WO2023129493A1 - Herbicides à base de cyclopropylpyrimidine substitués - Google Patents

Herbicides à base de cyclopropylpyrimidine substitués Download PDF

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WO2023129493A1
WO2023129493A1 PCT/US2022/053915 US2022053915W WO2023129493A1 WO 2023129493 A1 WO2023129493 A1 WO 2023129493A1 US 2022053915 W US2022053915 W US 2022053915W WO 2023129493 A1 WO2023129493 A1 WO 2023129493A1
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compound
inhibitors
methyl
trifluoromethyl
formula
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PCT/US2022/053915
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English (en)
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Eric Allen Marshall
Thomas Selby
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Fmc Corporation
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    • 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
    • C07D403/04—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 directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • A01P13/02—Herbicides; Algicides selective
    • 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
    • C07D401/14—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 three or more hetero rings
    • 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
    • C07D403/14—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 three or more hetero rings
    • 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
    • C07D417/04—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 directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain substituted cyclopropylpyrimidine herbicides, 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.
  • This invention is directed to compounds of Formula 1, all stereoisomers, N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides: wherein J is selected from the group consisting of , R 1 is halogen, C 1 –C 4 haloalkyl, C 1 –C 4 haloalkoxy, C 1 –C 4 alkoxy, C 1 –C 4 haloalkenyl, C 1 –C 4 haloalkynyl, C 1 –C 4 haloalkenyloxy, C 1 –C 4 haloalkynyloxy, C 1 –C 4 haloalkylthio, C 1 –C 4 alkylthio or -CN; R 2 is H or
  • 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 (b1) through (b17), and salts of compounds of (b1) through (b17), as described below.
  • 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 (b1) through (b17), and salts of compounds of (b1) through (b17), as described below.
  • compositions, 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.
  • the phrase “consisting of” appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.
  • transitional phrase “consisting essentially of” is used to define a composition or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention.
  • the term “consisting essentially of” occupies a middle ground between “comprising” and “consisting of”.
  • 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.
  • 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” refers reaction in which nucleophile displaces a leaving group such as halide or sulfonate from a carbon-containing radical. Unless otherwise indicated, the term “alkylating” does not limit the carbon-containing radical to alkyl.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • 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 CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • 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 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 .
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O)-, CH 3 CH 2 S(O)-, CH 3 CH 2 CH 2 S(O)-, (CH 3 ) 2 CHS(O)- and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 -, CH 3 CH 2 S(O) 2 -, CH 3 CH 2 CH 2 S(O) 2 -, (CH 3 ) 2 CHS(O) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 and NCCH 2 CH 2 (alternatively identified as CH 2 CH 2 CN).
  • Niroalkyl denotes an alkyl group substituted with one nitro group.
  • nitroalkyl examples include (NO 2 )CH 2 and (NO 2 )CH 2 CH 2 (alternatively identified as CH 2 CH 2 (NO 2 )).
  • Alkylamino includes an NH radical substituted with straight-chain or branched alkyl. Examples of “alkylamino” include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH. Examples of “dialkylamino” include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • cycloalkylalkyl denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • alkylcycloalkyl donotes an alkyl group bonded to a cycloalkyl moiety.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkoxy examples include CF 3 O- , CCl 3 CH 2 O-, HCF 2 CH 2 CH 2 O- and CF 3 CH 2 O-.
  • haloalkoxyalkyl examples include CF 3 OCH 2 -, CCl 3 CH 2 OCH 2 -, HCF 2 CH 2 CH 2 OCH 2 - and CF 3 CH 2 OCH 2 -.
  • haloalkylthio examples include CCl 3 S-, CF 3 S-, CCl 3 CH 2 S- and ClCH 2 CH 2 CH 2 S-.
  • haloalkynyl examples include HC ⁇ CCHCl-, CF 3 C ⁇ C-, CCl 3 C ⁇ C- and FCH 2 C ⁇ CCH 2 -.
  • alkoxycarbonylalkyl denotes a straight-chain or branched alkoxycarbonyl moiety bonded through an alkyl moiety.
  • alkylcarbonylalkyl denotes a straight or branched alkylcarbonyl moiety bonded through an alkyl moiety.
  • alkanediyl or alkenediyl refers to a linear or branched alkane or alkene linking chain respectively.
  • alkanediyl include —CH 2 –, –CH 2 CH(CH 3 )– and –CH 2 CH 2 CH 2 –.
  • the term “adjacent” in the context of locating a substituent means “next to” or “immediately next to”.
  • the total number of carbon atoms in a substituent group is indicated by the “C i –C j ” prefix where i and j are numbers from 1 to 8.
  • C 1 –C 4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 3 –C 8 alkylcarbonylalkyl can be, for example, CH 3 COCH 2 -, CH 3 COCH 2 CH 2 - or CH 3 CH 2 CH 2 COCH 2 CH 2 CH 2 CH 2 -
  • C 4 –C 7 alkylcycloalkyl can be, for example, methylcyclopropyl, methylcyclobutyl, ethylcyclopropyl, or propylcyclobutyl
  • 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 -
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four
  • ring system denotes two or more fused rings.
  • bicyclic ring system denotes a ring system consisting of two fused rings.
  • 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).
  • 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.
  • Non- crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice. Although polymorphs can have the same chemical composition, they can also differ in composition due to the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound 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.
  • crystallization using selected solvents and temperatures.
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides.
  • nitrogen-containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • salts of 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.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium.
  • the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
  • 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.
  • Embodiments of the present invention as described in the Summary of the Invention include those described below.
  • Formula 1 includes stereoisomers, N-oxides and salts thereof, and reference to “a compound of Formula 1” includes the definitions of substituents specified in the Summary of the Invention unless further defined in the Embodiments.
  • Embodiment 1. A compound of Formula 1, stereoisomers, N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides as described in the Summary of the Invention.
  • Embodiment 2. A compound of Formula 1 or Embodiment 1 wherein J is J-1, J-2, J-3, J-5, J-6, J-8,J-9 or J-10.
  • Embodiment 2a A compound of Formula 1 or Embodiment 2 wherein J is J-1, J-2 or J-3.
  • Embodiment 2b A compound of Embodiment 2a wherein J is J-1.
  • Embodiment 2c A compound of Embodiment 2a wherein J is J-2.
  • Embodiment 2d A compound of Embodiment 2a wherein J is J-3.
  • Embodiment 2e A compound of Formula 1 or Embodiment 2 wherein J is J-5, J-6 or J-8.
  • Embodiment 2f A compound of Embodiment 2e wherein J is J-5.
  • Embodiment 2g A compound of Embodiment 2e wherein J is J-6.
  • Embodiment 2h A compound of Embodiment 2e wherein J is J-8.
  • Embodiment 3a A compound of Embodiment 3 wherein G is G-1, G-2, G-3 or G-7.
  • Embodiment 3aa A compound of Embodiment 3a wherein G is G-1, G-2 or G-3.
  • Embodiment 3b A compound of Embodiment 3a where G is G-1 wherein W, X, and Y are independently N or CR 6 .
  • Embodiment 3c A compound of Embodiment 3b wherein X is N, Y is CR 6 and W is CR 6 .
  • Embodiment 3d A compound of Embodiment 3d.
  • Embodiment 3b wherein X is CR 6 , Y is N and W is CR 6 .
  • Embodiment 3dd A compound of Embodiment 3b wherein X is CR 6 , Y is CR 6 and W is N.
  • Embodiment 3e A compound of Embodiment 3b wherein X is CR 6 , Y is CR 6 and W is CR 6 .
  • Embodiment 3f A compound of Embodiment 3b wherein X is N, Y is N and W is CR 6 .
  • Embodiment 3g A compound of Embodiment 3 wherein G is G-2.
  • Embodiment 3h A compound of Embodiment 3 wherein G is G-3.
  • Embodiment 3i A compound of Embodiment 3 wherein G is G-4.
  • Embodiment 3j A compound of Embodiment 3 wherein G is G-7.
  • Embodiment 4. A compound of Formula 1 or any one of the preceding Embodiments wherein R 1 is halogen, C 1 –C 4 haloalkyl, C 1 –C 4 haloalkoxy, C 1 –C 4 alkoxy or C 1 –C 4 haloalkylthio.
  • Embodiment 4a A compound of Embodiment 4 wherein R 1 is C 1 –C 4 haloalkyl or C 1 – C 4 haloalkoxy.
  • Embodiment 4b A compound of Embodiment 4 wherein R 1 is C 1 –C 4 haloalkyl or C 1 – C 4 haloalkoxy.
  • Embodiment 4a wherein OCF 3 .
  • Embodiment 4c A compound of Embodiment 4a wherein haloalkyl.
  • Embodiment 4d A compound of Embodiment 4c wherein Embodiment 4e.
  • Embodiment 4a wherein haloalkoxy.
  • Embodiment 4f A compound of Embodiment 4e wherein Embodiment 5.
  • a compound of Formula 1 or any one of the preceding Embodiments wherein R 2 is H.
  • Embodiment 5a A compound of Formula 1 or any one of the preceding Embodiments wherein R 2 is halogen.
  • Embodiment 6a A compound of Embodiment 6 wherein R3 is C 1 –C 5 alkyl, halogen, C 1 –C 5 haloalkyl, C 1 –C 5 alkoxy or C 1 –C 5 haloalkoxy.
  • Embodiment 6b A compound of Formula 1 or any one of the preceding Embodiments wherein R 3 is C 1 –C 5 alkyl, halogen, C 3 –C 7 cycloalkyl, C 1 –C 5 haloalkyl, C 1 –C 5 alkoxy or C 1 –C 5 haloalkoxy.
  • Embodiment 6a wherein R 3 is halogen, C 1 –C 5 haloalkyl or C 1 –C 5 haloalkoxy.
  • Embodiment 6c A compound of Embodiment 6b wherein R 3 is halogen or C 1 –C 5 haloalkyl.
  • Embodiment 6d A compound of Embodiment 6c wherein R 3 is halogen.
  • Embodiment 6e A compound of Embodiment 6c wherein R 3 is C 1 –C 5 haloalkyl.
  • Embodiment 6f A compound of Embodiment 6c wherein R 3 is F, Cl or CF 3 .
  • Embodiment 6g A compound of Embodiment 6g.
  • Embodiment 7. A compound of Formula 1 or any one of the preceding Embodiments w herein R4 is H, C 1 –C 5 alkyl, halogen, -CN, C 1 –C 5 haloalkyl, C 1 –C 5 alkoxy or C 1 –C 5 alkylthio.
  • Embodiment 7b A compound of Embodiment 7a wherein R 4 is H, halogen, -CN or CF 3 .
  • Embodiment 7c A compound of Embodiment 7b wherein R 4 is H.
  • Embodiment 8a A compound of Embodiment 8 wherein Q is O or -CH 2 -.
  • Embodiment 8b A compound of Embodiment 8a wherein Q is O.
  • Embodiment 8c A compound of Embodiment 8a wherein Q is -CH 2 -.
  • Embodiment 8d A compound of Embodiment 8a wherein Q is -CH 2 -.
  • Embodiment 9 A compound of Formula 1 or any one of the preceding Embodiments w herein R5 is H, C 1 –C 5 alkyl, halogen, -CN, C 3 –C 5 alkenyl, C 3 –C 5 alkynyl, C 3 –C 7 cycloalkyl, C 1 –C 5 haloalkyl, C 1 –C 5 alkoxy, C 1 –C 5 haloalkoxy or C 1 –C 5 alkylthio.
  • E mbodiment 9a A compound of Embodiment 9 wherein R5 is H, C 1 –C 5 alkyl or halogen.
  • Embodiment 9b A compound of Embodiment 9 wherein R5 is H, C 1 –C 5 alkyl or halogen.
  • Embodiment 9a wherein R 5 is H.
  • E mbodiment 9c A compound of Embodiment 9a wherein R5 is C 1 –C 3 alkyl.
  • Embodiment 9d A compound of Embodiment 9a wherein R 5 is halogen.
  • Embodiments of this invention including Embodiments 1–9d 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 compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1.
  • Embodiment X A compound of Formula 1 as described in the Summary of the Invention wherein J is J-1, J-2, J-3, J-5, J-6, J-8, J-9 or J-10; and G is G-1, G-2, G-3 or G-7.
  • Embodiment XX A compound of Formula 1 as described in the Summary of the Invention wherein J is J-1, J-2, J-3, J-5, J-6, J-8, J-9 or J-10; and G is G-1, G-2, G-3 or G-7.
  • Embodiment X wherein R 1 is C 1 –C 4 haloalkyl or C 1 –C 4 haloalkoxy; R 3 is halogen or C 1 –C 5 haloalkyl; R 4 is H; and Q is O or -CH 2 -.
  • Embodiment XXX A compound of Embodiment XX wherein Q is O.
  • Embodiment A1. A compound of Embodiment X wherein J is J-1, J-2 or J-3; R 1 is CF 3 or OCF 3 ; and R 3 is F, Cl or CF 3 .
  • Embodiment A2. A compound of Embodiment A1 wherein J is J-1; and R 2 is H or halogen.
  • Embodiment A3 A compound of Embodiment A2 wherein R 2 is H. Embodiment A4. A compound of Embodiment A1 wherein J is J-2; and R 1 is CF 3 . Embodiment A5. A compound of Embodiment A1 wherein J is J-3; and R 1 is CF 3 .
  • Embodiment A6 A compound of Embodiment X wherein G is G-1, G-2 or G-3.
  • Embodiment A7 A compound of Embodiment A6 wherein G is G-1; X is N; Y is CH; W is CH; and R 5 is CF 3 .
  • Embodiment A8 A compound of Embodiment A6 wherein G is G-2; and R 3 is CF 3 .
  • Embodiment A11 A compound of Embodiment A6 wherein G is G-3; and R 3 is CF 3 .
  • Embodiment B1. A compound of Embodiment X wherein J is J-5, J-6 or J-8; R 1 is CF 3 or OCF 3 ; and R 3 is F, Cl, CF 3 .
  • Embodiment B2. A compound of Embodiment B1 wherein J is J-5.
  • Embodiment B4. A compound of Embodiment B1 wherein J is J-8.
  • Embodiment C A compound of Summary of the Invention wherein Q is O..
  • Specific embodiments include a compound of Formula 1 selected from the group consisting of: 5-cyclopropyl-4-[3-(trifluoromethyl)phenoxy]-2-[3-(trifluoromethyl)-1H-pyrazol-1- yl]pyrimidine; (Compound 1) 5-cyclopropyl-4-[3-(trifluoromethyl)phenoxy]-2-[4-(trifluoromethyl)phenyl]pyrimidine; (Compound 5) 5-cyclopropyl-2-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-4-[[2-(trifluoromethyl)-4- pyridinyl]oxy]pyrimidine; (Compound 9) 5-cyclopropyl-4-[3-(trifluoromethoxy)phenoxy]-2-[3-(trifluoromethyl)-1H-pyrazol-1- yl]pyrimidine; (Compound 10) 5-cyclopropyl-2-[3-(trifluoromethyl)-1H-
  • 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 (b1) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics, (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, (b10) auxin transport inhibitors, (b11) phytoene desaturase (PDS) inhibitors, (b12) 4-hydroxyphenyl-pyruvate dioxygena
  • Photosystem II inhibitors are chemical compounds that bind to the D-1 protein at the Q B -binding niche and thus block electron transport from Q A to Q B 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 Q B -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.
  • triazines such as atrazine
  • triazinones such as hexazinone
  • 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
  • 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, 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2-Pyridinecarboxylic 2-propyn-1-yl ester (CAS No.
  • EPSP 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, paraquat and 1-(2-carboxyethyl)-4-(2- pyrimidinyl)pyridazinium (CAS No.2285384-11-2).
  • 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, 3-[2-chloro-5-[3,6-dihydro-3-methyl-2,6-dioxo-4- (trifluoromethyl)-1(2H)-pyrimidinyl]-4-fluorophenyl]-4,5-dihydro-5-methyl-5- Isoxazolecarboxylic ethyl ester (CAS No.
  • GS 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 ((2S)-2-amino- 4-(hydroxymethylphosphinyl)butanoic acid) and bilanaphos.
  • VLCFA 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-(1-naphthalenyloxy)propanamide), pethoxamid, piperophos, pretilachlor, propachlor, propisochlor, pyroxasulfone, and thenylchlor, including resolved forms such as S-metolachlor and chloroacetamides and oxyace
  • 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-(1-naphthyl)phthalamic acid and 2-[(1-naphthalenylamino)carbonyl]benzoic acid).
  • PDS inhibitors 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 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]-1,3- cyclohexanedione), flusulfinam, iptriazopyrid, isoxachlortole, isoxaflutole, mesotrione, pyrasulfotole, pyrazolynate, pyrazoxyfen, sulcotrion
  • HST homogentisate solanesyltransferase inhibitors
  • HST inhibitors include cyclopyrimorate (6-chloro-3-(2- cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), haloxydine, pyriclor, 3-(2-chloro-3,6-difluorophenyl)-4-hydroxy-1-methyl-1,5-naphthyridin-2(1H)-one, 7-(3,5-dichloro-4-pyridinyl)-5-(2,2-difluoroethyl)-8-hydroxypyrido[2,3-b]pyrazin-6(5H)-one and 4-(2,6-diethyl-4-methylphenyl)-5-hydroxy-2,6-dimethyl-3(2H)-pyridazinone.
  • cyclopyrimorate 6-chloro-3-(2- cyclopropyl-6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate
  • Cellulose biosynthesis inhibitors inhibit the biosynthesis of cellulose in certain plants. They are most effective when applied preemergence or early postemergence on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, dichlobenil, flupoxam, indaziflam (N 2 -[(1R,2S)-2,3-dihydro-2,6-dimethyl-1H-inden-1-yl]-6- (1-fluoroethyl)-1,3,5-triazine-2,4-diamine), isoxaben and triaziflam.
  • DHODH (dihydroorotate dehydrogenase) inhibitors act through inhibiting catalysis of the fourth step of pyrimidine biosynthesis in plant systems. Inhibition of pyrimidine biosynthesis leads to the cessation of plant growth.
  • DOHDH inhibitors examples include tetflupyrolimet ((3S,4S)-N-(2-fluorophenyl)-1-methyl-2-oxo-4-[3- (trifluoromethyl)phenyl]-3-pyrrolidinecarboxamide) and (3S,4R)-N-(2,3-difluorophenyl)-1- methyl-4-[1-methyl-5-(trifluoromethyl)-1H-pyrazol-3-yl]-2-oxo-3-pyrrolidinecaboxamide.
  • “Other 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.
  • Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (b1) through (b14) or act through a combination of modes of action listed above.
  • herbicides examples include aclonifen, asulam, amitrole, bixlozone, broclozone, bromobutide, cinmethylin, clomazone, cumyluron, daimuron, difenzoquat, dimesulfazet, epyrifenacil, etobenzanid, fluometuron, flurenol, fosamine, fosamine-ammonium, dazomet, dymron, ipfencarbazone (1-(2,4-dichlorophenyl)-N-(2,4- difluorophenyl)-1,5-dihydro-N-(1-methylethyl)-5-oxo-4H-1,2,4-triazole-4-carboxamide), metam, methyldymron, oleic acid, oxaziclomefone, pelargonic acid, pyributicarb, 2,5- anhydro-3,4-dide
  • “Other herbicides” also include a compound of Formula (b16A) wherein R 12 is H, C 1 –C 6 alkyl, C 1 –C 6 haloalkyl or C 4 –C 8 cycloalkyl; R 13 is H, C 1 –C 6 alkyl or C 1 –C 6 alkoxy; Q 1 is an optionally substituted ring system selected from the group consisting of phenyl, thienyl, pyridinyl, benzodioxolyl, naphthyl, naphthalenyl, benzofuranyl, furanyl, benzothiophenyl and pyrazolyl, wherein when substituted said ring system is substituted by 1 to 3 R 14
  • R 12 is H or C 1 –C 6 alkyl; more preferably R 12 is H or methyl.
  • R 13 is H.
  • Q 1 is either a phenyl ring or a pyridinyl ring, each ring substituted by 1 to 3 R 14 ; more preferably Q 1 is a phenyl ring substituted by 1 to 2 R 14 .
  • Q 2 is a phenyl ring substituted by 1 to 3 R 15 ; more preferably Q 2 is a phenyl ring substituted by 1 to 2 R 15 .
  • each R 14 is independently halogen, C 1 –C 4 alkyl, C 1 –C 3 haloalkyl, C 1 –C 3 alkoxy or C 1 –C 3 haloalkoxy; more preferably each R 14 is independently chloro, fluoro, bromo, C 1 –C 2 haloalkyl, C 1 –C 2 haloalkoxy or C 1 –C 2 alkoxy.
  • each R 15 is independently halogen, C 1 –C 4 alkyl, C 1 –C 3 haloalkoxy; more preferably each R 15 is independently chloro, fluoro, bromo, C 1 –C 2 haloalkyl, C 1 –C 2 haloalkoxy or C 1 –C 2 alkoxy.
  • other herbicides include any one of the following (b16A-1) through (b16A-15):
  • “Other herbicides” also include a compound of Formula (b16B) wherein R 18 is H, C 1 –C 6 alkyl, C 1 –C 6 haloalkyl or C 4 –C 8 cycloalkyl; each R 19 is independently halogen, C 1 –C 6 haloalkyl or C 1 –C 6 haloalkoxy; p is an integer of 0, 1, 2 or 3; each R 20 is independently halogen, C 1 –C 6 haloalkyl or C 1 –C 6 haloalkoxy; and q is an integer of 0, 1, 2 or 3.
  • R 18 is H, methyl, ethyl or propyl; more preferably R 18 is H or methyl; most preferably R 18 is H.
  • each R 19 is independently chloro, fluoro, C 1 – C 3 haloalkyl or C 1 –C 3 haloalkoxy; more preferably each R 19 is independently chloro, fluoro, C 1 fluoroalkyl (i.e. fluoromethyl, difluoromethyl or trifluoromethyl) or C 1 fluoroalkoxy (i.e. trifluoromethoxy, difluoromethoxy or fluoromethoxy).
  • each R 20 is independently chloro, fluoro, C 1 haloalkyl or C 1 haloalkoxy; more preferably each R 20 is independently chloro, fluoro, C 1 fluoroalkyl (i.e. fluoromethyl, difluorormethyl or trifluromethyl) or C 1 fluoroalkoxy (i.e. trifluoromethoxy, difluoromethoxy or fluoromethoxy).
  • other herbicides include any one of the following (b15B-1) through (b16B-19):
  • 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, dietholate, 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, 1-bromo-4-[(chloromethyl)sulfonyl]benzene, 2-(dichloromethyl)-2-methyl-1,3-dioxolane (MG 19
  • Preferred for better control of undesired vegetation e.g., lower use rate such as from greater-than-additive effects, broader spectrum of weeds controlled, or enhanced crop safety
  • a herbicide selected from the group consisting of 4-amino-3-chloro-5-fluoro- 6-(7-fluoro-1H-indol-6-yl)- 2-Pyridinecarboxylic 2-propyn-1-yl ester (CAS No.2251111-17- 6), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)- 2-Pyridinecarboxylic cyanomethyl ester (CAS No.2251111-18-7), 2,5-anhydro-3,4-dideoxy-4-[[[(5S)-3-(3,5-difluorophenyl)-5- ethenyl-4,5-dihydr
  • Reacting a cyclopropyl dihalopyrimidine of Formula 2 (wherein X is a halogen as leaving group) with an appropriately substituted phenol or hydroxy heterocycle of Formula J-OH, in the presence of a suitable base and solvent, can provide intermediates of Formula 3.
  • suitable bases for this reaction include but are not limited to potassium carbonate, sodium hydroxide, potassium t-butoxide, sodium hydride or potassium hydroxide, and compatible solvents include but not limited to tetrahydrofuran, acetonitrile, toluene, dioxane or N,N-dimethylformamide.
  • Temperatures for this reaction generally range from 0° C to warming below or heating at the boiling point of the solvent.
  • halogen X at the 4-position of a pyrimidine of Formula 2 is generally favored as the leaving group over the halogen X at the 2-position, one skilled in the art will recognize that some regioisomeric side-product of intermediate 3 can form from displacement of the halogen at the 2-position and side-adduct may require separation from 3 by chromatography or recrystallization.
  • the halogen substituent X can be chlorine, bromine or in some cases iodine.
  • Preferable palladium catalysts include but are not limited to the commercially available chloro[2-(di-tert-butylphosphino)- 2′,4′,6′-triisopropyl-1,1′-biphenyl][2-(2-aminoethyl)phenyl)] palladium(II) [t-BuXPhos palladium(II) phenethylamine chloride, tBuXPhos-Pd-G1], chloro[(tri-tert-butylphosphine)- 2-(2-aminobiphenyl)] palladium(II) [P(t-Bu)3 Pd G2], methanesulfonato(2-di-t- butylphosphino-2;methanesulfonato(2-di-t-butylphosphino-2',4',
  • halogen X at the 4-position of a pyrimidine of Formula 2 is usually favored as the preferred leaving group over the halogen X at the 2-position
  • some regioisomeric side-product of intermediate 4 can form from displacement of the halogen at the 2-position. Separation by chromatography or recrystallization may be needed to isolate the desired isomers.
  • Reagents of Formula J-CH 2 -ZnX 1 are readily generated from commercially available benzyl and heteroarylmethyl halides by reacting with an appropriate zinc reagent (i.e.
  • the halogen substituent X can be chlorine, bromine or in some cases iodine.
  • compounds of Formula 1b can also be made without use of a palladium catalyst, instead by reacting an intermediate of Formula 4 with an azole of Formula (G-1)H in the presence of a base such as potassium carbonate, sodium hydride or sodium hydroxide in a compatible solvent for the particular base used.
  • a base such as potassium carbonate, sodium hydride or sodium hydroxide
  • solvents include but are not limited to tetrahydrofuran, acetonitrile, toluene, dioxane or N,N-dimethylformamide.
  • Temperatures for this nucleophilic displacement reaction can range from 0° C to ambient temperature to warming below or heating at the boiling point of the solvent.
  • a base preferably potassium carbonate, sodium hydride or sodium hydroxide
  • a compatible solvent i.e. acetonitrile, toluene, dioxane or N,N-dimethylformamide
  • the methyl sulfone substituent is now an activated leaving group, where upon reacting 7 with phenols and hydroxyheterocycles of Formula J-OH, in the presence of base and solvent (e.g. potassium carbonate in N,N-dimethylformamide) at ambient temperature to warming below the reflux temperature of the solvent, gives final products of Formula 1c.
  • base and solvent e.g. potassium carbonate in N,N-dimethylformamide
  • Heating the compound of Formula 10 in phosphorous oxychloride (and in some cases with thionyl chloride or oxalyl chloride, optionally with a cosolvent such as toluene or dichloromethane) provides chloropyrimidines of Formula 11.
  • Reacting a compound of Formula 11 with an appropriately substituted phenol or hydroxy heterocycle of Formula J- OH, in the presence of a suitable base and solvent, can provide final products of Formula 1d.
  • suitable bases for this reaction include but are not limited to potassium carbonate, sodium hydroxide, potassium t-butoxide, sodium hydride or potassium hydroxide; and compatible solvents include but not limited to tetrahydrofuran, acetonitrile, toluene, dioxane or N,N-dimethylformamide. Temperatures for this reaction generally range from 0° C to warming below or heating at the boiling point of the solvent.
  • 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.
  • step A of Synthesis Example 1 0.25 g, 0.79 mmol
  • 4-(trifluoromethyl)phenylboronic acid (0.18 g, 0.95 mmol
  • potassium phosphate tribasic (0.20 g, 0.95 mmol
  • Xphos Pd G2 0.063 g, 0.079 mmol
  • Dioxane (3.97 mL) was added and the vial was purged twice more with N 2 and heated at 70 °C overnight.
  • 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.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion, oil-in-water emulsion, flowable concentrate and suspo-emulsion.
  • the general types of nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • the general types of solid compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible (“wettable”) or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively, the entire formulation of active ingredient can be encapsulated (or “overcoated”). Encapsulation can control or delay release of the active ingredient.
  • An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation.
  • High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water, but occasionally another suitable medium like an aromatic or paraffinic hydrocarbon or vegetable oil. Spray volumes can range from about 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.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates (e.g., triethyl phosphate), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 –C 22 ), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants. When added to a liquid, surfactants (also known as “surface-active agents”) generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • surfactants can be classified as nonionic, anionic or cationic.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene oxide and reverse block polymers where the terminal blocks are prepared from propylene oxide
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon’s Emulsifiers and Detergents, annual American and International Editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon’s Volume 2: Functional Materials, annual International and North American editions published by McCutcheon’s Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions including emulsifiable concentrates, can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water. Active ingredient slurries, with particle diameters of up to 2,000 ⁇ m can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ m. Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S.3,060,084) or further processed by spray drying to form water-dispersible granules.
  • Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill).
  • Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, “Agglomeration”, Chemical Engineering, December 4, 1967, pp 147–48, Perry’s Chemical Engineer’s Handbook, 4th Ed., McGraw-Hill, New York, 1963, 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.
  • 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.
  • the compounds of the inention 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.
  • 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).
  • 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
  • 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.
  • 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.
  • Undesired vegetation includes at least one selected from the group consisting of grass weeds and broadleaf weeds.
  • Undesired vegetation is selected from the group consisting of annual bluegrass, Benghal dayflower, blackgrass, black nightshade, broadleaf signalgrass, Canada thistle, cheat, common cocklebur (Xanthium pensylvanicum), common ragweed, corn poppies, field violet, giant foxtail, goosegrass, green foxtail, guinea grass, hairy beggarticks, herbicide-resistant black grass, horseweed, Italian rye grass, jimsonweed, Johnson grass (Sorghum halepense), large crabgrass, little seed canary grass, morning glory, Pennsylvania smartweed, pitted morning glory, prickly sida, quackgrass, redroot pigweed, shattercane, shepherd's purse, silky windgrass, sunflower (as weed in potato), wild buckwheat (Polygonum convolvulus), wild mustard (Brass
  • 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. In one common embodiment, a compound of the invention is applied, typically in a formulated composition, to a locus comprising desired vegetation (e.g., crops) and undesired vegetation (i.e.
  • weeds both of which may be seeds, seedlings and/or larger plants, in contact with a growth medium (e.g., soil).
  • a composition comprising a compound of the invention can be directly applied to a plant or a part thereof, particularly of the undesired vegetation, and/or to the growth medium in contact with the plant.
  • compounds of the invention are used to control undesired vegetation
  • contact of desired vegetation in the treated locus with compounds of the invention may result in super-additive or enhanced effects with genetic traits in the desired vegetation, including traits incorporated through genetic modification. For example, resistance to phytophagous insect pests or plant diseases, tolerance to biotic/abiotic stresses or storage stability may be greater than expected from the genetic traits in the desired vegetation.
  • 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.
  • the present invention also pertains to a composition
  • 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.
  • 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), 4-amino-3-chloro-5-fluoro-6-(7-fluoro-1H-indol-6-yl)-2- Pyridinecarboxylic 2-propyn-1-yl ester (CAS No.2251111-17-6), 4-amino-3-chloro-5- fluoro-6-(7-fluoro-1H-indol-6-yl)- 2-Pyridinecarboxylic cyanomethyl ester (CAS No.
  • herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
  • bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc., Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
  • Preferred for better control of undesired vegetation e.g., lower use rate such as from enhanced effects, broader spectrum of weeds controlled, or enhanced crop safety
  • a herbicide selected from the group consisting of atrazine, azimsulfuron, S-beflubutamid, benzisothiazolinone, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron-methyl, clomazone, clopyralid potassium, cloransulam-methyl, 2-[(2,4-dichlorophenyl)methyl]- 4,4-dimethyl-3-isoxazolidinone, 2-[(2,5-dichlorophenyl)methyl]-4,4-dimethyl-3- isoxazolidinone, ethametsulfuron-methyl, flumetsulam, 4-(4-fluorophenyl)-6-[(2-hydroxy- 6-
  • Plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.
  • plant growth regulators such as aviglycine, N-(phenylmethyl)-1H-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl
  • plant growth modifying organisms such as Bacillus cereus strain BP01.
  • General references for agricultural protectants i.e. herbicides, herbicide safeners, insecticides
  • the mixing partners are typically used in the amounts similar to amounts customary when the mixture partners are used alone. More particularly in mixtures, active ingredients are often applied at an application rate between one-half and the full application rate specified on product labels for use of active ingredient alone. These amounts are listed in references such as The Pesticide Manual and The BioPesticide Manual.
  • 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.
  • 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.
  • 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. enhanced) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants.
  • 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.
  • 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, 1-bromo-4-[(chloromethyl)sulfonyl]benzene (BC
  • 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.
  • Compounds of the invention can also be mixed with: (1) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a herbicidal effect; or (2) polynucleotides including but not limited to DNA, RNA, and/or chemically modified nucleotides influencing the amount of a particular target through down regulation, interference, suppression or silencing of the genetically derived transcript that render a safening effect.
  • compositions 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 A1 lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention.
  • Compound No. (Compound Number) (i.e. Compound 1) in the Component (a) column is identified in Index Table A.
  • the second column of Table A1 lists the specific Component (b) compound (e.g., “2,4-D” in the first line).
  • the third, fourth and fifth columns of Table A1 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)).
  • the first line of Table A1 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 1:384 – 6:1.
  • the remaining lines of Table A1 are to be construed similarly.
  • Table A2 is constructed the same as Table A1 above except that entries below the “Component (a)” column heading are replaced with the respective Component (a) Column Entry shown below. Compound No. 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 2” (i.e. Compound 2 identified in Index Table A), and the first line below the column headings in Table A2 specifically discloses a mixture of Compound 2 with 2,4-D. Tables A3 through A60 are constructed similarly.
  • Preferred for better control of undesired vegetation e.g., lower use rate such as from enhanced effects, broader spectrum of weeds controlled, or enhanced crop safety
  • a herbicide selected from the group consisting of chlorimuron-ethyl, nicosulfuron, mesotrione, thifensulfuron-methyl, flupyrsulfuron-methyl, tribenuron, pyroxasulfone, pinoxaden, tembotrione, pyroxsulam, metolachlor and S-metolachlor.
  • the following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens.
  • the pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A and B below for compound descriptions.
  • the abbreviation “Cmpd.” stands for “Compound”, and the abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.
  • the numerical value reported in the column “MS” is the molecular weight of the highest isotopic abundance positively charged parent ion (M+1) formed by addition of H+ (molecular weight of 1) to the molecule having the highest isotopic abundance, or the highest isotopic abundance negatively charged ion (M–1) formed by loss of H+ (molecular weight of 1).
  • “Pyr” means “Pyridine”.
  • Przl means “Pyrazol”.
  • Thzl means “Thiazole”.
  • Imdzl mean “Imidazol”. The presence of molecular ions containing one or more higher atomic weight isotopes of lower abundance (e.g., 37Cl, 81Br) is not reported. The reported MS peaks were observed by mass spectrometry using electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI).
  • ESI electrospray ionization
  • APCI atmospheric pressure chemical ionization
  • BIOLOGICAL EXAMPLES OF THE INVENTION TEST A Seeds of plant species selected from blackgrass (Alopecurus myosuroides), corn (Zea mays), foxtail, giant (giant foxtail, Setaria faberi), goosegrass (Eleusine indica), kochia (Bassia scoparia), oat, wild (wild oat, Avena fatua), pigweed, palmer (palmer amaranth, palmer pigweed, Amaranthus palmeri), ragweed (common ragweed, Ambrosia artemisiifolia), ryegrass, Italian (italian ryegrass, Lolium multiflorum), soybean (Glycine max) and wheat (Triticum aestivum) 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.
  • plants selected from these crop and weed species and also galium (catchweed bedstraw, Galium aparine) and horseweed (Erigeron canadensis) 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 10 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.
  • 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 days, after which time all species were compared to controls and visually evaluated.
  • Plant response ratings, summarized in Table B, 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.

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Abstract

L'invention concerne des composés de formule I, y compris tous les stéréoisomères, N-oxydes, et sels de ceux-ci, des compositions à usage agricole les contenant et leur utilisation comme herbicides, J étant choisi dans le groupe constitué par J-1 à J-10, G étant choisi dans le groupe constitué par G-1 à G7 et R1, R2, R3, R4, R5, W, X, Y et Q étant tels que définis dans la description.
PCT/US2022/053915 2021-12-28 2022-12-23 Herbicides à base de cyclopropylpyrimidine substitués WO2023129493A1 (fr)

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