = O, R3 = 4,5-di-CF3 604 R2 = Me, Z = S, R3 = 3-CN
568 R2 = I, Z = O, R3 = 3-CN, 4-Me 605 R2 = Me, Z = S, R3 = 3-N02
569 R2 = I, Z = O, R3 = 3-CN, 4-F 606 R2 = Me, Z = S, R3 = 3-OMe
570 R2 = I, Z = O, R3 = 3-CN, 4-Br 607 R2 = Me, Z = S, R3 = 3-OCF3
571 R2 = I, Z = O, R3 = 3-CN, 4-OMe 608 R2 = Me, Z = S, R3 = 3-CF3
572 R2 = I, Z = O, R3 = 3-CN, 4-CF3 609 R2 = Me, Z = S, R3 = 3-CHF2
573 R2 = I, Z = O, R3 = 3-CN, 6-Me 610 R2 = Me, Z = S, R3 = 3-CH2F
574 R2 = I, Z = O, R3 = 3-CN, 6-F 611 R2 = Me, Z = S, R3 = 3-CHO
575 R2 = I, Z = O, R3 = 3-CN, 6-Br 612 R2 = Me, Z = S, R3 = 3-Me
576 R2 = I, Z = O, R3 = 3-CN, 6-OMe 613 R2 = Me, Z = S, R3 = 3-Et
577 R2 = I, Z = O, R3 = 3-CN, 6-CF3 614 R2 = Me, Z = S, R3 = 3-Ethynyl
578 R2 = Me, Z = O, R3 = H (m = 0) 615 R2 = Me, Z = S, R3 = 3-Ethenyl
579 R2 = Me, Z = O, R3 = 3-F 616 R2 = Me, Z = S, R3 = 3-S02Me
580 R2 = Me, Z = O, R3 = 3 -CI 617 R2 = Me, Z = S, R3 = 3-OAc
581 R2 = Me, Z = O, R3 = 3-Br 618 R2 = Me, Z = S, R3 = 3-c-Pr
582 R2 = Me, Z = O, R3 = 3-1 619 R2 = Me, Z = S, R3 = 3-z-Pr
583 R2 = Me, Z = O, R3 = 3-CN 620 R2 = Me, Z = S, R3 = 3-Ph
584 R2 = Me, Z = O, R3 = 3-N02 621 R2 = Me, Z = O, R3 = 4-F
585 R2 = Me, Z = O, R3 = 3-OMe 622 R2 = Me, Z = O, R3 = 4-Cl
586 R2 = Me, Z = O, R3 = 3-OCF3 623 R2 = Me, Z = O, R3 = 4-Br
587 R2 = Me, Z = O, R3 = 3-CF3 624 R2 = Me, Z = O, R3 = 4-1
588 R2 = Me, Z = O, R3 = 3-CHF2 625 R2 = Me, Z = O, R3 = 4-CN
589 R2 = Me, Z = O, R3 = 3-CH2F 626 R2 = Me, Z = O, R3 = 4-N02
590 R2 = Me, Z = O, R3 = 3-CHO 627 R2 = Me, Z = O, R3 = 4-OMe
591 R2 = Me, Z = O, R3 = 3-Me 628 R2 = Me, Z = O, R3 = 4-OCF3
592 R2 = Me, Z = O, R3 = 3-Et 629 R2 = Me, Z = O, R3 = 4-CF3
593 R2 = Me, Z = O, R3 = 3-Ethynyl 630 R2 = Me, Z = O, R3 = 4-CHF2
594 R2 = Me, Z = O, R3 = 3-Ethenyl 631 R2 = Me, Z = O, R3 = 4-CH2F
595 R2 = Me, Z = O, R3 = 3-S02Me 632 R2 = Me, Z = O, R3 = 4-CHO
596 R2 = Me, Z = O, R3 = 3-OAc 633 R2 = Me, Z = O, R3 = 4-Me
597 R2 = Me, Z = O, R3 = 3-c-Pr 634 R2 = Me, Z = O, R3 = 4-Et
598 R2 = Me, Z = O, R3 = 3-z-Pr 635 R2 = Me, Z = O, R3 = 4-Ethynyl
Figure imgf000074_0001
Table Header Row Table Header Row
636 R2 = Me, Z = O, R3 = 4-Ethenyl 673 R2 = Me, Z = O, R3 = 6-CH2F
637 R2 = Me, Z = O, R3 = 4-S02Me 674 R2 = Me, Z = O, R3 = 6-CHO
638 R2 = Me, Z = O, R3 = 4-OAc 675 R2 = Me, Z = O, R3 = 6-Me
639 R2 = Me, Z = O, R3 = 4-c-Pr 676 R2 = Me, Z = O, R3 = 6-Et
640 R2 = Me, Z = O, R3 = 4-z-Pr 677 R2 = Me, Z = O, R3 = 6-Ethynyl
641 R2 = Me, Z = O, R3 = 4-Ph 678 R2 = Me, Z = O, R3 = 6-Ethenyl
642 R2 = Me, Z = O, R3 = 5-F 679 R2 = Me, Z = O, R3 = 6-S02Me
643 R2 = Me, Z = O, R3 = 5-Cl 680 R2 = Me, Z = O, R3 = 6-OAc
644 R2 = Me, Z = O, R3 = 5-Br 681 R2 = Me, Z = O, R3 = 6-c-Pr
645 R2 = Me, Z = O, R3 = 5-1 682 R2 = Me, Z = O, R3 = 6-z-Pr
646 R2 = Me, Z = O, R3 = 5-CN 683 R2 = Me, Z = O, R3 = 6-Ph
647 R2 = Me, Z = O, R3 = 5-N02 684 R2 = Me, Z = O, R3 = 3,4-di-F
648 R2 = Me, Z = O, R3 = 5-OMe 685 R2 = Me, Z = O, R3 = 3,5-di-F
649 R2 = Me, Z = O, R3 = 5-OCF3 686 R2 = Me, Z = O, R3 = 3,6-di-F
650 R2 = Me, Z = O, R3 = 5-CF3 687 R2 = Me, Z = O, R3 = 4,5-di-F
651 R2 = Me, Z = O, R3 = 5-CHF2 688 R2 = Me, Z = O, R3 = 3,4-di-Cl
652 R2 = Me, Z = O, R3 = 5-CH2F 689 R2 = Me, Z = O, R3 = 3,5-di-Cl
653 R2 = Me, Z = O, R3 = 5-CHO 690 R2 = Me, Z = O, R3 = 3,6-di-Cl
654 R2 = Me, Z = O, R3 =5-Me 691 R2 = Me, Z = O, R3 = 4,5-di-Cl
655 R2 = Me, Z = O, R3 = 5-Et 692 R2 = Me, Z = O, R3 = 3,4-di-Br
656 R2 = Me, Z = O, R3 = 5-Ethynyl 693 R2 = Me, Z = O, R3 = 3,5-di-Br
657 R2 = Me, Z = O, R3 = 5-Ethenyl 694 R2 = Me, Z = O, R3 = 3,6-di-Br
658 R2 = Me, Z = O, R3 = 5-S02Me 695 R2 = Me, Z = O, R3 = 4,5-di-Br
659 R2 = Me, Z = O, R3 = 5-OAc 696 R2 = Me, Z = O, R3 = 3,4-di-CN
660 R2 = Me, Z = O, R3 = 5-c-Pr 697 R2 = Me, Z = O, R3 = 3,5-di-CN
661 R2 = Me, Z = O, R3 = 5-z-Pr 698 R2 = Me, Z = O, R3 = 3,6-di-CN
662 R2 = Me, Z = O, R3 = 5-Ph 699 R2 = Me, Z = O, R3 = 4,5-di-CN
663 R2 = Me, Z = O, R3 = 6-F 700 R2 = Me, Z = O, R3 = 3,4-di-Me
664 R2 = Me, Z = O, R3 = 6-Cl 701 R2 = Me, Z = O, R3 = 3,5-di-Me
665 R2 = Me, Z = O, R3 = 6-Br 702 R2 = Me, Z = O, R3 = 3,6-di-Me
666 R2 = Me, Z = O, R3 = 6-1 703 R2 = Me, Z = O, R3 = 4,5-di-Me
667 R2 = Me, Z = O, R3 = 6-CN 704 R2 = Me, Z = O, R3 = 3,4-di-OMe
668 R2 = Me, Z = O, R3 = 6-N02 705 R2 = Me, Z = O, R3 = 3,5-di-OMe
669 R2 = Me, Z = O, R3 = 6-OMe 706 R2 = Me, Z = O, R3 = 3,6-di-OMe
670 R2 = Me, Z = O, R3 = 6-OCF3 707 R2 = Me, Z = O, R3 = 4,5-di-OMe
671 R2 = Me, Z = O, R3 = 6-CF3 708 R2 = Me, Z = O, R3 = 3,4-di-CF3
672 R2 = Me, Z = O, R3 = 6-CHF2 709 R2 = Me, Z = O, R3 = 3,5-di-CF3
Figure imgf000075_0001
Table Header Row Table Header Row
710 R2 = Me, Z = O, R3 = 3,6-di-CF3 747 R2 = CN, Z = S, R3 = 3-1
711 R2 = Me, Z = O, R3 = 4,5-di-CF3 748 R2 = CN, Z = S, R3 = 3-CN
712 R2 = Me, Z = O, R3 = 3-CN, 4-Me 749 R2 = CN, Z = S, R3 = 3-N02
713 R2 = Me, Z = O, R3 = 3-CN, 4-F 750 R2 = CN, Z = S, R3 = 3-OMe
714 R2 = Me, Z = O, R3 = 3-CN, 4-Br 751 R2 = CN, Z = S, R3 = 3-OCF3
715 R2 = Me, Z = O, R3 = 3-CN, 4-OMe 752 R2 = CN, Z = S, R3 = 3-CF3
716 R2 = Me, Z = O, R3 = 3-CN, 4-CF3 753 R2 = CN, Z = S, R3 = 3-CHF2
717 R2 = Me, Z = O, R3 = 3-CN, 6-Me 754 R2 = CN, Z = S, R3 = 3-CH2F
718 R2 = Me, Z = O, R3 = 3-CN, 6-F 755 R2 = CN, Z = S, R3 = 3-CHO
719 R2 = Me, Z = O, R3 = 3-CN, 6-Br 756 R2 = CN, Z = S, R3 = 3-Me
720 R2 = Me, Z = O, R3 = 3-CN, 6-OMe 757 R2 = CN, Z = S, R3 = 3-Et
721 R2 = Me, Z = O, R3 = 3-CN, 6-CF3 758 R2 = CN, Z = S, R3 = 3-Ethynyl
722 R2 = CN, Z = O, R3 = H (m = 0) 759 R2 = CN, Z = S, R3 = 3-Ethenyl
723 R2 = CN, Z = O, R3 = 3-F 760 R2 = CN, Z = S, R3 = 3-S02Me
724 R2 = CN, Z = O, R3 = 3 -CI 761 R2 = CN, Z = S, R3 = 3-OAc
725 R2 = CN, Z = O, R3 = 3-Br 762 R2 = CN, Z = S, R3 = 3-c-Pr
726 R2 = CN, Z = O, R3 = 3-1 763 R2 = CN, Z = S, R3 = 3-z-Pr
727 R2 = CN, Z = O, R3 = 3-CN 764 R2 = CN, Z = S, R3 = 3-Ph
728 R2 = CN, Z = O, R3 = 3-N02 765 R2 = CN, Z = O, R3 = 4-F
729 R2 = CN, Z = O, R3 = 3-OMe 766 R2 = CN, Z = O, R3 = 4-Cl
730 R2 = CN, Z = O, R3 = 3-OCF3 767 R2 = CN, Z = O, R3 = 4-Br
731 R2 = CN, Z = O, R3 = 3-CF3 768 R2 = CN, Z = O, R3 = 4-1
732 R2 = CN, Z = O, R3 = 3-CHF2 769 R2 = CN, Z = O, R3 = 4-CN
733 R2 = CN, Z = O, R3 = 3-CH2F 770 R2 = CN, Z = O, R3 = 4-N02
734 R2 = CN, Z = O, R3 = 3-CHO 771 R2 = CN, Z = O, R3 = 4-OMe
735 R2 = CN, Z = O, R3 = 3-Me 772 R2 = CN, Z = O, R3 = 4-OCF3
736 R2 = CN, Z = O, R3 = 3-Et 773 R2 = CN, Z = O, R3 = 4-CF3
737 R2 = CN, Z = O, R3 = 3-Ethynyl 774 R2 = CN, Z = O, R3 = 4-CHF2
738 R2 = CN, Z = O, R3 = 3-Ethenyl 775 R2 = CN, Z = O, R3 = 4-CH2F
739 R2 = CN, Z = O, R3 = 3-S02Me 776 R2 = CN, Z = O, R3 = 4-CHO
740 R2 = CN, Z = 0, R3 = 3-OAc 777 R2 = CN, Z = O, R3 = 4-Me
741 R2 = CN, Z = O, R3 = 3-c-Pr 778 R2 = CN, Z = O, R3 = 4-Et
742 R2 = CN, Z = O, R3 = 3-z-Pr 779 R2 = CN, Z = O, R3 = 4-Ethynyl
743 R2 = CN, Z = O, R3 = 3-Ph 780 R2 = CN, Z = O, R3 = 4-Ethenyl
744 R2 = CN, Z = S, R3 = 3-F 781 R2 = CN, Z = O, R3 = 4-S02Me
745 R2 = CN, Z = S, R3 = 3-Cl 782 R2 = CN, Z = O, R3 = 4-OAc
746 R2 = CN, Z = S, R3 = 3-Br 783 R2 = CN, Z = O, R3 = 4-c-Pr
Figure imgf000076_0001
Table Header Row Table Header Row
784 R2 = CN, Z = O, R3 = 4-z-Pr 821 R2 = CN, Z = O, R3 = 6-Ethynyl
785 R2 = CN, Z = O, R3 = 4-Ph 822 R2 = CN, Z = O, R3 = 6-Ethenyl
786 R2 = CN, Z = O, R3 = 5-F 823 R2 = CN, Z = O, R3 = 6-S02Me
787 R2 = CN, Z = O, R3 = 5-Cl 824 R2 = CN, Z = O, R3 = 6-OAc
788 R2 = CN, Z = O, R3 = 5-Br 825 R2 = CN, Z = O, R3 = 6-c-Pr
789 R2 = CN, Z = O, R3 = 5-1 826 R2 = CN, Z = O, R3 = 6-z-Pr
790 R2 = CN, Z = O, R3 = 5-CN 827 R2 = CN, Z = O, R3 = 6-Ph
791 R2 = CN, Z = O, R3 = 5-N02 828 R2 = CN, Z = O, R3 = 3,4-di-F
792 R2 = CN, Z = O, R3 = 5-OMe 829 R2 = CN, Z = O, R3 = 3,5-di-F
793 R2 = CN, Z = O, R3 = 5-OCF3 830 R2 = CN, Z = O, R3 = 3,6-di-F
794 R2 = CN, Z = O, R3 = 5-CF3 831 R2 = CN, Z = O, R3 = 4,5-di-F
795 R2 = CN, Z = O, R3 = 5-CHF2 832 R2 = CN, Z = O, R3 = 3,4-di-Cl
796 R2 = CN, Z = O, R3 = 5-CH2F 833 R2 = CN, Z = O, R3 = 3,5-di-Cl
797 R2 = CN, Z = O, R3 = 5-CHO 834 R2 = CN, Z = O, R3 = 3,6-di-Cl
798 R2 = CN, Z = O, R3 =5-Me 835 R2 = CN, Z = O, R3 = 4,5-di-Cl
799 R2 = CN, Z = O, R3 = 5-Et 836 R2 = CN, Z = O, R3 = 3,4-di-Br
800 R2 = CN, Z = O, R3 = 5-Ethynyl 837 R2 = CN, Z = O, R3 = 3,5-di-Br
801 R2 = CN, Z = O, R3 = 5-Ethenyl 838 R2 = CN, Z = O, R3 = 3,6-di-Br
802 R2 = CN, Z = O, R3 = 5-S02Me 839 R2 = CN, Z = O, R3 = 4,5-di-Br
803 R2 = CN, Z = O, R3 = 5-OAc 840 R2 = CN, Z = O, R3 = 3,4-di-CN
804 R2 = CN, Z = O, R3 = 5-c-Pr 841 R2 = CN, Z = O, R3 = 3,5-di-CN
805 R2 = CN, Z = O, R3 = 5-z-Pr 842 R2 = CN, Z = O, R3 = 3,6-di-CN
806 R2 = CN, Z = O, R3 = 5-Ph 843 R2 = CN, Z = O, R3 = 4,5-di-CN
807 R2 = CN, Z = O, R3 = 6-F 844 R2 = CN, Z = O, R3 = 3,4-di-Me
808 R2 = CN, Z = O, R3 = 6-Cl 845 R2 = CN, Z = O, R3 = 3,5-di-Me
809 R2 = CN, Z = O, R3 = 6-Br 846 R2 = CN, Z = O, R3 = 3,6-di-Me
810 R2 = CN, Z = O, R3 = 6-1 847 R2 = CN, Z = O, R3 = 4,5-di-Me
811 R2 = CN, Z = O, R3 = 6-CN 848 R2 = CN, Z = O, R3 = 3,4-di-OMe
812 R2 = CN, Z = O, R3 = 6-N02 849 R2 = CN, Z = O, R3 = 3,5-di-OMe
813 R2 = CN, Z = O, R3 = 6-OMe 850 R2 = CN, Z = O, R3 = 3,6-di-OMe
814 R2 = CN, Z = O, R3 = 6-OCF3 851 R2 = CN, Z = O, R3 = 4,5-di-OMe
815 R2 = CN, Z = O, R3 = 6-CF3 852 R2 = CN, Z = O, R3 = 3,4-di-CF3
816 R2 = CN, Z = O, R3 = 6-CHF2 853 R2 = CN, Z = O, R3 = 3,5-di-CF3
817 R2 = CN, Z = O, R3 = 6-CH2F 854 R2 = CN, Z = O, R3 = 3,6-di-CF3
818 R2 = CN, Z = O, R3 = 6-CHO 855 R2 = CN, Z = O, R3 = 4,5-di-CF3
819 R2 = CN, Z = O, R3 = 6-Me 856 R2 = CN, Z = O, R3 = 3-CN, 4-Me
820 R2 = CN, Z = O, R3 = 6-Et 857 R2 = CN, Z = O, R3 = 3-CN, 4-F
Figure imgf000077_0001
Table Header Row Table Header Row
858 R2 = CN, Z = O, R3 = 3-CN, 4-Br 895 R2 = N02, Z = S, R3 = 3-OCF3
859 R2 = CN, Z = 0, R3 = 3-CN, 4-OMe 896 R2 = N02, Z = S, R3 = 3-CF3
860 R2 = CN, Z = 0, R3 = 3-CN, 4-CF3 897 R2 = NOo, Z = S, R3 = 3-CHF2
861 R2 = CN, Z = O, R3 = 3-CN, 6-Me 898 R2 = NOo, Z = S, R3 = 3-CH2F
862 R2 = CN, Z = O, R3 = 3-CN, 6-F 899 R2 = N02, Z = S, R3 = 3-CHO
863 R2 = CN, Z = O, R3 = 3-CN, 6-Br 900 R2 = N02, Z = S, R3 = 3-Me
864 R2 = CN, Z = O, R3 = 3-CN, 6-OMe 901 R2 = N02, Z = S, R3 = 3-Et
865 R2 = CN, Z = O, R3 = 3-CN, 6-CF3 902 R2 = N02, Z = S, R3 = 3-Ethynyl
866 R2 = N02, Z = O, R3 = H (m = 0) 903 R2 = N02, Z = S, R3 = 3-Ethenyl
867 R2 = N02, Z = 0, R3 = 3-F 904 R2 = N02, Z = S, R3 = 3-S02Me
868 R2 = N02, Z = O, R3 = 3-Cl 905 R2 = N02, Z = S, R3 = 3-OAc
869 R2 = N02, Z = 0, R3 = 3-Br 906 R2 = N02, Z = S, R3 = 3-c-Pr
870 R2 = N02, Z = 0, R3 = 3-I 907 R2 = N02, Z = S, R3 = 3-z-Pr
871 R2 = N02, Z = 0, R3 = 3-CN 908 R2 = N02, Z = S, R3 = 3-Ph
872 R2 = N02, Z = O, R3 = 3-N02 909 R2 = N02, Z = O, R3 = 4-F
873 R2 = N02, Z = O, R3 = 3-OMe 910 R2 = NOo, Z = O, R3 = 4-Cl
874 R2 = N02, Z = O, R3 = 3-OCF3 911 R2 = NOo, Z = O, R3 = 4-Br
875 R2 = N02, Z = O, R3 = 3-CF3 912 R2 = N02, Z = 0, R3 = 4-I
876 R2 = N02, Z = O, R3 = 3-CHF2 913 R2 = N02, Z = 0, R3 = 4-CN
877 R2 = N02, Z = O, R3 = 3-CH2F 914 R2 = N02, Z = O, R3 = 4-N02
878 R2 = N02, Z = O, R3 = 3-CHO 915 R2 = N02, Z = O, R3 = 4-OMe
879 R2 = N02, Z = O, R3 = 3-Me 916 R2 = NOo, Z = O, R3 = 4-OCF3
880 R2 = N02, Z = O, R3 = 3-Et 917 R2 = NOo, Z = O, R3 = 4-CF3
881 R2 = N02, Z = O, R3 = 3-Ethynyl 918 R2 = N02, Z = O, R3 = 4-CHF2
882 R2 = N02, Z = O, R3 = 3-Ethenyl 919 R2 = N02, Z = O, R3 = 4-CH2F
883 R2 = N02, Z = O, R3 = 3-S02Me 920 R2 = N02, Z = O, R3 = 4-CHO
884 R2 = N02, Z = O, R3 = 3-0 Ac 921 R2 = N02, Z = 0, R3 = 4-Me
885 R2 = N02, Z = O, R3 = 3-c-Pr 922 R2 = NOo, Z = O, R3 = 4-Et
886 R2 = N02, Z = O, R3 = 3-z-Pr 923 R2 = N02, Z = O, R3 = 4-Ethynyl
887 R2 = N02, Z = 0, R3 = 3-Ph 924 R2 = N02, Z = O, R3 = 4-Ethenyl
888 R2 = N02, Z = S, R3 = 3-F 925 R2 = N02, Z = O, R3 = 4-S02Me
889 R2 = N02, Z = S, R3 = 3-C1 926 R2 = N02, Z = O, R3 = 4-0 Ac
890 R2 = N02, Z = S, R3 = 3-Br 927 R2 = N02, Z = O, R3 = 4-c-Pr
891 R2 = N02, Z = S, R3 = 3-1 928 R2 = NOo, Z = O, R3 = 4-z-Pr
892 R2 = N02, Z = S, R3 = 3-CN 929 R2 = NOo, Z = O, R3 = 4-Ph
893 R2 = N02, Z = S, R3 = 3-N02 930 R2 = N02, Z = O, R3 = 5-F
894 R2 = N02, Z = S, R3 = 3-OMe 931 R2 = N02, Z = O, R3 = 5-Cl
Figure imgf000078_0001
Table Header Row Table Header Row
932 R2 = N02, Z = O, R3 = 5-Br 969 R2 = N02, Z = O, R3 = 6-c-Pr
933 R2 = N02, Z = 0, R3 = 5-I 970 R2 = N02, Z = O, R3 = 6-z-Pr
934 R2 = N02, Z = 0, R3 = 5-CN 971 R2 = N02, Z = O, R3 = 6-Ph
935 R2 = N02, Z = O, R3 = 5-N02 972 R2 = N02, Z = O, R3 = 3,4-di-F
936 R2 = N02, Z = O, R3 = 5-OMe 973 R2 = N02, Z = O, R3 = 3,5-di-F
937 R2 = N02, Z = O, R3 = 5-OCF3 974 R2 = N02, Z = O, R3 = 3,6-di-F
938 R2 = N02, Z = O, R3 = 5-CF3 975 R2 = N02, Z = O, R3 = 4,5-di-F
939 R2 = N02, Z = O, R3 = 5-CHF2 976 R2 = N02, Z = O, R3 = 3,4-di-Cl
940 R2 = N02, Z = O, R3 = 5-CH2F 977 R2 = N02, Z = O, R3 = 3,5-di-Cl
941 R2 = N02, Z = O, R3 = 5-CHO 978 R2 = N02, Z = O, R3 = 3,6-di-Cl
942 R2 = N02, Z = O, R3 =5-Me 979 R2 = N02, Z = O, R3 = 4,5-di-Cl
943 R2 = N02, Z = O, R3 = 5-Et 980 R2 = N02, Z = O, R3 = 3,4-di-Br
944 R2 = N02, Z = O, R3 = 5-Ethynyl 981 R2 = N02, Z = O, R3 = 3,5-di-Br
945 R2 = N02, Z = O, R3 = 5-Ethenyl 982 R2 = N02, Z = O, R3 = 3,6-di-Br
946 R2 = N02, Z = O, R3 = 5-S02Me 983 R2 = N02, Z = O, R3 = 4,5-di-Br
947 R2 = N02, Z = O, R3 = 5-0 Ac 984 R2 = N02, Z = O, R3 = 3,4-di-CN
948 R2 = N02, Z = O, R3 = 5-c-Pr 985 R2 = N02, Z = O, R3 = 3,5-di-CN
949 R2 = N02, Z = O, R3 = 5-z-Pr 986 R2 = N02, Z = O, R3 = 3,6-di-CN
950 R2 = N02, Z = O, R3 = 5-Ph 987 R2 = N02, Z = O, R3 = 4,5-di-CN
951 R2 = N02, Z = O, R3 = 6-F 988 R2 = N02, Z = O, R3 = 3,4-di-Me
952 R2 = N02, Z = O, R3 = 6-Cl 989 R2 = N02, Z = O, R3 = 3,5-di-Me
953 R2 = N02, Z = O, R3 = 6-Br 990 R2 = N02, Z = O, R3 = 3,6-di-Me
954 R2 = N02, Z = 0, R3 = 6-I 991 R2 = N02, Z = O, R3 = 4,5-di-Me
955 R2 = N02, Z = 0, R3 = 6-CN 992 R2 = N02, Z = O, R3 = 3,4-di-OMe
956 R2 = N02, Z = O, R3 = 6-N02 993 R2 = N02, Z = O, R3 = 3,5-di-OMe
957 R2 = N02, Z = O, R3 = 6-OMe 994 R2 = N02, Z = O, R3 = 3,6-di-OMe
958 R2 = N02, Z = O, R3 = 6-OCF3 995 R2 = N02, Z = O, R3 = 4,5-di-OMe
959 R2 = N02, Z = O, R3 = 6-CF3 996 R2 = N02, Z = O, R3 = 3,4-di-CF3
960 R2 = N02, Z = O, R3 = 6-CHF2 997 R2 = N02, Z = O, R3 = 3,5-di-CF3
961 R2 = N02, Z = O, R3 = 6-CH2F 998 R2 = N02, Z = O, R3 = 3,6-di-CF3
962 R2 = N02, Z = O, R3 = 6-CHO 999 R2 = N02, Z = O, R3 = 4,5-di-CF3
963 R2 = N02, Z = O, R3 = 6-Me 1000 R2 = N02, Z = O, R3 = 3-CN, 4-Me
964 R2 = N02, Z = O, R3 = 6-Et 1001 R2 = N02, Z = O, R3 = 3-CN, 4-F
965 R2 = N02, Z = O, R3 = 6-Ethynyl 1002 R2 = N02, Z = O, R3 = 3-CN, 4-Br
966 R2 = N02, Z = O, R3 = 6-Ethenyl 1003 R2 = N02, Z = O, R3 = 3-CN, 4-OMe
967 R2 = N02, Z = O, R3 = 6-S02Me 1004 R2 = N02, Z = O, R3 = 3-CN, 4-CF3
968 R2 = N02, Z = O, R3 = 6-0 Ac 1005
Figure imgf000079_0001
R2 = N02, Z = O, R3 = 3-CN, 6-Me Table Header Row Table Header Row
1006 R2 = N02, Z = O, R3 = 3-CN, 6-F 1043 R2 = OMe, Z = S, R3 = 3-CHO
1007 R2 = N02, Z = O, R3 = 3-CN, 6-Br 1044 R2 = OMe, Z = S, R3 = 3-Me
1008 R2 = N02, Z = O, R3 = 3-CN, 6-OMe 1045 R2 = OMe, Z = S, R3 = 3-Et
1009 R2 = N02, Z = O, R3 = 3-CN, 6-CF3 1046 R2 = OMe, Z = S, R3 = 3-Ethynyl
1010 R2 = OMe, Z = O, R3 = H (m = 0) 1047 R2 = OMe, Z = S, R3 = 3-Ethenyl
1011 R2 = OMe, Z = O, R3 = 3-F 1048 R2 = OMe, Z = S, R3 = 3-S02Me
1012 R2 = OMe, Z = O, R3 = 3 -CI 1049 R2 = OMe, Z = S, R3 = 3-OAc
1013 R2 = OMe, Z = O, R3 = 3-Br 1050 R2 = OMe, Z = S, R3 = 3-c-Pr
1014 R2 = OMe, Z = O, R3 = 3-1 1051 R2 = OMe, Z = S, R3 = 3-z-Pr
1015 R2 = OMe, Z = O, R3 = 3-CN 1052 R2 = OMe, Z = S, R3 = 3-Ph
1016 R2 = OMe, Z = O, R3 = 3-N02 1053 R2 = OMe, Z = O, R3 = 4-F
1017 R2 = OMe, Z = O, R3 = 3 -OMe 1054 R2 = OMe, Z = O, R3 = 4-Cl
1018 R2 = OMe, Z = O, R3 = 3-OCF3 1055 R2 = OMe, Z = O, R3 = 4-Br
1019 R2 = OMe, Z = O, R3 = 3-CF3 1056 R2 = OMe, Z = O, R3 = 4-1
1020 R2 = OMe, Z = O, R3 = 3-CHF2 1057 R2 = OMe, Z = O, R3 = 4-CN
1021 R2 = OMe, Z = O, R3 = 3-CH2F 1058 R2 = OMe, Z = O, R3 = 4-N02
1022 R2 = OMe, Z = O, R3 = 3-CHO 1059 R2 = OMe, Z = O, R3 = 4-OMe
1023 R2 = OMe, Z = O, R3 = 3-Me 1060 R2 = OMe, Z = O, R3 = 4-OCF3
1024 R2 = OMe, Z = O, R3 = 3-Et 1061 R2 = OMe, Z = O, R3 = 4-CF3
1025 R2 = OMe, Z = O, R3 = 3-Ethynyl 1062 R2 = OMe, Z = O, R3 = 4-CHF2
1026 R2 = OMe, Z = O, R3 = 3-Ethenyl 1063 R2 = OMe, Z = O, R3 = 4-CH2F
1027 R2 = OMe, Z = O, R3 = 3-S02Me 1064 R2 = OMe, Z = O, R3 = 4-CHO
1028 R2 = OMe, Z = O, R3 = 3-OAc 1065 R2 = OMe, Z = O, R3 = 4-Me
1029 R2 = OMe, Z = O, R3 = 3-c-Pr 1066 R2 = OMe, Z = O, R3 = 4-Et
1030 R2 = OMe, Z = O, R3 = 3-z-Pr 1067 R2 = OMe, Z = O, R3 = 4-Ethynyl
1031 R2 = OMe, Z = 0, R3 = 3-Ph 1068 R2 = OMe, Z = O, R3 = 4-Ethenyl
1032 R2 = OMe, Z = S, R3 = 3-F 1069 R2 = OMe, Z = O, R3 = 4-S02Me
1033 R2 = OMe, Z = S, R3 = 3 -CI 1070 R2 = OMe, Z = O, R3 = 4-OAc
1034 R2 = OMe, Z = S, R3 = 3-Br 1071 R2 = OMe, Z = O, R3 = 4-c-Pr
1035 R2 = OMe, Z = S, R3 = 3-1 1072 R2 = OMe, Z = O, R3 = 4-z-Pr
1036 R2 = OMe, Z = S, R3 = 3-CN 1073 R2 = OMe, Z = O, R3 = 4-Ph
1037 R2 = OMe, Z = S, R3 = 3-N02 1074 R2 = OMe, Z = O, R3 = 5-F
1038 R2 = OMe, Z = S, R3 = 3 -OMe 1075 R2 = OMe, Z = O, R3 = 5-Cl
1039 R2 = OMe, Z = S, R3 = 3-OCF3 1076 R2 = OMe, Z = O, R3 = 5-Br
1040 R2 = OMe, Z = S, R3 = 3-CF3 1077 R2 = OMe, Z = O, R3 = 5-1
1041 R2 = OMe, Z = S, R3 = 3-CHF2 1078 R2 = OMe, Z = O, R3 = 5-CN
1042 R2 = OMe, Z = S, R3 = 3-CH2F
Figure imgf000080_0001
1079 R2 = OMe, Z = O, R3 = 5-N02 Table Header Row
1080 R2 = OMe, Z = O, R3 = 5-OMe
1081 R2 = OMe, Z = O, R3 = 5-OCF3
1082 R2 = OMe, Z = O, R3 = 5-CF3
1083 R2 = OMe, Z = O, R3 = 5-CHF2
1084 R2 = OMe, Z = O, R3 = 5-CH2F
1085 R2 = OMe, Z = O, R3 = 5-CHO
1086 R2 = OMe, Z = O, R3 =5-Me
1087 R2 = OMe, Z = O, R3 = 5-Et
1088 R2 = OMe, Z = O, R3 = 5-Ethynyl
1089 R2 = OMe, Z = O, R3 = 5-Ethenyl
1090 R2 = OMe, Z = O, R3 = 5-S02Me
1091 R2 = OMe, Z = O, R3 = 5-OAc
1092 R2 = OMe, Z = O, R3 = 5-c-Pr
1093 R2 = OMe, Z = O, R3 = 5-z-Pr
1094 R2 = OMe, Z = O, R3 = 5-Ph
1095 R2 = OMe, Z = O, R3 = 6-F
1096 R2 = OMe, Z = O, R3 = 6-Cl
1097 R2 = OMe, Z = O, R3 = 6-Br
1098 R2 = OMe, Z = O, R3 = 6-1
1099 R2 = OMe, Z = O, R3 = 6-CN
1100 R2 = OMe, Z = O, R3 = 6-N02
1101 R2 = OMe, Z = O, R3 = 6-OMe
1102 R2 = OMe, Z = O, R3 = 6-OCF3
1103 R2 = OMe, Z = O, R3 = 6-CF3
1104 R2 = OMe, Z = O, R3 = 6-CHF2
1105 R2 = OMe, Z = O, R3 = 6-CH2F
1106 R2 = OMe, Z = O, R3 = 6-CHO
1107 R2 = OMe, Z = O, R3 = 6-Me
1108 R2 = OMe, Z = O, R3 = 6-Et
1109 R2 = OMe, Z = O, R3 = 6-Ethynyl
1110 R2 = OMe, Z = O, R3 = 6-Ethenyl
1111 R2 = OMe, Z = O, R3 = 6-S02Me
1112 R2 = OMe, Z = O, R3 = 6-OAc
1113 R2 = OMe, Z = O, R3 = 6-c-Pr
1114 R2 = OMe, Z = O, R3 = 6-z-Pr
1115 R2 = OMe, Z = O, R3 = 6-Ph
1116 R2 = OMe, Z = O, R3 = 3,4-di-F
Figure imgf000081_0001
Table Header Row Table Header Row
1154 R2 = CF3, Z = O, R3 = H (m = 0) 1191 R2 = CF3, Z = S, R3 = 3-Ethenyl
1155 R2 = CF3, Z = O, R3 = 3-F 1192 R2 = CF3, Z = S, R3 = 3-S02Me
1156 R2 = CF3, Z = O, R3 = 3 -CI 1193 R2 = CF3, Z = S, R3 = 3-OAc
1157 R2 = CF3, Z = O, R3 = 3-Br 1194 R2 = CF3, Z = S, R3 = 3-c-Pr
1158 R2 = CF3, Z = 0, R3 = 3-1 1195 R2 = CF3, Z = S, R3 = 3-z-Pr
1159 R2 = CF3, Z = O, R3 = 3-CN 1196 R2 = CF3, Z = S, R3 = 3-Ph
1160 R2 = CF3, Z = O, R3 = 3-N02 1197 R2 = CF3, Z = O, R3 = 4-F
1161 R2 = CF3, Z = O, R3 = 3-OMe 1198 R2 = CF3, Z = O, R3 = 4-Cl
1162 R2 = CF3, Z = O, R3 = 3-OCF3 1199 R2 = CF3, Z = O, R3 = 4-Br
1163 R2 = CF3, Z = O, R3 = 3-CF3 1200 R2 = CF3, Z = 0, R3 = 4-1
1164 R2 = CF3, Z = O, R3 = 3-CHF2 1201 R2 = CF3, Z = O, R3 = 4-CN
1165 R2 = CF3, Z = O, R3 = 3-CH2F 1202 R2 = CF3, Z = O, R3 = 4-N02
1166 R2 = CF3, Z = O, R3 = 3-CHO 1203 R2 = CF3, Z = O, R3 = 4-OMe
1167 R2 = CF3, Z = O, R3 = 3-Me 1204 R2 = CF3, Z = O, R3 = 4-OCF3
1168 R2 = CF3, Z = O, R3 = 3-Et 1205 R2 = CF3, Z = O, R3 = 4-CF3
1169 R2 = CF3, Z = O, R3 = 3-Ethynyl 1206 R2 = CF3, Z = O, R3 = 4-CHF2
1170 R2 = CF3, Z = O, R3 = 3-Ethenyl 1207 R2 = CF3, Z = O, R3 = 4-CH2F
1171 R2 = CF3, Z = O, R3 = 3-S02Me 1208 R2 = CF3, Z = O, R3 = 4-CHO
1172 R2 = CF3, Z = 0, R3 = 3-OAc 1209 R2 = CF3, Z = O, R3 = 4-Me
1173 R2 = CF3, Z = O, R3 = 3-c-Pr 1210 R2 = CF3, Z = O, R3 = 4-Et
1174 R2 = CF3, Z = 0, R3 = 3-z-Pr 1211 R2 = CF3, Z = O, R3 = 4-Ethynyl
1175 R2 = CF3, Z = O, R3 = 3-Ph 1212 R2 = CF3, Z = O, R3 = 4-Ethenyl
1176 R2 = CF3, Z = S, R3 = 3-F 1213 R2 = CF3, Z = O, R3 = 4-S02Me
1177 R2 = CF3, Z = S, R3 = 3 -CI 1214 R2 = CF3, Z = O, R3 = 4-OAc
1178 R2 = CF3, Z = S, R3 = 3-Br 1215 R2 = CF3, Z = O, R3 = 4-c-Pr
1179 R2 = CF3, Z = S, R3 = 3-1 1216 R2 = CF3, Z = 0, R3 = 4-z-Pr
1180 R2 = CF3, Z = S, R3 = 3-CN 1217 R2 = CF3, Z = O, R3 = 4-Ph
1181 R2 = CF3, Z = S, R3 = 3-N02 1218 R2 = CF3, Z = O, R3 = 5-F
1182 R2 = CF3, Z = S, R3 = 3-OMe 1219 R2 = CF3, Z = O, R3 = 5-Cl
1183 R2 = CF3, Z = S, R3 = 3-OCF3 1220 R2 = CF3, Z = O, R3 = 5-Br
1184 R2 = CF3, Z = S, R3 = 3-CF3 1221 R2 = CF3, Z = 0, R3 = 5-1
1185 R2 = CF3, Z = S, R3 = 3-CHF2 1222 R2 = CF3, Z = O, R3 = 5-CN
1186 R2 = CF3, Z = S, R3 = 3-CH2F 1223 R2 = CF3, Z = O, R3 = 5-N02
1187 R2 = CF3, Z = S, R3 = 3-CHO 1224 R2 = CF3, Z = O, R3 = 5-OMe
1188 R2 = CF3, Z = S, R3 = 3-Me 1225 R2 = CF3, Z = O, R3 = 5-OCF3
1189 R2 = CF3, Z = S, R3 = 3-Et 1226 R2 = CF3, Z = O, R3 = 5-CF3
1190 R2 = CF3, Z = S, R3 = 3-Ethynyl 1227 R2 = CF3, Z = O, R3 = 5-CHF2
Figure imgf000082_0001
Table Header Row Table Header Row
1228 R2 = CF3, Z = O, R3 = 5-CH2F 1265 R2 = CF3, Z = O, R3 = 3,5-di-Cl
1229 R2 = CF3, Z = O, R3 = 5-CHO 1266 R2 = CF3, Z = O, R3 = 3,6-di-Cl
1230 R2 = CF3, Z = O, R3 =5-Me 1267 R2 = CF3, Z = O, R3 = 4,5-di-Cl
1231 R2 = CF3, Z = O, R3 = 5-Et 1268 R2 = CF3, Z = O, R3 = 3,4-di-Br
1232 R2 = CF3, Z = O, R3 = 5-Ethynyl 1269 R2 = CF3, Z = O, R3 = 3,5-di-Br
1233 R2 = CF3, Z = O, R3 = 5-Ethenyl 1270 R2 = CF3, Z = O, R3 = 3,6-di-Br
1234 R2 = CF3, Z = O, R3 = 5-S02Me 1271 R2 = CF3, Z = O, R3 = 4,5-di-Br
1235 R2 = CF3, Z = 0, R3 = 5-OAc 1272 R2 = CF3, Z = O, R3 = 3,4-di-CN
1236 R2 = CF3, Z = O, R3 = 5-c-Pr 1273 R2 = CF3, Z = O, R3 = 3,5-di-CN
1237 R2 = CF3, Z = 0, R3 = 5-z-Pr 1274 R2 = CF3, Z = O, R3 = 3,6-di-CN
1238 R2 = CF3, Z = O, R3 = 5-Ph 1275 R2 = CF3, Z = O, R3 = 4,5-di-CN
1239 R2 = CF3, Z = O, R3 = 6-F 1276 R2 = CF3, Z = O, R3 = 3,4-di-Me
1240 R2 = CF3, Z = O, R3 = 6-Cl 1277 R2 = CF3, Z = O, R3 = 3,5-di-Me
1241 R2 = CF3, Z = O, R3 = 6-Br 1278 R2 = CF3, Z = O, R3 = 3,6-di-Me
1242 R2 = CF3, Z = 0, R3 = 6-1 1279 R2 = CF3, Z = O, R3 = 4,5-di-Me
1243 R2 = CF3, Z = O, R3 = 6-CN 1280 R2 = CF3, Z = O, R3 = 3,4-di-OMe
1244 R2 = CF3, Z = O, R3 = 6-N02 1281 R2 = CF3, Z = O, R3 = 3,5-di-OMe
1245 R2 = CF3, Z = O, R3 = 6-OMe 1282 R2 = CF3, Z = O, R3 = 3,6-di-OMe
1246 R2 = CF3, Z = O, R3 = 6-OCF3 1283 R2 = CF3, Z = O, R3 = 4,5-di-OMe
1247 R2 = CF3, Z = O, R3 = 6-CF3 1284 R2 = CF3, Z = O, R3 = 3,4-di-CF3
1248 R2 = CF3, Z = O, R3 = 6-CHF2 1285 R2 = CF3, Z = O, R3 = 3,5-di-CF3
1249 R2 = CF3, Z = O, R3 = 6-CH2F 1286 R2 = CF3, Z = O, R3 = 3,6-di-CF3
1250 R2 = CF3, Z = O, R3 = 6-CHO 1287 R2 = CF3, Z = O, R3 = 4,5-di-CF3
1251 R2 = CF3, Z = O, R3 = 6-Me 1288 R2 = CF3, Z = O, R3 = 3-CN, 4-Me
1252 R2 = CF3, Z = O, R3 = 6-Et 1289 R2 = CF3, Z = O, R3 = 3-CN, 4-F
1253 R2 = CF3, Z = O, R3 = 6-Ethynyl 1290 R2 = CF3, Z = O, R3 = 3-CN, 4-Br
1254 R2 = CF3, Z = O, R3 = 6-Ethenyl 1291 R2 = CF3, Z = O, R3 = 3-CN, 4-OMe
1255 R2 = CF3, Z = O, R3 = 6-S02Me 1292 R2 = CF3, Z = O, R3 = 3-CN, 4-CF3
1256 R2 = CF3, Z = O, R3 = 6-OAc 1293 R2 = CF3, Z = O, R3 = 3-CN, 6-Me
1257 R2 = CF3, Z = O, R3 = 6-c-Pr 1294 R2 = CF3, Z = O, R3 = 3-CN, 6-F
1258 R2 = CF3, Z = 0, R3 = 6-z-Pr 1295 R2 = CF3, Z = O, R3 = 3-CN, 6-Br
1259 R2 = CF3, Z = O, R3 = 6-Ph 1296 R2 = CF3, Z = O, R3 = 3-CN, 6-OMe
1260 R2 = CF3, Z = O, R3 = 3,4-di-F 1297 R2 = CF3, Z = O, R3 = 3-CN, 6-CF3
1261 R2 = CF3, Z = O, R3 = 3,5-di-F 1298 R2 = CHF2, Z = O, R3 = H (m = 0)
1262 R2 = CF3, Z = O, R3 = 3,6-di-F 1299 R2 = CHF2, Z = O, R3 = 3-F
1263 R2 = CF3, Z = O, R3 = 4,5-di-F 1300 R2 = CHF2, Z = O, R3 = 3 -CI
1264 R2 = CF3, Z = O, R3 = 3,4-di-Cl 1301 R2 = CHF2, Z = O, R3 = 3-Br
Figure imgf000083_0001
Table Header Row Table Header Row
1302 R2 = CHF2, Z = O, R3 = 3-1 1339 R2 = CHF2, Z = S, R3 = 3-Ph
1303 R2 = CHF2, Z = O, R3 = 3-CN 1340 R2 = CHF2, Z = O, R3 = 4-F
1304 R2 = CHF2, Z = O, R3 = 3-N02 1341 R2 = CHF2, Z = O, R3 = 4-Cl
1305 R2 = CHF2, Z = O, R3 = 3-OMe 1342 R2 = CHF2, Z = O, R3 = 4-Br
1306 R2 = CHF2, Z = O, R3 = 3-OCF3 1343 R2 = CHF2, Z = O, R3 = 4-1
1307 R2 = CHF2, Z = O, R3 = 3-CF3 1344 R2 = CHF2, Z = O, R3 = 4-CN
1308 R2 = CHF2, Z = O, R3 = 3-CHF2 1345 R2 = CHF2, Z = O, R3 = 4-N02
1309 R2 = CHF2, Z = O, R3 = 3-CH2F 1346 R2 = CHF2, Z = O, R3 = 4-OMe
1310 R2 = CHF2, Z = O, R3 = 3-CHO 1347 R2 = CHF2, Z = O, R3 = 4-OCF3
1311 R2 = CHF2, Z = O, R3 = 3 -Me 1348 R2 = CHF2, Z = O, R3 = 4-CF3
1312 R2 = CHF2, Z = O, R3 = 3-Et 1349 R2 = CHF2, Z = O, R3 = 4-CHF2
1313 R2 = CHF2, Z = O, R3 = 3-Ethynyl 1350 R2 = CHF2, Z = O, R3 = 4-CH2F
1314 R2 = CHF2, Z = O, R3 = 3-Ethenyl 1351 R2 = CHF2, Z = O, R3 = 4-CHO
1315 R2 = CHF2, Z = O, R3 = 3-S02Me 1352 R2 = CHF2, Z = O, R3 = 4-Me
1316 R2 = CHF2, Z = O, R3 = 3-OAc 1353 R2 = CHF2, Z = O, R3 = 4-Et
1317 R2 = CHF2, Z = O, R3 = 3-c-Pr 1354 R2 = CHF2, Z = O, R3 = 4-Ethynyl
1318 R2 = CHF2, Z = O, R3 = 3-z-Pr 1355 R2 = CHF2, Z = O, R3 = 4-Ethenyl
1319 R2 = CHF2, Z = O, R3 = 3-Ph 1356 R2 = CHF2, Z = O, R3 = 4-S02Me
1320 R2 = CHF2, Z = S, R3 = 3-F 1357 R2 = CHF2, Z = O, R3 = 4-OAc
1321 R2 = CHF2, Z = S, R3 = 3-Cl 1358 R2 = CHF2, Z = O, R3 = 4-c-Pr
1322 R2 = CHF2, Z = S, R3 = 3-Br 1359 R2 = CHF2, Z = O, R3 = 4-z-Pr
1323 R2 = CHF2, Z = S, R3 = 3-1 1360 R2 = CHF2, Z = O, R3 = 4-Ph
1324 R2 = CHF2, Z = S, R3 = 3-CN 1361 R2 = CHF2, Z = O, R3 = 5-F
1325 R2 = CHF2, Z = S, R3 = 3-N02 1362 R2 = CHF2, Z = O, R3 = 5-Cl
1326 R2 = CHF2, Z = S, R3 = 3-OMe 1363 R2 = CHF2, Z = O, R3 = 5-Br
1327 R2 = CHF2, Z = S, R3 = 3-OCF3 1364 R2 = CHF2, Z = O, R3 = 5-1
1328 R2 = CHF2, Z = S, R3 = 3-CHF2 1365 R2 = CHF2, Z = O, R3 = 5-CN
1329 R2 = CHF2, Z = S, R3 = 3-CH2F 1366 R2 = CHF2, Z = O, R3 = 5-N02
1330 R2 = CHF2, Z = S, R3 = 3-CHO 1367 R2 = CHF2, Z = O, R3 = 5-OMe
1331 R2 = CHF2, Z = S, R3 = 3 -Me 1368 R2 = CHF2, Z = O, R3 = 5-OCF3
1332 R2 = CHF2, Z = S, R3 = 3-Et 1369 R2 = CHF2, Z = O, R3 = 5-CF3
1333 R2 = CHF2, Z = S, R3 = 3-Ethynyl 1370 R2 = CHF2, Z = O, R3 = 5-CHF2
1334 R2 = CHF2, Z = S, R3 = 3-Ethenyl 1371 R2 = CHF2, Z = O, R3 = 5-CH2F
1335 R2 = CHF2, Z = S, R3 = 3-S02Me 1372 R2 = CHF2, Z = O, R3 = 5-CHO
1336 R2 = CHF2, Z = S, R3 = 3-OAc 1373 R2 = CHF2, Z = O, R3 =5-Me
1337 R2 = CHF2, Z = S, R3 = 3-c-Pr 1374 R2 = CHF2, Z = O, R3 = 5-Et
1338 R2 = CHF2, Z = S, R3 = 3-z-Pr 1375 R2 = CHF2, Z = O, R3 = 5-Ethynyl
Figure imgf000084_0001
Table Header Row Table Header Row
1376 R2 = CHF2, Z = O, R3 = 5-Ethenyl 1413 R2 = CHF2, Z = O, R3 = 3,6-di-Br
1377 R2 = CHF2, Z = O, R3 = 5-S02Me 1414 R2 = CHF2, Z = O, R3 = 4,5-di-Br
1378 R2 = CHF2, Z = O, R3 = 5-OAc 1415 R2 = CHF2, Z = O, R3 = 3,4-di-CN
1379 R2 = CHF2, Z = O, R3 = 5-c-Pr 1416 R2 = CHF2, Z = O, R3 = 3,5-di-CN
1380 R2 = CHF2, Z = O, R3 = 5-z-Pr 1417 R2 = CHF2, Z = O, R3 = 3,6-di-CN
1381 R2 = CHF2, Z = O, R3 = 5-Ph 1418 R2 = CHF2, Z = O, R3 = 4,5-di-CN
1382 R2 = CHF2, Z = O, R3 = 6-F 1419 R2 = CHF2, Z = O, R3 = 3,4-di-Me
1383 R2 = CHF2, Z = O, R3 = 6-Cl 1420 R2 = CHF2, Z = O, R3 = 3,5-di-Me
1384 R2 = CHF2, Z = O, R3 = 6-Br 1421 R2 = CHF2, Z = O, R3 = 3,6-di-Me
1385 R2 = CHF2, Z = O, R3 = 6-1 1422 R2 = CHF2, Z = O, R3 = 4,5-di-Me
1386 R2 = CHF2, Z = O, R3 = 6-CN 1423 R2 = CHF2, Z = O, R3 = 3,4-di-OMe
1387 R2 = CHF2, Z = O, R3 = 6-N02 1424 R2 = CHF2, Z = O, R3 = 3,5-di-OMe
1388 R2 = CHF2, Z = O, R3 = 6-OMe 1425 R2 = CHF2, Z = O, R3 = 3,6-di-OMe
1389 R2 = CHF2, Z = O, R3 = 6-OCF3 1426 R2 = CHF2, Z = O, R3 = 4,5-di-OMe
1390 R2 = CHF2, Z = O, R3 = 6-CF3 1427 R2 = CHF2, Z = O, R3 = 3,4-di-CF3
1391 R2 = CHF2, Z = O, R3 = 6-CHF2 1428 R2 = CHF2, Z = O, R3 = 3,5-di-CF3
1392 R2 = CHF2, Z = O, R3 = 6-CH2F 1429 R2 = CHF2, Z = O, R3 = 3,6-di-CF3
1393 R2 = CHF2, Z = O, R3 = 6-CHO 1430 R2 = CHF2, Z = O, R3 = 4,5-di-CF3
1394 R2 = CHF2, Z = O, R3 = 6-Me 1431 R2 = CHF2, Z = O, R3 = 3-CN, 4-Me
1395 R2 = CHF2, Z = O, R3 = 6-Et 1432 R2 = CHF2, Z = O, R3 = 3-CN, 4-F
1396 R2 = CHF2, Z = O, R3 = 6-Ethynyl 1433 R2 = CHF2, Z = O, R3 = 3-CN, 4-Br
1397 R2 = CHF2, Z = O, R3 = 6-Ethenyl 1434 R2 = CHF2, Z = O, R3 = 3-CN, 4-OMe
1398 R2 = CHF2, Z = O, R3 = 6-S02Me 1435 R2 = CHF2, Z = O, R3 = 3-CN, 4-CF3
1399 R2 = CHF2, Z = O, R3 = 6-OAc 1436 R2 = CHF2, Z = O, R3 = 3-CN, 6-Me
1400 R2 = CHF2, Z = O, R3 = 6-c-Pr 1437 R2 = CHF2, Z = O, R3 = 3-CN, 6-F
1401 R2 = CHF2, Z = O, R3 = 6-i-Pr 1438 R2 = CHF2, Z = O, R3 = 3-CN, 6-Br
1402 R2 = CHF2, Z = O, R3 = 6-Ph 1439 R2 = CHF2, Z = O, R3 = 3-CN, 6-OMe
1403 R2 = CHF2, Z = O, R3 = 3,4-di-F 1440 R2 = CHF2, Z = O, R3 = 3-CN, 6-CF3
1404 R2 = CHF2, Z = O, R3 = 3,5-di-F 1441 R2 = S02Me, Z = O, R3 = H (m = 0)
1405 R2 = CHF2, Z = O, R3 = 3,6-di-F 1442 R2 = S02Me, Z = O, R3 = 3-F
1406 R2 = CHF2, Z = O, R3 = 4,5-di-F 1443 R2 = S02Me, Z = O, R3 = 3 -CI
1407 R2 = CHF2, Z = O, R3 = 3,4-di-Cl 1444 R2 = SOoMe, Z = O, R3 = 3 -Br
1408 R2 = CHF2, Z = O, R3 = 3,5-di-Cl 1445 R2 = S02Me, Z = O, R3 = 3-1
1409 R2 = CHF2, Z = O, R3 = 3,6-di-Cl 1446 R2 = S02Me, Z = O, R3 = 3-CN
1410 R2 = CHF2, Z = O, R3 = 4,5-di-Cl 1447 R2 = S02Me, Z = O, R3 = 3-N02
1411 R2 = CHF2, Z = O, R3 = 3,4-di-Br 1448 R2 = S02Me, Z = O, R3 = 3-OMe
1412 R2 = CHF2, Z = O, R3 = 3,5-di-Br 1449 R2 = S02Me, Z = O, R3 = 3-OCF3
Figure imgf000085_0001
Table Header Row Table Header Row
1450 R2 = S02Me, Z = O, R3 = 3-CF3 1487 R2 = S02Me, Z = O, R3 = 4-1
1451 R2 = S02Me, Z = O, R3 = 3-CHF2 1488 R2 = S02Me, Z = O, R3 = 4-CN
1452 R2 = S02Me, Z = O, R3 = 3-CH2F 1489 R2 = S02Me, Z = O, R3 = 4-N02
1453 R2 = S02Me, Z = O, R3 = 3-CHO 1490 R2 = S02Me, Z = O, R3 = 4-OMe
1454 R2 = S02Me, Z = O, R3 = 3 -Me 1491 R2 = S02Me, Z = O, R3 = 4-OCF3
1455 R2 = S02Me, Z = O, R3 = 3-Et 1492 R2 = S02Me, Z = O, R3 = 4-CF3
1456 R2 = S02Me, Z = O, R3 = 3-Ethynyl 1493 R2 = S02Me, Z = O, R3 = 4-CHF2
1457 R2 = S02Me, Z = O, R3 = 3-Ethenyl 1494 R2 = S02Me, Z = O, R3 = 4-CH2F
1458 R2 = S02Me, Z = O, R3 = 3-S02Me 1495 R2 = S02Me, Z = O, R3 = 4-CHO
1459 R2 = S02Me, Z = O, R3 = 3-OAc 1496 R2 = S02Me, Z = O, R3 = 4-Me
1460 R2 = S02Me, Z = O, R3 = 3-c-Pr 1497 R2 = S02Me, Z = O, R3 = 4-Et
1461 R2 = S02Me, Z = O, R3 = 3-z-Pr 1498 R2 = S02Me, Z = O, R3 = 4-Ethynyl
1462 R2 = S02Me, Z = O, R3 = 3-Ph 1499 R2 = S02Me, Z = O, R3 = 4-Ethenyl
1463 R2 = S02Me, Z = S, R3 = 3-F 1500 R2 = S02Me, Z = O, R3 = 4-S02Me
1464 R2 = S02Me, Z = S, R3 = 3 -CI 1501 R2 = S02Me, Z = O, R3 = 4-OAc
1465 R2 = S02Me, Z = S, R3 = 3 -Br 1502 R2 = S02Me, Z = O, R3 = 4-c-Pr
1466 R2 = S02Me, Z = S, R3 = 3-1 1503 R2 = S02Me, Z = O, R3 = 4-z-Pr
1467 R2 = S02Me, Z = S, R3 = 3-CN 1504 R2 = S02Me, Z = O, R3 = 4-Ph
1468 R2 = S02Me, Z = S, R3 = 3-N02 1505 R2 = S02Me, Z = O, R3 = 5-F
1469 R2 = S02Me, Z = S, R3 = 3-OMe 1506 R2 = S02Me, Z = O, R3 = 5-Cl
1470 R2 = S02Me, Z = S, R3 = 3-OCF3 1507 R2 = S02Me, Z = O, R3 = 5-Br
1471 R2 = S02Me, Z = S, R3 = 3-CF3 1508 R2 = S02Me, Z = O, R3 = 5-1
1472 R2 = S02Me, Z = S, R3 = 3-CHF2 1509 R2 = S02Me, Z = O, R3 = 5-CN
1473 R2 = S02Me, Z = S, R3 = 3-CH2F 1510 R2 = S02Me, Z = O, R3 = 5-N02
1474 R2 = S02Me, Z = S, R3 = 3-CHO 1511 R2 = S02Me, Z = O, R3 = 5-OMe
1475 R2 = S02Me, Z = S, R3 = 3 -Me 1512 R2 = S02Me, Z = O, R3 = 5-OCF3
1476 R2 = S02Me, Z = S, R3 = 3-Et 1513 R2 = S02Me, Z = O, R3 = 5-CF3
1477 R2 = S02Me, Z = S, R3 = 3-Ethynyl 1514 R2 = S02Me, Z = O, R3 = 5-CHF2
1478 R2 = S02Me, Z = S, R3 = 3-Ethenyl 1515 R2 = S02Me, Z = O, R3 = 5-CH2F
1479 R2 = S02Me, Z = S, R3 = 3-S02Me 1516 R2 = S02Me, Z = O, R3 = 5-CHO
1480 R2 = S02Me, Z = S, R3 = 3-OAc 1517 R2 = S02Me, Z = O, R3 =5-Me
1481 R2 = S02Me, Z = S, R3 = 3-c-Pr 1518 R2 = S02Me, Z = O, R3 = 5-Et
1482 R2 = S02Me, Z = S, R3 = 3-z-Pr 1519 R2 = S02Me, Z = O, R3 = 5-Ethynyl
1483 R2 = S02Me, Z = S, R3 = 3-Ph 1520 R2 = S02Me, Z = O, R3 = 5-Ethenyl
1484 R2 = S02Me, Z = O, R3 = 4-F 1521 R2 = S02Me, Z = O, R3 = 5-S02Me
1485 R2 = S02Me, Z = O, R3 = 4-Cl 1522 R2 = S02Me, Z = O, R3 = 5-OAc
1486 R2 = S02Me, Z = O, R3 = 4-Br 1523
Figure imgf000086_0001
R2 = S02Me, Z = O, R3 = 5-c-Pr Table Header Row
1524 R2 = S02Me, Z = O, R3 = 5-z-Pr
1525 R2 = S02Me, Z = O, R3 = 5-Ph
1526 R2 = S02Me, Z = O, R: ! = 6-F
1527 R2 = S02Me, Z = O, R3 = 6-Cl
1528 R2 = S02Me, Z = O, R3 = 6-Br
1529 R2 = S02Me, Z = O, R 5 = 6-1
1530 R2 = S02Me, Z = O, R3 = 6-CN
1531 R2 = S02Me, Z = O, R3 = = 6-N02
1532 R2 = S02Me, Z = O, R3 = = 6-OMe
1533 R2 = S02Me, Z = O, R3 = 6-OCF3
1534 R2 = S02Me, Z = O, R3 = 6-CF3
1535 R2 = S02Me, Z = O, R3 = 6-CHF2
1536 R2 = S02Me, Z = O, R3 = 6-CH2F
1537 R2 = S02Me, Z = O, R3 = = 6-CHO
1538 R2 = S02Me, Z = O, R3 = 6-Me
1539 R2 = S02Me, Z = O, R3 = 6-Et
1540 R2 = S02Me, Z = O, R3 = 6-Ethynyl
1541 R2 = S02Me, Z = O, R3 = 6-Ethenyl
1542 R2 = S02Me, Z = O, R3 = 6-S02Me
1543 R2 = S02Me, Z = O, R3 = = 6-OAc
1544 R2 = S02Me, Z = O, R3 = 6-c-Pr
1545 R2 = S02Me, Z = O, R3 = 6-z-Pr
1546 R2 = S02Me, Z = O, R3 = 6-Ph
1547 R2 = S02Me, Z = O, R3 = 3,4-di-F
1548 R2 = S02Me, Z = O, R3 = 3,5-di-F
1549 R2 = S02Me, Z = O, R3 = 3,6-di-F
1550 R2 = S02Me, Z = O, R3 = 4,5-di-F
1551 R2 = S02Me, Z = O, R3 = 3,4-di-Cl
1552 R2 = S02Me, Z = O, R3 = 3,5-di-Cl
1553 R2 = S02Me, Z = O, R3 = 3,6-di-Cl
1554 R2 = S02Me, Z = O, R3 = 4,5-di-Cl
Figure imgf000087_0001
A compound of this invention will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serves as a carrier. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include both liquid and solid compositions. Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions, oil-in -water emulsions, flowable concentrates and/or suspoemulsions) and the like, which optionally can be thickened into gels. The general types of aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion. The general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
The general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffmic hydrocarbon or vegetable oil. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight. Weight Percent
Active
Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 0.001-90 0-99.999 0-15
Granules, Tablets and Powders
Oil Dispersions, Suspensions, 1-50 40-99 0-50
Emulsions, Solutions (including
Emulsifiable Concentrates)
Dusts 1-25 70 -99 0- -5
Granules and Pellets 0.001-99 5- 99.999 0- -15
High Strength Compositions 90-99 0- 10 0- -2
Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexyl acetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetate and isobornyl acetate, other esters such as alkylated lactate esters, dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, and alcohols, which can be linear, branched, saturated or unsaturated, such as methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutyl alcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecyl alcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecyl alcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol, diacetone alcohol, cresol and benzyl alcohol. Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C6-C22), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof. Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
The solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as "surface-active agents") generally modify, most often reduce, the surface tension of the liquid. Depending on the nature of the hydrophilic and lipophilic groups in a surfactant molecule, surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
Surfactants can be classified as nonionic, anionic or cationic. Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide; ethoxylated fatty acids; ethoxylated fatty esters and oils; ethoxylated methyl esters; ethoxylated tristyrylphenol (including those prepared from ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); fatty acid esters, glycerol esters, lanolin-based derivatives, polyethoxylate esters such as polyethoxylated sorbitan fatty acid esters, polyethoxylated sorbitol fatty acid esters and polyethoxylated glycerol fatty acid esters; other sorbitan derivatives such as sorbitan esters; polymeric surfactants such as random copolymers, block copolymers, alkyd peg (polyethylene glycol) resins, graft or comb polymers and star polymers; polyethylene glycols (pegs); polyethylene glycol fatty acid esters; silicone-based surfactants; and sugar-derivatives such as sucrose esters, alkyl polyglycosides and alkyl polysaccharides.
Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of ethoxylated alcohols; sulfonates of amines and amides such as N,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, and dodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes; sulfonates of naphthalene and alkyl naphthalene; sulfonates of fractionated petroleum; sulfosuccinamates; and sulfosuccinates and their derivatives such as dialkyl sulfosuccinate salts.
Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
Also useful for the present compositions are mixtures of nonionic and anionic surfactants or mixtures of nonionic and cationic surfactants. Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
Compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants). Such formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes. Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes. Examples of formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
The compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 μιη can be wet milled using media mills to obtain particles with average diameters below 3 μιη. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 μιη range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, The Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; Hance et al, Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989; and Developments in formulation technology, PJB Publications, Richmond, UK, 2000.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except where otherwise indicated. Example A
High Strength Concentrate
Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%
Example B
Wettable Powder
Compound 12 65.0% dodecylphenol polyethylene glycol ether 2.0%> sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%
Example C
Granule
Compound 15 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)
Example D
Extruded Pellet
Compound 21 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0%> sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%
Example E
Emulsifiable Concentrate
Compound 23 10.0% polyoxyethylene sorbitol hexoleate 20.0%
C^-Cio fatty acid methyl ester 70.0%>
Example F
Microemulsion
Compound 24 5.0% polyvinylpyrrolidone -vinyl acetate copolymer 30.0% alkylpolyglycoside 30.0%> glyceryl monooleate 15.0% water 20.0% Example G
Suspension Concentrate
Compound 27 35% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%> styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% water 53.7%
Example H
Emulsion in Water
Compound 32 10.0% butyl polyoxyethylene/polypropylene block copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%> silicone based defoamer 0.1 % l,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0 water 58.7%
Example I
Oil Dispersion
Compound 42 25% polyoxy ethylene sorbitol hexaoleate 15% organically modified bentonite clay 2.5% fatty acid methyl ester 57.5%
Example J
Suspoemulsion
Compound 1 10.0% imidacloprid 5.0%> butyl polyoxyethylene/polypropylene block copolymer 4.0%> stearic acid/polyethylene glycol copolymer 1.0%) styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%> silicone based defoamer 0.1% l,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon 20.0% water 53.7%
Test results indicate that the compounds of the present invention are highly active preemergent and/or postemergent herbicides and/or plant growth regulants. The compounds of the mention generally show highest activity for postemergence weed control (i.e. applied after weed seedlings emerge from the soil) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and broadleaf weeds within a crop/weed mixture. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays. Compounds of this invention may show tolerance to important agronomic crops including, but is not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass). Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, the subject compounds are useful to modify plant growth.
As the compounds of the invention have both preemergent and postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.
A herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.001 to 20 kg/ha with a preferred range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
Compounds of the invention are useful in treating all plants and plant parts. Plant varieties and cultivars can be obtained by conventional propagation and breeding methods or by genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgene) has been stably integrated into the plant's genome. A transgene that is defined by its particular location in the plant genome is called a transformation or transgenic event.
Genetically modified plant cultivars which can be treated according to the invention include those that are resistant against one or more biotic stresses (pests such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, cold temperature, soil salinity, etc.), or that contain other desirable characteristics. Plants can be genetically modified to exhibit traits of, for example, herbicide tolerance, insect-resistance, modified oil profiles or drought tolerance. Useful genetically modified plants containing single gene transformation events or combinations of transformation events are listed in Exhibit C. Additional information for the genetic modifications listed in Exhibit C can be obtained from publicly available databases maintained, for example, by the U.S. Department of Agriculture.
The following abbreviations, 1 through 37, are used in Exhibit C for traits. A "-" means the entry is not available.
Trait Description Trait Description Trait Description
1 Glyphosate tolerance 15 Cold tolerance 27 High tryptophan
2 High lauric acid oil 16 Imidazolinone herb. tol. 28 Erect leaves semidwarf
3 Glufosinate tolerance 17 Modified alpha-amylase 29 Semidwarf
4 Phytate breakdown 18 Pollination control 30 Low iron tolerance
5 Oxynil tolerance 19 2,4-D tolerance 31 Modified oil/fatty acid
6 Disease resistance 20 Increased lysine 32 HPPD tolerance
7 Insect resistance 21 Drought tolerance 33 High oil
9 Modified flower color 22 Delayed ripening/senescence 34 Aryloxyalkanoate tol.
11 ALS Herbicide Tol. 23 Modified product quality 35 Mesotrione tolerance
12 Dicamba Tolerance 24 High cellulose 36 Reduced nicotine
13 Anti- allergy 25 Modified starch/carbohydrate 37 Modified product
14 Salt tolerance 26 Insect & disease resist.
Exhibit C Crop Trait(s) Gene(s)
Alfalfa 1 cp4 epsps (aroA:CP4)
Alfalfa 1 cp4 epsps (aroA:CP4)
Canola* 2 te
Canola* 2 te
Canola* 1 gat4621
Canola* 1 gat4621
Canola* 1 cp4 epsps (aroA:CP4); goxv247
Canola* 1 cp4 epsps (aroA:CP4); goxv247
Canola* 3 bar
Canola* 3 pat (syn)
Canola* 3 bar
Canola* 1 cp4 epsps (aroA:CP4)
Canola* 4 phyA
Canola* 4 phyA
Canola* 4 phyA
Canola* 4 phyA
Canola* 4 phyA
Canola* 3 bar
Canola* 3 bar
Canola* 5 bxn
Canola* 3 bar
Canola* 3 bar
Canola* 3 bar
Canola* 3 bar
Canola* 3 bar
Canola* 3 bar
Canola* 3 bar
Bean 6 acl (sense and antisense)
Brinjal # 7 cry 1 Ac
Cotton 11 S4-HrA
Cotton 3,7 pat (syn); cry IF
Cotton 3,7 pat (syn); cry 1 Ac
Cotton 5,7 bxn; crylAc
Cotton 5,7 bxn; crylAc
Cotton 5,7 bxn; crylAc
Cotton 5,7 bxn; crylAc
Cotton 5,7 bxn; crylAc
Cotton 7 crylAc
Cotton 5 bxn; crylAc
Cotton
Figure imgf000097_0001
5 bxn; crylAc Cotton bxn; crylAc
Cotton bxn; crylAc
Cotton vip3A(a)
Cotton crylAb
Cotton vip3A
Cotton crylAc
Cotton crylAb-Ac
Cotton cry2Ae
Cotton 2mepsps
Cotton crylAb-Ac
Cotton bar
Cotton crylC
Cotton crylAc
Cotton cp4 epsps (aroA:CP4)
Cotton crylAc; cry2Ab2
Cotton cp4 epsps (aroA:CP4)
Cotton crylAc
Cotton crylAc
Cotton cp4 epsps (aroA:CP4)
Cotton
Cotton crylA; CpTI
Cotton crylAb; bar
Cotton crylAb; bar
Cotton crylAb
Cotton crylAb
Cotton crylAb
Cotton crylAb
Cotton crylAb
Cotton crylAb
Cotton cp4 epsps (aroA:CP4)
Cotton mepsps
Cotton crylAb
Cotton Modified dmo; bar
Cotton Modified Cryj
Flax als
Lentil als
Maize amy797E
Maize ecry3.1Ab
Maize cry34Abl ; cry35Abl ; pat
Maize pat; dam
Maize pat; dam
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Maize
Melon
Figure imgf000099_0001
Figure imgf000100_0001
Rice
Rice
Rice
Rice
Rice
Rice
Rose
Rose
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Soybean
Squash
Squash
Sugar Beet
Sugar Beet
Sugar Beet
Sugar Beet
Sugarcane
Figure imgf000101_0001
Sunflower X81359 16 als Pepper PK-SP01 6 cmv cp
Tobacco C/F/93/08-02 5 bxn
Tobacco Vector 21-41 36 NtQPTl (antisense) Wheat MON71800 MON-71800-3 1 cp4 epsps (aroA:CP4) * Argentine (Brassica napus), ** Polish (B. rapa), # Eggplant
Treatment of genetically modified plants with compounds of the invention may result in super-additive or synergistic effects. For example, reduction in application rates, broadening of the activity spectrum, increased tolerance to biotic/abiotic stresses or enhanced storage stability may be greater than expected from just simple additive effects of the application of compounds of the invention on genetically modified plants.
Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Thus the present invention also pertains to a composition comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent. The other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent. For mixtures of the present invention, one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
A mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzobicyclon, benzofenap, bicyclopyrone, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromofenoxim, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim, butylate, cafenstrole, carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clacyfos, clefoxydim, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam- methyl, cumyluron, cyanazine, cycloate, cyclopyrimorate, cyclosulfamuron, cycloxydim, cyhalofop-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethenamid-P, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethiozin, ethofumesate, ethoxyfen, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenoxasulfone, fenquinotrione, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, flucetosulfuron, fluchloralin, flufenacet, flufenpyr, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, flurenol, flurenol-butyl, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, glufosinate, glufosinate-ammonium, glufosinate-P, glyphosate and its salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate), halauxifen, halauxifen-methyl, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, indaziflam, iofensulfuron, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, ipfencarbazone, isoproturon, isouron, isoxaben, isoxaflutole, isoxachlortole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its salts (e.g., MCPA-dimethylammonium, MCPA-potassium and MCPA-sodium, esters (e.g., MCPA-2-ethylhexyl, MCPA-butotyl) and thioesters (e.g., MCPA-thioethyl), MCPB and its salts (e.g., MCPB-sodium) and esters (e.g., MCPB-ethyl), mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, metazosulfuron, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, metobenzuron, metobromuron, metolachlor, S-metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, napropamide-M, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, orthosulfamuron, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfiuorfen, paraquat dichloride, pebulate, pelargonic acid, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, pethoxyamid, phenmedipham, picloram, picloram-potassium, picolinafen, pinoxaden, piperophos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyrisulfuron, propyzamide, prosulfocarb, prosulfuron, pyraclonil, pyrafiufen-ethyl, pyrasulfotole, pyrazogyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrimisulfan, pyrithiobac, pyrithiobac-sodium, pyroxasulfone, pyroxsulam, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, safiufenacil, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6- TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tefuryltrione, tembotrione, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiazopyr, thiencarbazone, thifensulfuron-methyl, thiobencarb, tiafenacil, tiocarbazil, topramezone, tralkoxydim, tri-allate, triafamone, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron, vernolate, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-l- methyl- 1 ,5-naphthyridin-2(lH)-one, 5-chloro-3-[(2-hydroxy-6-oxo- 1 -cyclohexen- 1 - yl)carbonyl]- 1 -(4-methoxyphenyl)-2( lH)-quinoxalinone, 2-chloro-N-( 1 -methyl- lH-tetrazol- 5-yl)-6-(trifluoromethyl)-3-pyridinecarboxamide, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2- difluoroethyl)-8-hydroxypyrido[2,3-¾]pyrazin-6(5H)-one), 4-(2,6-diethyl-4-methylphenyl)- 5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone), 5-[[(2,6-difluorophenyl)methoxy]methyl]-4,5- dihydro-5-methyl-3-(3-methyl-2-thienyl)isoxazole (previously methioxolin), 3-[7-fluoro-3,4- dihydro-3-oxo-4-(2-propyn- 1 -yl)-2H- 1 ,4-benzoxazin-6-yl]dihydro- 1 ,5-dimethyl-6-thioxo- 1 ,3,5-triazine-2,4(lH,3H)-dione, 4-(4-fluorophenyl)-6-[(2-hydroxy-6-oxo- 1 -cyclohexen- 1 - yl)carbonyl] -2 -methyl- 1 ,2,4-triazine-3,5(2H,4H)-dione, methyl 4-amino-3-chloro-6-(4- chloro-2-fluoro-3-methoxyphenyl)-5-fluoro-2-pyridinecarboxylate, 2-methyl-3- (methylsulfonyl)-N-(l -methyl- lH-tetrazol-5-yl)-4-(trifluoromethyl)benzamide and 2-methyl- N-(4-methyl-l,2,5-oxadiazol-3-yl)-3-(methylsulfinyl)-4-(trifluoromethyl)benzamide. Other herbicides also include bioherbicides such as Alternaria destruens Simmons, CoUetotrichum gloeosporiodes (Penz.) Penz. & Sacc, Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A4 and A7, harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.
General references for agricultural protectants (i.e. herbicides, herbicide safeners, insecticides, fungicides, nematocides, acaricides and biological agents) include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2003 and The BioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British Crop Protection Council, Farnham, Surrey, U.K., 2001.
For embodiments where one or more of these various mixing partners are used, the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300: 1 (for example ratios between about 1 :30 and about 30: 1). One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.
In certain instances, combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable. When synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load. When safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.
Of note is a combination of a compound of the invention with at least one other herbicidal active ingredient. Of particular note is such a combination where the other herbicidal active ingredient has different site of action from the compound of the invention. In certain instances, a combination with at least one other herbicidal active ingredient having a similar spectrum of control but a different site of action will be particularly advantageous for resistance management. Thus, a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.
Compounds of this invention can also be used in combination with herbicide safeners such as allidochlor, benoxacor, cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, dicyclonon, dietholate, dimepiperate, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr- diethyl, mephenate, methoxyphenone naphthalic anhydride (1,8-naphthalic anhydride), oxabetrinil, N-(aminocarbonyl)-2-methylbenzenesulfonamide, N-(aminocarbonyl)- 2-fluorobenzenesulfonamide, l-bromo-4-[(chloromethyl)sulfonyl]benzene (BCS), 4- (dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl- 1,3-dioxolane (MG 191), ethyl l,6-dihydro-l-(2-methoxyphenyl)-6-oxo-2-phenyl-5- pyrimidinecarboxylate, 2-hydroxy-N,N-dimethyl-6-(trifluoromethyl)pyridine-3- carboxamide, and 3-oxo-l-cyclohexen-l-yl l-(3,4-dimethylphenyl)-l,6-dihydro-6-oxo-2- phenyl-5-pyrimidinecarboxylate to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.
Of note is a composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
Table Al lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention. Compound 1 in the Component (a) column is identified in Index Table A. The second column of Table Al lists the specific Component (b) compound (e.g., "2,4-D" in the first line). The third, fourth and fifth columns of Table Al lists ranges of weight ratios for rates at which the Component (a) compound is typically applied to a field-grown crop relative to Component (b) (i.e. (a):(b)). Thus, for example, the first line of Table Al specifically discloses the combination of Component (a) (i.e. Compound 1 in Index Table A) with 2,4-D is typically applied in a weight ratio between 1 : 168 - 6: 1. The remaining lines of Table Al are to be construed similarly. TABLE Al
Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 2,4-D 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Acetochlor 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Acifluorfen 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Aclonifen 1:750 to 2:1 1:250 to 1:3 1:75 to 1:9
1 Alachlor 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Ametryn 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Amicarbazone 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Amidosulfuron 1:6 to 150:1 1:2 to 50:1 1:1 to 15:1
1 Aminocyclopyrachlor 1:42 to 22:1 1:14 to 8:1 1:4 to 3:1
1 Aminopyralid 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Amitrole 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Anilofos 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Asulam 1:840 to 2:1 1:280 to 1:3 1:84 to 1:10
1 Atrazine 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Azimsulfuron 1:6 to 150:1 1:2 to 50:1 1:1 to 15:1
1 Beflubutamid 1:300 to 3:1 1:100 to 1:1 1:30 to 1:4
1 Benfuresate 1:540 to 2:1 1:180 to 1:2 1:54 to 1:6
1 Bensulfuron-methyl 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Bentazon 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Benzobicyclon 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1
1 Benzofenap 1:225 to 4:1 1:75 to 2:1 1:22 to 1:3
1 Bicyclopyrone 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Bifenox 1:225 to 4:1 1:75 to 2:1 1:22 to 1:3
1 Bispyribac-sodium 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Bromacil 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Bromobutide 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Bromoxynil 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Butachlor 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Butafenacil 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Butylate 1:1350 to 1:2 1:450 to 1:5 1:135 to 1:15
1 Carfenstrole 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Carfentrazone-ethyl 1:112 to 8:1 1:37 to 3:1 1:11 to 1:2
1 Chlorimuron-ethyl 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Chlorotoluron 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Chlorsulfuron 1:6 to 150:1 1:2 to 50:1 1:1 to 15:1
1 Cincosulfuron 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Cinidon-ethyl 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Cinmethylin 1:30 to 30:1 l:10to 10:1 1:3 to 3:1
1 Clacyfos 1:84 to 6:1 1:28 to 2:1 1:16 to 1:2
1 Clethodim 1:42 to 22:1 1:14 to 8:1 1:4 to 3:1
1 Clodinafop-propargyl 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Clomazone 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Clomeprop 1:150 to 6:1 1:50 to 2:1 1:15 to 1:2
1 Clopyralid 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Cloransulam-methyl 1:10 to 86:1 1:3 to 29:1 1:1 to 9:1
1 Cumyluron 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Cyanazine 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Cyclopyrimorate 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Cyclosulfamuron 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Cycloxydim 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Cyhalofop 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Daimuron 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Desmedipham 1:282 to 4:1 1:94 to 2:1 1:28 to 1:4
1 Dicamba 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Dichlobenil 1:1200 to 1:2 1:400 to 1:4 1:120 to 1:14
1 Dichlorprop 1:810 to 2:1 1:270 to 1:3 1:81 to 1:9
1 Diclofop-methyl 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Diclosulam 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Difenzoquat 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Diflufenican 1:750 to 2:1 1:250 to 1:3 1:75 to 1:9
1 Diflufenzopyr 1:10 to 86:1 1:3 to 29:1 1:1 to 9:1
1 Dimethachlor 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Dimethametryn 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Dimethenamid-p 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Dithiopyr 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Diuron 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 EPTC 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Esprocarb 1:1200 to 1:2 1:400 to 1:4 1:120 to 1:14
1 Ethalfluralin 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Ethametsulfuron-methyl 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Ethoxyfen 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Ethoxysulfuron 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Etobenzanid 1:225 to 4:1 1:75 to 2:1 1:22 to 1:3
1 Fenoxaprop-ethyl 1:105 to 9:1 1:35 to 3:1 1:10 to 1:2
1 Fenoxasulfone 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1
1 Fenquinotrione 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Fentrazamide 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Flazasulfuron 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Florasulam 1:2 to 375:1 1:1 to 125:1 4:1 to 38:1
1 Fluazifop-butyl 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Flucarbazone 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Flucetosulfuron 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Flufenacet 1:225 to 4:1 1:75 to 2:1 1:22 to 1:3
1 Flumetsulam 1:21 to 43:1 1:7 to 15:1 1:2 to 5:1
1 Flumiclorac-pentyl 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Flumioxazin 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Fluometuron 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Flupyrsulfuron-methyl 1:3 to 300:1 1:1 to 100:1 3:1 to 30:1
1 Fluridone 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Fluroxypyr-meptyl 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Flurtamone 1:750 to 2:1 1:250 to 1:3 1:75 to 1:9
1 Fluthiacet-methyl 1:42 to 38:1 1:14 to 13:1 1:2 to 5:1
1 Fomesafen 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Foramsulfuron 1:12 to 75:1 1:4 to 25:1 1:1 to 8:1
1 Glufosinate 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Glyphosate 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Halauxifen 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Halauxifen-methyl 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Halosulfuron-methyl 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Haloxyfop-methyl 1:30 to 30:1 l:10to 10:1 1:3 to 3:1
1 Hexazinone 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Imazamox 1:12 to 75:1 1:4 to 25:1 1:1 to 8:1
1 Imazapic 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Imazapyr 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Imazaquin 1:30 to 30:1 1:10 to 10:1 1:3 to 3:1
1 Imazethabenz-methyl 1:150 to 6:1 1:50 to 2:1 1:15 to 1:2
1 Imazethapyr 1:21 to 43:1 1:7 to 15:1 1:2 to 5:1
1 Imazosulfuron 1:24 to 38:1 1:8 to 13:1 1:2 to 4:1
1 Indanofan 1:300 to 3:1 1:100 to 1:1 1:30 to 1:4
1 Indaziflam 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 lodosulfuron-methyl 1:3 to 300:1 1:1 to 100:1 3:1 to 30:1
1 Ioxynil 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Ipfencarbazone 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1
1 Isoproturon 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Isoxaben 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Isoxaflutole 1:52 to 18:1 1:17 to 6:1 1:5 to 2:1
1 Lactofen 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Lenacil 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Linuron 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 MCPA 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 MCPB 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Mecoprop 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Mefenacet 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Mefluidide 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Mesosulfuron-methyl 1:4 to 200:1 1:1 to 67:1 2:1 to 20:1
1 Mesotrione 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Metamifop 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Metazachlor 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Metazosulfuron 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Methabenzthiazuron 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Metolachlor 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Metosulam 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Metribuzin 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Metsulfuron-methyl 1:1 to 500:1 1:1 to 167:1 5:1 to 50:1
1 Molinate 1:900 to 1:1 1:300 to 1:3 1:90 to 1:10
1 Napropamide 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Napropamide-M 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Naptalam 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Nicosulfuron 1:10 to 86:1 1:3 to 29:1 1:1 to 9:1 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Norflurazon 1:1008 to 1:2 1:336 to 1:4 1:100 to 1:12
1 Orbencarb 1:1200 to 1:2 1:400 to 1:4 1:120 to 1:14
1 Orthosulfamuron 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Oryzalin 1:450 to 2:1 1:150 to 1:2 1:45 to 1:5
1 Oxadiargyl 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Oxadiazon 1:480 to 2:1 1:160 to 1:2 1:48 to 1:6
1 Oxasulfuron 1:24 to 38:1 1:8 to 13:1 1:2 to 4:1
1 Oxaziclomefone 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Oxyfluorfen 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Paraquat 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Pendimethalin 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Penoxsulam 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Penthoxamid 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Pentoxazone 1:90 to 10:1 1:30 to 4:1 1:9 to 1:1
1 Phenmedipham 1:90 to 10:1 1:30 to 4:1 1:9 to 1:1
1 Picloram 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Picolinafen 1:30 to 30:1 l:10to 10:1 1:3 to 3:1
1 Pinoxaden 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Pretilachlor 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Primisulfuron-methyl 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Prodiamine 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Profoxydim 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Prometryn 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Propachlor 1:1008 to 1:2 1:336 to 1:4 1:100 to 1:12
1 Propanil 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Propaquizafop 1:42 to 22:1 1:14 to 8:1 1:4 to 3:1
1 Propoxycarbazone 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Propyrisulfuron 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Propyzamide 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Prosulfocarb 1:1050 to 1:2 1:350 to 1:4 1:105 to 1:12
1 Prosulfuron 1:6 to 150:1 1:2 to 50:1 1:1 to 15:1
1 Pyraclonil 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Pyraflufen-ethyl 1:4 to 200:1 1:1 to 67:1 2:1 to 20:1
1 Pyrasulfotole 1:12 to 75:1 1:4 to 25:1 1:1 to 8:1
1 Pyrazolynate 1:750 to 2:1 1:250 to 1:3 1:75 to 1:9 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Pyrazosulfuron-ethyl 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Pyrazoxyfen 1:4 to 200:1 1:1 to 67:1 2:1 to 20:1
1 Pyribenzoxim 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Pyributicarb 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Pyridate 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Pyriftalid 1:9 to 100:1 1:3 to 34:1 1:1 to 10:1
1 Pyriminobac -methyl 1:18 to 50:1 1:6 to 17:1 1:1 to 5:1
1 Pyrimisulfan 1:15 to 60:1 1:5 to 20:1 1:1 to 6:1
1 Pyrithiobac 1:21 to 43:1 1:7 to 15:1 1:2 to 5:1
1 Pyroxasulfone 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1
1 Pyroxsulam 1:4 to 200:1 1:1 to 67:1 2:1 to 20:1
1 Quinclorac 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Quizalofop-ethyl 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Rimsulfuron 1:12 to 75:1 1:4 to 25:1 1:1 to 8:1
1 Saflufenacil 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Sethoxydim 1:84 to 11:1 1:28 to 4:1 1:8 to 2:1
1 Simazine 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Sulcotrione 1:105 to 9:1 1:35 to 3:1 1:10 to 1:2
1 Sulfentrazone 1:129 to 7:1 1:43 to 3:1 1:12 to 1:2
1 Sulfometuron-methyl 1:30 to 30:1 1:10 to 10:1 1:3 to 3:1
1 Sulfosulfuron 1:7 to 120:1 1:2 to 40:1 1:1 to 12:1
1 Tebuthiuron 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Tefuryltrione 1:37 to 24:1 1:12 to 8:1 1:3 to 3:1
1 Tembotrione 1:27 to 33:1 1:9 to 11:1 1:2 to 4:1
1 Tepraloxydim 1:22 to 40:1 1:7 to 14:1 1:2 to 4:1
1 Terbacil 1:252 to 4:1 1:84 to 2:1 1:25 to 1:3
1 Terbuthylatrazine 1:750 to 2:1 1:250 to 1:3 1:75 to 1:9
1 Terbutryn 1:168 to 6:1 1:56 to 2:1 1:16 to 1:2
1 Thenylchlor 1:75 to 12:1 1:25 to 4:1 1:7 to 2:1
1 Thiazopyr 1:336 to 3:1 1:112 to 1:2 1:33 to 1:4
1 Thiencarbazone 1:3 to 300:1 1:1 to 100:1 3:1 to 30:1
1 Thifensulfuron-methyl 1:4 to 200:1 1:1 to 67:1 2:1 to 20:1
1 Thiobencarb 1:672 to 2:1 1:224 to 1:3 1:67 to 1:8
1 Topramazone 1:6 to 150:1 1:2 to 50:1 1:1 to 15:1
1 Tralkoxydim 1:60 to 15:1 1:20 to 5:1 1:6 to 2:1 Component (a) Typical More Typical Most Typical (Compound #) Component (b) Weight Ratio Weight Ratio Weight Ratio
1 Triafamone 1:3 to 38:1 1:1 to 13:1 1: 1 to 8:1
1 Triallate 1:672 to 2: 1 1:224 to 1:3 1:67 to 1:8
1 Triasulfuron 1:4 to 200: 1 1:1 to 67:1 2:1 to 20:1
1 Triaziflam 1:150 to 6: 1 1:50 to 2:1 1: 15 to 1:2
1 Tribenuron-methyl 1:3 to 300: 1 1: 1 to 100: 1 3:1 to 30: 1
1 Triclopyr 1:168 to 6: 1 1:56 to 2:1 1:16 to 1:2
1 Trifloxysulfuron 1:2 to 375: 1 1: 1 to 125: 1 4:1 to 38: 1
1 Trifluralin 1:252 to 4: 1 1:84 to 2: 1 1:25 to 1:3
1 Triflusulfuron-methyl 1: 15 to 60: 1 1:5 to 20:1 1: 1 to 6:1
1 Tritosulfuron 1: 12 to 75: 1 1:4 to 25:1 1: 1 to 8:1
Table A2 is constructed the same as Table Al above except that entries below the "Component (a)" column heading are replaced with the respective Component (a) Column Entry shown below. Compound 1 in the Component (a) column is identified in Index Table A. Thus, for example, in Table A2 the entries below the "Component (a)" column heading all recite "Compound 12" (i.e. Compound 12 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 12 with 2,4-D. Tables A3 through A9 are constructed similarly.
Table Number Component (a) Column Entries Table Number Component (a) Column Entries
A2 Compound 12 Al l Compound 53
A3 Compound 15 A12 Compound 55
A4 Compound 21 A13 Compound 62
A5 Compound 23 A14 Compound 63
A6 Compound 24 A15 Compound 144
A7 Compound 27 A16 Compound 145
A8 Compound 32 A17 Compound 168
A9 Compound 42 A18 Compound 200
A10 Compound 35
Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds are mixtures of a compound of this invention with a herbicide selected from the group consisting of chlorimuron-ethyl, nicosulfuron, diuron, hexazinoe, thifensulfuron-methyl and S-metolachlor.
The compounds of the present invention are useful for the control of weed species that are resistant to herbicides with the AHAS-inhibitor or (b2) [chemical compound that inhibits acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS)] mode of action.
The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Table A for compound descriptions. Mass spectra are reported as the molecular weight of the highest isotopic abundance parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule, observed by mass spectrometry using atmospheric pressure chemical ionization (AP+) or electrospray ionization (ESI). The following abbreviations are used in the Index Table A which follow: Ph is phenyl, pyridyl is pyridinyl, OEt is ethoxy, CN is cyano, , CHO is formyl, t-Bu is tertiary-butyl, z'-Pr is z'so-propyl, c-Pr is cyclopropyl, Me is methyl, Et is ethyl and C(=0)CH3 is acyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
Figure imgf000114_0001
M.S.(AP+)
No. Q (R3)m or m.p.
1 5-Cl-2-pyridyl CI m = 0
2 6-N(CH3)2-3 -pyridyl CI m = 0 327a
3 5-Cl-2-pyrimidinyl CI m = 0 320a
4 3 -pyridyl CI m = 0 285a
5 l,3,4-oxadiazol-2-yl Br m = 0 319
6 l,3,4-oxadiazol-2-yl CI m = 0 275
7 5-oxazolyl CI m = 0 274a
8 4- thiazolyl CI m = 0 290
9 5- thiazolyl CI m = 0 290
10 l-CH3-l#-pyrazol-3-yl CI m = 0
11 l-CH3-l#-pyrazol-4-yl CI m = 0
12 3 -Br-5 -isoxazolyl CI m = 0 352
13 5-thiazolyl CF3 m = 0 324
14 4-thiazolyl CF3 m = 0 324
15 2-Br-5-thiazolyl CF3 m = 0 402 M.S.(AP+)
No. Q R2 (R3)m or m.p.
16 6-Cl-2-pyridyl CI m = 0 319a *
17 6-Cl-2-pyridyl Br m = 0 363a *
18 4-Cl-2-pyrimidinyl CI m = 0 320a *
19 6-CF3-2-pyridyl CI m = 0 352a *
20 2-CF3 -4-pyrmidinyl CI m = 0 353a *
21 2-CF3 -4-pyrmidinyl Br m = 0 398a *
22 6-CF3-3-pyridyl CI 4-CH3 366a
23 5-Cl-2-pyidyl CI 3 -CI *
24 2-CF3-4-pyridyl CI 4-CH3 366
25 4-CF3-2-pyridyl CI m = 0 352
26 4-CF3-2-pyridyl Br m = 0 397
27 5-CF3-2-pyridyl CI m = 0 352
28 5-CF3-2-pyridyl Br m = 0 397
29 l-CH3-3-CF3-l /-pyrazol-5-yl CI m = 0 355
30 1 -CH3 -3 -CF3 - l#-pyrazol-5-yl Br m = 0 399
31 5-CH2OH-3-isoxazolyl CI m = 0 304
32 5-CH2F-3-isoxazolyl CI m = 0 306
33 5 -CHO-3 -isoxazolyl CI m = 0 302
34 5-CH2Cl-3-isoxazolyl CI m = 0 322
35 5-CF2H-3-isoxazolyl CI m = 0 324
36 5-CH2CN-3-isoxazolyl CI m = 0 31 1b
37 5-CH=NOH-3-isoxazolyl CI m = 0 317
38 5-CN-3-isoxazolyl CI m = 0 299a
39 3-CF3-PI1 CI 4-CH3 365
40 3-OCF3-PI1 CI m = 0 367a *
41 3,5-di-Cl-Ph CI m = 0 352a
42 4-OCF3-PI1 CI m = 0 367a
Figure imgf000115_0001
44 3-OCF3-PI1 CI 4-CH3 381a *
45 3-OCF3-PI1 CI 6-OCF3 397a
46 3-OCF3-PI1 CI 3-F 385a *
47 1 -methyl- l /-tetrazol-5-yl CI m = 0 289
48 2-methyl-2 /-tetrazol-5-yl CI m = 0 289
49 1 -methyl- l /-tetrazol-5-yl Br m = 0 334
50 2-methyl-2 /-tetrazol-5-yl Br m = 0 334
51 1 -methyl- IH- 1 ,2,3 -triazol-4-yl CI m = 0 288 M.S.(AP+)
No. Q R2 (R3)m or m.p.
52 1 -methyl- \H- l,2,3-triazol-5-yl CI m = 0 288
53 3-CHF2-5-isoxazolyl CI m = 0 324
54 6-CF3 -4-pyrimidinyl CI m = 0 *
55 5 -CHF2 -3 -isoxazolyl CI 3-F 96-98
56 5-CHO-3-isoxazolyl CI 3-F 137-139
57 5-CH2F-3-isoxazolyl CI 3-F 324
58 3 -CH3 -5 - isoxazolyl CI m = 0 288
59 5 - ( /-Bu) - 3 -i sox azolyl CI m = 0 330
60 5 -CH 3 -3 -isoxazolyl CI m = 0 288
61 2-oxazolyl CI m = 0 274
62 5-CHF2-3-isoxazolyl Br m = 0 89-93
63 3-CF3-5-isoxazolyl CI m = 0 342
64 3 -CF3 -5-isoxazolyl Br m = 0 388
65 3-CHF2-5-isoxazolyl CI 5-F 342
66 3-CHF2-5-isoxazolyl Br 5-F 387
67 3-CClF2-5-isoxazolyl CI m = 0 359
68 3-CHF2-5-isoxazolyl CI 6-F 342
69 3-CHF2-5-isoxazolyl Br 6-F 387
70 2-CH3-4-oxazolyl CI m = 0 288
71 2-CF3-4-pyridinyl CI m = 0 352
72 2-CF3 -4-pyridinyl Br m = 0 396
73 1 -(z-Pr)- IH- 1 ,2,4-triazol-3 -yl CI m = 0 316
74 3-(c-Pr)-5-isoxazolyl CI m = 0 314
75 3-CHF2-5-isoxazolyl CI 4-F 342
76 3-CHF2-5-isoxazolyl Br 4-F 387
77 3,5-di-Me-4-isoxazolyl CI 3-F 320
78 3 , 5 -di-Me-4-isoxazolyl CI m = 0 302
79 2-CH2CF3-2//-l,2,4-triazol-3-yl CI m = 0 102-106
80 2-CF3 -4-pyridinyl F m = 0 336
81 2-CF3 -4-pyridinyl CI 3-F 370
82 2-CF3-4-pyridinyl Br 3-F 414
83 2-CF3 -4-pyridinyl CH3 3-F 350
84 3-CF3-5-isoxazolyl CI 4-F 360
85 3 -CF3 -5 -isoxazolyl Br 4-F 405
86 5-(C≡CH)-3-isoxazolyl CI m = 0 156-160
87 2-CF3 -4-pyridinyl F 3-F 354 M.S.(AP+) o. Q R2 (R3)m or m.p.
88 5-(OCH2CF2H)-3-isoxazolyl CI m = 0 352
89 1 -Et-3-CF3 - l#-pyrazol-5-yl CI 3-CN 394
90 l-(/-Pr)-3-CF3-l//-pyrazol-5-yl CI 3-CN 408
91 5-(CH=CF2)-3-isoxazolyl CI 3-F 354
92 3-(c-Pr)-5-isoxazolyl Br m = 0 359
93 1 -CH2CF3 - IH- 1 ,2,4-triazol-3 -yl CI m = 0 155-158
94 5-(OCH2CF3)-3-isoxazolyl CI m = 0 85-89
95 3-CHF2-5-isoxazolyl CF3 3-F 376
96 5-CHF2-3-isoxazolyl CI 3-Cl, 4-F 376
97 5-CHCl2-3-isoxazolyl CI m = 0 88-91
98 3-CHF2-5-isoxazolyl CF3 m = 0 358
99 5-(C≡CCF3)-3-isoxazolyl CI m = 0 63-65
100 3 -CHF2- 1 ,2,4-oxadiazol-5-yl CI m = 0 107-109
101 3-CHF2-5-isoxazolyl CI 3-CH3 338
102 3-CHF2-5-isoxazolyl Br 3-CH3 383
103 3-CHF2-5-isoxazolyl CI 3-OMe 354
104 3 -CF3 -5-isoxazolyl CI 3-OMe 372
105 5 -CF3 -3 -isoxazolyl CI 3-OMe 372
106 5-CH3-l,3,4-oxadiazol-2-yl CI m = 0 289
107 3-CHF2-5-isoxazolyl CI 3,5-di-F 358
108 3-CH(OEt)2-5-isoxazolyl CI m = 0 398c
109 5-CHF2-3-isoxazolyl CI 3-OMe 354
1 10 3-CH3-5-isoxazolyl CI 3-OMe 318
1 1 1 3-CH3-5-isoxazolyl F 3-OMe 302
1 12 3-thienyl CI 3-CN 103-105
1 13 5-CHF2-3-isoxazolyl CI 3,4-di-F 102-105
1 14 5-CHF2-3-isoxazolyl CI 3 -Br, 4-F 420
1 15 l-CH3-l#-l,2,4-triazol-3-yl CI m = 0 1 19-122
1 16 5-CHClF-3-isoxazolyl CI m = 0 108-1 12
1 17 1 -CH3 - IH- 1 ,2,4-triazol-5-yl CI m = 0 134-138
1 18 5-CHF2-3-isoxazolyl Br 3-F 386
1 19 3 -Br-5 -isoxazolyl Br m = 0 398
120 3-CHF2-5-isoxazolyl CI 3-Cl 359
121 3-CHF2-5-isoxazolyl Br 3-Cl 403
122 5-(c-Pr)- 1 ,3 ,4-oxadiazol-2-yl CI m = 0 315
123 1 -(z'-Pr)- IH- 1 ,2,4-triazol-5-yl CI m = 0 316 M.S.(AP+) o. Q 2 (R3)m or m.p.
124 3-CF3-5-isoxazolyl CI 5-F 360
125 3-CF3-5-isoxazolyl Br 5-F 405
126 3 -CF3 -5 -isoxazolyl CI 3 -CI 377
127 3 -CF3 -5 -isoxazolyl Br 3 -CI 421
128 3 -(CH2OCH2CF3 )-5-isoxazolyl CI m = 0 386
129 3-(CH2OCH2CF3)-5-isoxazolyl Br m = 0 430a
130 5-(c-Pr)-3-isoxazolyl CI 3-F 332
131 5 -CHF2 -3 -isoxazolyl CI 3-OCHF2 390
132 3-CHF2-5-isoxazolyl CI 3-OCHF2 390
133 5-CHFCF3-3-isoxazolyl CI m = 0 374
134 3,5-di-Me-4-isoxazolyl CI 3-CN *
135 5-Cl-2-pyridinyl CI 3 -Br *
136 2-Me-5-CF3-2 /-pyrazol-3-yl CI 3-CN 380
137 4-CF3-2-thiazolyl CI m = 0 358
138 4-CF3-2-thiazolyl I m = 0 450
139 4-CF3-2-thiazolyl Br m = 0 403
140 5-CHO-3-furanyl CI m = 0 *
141 5-CHF2-3-furanyl CI m = 0 *
142 5-CF2CF3 -3 -isoxazolyl CI m = 0 392
143 5-CF2Cl-3-isoxazolyl CI m = 0 358
144 3-CHF2-5-isoxazolyl CI 3-F 342
145 3-CHF2-5-isoxazolyl Br 3-F 387
146 l-Me-5-CF3-l#-pyrazol-3-yl CI 3-CN 380
147 1 -Me-5-CF3 - l /-pyrazol-3 -yl CI 3 -Br 434
148 5-C02Et-3-isoxazolyl CI m = 0 346
149 5-CF2CH3-3-isoxazolyl Br m = 0 *
150 5-C(=0)CH3-3-isoxazolyl Br m = 0 360
151 1 -Me- l//-imidazol-2-yl CI m = 0 287
152 1 -Me- li/-imidazol-2-yl Br m = 0 332
153 5-CH3-3-isoxazolyl CI m = 0 288
154 5-isoxazolyl CI m = 0 274
155 5-isoxazolyl Br m = 0 319
156 5-CF3-3-isoxazolyl CI 3-1 *
157 5-CF3-3-isoxazolyl CI 3-CN 367
158 4-CF3 -2-pyridinyl CI 3-CN 377
159 4-CF3-2-pyridinyl CI 3 -CI 386 M.S.(AP+) o. Q R2 (R3)m or m.p.
160 5-CF3-2-pyridinyl CI 3 -CI 386
161 1 -CH2CF3- l#-imidazol-4-yl CI m = 0 *
162 5-CBrF2-3-isoxazolyl CI m = 0 402
163 2-pyrazinyl CI m = 0 79-82
164 2-pyrazinyl F m = 0 95-97
165 2-pyrazinyl CI 3-F 303
166 2-pyrazinyl F 3-F 287
167 4-Me-5-CF3-3-isoxazolyl CI m = 0 356
168 5 -CF3 -3 -isoxazolyl CI 3-F 360
169 5 -CF3 -3 -isoxazolyl CI 3 -CI 376
170 5 -CF3 -3 -isoxazolyl CI 3 -Br 420
171 3 -CH3 -5-isothiazolyl CI m = 0 304
172 1 ,2,4-thiadiazol-5-yl CI m = 0 132-135
173 5 -CF2CH3 -3 -isoxazolyl CH3 m = 0 *
174 4-Cl-2-pyridinyl CI m = 0 319
175 4-F-2-pyridinyl CI m = 0 302
176 3-(OCH2CF3)-5-isoxazolyl CI m = 0 372
177 3-Et-5-isoxazolyl CI m = 0 318
178 3 -CF2CH3 -5 -isoxazolyl CI m = 0 338
179 5-CHF2-3-isoxazolyl CI 3 -CI 358
180 5-CHF2-3-isoxazolyl CI 3-CN 349
181 5-Br-2-thienyl CI m = 0 368
182 2-thienyl CI m = 0 290
183 5-(c-Pr)-3-isoxazolyl CI m = 0 314
184 6-CHF2-4-pyrimidinyl CI m = 0 334
185 3 -isoxazolyl CI m = 0 274
186 6-C1-3 -pyridazinyl CI m = 0 319
187 4-Me-2-pyridinyl CI m = 0 298
188 4-CN-2-pyridinyl CI m = 0 309
189 5-Cl-3-pyridazinyl CI m = 0 320
190 6-Cl-4-pyrimidinyl CI m = 0 320
191 5 -CH2F-3 -isoxazolyl CI 3 -Br 384
192 5-Cl-3-isothiazolyl CI m = 0 86-88
193 5-Cl-3-isothiazolyl F m = 0 100-102
194 5-Cl-3-isothiazolyl CH3 m = 0 78-82
195 5-CHO-3-isoxazolyl CI 3 -Br 379 M.S.(AP+)
No. Q R2 (R3)m or m.p.
196 3-C(CH3)=CH2-5-isoxazolyl CI m = 0 314
197 3-C(CH3)=CH2-5-isoxazolyl Br m = 0 359
198 5-CFCl2-3-isoxazolyl CI m = 0 374
199 2-thiazolyl CI m = 0 290
200 5 -CF3 -3 -isoxazolyl CI m = 0 342
201 3-N02,5-Cl-2-pyridinyl CI m = 0 363a
202 5-Cl-2-pyridinyl CI 3-CN 344
203 5-Cl-2-pyridinyl CI 5-Br 398
204 5-Cl-2-pyridinyl Br 3-CN 388
205 5-Cl-2-pyridinyl CI 3-1 445
206 5-CF3-3-isoxazolyl F m = 0 326
207 5-Cl-2-pyridinyl F 3-CN 327
208 5-Cl-2-pyridinyl CI 3-& 464
209 4-Br- l /-pyrazol- 1 -yl CI 6-CN 377
210 3-CHF2-5-isoxazolyl F m = 0 308
21 1 3-CHF2-5-isoxazolyl CH3 m = 0 304
212 3-CHF2-5-isoxazolyl Br m = 0 369
213 3 -CHF2-5-isoxazolyl OMe m = 0 320
214 4-oxazolyl CI m = 0 274
215 5-C(=0)CH3 -3 -isoxazolyl CI m = 0 316
216 4-CH3-2-thienyl CI m = 0 303
217 1 -CH2CF3- l^-imidazol-4-yl CI 3-F 373
218 3 -C(=0)CH3 -5-isoxazolyl CI m = 0 316
219 4-OMe-2-pyridinyl CI m = 0 314
220 5 -CF2CH3 -3 -isoxazolyl CI m = 0 338
221 5-CFCl2-3-isoxazolyl CI 4-F 129-132
222 5-CN-3-isoxazolyl CI 3-F 317
223 3-CN-5-isoxazolyl CI m = 0 297
224 3 -CH2F -5 -isoxazolyl CI m = 0 306
225 3-C02Et-5-isoxazolyl CI m = 0 346
226 5-CFH2-3-isoxazolyl CI m = 0 320
227 6-OCH2CF3 -4-pyrimidinyl CI m = 0 383
228 3 -CF3 -5 -isoxazolyl CI 3-F 360
229 3 -CH3 -5 -isoxazolyl CI 3-F 306
230 3 -CH3 -5-isoxazolyl Br 3-F 351
231 3-thienyl CI m = 0 289 M.S.(AP+)
No. Q R2 (R3)m or m.p.
232 3-thienyl Br m = 0 334
233 5-isothiazolyl CI m = 0 290
234 5-isothiazolyl Br m = 0 335
235 5-C02 e-3-isoxazolyl CI m = 0 332
236 5-CF(CH3)2-3-isoxazolyl CI m = 0 334
237 1 -Me-5-CF3 - l#-pyrazol-3 -yl CI m = 0 355
a ES+ b AP-, CM+Na.
* See Index Table B for lR NMR data.
& 4-Br-l /-pyrazol-l-yl
INDEX TABLE B
Cmpd ^H NMR (CDCI3 solution unless indicated otherwise)2
I 8.54 (d, IH), 8.39 (s, 2H), 7.87 (d, IH), 7.69 (d, IH), 7.60 (m, IH), 7.50 (m, IH), 7.42 (m, IH), 7.24 (d, IH)
10 8.43 (s, 2H), 8.03 (m, 2H), 7.36 (m, 2H), 7.26 (m, IH), 7.19 (m, IH), 6.56 (s, IH), 3.85 (s, 3H)
I I 8.45 (s, 2H), 7.77 (s, IH), 7.72 (s, IH), 7.62 (m, IH), 7.32 (m, 2H), 7.18 (m, IH), 3.86 (s, 3H)
16 8.41 (s, 2H), 7.88 (m, IH), 7.64 (m, IH), 7.59 (m, IH), 7.50 (m, IH), 7.40 (m, IH), 7.24 (m, IH), 7.18 (m, IH)
17 8.49 (s, 2H), 7.88 (m, IH), 7.64 (m, IH), 7.58 (m, IH), 7.50 (m, IH), 7.41 (m, IH), 7.25 (m, IH), 7.17 (m, IH)
18 8.55 (m, IH), 8.43 (s, 2H), 8.05 (m, IH), 7.75 (m, IH), 7.58 (m, IH), 7.45 (m, IH), 7.26 (m, IH)
19 8.41 (s, 2H), 7.89 (m, 2H), 7.82 (m, IH), 7.54 (m, 2H), 7.43 (m, lH), 7.26 (m, IH)
20 8.82 (m, IH), 8.52 (s, 2H), 8.06 (m, IH), 7.96 (m, IH), 7.61 (m, IH), 7.48 (m, IH), 7.30 (m, IH)
21 8.83 (d, IH), 8.52 (s, 2H), 8.08 (m, IH), 7.97 (d, IH), 7.62 (m,lH), 7.47 (m, IH), 7.30 (m, IH) 23 8.52 (m, IH), 8.40 (s, 2H), 7.66 (m, IH), 7.43 (m, 2H), 7.33 (m, IH), 7.18 (m, IH)
40 8.26 (s, 2H), 7.39 (m, 2H), 7.32 (m, 2H), 7.27 (m, IH), 7.24 (s, IH), 7.17 (m, IH), 7.02 (d, IH)
44 8.33 (s, 2H), 7.39 (s, IH), 7.28-7.34 (m, 2H), 7.25 (m, 2H), 7.12 (d, IH), 7.07 (m, IH), 2.43 (s, 3H)
46 (300 MHz) 8.33 (S, 2H), 7.43 (m, IH), 7.34 (m, 2H), 7.22 (s, IH), 7.10 (m, 3H)
54 9.42 (s, lH), 8.43 (s,2H), 8.12 (s,lH), 8.05 (d, lH), 7.72 (m,lH), 7.53 (m, lH), 7.32 (m,lH)
134 8.36 (s, 2 H), 7.74 (m, 1 H), 7.62 (m, 1 H), 7.48 - 7.56 (m, 1 H), 2.33 (s, 3 H), 2.22 (s, 3 H)
135 7.22 (m, IH), 7.31 (m, IH), 7.36 (m, IH), 7.65 (m, 2H), 8.40 (s, 2H), 8.52 (m, IH)
140 9.60 (s, lH), 8.44 (s,2H), 8.05 (s,lH), 7.59 (d, lH), 7.54 (s,lH), 7.43 (t,lH), 7.37 (t,lH), 7.23 (d,lH)
141 8.43 (s,2H), 7.86 (s,lH), 7.57 (d,lH), 7.37 (t,lH), 7.34 (t,lH), 7.22 (d,lH), 6.98 (s, lH), 6.57 (t,lH) 149 8.54 (2, 2H), 7.96 (dd, 1H), 7.49-7.63 (m, 1H), 7.42 (t, 1H), 7.26-7.29 (m, 1H), 6.86 (t, 1H), 2.00 (t, 3H)
156 7.06 - 7.08 (m, 1 H) 7.18 (s, 1 H) 7.93 (s, 1 H) 8.01 - 8.06 (m, 1 H) 8.46 (s, 2 H)
161 8.34 (s,2H), 6.59 (s,lH), 6.56 (t,lH), 6.40-6.48 (m,2H), 7.28 (d, lH), 6.92 (s,lH), 6.55 (q,2H)
173 8.34 (s, 2H), 7.99 (dd, 1H), 7.51-7.59 (m, 1H), 7.38 (dt, 1H), 7.26-7.31 (m, 1H), 6.90 (t, 1H), 2.25 (s, 3H), 1.99 (t, 3H)
z NMR data are in ppm downfield from tetramethylsilane at 500 MHz unless otherwise indicated.
Couplings are designated by (s)-singlet, (d)-doublet and (m)-multiplet.
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
Seeds of plant species selected from downy bromegrass (Bromus tectorum), cocklebur (common cocklebur, Xanthium strumarium), wild oat (Avena fatua), barnyardgrass (Echinochloa crus-galli), large (Lg) crabgrass {Digitaria sanguinalis), giant foxtail {Setaria faberii), morningglory {Ipomoea spp.), velvetleaf {Abutilon theophrasti), and sorghum {Sorghum vulgare) were planted into a sandy loam soil and treated preemergence by soil drench using test a chemical formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time these species were also treated postemergence sprayed to runoff using a test chemical formulated in the same manner.
Plants ranged in height from 2 to 18 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately 11 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table A Compound Table A Compo"
1000 g ai/ha 39 2000 g ai/ha 39
Post Sprayed to Runoff Pre Soil Drench
Barnyardgrass 50 Barnyardgrass 90
Bromegrass, Downy 20 Bromegrass, Downy 70
Cocklebur 40 Cocklebur 0
Crabgrass, Large 50 Crabgrass, Large 90
Foxtail, Giant 30 Foxtail, Giant 100
Morningglory 30 Morningglory 0
Oat, Wild 20 Oat, Wild 90
Sorghum 30 Sorghum 50
Velvetleaf 60 Velvetleaf 70 TEST B
Seeds of plant species selected from barnyardgrass {Echinochloa crus-galli), kochia (Kochia scoparia), ragweed (common ragweed, Ambrosia elatior), Italian ryegrass (Lolium multiflorum), large (Lg) crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberii), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), and corn (Zea mays) were planted into a blend of loam soil and sand and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these crop and weed species and also blackgrass (Alopecurus myosuroides), and galium (catchweed bedstraw, Galium aparine) were planted in pots containing the same blend of loam soil and sand and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 10 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately 10 days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table B, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table B Compounds
1000 g ai/ha 1 2 3 5 6 7 8 9 10 12 23 31 33 34
Postemergence
Barnyardgrass 70 0 50 20 0 10 0 10 10 40 50 10 0 0
Blackgrass
Corn 10 0 10 0 0 10 0 10 0 0 20 0 0 0
Crabgrass, Large 70 0 10 0 20 20 10 50 10 30 60 50 10 10
Foxtail, Giant 80 0 20 0 0 20 0 20 10 40 70 30 10 0
Galium
Kochia
Morningglory 60 40 60 20 20 40 10 50 10 30 70 30 10 0
Pigweed 100 70 70 70 70 20 70 60 50 100 100 30 10 40
Ragweed
Ryegrass, Italian
Velvetleaf 100 50 100 30 30 10 30 40 20 90 70 30 0 20
Wheat 0 0 10 0 0 10 0 10 0 10 0 0 0 0
Table B Compounds
1000 g ai/ha 35 36 40 46 55 57 61 148 171 172 186 191 192 193
Postemergence Barnyardgrass 100 90 30 90 100 100 10 10 30 10 0 100 100 90
Blackgrass - - - - 100 90 10 80 0 20 100 90 90
Corn 90 50 20 20 100 90 0 10 10 0 60 30 10
Crabgrass, Large 100 80 50 100
Foxtail, Giant 90 90 50 100 100 100 10 100 10 30 100 90 90
Galium - - - - 100 90 0 100 10 20 100 100 100
Kochia - - - - 100 90 0 100 30 30 100 100 100
Morningglory 100 20 100 70
Pigweed 100 90 100 100 100 100 0 100 80 20 100 100
Ragweed - - - - 100 100 0 30 10 50 90 60
Ryegrass, Italian - - - - 100 80 0 10 0 0 100 50 30
Velvetleaf 100 100 100 100
Wheat 80 50 10 20 100 90 0 30 0 0 30 30 20
Table B Compounds Table B Compounds
1000 g ai/ha 194 195 235 1000 g ai/ha 194 195 235
Postemergence Postemergence
Barnyardgrass 100 10 0 Morningglory
Blackgrass 90 0 0 Pigweed 90 50 0
Corn 60 10 0 Ragweed 80 10 0
Crabgrass, Large - - - Ryegrass, Itali 50 10 0
Foxtail, Giant 90 10 0 Velvetleaf
Galium 100 10 0 Wheat 20 0 0
Kochia 100 10 0
Table B Compounds
500 g ai/ha 4 10 11 13 14 16 17 18 19 20 21 22 23 24 Postemergence
Barnyardgrass 10 0 10 0 0 0 0 0 0 0 60 0 50 60
Blackgrass
Corn - 0 0 10 30 0 0 0 0 0 40 0 20 40
Crabgrass, Large 50 0 10 10 10 0 0 0 0 20 30 10 50 90
Foxtail, Giant 30 0 0 0 10 0 0 0 0 20 60 0 70 90
Galium
Kochia
Morningglory 30 30 20 10 0 - - 0 0 50 90 10 40 100
Pigweed 100 20 20 40 50 30 10 0 0 90 100 0 100 40
Ragweed
Ryegrass, Italian Velvetleaf 60 20 20 60 30 20 20 0 0 30 40 60 70 70
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
500 g ai/ha 25 26 27 28 29 30 32 37 41 42 43 44 45 47
Postemergence
Barnyardgrass 30 20 50 50 0 0 90 0 20 30 20 20 20 0
Blackgrass - - - - - - - 0 - - - - - 0
Corn 30 20 30 20 0 0 50 0 10 20 10 20 10 0
Crabgrass, Large 50 30 90 40 10 10 90 - 20 50 20 20 40 -
Foxtail, Giant 60 30 70 40 0 10 90 10 20 30 20 10 20 50
Galium - - - - - - - 0 - - - - - 60
Kochia - - - - - - - 0 - - - - - 80
Morningglory 70 50 50 30 0 10 90 - 10 60 20 30 30 -
Pigweed 90 80 100 100 10 10 100 20 70 80 70 50 60 70
Ragweed - - - - - - - 0 - - - - - 30
Ryegrass, Italian - - - - - - - 0 - - - - - 0
Velvetleaf 80 80 100 100 0 30 100 - 30 100 70 70 60 -
Wheat 10 10 0 0 0 0 60 0 0 0 0 0 0 10
Table B Compounds
500 g ai/ha 48 49 50 51 52 53 54 58 59 60 62 63 64 123
Postemergence
Barnyardgrass 0 10 0 0 10 100 100 90 10 100 100 100 100 0
Blackgrass 60 10 60 50 10 100 80 90 40 100 - - - 0
Corn 10 10 0 0 10 70 0 50 10 90 50 20 30 0
Crabgrass, Large 90 90 90 -
Foxtail, Giant 40 10 10 50 0 100 100 90 50 100 90 80 80 0
Galium 100 60 100 90 50 100 100 100 90 100 - - - 0
Kochia 100 30 80 100 50 100 100 100 20 100 - - - 0
Morningglory 100 100 100 -
Pigweed 100 30 100 80 60 100 100 100 50 100 100 100 100 0
Ragweed 70 30 60 60 20 90 60 100 0 90 - - - 0
Ryegrass, Italian 0 0 50 0 0 100 60 80 0 80 - - - 0
Velvetleaf 100 100 100 -
Wheat 0 20 20 10 20 80 0 50 10 90 30 50 10 0
Table B Compounds
500 g ai/ha 134 135 136 137 138 139 151 152 153 156 157 158 159 160
Postemergence Barnyardgrass 90 40 90 10 0 0 0 0 70 20 60 100 20 80
Blackgrass - - - 0 0 0 0 0 90 40 90 90 30 90
Corn 80 30 70 20 0 0 0 0 40 40 40 90 30 90
Crabgrass, Large 100 50 90
Foxtail, Giant 90 60 80 20 0 0 0 0 90 90 80 100 70 100
Galium - - - 20 0 0 0 0 100 100 100 100 100 100
Kochia - - - 60 0 0 0 0 90 90 100 90 80 90
Morningglory 90 50 90
Pigweed 100 100 100 90 0 0 0 0 100 100 100 100 100 100
Ragweed - - - 0 0 0 0 0 100 40 50 30 0 30
Ryegrass, Italian - - - 0 0 0 0 0 60 70 100 70 0 90
Velvetleaf 90 80 100
Wheat 30 10 40 0 0 0 0 0 50 30 70 70 20 80
Table B Compounds
500 g ai/ha 161 167 168 169 170 179 180 181 182 183 184 185 190 199
Postemergence
Barnyardgrass 0 10 100 30 20 80 90 20 10 70 50 40 0 0
Blackgrass 0 10 90 90 60 100 90 10 10 90 60 50 0 -
Corn 0 20 100 20 20 40 70 10 20 30 20 10 0 0
Crabgrass, Large 10
Foxtail, Giant 0 10 100 60 50 80 100 20 50 80 70 70 0 0
Galium 0 60 100 100 100 100 100 50 50 100 100 70 10 -
Kochia 0 60 90 90 100 100 100 50 80 100 100 100 0 -
Morningglory 10
Pigweed 0 70 100 100 100 100 100 90 80 100 100 100 20 30
Ragweed 0 0 90 30 50 30 70 10 10 30 40 100 10 -
Ryegrass, Italian 0 0 90 50 20 100 100 0 0 70 20 0 0 -
Velvetleaf 10
Wheat 0 20 100 0 30 90 90 0 0 60 10 0 0 0
Table B Compounds
500 g ai/ha 200 201 202 203 204 205 206 207 208 209 215 217
Postemergence
Barnyardgrass 100 0 40 0 10 10 10 70 20 0 90 0
Blackgrass 40 0
Corn 90 0 30 0 0 10 0 0 0 0 40 0
Crabgrass, Large 100 0 70 0 40 20 20 30 0 30 - -
Foxtail, Giant 100 0 80 0 30 20 20 30 0 30 80 0 Galium 70 30
Kochia 10 30
Morningglory 100 0 40 0 10 10 30 30 0 30 - -
Pigweed 100 0 100 0 90 90 70 100 60 100 100 60
Ragweed 20 30
Ryegrass, Italian 50 0
Velvetleaf 100 0 30 0 10 10 60 60 30 30 - -
Wheat 100 0 0 0 0 0 0 0 0 0 20 0
Table B Compounds
125 g ai/ha 4 10 11 13 14 15 16 17 18 19 20 21 22 23
Postemergence
Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Blackgrass
Corn - 0 0 0 0 0 0 0 0 0 0 0 0 10
Crabgrass, Large 20 0 10 0 0 10 0 0 0 0 0 0 0 10
Foxtail, Giant 0 0 0 0 0 0 0 0 0 0 0 0 0 10
Galium
Kochia
Morningglory 0 20 10 0 0 10 - - 0 0 0 20 0 20
Pigweed 30 0 10 0 0 70 0 0 0 0 40 80 0 70
Ragweed
Ryegrass, Italian
Velvetleaf 30 0 10 30 20 0 0 0 0 0 0 20 50 40
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 24 25 26 27 28 29 30 32 38 41 42 43 44 45
Postemergence
Barnyardgrass 0 0 0 20 0 0 0 70 0 0 20 0 10 0
Blackgrass - - - - - - - - 0 - - - - -
Corn 0 10 10 0 0 0 0 10 0 0 20 0 0 0
Crabgrass, Large 80 10 10 20 20 0 0 60 - 10 30 0 10 10
Foxtail, Giant 30 0 0 20 20 0 0 70 0 10 10 0 0 10
Galium - - - - - - - - 30 - - - - -
Kochia - - - - - - - - 30 - - - - -
Morningglory 50 10 10 10 0 0 0 70 - 0 20 0 20 30
Pigweed 20 30 30 50 30 0 0 100 20 40 60 30 20 10
Ragweed - - - - - - - - 0 - - - - - Ryegrass, Italian - - - - - - - - 0 - - - - -
Velvetleaf 40 20 10 70 40 0 10 90 - 10 100 20 30 50
Wheat 0 0 0 0 0 0 0 30 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 47 48 49 50 51 52 53 54 58 59 60 62 63 64
Postemergence
Barnyardgrass 0 0 0 0 0 0 100 20 70 10 50 90 80 90
Blackgrass 0 40 0 40 0 0 100 70 70 0 50 - - -
Corn 0 0 0 0 0 0 10 0 0 0 30 10 20 20
Crabgrass, Large 70 80 60
Foxtail, Giant 0 0 0 0 10 0 100 80 70 10 50 80 70 60
Galium 30 70 20 90 60 40 100 100 100 40 100 - - -
Kochia 60 50 30 60 70 20 100 100 100 0 90 - - -
Morningglory 90 100 70
Pigweed 50 70 10 70 70 30 100 100 100 40 100 100 100 100
Ragweed 20 50 30 20 20 20 60 50 100 0 60 - - -
Ryegrass, Italian 0 0 0 0 0 0 80 30 20 0 0 - - -
Velvetleaf 100 100 100
Wheat 0 0 10 0 0 0 40 0 0 0 30 0 0 0
Table B Compounds
125 g ai/ha 70 73 89 90 91 96 97 103 104 105 106 107 108 109
Postemergence
Barnyardgrass 0 0 30 0 0 30 20 40 60 70 0 0 0 90
Blackgrass 0 0 20 0 0 70 0 90 100 100 0 0 0 90
Corn 0 0 30 0 0 20 20 30 30 20 0 0 10 60
Crabgrass, Large
Foxtail, Giant 0 0 40 0 0 50 30 70 80 80 0 0 0 90
Galium 0 10 50 30 0 100 50 100 100 100 0 0 50 100
Kochia 0 0 70 10 0 100 90 30 80 70 0 0 0 30
Morningglory
Pigweed 20 10 90 10 0 100 90 80 90 100 0 0 0 100
Ragweed 0 0 10 0 0 60 50 60 10 30 0 0 0 90
Ryegrass, Italian 0 0 0 0 0 60 0 10 30 10 0 0 0 50
Velvetleaf
Wheat 0 0 0 0 0 0 0 0 10 10 0 0 0 10
Table B Compounds
125 g ai/ha 110 111 112 113 114 115 116 117 118 119 120 121 122 123 Postemergence
Barnyardgrass 50 10 30 90 20 0 30 0 100 0 90 90 0 0
Blackgrass 40 40 20 90 40 0 30 0 100 0 90 80 0 0
Corn 10 10 20 30 50 0 40 0 100 0 40 40 0 0
Crabgrass, Large
Foxtail, Giant 70 60 60 90 60 0 90 0 100 10 90 90 0 0
Galium 70 20 50 100 100 0 70 0 100 60 100 100 20 0
Kochia 50 30 70 100 90 0 90 0 100 30 90 90 20 0
Morningglory
Pigweed 30 20 30 100 100 0 100 0 100 80 100 100 20 0
Ragweed 40 20 30 80 20 0 40 0 50 10 70 60 10 0
Ryegrass, Italian 0 0 0 70 60 0 30 0 80 0 90 70 0 0
Velvetleaf
Wheat 0 0 0 10 20 0 20 0 60 0 40 30 20 0
Table B Compounds
125 g ai/ha 124 125 126 127 128 129 130 131 132 133 134 135 137 138
Postemergence
Barnyardgrass 20 30 100 100 10 10 100 90 50 60 20 10 0 0
Blackgrass 30 30 90 90 20 0 80 80 50 70 - - 0 0
Corn 10 10 70 50 10 10 40 40 30 30 10 10 0 0
Crabgrass, Large 10 10 - -
Foxtail, Giant 20 20 90 90 10 10 80 90 70 50 10 10 0 0
Galium 100 100 100 100 30 10 90 90 90 100 - - 0 0
Kochia 80 80 90 90 50 10 90 70 60 90 - - 0 0
Morningglory 10 20 - -
Pigweed 90 90 100 100 60 30 100 100 100 100 60 100 30 0
Ragweed 20 20 40 50 10 0 60 70 30 30 - - 0 0
Ryegrass, Italian 0 10 100 90 0 0 60 70 40 30 - - 0 0
Velvetleaf 40 40 - -
Wheat 0 0 40 20 0 0 40 30 10 10 10 0 0 0
Table B Compounds
125 g ai/ha 139 140 141 142 143 144 145 146 147 149 150 151 152 153
Postemergence
Barnyardgrass 0 0 0 0 90 100 100 20 0 40 20 0 0 0
Blackgrass 0 0 0 0 60 90 90 30 0 60 10 0 0 40
Corn 0 0 30 20 30 90 70 0 0 20 10 0 0 30
Crabgrass, Large Foxtail, Giant 0 0 0 0 80 100 90 20 0 60 10 0 0 20
Galium 0 0 0 10 100 100 100 50 0 90 10 0 0 90
Kochia 0 0 0 20 100 100 100 60 0 100 0 0 0 90
Morningglory
Pigweed 0 0 20 20 100 100 100 60 0 100 20 0 0 100
Ragweed 0 0 0 0 20 60 50 0 0 20 0 0 0 20
Ryegrass, Italian 0 0 0 0 50 100 80 0 0 20 0 0 0 30
Velvetleaf
Wheat 0 0 0 0 30 90 70 0 0 10 0 0 0 30
Table B Compounds
125 g ai/ha 154 155 156 157 158 159 160 161 162 163 164 165 166 167
Postemergence
Barnyardgrass 0 0 0 20 60 0 0 0 90 0 0 20 0 0
Blackgrass 0 0 20 70 30 0 50 0 30 20 0 30 0 0
Corn 0 0 20 0 30 20 30 0 40 10 0 0 10 0
Crabgrass, Large
Foxtail, Giant 0 0 20 70 50 0 30 0 90 10 0 20 0 0
Galium 0 0 90 100 30 70 70 0 90 30 30 40 30 10
Kochia 0 0 90 90 70 20 40 0 100 50 0 40 0 10
Morningglory
Pigweed 0 0 90 100 80 90 90 0 100 30 30 50 30 10
Ragweed 0 0 20 10 0 0 0 0 40 30 30 60 30 0
Ryegrass, Italian 0 0 30 90 0 0 0 0 50 0 0 0 0 0
Velvetleaf
Wheat 0 0 20 50 20 20 20 0 30 0 0 0 0 10
Table B Compounds
125 g ai/ha 168 169 170 173 174 175 176 177 178 179 180 181 182 183
Postemergence
Barnyardgrass 100 10 0 70 10 10 30 30 40 10 50 10 0 40
Blackgrass 90 50 50 70 50 0 30 30 40 80 90 0 0 80
Corn 100 10 20 40 0 0 30 10 20 10 20 10 10 10
Crabgrass, Large
Foxtail, Giant 100 30 30 90 0 0 50 40 60 40 80 0 0 60
Galium 100 100 80 90 70 40 90 100 100 100 100 10 30 100
Kochia 90 90 70 100 70 30 100 70 100 90 100 30 30 100
Morningglory
Pigweed 100 100 100 80 50 60 100 100 100 100 100 50 40 100 Ragweed 90 20 10 60 30 30 20 20 10 10 50 10 0 20
Ryegrass, Italian 90 20 0 20 0 0 10 0 30 90 100 0 0 40
Velvetleaf
Wheat 100 0 0 0 0 0 0 0 10 40 60 0 0 10
Table B Compounds
125 g ai/ha 184 185 187 188 189 190 196 197 198 199 200 201 202 203
Postemergence
Barnyardgrass 0 10 0 20 0 0 10 0 50 0 90 0 10 0
Blackgrass 10 0 0 20 0 0 0 0 40 - - - - -
Corn 10 0 0 30 0 0 0 0 20 0 50 0 0 0
Crabgrass, Large 0 100 0 10 0
Foxtail, Giant 10 10 0 20 0 0 10 0 90 0 100 0 30 0
Galium 70 40 0 50 0 0 100 50 100 - - - - -
Kochia 70 90 0 90 0 0 40 0 80 - - - - -
Morningglory 0 90 0 10 0
Pigweed 90 90 0 60 0 0 60 10 100 10 100 0 90 0
Ragweed 20 70 0 20 0 10 20 0 20 - - - - -
Ryegrass, Italian 0 0 0 0 0 0 0 0 50 - - - - -
Velvetleaf 0 100 0 10 0
Wheat 0 0 0 20 0 0 0 0 10 0 60 0 0 0
Table B Compounds
125 g ai/ha 204 205 206 207 208 209 210 211 212 213 214 215 216 217
Postemergence
Barnyardgrass 0 0 0 0 0 0 0 10 30 0 0 20 10 0
Blackgrass - - - - - - 30 50 50 10 0 0 10 0
Corn 0 0 0 0 0 0 10 10 20 10 0 20 10 0
Crabgrass, Large 10 10 10 0 0 10
Foxtail, Giant 0 0 0 0 0 0 40 50 70 20 0 20 0 0
Galium - - - - - - 90 100 100 80 10 20 50 10
Kochia - - - - - - 80 90 100 100 0 0 20 10
Morningglory 0 0 20 10 0 30
Pigweed 50 60 40 70 20 90 80 50 100 80 10 20 30 10
Ragweed - - - - - - 30 30 60 60 0 0 0 10
Ryegrass, Italian - - - - - - 0 0 20 0 0 0 0 0
Velvetleaf 0 0 30 10 20 30
Wheat 0 0 0 0 0 0 20 0 10 10 0 0 0 0 Table B Compounds
125 g ai/ha 218 219 220 221 222 223 224 225 226 227 228 229 230 231
Postemergence
Barnyardgrass 0 0 40 90 0 10 50 0 70 60 70 70 60 10
Blackgrass 0 0 90 60 10 0 70 0 70 70 100 80 70 0
Corn 0 0 20 50 30 0 20 0 30 20 30 30 10 0
Crabgrass, Large
Foxtail, Giant 0 0 80 90 0 10 50 0 70 60 90 80 70 10
Galium 10 30 100 100 90 50 100 0 100 80 100 100 100 20
Kochia 0 0 100 100 30 10 100 0 100 80 100 100 100 40
Morningglory
Pigweed 40 10 100 90 100 60 100 0 100 90 100 100 90 40
Ragweed 0 30 10 50 20 10 100 0 40 30 40 100 100 0
Ryegrass, Italian 0 0 40 40 0 0 0 0 50 30 90 20 0 0
Velvetleaf
Wheat 0 0 50 30 20 0 0 0 50 20 50 40 10 0
Table B Compounds
125 g ai/ha 232 233 234 236 237 238 239
Postemergence
Barnyardgrass 0 10 0 30 0 30 0
Blackgrass 0 10 10 40 0 0 0
Corn 0 10 10 30 0 20 20
Crabgrass, Large - - - - - - -
Foxtail, Giant 0 0 0 30 0 10 0
Galium 0 0 0 100 0 40 0
Kochia 0 0 0 90 0 80 0
Morningglory - - - - - - -
Pigweed 40 20 20 70 0 20 20
Ragweed 0 0 10 20 0 0 0
Ryegrass, Italian 0 0 0 20 0 0 0
Velvetleaf - - - - - - -
Wheat 0 0 0 20 0 0 0
Table B Compounds
31 g ai/ha 15 38 70 73 89 90 91 96 97 103 104 105 106 107
Postemergence
Barnyardgrass 0 0 0 0 10 0 0 10 0 0 10 10 0 0
Blackgrass - 0 0 0 10 0 0 10 0 30 70 70 0 0 Corn 0 0 0 0 10 0 0 0 0 0 10 10 0 0
Crabgrass, Large 0
Foxtail, Giant 0 0 0 0 10 0 0 0 0 40 20 40 0 0
Galium - 20 0 0 10 0 0 100 10 90 90 70 0 0
Kochia - 0 0 0 50 0 0 70 60 0 50 30 0 0
Morningglory 0
Pigweed 60 0 10 0 60 0 0 100 60 30 90 90 0 0
Ragweed - 0 0 0 10 0 0 50 20 20 10 10 0 0
Ryegrass, Italian - 0 0 0 0 0 0 30 0 0 0 0 0 0
Velvetleaf 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
31 g ai/ha 108 109 110 111 112 113 114 115 116 117 118 119 120 121
Postemergence
Barnyardgrass 0 60 0 0 10 60 10 0 10 0 70 0 50 50
Blackgrass 0 50 0 0 0 60 10 0 20 0 60 0 70 50
Corn 0 10 0 0 10 10 30 0 20 0 50 0 30 20
Crabgrass, Large
Foxtail, Giant 0 60 0 0 10 60 20 0 20 0 90 0 40 70
Galium 30 50 20 10 30 90 70 0 60 0 100 30 100 100
Kochia 0 0 10 20 60 100 70 0 90 0 100 0 90 90
Morningglory
Pigweed 0 80 10 0 30 100 100 0 100 0 100 40 100 100
Ragweed 0 60 30 10 20 50 0 0 20 0 30 10 40 50
Ryegrass, Italian 0 10 0 0 0 20 10 0 0 0 20 0 30 50
Velvetleaf
Wheat 0 0 0 0 0 0 10 0 10 0 20 0 0 0
Table B Compounds
31 g ai/ha 122 124 125 126 127 128 129 130 131 132 133 140 141 142
Postemergence
Barnyardgrass 0 0 10 80 30 0 0 40 50 20 20 0 0 0
Blackgrass 0 0 10 60 30 0 0 50 50 20 30 0 0 0
Corn 0 0 0 20 20 0 0 20 20 10 10 0 0 0
Crabgrass, Large
Foxtail, Giant 0 0 0 60 50 0 0 50 50 30 20 0 0 0
Galium 10 60 50 90 80 10 10 80 80 80 70 0 0 0
Kochia 10 40 60 90 90 20 0 90 60 30 90 0 0 0 Morningglory
Pigweed 20 70 70 100 100 20 10 90 100 70 90 0 0 10
Ragweed 0 10 0 30 20 0 0 40 40 20 20 0 0 0
Ryegrass, Italian 0 0 0 40 30 0 0 30 40 10 10 0 0 0
Velvetleaf
Wheat 0 0 0 10 10 0 0 30 0 0 0 0 0 0
Table B Compounds
31 g ai/ha 143 144 145 146 147 149 150 154 155 162 163 164 165 166
Postemergence
Barnyardgrass 10 30 40 0 0 10 0 0 0 10 0 0 0 0
Blackgrass 30 80 70 0 0 10 0 0 0 30 20 0 20 0
Corn 40 30 30 0 0 10 0 0 0 20 0 0 0 0
Crabgrass, Large
Foxtail, Giant 10 80 70 0 0 10 0 0 0 10 0 0 10 0
Galium 50 100 100 30 0 90 0 0 0 90 20 10 20 20
Kochia 100 100 100 50 0 90 0 0 0 90 10 0 20 0
Morningglory
Pigweed 90 100 100 30 0 90 10 0 0 100 20 0 30 20
Ragweed 0 20 20 0 0 10 0 0 0 0 30 20 30 10
Ryegrass, Italian 0 20 20 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf
Wheat 20 30 20 0 0 0 0 0 0 20 0 0 0 0
Table B Compounds
31 g ai/ha 173 174 175 176 177 178 187 188 189 196 197 198 210 211
Postemergence
Barnyardgrass 30 0 0 10 10 0 0 0 0 0 0 10 0 0
Blackgrass 30 40 0 0 0 10 0 0 0 0 0 10 10 10
Corn 10 0 0 10 0 0 0 0 0 0 0 10 0 0
Crabgrass, Large
Foxtail, Giant 30 0 0 20 10 10 0 0 0 0 0 30 0 10
Galium 50 60 20 30 50 80 0 0 0 60 10 100 50 60
Kochia 70 60 0 30 30 80 0 0 0 0 0 80 50 40
Morningglory
Pigweed 60 50 50 90 50 100 0 0 0 20 10 100 50 20
Ragweed 40 20 20 10 10 10 0 0 0 10 0 10 10 0
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 10 0 0 Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
31 g ai/ha 212 213 214 216 218 219 220 221 222 223 224 225 226 227
Postemergence
Barnyardgrass 0 0 0 10 0 0 10 10 0 0 30 0 10 10
Blackgrass 10 0 0 0 0 0 60 30 0 0 40 0 10 10
Corn 10 0 0 0 0 0 10 20 0 0 0 0 20 10
Crabgrass, Large
Foxtail, Giant 10 0 0 0 0 0 30 10 0 0 20 0 10 10
Galium 60 50 0 20 0 20 90 90 30 30 80 0 60 70
Kochia 90 60 0 10 0 0 90 80 20 0 70 0 100 40
Morningglory
Pigweed 90 30 0 10 0 10 100 90 30 20 70 0 50 60
Ragweed 20 10 0 0 0 20 0 10 0 0 50 0 10 10
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 10 0
Velvetleaf
Wheat 0 0 0 0 0 0 10 20 0 0 0 0 0 0
Table B Compounds
31 g ai/ha 228 229 230 231 232 233 234 236 237 238 239
Postemergence
Barnyardgrass 30 20 0 0 0 0 0 0 0 0 0
Blackgrass 60 30 20 0 0 0 0 20 0 0 0
Corn 20 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large
Foxtail, Giant 40 50 0 0 0 0 0 0 0 0 0
Galium 100 80 80 0 0 0 0 30 0 0 0
Kochia 100 90 80 20 0 0 0 20 0 20 0
Morningglory
Pigweed 100 70 60 20 10 0 0 30 0 10 0
Ragweed 30 100 70 0 0 0 0 0 0 0 0
Ryegrass, Italian 20 0 0 0 0 0 0 0 0 0 0
Velvetleaf
Wheat 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
1000 g ai/ha 1 2 3 5 6 7 8 9 10 12 23 31 33 34
Preemergence
Barnyardgrass 80 0 60 0 0 10 30 20 0 20 40 0 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 100 10 40 0 0 40 80 70 10 80 100 80 80 10
Foxtail, Giant 100 10 70 0 0 20 60 60 0 90 100 30 10 10
Kochia
Morningglory 20 0 0 0 0 0 0 0 0 0 0 0 0 0
Pigweed 100 100 50 90 70 40 100 90 10 90 100 0 40 100
Ragweed
Ryegrass, Italian
Velvetleaf 80 20 90 20 20 10 30 10 0 70 80 0 0 10
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
1000 g ai/ha 35 36 40 46 55 57 61 148 171 172 186 191 192 193
Preemergence
Barnyardgrass 100 30 50 80 100 100 20 0 70 0 20 100 100 100
Corn 30 0 0 0 - - 0 - - - - - - -
Crabgrass, Large 100 100 70 100 - - 50 - - - - - - -
Foxtail, Giant 100 90 100 100 100 100 40 0 100 30 100 100 100 100
Kochia - - - - 100 100 - 0 90 20 100 100 100 100
Morningglory 90 10 0 10 - - 0 - - - - - - -
Pigweed 10 100 100 100 100 90 90 0 100 90 100 100 100 100
Ragweed - - - - 100 90 - - 0 0 70 90 20 80
Ryegrass, Italian - - - - 100 80 - 0 10 0 0 90 50 0
Velvetleaf 100 - 90 20 - - 50 - - - - - - -
Wheat 60 0 0 10 - - 0 - - - - - - -
Table B Compounds Table B Compounds
1000 g ai/ha 194 195 235 1000 g ai/ha 194 195 235 Preemergence Preemergence
Barnyardgrass 100 40 0 Pigweed 100 60 0 Corn Ragweed 30 10 0
Crabgrass, Large Ryegrass, Italian 50 0 0 Foxtail, Giant 100 30 Velvetleaf
Kochia 100 0 Wheat
Morningglory
Table B Compounds
500 g ai/ha 10 11 13 14 16 17 18 19 20 21 22 23 24 Preemergence
Barnyardgrass 0 0 0 0 0 0 0 50 0 30 80 Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 40
Crabgrass, Large 80 0 0 10 20 10 10 20 50 70 100 0 80 100
Foxtail, Giant 50 0 0 10 30 10 0 10 70 60 100 0 70 90
Kochia
Morningglory 0 0 - 0 0 - - 0 0 0 0 0 0 0
Pigweed 70 30 30 80 100 20 0 30 20 20 90 0 90 40
Ragweed
Ryegrass, Italian
Velvetleaf 30 0 10 10 20 20 10 0 0 20 20 0 50 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
500 g ai/ha 25 26 27 28 29 30 32 37 41 42 43 44 45 47
Preemergence
Barnyardgrass 70 30 80 60 0 0 90 0 0 70 20 10 0 0
Corn 0 0 0 0 0 0 0 - 0 0 0 0 0 -
Crabgrass, Large 100 100 100 100 30 20 100 - 10 90 30 70 20 -
Foxtail, Giant 90 90 90 90 10 10 100 0 20 100 70 10 20 30
Kochia - - - - - - - 0 - - - - - 70
Morningglory 10 0 0 0 0 0 30 - 0 0 10 0 0 -
Pigweed 100 100 100 80 50 30 100 40 0 90 0 10 0 60
Ragweed - - - - - - - 0 - - - - - 60
Ryegrass, Italian - - - - - - - 0 - - - - - 0
Velvetleaf 100 80 60 60 0 0 100 - 0 70 10 20 0 -
Wheat 0 0 0 0 0 0 10 - 0 0 0 0 0 -
Table B Compounds
500 g ai/ha 48 49 50 51 52 53 54 58 59 60 62 63 64 123
Preemergence
Barnyardgrass 40 0 10 10 0 100 100 100 10 100 100 100 100 0
Corn 20 30 20 -
Crabgrass, Large 100 100 100 -
Foxtail, Giant 50 20 50 60 0 100 100 100 60 100 100 100 100 0
Kochia 80 70 60 70 30 100 100 100 0 100 - - - 0
Morningglory 90 60 60 -
Pigweed 100 30 100 100 50 100 100 100 30 100 100 100 100 0
Ragweed 60 0 50 50 0 50 70 80 0 50 - - - 0
Ryegrass, Italian 50 0 50 0 0 40 60 20 0 30 - - - 0
Velvetleaf 100 90 90 - Wheat 30 40 30 -
Table B Compounds
500 g ai/ha 134 135 136 137 138 139 151 152 153 156 157 158 159 160
Preemergence
Barnyardgrass 90 60 100 10 0 0 0 0 100 20 80 100 60 80
Corn 60 0 40
Crabgrass, Large 100 100 100
Foxtail, Giant 100 100 100 0 0 0 0 0 100 80 100 100 90 100
Kochia - - - 10 0 0 0 0 100 40 100 100 30 90
Morningglory 80 10 90
Pigweed 100 100 100 20 0 0 0 0 100 100 100 100 100 100
Ragweed - - - 0 0 0 0 0 40 0 70 20 0 0
Ryegrass, Italian - - - 0 0 0 0 0 20 0 90 20 0 0
Velvetleaf 100 60 100
Wheat 20 0 30
Table B Compounds
500 g ai/ha 161 167 168 169 170 179 180 181 182 183 184 185 190 199
Preemergence
Barnyardgrass 0 10 100 30 20 90 80 10 20 80 90 70 0 0
Corn 0
Crabgrass, Large 10
Foxtail, Giant 0 30 100 90 90 100 100 40 40 90 90 90 10 0
Kochia 0 30 100 90 80 100 100 0 30 100 100 100 0 -
Morningglory 0
Pigweed 0 20 100 100 100 100 100 80 40 100 100 100 10 30
Ragweed 0 10 80 20 60 40 70 0 10 60 50 90 0 -
Ryegrass, Italian 0 0 100 20 20 40 70 0 10 40 10 0 0 -
Velvetleaf 10
Wheat 0
Table B Compounds
500 g ai/ha 200 201 202 203 204 205 206 207 208 209 215 217
Preemergence
Barnyardgrass 100 0 80 0 30 10 30 90 0 10 90 10
Corn 100 0 0 0 0 0 0 0 0 0 - -
Crabgrass, Large 100 0 100 0 100 70 60 100 0 100 - -
Foxtail, Giant 100 0 100 0 100 70 60 100 0 100 90 30 Morningglory 100 0 20 0 10 0 0 30 0 0 - -
Pigweed 100 0 100 0 100 90 80 100 90 100 90 70
Ragweed 0 0
Ryegrass, Italian 0 10
Velvetleaf 90 0 60 0 60 0 40 30 10 0 - -
Wheat 90 0 20 0 0 0 0 0 0 0 - -
Table B Compounds
125 g ai/ha 4 10 11 13 14 15 16 17 18 19 20 21 22 23
Preeraergence
Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 10 0 0 0 0 0 0 0 0 0 10 60 0 40
Foxtail, Giant 10 0 0 0 0 0 0 0 0 0 10 70 0 20
Kochia
Morningglory 0 0 0 0 0 0 - - 0 0 0 0 0 0
Pigweed 30 0 0 0 0 0 0 0 0 0 0 30 0 50
Ragweed
Ryegrass, Italian
Velvetleaf 0 0 10 0 0 0 0 0 0 0 0 0 0 10
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 24 25 26 27 28 29 30 32 38 41 42 43 44 45
Preeraergence
Barnyardgrass 10 10 0 10 0 0 0 90 0 0 20 0 0 0
Corn 0 0 0 0 0 0 0 0 - 0 0 0 0 0
Crabgrass, Large 100 50 10 80 40 10 0 100 - 0 50 0 10 0
Foxtail, Giant 20 40 0 60 30 0 0 90 0 0 70 0 0 0
Kochia - - - - - - - - 0 - - - - -
Morningglory 0 0 0 0 0 0 0 0 - 0 0 0 0 0
Pigweed 0 60 0 80 40 20 0 100 40 0 50 0 0 0
Ragweed - - - - - - - - 0 - - - - -
Ryegrass, Italian - - - - - - - - 0 - - - - -
Velvetleaf 0 10 10 20 0 0 0 90 - 0 50 0 0 0
Wheat 0 0 0 0 0 0 0 0 - 0 0 0 0 0
Table B Compounds
125 g ai/ha 47 48 49 50 51 52 53 54 58 59 60 62 63 64
Preemergence Barnyardgrass 0 0 0 0 0 0 90 60 60 0 80 80 90 60
Corn 0 10 0
Crabgrass, Large 100 100 100
Foxtail, Giant 10 10 0 0 10 0 90 100 90 10 80 100 100 90
Kochia 60 60 0 10 10 0 100 80 80 0 90 - - -
Morningglory 60 30 0
Pigweed 30 80 20 60 50 40 100 100 100 0 100 100 100 100
Ragweed 10 50 0 0 50 0 10 60 70 0 20 - - -
Ryegrass, Italian 0 40 0 20 0 0 10 30 0 0 0 - - -
Velvetleaf 90 70 80
Wheat 20 20 0
Table B Compounds
125 g ai/ha 70 73 89 90 91 96 97 103 104 105 106 107 108 109
Preemergence
Barnyardgrass 0 0 70 0 0 20 0 50 80 90 0 0 0 100
Corn
Crabgrass, Large
Foxtail, Giant 0 0 90 0 0 40 30 90 100 100 0 0 0 100
Kochia 0 0 0 0 0 70 30 10 10 10 0 0 0 30
Morningglory
Pigweed 0 0 100 20 0 100 50 100 100 100 0 0 0 100
Ragweed 0 0 0 0 0 0 0 10 0 0 0 0 0 70
Ryegrass, Italian 0 0 0 0 0 0 0 0 10 20 0 0 0 10
Velvetleaf
Wheat
Table B Compounds
125 g ai/ha 110 111 112 113 114 115 116 117 118 119 120 121 122 123
Preemergence
Barnyardgrass 40 20 30 100 20 0 30 0 100 0 100 90 0 0
Corn
Crabgrass, Large
Foxtail, Giant 70 50 70 100 30 0 90 0 100 50 100 100 0 0
Kochia 0 10 50 100 20 0 60 0 100 10 90 100 10 0
Morningglory
Pigweed 70 80 70 100 80 0 100 0 100 50 100 100 50 0
Ragweed 0 10 0 70 20 0 20 0 30 0 30 20 0 0
Ryegrass, Italian 0 0 10 60 20 0 20 0 80 0 90 80 0 0 Compounds
125 g ai/ha 124 125 126 127 128 129 130 131 132 133 134 135 137 138
Preemergence
Barnyardgrass 30 50 100 90 0 0 90 100 60 70 70 10 0 0
Corn 20 0 - -
Crabgrass, Large 100 80 - -
Foxtail, Giant 100 90 100 100 10 0 100 100 90 90 90 60 0 0
Kochia 60 40 90 90 0 0 70 10 0 90 - - 0 0
Morningglory 10 0 - -
Pigweed 100 80 100 100 40 0 100 100 100 100 100 90 0 0
Ragweed 10 0 10 30 0 0 20 60 40 10 - - 0 0
Ryegrass, Italian 10 10 100 90 0 0 50 90 30 50 - - 0 0
Velvetleaf 40 20 - -
Wheat 20 0 - -
Table B Compounds
125 g ai/ha 139 140 141 142 143 144 145 146 147 149 150 151 152 153
Preemergence
Barnyardgrass 0 0 0 0 90 100 100 30 0 70 20 0 0 0
Corn
Crabgrass, Large
Foxtail, Giant 0 0 0 20 100 100 100 20 0 100 20 0 0 30
Kochia 0 0 0 0 90 100 100 0 0 80 0 0 0 20
Morningglory
Pigweed 0 0 0 0 100 100 100 70 0 100 20 0 0 100
Ragweed 0 0 0 0 30 50 20 0 0 0 0 0 0 0
Ryegrass, Italian 0 0 0 0 60 90 40 0 0 10 0 0 0 0
Velvetleaf
Wheat
Table B Compounds
125 g ai/ha 154 155 156 157 158 159 160 161 162 163 164 165 166 167
Preemergence
Barnyardgrass 0 0 0 20 90 0 0 0 100 0 0 10 0 0
Corn
Crabgrass, Large
Foxtail, Giant 0 0 20 80 90 20 50 0 100 0 0 10 0 0 Kochia 0 0 20 100 100 0 30 0 70 0 0 60 0 0
Morningglory
Pigweed 0 0 80 100 90 40 90 0 100 30 30 80 60 0
Ragweed 0 0 0 20 0 0 0 0 20 40 0 50 20 0
Ryegrass, Italian 0 0 0 20 0 0 0 0 40 0 0 0 0 0
Velvetleaf
Wheat
Table B Compounds
125 g ai/ha 168 169 170 173 174 175 176 177 178 179 180 181 182 183 Preemergence
Barnyardgrass 100 20 0 90 0 0 50 50 70 10 20 0 0 30 Corn
Crabgrass, Large
Foxtail, Giant 100 50 60 100 40 0 90 70 90 80 90 0 0 80 Kochia 100 70 30 100 0 0 20 20 20 100 100 0 0 80
Morningglory
Pigweed 100 100 100 100 80 70 90 90 100 100 100 10 0 90
Ragweed 70 10 20 70 0 0 0 0 0 10 50 0 0 0
Ryegrass, Italian 80 0 0 20 0 0 10 0 10 20 20 0 0 20
Velvetleaf
Wheat
Table B Compounds
125 g ai/ha 184 185 187 188 189 190 196 197 198 199 200 201 202 203 Preemergence
Barnyardgrass 10 20 0 20 0 0 10 0 40 0 100 0 10 0 Corn - - - - - - - - - 0 20 0 0 0
Crabgrass, Large - - - - - - - - - 0 100 0 90 0 Foxtail, Giant 20 30 0 40 0 0 20 0 90 0 100 0 70 0 Kochia 20 40 0 30 0 0 0 0 30 - - - - -
Morningglory - - - - - - - - - 0 20 0 0 0
Pigweed 80 90 0 100 0 0 10 0 100 0 100 0 100 0
Ragweed 0 10 0 0 0 0 0 0 10 - - - - -
Ryegrass, Italian 0 0 0 0 0 0 0 0 20 - - - - -
Velvetleaf - - - - - - - - - 0 80 0 0 0
Wheat - - - - - - - - 0 20 0 0 0
Table B Compounds
125 g ai/ha 204 205 206 207 208 209 210 211 212 213 214 215 216 217 Preemergence
Barnyardgrass 0 0 0 10 0 0 80 50 60 40 0 40 10 0
Corn 0 0 0 0 0 0
Crabgrass, Large 90 30 10 100 0 70
Foxtail, Giant 60 20 10 70 0 30 90 100 100 80 0 20 0 0
Kochia - - - - - - 90 80 90 50 0 0 0 0
Morningglory 0 0 0 0 0 0
Pigweed 100 10 50 90 0 90 100 100 100 100 0 20 0 10
Ragweed - - - - - - 20 30 40 0 0 0 0 0
Ryegrass, Italian - - - - - - 10 0 40 0 0 0 0 0
Velvetleaf 0 0 30 0 0 0
Wheat 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 218 219 220 221 222 223 224 225 226 227 228 229 230 231
Preemergence
Barnyardgrass 50 0 100 90 0 0 50 0 100 50 100 90 70 10
Corn
Crabgrass, Large
Foxtail, Giant 60 0 100 90 0 0 90 0 100 90 100 90 90 10
Kochia 0 0 90 70 0 0 90 0 90 50 100 100 100 0
Morningglory
Pigweed 90 0 100 100 90 10 100 0 100 80 100 100 100 20
Ragweed 0 0 10 0 0 0 - 0 20 0 30 90 80 0
Ryegrass, Italian 0 0 30 40 0 0 0 0 20 10 70 30 0 0
Velvetleaf
Wheat
Table B Compounds
125 g ai/ha 232 233 234 236 237 238 239
Preemergence
Barnyardgrass 20 0 0 80 0 40 0
Corn - - - - - - -
Crabgrass, Large - - - - - - -
Foxtail, Giant 10 0 0 90 0 20 0
Kochia 0 0 0 100 0 0 0
Morningglory - - - - - - -
Pigweed 30 0 0 100 0 10 0
Ragweed 0 0 - 0 0 0 0 Ryegrass, Italian 0 0 0 30 0 0 0
Velvetleaf - - - - - - -
Wheat - - - - - - -
Table B Compounds
31 g ai/ha 15 38 70 73 89 90 91 96 97 103 104 105 106 107
Preemergence
Barnyardgrass 0 0 0 0 10 0 0 0 0 0 20 20 0 0
Corn 0
Crabgrass, Large 0
Foxtail, Giant 0 0 0 0 40 0 0 10 10 50 40 70 0 0
Kochia - 0 0 0 0 0 0 50 0 0 0 0 0 0
Morningglory 0
Pigweed 0 0 0 0 100 0 0 90 20 100 80 100 0 0
Ragweed - 0 0 0 0 0 0 0 0 0 0 0 0 0
Ryegrass, Italian - 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0
Wheat 0
Table B Compounds
31 g ai/ha 108 109 110 111 112 113 114 115 116 117 118 119 120 121
Preemergence
Barnyardgrass 0 40 0 0 10 70 0 0 0 0 70 0 90 70
Corn
Crabgrass, Large
Foxtail, Giant 0 80 0 0 10 90 10 0 40 0 100 0 100 100
Kochia 0 0 0 0 0 100 20 0 60 0 80 0 80 60
Morningglory
Pigweed 0 90 10 10 30 100 70 0 70 0 100 0 100 100
Ragweed 0 20 0 0 0 30 0 0 0 0 20 0 10 10
Ryegrass, Italian 0 0 0 0 0 10 0 0 0 0 20 0 40 30
Velvetleaf
Wheat
Table B Compounds
31 g ai/ha 122 124 125 126 127 128 129 130 131 132 133 140 141 142
Preemergence
Barnyardgrass 0 0 0 90 70 0 0 50 80 20 30 0 0 0 Foxtail, Giant 0 20 10 100 100 0 0 90 100 60 70 0 0 0
Kochia 0 10 0 80 80 0 0 50 0 0 50 0 0 0
Morningglory
Pigweed 10 40 0 100 100 0 0 100 100 90 90 0 0 0
Ragweed 0 0 0 10 10 0 0 10 20 0 0 0 0 0
Ryegrass, Italian 0 0 0 40 30 0 0 20 20 0 0 0 0 0
Velvetleaf
Wheat
Table B Compounds
31 g ai/ha 143 144 145 146 147 149 150 154 155 162 163 164 165 166 Preemergence
Barnyardgrass 20 80 70 0 0 10 0 0 0 20 0 0 0 0
Corn
Crabgrass, Large
Foxtail, Giant 70 100 90 0 0 70 0 0 0 90 0 0 0 0
Kochia 30 90 90 0 0 20 0 0 0 70 0 0 0 0
Morningglory
Pigweed 90 100 100 0 0 80 0 0 0 80 0 0 30 40
Ragweed 0 0 0 0 0 0 0 0 0 0 0 0 20 0
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf
Wheat
Table B Compounds
31 g ai/ha 173 174 175 176 177 178 187 188 189 196 197 198 210 211
Preemergence
Barnyardgrass 60 0 0 10 0 20 0 0 0 0 0 10 10 10
Corn
Crabgrass, Large
Foxtail, Giant 50 0 0 60 10 60 0 0 0 0 0 70 40 10
Kochia 70 - 0 0 0 10 0 0 0 0 0 0 50 20
Morningglory
Pigweed 80 60 0 30 50 90 0 0 0 0 0 30 100 100
Ragweed 10 0 0 0 0 0 0 0 0 0 0 0 0 0
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf
Wheat Table B Compounds
31 g ai/ha 212 213 214 216 218 219 220 221 222 223 224 225 226 227
Preemergence
Barnyardgrass 10 0 0 0 0 0 10 20 0 0 10 0 30 10
Corn
Crabgrass, Large
Foxtail, Giant 60 0 0 0 0 0 70 50 0 0 40 0 60 40
Kochia 40 10 0 0 0 0 50 50 0 0 60 0 70 0
Morningglory
Pigweed 100 80 0 0 0 0 100 100 20 0 90 0 100 40
Ragweed 0 0 0 0 0 0 0 0 0 0 - 0 0 0
Ryegrass, Italian 0 0 0 0 0 0 0 20 0 0 0 0 0 0
Velvetleaf
Wheat
Table B Compounds
31 g ai/ha 228 229 230 231 232 233 234 236 237 238 239
Preemergence
Barnyardgrass 50 50 10 0 0 0 0 10 0 0 0
Corn
Crabgrass, Large
Foxtail, Giant 90 90 60 0 0 0 0 10 0 0 0
Kochia 70 80 60 0 0 0 0 30 0 0 0
Morningglory
Pigweed 100 100 90 0 20 0 0 60 0 0 0
Ragweed 0 70 20 0 0 0 0 0 0 0 0
Ryegrass, Italian 30 0 0 0 0 0 0 0 0 0 0
Velvetleaf
Wheat TEST C
Plant species in the flooded paddy test selected from rice {Oryza sativa), small-flower umbrella sedge (Cyperus difformis), ducksalad {Heter anther a limosa), and barnyardgrass {Echinochloa crus-galli) were grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table C Compounds
250 g ai/ha 4 10 11 12 13 14 16 17 18 19 20 21 22 23
Flood
Barnyardgrass 0 0 0 10 0 0 0 0 0 0 0 0 0 0
Ducksalad 0 0 0 40 40 40 0 0 0 0 0 0 0 60
Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sedge, Umbrella 0 0 0 0 0 0 0 0 0 0 0 0 0 40
Table C Compounds
250 g ai/ha 24 25 26 27 28 29 30 32 35 38 41 42 43 44
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 65 0 0 0 0 0
Ducksalad 0 30 0 30 0 0 0 90 100 60 0 0 0 0
Rice 0 0 0 0 0 0 0 20 80 0 0 0 0 0
Sedge, Umbrella 40 20 0 40 0 0 0 85 100 30 0 0 0 0
Table C Compounds
250 g ai/ha 45 46 47 48 49 50 51 52 53 54 55 57 58 59
Flood
Barnyardgrass 0 20 0 0 0 0 0 0 20 0 25 0 0 0
Ducksalad 0 60 0 0 0 30 30 0 80 60 100 90 80 0
Rice 0 35 0 0 0 0 0 0 20 0 25 0 0 0
Sedge, Umbrella 0 50 0 0 0 0 0 0 75 0 90 75 40 0
Table C Compounds
250 g ai/ha 60 62 63 64 70 73 89 90 96 97 103 104 105 106
Flood
Barnyardgrass 20 35 60 35 0 0 0 0 15 0 60 20 45 0
Ducksalad 80 100 100 95 0 0 30 0 90 0 40 75 40 0
Rice 30 40 25 0 0 0 0 0 30 0 30 0 35 0
Sedge, Umbrella 50 90 85 80 0 0 80 0 100 50 80 80 70 0
Table C Compounds
250 g ai/ha 107 108 109 110 111 112 113 114 115 116 117 118 119 120
Flood
Barnyardgrass 0 0 30 0 0 0 0 0 0 0 0 50 0 90 Ducksalad 0 0 85 30 0 30 95 75 0 95 0 100 40 100
Rice 0 0 35 0 0 0 15 15 0 30 0 45 0 90
Sedge, Umbrella 0 0 80 60 0 95 95 75 0 90 0 100 40 95
Table C Compounds
250 g ai/ha 121 122 123 124 125 126 127 128 129 130 131 132 133 134
Flood
Barnyardgrass 60 0 0 0 0 95 50 0 0 65 75 30 40 0
Ducksalad 90 0 0 80 80 100 100 0 0 90 95 40 80 40
Rice 45 0 0 0 0 75 60 0 0 30 60 20 40 0
Sedge, Umbrella 90 0 30 85 90 100 100 0 0 90 95 75 80 75
Table C Compounds
250 g ai/ha 135 136 137 138 139 140 141 142 143 144 145 146 147 149
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 30 98 45 0 0 0
Ducksalad 0 40 20 20 30 0 30 0 85 90 90 0 0 80
Rice 0 0 0 0 20 0 0 0 35 40 35 0 0 0
Sedge, Umbrella 0 40 0 0 0 0 0 0 100 85 95 0 0 65
Table C Compounds
250 g ai/ha 150 151 152 153 154 155 156 157 158 159 160 161 162 163
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Ducksalad 0 0 0 0 0 0 0 40 50 0 0 0 0 0
Rice 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sedge, Umbrella 0 0 0 0 0 0 0 40 0 0 0 0 0 0
Table C Compounds
250 g ai/ha 164 165 166 167 168 169 170 171 173 174 175 176 177 178
Flood
Barnyardgrass 0 0 0 0 90 0 0 0 0 0 0 0 0 40
Ducksalad 0 0 0 0 90 0 0 0 80 0 0 75 60 90
Rice 0 0 0 0 40 0 0 0 0 0 0 0 20 0
Sedge, Umbrella 0 0 0 0 90 0 0 0 60 0 0 30 40 85
Table C Compounds
250 g ai/ha 179 180 181 182 183 184 185 186 187 188 189 190 191 192
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0 0 20 0
Ducksalad 80 90 0 0 85 0 0 0 50 30 0 0 80 60 Rice 40 0 0 0 0 0 0 0 0 0 0 0 0 0
Sedge, Umbrella 80 80 0 0 75 0 0 0 0 0 0 0 85 40
Table C Compounds
250 g ai/ha 193 194 196 197 198 199 200 201 202 203 204 205 206 207
Flood
Barnyardgrass 0 0 30 20 40 0 90 0 0 0 0 0 0 0
Ducksalad 65 80 55 0 85 0 100 0 80 0 0 0 70 30
Rice 0 0 0 0 25 0 35 0 0 0 0 0 0 0
Sedge, Umbrella 0 0 70 0 100 80 100 0 80 0 0 0 70 30
Table C Compounds
250 g ai/ha 208 209 210 211 212 213 214 215 216 217 218 219 220 221
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 0 20 0 0 20 0
Ducksalad 0 0 85 70 75 75 0 0 0 40 0 0 80 100
Rice 0 0 0 0 20 0 0 0 0 0 0 0 0 0
Sedge, Umbrella 0 0 40 20 75 0 0 0 0 0 0 0 75 95
Table C Compounds
250 g ai/ha 222 223 224 225 226 227 228 229 230 231 232 233 234 236
Flood
Barnyardgrass 0 0 0 0 20 0 40 55 40 0 0 0 0 0
Ducksalad 30 65 70 0 85 98 85 90 85 65 0 0 0 75
Rice 0 0 0 0 20 0 0 15 20 0 0 0 0 0
Sedge, Umbrella 0 70 65 0 65 85 90 90 85 70 0 0 0 40
Table C Compounds
250 g ai/ha 237 238 239
Flood
Barnyardgrass 0 20 0
Ducksalad 0 45 0
Rice 0 15 0
Sedge, Umbrella 0 65 0
TEST D
Seeds of plant species selected from blackgrass (Alopecurus myos roides), Italian ryegrass (Lolium multiflorum), winter wheat {Triticum aestivum), galium (catchweed bedstraw, Galium aparine), corn {Zea mays), large (Lg) crabgrass {Digitaria sanguinalis). giant foxtail (Setaria faberii), johnsongrass (Sorghum halepense), lambsquarters (Chenopodium album), morningglory (Ipomoea coccinea), yellow nutsedge (Cyperus esculentus), pigweed (Amaranthus retroflexus), ragweed (common ragweed, Ambrosia elatior), soybean (Glycine max), barnyardgrass (Echinochloa crus-galli), oilseed rape (Brassica napus), waterhemp (common waterhemp, Amaranthus rudis), and velvetleaf (Abutilon theophrasti) were planted into a blend of loam soil and sand and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these crop and weed species and also kochia (Kochia scoparia), wild oat (Avena fatud), and chickweed (common chickweed, Stellaria media) were planted in pots containing Redi-Earth® planting medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) comprising spaghnum peat moss, vermiculite, wetting agent and starter nutrients and treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
Plant species in the flooded paddy test consisted of rice (Oryza sativa), small-flower umbrella sedge (Cyperus difformis), ducksalad (Heteranthera limosa), and barnyardgrass (Echinochloa crus-galli) grown to the 2-leaf stage for testing. At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test.
Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table D, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table D Compound Table D Compound
250 g ai/ha 62 250 g ai/ha 62
Postemergence Postemergence
Barnyardgrass 95 Nutsedge, Yellow 10
Blackgrass 60 Oat, Wild 60
Chickweed 100 Oilseed Rape 100
Corn 10 Pigweed 100
Crabgrass, Large 65 Ragweed 85
Foxtail, Giant 55 Ryegrass, Italian 40
Galium 100 Soybean 98
Johnsongrass 85 Velvetleaf 85
Kochia 100 Waterhemp 100 Lambsquarters 100 Wheat 40
Morningglory 98
Table D Compounds
125 g ai/ha 50 53 54 55 57 58 60 62 63 96 113 116 118 120
Postemergence
Barnyardgrass 0 35 10 15 10 5 10 30 10 5 25 30 30 40
Blackgrass 0 30 5 50 15 5 20 40 25 20 40 35 35 55
Chickweed 5 90 5 100 75 30 75 98 100 98 95 90 98 100
Corn 5 0 5 20 10 5 5 15 10 5 25 10 15 15
Crabgrass, Large 5 30 5 15 10 5 5 50 35 10 25 40 20 65
Foxtail, Giant 35 30 50 75 20 30 10 20 20 10 10 60 20 25
Galium 60 90 75 90 95 55 65 100 70 98 90 90 98 100
Johnsongrass 0 5 5 15 5 5 5 75 45 10 10 - 45 85
Kochia 15 100 80 100 .00 80 90 100 100 100 100 100 100 100
Lambsquarters 5 100 70 98 80 90 75 100 90 95 90 100 95 100
Morningglory 20 55 85 85 65 65 40 95 70 30 80 30 80 100
Nutsedge, Yellow - - - 5 5 0 5 5 5 5 15 25 10 15
Oat, Wild 0 20 5 40 15 0 5 50 35 20 25 15 50 60
Oilseed Rape 30 85 60 100 90 75 90 98 100 65 90 70 95 95
Pigweed 30 100 60 100 75 75 70 100 95 98 100 90 98 100
Ragweed 15 55 35 90 98 60 70 65 55 40 90 75 85 85
Ryegrass, Italian 0 5 0 15 0 0 0 30 30 10 5 10 5 50
Soybean 40 98 80 95 90 75 95 98 98 35 75 95 90 95
Velvetleaf 40 100 40 85 80 85 80 75 40 35 70 75 85 100
Waterhemp 40 100 75 100 98 75 70 98 98 100 90 100 98 100
Wheat 5 0 5 35 20 10 20 10 5 10 5 5 5 0
Table D Compounds
125 g ai/ha 121 130 131 143 .44 145 149 153 162 168 169 170 178 179
Postemergence
Barnyardgrass 45 25 20 65 15 30 10 5 15 75 5 5 20 5
Blackgrass 50 30 30 30 75 80 30 0 45 20 25 5 15 20
Chickweed 100 95 100 80 95 100 60 25 85 100 80 100 80 95
Corn 25 10 25 10 5 10 5 5 5 20 10 5 10 15
Crabgrass, Large 55 25 20 35 20 20 15 10 20 40 10 10 15 5
Foxtail, Giant 40 25 15 50 25 20 30 5 20 60 55 40 25 30
Galium 95 100 95 100 95 90 95 80 80 100 75 80 85 75
Johnsongrass 60 10 45 30 50 40 10 10 20 20 5 5 10 5 Kochia 100 100 100 100 100 100 100 60 100 100 95 100 100 100
Lambsquarters 100 100 100 100 95 95 85 50 95 90 80 80 90 100
Morningglory 98 85 95 100 - 80 80 25 75 85 65 98 90 90
Nutsedge, Yellow 20 25 10 5 5 10 5 5 10 15 5 10 5 5
Oat, Wild 70 60 35 5 10 15 5 0 10 30 10 10 5 20
Oilseed Rape 95 95 85 65 - - 85 85 - 100 60 25 95 100
Pigweed 100 98 100 100 100 98 90 70 100 98 98 98 90 98
Ragweed 98 40 75 30 75 65 45 55 50 55 35 10 35 60
Ryegrass, Italian 55 15 25 15 10 10 0 0 5 15 15 5 5 20
Soybean 95 95 65 60 - 75 65 90 50 90 25 35 45 70
Velvetleaf 85 100 85 65 98 80 65 50 - 90 30 25 75 70
Waterhemp 100 98 98 100 100 100 100 65 100 98 90 85 90 98
Wheat 0 35 0 5 10 10 10 10 5 35 10 15 10 35
Table D Compounds
125 g ai/ha 180 183 185 191 192 198 200 212 221 224 228 229 230
Postemergence
Barnyardgrass 5 5 5 10 5 35 15 25 10 15 35 10 5
Blackgrass 5 20 0 5 5 15 90 10 40 0 35 10 10
Chickweed 95 70 5 90 55 95 100 80 100 80 100 85 80
Corn 15 20 5 10 10 15 15 15 10 5 10 5 15
Crabgrass, Large 5 10 10 20 10 30 35 15 30 10 45 5 10
Foxtail, Giant 45 5 5 5 15 25 15 10 35 40 40 15 10
Galium 100 95 5 85 50 98 100 80 100 60 100 80 95
Johnsongrass 5 10 5 5 5 35 40 20 15 5 60 25 5
Kochia 100 100 30 90 95 100 100 100 100 100 100 98 100
Lambsquarters 98 75 20 85 75 75 98 98 98 85 95 85 70
Morningglory 90 90 65 85 45 85 98 98 85 80 75 35 70
Nutsedge, Yellow 15 5 30 10 5 10 15 5 10 5 10 10 5
Oat, Wild 30 25 5 5 5 10 55 10 35 0 55 10 10
Oilseed Rape 90 100 0 90 50 90 100 35 90 98 98 80 75
Pigweed 98 95 50 60 55 100 98 100 100 90 98 80 85
Ragweed 65 65 25 65 45 60 40 60 75 70 60 60 55
Ryegrass, Italian 20 10 0 5 0 10 35 5 10 0 25 5 5
Soybean 85 90 45 95 85 60 98 90 90 75 80 70 85
Velvetleaf 55 55 25 50 55 55 75 90 100 60 80 70 65
Waterhemp 98 98 30 65 70 98 100 100 100 85 100 85 80
Wheat 30 30 0 0 5 5 20 15 0 15 10 10 15 Table D Compounds
62 g ai/ha 35 50 53 54 55 57 58 60 62 63 96 113 116 118
Postemergence
Barnyardgrass 20 0 25 5 15 5 0 10 35 10 5 20 20 20
Blackgrass 60 0 20 5 30 0 0 5 25 20 10 10 5 15
Chickweed 100 5 80 5 98 55 15 60 95 98 90 90 30 90
Corn 20 0 0 5 10 5 5 5 10 5 5 20 5 15
Crabgrass, Large 10 0 15 5 10 10 5 5 35 10 5 25 25 15
Foxtail, Giant 15 5 25 10 40 20 15 5 25 10 10 10 10 10
Galium 85 5 95 55 90 65 60 50 85 70 80 90 70 90
Johnsongrass 35 0 5 5 10 5 0 0 25 25 5 5 20 10
Kochia 100 5 100 80 100 95 60 55 100 98 85 100 100 95
Lambsquarters 95 50 100 5 98 70 60 55 98 85 90 95 80 90
Morningglory 98 10 85 75 80 45 45 25 95 98 40 85 10 85
Nutsedge, Yellow 5 - - - 5 5 0 0 5 5 5 5 10 10
Oat, Wild 45 0 30 5 40 5 0 0 40 25 20 10 10 15
Oilseed Rape 98 10 95 50 100 75 60 65 90 98 65 90 55 60
Pigweed 95 5 90 80 98 55 40 55 100 90 98 95 90 95
Ragweed 75 5 55 5 65 60 65 40 60 55 10 90 60 55
Ryegrass, Italian 20 0 5 0 10 0 0 0 5 5 10 5 5 5
Soybean 95 20 95 50 90 85 60 95 95 55 55 65 30 60
Velvetleaf 65 0 70 40 75 70 60 65 70 40 35 70 70 70
Waterhemp 98 0 90 80 98 75 55 50 98 98 98 85 90 95
Wheat 10 5 0 0 30 15 10 5 20 5 0 5 5 0
Table D Compounds
62 g ai/ha 120 121 130 131 143 144 145 149 153 156 162 168 169 170
Postemergence
Barnyardgrass 25 25 10 10 10 10 10 5 5 5 15 10 5 5
Blackgrass 60 30 20 5 20 15 25 0 0 5 30 15 0 5
Chickweed 100 100 80 98 60 95 95 30 20 70 60 100 70 90
Corn 10 20 10 10 5 10 5 5 5 5 5 10 10 5
Crabgrass, Large 35 40 20 10 15 15 10 10 5 10 10 15 10 5
Foxtail, Giant 15 15 10 15 10 25 20 10 5 35 10 40 25 40
Galium 100 100 95 95 70 90 80 70 70 70 60 95 70 65
Johnsongrass 40 60 5 25 30 10 5 15 5 10 10 5 0 0
Kochia 100 100 100 95 100 100 100 100 40 45 100 100 90 85
Lambsquarters 100 100 100 98 98 90 85 80 30 40 75 85 35 40 Morningglory 80 90 85 75 90 85 85 70 15 65 75 85 55 70
Nutsedge, Yellow 10 5 20 5 5 5 5 5 5 5 5 10 0 5
Oat, Wild 55 70 35 20 5 5 15 0 0 0 5 20 5 5
Oilseed Rape 90 95 75 80 60 95 - 60 60 45 40 100 10 40
Pigweed 100 100 98 98 100 100 98 95 40 75 100 95 80 98
Ragweed 70 75 75 65 10 70 50 30 25 15 40 55 25 10
Ryegrass, Italian 10 40 10 5 0 10 10 0 0 0 5 5 5 5
Soybean 70 90 98 75 60 95 75 65 70 30 40 40 15 10
Velvetleaf 100 80 75 80 50 75 75 40 60 25 75 45 20 25
Waterhemp 100 100 98 90 100 100 100 95 35 90 100 98 90 100
Wheat 0 0 30 0 5 10 5 0 5 10 5 30 10 10
Table D Compounds
62 g ai/ha 178 179 180 183 185 191 192 198 200 212 221 224 228 229
Postemergence
Barnyardgrass 10 5 5 5 0 5 5 20 10 15 5 10 20 5
Blackgrass 10 15 5 5 0 0 0 10 40 0 5 5 25 15
Chickweed 60 95 85 65 5 70 50 60 100 30 80 40 98 80
Corn 5 10 10 15 5 10 5 15 10 10 5 5 10 5
Crabgrass, Large 20 5 5 5 10 10 10 20 25 10 25 10 35 5
Foxtail, Giant 5 40 30 5 5 5 25 15 10 15 5 5 20 5
Galium 98 70 100 95 5 85 50 98 100 65 100 60 98 65
Johnsongrass 15 5 5 5 5 5 5 35 45 20 15 5 25 0
Kochia 100 100 100 100 5 85 90 100 100 100 100 95 100 98
Lambsquarters 75 75 98 65 15 70 40 70 85 98 95 80 90 70
Morningglory 100 85 90 90 10 60 10 80 85 75 80 35 80 25
Nutsedge, Yellow 10 5 10 5 0 5 0 15 5 10 5 5 5 10
Oat, Wild 5 15 5 10 0 5 0 10 30 5 10 0 40 10
Oilseed Rape 80 85 80 100 0 60 5 60 100 20 90 50 80 60
Pigweed 85 98 75 85 35 30 55 90 85 100 98 85 95 70
Ragweed 20 50 35 60 15 60 15 55 60 55 45 55 60 70
Ryegrass, Italian 5 5 5 5 0 0 0 10 35 0 20 0 15 0
Soybean 35 70 70 75 35 75 55 30 90 85 85 65 80 45
Velvetleaf 60 30 35 55 10 30 30 55 70 60 80 30 65 45
Waterhemp 85 95 90 75 25 70 55 95 98 100 100 85 95 80
Wheat 5 30 15 30 0 0 5 5 25 5 5 0 10 5
Table D Compound Table D Compound
62 g ai/ha 230 62 g ai/ha 230 Postemergence Postemergence
Barnyardgrass 10 Nutsedge, Yellow 5
Blackgrass 10 Oat, Wild 5
Chickweed 75 Oilseed Rape 75
Corn 0 Pigweed 70
Crabgrass, Large 5 Ragweed 55
Foxtail, Giant 10 Ryegrass, Italian 5
Galium 85 Soybean 65
Johnsongrass 5 Velvetleaf 55
Kochia 100 Waterhemp 75
Lambsquarters 80 Wheat 5
Morningglory 5
Table D Compounds
31 g ai/ha 35 50 53 54 55 57 58 60 62 63 96 113 116 118
Postemergence
Barnyardgrass 20 0 10 5 10 5 0 0 50 10 0 15 5 20
Blackgrass 40 0 40 5 10 0 0 0 20 10 10 15 5 10
Chickweed 85 0 80 5 75 50 10 50 70 65 85 85 15 70
Corn 10 0 0 0 10 5 0 0 10 5 15 10 10 10
Crabgrass, Large 10 0 20 5 10 5 5 5 55 5 5 20 5 10
Foxtail, Giant 10 0 20 30 50 10 0 5 25 5 5 5 5 15
Galium 75 15 85 55 90 50 45 40 85 70 90 80 60 90
Johnsongrass 5 0 0 0 5 0 0 0 25 5 0 5 20 5
Kochia 100 0 100 55 100 90 50 50 98 95 60 100 100 95
Lambsquarters 85 5 80 5 85 40 75 20 98 70 65 85 60 85
Morningglory 85 0 80 75 70 45 45 40 85 50 40 75 10 85
Nutsedge, Yellow 5 - - - 5 5 0 0 5 0 5 5 5 5
Oat, Wild 40 0 10 0 15 0 0 0 30 20 20 15 5 10
Oilseed Rape 80 5 80 20 95 55 10 50 80 90 45 50 10 30
Pigweed 90 5 90 80 85 55 25 35 98 85 95 90 75 95
Ragweed 85 5 50 0 40 50 45 30 65 40 10 60 35 45
Ryegrass, Italian 5 0 5 0 5 0 0 0 5 0 5 5 0 0
Soybean 80 5 90 10 75 70 40 65 80 45 50 55 55 60
Velvetleaf 55 0 60 5 50 50 35 50 60 25 35 60 65 75
Waterhemp 95 0 90 60 90 55 40 30 98 85 95 80 90 90
Wheat 5 0 0 0 25 5 5 5 30 0 0 0 0 0 Table D Compounds
31 g ai/ha 120 121 130 131 143 144 145 149 153 156 157 162 168 169
Postemergence
Barnyardgrass 15 25 10 10 5 5 5 5 5 0 5 10 5 5
Blackgrass 35 25 5 5 10 15 20 0 0 5 5 30 15 0
Chickweed 100 100 80 80 50 80 80 30 20 45 75 60 98 40
Corn 15 20 25 5 5 5 5 5 0 5 5 5 5 5
Crabgrass, Large 25 10 20 5 10 10 10 5 5 5 5 5 5 5
Foxtail, Giant 10 10 5 10 10 10 10 10 0 10 20 10 35 5
Galium 98 90 90 85 70 85 80 60 70 60 70 60 95 70
Johnsongrass 30 35 5 5 5 10 5 10 0 5 0 5 5 0
Kochia 100 100 95 90 100 100 100 90 50 30 90 100 100 60
Lambsquarters 100 100 100 98 80 80 85 70 35 35 55 65 85 40
Morningglory 98 75 80 75 - 85 85 60 5 15 35 65 85 15
Nutsedge, Yellow 10 10 5 0 5 5 5 0 0 5 10 0 5 0
Oat, Wild 40 45 15 15 0 0 10 0 0 0 10 5 10 5
Oilseed Rape 85 80 80 45 50 80 70 30 40 40 25 5 100 5
Pigweed 100 98 95 98 90 98 95 85 20 60 65 90 85 80
Ragweed 55 65 60 45 5 60 50 30 10 10 25 30 50 5
Ryegrass, Italian 5 10 5 5 0 5 0 0 0 0 5 0 5 0
Soybean 70 60 55 15 30 80 60 40 40 25 35 10 75 5
Velvetleaf 85 80 80 65 30 55 70 30 20 15 40 40 40 10
Waterhemp 100 95 85 90 100 85 90 80 10 70 75 98 90 90
Wheat 0 0 5 0 5 10 5 0 0 5 0 0 10 5
Table D Compounds
31 g ai/ha 170 178 179 180 183 185 191 192 198 200 212 221 224 228
Postemergence
Barnyardgrass 0 15 0 0 5 0 5 5 10 10 5 5 5 20
Blackgrass 0 5 5 0 5 0 0 0 5 30 0 10 0 15
Chickweed 65 50 80 60 60 0 55 50 60 95 30 85 15 85
Corn 5 5 10 5 15 0 5 0 10 5 5 0 5 10
Crabgrass, Large 5 10 5 5 5 0 10 5 15 10 10 10 5 20
Foxtail, Giant 30 5 5 50 5 5 5 25 15 20 10 5 5 10
Galium 50 80 80 75 65 0 70 50 75 100 60 80 50 98
Johnsongrass 0 10 5 0 5 0 5 5 20 20 5 5 5 10
Kochia 60 95 100 90 95 0 80 80 95 100 100 100 70 100
Lambsquarters 40 70 75 80 65 10 70 50 55 80 80 95 75 85 Morningglory 30 100 65 55 75 25 65 0 55 50 98 65 35 65
Nutsedge, Yellow 5 5 5 0 5 0 5 5 5 5 5 5 0 5
Oat, Wild 5 0 5 5 5 0 0 0 5 30 0 10 0 20
Oilseed Rape 5 80 75 60 85 0 40 0 50 85 - 70 10 85
Pigweed 90 85 90 75 85 35 30 20 98 85 100 95 85 95
Ragweed 5 5 25 40 35 20 40 5 55 55 40 50 55 35
Ryegrass, Italian 0 0 5 0 0 0 0 0 0 25 0 5 0 5
Soybean 10 35 45 60 55 30 65 30 25 85 70 25 40 55
Velvetleaf 5 40 20 40 55 10 30 20 45 60 50 65 25 40
Waterhemp 80 80 90 75 80 25 60 40 85 90 98 85 75 95
Wheat 20 5 10 5 20 0 0 0 0 10 5 0 0 5
Table D Compounds Table D Compounds
31 g ai/ha 229 230 31 g ai/ha 229 230
Postemergence Postemergence
Barnyardgrass 5 5 Nutsedge, Yellow 0 0
Blackgrass 10 10 Oat, Wild 10 0
Chickweed 60 65 Oilseed Rape 70 60
Corn 20 0 Pigweed 60 65
Crabgrass, Large 0 5 Ragweed 50 40
Foxtail, Giant 5 5 Ryegrass, Italian 0 0
Galium 70 85 Soybean 40 55
Johnsongrass 0 0 Velvetleaf 60 40
Kochia 90 85 Waterhemp 70 70
Lambsquarters 70 70 Wheat 10 5
Morningglory 25 5
Table D Compounds
16 g ai/ha 35 50 53 54 55 57 58 60 63 96 113 116 118 120
Postemergence
Barnyardgrass 15 0 5 0 5 0 0 0 5 0 10 5 10 10
Blackgrass 35 0 5 0 5 0 0 0 5 0 5 0 5 20
Chickweed 85 0 50 5 70 30 5 45 60 60 70 5 75 95
Corn 5 0 0 0 10 0 0 0 5 5 5 5 5 15
Crabgrass, Large 10 0 10 5 5 5 5 5 5 5 10 5 10 30
Foxtail, Giant 5 0 40 0 40 0 0 0 0 0 5 5 5 10
Galium 70 30 60 50 80 40 40 30 60 70 80 60 85 98
Johnsongrass 10 0 0 0 5 0 0 0 5 0 5 10 5 5
Kochia 100 0 90 50 98 75 35 50 90 25 90 100 95 98 Lambsquarters 80 0 70 0 75 60 10 20 10 65 70 40 75 100
Morningglory 60 0 50 5 70 5 20 0 50 85 85 15 85 85
Nutsedge, Yellow 5 - - - 0 0 0 0 0 0 5 5 5 5
Oat, Wild 10 0 5 0 5 0 0 5 0 15 10 5 5 35
Oilseed Rape 45 5 70 5 95 30 5 60 60 40 80 50 5 80
Pigweed 80 0 85 60 85 30 20 20 85 98 90 75 80 98
Ragweed 45 5 50 0 25 20 20 15 10 0 80 40 80 40
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 5 0 0 5
Soybean 65 5 60 15 65 40 55 65 35 15 80 40 75 90
Velvetleaf 50 0 55 0 35 10 60 40 10 20 60 55 65 70
Waterhemp 75 0 80 45 85 60 35 15 85 85 85 70 85 90
Wheat 0 0 0 0 5 0 0 0 0 0 0 70 0 0
Table D Compounds
16 g ai/ha 121 130 131 143 144 145 149 153 156 157 162 168 169 170
Postemergence
Barnyardgrass 20 10 10 5 5 5 5 5 0 5 5 5 5 0
Blackgrass 5 0 5 10 5 15 0 0 0 5 0 10 0 0
Chickweed 95 80 65 45 70 70 5 20 5 50 50 65 5 30
Corn 10 10 5 5 5 5 0 0 5 5 5 5 0 5
Crabgrass, Large 15 10 5 10 5 5 5 0 5 5 5 5 5 5
Foxtail, Giant 10 5 10 5 5 5 5 0 5 40 10 35 0 5
Galium 80 65 80 50 80 80 60 70 20 60 60 70 55 50
Johnsongrass 35 0 5 0 5 5 5 0 0 0 5 5 0 0
Kochia 98 90 85 100 100 100 90 50 10 80 100 100 40 5
Lambsquarters 98 85 95 80 85 70 55 15 25 25 50 55 5 10
Morningglory 65 55 70 95 85 85 25 5 5 20 45 40 15 30
Nutsedge, Yellow 5 0 0 0 5 5 0 0 0 5 0 5 0 0
Oat, Wild 25 5 10 0 0 5 0 0 0 0 5 10 0 0
Oilseed Rape 70 60 60 50 25 60 20 50 5 5 5 85 0 5
Pigweed 98 85 85 75 85 90 85 20 65 65 75 60 75 60
Ragweed 20 70 30 0 25 10 5 10 5 20 20 20 5 5
Ryegrass, Italian 0 0 0 0 0 0 0 0 0 0 0 5 0 0
Soybean 55 50 30 30 60 50 30 35 15 10 25 45 5 10
Velvetleaf 75 80 45 30 35 60 10 5 10 10 20 40 10 5
Waterhemp 95 75 85 85 85 85 80 5 35 75 95 80 55 65
Wheat 0 5 0 0 5 5 0 0 0 0 0 10 0 0 Table D Compounds
16 g ai/ha 178 179 .80 183 185 191 192 198 200 212 220 221 224 228
Postemergence
Barnyardgrass 10 0 0 5 0 5 5 10 5 5 10 0 5 15
Blackgrass 0 5 0 0 0 0 0 5 30 0 5 5 0 15
Chickweed 50 70 60 30 0 50 0 5 60 10 40 75 10 85
Corn 0 5 5 10 0 5 0 5 5 5 5 0 0 5
Crabgrass, Large 5 5 5 5 0 5 5 10 10 5 15 10 5 15
Foxtail, Giant 0 5 60 5 35 5 10 10 5 10 5 35 0 10
Galium 75 70 65 65 0 40 35 70 75 60 60 80 40 85
Johnsongrass 10 0 0 0 0 5 0 5 15 5 5 0 5 10
Kochia 90 90 85 90 0 50 50 60 95 90 100 98 35 100
Lambsquarters 25 70 70 35 10 50 35 10 70 40 70 85 55 85
Morningglory 70 30 40 65 0 65 0 55 55 75 75 65 15 65
Nutsedge, Yellow 5 5 0 5 0 0 0 5 5 10 5 5 0 5
Oat, Wild 0 0 0 0 0 0 0 5 20 0 5 5 0 10
Oilseed Rape 35 40 5 5 0 0 0 30 70 10 10 70 0 65
Pigweed 80 80 70 55 10 35 15 85 90 100 85 95 85 85
Ragweed 5 30 30 15 10 30 0 30 30 35 25 35 30 20
Ryegrass, Italian 0 0 0 0 0 0 0 0 20 0 0 5 0 0
Soybean 15 25 45 65 15 45 10 10 60 60 10 35 35 60
Velvetleaf 60 15 45 30 5 15 20 50 30 20 25 70 10 35
Waterhemp 70 60 40 80 5 25 20 85 80 80 80 70 70 90
Wheat 0 5 5 5 0 0 0 0 5 0 0 0 0 0
Table D Compounds Table D Compounds
16 g ai/ha 229 230 8 g ai/ha 35 156 157 220
Postemergence Postemergence
Barnyardgrass 5 5 Barnyardgrass 10 0 0 10
Blackgrass 0 0 Blackgrass 30 0 0 0
Chickweed 60 65 Chickweed 50 5 10 40
Corn 5 0 Corn 5 0 0 5
Crabgrass, Large 0 0 Crabgrass, Large 5 0 5 5
Foxtail, Giant 0 5 Foxtail, Giant 5 0 20 5
Galium 70 80 Galium 80 20 50 55
Johnsongrass 0 0 Johnsongrass 0 0 0 0
Kochia 85 65 Kochia 95 0 20 100
Lambsquarters 60 55 Lambsquarters 75 10 25 35 Morningglory 40 5 Morningglory 25 5 5 25
Nutsedge, Yellow 0 0 Nutsedge, Yellow 5 0 5 0
Oat, Wild 0 0 Oat, Wild 5 0 0 0
Oilseed Rape 45 50 Oilseed Rape 5 5 5 5
Pigweed 55 60 Pigweed 80 15 70 80
Ragweed 35 30 Ragweed 40 0 15 15
Ryegrass, Italian 0 0 Ryegrass, Italian 0 0 0 0
Soybean 20 50 Soybean 40 5 10 10
Velvetleaf 15 25 Velvetleaf 30 0 5 10
Waterhemp 60 65 Waterhemp 75 5 55 70
Wheat 0 5 Wheat 0 0 0 0
Table D Compounds Table D Compound
4 g ai/ha 157 220 2 g ai/ha 220
Postemergence Postemergence
Barnyardgrass 0 5 Barnyardgrass 5
Blackgrass 0 0 Blackgrass 0
Chickweed 5 10 Chickweed 5
Corn 0 5 Corn 0
Crabgrass, Large 0 5 Crabgrass, Large 5
Foxtail, Giant 0 5 Foxtail, Giant 0
Galium 10 50 Galium 50
Johnsongrass 0 0 Johnsongrass 0
Kochia 0 50 Kochia 20
Lambsquarters 20 45 Lambsquarters 55
Morningglory 0 15 Morningglory 35
Nutsedge, Yellow 0 0 Nutsedge, Yellow 0
Oat, Wild 0 0 Oat, Wild 0
Oilseed Rape 0 5 Oilseed Rape 0
Pigweed 35 75 Pigweed 70
Ragweed 50 15 Ragweed 5
Ryegrass, Italian 0 0 Ryegrass, Italian 0
Soybean 5 10 Soybean 15
Velvetleaf 5 15 Velvetleaf 5
Waterhemp 20 60 Waterhemp 15
Wheat 0 0 Wheat 0 Table D Compound Table D Compound 250 g ai/ha 62 250 g ai/ha 62
Preemergence Preemergence
Barnyardgrass 100 Nutsedge, Yellow 60
Blackgrass 90 Oilseed Rape 100
Corn 70 Pigweed 100
Crabgrass, Large 100 Ragweed 85
Foxtail, Giant 100 Ryegrass, Italian 95
Galium 100 Soybean 95
Johnsongrass 98 Velvetleaf 100
Lambsquarters 100 Waterhemp 100
Morningglory 100 Wheat 50
Table D Compounds
125 g ai/ha 53 54 55 57 58 60 62 63 104 113 118 120 131 144
Preemergence
Barnyardgrass 95 95 100 85 80 75 100 100 70 100 100 100 100 100
Blackgrass 95 70 90 60 95 70 90 90 30 80 90 90 95 95
Corn 5 0 80 30 20 5 60 15 0 40 30 75 65 65
Crabgrass, Large 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Foxtail, Giant 100 95 100 100 98 95 100 100 100 100 100 100 100 100
Galium 98 85 100 90 100 98 100 98 70 90 95 90 90 98
Johnsongrass 55 40 100 80 50 45 90 85 65 100 100 98 85 100
Lambsquarters 100 85 98 100 100 100 98 95 90 98 98 100 98 100
Morningglory 40 15 100 45 45 20 98 60 25 95 90 75 85 100
Nutsedge, Yellow 5 15 70 20 15 5 10 5 0 60 65 45 70 85
Oilseed Rape 100 100 100 100 100 100 100 98 50 100 100 100 95 100
Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Ragweed 85 35 95 100 100 90 75 70 60 90 85 100 25 100
Ryegrass, Italian 60 30 95 50 5 30 90 90 5 70 60 90 90 98
Soybean 80 20 98 95 85 95 85 60 25 80 95 50 85 95
Velvetleaf 100 100 100 100 100 100 100 100 65 100 100 100 98 100
Waterhemp 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Wheat 5 0 60 5 0 0 40 45 5 20 5 5 5 25
Table D Compounds
125 g ai/ha 145 158 168 179 180 183 200 229
Preemergence Barnyardgrass 100 20 100 35 80 90 100 100
Blackgrass 95 90 90 80 70 50 90 85
Corn 45 15 55 5 30 5 20 40
Crabgrass, Large 100 100 100 100 100 100 100 100
Foxtail, Giant 100 100 100 85 100 100 100 98
Galium 100 100 100 98 98 95 95 98
Johnsongrass 95 40 100 65 90 45 100 70
Lambsquarters 100 80 98 100 90 100 100 95
Morningglory 100 70 100 15 100 40 90 45
Nutsedge, Yellow 45 5 45 25 30 5 15 45
Oilseed Rape 100 98 100 100 100 100 100 100
Pigweed 100 100 100 100 100 100 100 100
Ragweed 100 50 100 60 55 10 80 95
Ryegrass, Italian 85 20 95 80 65 50 90 60
Soybean 90 95 85 45 80 80 85 95
Velvetleaf 100 70 100 100 100 100 100 100
Waterhemp 100 100 100 100 100 100 100 98
Wheat 10 0 85 35 30 0 40 15
Table D Compounds
62 g ai/ha 32 35 53 54 55 57 58 60 62 63 104 113 118 120
Preemergence
Barnyardgrass 98 100 40 10 100 75 65 30 98 98 25 98 100 90
Blackgrass 35 90 90 40 90 50 80 10 90 90 0 70 60 90
Corn 0 15 100 0 35 5 10 0 30 15 0 25 30 25
Crabgrass, Large 100 100 98 90 100 100 100 100 100 98 98 100 100 100
Foxtail, Giant 95 100 98 95 100 100 85 40 100 98 90 100 100 98
Galium 75 100 100 60 100 90 100 100 100 98 75 98 95 90
Johnsongrass 85 98 35 10 85 40 20 15 75 70 15 90 85 95
Lambsquarters 100 100 100 85 100 100 100 85 95 90 90 98 95 90
Morningglory 0 90 45 5 100 35 0 10 55 25 25 85 85 60
Nutsedge, Yellow 25 5 0 0 55 20 0 0 5 0 0 15 15 35
Oilseed Rape 100 100 100 100 100 100 100 90 98 98 30 100 100 95
Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Ragweed 70 80 55 10 90 100 75 65 65 55 55 85 70 25
Ryegrass, Italian 10 80 15 5 85 5 0 0 60 80 0 60 65 90
Soybean 65 85 55 20 95 95 80 65 70 45 25 90 80 60
Velvetleaf 85 100 100 85 100 100 100 100 100 100 70 100 100 100 Waterhemp 98 100 100 100 100 100 100 100 100 100 100 100 100 100
Wheat 5 15 0 0 25 0 0 0 10 10 5 10 0 5
Table D Compounds
62 g ai/ha 131 143 144 145 158 168 179 180 183 200 229
Preemergence
Barnyardgrass 85 98 100 85 35 100 15 35 30 100 65
Blackgrass 90 90 95 95 50 90 45 60 0 90 70
Corn 60 100 15 10 5 25 0 5 0 10 5
Crabgrass, Large 100 100 100 100 85 100 75 100 98 100 100
Foxtail, Giant 100 100 100 100 85 100 85 85 80 100 90
Galium 90 80 98 100 100 100 90 98 95 100 98
Johnsongrass 80 80 100 90 10 85 20 60 20 85 45
Lambsquarters 85 85 100 100 100 100 100 100 90 95 80
Morningglory 35 55 100 90 15 80 0 5 5 70 35
Nutsedge, Yellow 5 5 50 30 5 15 0 0 0 0 10
Oilseed Rape 85 95 100 100 90 100 - 100 100 100 100
Pigweed 100 100 100 100 100 100 100 100 100 100 100
Ragweed 0 40 100 75 70 100 40 15 0 70 55
Ryegrass, Italian 35 70 80 70 0 95 15 50 15 85 20
Soybean 50 25 90 75 45 55 30 60 35 40 60
Velvetleaf 80 85 100 100 40 100 85 90 90 100 100
Waterhemp 100 100 100 100 100 100 90 95 95 100 98
Wheat 0 0 25 5 0 45 0 0 0 20 0
Table D Compounds
31 g ai/ha 32 35 53 54 55 57 58 60 62 63 104 113 118 120
Preemergence
Barnyardgrass 55 75 5 5 85 20 5 5 50 65 10 95 60 75
Blackgrass 30 90 25 5 90 5 5 5 5 85 0 40 10 60
Corn 0 0 10 0 20 0 20 0 35 5 0 0 5 35
Crabgrass, Large 98 100 95 75 100 85 90 55 95 98 85 100 100 100
Foxtail, Giant 85 98 85 10 100 90 15 5 95 80 80 100 100 98
Galium 65 100 95 85 100 70 98 85 100 98 80 90 98 98
Johnsongrass 75 60 0 0 75 10 10 0 30 35 20 70 70 55
Lambsquarters 98 98 100 60 100 100 100 80 100 90 80 98 90 95
Morningglory 5 55 0 0 50 20 25 0 25 0 5 35 5 30
Nutsedge, Yellow 0 5 0 0 10 10 0 0 0 0 0 10 0 5
Oilseed Rape 100 100 100 85 100 100 98 98 100 98 0 100 98 90 Pigweed 98 100 100 100 100 85 100 100 100 100 100 100 100 100
Ragweed 75 75 40 40 75 35 35 55 0 20 25 55 20 0
Ryegrass, Italian 0 30 10 5 35 0 0 0 40 40 0 10 5 35
Soybean 25 60 25 10 35 65 35 55 60 15 20 40 75 10
Velvetleaf 55 85 100 70 100 100 100 100 90 100 50 85 70 75
Waterhemp 100 100 100 85 100 90 100 100 100 100 100 100 100 100
Wheat 0 5 0 0 0 0 0 0 0 0 0 5 0 0
Table D Compounds
31 g ai/ha 131 143 144 145 157 158 168 179 180 183 200 229
Preemergence
Barnyardgrass 75 70 80 85 5 5 75 5 0 5 95 55
Blackgrass 80 15 95 90 5 15 90 30 0 0 90 15
Corn 10 5 5 5 0 0 15 0 0 0 0 5
Crabgrass, Large 100 100 98 100 40 90 100 65 75 70 100 85
Foxtail, Giant 100 100 100 100 20 55 100 30 60 35 100 70
Galium 30 80 98 98 85 50 100 90 80 50 98 80
Johnsongrass 30 60 75 75 5 0 95 0 10 5 60 10
Lambsquarters 80 85 100 100 100 100 100 100 100 85 98 80
Morningglory 40 35 75 55 10 15 70 0 0 0 45 0
Nutsedge, Yellow 5 0 30 0 0 0 5 0 0 0 0 0
Oilseed Rape 50 85 100 100 100 50 100 95 95 100 100 100
Pigweed 100 100 100 100 100 75 100 100 98 60 100 100
Ragweed 0 30 85 60 0 60 45 30 5 0 5 50
Ryegrass, Italian 20 5 60 35 5 0 95 5 0 0 80 20
Soybean 10 10 75 60 50 25 30 0 25 10 10 35
Velvetleaf 65 75 100 100 75 25 100 65 85 80 100 90
Waterhemp 100 98 100 100 100 100 100 90 95 100 100 100
Wheat 0 0 5 0 5 0 5 0 0 0 5 0
Table D Compounds
16 g ai/ha 32 35 53 54 55 57 58 60 63 104 113 118 120 131
Preemergence
Barnyardgrass 5 65 0 0 25 5 5 0 30 0 30 10 25 30
Blackgrass 0 70 5 5 15 5 0 0 30 0 10 0 70 5
Corn 0 0 5 0 5 0 5 0 0 0 0 0 0 0
Crabgrass, Large 90 100 65 10 100 75 25 5 65 65 98 100 98 98
Foxtail, Giant 35 90 10 0 100 50 0 0 30 30 85 98 95 80
Galium 25 100 85 50 100 80 0 98 75 90 90 60 90 95 Johnsongrass 45 10 0 0 30 0 10 0 5 5 10 10 50 0
Lambsquarters 95 100 100 5 100 80 25 10 95 65 85 90 70 75
Morningglory 0 0 0 0 10 10 10 0 0 5 20 30 0 0
Nutsedge, Yellow 65 0 20 0 0 0 0 0 0 0 0 0 0 0
Oilseed Rape 80 98 80 60 100 100 60 80 70 0 98 85 50 10
Pigweed 100 100 95 5 100 75 50 75 95 100 100 100 100 100
Ragweed 60 40 0 10 70 25 100 15 75 40 40 85 0 0
Ryegrass, Italian 0 0 0 0 15 0 0 0 0 0 5 0 5 0
Soybean 15 30 0 0 25 - 30 35 5 10 35 80 75 5
Velvetleaf 40 85 100 15 90 100 85 60 40 25 70 80 50 20
Waterhemp 100 100 100 25 100 100 100 80 90 100 100 100 100 100
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table D Compounds
16 g ai/ha 143 144 145 157 158 168 179 180 183 200 229
Preemergence
Barnyardgrass 20 70 65 0 0 35 0 0 5 35 15
Blackgrass 10 55 15 0 0 85 0 0 0 85 15
Corn 0 0 0 5 0 0 0 0 0 0 0
Crabgrass, Large 98 90 85 5 25 100 10 30 5 98 75
Foxtail, Giant 85 100 85 0 5 100 5 5 5 95 5
Galium 10 95 90 80 0 100 90 75 50 85 40
Johnsongrass 15 20 10 0 0 35 0 0 0 25 10
Lambsquarters 70 100 100 100 75 90 75 95 80 75 35
Morningglory 10 20 15 0 5 5 0 0 0 5 0
Nutsedge, Yellow 0 15 0 0 0 5 0 0 0 0 0
Oilseed Rape 0 98 40 40 40 95 30 70 50 85 90
Pigweed 100 100 100 100 70 85 30 80 50 100 100
Ragweed 0 75 25 0 80 35 25 0 0 0 35
Ryegrass, Italian 5 5 0 0 0 70 0 0 0 30 0
Soybean 5 35 10 0 0 5 0 5 0 100 5
Velvetleaf 30 100 90 45 35 85 15 75 40 100 70
Waterhemp 100 100 100 100 100 100 75 40 10 98 95
Wheat 0 0 0 0 0 0 0 0 0 0 0
Table D Compounds Table D Compound
8 g ai/ha 32 35 143 4 g ai/ha 157
Preemergence Preemergence
Barnyardgrass 0 5 5 Barnyardgrass 0 Blackgrass 0 70 0 0 Blackgrass 0
Corn 0 0 0 0 Corn 0
Crabgrass, Large 100 80 60 0 Crabgrass, Large 0
Foxtail, Giant 0 70 40 0 Foxtail, Giant 0
Galium 0 85 10 80 Galium 70
Johnsongrass 0 0 35 0 Johnsongrass 0
Lambsquarters 95 100 25 25 Lambsquarters 0
Morningglory 0 0 0 0 Morningglory 0
Nutsedge, Yellow 60 0 0 0 Nutsedge, Yellow 0
Oilseed Rape 50 85 0 0 Oilseed Rape 0
Pigweed 100 100 90 100 Pigweed 20
Ragweed 75 55 0 0 Ragweed 0
Ryegrass, Italian 0 0 0 0 Ryegrass, Italian 0
Soybean 10 10 0 0 Soybean 0
Velvetleaf 5 65 35 5 Velvetleaf 0
Waterhemp 100 100 95 70 Waterhemp 0
Wheat 0 0 0 0 Wheat 0
Table D Compounds
250 g ai/ha 1 32 40 53 55 144 145 178 180 221
Flood
Barnyardgrass 0 20 0 0 30 35 35 0 10 60
Ducksalad 0 95 40 80 90 100 95 70 75 90
Rice 0 15 0 0 0 40 35 0 0 40
Sedge, Umbrella 0 90 50 75 100 95 90 75 80 95
Table D Compounds
125 g ai/ha 1 32 40 53 55 144 145 178 180
Flood
Barnyardgrass 0 10 0 0 10 15 0 0 10
Ducksalad 0 65 20 80 85 90 95 70 75
Rice 0 0 0 0 0 25 15 0 0
Sedge, Umbrella 0 65 30 70 85 95 90 60 75
Table D Compounds
62 g ai/ha 1 32 40 53 55 144 145 178 180 221
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 0 40
Ducksalad 0 60 0 50 80 85 85 65 0 80
Rice 0 0 0 0 0 15 15 0 0 15 Sedge, Umbrella 0 40 0 0 75 80 75 60 50
Table D Compounds
31 g ai/ha 1 32 40 53 55 144 145 178 180
Flood
Barnyardgrass 0 0 0 0 0 0 0 0 0
Ducksalad 0 0 0 40 75 75 80 40 0
Rice 0 0 0 0 0 0 0 0 0
Sedge, Umbrella 0 0 0 0 75 65 60 30 0
TEST E
Seeds of plant species selected from bluegrass (annual bluegrass, Poa annua), blackgrass (Alopecurus myosuroides), canarygrass (Phalaris minor), chickweed (common chickweed, Stellaria media), galium (catchweed bedstraw, Galium aparine), downy bromegrass (Bromus tectorum), field poppy (Papaver rhoeas), field violet (Viola arvensis), green foxtail (Setaria viridis), deadnettle (henbit deadnettle, Lamium amplexicaule), Italian ryegrass (Lolium multiflorum), kochia (Kochia scoparia), lambsquarters (Chenopodium album), oilseed rape (Brassica napus), pigweed (Amaranthus retroflexus), Russian thistle (Salsola iberica), chamomile (scentless chamomile, Matricaria inodora), speedwell (bird's- eye speedwell, Veronica persica), spring barley (Hordeum vulgare), spring wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua), wild radish (Raphanus raphanistrum), windgrass (Apera spica-venti), winter barley (Hordeum vulgare), and winter wheat (Triticum aestivum) were planted into a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, these species were planted in pots containing Redi-Earth® planting medium (Scotts Company, 14111 Scottslawn Road, MarysviUe, Ohio 43041) comprising spaghnum peat moss, vermiculite, wetting agent and starter nutrients and treated with postemergence applications of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage).
Treated plants and controls were maintained in a controlled growth environment for 7 to 21 days after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table E, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table E Compounds
125 g ai/ha 35 53 55 62 144 145 168 200
Postemergence
Barley, Spring 25 10 20 25 45 30 25 35
Barley, Winter 30 10 10 35 45 40 15 25
Blackgrass 60 25 40 75 85 80 60 75 Bluegrass 60 5 25 60 65 70 15 70
Bromegrass, Downy 30 5 10 40 75 55 35 35
Buckwheat, Wild 95 95 95 100 100 100 100 100
Canarygrass 60 40 30 55 85 65 55 60
Chamomile 10 0 5 10 95 30 10 15
Chickweed 100 65 70 90 100 95 90 100
Deadnettle 80 65 80 70 - 100 80 90
Field Poppy 100 80 95 75 100 100 100 100
Field Violet 75 70 90 85 100 100 95 95
Foxtail, Green 55 25 60 65 100 98 75 55
Galium 85 75 85 90 100 100 85 90
Kochia 90 80 85 95 100 100 85 90
Lambsquarters 90 75 90 95 100 95 95 95
Mustard, Wild 100 95 95 100 100 100 95 100
Oat, Wild 60 25 50 60 90 80 65 35
Oilseed Rape 100 80 95 100 100 100 100 100
Pigweed 90 90 95 95 100 100 95 90
Radish, Wild 95 90 80 100 100 100 85 95
Russian Thistle - - - - 98 100 - -
Ryegrass, Italian 60 5 20 35 65 40 25 40
Speedwell 100 100 100 100 100 100 100 100
Wheat, Spring 40 35 45 40 75 55 40 35
Wheat, Winter 40 35 40 35 70 55 35 25
Windgrass 40 20 40 65 55 60 40 45
Table E Compounds
62 g ai/ha 35 53 55 62 144 145 168 200
Postemergence
Barley, Spring 10 10 15 20 35 20 15 25
Barley, Winter 5 5 5 20 35 30 10 20
Blackgrass 55 10 20 40 60 65 35 55
Bluegrass 40 5 15 55 55 65 10 55
Bromegrass, Downy 15 5 10 20 40 55 25 25
Buckwheat, Wild 90 90 95 95 100 100 95 95
Canarygrass 55 25 30 45 65 40 25 45
Chamomile 5 5 5 5 80 30 10 10
Chickweed 75 60 70 80 100 100 70 100
Deadnettle 70 60 70 65 - 100 75 80 Field Poppy 80 80 100 70 100 100 100 100
Field Violet 75 70 85 70 100 90 90 75
Foxtail, Green 55 10 50 25 80 40 60 45
Galium 75 75 80 75 100 98 80 75
Kochia 80 70 85 90 100 100 85 85
Lambsquarters 85 65 85 95 98 95 90 90
Mustard, Wild 85 95 95 100 100 100 95 100
Oat, Wild 35 10 40 35 65 40 40 30
Oilseed Rape 95 80 90 80 100 100 95 100
Pigweed 90 90 95 95 100 100 95 90
Radish, Wild 85 90 80 90 100 100 80 85
Russian Thistle - - - - 95 90 - -
Ryegrass, Italian 25 5 15 30 40 25 20 25
Speedwell 100 95 100 100 100 100 90 100
Wheat, Spring 25 20 25 25 45 45 25 20
Wheat, Winter 25 15 30 30 35 35 25 15
Windgrass 30 10 25 30 25 20 25 35
Table E Compounds
31 g ai/ha 35 53 55 62 144 145 168 200
Postemergence
Barley, Spring 5 5 10 15 25 15 15 15
Barley, Winter 0 5 0 10 20 15 10 10
Blackgrass 35 5 10 30 50 35 25 35
Bluegrass 20 0 0 35 45 60 5 35
Bromegrass, Downy 5 0 0 15 35 35 15 10
Buckwheat, Wild 85 65 95 80 95 100 95 70
Canarygrass 25 10 20 35 60 25 15 35
Chamomile 5 5 5 5 75 30 5 10
Chickweed 75 50 55 70 100 85 45 75
Deadnettle 60 30 50 35 - 100 55 60
Field Poppy 75 65 90 55 100 100 85 80
Field Violet 65 50 70 65 90 100 75 80
Foxtail, Green 35 10 45 20 50 30 60 35
Galium 80 75 85 70 95 95 75 75
Kochia 75 55 70 75 100 100 80 85
Lambsquarters 80 70 80 95 95 90 85 85
Mustard, Wild 85 75 85 100 100 100 95 95 Oat, Wild 15 5 15 25 25 30 10 20
Oilseed Rape 80 75 75 80 100 100 85 85
Pigweed 90 85 90 90 100 100 80 90
Radish, Wild 75 60 70 70 100 100 75 80
Russian Thistle - - - - 90 85 - -
Ryegrass, Italian 5 0 20 20 15 10 10 10
Speedwell 100 60 80 95 100 100 75 100
Wheat, Spring 10 10 15 20 35 35 20 10
Wheat, Winter 15 5 15 20 30 20 10 5
Windgrass 25 5 10 20 20 10 15 20
Table E Compounds
16 g ai/ha 35 53 55 62 144 145 168 200
Postemergence
Barley, Spring 5 5 10 10 15 15 10 10
Barley, Winter 0 5 0 5 30 15 5 5
Blackgrass 20 0 5 15 25 25 15 15
Bluegrass 15 0 0 10 25 15 10 20
Bromegrass, Downy 5 0 5 10 25 25 5 5
Buckwheat, Wild 75 70 65 75 100 100 65 65
Canarygrass 10 5 10 25 35 15 15 10
Chamomile 5 5 5 0 80 20 5 5
Chickweed 65 30 55 65 85 80 50 65
Deadnettle 40 20 20 35 - 100 20 50
Field Poppy 70 60 85 40 100 100 55 75
Field Violet 60 25 65 60 95 65 75 70
Foxtail, Green 20 10 30 15 40 15 20 25
Galium 70 75 70 70 80 95 75 70
Kochia 75 50 65 65 100 98 80 70
Lambsquarters 80 65 75 75 80 90 75 75
Mustard, Wild 90 65 70 75 100 100 75 75
Oat, Wild 10 5 10 15 20 15 5 10
Oilseed Rape 70 70 75 65 100 70 70 75
Pigweed 85 85 85 90 98 100 90 85
Radish, Wild 65 60 75 65 100 95 70 65
Russian Thistle - - - - 85 80 - -
Ryegrass, Italian 0 0 20 10 5 5 5 5
Speedwell 75 60 75 70 100 100 80 70 Wheat, Spring 0 10 5 5 25 30 10 5
Wheat, Winter 5 5 0 10 20 15 5 0
Windgrass 10 5 5 10 10 5 10 10
Table E Compounds
125 g ai/ha 35 53 55 62 144 145 168 200
Preemergence
Barley, Spring - 35 50 0 65 80 35 -
Barley, Winter - 25 35 5 55 85 40 -
Blackgrass 95 30 100 65 100 75 100 100
Bluegrass 70 25 100 75 85 90 100 100
Bromegrass, Downy 25 15 55 20 55 60 40 80
Buckwheat, Wild 100 100 100 100 100 100 100 100
Canarygrass 100 95 100 90 100 100 100 100
Chamomile 70 - - 65 100 100 - 75
Chickweed 100 100 100 100 100 100 100 100
Deadnettle 95 65 0 100 100 100 100 100
Field Poppy 90 100 100 100 100 100 100 95
Field Violet 100 100 100 100 100 100 100 100
Foxtail, Green 100 55 100 85 100 100 100 100
Galium 100 100 100 100 100 100 100 100
Kochia 100 100 100 100 100 100 100 100
Lambsquarters 100 100 100 100 100 100 100 100
Mustard, Wild 95 100 100 100 100 100 100 100
Oat, Wild 35 25 45 20 75 85 50 75
Oilseed Rape 100 100 100 100 100 100 100 100
Pigweed 100 100 100 100 100 100 100 100
Radish, Wild 100 90 100 100 100 100 100 95
Russian Thistle - - - - 100 100 - -
Ryegrass, Italian 75 25 50 25 100 70 75 85
Speedwell 100 100 100 100 100 100 100 100
Wheat, Spring - 10 35 10 55 70 30 -
Wheat, Winter - 30 20 5 35 75 30 -
Windgrass 100 50 100 50 100 98 100 100
Table E Compounds
62 g ai/ha 35 53 55 62 144 145 168 200
Preemergence
Barley, Spring - 35 45 0 45 45 30 - Barley, Winter - 30 10 5 55 30 25 -
Blackgrass 65 25 60 15 98 60 100 90
Bluegrass 35 20 10 10 40 10 80 95
Bromegrass, Downy 35 15 55 10 35 35 10 45
Buckwheat, Wild 90 100 100 80 100 85 100 100
Canarygrass 95 65 100 50 100 100 100 100
Chamomile 70 - - 60 100 100 - 60
Chickweed 95 100 100 100 100 100 100 100
Deadnettle 95 50 0 40 100 100 80 100
Field Poppy 90 100 100 100 100 100 100 95
Field Violet 90 60 100 35 100 100 100 -
Foxtail, Green 90 20 100 65 95 55 100 100
Galium 100 60 70 65 100 100 100 55
Kochia 100 55 100 85 100 100 100 100
Lambsquarters 90 100 100 95 100 100 100 100 Mustard, Wild 95 100 100 95 100 100 95 85 Oat, Wild 45 10 35 15 65 30 35 30 Oilseed Rape 100 100 100 65 100 100 65 100 Pigweed 100 100 100 100 100 100 100 100 Radish, Wild 100 100 100 95 100 85 100 95 Russian Thistle - - - - 100 60 - - Ryegrass, Italian 35 25 50 15 70 50 30 30 Speedwell 100 100 100 95 100 100 100 100 Wheat, Spring - 10 15 0 40 20 20 - Wheat, Winter - 25 10 0 25 25 10 - Windgrass 85 35 100 50 100 75 100 100
Table E Compounds
31 g ai/ha 35 53 55 62 144 145 168 200
Preemergence
Barley, Spring - 35 10 0 25 25 15 -
Barley, Winter - 10 10 0 35 15 5 -
Blackgrass 60 10 15 15 75 50 35 75
Bluegrass 35 10 10 5 15 0 10 70
Bromegrass, Downy 35 15 20 0 10 20 10 35
Buckwheat, Wild 75 100 100 35 100 100 65 75
Canarygrass 55 20 20 0 80 75 15 55
Chamomile 10 - - 65 20 100 - 25 Chickweed 100 100 100 75 100 100 80 90
Deadnettle 80 10 0 20 100 100 50 90
Field Poppy 80 100 100 75 100 100 100 90
Field Violet 70 25 80 10 100 100 100 50
Foxtail, Green 90 10 25 40 35 45 100 25
Galium 55 30 100 60 70 100 60 25
Kochia 65 15 100 5 100 100 100 100
Lambsquarters 85 75 100 85 100 100 100 85
Mustard, Wild 60 100 100 80 100 100 80 95
Oat, Wild 0 0 15 10 30 30 10 0
Oilseed Rape 95 75 100 25 80 100 40 100
Pigweed 95 20 100 100 100 100 100 100
Radish, Wild 95 70 100 40 80 15 45 70
Russian Thistle - - - - 65 10 - -
Ryegrass, Italian 25 10 0 0 25 20 0 25
Speedwell 100 70 100 95 100 100 100 100
Wheat, Spring - 5 15 0 15 15 15 -
Wheat, Winter - 15 10 0 15 20 10 -
Windgrass 80 15 25 15 75 25 15 55
Table E Compounds
16 g ai/ha 35 53 55 62 144 145 168 200
Preemergence
Barley, Spring - 35 10 0 10 15 0 -
Barley, Winter - 15 5 0 30 10 0 -
Blackgrass 30 10 0 5 15 10 10 25
Bluegrass 0 10 0 0 10 0 0 20
Bromegrass, Downy 0 0 20 0 10 10 0 10
Buckwheat, Wild 60 65 65 25 85 100 0 65
Canarygrass 40 10 10 0 35 40 15 10
Chamomile 5 - - 0 15 5 - 25
Chickweed 55 100 65 65 100 100 100 70
Deadnettle 35 10 0 15 90 0 10 60
Field Poppy 75 100 100 65 100 100 80 80
Field Violet 15 50 70 0 95 100 85 -
Foxtail, Green 5 10 10 20 20 0 10 -
Galium 25 25 10 5 20 25 60 15
Kochia 25 10 55 0 98 60 35 70 Lambsquarters 65 60 95 35 100 100 45 10
Mustard, Wild 20 90 80 25 90 95 80 85
Oat, Wild 0 0 0 0 35 25 10 0
Oilseed Rape 60 50 20 10 35 50 10 60
Pigweed 90 30 75 95 100 100 55 100
Radish, Wild 100 50 70 25 80 15 0 80
Russian Thistle - - - - 15 0 - -
Ryegrass, Italian 0 10 0 0 10 10 0 0
Speedwell 100 100 100 95 100 95 100 100
Wheat, Spring - 5 15 0 5 15 15 -
Wheat, Winter - 15 5 0 0 0 5 -
Windgrass 35 0 5 0 10 10 0 15
TEST F
Seeds of plant species selected from corn (Zea mays), soybean (Glycine max), velvetleaf (Abutilon theophrasti), lambsquarters (Chenopodium album), wild poinsettia (Euphorbia heterophylla), palmer pigweed (Amaranthus palmeri), waterhemp (common waterhemp, Amaranthus rudis), Surinam grass (Brachiaria decumbens), large (Lg) crabgrass (Digitaria sanguinalis), Brazilian crabgrass (Digitaria horizontalis), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), goosegrass (Eleusine indica), johnsongrass (Sorghum halepense), ragweed (common ragweed, Ambrosia elatior), barnyardgrass (Echinochloa crus-galli), sandbur (southern sandbur, Cenchrus echinatus), arrowleaf sida (Sida rhombifolia), Italian ryegrass (Lolium multiflorum), dayflower (Virginia (VA) dayflower, Commelina virginica), field bindweed (Convolvulus arvensis), cocklebur (common cocklebur, Xanthium strumarium), morningglory (Ipomoea coccinea), nightshade (eastern black nightshade, Solanum ptycanthum), kochia (Kochia scoparia), yellow nutsedge (Cyperus esculentus), and hairy beggarticks (Bidens pilosa), were planted into a silt loam soil and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants from these crop and weed species and also waterhemp RESl, (ALS & Triazine resistant common waterhemp, Amaranthus rudis), and waterhemp_RES2, (ALS & HPPD resistant common waterhemp, Amaranthus rudis) were treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm for postemergence treatments (1- to 4-leaf stage).
Treated plants and controls were maintained in a greenhouse for 14 to 21 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table F, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result. Table F Compounds
125 g ai/ha 35 53 58 62 96 144 145 149 179 200 212 221
Postemergence
Arrowleaf Sida 98 98 90 98 95 100 95 98 100 95 100 98
Barnyardgrass 20 10 5 20 20 75 70 10 0 25 10 70
Beggarticks 70 60 65 80 40 75 70 50 50 10 40 70
Corn 20 10 5 10 10 10 20 15 15 25 0 20
Crabgrass, Brazil 40 20 10 10 25 55 50 25 30 20 35 75
Dayflower, VA 80 60 10 65 70 85 85 50 - 35 50 80
Field Bindweed 70 60 50 75 50 90 90 75 50 35 70 80
Horseweed - - - - 10 25 40 20 10 - 10 30
Kochia - 98 75 - 95 95 100 95 95 - 100 100
Panicum, Fall 50 60 15 60 25 60 80 40 10 15 10 60
Pigweed, Palmer 100 100 60 100 90 100 100 100 85 100 98 100
Poinsettia, Wild 80 70 60 50 50 65 80 70 35 80 60 80
Ragweed - - - - 40 90 70 35 50 - 50 80
Ryegrass, Italian 0 0 0 10 10 40 15 5 0 20 0 5
Sandbur 0 10 10 0 0 20 15 10 10 5 10 0
Soybean 98 95 95 85 80 95 95 90 90 90 95 95
Waterhemp 100 100 90 100 95 100 100 98 100 100 100 100
Waterhemp RESl 100 100 75 100 95 100 100 100 100 98 98 98
Waterhemp RES2 100 100 80 100 95 100 100 100 100 98 100 100
Table F Compounds
62 g ai/ha 35 53 55 58 62 96 144 145 149 179 200 212 221
Postemergence
Arrowleaf Sida 98 100 100 75 98 90 100 98 95 85 95 85 98
Barnyardgrass 10 0 35 0 20 20 50 50 10 0 15 0 30
Beggarticks 65 50 70 50 50 40 70 65 40 40 10 40 70
Corn 15 0 20 5 5 10 10 20 10 10 20 0 10
Crabgrass, Brazil 35 20 30 10 15 20 40 40 20 20 20 30 45
Dayflower, VA 50 50 - 20 25 70 60 75 40 - 15 40 80
Field Bindweed 50 50 70 30 50 20 80 80 50 35 35 60 -
Horseweed - - 20 - - 0 10 20 10 10 - 15 10
Kochia - 95 98 60 - 75 95 95 90 90 - 100 100
Panicum, Fall 50 15 30 10 10 10 35 50 20 15 5 10 40
Pigweed, Palmer 100 100 98 70 100 95 100 100 98 85 100 100 100
Poinsettia, Wild 50 70 45 50 50 60 70 80 60 20 60 50 70 Ragweed - - 55 - - 20 85 60 30 40 - 30 70
Ryegrass, Italian 0 5 10 0 10 0 20 10 10 0 15 0 0
Sandbur 0 5 15 0 0 0 20 5 15 5 0 0 0
Soybean 95 95 95 90 65 40 98 95 90 75 65 75 98
Waterhemp 100 100 100 80 100 100 100 100 95 95 98 95 95
Waterhemp RESl 100 95 100 70 100 95 100 100 90 100 95 95 100
Waterhemp RES2 100 100 100 75 100 90 100 100 100 100 98 98 95
Table F Compounds
31 g ai/ha 35 53 55 58 62 96 144 145 149 179 200 212 221
Postemergence
Arrowleaf Sida 95 98 95 60 95 80 100 95 85 80 85 70 90
Barnyardgrass 0 0 50 0 20 10 30 25 5 0 0 0 25
Beggarticks 60 40 55 50 10 30 60 50 30 50 5 40 60
Corn 15 0 15 0 0 5 5 10 10 0 10 0 10
Crabgrass, Brazil 30 15 40 5 10 5 50 20 20 20 15 30 25
Dayflower, VA 40 30 70 10 5 40 50 60 20 - 25 20 70
Field Bindweed 35 50 25 20 35 10 75 75 50 25 35 40 75
Horseweed - - 15 - - 0 0 20 20 0 - 0 5
Kochia - 80 95 30 - 75 95 100 80 75 - 90 98
Panicum, Fall 40 20 40 0 5 15 30 10 20 10 5 0 15
Pigweed, Palmer 95 90 98 50 95 80 100 100 95 90 98 75 90
Poinsettia, Wild 50 60 35 60 40 30 50 75 40 15 40 40 75
Ragweed - - 55 - - 20 50 50 40 40 - 20 60
Ryegrass, Italian 0 0 0 0 0 0 20 5 10 0 0 0 0
Sandbur 0 0 25 0 0 0 15 5 5 0 0 0 0
Soybean 85 95 70 70 40 - 95 95 85 50 40 50 95
Waterhemp 90 98 90 65 100 90 100 98 95 95 95 90 98
Waterhemp RESl 90 90 100 65 100 90 95 98 85 90 90 80 95
Waterhemp RES2 95 90 100 70 100 90 100 90 95 100 95 95 98
Table F Compounds
16 g ai/ha 35 53 58 62 96 144 145 149 179 200 212 221
Postemergence
Arrowleaf Sida 80 90 70 80 70 100 95 75 70 75 75 80
Barnyardgrass 0 0 0 15 0 10 10 0 0 0 0 15
Beggarticks 50 30 40 5 0 70 55 5 20 0 25 50
Corn 10 0 0 0 0 10 5 0 5 0 0 5
Crabgrass, Brazil 20 10 5 0 0 40 20 20 10 10 20 20 Dayflower, VA 40 40 5 0 20 50 50 10 - 0 30 60
Field Bindweed 30 55 10 40 5 70 70 60 15 20 30 70
Horseweed - - - - 0 0 0 0 0 - 0 0
Kochia - 60 40 - 65 95 98 60 65 - 50 95
Panicura, Fall 40 5 0 0 0 25 10 10 15 5 0 10
Pigweed, Palmer 75 65 50 70 70 90 95 65 70 95 30 85
Poinsettia, Wild 40 50 30 35 0 50 70 50 15 50 35 65
Ragweed - - - - 15 50 30 10 45 - 20 50
Ryegrass, Italian 0 0 0 0 0 10 10 0 0 0 0 0
Sandbur 0 0 0 0 0 10 5 0 0 0 0 0
Soybean 80 80 50 20 40 65 95 50 60 20 50 60
Waterhemp 85 95 60 90 75 100 95 85 70 80 90 90
Waterhemp RESl 80 85 20 85 85 90 95 80 90 75 70 85
Waterhemp RES2 90 80 60 80 85 98 95 95 95 95 70 90
Table F Compounds
8 g ai/ha 35 53 58 62 200
Postemergence
Arrowleaf Sida 60 70 50 65 65
Barnyardgrass 0 0 0 10 0
Beggarticks 50 15 40 5 0
Corn 10 0 0 0 0
Crabgrass, Brazil 10 0 5 0 10
Dayflower, VA 10 30 5 0 0
Field Bindweed 20 30 10 40 20
Kochia - 50 30 - -
Panicum, Fall 30 0 15 0 5
Pigweed, Palmer 60 70 50 90 85
Poinsettia, Wild 30 50 30 25 35
Ryegrass, Italian 0 0 0 0 0
Sandbur 0 0 0 0 0
Soybean 70 40 50 10 15
Waterhemp 70 80 65 80 75
Waterhemp RESl 90 70 10 80 70
Waterhemp RES2 90 70 65 80 75
Table F Compounds
125 g ai/ha 35 53 58 62 96 144 145 149 168 179 200
Preemergence Arrowleaf Sida 100 100 98 100 90 100 98 100 100 90 100
Barnyardgrass 65 50 15 25 0 100 75 35 100 5 60
Beggarticks 50 20 20 0 20 0 25 0 0 0 0
Cocklebur 0
Corn 20 15 0 0 0 35 60 0 35 40 0
Crabgrass, Brazil 100 90 75 100 5 100 100 85 100 25 100
Crabgrass, Large 100 98 80 98 95 100 100 85 100 60 100
Dayflower, VA 95 95 80 80 20 95 70 40 90 85 90
Field Bindweed 50 0 0 0 40 70 95 25 70 0 30
Foxtail, Giant 100 95 40 75 20 100 100 85 100 20 100
Foxtail, Green 98 90 25 90 25 100 100 50 100 15 100
Goosegrass 95 60 75 75 60 100 95 60 100 0 98
Johnsongrass 65 5 20 40 98 70 85 15 100 10 90
Kochia 100 100 30 95 90 100 100 90 100 98 100
Lambsquarters 100 98 100 100 100 100 100 100 100 100 100
Morningglory 65 0 10 50 25 95 35 10 75 25 15
Nightshade 100 98 98 100 90 100 98 100 98 100 98
Nutsedge, Yellow 35 20 0 0 0 0 0 15 20 0 35
Panicura, Fall 100 98 100 100 70 100 100 100 100 75 100 Pigweed, Palmer 100 35 100 100 100 100 100 100 65 100
Poinsettia, Wild 40 0 20 35 25 35 65 35 90 0 70
Ragweed 70 40 75 35 35 85 80 20 98 0 40
Ryegrass, Italian 70 0 0 40 30 100 90 40 70 10 40
Sandbur 65 0 0 35 30 95 95 10 90 0 75
Soybean 90 35 75 40 0 75 40 30 40 35 50
Surinam Grass 35 0 0 10 0 80 25 15 100 0 35
Velvetleaf 100 100 100 100 80 100 100 100 100 100 100
Waterhemp 100 100 100 100 100 100 100 100 100 100 100
Table F Compounds
62 g ai/ha 35 53 55 58 62 96 144 145 149 168 179 200 Preemergence
Arrowleaf Sida 100 100 100 75 95 80 100 98 65 100 80
Barnyardgrass 10 20 85 0 0 0 70 30 15 80 0
Beggarticks 20 30 0 10 0 0 0 30 0 0 0
Corn 0 0 40 0 0 0 40 40 0 40 0
Crabgrass, Brazil 100 85 100 35 100 0 98 95 35 100 15
Crabgrass, Large 75 80 100 65 70 65 100 98 70 98 35 Dayflower, VA 90 50 40 - 30 0 85 35 5 70 35 70
Field Bindweed 50 0 10 0 0 60 65 65 35 50 0 30
Foxtail, Giant 70 70 98 0 65 0 95 85 40 100 30 100
Foxtail, Green 75 20 70 0 40 35 98 100 50 100 0 100
Goosegrass 75 10 50 5 5 40 95 80 40 98 0 95
Johnsongrass 35 0 90 0 35 50 30 100 0 35 10 35
Kochia 100 50 100 0 35 65 100 100 75 100 70 80
Lambsquarters 100 95 100 90 95 100 100 100 100 100 100 98
Morningglory 30 0 98 10 0 35 65 15 0 15 35 0
Nightshade 98 98 98 90 98 65 100 98 98 98 100 98
Nutsedge, Yellow 10 0 0 0 0 0 0 0 0 0 0 10
Panicura, Fall 100 95 100 90 95 50 100 95 98 100 50 98
Pigweed, Palmer - 100 100 35 100 100 100 100 100 100 35 100
Poinsettia, Wild 70 0 30 20 25 0 20 65 0 50 0 60
Ragweed 40 30 50 25 40 50 95 65 35 65 0 35
Ryegrass, Italian 65 0 30 0 0 30 40 40 20 65 0 20
Sandbur 40 0 0 0 0 40 50 25 0 65 0 40
Soybean 70 0 50 35 10 0 40 15 0 20 0 30
Surinam Grass 20 0 10 0 15 0 75 0 15 70 0 10
Velvetleaf 100 100 100 100 100 80 100 100 85 100 90 100
Waterhemp 100 100 100 90 100 100 100 100 100 100 100 100
Table F Compounds
31 g ai/ha 35 53 55 58 62 96 144 145 149 168 179 200
Preemergence
Arrowleaf Sida 100 65 98 35 70 70 100 90 35 100 80 100
Barnyardgrass 20 0 10 0 0 0 20 5 0 25 0 0
Beggarticks 20 0 0 0 0 0 0 35 0 0 0 0
Cocklebur 0
Corn 30 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Brazil 98 5 75 0 75 0 95 80 15 100 0 98
Crabgrass, Large 75 15 98 50 25 30 100 95 0 95 0 85
Dayflower, VA 65 0 60 0 0 0 30 0 0 10 0 50
Field Bindweed 50 0 0 0 0 0 60 50 50 60 0 30
Foxtail, Giant 70 20 90 0 35 0 90 65 20 98 0 65
Foxtail, Green 30 0 20 0 10 30 95 40 0 100 0 98
Goosegrass 60 0 5 5 0 40 60 70 0 95 0 80
Johnsongrass 0 0 20 0 20 60 0 20 0 30 0 5 Kochia 85 20 100 0 20 0 100 98 0 100 0 50
Lambsquarters 100 95 100 65 95 100 100 100 0 100 100 98
Morningglory 0 0 30 10 0 35 0 10 0 0 0 0
Nightshade 98 90 98 80 70 0 98 80 80 98 65 60
Nutsedge, Yellow 0 0 0 0 0 0 0 0 0 0 0 0
Panicum, Fall 100 0 90 65 0 40 100 80 80 95 0 35
Pigweed, Palmer - 90 75 0 75 98 100 100 90 100 0 100
Poinsettia, Wild 35 0 0 20 30 0 0 0 0 0 0 20
Ragweed 0 0 40 0 25 20 0 70 25 35 0 10
Ryegrass, Italian 15 0 0 0 0 0 0 20 0 30 0 0
Sandbur 10 0 0 0 0 10 10 35 0 30 0 5
Soybean 40 0 40 20 0 0 10 0 0 0 0 20
Surinam Grass 0 0 0 0 15 0 75 0 0 65 0 0
Velvetleaf 70 90 100 100 75 60 100 98 70 75 65 80
Waterhemp 100 95 100 75 98 100 100 100 100 100 95 100
Table F Compounds
16 g ai/ha 35 53 58 62 96 144 145 149 168 179 200
Preemergence
Arrowleaf Sida 80 20 0 20 50 95 65 0 95 0 65
Barnyardgrass 0 0 0 0 0 0 0 0 0 0 0
Beggarticks 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Brazil 95 0 0 0 0 75 5 0 65 0 90
Crabgrass, Large 60 0 20 0 0 80 10 0 65 0 50
Dayflower, VA 25 0 0 0 0 0 0 0 5 0 15
Field Bindweed 35 0 0 0 0 40 0 0 40 0 0
Foxtail, Giant 10 0 0 15 0 15 0 0 65 0 35
Foxtail, Green 0 0 0 0 25 25 5 0 70 0 10
Goosegrass 0 0 0 0 50 75 0 0 80 0 70
Johnsongrass 0 0 0 0 20 0 0 0 0 0 0
Kochia 40 0 0 - 0 98 75 0 95 0 25
Lambsquarters 98 65 0 90 5 100 100 - 100 98 0
Morningglory 0 0 0 0 35 0 0 0 0 0 0
Nightshade 95 35 65 0 0 98 90 0 5 - 35
Nutsedge, Yellow 0 0 0 0 0 0 0 0 0 0 0
Panicum, Fall 35 0 35 0 - 95 65 0 35 0 70
Pigweed, Palmer - 0 0 80 80 100 100 25 98 0 85 Poinsettia, Wild 30 0 0 0 0 0 0 0 0 0 0
Ragweed 0 0 0 20 0 0 0 20 10 0 0
Ryegrass, Italian 0 0 0 0 0 0 25 0 15 0 0
Sandbur 10 0 0 0 0 0 0 0 10 0 5
Soybean 35 0 10 0 0 - 0 0 0 0 0
Surinam Grass 0 0 0 0 0 0 0 0 50 0 0
Velvetleaf 70 65 70 35 0 80 35 10 35 15 25
Waterhemp 100 0 75 85 40 98 100 35 100 95 98
Table F Compounds
8 g ai/ha 35 53 58 62 200
Preemergence
Arrowleaf Sida 50 0 20 0 0
Barnyardgrass 0 0 0 0 0
Beggarticks 0 0 0 0 0
Corn 0 0 0 0 0
Crabgrass, Brazil 0 0 0 0 0
Crabgrass, Large 0 0 0 0 0
Dayflower, VA 0 0 0 0 0
Field Bindweed 0 0 0 0 0
Foxtail, Giant 0 0 0 0 0
Foxtail, Green 0 0 0 0 0
Goosegrass 0 0 0 0 10
Johnsongrass 0 0 0 0 0
Kochia 0 0 0 10 20
Lambsquarters 90 65 - 70 0
Morningglory 0 0 0 0 0
Nightshade 75 - 0 0 0
Nutsedge, Yellow 0 0 0 0 0
Panicum, Fall 0 0 0 0 0
Pigweed, Palmer - 0 0 10 0
Poinsettia, Wild 20 0 0 0 0
Ragweed 0 0 0 0 0
Ryegrass, Italian 0 0 0 0 0
Sandbur 0 0 0 0 0
Soybean 0 0 0 0 0
Surinam Grass 0 0 0 0 0
Velvetleaf 40 0 20 0 0 Waterhemp 100 0 20 80 70
TEST G
Three plastic pots (ca. 16-cm diameter) per rate were partially filled with sterilized Tama silt loam soil comprising a 35:50: 15 ratio of sand, silt and clay and 2.6% organic matter. Separate plantings for each of the three pots were as follows. Seeds from the U.S. of monochoria {Monochoria vaginalis), small-flower umbrella sedge (Cyperus difformis), hardstem bulrush (Scirpus juncoides), and redstem (purple redstem, Ammannia coccinea), were planted into one 16-cm pot for each rate. Seeds from the U.S. of rice flatsedge {Cyperus iria), bearded sprangletop (Leptochloa fascicularis), one stand of 9 or 10 water seeded rice seedlings (Indica rice, Oryza sativa), and two stands of 3 or 4 transplanted rice seedlings (Oryza sativa cv. 'Japonica - M202') were planted into one 16-cm pot for each rate. Seeds from the U.S. of barnyardgrass (Echinochloa crus-galli), and late watergrass (Echinochloa oryzicola) were planted into one 16-cm pot for each rate. Plantings were sequential so that crop and weed species were at the 2.0 to 2.5-leaf stage at time of treatment.
Potted plants were grown in a greenhouse with day/night temperature settings of
30/27 °C, and supplemental balanced lighting was provided to maintain a 16-hour photoperiod. Test pots were maintained in the greenhouse until test completion.
At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Effects of treatments on rice and weeds were visually evaluated by comparison to untreated controls after 21 days. Plant response ratings, summarized in Table G, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table G Compounds Table G ' Compounds
250 g ai/ha 35 55 125 g ai/ha 35 55
Flood Flood
Barnyardgrass 100 100 Barnyardgrass 100 100
Bulrush, Hardstem 100 100 Bulrush, Hardstem 100 100
Flatsedge, Rice 100 100 Flatsedge, Rice 100 100
Monochoria 100 100 Monochoria 100 100
Redstem 100 100 Redstem 90 100
Rice, Transplanted 100 100 Rice, Transplanted 45 80
Rice, Water Seeded 100 100 Rice, Water Seeded 100 100
Sedge, Umbrella 100 100 Sedge, Umbrella 100 100
Sprangletop, Brdd. 100 100 Sprangletop, Brdd. 100 100
Watergrass, Late 100 100 Watergrass, Late 40 75 Table G Compounds Table G Compound;
64 g ai/ha 35 55 32 g ai/ha 35 55
Flood Flood
Barnyardgrass 45 75 Barnyardgrass 30 0
Bulrush, Hardstem 95 100 Bulrush, Hardstem 0 80
Flatsedge, Rice 100 100 Flatsedge, Rice 100 85
Monochoria 100 100 Monochoria 98 100
Redstem 85 95 Redstem 0 85
Rice, Transplanted 30 60 Rice, Transplanted 15 20
Rice, Water Seeded 70 100 Rice, Water Seeded 60 45
Sedge, Umbrella 98 100 Sedge, Umbrella 0 98
Sprangletop, Brdd. 100 80 Sprangletop, Brdd. 60 45
Watergrass, Late 30 0 Watergrass, Late 0 0

Claims

What is claimed is:
A compound selected from Formula 1, N-oxides and salts thereof,
Figure imgf000184_0001
Q is a 5- or 6-membered aromatic heterocylic ring, bound to the remainder of
Formula 1 through a carbon atom, and optionally substituted with 1 to 4 R1; Z is O or S;
each R1 is independently halogen, cyano, nitro, SF5, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-Cg alkylcycloalkyl, C4-Cg cycloalkylalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C2-Cg alkylaminocarbonyl, C3-C10 dialkylaminocarbonyl, C^-C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Cj-C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-Cg cycloalkylalkoxy, C2-Cg alkoxyalkyl,
Figure imgf000184_0002
haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C2-Cg alkoxyalkoxy, C2-C4 alkylcarbonyloxy,
Figure imgf000184_0003
cyanoalkyl, C2-C£ cyanoalkoxy, C^-C4 hydroxyalkyl, C2-C4 alkylthioalkyl, SOnR1A, Si(CH3)3 or B(-OC(R1B)2C(R1B)20-); or a phenyl ring optionally substituted with up to 5 substituents independently selected from R1C; or a 5- or
6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R1C on carbon atom ring members and R1D on nitrogen atom ring members;
R2 is halogen, cyano, nitro, Cj-C4 alkoxy, Cj-C4 alkyl, C2-C£ alkenyl, C2-C£ alkynyl,
SOnR2A, C1-C4 haloalkyl or C3-C6 cycloalkyl;
each R3 is independently halogen, cyano, hydroxy, nitro, amino, CHO, C(=0)NH2, C(=S)NH2, S02NH2, CrC4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, CrC4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-Cg alkylcycloalkyl, C4-Cg cycloalkylalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C3-C7 cycloalkylcarbonyl, C 1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, C1 -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C4-C8 cycloalkylalkoxy, C2-Cg alkoxyalkyl, C2-Cg haloalkoxyalkyl, C2-Cg alkoxyhaloalkyl, C2~Cg alkoxyalkoxy, C2-C4 alkylcarbonyloxy, C2-Cg cyanoalkyl, C2-Cg cyanoalkoxy, C2-C4 alkylthioalkyl,
Si(CH3)3, C≡CSi(CH3)3, C(=0)N(R3A)(R3B), C(=NOR3C)H, C(=NR3D)H, SOnR E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R F on carbon atom ring members and R3G on nitrogen atom ring members; or pyrimidinyloxy;
m is 0, 1, 2 or 3;
each n is independently 0, 1 or 2;
each R1A, R2A and R3E is independently CrC4 alkyl, CrC4 haloalkyl, CrC4
alkylamino or C2-Cg dialkylamino;
each R1B is independently H or Ci -C4 alkyl;
each R1C is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy;
each R1D is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2- Cg alkylcarbonyl;
each R3A is independently Ci -C4 alkyl or Ci -C4 haloalkyl;
each R B is independently H, Ci -C4 alkyl or Ci -C4 haloalkyl;
each R C is independently H or Ci -C4 alkyl;
each R3D is independently H, amino, Ci -C4 alkyl or Ci -C4 alkylamino;
each R F is independently hydroxy, halogen, cyano, nitro, C^-Cg alkyl, C^-Cg
haloalkyl, C^-Cg alkoxy or C^-Cg haloalkoxy; and
each R G is independently cyano, C^-Cg alkyl, C^-Cg haloalkyl, C^-Cg alkoxy or C2- Cg alkylcarbonyl;
2. A compound of Claim 1 wherein
Q is selected from Q-l through Q-55 wherein r is 0, 1, 2 or 3; and s is 0 or 1;
each R1 is independently halogen, cyano, SF5, CHO, Ci -C4 alkyl, C2-C4 alkenyl,
C2-C4 alkynyl, Ci -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C2~Cg alkylcarbonyl, C2~Cg haloalkylcarbonyl, C2~Cg alkoxycarbonyl, Ci -C4 alkoxy,
C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, C 1 -C4 hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A;
R3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, Ci -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C8 alkylcycloalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3- C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4
haloalkynyloxy, C3-C6 cycloalkoxy, C3-C6 halocycloalkoxy, C2-Cg
alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C4 alkylcarbonyloxy, C2-C6 cyanoalkyl, C(=0)N(R3A)(R3B), C(=NOR3C)H, SOnR3E; or a phenyl ring optionally substituted with up to 5 substituents independently selected from R3F; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members;
Z is O; and
m is 0, 1 or 2.
3. A compound of Claim 2 wherein
each R1 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C1 -C4 alkoxy, C3-C4 alkenyloxy, C3-C4 alkynyloxy, Ci -C4 haloalkoxy, C3-C4 haloalkenyloxy, C3-C4 haloalkynyloxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C1 -C4 hydroxyalkyl, C2-C4 alkylthioalkyl or SOnR1A;
R2 is halogen, Ci -C4 alkyl or Ci -C4 haloalkyl;
each R3 is independently halogen, cyano, CHO, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C 1 -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C2-C6 alkylcarbonyl, C2-C6
haloalkylcarbonyl, C2-C6 alkoxycarbonyl, Ci -C4 alkoxy, Ci -C4 haloalkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl, C2-C6 cyanoalkyl, SOnR3E; or a 5- or 6-membered heteroaromatic ring containing ring members selected from carbon atoms and up to 4 heteroatoms independently selected from up to 2 O, up to 2 S and up to 4 N atoms, each ring optionally substituted with up to 3 substituents independently selected from R3F on carbon atom ring members and R3G on nitrogen atom ring members; and
m is 0 or 1.
4. A compound of Claim 3 wherein Q is selected from Q-7 through Q-24;
each R1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
CrC4 haloalkoxy or SOnR1A;
R2 is halogen or Ci -C4 alkyl;
each R3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1 -C4 haloalkyl, C2-Cg alkylcarbonyl, C2-Cg haloalkylcarbonyl, C2-Cg alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and
each R1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
5. A compound of Claim 4 wherein
Q is selected from Q-16 and Q-18;
each R1 is independently halogen, Ci -C4 alkyl, Ci -C4 haloalkyl or Ci -C4 haloalkoxy; R2 is halogen or CH3; and
each R3 is independently halogen, cyano, Ci -C4 alkyl or Ci -C4 haloalkyl.
6. A compound of Claim 3 wherein
Q is selected from Q-43, Q-44, Q-45, Q-48, Q-49 and Q-50;
each R1 is independently halogen, cyano, Ci -C4 alkyl, Ci -C4 haloalkyl, Ci -C4 alkoxy,
CrC4 haloalkoxy or SOnR1A;
R2 is halogen or Ci -C4 alkyl;
each R3 is independently halogen, cyano, Ci -C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C1 -C4 haloalkyl, C2-C6 alkylcarbonyl, C2-C6 haloalkylcarbonyl, C2-C6 alkoxycarbonyl, C1 -C4 alkoxy, C 1 -C4 haloalkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; and
each R1A is independently Ci -C4 alkyl or Ci -C4 haloalkyl.
7. A compound of Claim 6 wherein
Q is selected from Q-43, Q-44 and Q-45;
each R1 is independently halogen, Ci -C4 alkyl, Ci -C4 haloalkyl or Ci -C4 haloalkoxy; R2 is halogen or CH3; and
each R3 is independently halogen, cyano, Ci -C4 alkyl or Ci -C4 haloalkyl.
8. A compound of Claim 1 selected from the group consisting of
5-chloro-2-[2-(5-chloro-2-pyridinyl)phenoxy]pyrimidine,
5-chloro-2-[2-[5-(fluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine,
2- [2-(3 -bromo-5 -isoxazolyl)phenoxy] -5 -chloropyrimidine,
5 -chloro-2- [2- [5 -(trifluoromethyl)-2-pyridinyl]phenoxy]pyrimidine,
5-chloro-2-[3-chloro-2-(5-chloro-2-pyridinyl)phenoxy]pyrimidine,
4-[2-[(5-bromo-2-pyrimidinyl)oxy]phenyl]-2-(trifluoromethyl)pyrimidine, 2- [2-(2-bromo-5 -thiazolyl)phenoxy] -5 -(trifluoromethyl)pyrimidine,
5 -chloro-2- [4-methyl-2- [2-(trifluoromethyl)-4-pyridinyl]phenoxy]pyrimidine,
5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine,
5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine,
5-chloro-2-[2-[5-(difluoromethyl)-3-isoxazolyl]-3-fiuorophenoxy]pyrimidine,
5-bromo-2-[2-[5-(difluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine,
5-chloro-2-[2-[3-(trifluoromethyl)-5-isoxazolyl]phenoxy]pyrimidine,
5-chloro-2-[2-[3-(difluoromethyl)-5-isoxazolyl]-3-fiuorophenoxy]pyrimidine,
5 -bromo-2- [2- [3 -(difluoromethyl)-5 -isoxazolyl]-3 -fluorophenoxy]pyrimidine,
5 -chloro-2- [2- [5 -(trifluoromethyl)-3 -isoxazolyl] -3 -fluorophenoxy]pyrimidine and
5-chloro-2-[2-[5-(trifluoromethyl)-3-isoxazolyl]phenoxy]pyrimidine.
9. A herbicidal composition comprising a compound of Claim 1 and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
10. A herbicidal composition comprising a compound of Claim 1, at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners, and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
11. A herbicidal mixture comprising (a) a compound of Claim 1 , and (b) at least one additional active ingredient selected from (bl) through (bl6) and salts of compounds of (bl) through (b 16).
12. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.
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Publication number Priority date Publication date Assignee Title
WO2016149315A1 (en) * 2015-03-18 2016-09-22 E. I. Du Pont De Nemours And Company Substituted pyrimidinyloxy pyridine derivatives as herbicides
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CN113853436A (en) * 2019-05-20 2021-12-28 先正达农作物保护股份公司 Compositions and methods for weed control
WO2022002838A1 (en) * 2020-06-30 2022-01-06 Bayer Aktiengesellschaft Substituted heteroaryloxypyridines, the salts thereof and their use as herbicidal agents
WO2022084334A1 (en) 2020-10-19 2022-04-28 Syngenta Crop Protection Ag Mixtures of pyrimidines as herbicidal compositions
WO2023066783A1 (en) * 2021-10-18 2023-04-27 Syngenta Crop Protection Ag Herbicidal imidazole compounds
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US11834434B2 (en) 2018-06-25 2023-12-05 Bayer Aktiengesellschaft Substituted 2-heteroaryloxypyridines and salts thereof and their use as herbicidal agents

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BR112019022493B1 (en) 2017-05-02 2024-01-16 Fmc Corporation COMPOUND, HERBICIDAL COMPOSITIONS, HERBICIDAL MIXTURES AND METHODS FOR CONTROLING THE GROWTH OF UNWANTED VEGETATION
CN111712495A (en) * 2017-12-22 2020-09-25 拜耳公司 Hydroxy isoxazolines and derivatives thereof
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CN111217762B (en) * 2018-11-23 2021-08-20 华中师范大学 Polyhalogenated 5- (2-hydroxyphenyl) isoxazole compound and preparation method and application thereof
AU2020206874A1 (en) * 2019-01-09 2021-08-19 Upl Ltd Herbicidal combination

Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
DE3246493A1 (en) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING WATER-DISPERSIBLE GRANULES
JPS61236766A (en) 1985-04-15 1986-10-22 Sumitomo Chem Co Ltd O-substituted phenoxy heterocyclic compound, production thereof and herbicide containing said compound as active constituent
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
WO1994017059A1 (en) 1993-01-29 1994-08-04 Nippon Soda Co., Ltd. Heterocyclic derivative
WO2003024222A1 (en) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Anthranilamide arthropodicide treatment
WO2007043278A1 (en) 2005-10-14 2007-04-19 Asahi Glass Company, Limited Method of regenerating basic anion-exchange resin
US8080566B1 (en) 2008-06-11 2011-12-20 Kalypsys, Inc Carbazole inhibitors of histamine receptors for the treatment of disease

Family Cites Families (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US962685A (en) 1907-05-29 1910-06-28 Krell Auto Grand Piano Co Of America Music-spool.
US3013054A (en) 1958-08-04 1961-12-12 Velsicol Chemical Corp 2-methoxy-3, 6-dichlorobenzoates
US4248618A (en) * 1977-05-06 1981-02-03 Ici Australia Limited Derivatives of (pyrimidyloxy)phenoxy-alkanecarboxylic acid and herbicidal compositions thereof
NZ188244A (en) * 1977-09-13 1981-04-24 Ici Australia Ltd 2-substituted pyrimidines compositions growth regulating processes
AU535637B2 (en) 1977-09-13 1984-03-29 Ici Australia Limited 2-phenoxypyrimidines and their. use as herbicides
JPS54117486A (en) * 1978-03-03 1979-09-12 Sankyo Co Ltd 2-phenoxypyrimidine derivative
JPS5524195A (en) * 1978-08-08 1980-02-21 Ici Australia Ltd Herbicide compound and composition*their manufacture and their use
NZ191078A (en) 1978-08-08 1982-05-31 Ici Australia Ltd Bis(pyrimidyloxy) benzenes bis(pyrimidylthio)benzenes and prymidyloxy-pyrimidyl thiobenzens and herbicidal compositions
NZ192708A (en) 1979-02-16 1984-12-14 Ici Australia Ltd Substituted pyrimidines and compositions
NL178063C (en) 1979-03-27 1986-01-16 Wavin Bv EXTRUSION HEAD WITH RING-SHAPED EXTRUSION CHANNEL AND A PLASTIC TUBE WITH LONG-WINDING HOLLOW CHANNELS OBTAINED IN THE WALL USING SUCH EXTRUSION HEAD.
NO810064L (en) 1980-01-10 1981-07-13 Nyegaard & Co As PROCEDURE FOR THE PREPARATION OF PHYSIOLOGICALLY ACTIVE PYRIMIDINE-2-SULPHIDES AND S-OXIDES THEREOF
US4634649A (en) 1980-12-24 1987-01-06 Xerox Corporation Developer compositions
US4371736A (en) 1981-03-27 1983-02-01 E. I. Du Pont De Nemours And Company Herbicidal pyridinyloxy(pyrimidinyloxy)benzenes
US4432979A (en) 1981-10-26 1984-02-21 William H. Rorer, Inc. Pyridone compounds
DE3602016A1 (en) 1985-12-05 1987-06-11 Bayer Ag PYRI (MI) DYL-OXY AND THIO-BENZOESIC ACID DERIVATIVES
AU594098B2 (en) 1985-12-11 1990-03-01 Ishihara Sangyo Kaisha Ltd. N-benzoyl urea compounds, antitumorous compositions containing them, and process for their preparation
US4889552A (en) 1987-04-14 1989-12-26 Kumiai Chemical Industry Co., Ltd. 2-Phenoxypyrimidine derivative and herbidical composition
GB8917222D0 (en) 1989-07-27 1989-09-13 Schering Agrochemicals Ltd Herbicides
GB8924465D0 (en) 1989-10-31 1989-12-20 Ici Plc Herbicides
JPH04108777A (en) 1990-08-30 1992-04-09 Kumiai Chem Ind Co Ltd Pyrimidine derivative and herbicide
AU5161193A (en) 1992-10-16 1994-05-09 Nippon Soda Co., Ltd. Pyrimidine derivative
DE4438824A1 (en) 1993-10-16 1995-04-20 Schering Ag Triazole derivatives, process for their preparation and their use in medicaments
US5747516A (en) * 1993-11-19 1998-05-05 E. I. Du Pont De Nemours And Company Dihydroazole compounds and their use for controlling fungal plant diseases
US5962685A (en) 1994-08-02 1999-10-05 Nippon Soda Co., Ltd. Oxazole derivatives, process for producing the same, and herbicide
WO1996033994A1 (en) 1995-04-28 1996-10-31 Nippon Soda Co., Ltd. Amino-substituted derivatives, process for the preparation thereof, and herbicide
US6268310B1 (en) 1997-01-28 2001-07-31 Nippon Soda Co., Ltd. Oxazole derivative, process for producing the same, and herbicide
AU725548B2 (en) 1997-03-11 2000-10-12 E.I. Du Pont De Nemours And Company Heteroaryl azole herbicides
JPH10251255A (en) 1997-03-14 1998-09-22 Nissan Chem Ind Ltd Azine derivative
DE19721031A1 (en) 1997-05-20 1998-11-26 Bayer Ag Substituted pyridylpyrazoles
CA2619101A1 (en) 2005-08-23 2007-03-01 Irm Llc Immunosuppressant compounds and compositions
US8748627B2 (en) 2006-02-15 2014-06-10 Abbvie Inc. Acetyl-CoA carboxylase (ACC) inhibitors and their use in diabetes, obesity and metabolic syndrome
CN101415681A (en) 2006-03-29 2009-04-22 弗·哈夫曼-拉罗切有限公司 Pyridine and pyrimidine derivatives as mGluR2 antagonists
GB0614579D0 (en) 2006-07-21 2006-08-30 Black James Foundation Pyrimidine derivatives
TW200831080A (en) 2006-12-15 2008-08-01 Irm Llc Compounds and compositions as inhibitors of cannabinoid receptor 1 activity
CN102786480B (en) 2007-10-02 2016-02-10 陶氏益农公司 -6-amino-5-the alkyl that 2-replaces, alkenyl or alkynyl-pyrimidine-4-carboxylic acid and the purposes as weedicide thereof
US20090291971A1 (en) 2007-11-01 2009-11-26 Wyeth Heteroaryl ethers and processes for their preparation
HUE026200T2 (en) 2008-01-22 2016-05-30 Dow Agrosciences Llc 5-fluoro pyrimidine derivatives as fungicides
NZ713361A (en) 2009-08-17 2017-06-30 Memorial Sloan Kettering Cancer Center Heat shock protein binding compounds, compositions, and methods for making and using same
JP2012012299A (en) 2010-06-29 2012-01-19 Nissan Chem Ind Ltd Solid agrochemical preparation capable of controlling release of agrochemical active ingredient
WO2012039141A1 (en) 2010-09-24 2012-03-29 クミアイ化学工業株式会社 6-acylpyridin-2-one derivative and herbicide
JP5913357B2 (en) 2010-12-06 2016-04-27 アウトイフオンイ トヘラペウトイクス リミテッド Hydantoin derivatives useful as KV3 inhibitors
CA2830027C (en) * 2011-03-31 2016-04-26 Pfizer Inc. Novel bicyclic pyridinones
TW201609710A (en) 2013-12-10 2016-03-16 杜邦股份有限公司 Herbicidal substituted pyrimidinyloxy benzene compounds
TW201625554A (en) 2014-07-14 2016-07-16 杜邦股份有限公司 Bis(aryl)catechol derivatives as herbicides
AR101264A1 (en) 2014-07-25 2016-12-07 Du Pont PIRIDONAS AS HERBICIDES
MX2017009792A (en) 2015-03-18 2017-10-27 Du Pont Substituted pyrimidinyloxy pyridine derivatives as herbicides.
TW202400564A (en) 2015-06-05 2024-01-01 美商艾佛艾姆希公司 Pyrimidinyloxy benzene derivatives as herbicides
RU2745802C2 (en) 2015-07-13 2021-04-01 Фмк Корпорейшн Aryloxy-pyrimidinyl esters as herbicides
BR112019022493B1 (en) 2017-05-02 2024-01-16 Fmc Corporation COMPOUND, HERBICIDAL COMPOSITIONS, HERBICIDAL MIXTURES AND METHODS FOR CONTROLING THE GROWTH OF UNWANTED VEGETATION

Patent Citations (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2891855A (en) 1954-08-16 1959-06-23 Geigy Ag J R Compositions and methods for influencing the growth of plants
US3060084A (en) 1961-06-09 1962-10-23 Du Pont Improved homogeneous, readily dispersed, pesticidal concentrate
US3235361A (en) 1962-10-29 1966-02-15 Du Pont Method for the control of undesirable vegetation
US3299566A (en) 1964-06-01 1967-01-24 Olin Mathieson Water soluble film containing agricultural chemicals
US3309192A (en) 1964-12-02 1967-03-14 Du Pont Method of controlling seedling weed grasses
US4144050A (en) 1969-02-05 1979-03-13 Hoechst Aktiengesellschaft Micro granules for pesticides and process for their manufacture
US3920442A (en) 1972-09-18 1975-11-18 Du Pont Water-dispersible pesticide aggregates
US4172714A (en) 1976-12-20 1979-10-30 E. I. Du Pont De Nemours And Company Dry compactible, swellable herbicidal compositions and pellets produced therefrom
GB2095558A (en) 1981-03-30 1982-10-06 Avon Packers Ltd Formulation of agricultural chemicals
DE3246493A1 (en) 1982-12-16 1984-06-20 Bayer Ag, 5090 Leverkusen METHOD FOR PRODUCING WATER-DISPERSIBLE GRANULES
JPS61236766A (en) 1985-04-15 1986-10-22 Sumitomo Chem Co Ltd O-substituted phenoxy heterocyclic compound, production thereof and herbicide containing said compound as active constituent
US5180587A (en) 1988-06-28 1993-01-19 E. I. Du Pont De Nemours And Company Tablet formulations of pesticides
US5208030A (en) 1989-08-30 1993-05-04 Imperial Chemical Industries Plc Active ingredient dosage device
WO1991013546A1 (en) 1990-03-12 1991-09-19 E.I. Du Pont De Nemours And Company Water-dispersible or water-soluble pesticide granules from heat-activated binders
US5232701A (en) 1990-10-11 1993-08-03 Sumitomo Chemical Company, Limited Boron carbonate and solid acid pesticidal composition
WO1994017059A1 (en) 1993-01-29 1994-08-04 Nippon Soda Co., Ltd. Heterocyclic derivative
WO2003024222A1 (en) 2001-09-21 2003-03-27 E. I. Du Pont De Nemours And Company Anthranilamide arthropodicide treatment
WO2007043278A1 (en) 2005-10-14 2007-04-19 Asahi Glass Company, Limited Method of regenerating basic anion-exchange resin
US8080566B1 (en) 2008-06-11 2011-12-20 Kalypsys, Inc Carbazole inhibitors of histamine receptors for the treatment of disease

Non-Patent Citations (42)

* Cited by examiner, † Cited by third party
Title
"Comprehensive Heterocyclic Chemistry", 1984, PERGAMON PRESS
"Comprehensive Heterocyclic Chemistry", vol. II, 1996, PERGAMON PRESS
"Developments in formulation technology", 2000, PJB PUBLICATIONS
"McCutcheon's Emulsifiers and Detergents", THE MANUFACTURING CONFECTIONER PUBLISHING CO.
"McCutcheon's Volume 2: Functional Materials", vol. 2, THE MANUFACTURING CONFECTIONER PUBLISHING CO.
"Metal-Catalyzed Cross-Coupling Reactions", vol. 1, 2, 2004, WILEY-VCH
"Perry's Chemical Engineer's Handbook", 1963, MCGRAW-HILL, pages: 8 - 57
"Polymorphism in the Pharmaceutical Industry", 2006, WILEY-VCH
"The BioPesticide Manual", 2001, BRITISH CROP PROTECTION COUNCIL
"The Pesticide Manual", 2003, BRITISH CROP PROTECTION COUNCIL
A. S. DAVIDSON; B. MILWIDSKY: "Synthetic Detergents", 1987, JOHN WILEY AND SONS
ACCOUNTS OF CHEMICAL RESEARCH, vol. 45, 2012, pages 777 - 958
ANGEWANDTE CHEMIE INTERNATIONAL EDITION, vol. 45, 2006, pages 3484
BIOORGANIC MED. CHEM., vol. 12, 2004, pages 3965
BROWNING: "Agglomeration", CHEMICAL ENGINEERING, 4 December 1967 (1967-12-04), pages 147 - 48
CHEMICAL REVIEWS, vol. 107, no. 1, 2007, pages 133 - 173
CHEMICAL REVIEWS, vol. 110, 2010, pages 575 - 1211
DAS ET AL., TET. LETT., vol. 44, 2003, pages 5465 - 5468
DAS ET AL., TETRAHEDRON, vol. 59, 2003, pages 1049 - 1054
G. W. H. CHEESEMAN; E. S. G. WERSTIUK: "Advances in Heterocyclic Chemistry", vol. 22, ACADEMIC PRESS, pages: 390 - 392
GREENE, T. W.; WUTS, P. G. M.: "Protective Groups in Organic Synthesis", 1991, WILEY
HANCE ET AL.: "Weed Control Handbook", 1989, BLACKWELL SCIENTIFIC PUBLICATIONS
KATRITSKY: "Advances in Heterocyclic Chemistry", vol. 1-104, ELSEVIER
KLINGMAN: "Weed Control as a Science", 1961, JOHN WILEY AND SONS, INC., pages: 81 - 96
LAROCK, R. C.: "Comprehensive Organic Transformations: A Guide to Functional Group Preparations", 1999, WILEY-VCH
LLOYD-JONES; GUY C., SYNTHESIS, 2008, pages 661 - 689
M. R. GRIMMETT; B. R. T. KEENE: "Advances in Heterocyclic Chemistry", vol. 43, ACADEMIC PRESS, pages: 149 - 161
M. TISLER; B. STANOVNIK: "Advances in Heterocyclic Chemistry", vol. 9, ACADEMIC PRESS, pages: 285 - 291
M. TISLER; B. STANOVNIK: "Comprehensive Heterocyclic Chemistry", vol. 3, PERGAMON PRESS, pages: 18 - 20
MARSDEN: "Solvents Guide", 1950, INTERSCIENCE
NARENDER, T. ET AL., SYNTHETIC COMMUNICATIONS, vol. 39, no. 11, 2009, pages 1949 - 1956
ORGAN, MICHAEL G., ANGEW. CHEM. INT. ED., vol. 51, 2012, pages 3314 - 3322
ORGANIC LETTERS, vol. 13, no. 6, 2011, pages 1366
ORGANIC LETTERS, vol. 14, no. 2, 2012, pages 600
QI, JUNSHENG, CHIN. J. CHEM., vol. 28, 2010, pages 1441 - 1443
SISELY; WOOD: "Encyclopedia of Surface Active Agents", 1964, CHEMICAL PUBL. CO., INC.
T. L. GILCHRIST: "Comprehensive Organic Synthesis", vol. 7, PERGAMON PRESS, pages: 748 - 750
T. S. WOODS: "Pesticide Chemistry and Bioscience, The Food-Environment Challenge", 1999, THE ROYAL SOCIETY OF CHEMISTRY, article "The Formulator's Toolbox - Product Forms for Modern Agriculture", pages: 120 - 133
TAKASHIRO ITOH, J. ORG. CHEM., vol. 71, 2006, pages 2203 - 2206
TETRAHEDRON LETTERS, vol. 58, no. 14, 2002, pages 2885
WATKINS ET AL.: "Handbook of Insecticide Dust Diluents and Carriers", DORLAND BOOKS
WENCEL-DELORD ET AL., NATURE CHEMISTRY, vol. 5, 2013, pages 369 - 375

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11006631B2 (en) 2015-03-18 2021-05-18 Fmc Corporation Substituted pyrimidinyloxy pyridine derivatives as herbicides
RU2735278C2 (en) * 2015-03-18 2020-10-29 ЭфЭмСи Корпорейшн Substituted pyrimidinyloxy-pyridine derivatives as herbicides
WO2016149315A1 (en) * 2015-03-18 2016-09-22 E. I. Du Pont De Nemours And Company Substituted pyrimidinyloxy pyridine derivatives as herbicides
US11053204B2 (en) 2015-06-05 2021-07-06 Fmc Corporation Pyrimidinyloxy benzene derivatives as herbicides
US10485235B2 (en) 2015-07-13 2019-11-26 Fmc Corporation Aryloxypyrimidinyl ethers as herbicides
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WO2019171234A1 (en) * 2018-03-09 2019-09-12 Pi Industries Ltd. Heterocyclic compounds as fungicides
US11834434B2 (en) 2018-06-25 2023-12-05 Bayer Aktiengesellschaft Substituted 2-heteroaryloxypyridines and salts thereof and their use as herbicidal agents
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US12052991B2 (en) 2018-12-18 2024-08-06 Bayer Aktiengesellschaft Substituted pyridinyloxybenzenes and salts thereof and use thereof as herbicidal agents
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WO2021094504A1 (en) 2019-11-15 2021-05-20 Syngenta Crop Protection Ag Herbicidal thiazole compounds
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