EP0922032A1 - Herbicidal pyridinyl and pyrazolylphenyl ketones - Google Patents

Herbicidal pyridinyl and pyrazolylphenyl ketones

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Publication number
EP0922032A1
EP0922032A1 EP97928809A EP97928809A EP0922032A1 EP 0922032 A1 EP0922032 A1 EP 0922032A1 EP 97928809 A EP97928809 A EP 97928809A EP 97928809 A EP97928809 A EP 97928809A EP 0922032 A1 EP0922032 A1 EP 0922032A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
compound
cyano
nitro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97928809A
Other languages
German (de)
French (fr)
Inventor
Kanu Maganbhai Patel
Morris Padgett Rorer
Chi-Ping Tseng
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EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
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Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0922032A1 publication Critical patent/EP0922032A1/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/24—Radicals substituted by oxygen atoms
    • 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
    • C07D401/10—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 carbon chain containing aromatic rings

Definitions

  • This invention relates to certain phenyl ketones, their JV-oxides, agriculturally suitable 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, corn (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 which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • WO 96/26200 discloses pyrazoles of Formula i as herbicides:
  • Q represents a cyclohexane- 1,3-dione ring
  • L and M are hydrogen, C r C 6 alkyl, C ⁇ -C 4 alkoxy, halogen or nitro;
  • Z represents a five to six-membered heterocyclic saturated or unsaturated group.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, TV-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
  • A is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be fully aromatic or partially saturated, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 2 oxygens and no more than 2 sulfurs, and each ring system is optionally substituted with one to three R 2 , provided that when a nitrogen atom of a heterocyclic ring is substituted with R 2 , then R 2 is other than halogen; each R 1 is independently H, C ⁇ -C 6 alkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano, nitro, -(Y) r S(O) n R 15 or -(Y) t -C(O)R 15 ;
  • W is N or CH
  • Y is O or NR 12 ;
  • R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C r C 6 alkoxy, C C 6 haloalkoxy, C 3 -C 6 alkenyloxy, C ⁇ -C ⁇ alkynyloxy, mercapto, C j -C 6 alkylthio, C j -C 3 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 -C 6 alkynylthio, C 2 -C 5 alkoxyalkylthio, C 3 -C 5 acetylalkylthio, C 3 -C 6 alkoxycarbonylalkylthio, C2-C 4 cyanoal
  • R 2 is phenyl or benzylthio, each optionally substituted on the phenyl ring with C ] -C 3 alkyl, C r C 3 haloalkyl, C ⁇ -C 3 alkoxy, C j -C 3 haloalkoxy, 1-2 halogen, cyano or nitro;
  • R 3 is OR 14 , SH, C C 6 alkylthio, C,-C 6 haloalkylthio, C r C 6 alkylsulfinyl, C r C 6 haloalkylsulfinyl, C j -Cg alkylsulfonyl, C j -C 6 haloalkylsulfonyl, halogen or
  • R 3 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C ] -C 3 alkyl, halogen, cyano or nitro; each R 4 is independently C r C 3 alkyl, C j -C 3 alkoxy, C j -C 3 alkylthio or halogen; or when two R 4 are attached to the same carbon atom, then said R 4 pair can be taken together to form -OCH 2 CH 2 O-, -OCH 2 CH 2 CH 2 O-, -SCH 2 CH 2 S- or -SCH 2 CH 2 CH 2 S-, each group optionally substituted with 1-4 CH 3 ;
  • R 5 is OR 14 , SH, C r C 6 alkylthio, C r C 6 haloalkylthio, C r C 6 alkylsulfinyl, C,-C 6 haloalkylsulfinyl, C r C 6 alkylsulfonyl, C j -C 6 haloalkylsulfonyl, halogen or NR 12 R 13 ; or R 5 is phenylthio, phenylsulfonyl or -SCH 2 C(O)Ph, each optionally substituted with C ⁇ -C 3 alkyl, halogen, cyano or nitro;
  • R 6 is H, C,-C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or
  • R 6 is phenyl or benzyl, each optionally substituted on the phenyl ring with Cj-C 3 alkyl, halogen, cyano or nitro;
  • R 7 is H, C ] -C 6 alkyl, C ⁇ -C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy, halogen, cyano or nitro;
  • R8 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl or C 3 -C 6 halocycloalkyl;
  • R 9 is H, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 haloalkoxy carbonyl, CO 2 H or cyano;
  • R 10 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 cycloalkyl optionally substituted with 1-4 C r C 3 alkyl or C 3 -C 6 halocycloalkyl;
  • R 1 ! is cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, S(O) n R 13 or
  • each R 12 is independently H or C r C 6 alkyl
  • R 13 is C r C 6 alkyl or C r C 6 alkoxy
  • R 12 and R 13 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -;
  • R 14 is H, C,-C 6 alkyl, C C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C(O)NR 12 R 13 , C,-C 6 alkylsulfonyl or C j -C ⁇ haloalkylsulfonyl; or R 14 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R 15 is NR 12 R 13 , C r C 6 alkoxy, C,-C 6 haloalkoxy, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C£ alkenyl, C 3
  • C j -C 3 haloalkyl C ⁇ -C 3 alkoxy, C C 3 haloalkoxy, 1-2 halogen, cyano or nitro
  • R 16 is C r C 3 alkoxy, C 2 -C alkoxycarbonyl, C r C 3 alkylthio, C j -C 3 alkylsulfinyl or C r C 3 alkylsulfonyl; or R 16 is phenyl optionally substituted with C r C 3 alkyl, Cj-C 3 haloalkyl, C1-C3 alkoxy, C r C 3 haloalkoxy, 1-2 halogen, cyano or nitro;
  • m is O, 1, 2 or 3;
  • n is 0, 1 or 2;
  • p is O, 1, 2, 3 or 4;
  • r is 1, 2 or 3; and
  • t is 0 or 1 ; provided that when W is CH and A is in the meta position with respect to
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, H-propyl, -propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl.
  • Alkenyl includes straight-chain or branched alkenes such as 1-propenyl, 2-pro ⁇ enyl, 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 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.
  • 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 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • 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.
  • alkylamino “dialkylamino”, and the like, 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”, includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 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.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • the total number of carbon atoms in a substituent group is indicated by the "C j -Cj" prefix where i and j are numbers from 1 to 6.
  • C ] -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 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 carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • 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 skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, /V-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • Some compounds of this invention can exist as one or more tautomers.
  • compounds of Formula la (Formula I where Q is Q-1, R 3 is OR 14 , and R 14 is H) can also exist as the tautomers of Formulae lb and Ic as shown below.
  • said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects.
  • the present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or enol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred salts include the lithium, sodium, potassium, triethylammonium, and quaternary ammonium salts of the compounds of the invention.
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • A is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl;
  • each R 1 is independently C ] -C 3 alkyl, C j -C 3 alkoxy, halogen or nitro;
  • R3 is OR 14 ;
  • R 14 is ⁇ or C j -C alkylsulfonyl; or R 14 is benzoyl or phenylsulfonyl, each optionally substituted with C C 3 alkyl, halogen, cyano or nitro.
  • Preferred 4 Compounds of Preferred 3 wherein:
  • A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl;
  • R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 ⁇ or cyano;
  • R15 is C r C 6 alkyl; t is 0; and n is 2.
  • Q is Q-2;
  • Preferred 6 Compounds of Preferred 5 wherein: each R 1 is independently Cj-C 3 alkyl, C r C 3 alkoxy, halogen or nitro; R5 is OR 14 ;
  • R 14 is H or C
  • R 6 is H, C r C 6 alkyl, or C 3 -C 6 alkenyl; and R7 is H;
  • A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl;
  • R 2 is -(Y) t -S(O) n R 15 , CF 3 , OCF 3 , OCF 2 ⁇ or cyano;
  • Rl5 is C r C 6 alkyl; t is 0; and n is 2.
  • Preferred 8 Compounds of Preferred 1 wherein: Q is Q-3.
  • each R 1 is independently C j -C 3 alkyl, C j -C 3 alkoxy, halogen or nitro;
  • R 8 is H, C.-C 3 alkyl, or cyclopropyl; and
  • R 9 is H or C 2 -C 3 alkoxycarbonyl.
  • A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl;
  • R 2 is -(Y),-S(O) n R 15 , CF 3 , OCF 3 , OCF 2 ⁇ or cyano;
  • R15 is C,-C 6 alkyl; t is 0; and n is 2.
  • each R 1 is independently C r C 3 alkyl, C C 3 alkoxy, halogen or nitro;
  • R 10 is CyCf, cycloalkyl or C 3 -C6 halocycloalkyl, each optionally substituted with 1-4 C j -C 3 alkyl; and
  • R 1 * is cyano or C 2 -Cg alkoxycarbonyl.
  • Preferred 13 Compounds of Preferred 12 wherein:
  • A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl;
  • R 2 is -(Y) r S(O) n R 15 , CF 3 , OCF 3 , OCF 2 ⁇ or cyano;
  • R'5 is C r C 6 alkyl; t is 0; and n is 2.
  • Most preferred are compounds of Formula la above, and sodium, potassium, and quaternary ammonium salts thereof, selected from the group: a) 3-hydroxy-2-[[6-(trifluoromethyl)[2,4'-bipyridin]-3-yl]carbonyl]-2- cyclohexen-1-one; b) 2-[2-chloro-4-(4-pyridinyl)benzoyl]-3-hydroxy-2-cyclohexen- 1 -one; and c) 2-[2,5-dimethyl-3-( 1 -methyl- lH-pyrazol-3-yl)-4-(methylsulfonyl)benzoyl]- 3-hydroxy-2-cyclohexen-l-one.
  • This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • 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 preferred methods of use are those involving the above preferred compounds.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-22.
  • the definitions of W, Y, A, R ! -R 16 , m, n, p, r, and t in the compounds of Formulae 1-22 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae Ia-Ig are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ig are as defined above for Formula I.
  • Id Scheme 1 illustrates the preparation of compounds of Formula Id (R 3 is OR 17 and R 17 is the same as R 14 as described in the Summary of the Invention excluding H) whereby a compound of Formula Id (R 3 is OH) is reacted with a reagent of Formula 1 in the presence of a base wherein X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc) and R 17 is as previously defined.
  • X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc) and R 17 is as previously defined.
  • the coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054.
  • R' 7 is the same as R' as described in the Summary of the Invention excluding H;
  • X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc)
  • Scheme 2 illustrates the preparation of compounds of Formula Id (R 3 is SO n R 18 ; n is 1 or 2; and R 18 is Cj-Cg alkyl or C]-C 6 haloalkyl) whereby a compound of Formula Id (R 3 is SR 18 ) is reacted with an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®, available from Aldrich Chemical Company), or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate).
  • an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®, available from Aldrich Chemical Company), or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate).
  • the oxidation is carried
  • R ⁇ is C1-C6 alkyl or C ⁇ -C(, haloalkyl
  • Nu is SR 18 or OR 19 ; M is Na, K or Li; and R 19 is Cj-C6 alkyl, Cj-C ⁇ haloalkyl or C -C6 alkoxyalkyl
  • Compounds of Formula Id (R 3 is halogen) can be prepared by reacting a compound of Formula Id (R 3 is OH) with a halogenating reagent such as oxalyl bromide or oxalyl chloride (Scheme 4). This conversion is carried out by methods known in the art (or by slight modification of these methods): for example see S. Muller, et al., WO 94/13619; S. Muller, et al., DE 4,241,999.
  • a halogenating reagent such as oxalyl bromide or oxalyl chloride
  • Halogenating reagent e.g., oxalyl bromide, oxalyl chloride
  • Scheme 5 illustrates the preparation of compounds of Formula Id (R 3 is OH), whereby an enol ester of Formula 3 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide).
  • cyanide source e.g., acetone cyanohydrin or potassium cyanide.
  • Enol esters of Formula 3 can be prepared by reacting a dione of Formula 4 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 6).
  • a base such as triethylamine
  • an inert organic solvent such as acetonitrile, methylene chloride or toluene
  • the acid chlorides of Formula 5 can be prepared by one skilled in the art by reacting an acid of Formula 6 with oxalyl chloride (or thionyl chloride) and a catalytic amount of dimethylformamide (Scheme 7). This chlorination is well known in the art: for example, see W. J. Michaely, EP 369,803.
  • Enol esters of Formula 3a can also be prepared by directly reacting the acid of Formula 6a with N-methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the dione of Formula 4 in the presence of a base such as triethylamine (Scheme 8).
  • This coupling is carried out be methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433. 530
  • Scheme 9 illustrates the preparation of acids of Formula 6 (R 1 is S(O) n R 15 and n is 1 or 2) whereby an acid of Formula 6 (R 1 is SR 15 ) is reacted with an oxidizing reagent such as peroxyacetic acid, w-chloroperoxybenzoic acid, Oxone®, or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate).
  • an oxidizing reagent such as peroxyacetic acid, w-chloroperoxybenzoic acid, Oxone®, or hydrogen peroxide
  • a base such as sodium acetate or sodium carbonate
  • R 1 is S(0) n R 15 and n is 0 wherein R 1 is S(0) n R 15 and n is 1 or 2
  • Scheme 10 illustrates the preparation of acids of Formula 6 (n is 0 if R 1 is S(O) n R 15 ) whereby a phenyl bromide of Formula 7 (n is 0 if R 1 is S(O) n R 15 ) is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid.
  • This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. A.
  • acids of Formula 6 can also be prepared, as shown in Scheme 1 1 , whereby an ester of Formula 8 is saponified (for example, potassium hydroxide in methanol, then acidification with an acid such as hydrochloric acid), or, alternatively, hydrolyzed in acid (for example, 5/V hydrochloric acid in acetic acid) by methods known in the art (or slight modification of these methods); see for example, M. A. Ogliaruso, et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, John Wiley & Sons,
  • R " is CH 3 or CH 2 CH 3 530
  • Esters of Formula 8 can be prepared using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, volumes 2-6, Pergamon Press.
  • Esters of Formula 8a or 8b can also be prepared as shown in Scheme 12, whereby an ester of Formula 9a or 9b is contacted with an appropriate nucleophilic heterocycle Nu 1 and a suitable base in an inert solvent.
  • This reaction can be carried out by a variety of well-known methods, preferably with potassium carbonate or potassium tert-butoxide as the base with N,N-dimethylfoimamide as the solvent and at a reaction temperature range of from approximately 0 to 100 °C.
  • X 3 is Cl, F or CF 3 S0 0, wherein A l is 1 /-imidazole, l/Z-pyrazole, l -l,2,4-t ⁇ azole or 4/7-1,2,4-t ⁇ azole
  • Nu ' is an imidazole, pyrazole or t ⁇ azole
  • Esters of Formula 9a and 9b are commercially available or can be prepared using methods known in the art (or by slight modification of these methods).
  • Scheme 13 illustrates the preparation of acids of Formula 6a whereby an aryl bromide of Formula 9c is treated with an aryl tin reagent in the presence of a palladium catalyst. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. Fujta, et al., Tetrahedron Letters, (1995), 29, 5247-5250; Y. Yamamoto, et al., Heterocycles, (1996), 42, 189-194. Saponification of the ester with a base such as sodium hydroxide provides the acids of Formula 6a.
  • Bromides of Formula 9c are either commercially available or can easily be prepared by methods known in the art (or by slight modification of these methods): for example, see T. Bryson, et al., J. Org. Chem., (1976), 41, 2066; Andrea, T. A. and
  • Aryl and heteroaryl organotin compounds can be prepared by methods known in the art (or by slight modification of these methods): for example, see D. Peters, et al., J. Heterocyclic Chem., (1990), 27, 2165.
  • Bromides of Formula 7 (n is 0 if Rl is S(O) n R 15 ) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tel. Lett. (1964), p. 617; M. A. ahn, et al., Rev. Latinoam. Quim. (1972), 3, p. 1 19; M. Kosugi, et al., Bull. Chem. Soc. Jpn. (1986), 59 (2), p. 677.
  • bromides of Formula 7 (n is 0 if R 1 is S(O) n Rl 5 ) can also be prepared by bromination of the corresponding substituted benzenes of Formula 8 (n is 0 if Rl is S(O) n R l5 ) with the bromine or other equivalent reagent in an inert organic solvent as shown in Scheme 14.
  • This bromination is carried out by general methods known in the art; see, for example, E. Campaigne, et al., J. Heterocycl. Chem. (1969), 6, p. 517; H. Gilman, J. Am. Chem. Soc. (1955), 77, p. 6059;
  • the compounds of Formula 8 (n is 0 if R 1 is S(O) n R 15 ) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et. al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tet. Lett. (1964), p. 617; 530
  • Scheme 15 illustrates the preparation of compounds of Formula le (R 14 is R 14a and R ⁇ 4a is the same as R l as described in the Summary of the Invention excluding H) whereby a compound of Formula le ( R' 4 is H) is reacted with a reagent of Formula 9 in the presence of a base wherein X 2 is chlorine, bromine, fluorine, OTf or OAc and R , 4a is as previously defined.
  • This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054.
  • Scheme 16 illustrates the preparation of compounds of Formula le (R 14 is H). whereby an ester of Formula 10 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide).
  • cyanide source e.g., acetone cyanohydrin or potassium cyanide.
  • Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula 11 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 17).
  • a base such as triethylamine
  • an inert organic solvent such as acetonitrile, methylene chloride or toluene
  • Scheme 18 illustrates the preparation of compounds of Formula If whereby a compound of Formula 12 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate.
  • a base or acid acceptor such as triethylamine or sodium acetate.
  • the substituents of the immediate products may be further modified if appropriate. This cyclization is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. 530
  • L is a leaving group such as C ] -C 4 alkoxy (e.g. OC 2 H5) or V-dialkylamino (e.g. dimethyl amino)
  • R 9 a is R 9 or CONH 2
  • Scheme 19 illustrates the preparation of compounds of Formula 12 whereby a compound of Formula 13 is reacted with a reagent of Formula 14 or Formula 15. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
  • Scheme 20 illustrates the preparation of compounds of Formula 13 whereby a ester of Formula 16 is decarboxylated in the presence of a catalyst, such as -toluenesulfonic acid, in an inert solvent such as toluene.
  • a catalyst such as -toluenesulfonic acid
  • an inert solvent such as toluene.
  • Esters of Formula 16 can be prepared by reacting the metal salt of a compound of
  • Scheme 22 illustrates the preparation of compounds of Formula Ig whereby a compound of Formula 5 is reacted with a compound of Formula 18 in the presence of a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt) 2 in an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.
  • a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt) 2
  • an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.
  • Step B Preparation of 2,3-dihvdro-5,8-dimethyl-4H-l -benzopyran-4-one
  • Step C Preparation of 6-bromo-2,3-dihvdro-5,8-dimethyl-4H- 1 -benzothiopyran-
  • Step D Preparation of 6-bromo-5,8-dimethyl-4H- 1 -benzothiopyran-4-one
  • Step E Preparation of 3-[3-bromo-2,5-dimethyl-6-(methylthio)phenvn- 1-methyl- lH-pyrazole 13.25 g (0.049 mol) of the title compound of step D and 2.88 mL (0.054 mol) of methylhydrazine (purchased from Aldrich Chemical Company) was added to 150 mL of absolute ethanol. After stirring at reflux under nitrogen for 5 hr the mixture was allowed to warm to room temperature and stir for 2.5 days.
  • step E 5.9 g (0.019 mol) of the title compound of step E was added to 100 mL of tetrahydrofuran and cooled to -70 °C. 9.1 mL (0.023 mol) of 2.5M ⁇ -butyllithium (purchased from Aldrich Chemical Company) was added dropwise keeping the temperature below -65 C. Solid carbon dioxide was added in one portion and the mixture warmed to room temperature. 200 mL of hexane was added and the mixture was filtered. The solid collected was added to water and acidified to about p ⁇ 1 with concentrated hydrochloric acid.
  • Step G Preparation of 2,5-dimethyl-3-(l -methyl- lH-pyrazol-3-yl)-4-
  • Step H Preparation of 3-oxo-l-cylcohexen-l-yl 2,5-dimethyl-3-(l-methyl-lH- pyrazol-3-yl)-4-(methylsulfonyl)benzoate 1.39 g (0.0045 mol) of the title compound of step G, 1.18 mL (0.0135 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were added to 50 mL of methylene chloride. The mixture was refluxed under nitrogen for 2.5 hr and was then evaporated to dryness. 50 mL of methylene chloride was added to the residue and the solution was again evaporated to dryness.
  • Step B Preparation of 3-oxo- 1 -cyclohexen- 1 -yl 2-r3-(trifluoromethyl)- 1 H- pyrazol- 1 -yllbenzoate
  • oxalyl chloride oxalyl chloride
  • the suspension was refluxed for about 3 hours and then concentrated under reduced pressure.
  • the residue was azeotroped with dichloromethane (two times with 20 mL at 60 °C) to yield an oil which solidified upon cooling and melted at 64-68 °C.
  • Step C Preparation of 3-hvdroxy-2-r2-f3-(trifluoromethyl)-lH-pyrazol- l- yllbenzovn-2-cvclohexen-l-one To 20 mL of acetonitrile was added sequentially 1.8 g (0.005 mol) of the title compound of Step B, 1.0 g (0.01 mol) of triethylamine, and 8 drops of acetone cyanohydrin.
  • Step D Preparation of 3-hvdroxy-2-f[6-(trifluoromethyl)f2,4'-bipyridin1-3- yllcarbonvn-2-cvclohexen- 1 -one To a solution of 1.22 g (3.5 mmol) of the title compound of Step C in 25 mL of acetonitrile was added 1.16 mL (8.36 mmol) of triethylamine, followed by 2 drops of acetonecyanohydrin.
  • A-53 (3-methyl- l,2,4-oxad ⁇ azol-5-yl)-
  • A-79 (4-methyl-2-py ⁇ m ⁇ d ⁇ nyl)-
  • A-60 (3-methyl l ,2,4-th ⁇ ad ⁇ azol-5-yl)-
  • A-86 (6-methyl-2-pyrazmyl)-
  • A-61 (5-methyl-l ,2,4-th ⁇ ad ⁇ azol-3-yl)-
  • A-87 (2-pyraz ⁇ nyl)-
  • A-62 (4-methyl- l ,2,5-th ⁇ ad ⁇ azol-3-yl)-
  • A-88 (4,6-d ⁇ methyl- I ,3,5-t ⁇ az ⁇ n-2-yl)-
  • A-63 (5-methyl- l ,3,4-th ⁇ ad ⁇ azol-2-yl)-
  • A-89 (4,6-d ⁇ chloro- l,3,5-t ⁇ az ⁇ n-2-yl)-
  • A-64 (l-methyl-l/7-tetrazol-5-yl)-
  • A-90 (l ,3,5-t ⁇ az ⁇ n-2-yl)-
  • A-65 (l//-tetrazol-5-yl)-
  • A-91 (4-methyl- 1,3,5-t ⁇ az ⁇ n- 2-yl)-
  • A-66 (5-methyl-l /-tetrazol-l-yI)-
  • A-92 (3-methyl- l ,2,4-t ⁇ az ⁇ n-5-yl)-
  • A-67 (2-methyl-2/ -tetrazol-5-yl)-
  • A-93 (3-methyl- l,2,4-t ⁇ az ⁇ n-6-yl)-
  • A-68 (2-ethyl-2/ -tetrazol-5-yl)-
  • A-69 (5-methyl-2 /-tetrazol-2-yl)-
  • A-70 (2 -tetrazol-2-yl)-
  • A-71 (2-py ⁇ d ⁇ nyl)-
  • A-72 (6-methyl-2-py ⁇ d ⁇ nyl)-
  • A-73 (4-py ⁇ d ⁇ nyl)-
  • A-74 (3-py ⁇ d ⁇ nyl)-
  • A-75 (6-methyl-3-py ⁇ daz ⁇ nyl)-
  • A-76 (5-methyl -3-py ⁇ daz ⁇ nyl)- 97/46530
  • R 15 is CT and R 6 is CH 2 CH 3
  • A-42 S0 2 N(CH 3 ) 2 CH 3 CH 3
  • A-44 S0 2 N(CH 3 ) 2 CH 3 CH 3
  • A-42 S0 2 OCH 2 CF 3 CH 3 CH 3
  • A-44 S0 2 OCH 2 CF 3 CH 3 CH 3
  • R la is CH, R lb is CN, and W is N
  • Rla is Cl.
  • R lb is Cl. and W is CH
  • Rla is CH .
  • R lb is SO 2 CH ? . and W is N
  • R ⁇ a is CH , R b is H, and W is N
  • Rl a isCl.R lb isCl.andWisCH
  • Rla is isCH
  • Rla is Cl.
  • R l b is Cl. and W is N
  • Rla is Cl.
  • R lb is Cl. and W is CH
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • 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 liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble.
  • 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.
  • Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • 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.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, ⁇ /,/V-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-mefhyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. 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.
  • 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.
  • Example A High Strength Concentrate Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
  • Compound 15 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Granule Compound 25 10.0% attapulgite granules (low volatile matter
  • Example D Extruded Pellet Compound 26 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. 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.
  • Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are 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 which include but are not limited to alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato,
  • 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 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
  • Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • 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, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
  • combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds.
  • Preferred for better control of undesired vegetation (e.g., lower use rate, 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 nicosulfuron, rimsulfuron, nicosulfuron in combination with rimsulfuron, imazethapyr, sethoxydim, glyphosate, and glufosinate.
  • 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 Tables A-D for compound descriptions. The abbreviation “dec.” indicates that the compound appeared to decompose on melting. The abbreviation “Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A
  • Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
  • the compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application).
  • preemergence application to water that covered the soil surface
  • postemergence application to plants that were in the one-to-four leaf stage
  • a sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.
  • Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays v.
  • Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass2 (Echinochloa crus-galli) and Late watergrass (Echinochloa oryzicola grown to the 2 leaf stage for testing.
  • Plastic pots were partially filled with silt loam soil. The soil was then saturated with water.
  • Indica Rice Oryza saliva seed or seedlings at the 2.0 to 3.5 leaf stage; seeds, tubers or plant parts selected from arrowhead (Sagittaria rigida), barnyardgrass (Echinochloa crus- galli), ducksalad (Heteranthera limosa), early watergrass (Echinochloa oryzoides), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammonia species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloafasicularis), were planted into this soil.
  • Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the two leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied directly to the paddy water, by pipette, or to the plant foliage, by an air-pressure assisted, calibrated belt-conveyer spray system.
  • alexandergrass (Brachiaria plantaginea), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylla), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), cotton (Gossypium hirsutum), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltat ⁇ ), Johnson grass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanuts (Arachis hypogaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), and Surinam grass (Brachiaria plantaginea), ber
  • Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table D, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.
  • soybean2 Glycine max v. Asgrow 3304
  • sunflower Helianthus annuus
  • velvetleaf Abutilon theophrasti
  • wild proso Pancium miliaceum
  • woolly cupgrass Eriochloa villosa
  • yellow foxtail Setaria lutescens
  • purple nutsedge Cyperus rotundus tubers
  • Crop and weed species include arrowleaf sida (Sida rhombifoli ⁇ ), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common lambsquarters (Chenopodium album), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), Florida beggarweed (Desmodium purpureum), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladys
  • Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table F, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.
  • Crop and weed species include bristly starbur (Acanthospermun hispidum) alexandergrass (Brachiaria plantaginea), american black nightshade (Solanum americanum), apple-of-Peru (Nicandra physaloides), arrowleaf sida (Sida rhombifolia), Brazilian sicklepod (Cassia tora Brazilian), Surinam grass (Brachiaria decumbens), capim- colchao (Digitaria horizontalis), Crist, soybean (Glycine max v.
  • Cristalina florida beggarweed (Desmodium purpureum), hairy beggarticks (Bidens pilosa), slender amaranth (Amaranthus viridis), southern sandbur (Cenchrus echinatus), tall morningglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis), W20 Soybean (Glycine max v. W20), W4-4 Soybean (Glycine max v. W4-4), corn (Zea mays v. Pioneer 3394) and wild pointsettia (Eupohorbia heterophylla).
  • Treated plants and untreated controls were maintained in a greenhouse for approximately 13 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table G, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control.
  • Braz Sicklepod 60 Braz Sicklepod 35 Braz Sicklepod 10
  • Capim-Colch 100 Capim-Colch 65
  • Capim-Colch 60 Corn 0 Corn 0 Corn 0
  • Morningglory 70 Morningglory 65 Morningglory 60
  • Crop and weed species include annual bluegrass (Poa annu ⁇ ), blackgrass (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed
  • Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table H, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result.

Abstract

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein Q is Q-1, Q-2, Q-3 or Q-4; and A, W, R?1, R3-R11¿, and m are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description

TITLE HERBICIDAL PYRIDINYL, AND PYRAZOLYLPHENYL KETONES BACKGROUND OF THE INVENTION This invention relates to certain phenyl ketones, their JV-oxides, agriculturally suitable 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, corn (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 which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
WO 96/26200 discloses pyrazoles of Formula i as herbicides:
wherein, inter alia
Q represents a cyclohexane- 1,3-dione ring;
L and M are hydrogen, CrC6 alkyl, Cι-C4 alkoxy, halogen or nitro; and
Z represents a five to six-membered heterocyclic saturated or unsaturated group.
The phenyl ketones of the present invention are not disclosed in this publication.
SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I including all geometric and stereoisomers, TV-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
wherein Q is
Q-l 0-2
Q-3 Q-4
A is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be fully aromatic or partially saturated, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 2 oxygens and no more than 2 sulfurs, and each ring system is optionally substituted with one to three R2, provided that when a nitrogen atom of a heterocyclic ring is substituted with R2, then R2 is other than halogen; each R1 is independently H, Cι-C6 alkyl, CrC6 haloalkyl, CrC6 alkoxy, CrC6 haloalkoxy, halogen, cyano, nitro, -(Y)rS(O)nR15 or -(Y)t-C(O)R15;
W is N or CH;
Y is O or NR12;
R2 is CrC6 alkyl, CrC6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, CrC6 alkoxy, C C6 haloalkoxy, C3-C6 alkenyloxy, C^-C^ alkynyloxy, mercapto, Cj-C6 alkylthio, Cj-C3 haloalkylthio, C3-C6 alkenylthio, C3-C6 haloalkenylthio, C3-C6 alkynylthio, C2-C5 alkoxyalkylthio, C3-C5 acetylalkylthio, C3-C6 alkoxycarbonylalkylthio, C2-C4 cyanoalkylthio, Cj-Cg alkylsulfinyl, Cj-C6 haloalkylsulfinyl, CrC6 alkylsulfonyl, CrC6 haloalkylsulfonyl, aminosulfonyl, C1-C2 alkylaminosulfonyl, C2-C4 dialkylaminosulfonyl,
(CH2)rR16, NR12R13, halogen, cyano or nitro; or R2 is phenyl or benzylthio, each optionally substituted on the phenyl ring with C]-C3 alkyl, CrC3 haloalkyl, Cι-C3 alkoxy, Cj-C3 haloalkoxy, 1-2 halogen, cyano or nitro;
R3 is OR14, SH, C C6 alkylthio, C,-C6 haloalkylthio, CrC6 alkylsulfinyl, CrC6 haloalkylsulfinyl, Cj-Cg alkylsulfonyl, Cj-C6 haloalkylsulfonyl, halogen or
NR12R13; or R3 is phenylthio, phenylsulfonyl or -SCH2C(O)Ph, each optionally substituted with C]-C3 alkyl, halogen, cyano or nitro; each R4 is independently CrC3 alkyl, Cj-C3 alkoxy, Cj-C3 alkylthio or halogen; or when two R4 are attached to the same carbon atom, then said R4 pair can be taken together to form -OCH2CH2O-, -OCH2CH2CH2O-, -SCH2CH2S- or -SCH2CH2CH2S-, each group optionally substituted with 1-4 CH3;
R5 is OR14, SH, CrC6 alkylthio, CrC6 haloalkylthio, CrC6 alkylsulfinyl, C,-C6 haloalkylsulfinyl, CrC6 alkylsulfonyl, Cj-C6 haloalkylsulfonyl, halogen or NR12R13; or R5 is phenylthio, phenylsulfonyl or -SCH2C(O)Ph, each optionally substituted with Cι-C3 alkyl, halogen, cyano or nitro;
R6 is H, C,-C6 alkyl, CrC6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl or
-CH2CH2OR12; or R6 is phenyl or benzyl, each optionally substituted on the phenyl ring with Cj-C3 alkyl, halogen, cyano or nitro;
R7 is H, C]-C6 alkyl, Cι-C6 haloalkyl, CrC6 alkoxy, CrC6 haloalkoxy, halogen, cyano or nitro;
R8 is H, CrC6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;
R9 is H, C2-C6 alkoxycarbonyl, C2-C6 haloalkoxy carbonyl, CO2H or cyano;
R10 is CrC6 alkyl, CrC6 haloalkyl, C3-C6 cycloalkyl optionally substituted with 1-4 CrC3 alkyl or C3-C6 halocycloalkyl; R1 ! is cyano, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, S(O)nR13 or
C(O)NR12R13; each R12 is independently H or CrC6 alkyl;
R13 is CrC6 alkyl or CrC6 alkoxy; or
R12 and R13 can be taken together as -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-;
R14 is H, C,-C6 alkyl, C C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C(O)NR12R13, C,-C6 alkylsulfonyl or C j-C^ haloalkylsulfonyl; or R14 is phenyl, benzyl, benzoyl, -CH2C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro; R15 is NR12R13, CrC6 alkoxy, C,-C6 haloalkoxy, CrC6 alkyl, CrC6 haloalkyl, C3-C£ alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl or 3-C<5 cycloalkyl; or R15 is phenyl optionally substituted with C] -C3 alkyl,
Cj-C3 haloalkyl, Cι-C3 alkoxy, C C3 haloalkoxy, 1-2 halogen, cyano or nitro; R16 is CrC3 alkoxy, C2-C alkoxycarbonyl, CrC3 alkylthio, Cj-C3 alkylsulfinyl or CrC3 alkylsulfonyl; or R16 is phenyl optionally substituted with CrC3 alkyl, Cj-C3 haloalkyl, C1-C3 alkoxy, CrC3 haloalkoxy, 1-2 halogen, cyano or nitro; m is O, 1, 2 or 3; n is 0, 1 or 2; p is O, 1, 2, 3 or 4; r is 1, 2 or 3; and t is 0 or 1 ; provided that when W is CH and A is in the meta position with respect to the group Q-C(O)- of Formula I, then m is 3 and R1 is other than H. 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, H-propyl, -propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl. "Alkenyl" includes straight-chain or branched alkenes such as 1-propenyl, 2-proρenyl, 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 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 CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "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", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3G≡C, CC13C=C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 6. For example, C]-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C 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. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a group contains a substituent which can be hydrogen, for example R1 or R14, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. 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. Accordingly, the present invention comprises compounds selected from Formula I, /V-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. Some compounds of this invention can exist as one or more tautomers. One skilled in the art will recognize, for example, that compounds of Formula la (Formula I where Q is Q-1, R3 is OR14, and R14 is H) can also exist as the tautomers of Formulae lb and Ic as shown below. One skilled in the art will recognize that said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects. The present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I.
Ib Ic
The salts of the compounds of the invention 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. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or enol. Preferred salts include the lithium, sodium, potassium, triethylammonium, and quaternary ammonium salts of the compounds of the invention.
Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I, and N-oxides and agriculturally-suitable salts thereof, wherein: A is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-l,2,3-triazolyl; 2H-l,2,3-triazolyl; lH-l,2,4-triazolyl; 4H-l,2,4-triazolyl;
1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl; 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl; 1,2,4-triazinyl; and A may optionally be substituted by one to three R2, provided that when a nitrogen atom of a heterocyclic ring is substituted with R2, then R2 is other than halogen; Preferred 2. Compounds of Preferred 1 wherein:
Q is Q-1. Preferred 3. Compounds of Preferred 2 wherein: each R1 is independently C]-C3 alkyl, Cj-C3 alkoxy, halogen or nitro;
R3 is OR14; and
R14 is Η or Cj-C alkylsulfonyl; or R14 is benzoyl or phenylsulfonyl, each optionally substituted with C C3 alkyl, halogen, cyano or nitro. Preferred 4. Compounds of Preferred 3 wherein:
A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2Η or cyano; R15 is CrC6 alkyl; t is 0; and n is 2.
Preferred 5. Compounds of Preferred 1 wherein:
Q is Q-2; Preferred 6. Compounds of Preferred 5 wherein: each R1 is independently Cj-C3 alkyl, CrC3 alkoxy, halogen or nitro; R5 is OR14;
R14 is H or C|-C4 alkylsulfonyl; or R14 is benzoyl or phenylsulfonyl, each optionally substituted with CrC3 alkyl, halogen, cyano or nitro. R6 is H, CrC6 alkyl, or C3-C6 alkenyl; and R7 is H;
Preferred 7. Compounds of Preferred 6 wherein:
A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2Η or cyano; Rl5 is CrC6 alkyl; t is 0; and n is 2. Preferred 8. Compounds of Preferred 1 wherein: Q is Q-3.
Preferred 9. Compounds of Preferred 8 wherein: each R1 is independently Cj-C3 alkyl, Cj-C3 alkoxy, halogen or nitro; R8 is H, C.-C3 alkyl, or cyclopropyl; and R9 is H or C2-C3 alkoxycarbonyl. Preferred 10. Compounds of Preferred 9 wherein:
A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R2 is -(Y),-S(O)nR15, CF3, OCF3, OCF2Η or cyano; R15 is C,-C6 alkyl; t is 0; and n is 2.
Preferred 11. Compounds of Preferred 1 wherein:
Q is Q-4. Preferred 12. Compounds of Preferred 11 wherein: each R1 is independently CrC3 alkyl, C C3 alkoxy, halogen or nitro; R10 is CyCf, cycloalkyl or C3-C6 halocycloalkyl, each optionally substituted with 1-4 Cj-C3 alkyl; and R1 * is cyano or C2-Cg alkoxycarbonyl. Preferred 13. Compounds of Preferred 12 wherein:
A is pyridinyl, pyridazinyl, pyrimidinyl or lH-pyrazolyl; R2 is -(Y)rS(O)nR15, CF3, OCF3, OCF2Η or cyano;
R'5 is CrC6 alkyl; t is 0; and n is 2. Most preferred are compounds of Formula la above, and sodium, potassium, and quaternary ammonium salts thereof, selected from the group: a) 3-hydroxy-2-[[6-(trifluoromethyl)[2,4'-bipyridin]-3-yl]carbonyl]-2- cyclohexen-1-one; b) 2-[2-chloro-4-(4-pyridinyl)benzoyl]-3-hydroxy-2-cyclohexen- 1 -one; and c) 2-[2,5-dimethyl-3-( 1 -methyl- lH-pyrazol-3-yl)-4-(methylsulfonyl)benzoyl]- 3-hydroxy-2-cyclohexen-l-one.
This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.
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 preferred methods of use are those involving the above preferred compounds.
DETAILS OF THE INVENTION
The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-22. The definitions of W, Y, A, R!-R16, m, n, p, r, and t in the compounds of Formulae 1-22 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ig are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ig are as defined above for Formula I.
Compounds of General Formula Id can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 1-14 of this section as well as by following the specific procedures given in Example 1.
Id Scheme 1 illustrates the preparation of compounds of Formula Id (R3 is OR17 and R17 is the same as R14 as described in the Summary of the Invention excluding H) whereby a compound of Formula Id (R3 is OH) is reacted with a reagent of Formula 1 in the presence of a base wherein X1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc) and R17 is as previously defined. The coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054. Scheme 1
Id (R3 is OH) + Rl7χl Id (R3 is OR I7)
Base
wherein R'7 is the same as R' as described in the Summary of the Invention excluding H;
X 1 is chlorine, bromine, fluorine, trifluorosulfonyloxy (OTf) or acetyloxy (OAc)
Scheme 2 illustrates the preparation of compounds of Formula Id (R3 is SOnR18; n is 1 or 2; and R18 is Cj-Cg alkyl or C]-C6 haloalkyl) whereby a compound of Formula Id (R3 is SR18) is reacted with an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, potassium peroxymonosulfate (e.g., Oxone®, available from Aldrich Chemical Company), or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate). The oxidation is carried out by methods known in the art (or by slight modification of these methods): for example, see B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons, Protecting and deprotecting functional groups not compatible with the reaction condition may be necessary for compounds with such a functional group (for procedures, see T. W. Greene, et al., Protective Groups in Organic Synthesis, Second Edition, John Wiley & Sons, Inc.).
Scheme 2
Id (R3 is SR1 8) *• Id (R3 is S(0)nR1 ; n is 1 or 2) oxidizing agent
wherein R^ is C1-C6 alkyl or C\-C(, haloalkyl
Compounds of Formula Id (R3 is Nu; Nu is SR18or OR19; R18 is as defined previously ; R19 is CrC6 alkyl, haloalkyl or C2-C6 alkoxyalkyl) can be prepared by one skilled in the art from a compound of Formula Id (R3 is halogen) by treatment with a nucleophile of Formula 2 (Nu is SR18or OR19; M is Na, K or Li) as shown in Scheme 3 using methods well documented in the literature (or slight modification of these methods): for example, see S. Miyano, et al., Chem. Soc, Perkin Trans. 1 (1976), 1 146. Scheme 3
Id (R3 is halogen) + MNu >■ Id (R3 is SR18 or OR19)
2 wherein Nu is SR18 or OR19; M is Na, K or Li; and R19 is Cj-C6 alkyl, Cj-Cό haloalkyl or C -C6 alkoxyalkyl
Compounds of Formula Id (R3 is halogen) can be prepared by reacting a compound of Formula Id (R3 is OH) with a halogenating reagent such as oxalyl bromide or oxalyl chloride (Scheme 4). This conversion is carried out by methods known in the art (or by slight modification of these methods): for example see S. Muller, et al., WO 94/13619; S. Muller, et al., DE 4,241,999.
Scheme 4
Id (R3 is OH) >■ Id (R3 is halogen)
Halogenating reagent (e.g., oxalyl bromide, oxalyl chloride)
Scheme 5 illustrates the preparation of compounds of Formula Id (R3 is OH), whereby an enol ester of Formula 3 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by slight modification of these methods): for example see W. J. Michaely,
EP 369,803.
Scheme 5
3 Enol esters of Formula 3 can be prepared by reacting a dione of Formula 4 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 6). This type of coupling is known in the art: for example, see W. J. Michaely, EP 369,803.
Scheme 6
The acid chlorides of Formula 5 can be prepared by one skilled in the art by reacting an acid of Formula 6 with oxalyl chloride (or thionyl chloride) and a catalytic amount of dimethylformamide (Scheme 7). This chlorination is well known in the art: for example, see W. J. Michaely, EP 369,803.
Scheme 7
Enol esters of Formula 3a can also be prepared by directly reacting the acid of Formula 6a with N-methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the dione of Formula 4 in the presence of a base such as triethylamine (Scheme 8). This coupling is carried out be methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433. 530
13
Scheme 8
3a
Scheme 9 illustrates the preparation of acids of Formula 6 (R1 is S(O)nR15 and n is 1 or 2) whereby an acid of Formula 6 (R1 is SR15) is reacted with an oxidizing reagent such as peroxyacetic acid, w-chloroperoxybenzoic acid, Oxone®, or hydrogen peroxide (the reaction may be buffered with a base such as sodium acetate or sodium carbonate). The oxidation is carried out by methods known in the art (or by slight modification of these methods): for example, see B. M. Trost, et al., J. Org. Chem.
(1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, et al.,
The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons. For some acids of
Formula 6 (R1 is SR15) with a functional group not compatible with the reaction conditions, the functional group may be protected before the oxidation and then be deprotected after the oxidation. The protecting and deprotecting procedures are well known in the literature: for example see T. W. Greene, et al., Protective Groups in
Organic Synthesis (Second Edition), John Wiley & Sons, Inc.
Scheme 9
oxidizing agent
wherein R1 is S(0)nR15 and n is 0 wherein R 1 is S(0)nR15 and n is 1 or 2 Scheme 10 illustrates the preparation of acids of Formula 6 (n is 0 if R1 is S(O)nR15) whereby a phenyl bromide of Formula 7 (n is 0 if R1 is S(O)n R15) is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. A. Ogliaruso, et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, pp 27-28, John Wiley & Sons; A. J. Bridges, et al., J. Org. Chem. (1990), 55, 113; C. Franke, et al., Angew. Chem. Int. Ed. (1969), 8, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such a functional group.
Scheme 10
wherein W is CH, and if R 1 is S(0)nRl5, then n is 0
Many acids of Formula 6 can also be prepared, as shown in Scheme 1 1 , whereby an ester of Formula 8 is saponified (for example, potassium hydroxide in methanol, then acidification with an acid such as hydrochloric acid), or, alternatively, hydrolyzed in acid (for example, 5/V hydrochloric acid in acetic acid) by methods known in the art (or slight modification of these methods); see for example, M. A. Ogliaruso, et al., Synthesis of Carboxylic Acids, Esters and Their Derivatives, John Wiley & Sons,
(1991), pages 5-7.
Scheme 11
wherein R " is CH3 or CH2CH3 530
15
Esters of Formula 8 can be prepared using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, volumes 2-6, Pergamon Press.
Esters of Formula 8a or 8b can also be prepared as shown in Scheme 12, whereby an ester of Formula 9a or 9b is contacted with an appropriate nucleophilic heterocycle Nu1 and a suitable base in an inert solvent. This reaction can be carried out by a variety of well-known methods, preferably with potassium carbonate or potassium tert-butoxide as the base with N,N-dimethylfoimamide as the solvent and at a reaction temperature range of from approximately 0 to 100 °C.
Scheme 12
wherein X3 is Cl, F or CF3S0 0, wherein A l is 1 /-imidazole, l/Z-pyrazole, l -l,2,4-tπazole or 4/7-1,2,4-tπazole
Nu ' is an imidazole, pyrazole or tπazole
Esters of Formula 9a and 9b are commercially available or can be prepared using methods known in the art (or by slight modification of these methods). Scheme 13 illustrates the preparation of acids of Formula 6a whereby an aryl bromide of Formula 9c is treated with an aryl tin reagent in the presence of a palladium catalyst. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see M. Fujta, et al., Tetrahedron Letters, (1995), 29, 5247-5250; Y. Yamamoto, et al., Heterocycles, (1996), 42, 189-194. Saponification of the ester with a base such as sodium hydroxide provides the acids of Formula 6a. Scheme 13
9c 6a
Bromides of Formula 9c are either commercially available or can easily be prepared by methods known in the art (or by slight modification of these methods): for example, see T. Bryson, et al., J. Org. Chem., (1976), 41, 2066; Andrea, T. A. and
Liang, P. H., U.S. 5,393,734. Aryl and heteroaryl organotin compounds can be prepared by methods known in the art (or by slight modification of these methods): for example, see D. Peters, et al., J. Heterocyclic Chem., (1990), 27, 2165.
Bromides of Formula 7 (n is 0 if Rl is S(O)n R15) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tel. Lett. (1964), p. 617; M. A. ahn, et al., Rev. Latinoam. Quim. (1972), 3, p. 1 19; M. Kosugi, et al., Bull. Chem. Soc. Jpn. (1986), 59 (2), p. 677. Alternatively some of the bromides of Formula 7 (n is 0 if R1 is S(O)nRl5) can also be prepared by bromination of the corresponding substituted benzenes of Formula 8 (n is 0 if Rl is S(O)nRl5) with the bromine or other equivalent reagent in an inert organic solvent as shown in Scheme 14. This bromination is carried out by general methods known in the art; see, for example, E. Campaigne, et al., J. Heterocycl. Chem. (1969), 6, p. 517; H. Gilman, J. Am. Chem. Soc. (1955), 77, p. 6059;
Scheme 14
Br2 or other equivalent brominating reagent
The compounds of Formula 8 (n is 0 if R1 is S(O)nR15) can be prepared by one skilled in the art by using methods known in the art (or by slight modification of these methods): for example, see A. R. Katritzky, et. al., Comprehensive Heterocyclic Chemistry, Volume 2-6, Pergamon Press; B. M. Lynch, et al., Tet. Lett. (1964), p. 617; 530
17
M. A. Kahn, et al., Rev. Latinoam. Quim. (1972), 3, p. 119; M. Kosugi, et al., Bull. Chem. Soc. Jpn. (1986), 59, (2), p. 677.
Compounds of General Formula le can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 15-17 of this section.
le
Scheme 15 illustrates the preparation of compounds of Formula le (R14 is R14a and Rϊ4a is the same as Rl as described in the Summary of the Invention excluding H) whereby a compound of Formula le ( R'4 is H) is reacted with a reagent of Formula 9 in the presence of a base wherein X2 is chlorine, bromine, fluorine, OTf or OAc and R, 4a is as previously defined. This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see K. Nakamura, et al., WO 95/04054.
Scheme 15
le (Rl4 is H) + R14^2— »► le (RM is R'4a)
9 Scheme 16 illustrates the preparation of compounds of Formula le (R14 is H). whereby an ester of Formula 10 is reacted with a base such as triethylamine in the presence of a catalytic amount of cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803.
Scheme 16
or potassium cyanide)
10 Esters of Formula 10 can be prepared by reacting a hydroxypyrazole of Formula 11 with an acid chloride of Formula 5 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 17). This type of coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see W. J. Michaely, EP 369,803.
Scheme 17
1 1
Compounds of General Formula If can be readily prepared by one skilled in the art by using the reactions and techniques described in Schemes 18-21 of this section.
If Scheme 18 illustrates the preparation of compounds of Formula If whereby a compound of Formula 12 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate. The substituents of the immediate products may be further modified if appropriate. This cyclization is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622. 530
19 Scheme 18
12 wherein
L is a leaving group such as C ]-C4alkoxy (e.g. OC2H5) or V-dialkylamino (e.g. dimethyl amino) R9a is R9 or CONH2
Scheme 19 illustrates the preparation of compounds of Formula 12 whereby a compound of Formula 13 is reacted with a reagent of Formula 14 or Formula 15. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
Scheme 19
Scheme 20 illustrates the preparation of compounds of Formula 13 whereby a ester of Formula 16 is decarboxylated in the presence of a catalyst, such as -toluenesulfonic acid, in an inert solvent such as toluene. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
Scheme 20
16 Esters of Formula 16 can be prepared by reacting the metal salt of a compound of
Formula 17 with an acid chloride of Formula 5 (Scheme 21). This type of coupling is known in the art: for example see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al.,
EP 636,622.
Scheme 21
17 Scheme 22 illustrates the preparation of compounds of Formula Ig whereby a compound of Formula 5 is reacted with a compound of Formula 18 in the presence of a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt)2 in an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.
Ig
This conversion is carried out by methods known in the art (or slight modification of these methods); for example, see J. W. Ashmore, EP 213,892 and P. A. Cain, EP 496,631 Al.
Scheme 22
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group intercon versions 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 I. 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 sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I 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. 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; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet.
EXAMPLE 1 Step A: Preparation of 3-r(2,5-dimethylphenyl)thiolpropanoic acid
43.4 g (1.086 mol) of sodium hydroxide was added to 230 mL of water, 75.0 g (0.543 mol) of 2,5-dimethylthiophenol (purchased from Aldrich Chemical Company) was then added and the mixture was cooled to about 10 C. 91.30 g (0.597 mol) of 3- bromopropionic acid (purchased from Aldrich Chemical Company) was added in portions keeping the temperature below 25 °C. The mixture was warmed to room temperature, stirred for 2 hr under nitrogen, and was then washed with diethyl ether (3 x 500 mL). The aqueous layer was acidified with IN HCl and filtered to yield 112.79 g of the title compound of step A as a solid, m.p. 97-98 °C.
IH NMR (CDCI3): 52.3 (s, 3H), 2.34 (s, 3H), 2.68 (t, 2H), 3.1 (t, 2H), 6.9 (d, IH), 7.06-7.14 (2H).
Step B: Preparation of 2,3-dihvdro-5,8-dimethyl-4H-l -benzopyran-4-one
530 mL of concentrated sulfuric acid was added to 24.91 g (0.1 19 mol) of the title compound of step A while being cooled with an acetone/ice bath. The ice bath was removed, the mixture was stirred for 1 hr and was then poured over crushed ice. The aqueous phase was extracted with a mixture of diethyl ether : hexane (1:9, 6 x 500 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 11.75 g of the title compound of step B as an oil. IH NMR (CDCI3): δ 2.3 (s, 3H), 2.6 (s, 3H), 2.97 (m, 2H), 3.2 (m, 2H), 6.9-7.1
(2H).
Step C: Preparation of 6-bromo-2,3-dihvdro-5,8-dimethyl-4H- 1 -benzothiopyran-
4-one A solution of 4.07 g (0.021 mol) of the title compound of step B in 25 mL of methylene chloride was added dropwise to a mixture of 7.07 g (0.053 mol) of aluminum chloride (purchased from Aldrich Chemical Company) in 25 mL of methylene chloride. The suspension was stirred for approximately 15 minutes, 1.14 mL (0.022 mol) of bromine (purchased from Janssen) was added dropwise, and the mixture was then refluxed for 10 minutes. The warm mixture was poured into 10 mL of concentrated hydrochloric acid containing 75 g of ice, stirred for 10 minutes, diluted with 50 mL of water, and extracted with diethyl ether (2 x 200 mL). The combined organic layers were washed with water (2 x 200 mL), dried (Na2SO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate : hexane (5:95) to yield 2.62 g of the title compound of step C as a solid, m.p. 87-88 °C. lΗ NMR (CDCI3): δ 2.3 (s, 3Η), 2.6 (s, 3H), 3.0 (m, 2H), 3.2 (m, 2H), 7.45 (s, IH).
Step D: Preparation of 6-bromo-5,8-dimethyl-4H- 1 -benzothiopyran-4-one
30 g (0.11 mol) of the title compound of step C and 8.95 mL (0.1 1 mol) of pyridine were added to 250 mL of methylene chloride. The solution was cooled to about 0 °C and 14.76 g (0.11 mol) of N-chlorosuccinimide was added. The mixture was stirred overnight under nitrogen while warming to room temperature and then refluxed for 12 h. The reaction was evaporated to dryness, the residue was stirred in diethyl ether, and filtered. The filtrate was dried (MgSO4), filtered, and evaporated to dryness to yield 13.25 g of the title compound of step D as a solid, m.p. 123-124 °C. 1H NMR (CDCI3): δ 2.5 (s, 3Η), 2.9 (s, 3H), 7.0 (d, IH), 7.7 (m, 2H). Step E: Preparation of 3-[3-bromo-2,5-dimethyl-6-(methylthio)phenvn- 1-methyl- lH-pyrazole 13.25 g (0.049 mol) of the title compound of step D and 2.88 mL (0.054 mol) of methylhydrazine (purchased from Aldrich Chemical Company) was added to 150 mL of absolute ethanol. After stirring at reflux under nitrogen for 5 hr the mixture was allowed to warm to room temperature and stir for 2.5 days. The mixture was refluxed for 3 hr after which time 0.5 mL of acetic acid was added and the reaction was refluxed overnight. After cooling to room temperature, 12.35 mL (0.054 mol) of sodium methoxide (25% in methanol) and 3.66 mL (0.059 mol) of iodomethane were added and the reaction stirred for 2 hr. The mixture was evaporated to dryness. The residue was stirred in water, extracted with methylene chloride (250 mL), dried (MgSO4), filtered, and evaporated to dryness. The crude product was chromatographed over silica gel eluting with methylene chloride to yield 5.97 g of the title compound of step E as an oil.
1H NMR (CDCI3): δ 2.0 (s, 3H), 2.1 (s, 3H), 2.5 (s, 3H), 3.6 (s, 3H), 6.2 (s, IH), 7.6 (m, 2H). Step F: Preparation of 2,5-dimethyl-3-(l -methyl- lH-pyrazol-3-yl)-4- (methylthio)benzoic acid
5.9 g (0.019 mol) of the title compound of step E was added to 100 mL of tetrahydrofuran and cooled to -70 °C. 9.1 mL (0.023 mol) of 2.5M Η-butyllithium (purchased from Aldrich Chemical Company) was added dropwise keeping the temperature below -65 C. Solid carbon dioxide was added in one portion and the mixture warmed to room temperature. 200 mL of hexane was added and the mixture was filtered. The solid collected was added to water and acidified to about pΗ 1 with concentrated hydrochloric acid. The aqueous was extracted with methylene chloride (3 x 100 mL), dried (MgSO4), filtered, and evaporated to dryness to yield 3.13 g of the title compound of step F as a semi-solid. ! Η NMR (CDCI3): δ 2.1 (s, 3Η), 2.3 (s, 3H), 2.6 (s, 3H), 3.6 (s, 3H), 6.2 (m,
IH), 7.6 (d, lH), 7.97 (s, lH).
Step G: Preparation of 2,5-dimethyl-3-(l -methyl- lH-pyrazol-3-yl)-4-
(methylsulfonyl)benzoic acid 4.5 mL (0.046 mol) of hydrogen peroxide (35%) was added to 25 mL of trifluoroacetic acid. The mixture was allowed to stir for 30 min under nitrogen and was then cooled to 0 C. A solution of 3.1 g (0.011 mol) of the title compound of step F in 25 mL of trifluoroacetic acid was added dropwise keeping the temperature below 10 °C. The mixture was warmed to room temperature and stirred for 3 days. 2 mL of dimethylsulfide was added and the reaction stirred for 30 min. The mixture was then evaporated to dryness, and the residue was triturated with water and filtered. The collected solid was dissolved in methylene chloride, dried (MgSO4), filtered, and evaporated to dryness to yield 1.41 g of the title compound of step G as a solid, m.p. 60t°C (dec). lΗ NMR (CDCI3): δ 2.2 (s, 3Η), 2.8 (s, 3H), 3.0 (s, 3H), 3.7 (s, 3H), 6.2 (m, lH), 7.7 (m, lH), 8.0 (s, IH). Step H: Preparation of 3-oxo-l-cylcohexen-l-yl 2,5-dimethyl-3-(l-methyl-lH- pyrazol-3-yl)-4-(methylsulfonyl)benzoate 1.39 g (0.0045 mol) of the title compound of step G, 1.18 mL (0.0135 mol) of oxalyl chloride (purchased from Janssen), and 2 drops of N,N-dimethylformamide were added to 50 mL of methylene chloride. The mixture was refluxed under nitrogen for 2.5 hr and was then evaporated to dryness. 50 mL of methylene chloride was added to the residue and the solution was again evaporated to dryness. Another 50 mL of methylene chloride was added to the residue, and the solution was cooled to about 0 °C. 0.56 g (0.0049 mol) of 1,3-cyclohexanedione (purchased from Aldrich Chemical Company) was added followed by 1.94 mL (0.0139 mol) of triethylamine, and the mixture was stirred overnight while warming to room temperature. The mixture was evaporated to dryness and the crude product was chromatographed over silica gel eluting with a mixture of ethyl acetate:hexane (6:4, then 7:3) to yield 0.47 g of the title compound of step Η as a solid, m.p. 165 - 167 C. 2Η NMR (CDCI3): 6 2.1 - 2.2 (m, 5Η), 2.5 (m, 2H), 2.7 (m, 2H), 2.8 (s, 3H),
2.98 (s, 3H), 3.6 (s, 3H), 6.0 (s, IH), 6.1 (m, IH), 7.6 (m, IH), 7.9 (s, IH). Step I: Preparation of 2-r2,5-dimethyl-3-(l-methyl-lH-pyrazol-3-yl)-4-
(methylsulfonyl)benzoyll-l,3-cvcIohexanedione 0.47 g (0.0012 mol) of the title compound of step Η, 1 drop of acetone cyanohydrin (purchased from Aldrich Chemical Company), and 0.29 mL (0.0020 mol) of triethylamine were added to 25 mL of acetonitrile and allowed to stir overnight at room temperature under nitrogen. The mixture was evaporated to dryness, water was added to the residue, and the solution was acidified to pΗ 1 with concentrated hydrochloric acid. The aqueous was extracted with methylene chloride, dried (MgSO4), filtered, and evaporated to dryness to yield 0.27 g of the title compound of example 1 , a compound of the invention, as a solid, m.p. 93 C (decomposed). lΗ NMR (CDCI3): δ 1.8 (s, 3Η), 2.1 (m, 2H), 2.4 (m, 2H), 2.7 (s, 3H), 2.8 (m, 2H), 2.98 (s, 3H), 3.7 (s, 3H), 6.2 (s, IH), 7.1 (s, IH), 7.6 (s, IH).
EXAMPLE 2 Step A: Preparation of 2-r3-(trifluoromethyl)-lH-pyrazol-l-yllbenzoic acid
To 100 mL of dimethylformamide was added sequentially 19.3 g (0.125 mol) of methyl 2-fluorobenzoate, 18.7 g (0.138 mol) of 3-(trifluoromethyl)pyrazole (purchased from Maybridge Chemical Company), and 19.0 g (0.138 mol) of potassium carbonate. The suspension was stirred and heated at about 100 °C for 16 hours, then cooled to 25 °C and poured into excess water. The aqueous suspension was extracted three times with 75 mL of diethyl ether and the combined ether layers were dried over magnesium sulfate and concentrated under reduced pressure. The residual oil was chromatographed over silica gel eluting with hexane:ethyl acetate (9.6:0.4, then 100% ethyl acetate) to yield 15.3 g of crude methyl 2-[3-(trifluoromethyl)-lH-pyrazol-l-yl]benzoate as an oil. 14 g (0.052 mol) of this oil was added to a solution of 3.8 g (0.057 mol) of potassium hydroxide (85%) dissolved in 60 mL of methanol. The solution was stirred at 25 °C for one hour, refluxed for 5 hours, stirred at 25 °C for 48 hours, and finally concentrated under reduced pressure. 100 mL of water was added to the residue and the cloudy solution was extracted twice with 40 mL of diethyl ether. The clear aqueous layer was acidified with concentrated ΗC1 and filtered. The collected solid was dissolved in dichloromethane, dried over magnesium sulfate, and the solvent was removed under reduced pressure to yield 5.0 g of the title compound of Step A as a solid melting at 138-144 °C. lΗ NMR (CDC13): δ 6.95 (d, 1Η), 7.65 (m, 2Η), 7.7 (m, IH), 7.85 (m, IH), 8.35 (d, IH), 13.15 (s, IH).
Step B: Preparation of 3-oxo- 1 -cyclohexen- 1 -yl 2-r3-(trifluoromethyl)- 1 H- pyrazol- 1 -yllbenzoate To 20 mL of oxalyl chloride was added portionwise 4.0 g of the title compound of Step A. The suspension was refluxed for about 3 hours and then concentrated under reduced pressure. The residue was azeotroped with dichloromethane (two times with 20 mL at 60 °C) to yield an oil which solidified upon cooling and melted at 64-68 °C. 2.0 g (0.0073 mol) of this acid chloride was added to 20 mL of dichloromethane, followed by the addition of 0.99 g (0.0088 mol) of 1,3-cyclohexanedione, and 2.2 g (0.022 mol) of triethylamine. The suspension was stirred overnight and then concentrated under reduced pressure. The residue was dissolved in diethyl ether and the solution was then extracted with water, dried over magnesium sulfate, and concentrated under reduced pressure to yield 2.0 g of the title compound of Step B as an oil. *Η NMR (CDCI3): δ 2.0 (m, 2H), 2.35 (m, 2H), 2.5 (m, 2H), 5.85 (s, IH), 6.75
(d, IH), 7.5 (m, IH), 7.6 (m, IH), 7.7 (m, IH), 7.8 (d, IH), 8.0 (m, IH). Step C: Preparation of 3-hvdroxy-2-r2-f3-(trifluoromethyl)-lH-pyrazol- l- yllbenzovn-2-cvclohexen-l-one To 20 mL of acetonitrile was added sequentially 1.8 g (0.005 mol) of the title compound of Step B, 1.0 g (0.01 mol) of triethylamine, and 8 drops of acetone cyanohydrin. The solution was stirred under a nitrogen atmosphere at 25 °C overnight, and then diluted with 40 mL of water and acidified by the addition of concentrated hydrochloric acid (red to litmus paper). The suspension was filtered, and the collected solid was washed three times with 20 mL of water, suction dried, and then recrystallized from 2-propanol to yield 0.97 g of the title compound of Step C, a compound of this invention, as a solid melting at 141-143 °C.
*Η NMR (CDCI3): δ 1.8 (m, 2Η), 2.1 (m, 2H), 2.6 (m, 2H), 6.6 (d, IH), 7.4-7.6 (m, 4H), 7.75 (d, IH), 16.6 (s, IH). EXAMPLE 3 Step A: Preparation of methyl 6-(trifluoromethyl)[2,4'-bipyridinel-3-carboxylate
To a stirred solution of 8.49 g (0.03 mol) of methyl 2-bromo-6-(trifluoromethyl)- 3-ρyridine carboxylate (prepared as described by Andrea T. A. and Liang P. H., U.S. Patent 5,393,734) in 25 mL of N,/V-dimethylformamide under a nitrogen atmosphere was added 0.5 g of tetrakis(triphenylphosphine)palladium(0) and the mixture was heated at 100 °C for 30 minutes. 11 g (0.03 mol) of 4-tributylstannylpyridine (prepared by a modification of the procedure described by A. Lee and W. Dai, Tetrahedron Letters (1996), 37, 495-498) was added and heating was continued at 100 °C for 24 hours. The reaction mixture was cooled to room temperature and N,N-dimethylformamide was removed by distillation under high vacuum. The residue was purified by flash chromatography over silica gel utilizing dichloromethane:ethyl acetate (8:2) to provide 4.0 g of the title compound of Step A as a red oil.
JH NMR (CDCI3): δ 8.76 (d, 2H), 8.4 (d, IH), 7.8 (d, IH), 7.47 (m, 2H), 3.76 (s, 3H).
Step B: Preparation of 6-(trifluoromethvDf2,4'-bipyridinel-3-carboxylic acid
To a solution of 1.7 g of the title compound of Step A in 20 mL of methanol was added 2 mL of 50% aqueous sodium hydroxide and the reaction was stirred at room temperature for 24 hours. The mixture was concentrated and acidified with 6Λ aqueous hydrochloric acid to pH 3 and extracted three times with 20 mL of ethyl acetate. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure to provide 1.6 g of title compound of Step B as a crude solid. iH NMR (CD3)2SO): δ 9.02 (d, 2H), 8.26 (d, IH), 8.22 (m, IH), 8.14 (d, 2H). Step C: Preparation of 3-oxo-l-cvclohexen-l-yl 6-(trifluoromethyl)[2,4'- bipyridinel-3-carboxylate
To a suspension of 1.6 g (6 mmol) of the title compound of Step B in 100 mL of dichloromethane was added 0.78 g (7 mmol) of 1,3-cyclohexanedione followed by 2.4 mL (16 mmol) of triethylamine and 1.8 g (7 mmol) of 2-chloro-l-methylpyridinium iodide. The mixture was stirred at room temperature under nitrogen for 24 hours and then applied directly to a silica gel column and purified by flash chromatography using ethyl acetate/dichloromethane (2:8) to afford 1.34 g of the title compound of Step C as a tan solid melting at 49-56 °C.
IH NMR (CDCI3): δ 8.78 (d, 2H), 8.6 (d, IH), 7.51 (d, 2H), 5.93 (s, IH), 2.2 (m, 2H), 2.1 (m, 2H), 2.0 (m, 2H). Step D: Preparation of 3-hvdroxy-2-f[6-(trifluoromethyl)f2,4'-bipyridin1-3- yllcarbonvn-2-cvclohexen- 1 -one To a solution of 1.22 g (3.5 mmol) of the title compound of Step C in 25 mL of acetonitrile was added 1.16 mL (8.36 mmol) of triethylamine, followed by 2 drops of acetonecyanohydrin. The mixture was stirred under nitrogen for 18 hours. The mixture was then concentrated under reduced pressure, and the residual oil was acidified with aqueous IN hydrochloric acid and extracted three times with 20 mL of dichloromethane. The combined organic layers were dried over magnesium sulfate and concentrated under reduced pressure to afford 0.4 g of the title compound of Step D, a compound of this invention, as a white solid melting at 137-145 °C.
IH NMR (CDC13): δ 8.66 (m, 2H), 7.79 (m, 2H), 7.45 (m, 2H), 2.8 (m, 2H), 2.0 (m, 2H), 1.8 (m, 2H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 20 can be prepared. The following abbreviations are used in the Tables which follow: NO2 = nitro and Ph = phenyl.
The following notations have been used in Tables 1-20:
A-51 = (5-methyl-l,2,3-oxadιazol-4-yl)- A-77 = (3-pyπdazmyl)-
A-52 = (l,2,3-oxadιazol-4-yl)- A-78 = (4,6-dιmethyl-2-pyrιmιdmyl)-
A-53 = (3-methyl- l,2,4-oxadιazol-5-yl)- A-79 = (4-methyl-2-pyπmιdιnyl)-
A-54 = (5-methyl-l,2,4-oxadιazol-3-yl)- A-80 = (2-pyπmιdιnyl)-
A-55 = (4-methyl-3-furazanyl)- A-81 = (2-methyl-4-pyπmιdιnyl)-
A-56 = (3-furazanyl)- A-82 = (2-chloro-4-pyπmιdιnyl)-
A-57 = (5-methyl-l,3,4-oxadιazol-2-yl)- A-83 = (2,6-dιmethyl-4-pyπmιdιnyl)-
A-58 = (5-methyl-l,2,3-thιadιazol-4-yl)- A-84 = (4-pyπmιdιnyl)-
A-59 = (l,2,3-thιadιazol-4-yl)- A-85 = (2-methyl-5-pyπmιdιnyl)
A-60 = (3-methyl l ,2,4-thιadιazol-5-yl)- A-86 = (6-methyl-2-pyrazmyl)-
A-61 = (5-methyl-l ,2,4-thιadιazol-3-yl)- A-87 = (2-pyrazιnyl)-
A-62 = (4-methyl- l ,2,5-thιadιazol-3-yl)- A-88 = (4,6-dιmethyl- I ,3,5-tπazιn-2-yl)-
A-63 = (5-methyl- l ,3,4-thιadιazol-2-yl)- A-89 = (4,6-dιchloro- l,3,5-tπazιn-2-yl)-
A-64 = (l-methyl-l/7-tetrazol-5-yl)- A-90 = (l ,3,5-tπazιn-2-yl)-
A-65 = (l//-tetrazol-5-yl)- A-91 = (4-methyl- 1,3,5-tπazιn- 2-yl)-
A-66 = (5-methyl-l /-tetrazol-l-yI)- A-92 = (3-methyl- l ,2,4-tπazιn-5-yl)-
A-67 = (2-methyl-2/ -tetrazol-5-yl)- A-93 = (3-methyl- l,2,4-tπazιn-6-yl)-
A-68 = (2-ethyl-2/ -tetrazol-5-yl)-
A-69 = (5-methyl-2 /-tetrazol-2-yl)-
A-70 = (2 -tetrazol-2-yl)-
A-71 = (2-pyπdιnyl)-
A-72 = (6-methyl-2-pyπdιnyl)-
A-73 = (4-pyπdιnyl)-
A-74 = (3-pyπdιnyl)-
A-75 = (6-methyl-3-pyπdazιnyl)-
A-76 = (5-methyl -3-pyπdazιnyl)- 97/46530
30 TABLE 1
O 97/46530
31
TABLE 2
TABLE 3
97/46530
33
R15 is CT and R6 is CH2CH3
TABLE 4
TABLE 5
O 97/46530
37
TABLE 6
TABLE 7
a Rib CH,
CH3
Cl
CH, Cl O 97/46530
39
O 97/46530
41
CH3 Cl CH3 CH,
Cl
A-24 S02CH3 Cl Cl A-33 S02CH3 Cl Cl
A-24 S02CH2CH3 Cl CH3 A-33 S02CH2CH3 Cl CH3
A-24 S02CH2CH3 Cl Cl A-33 S02CH2CH3 Cl Cl
A-24 S02CH2CH2CH3 Cl CH3 A-33 S02CH2CH2CH3 Cl CH3
A-24 S02CH2CH2CH3 Cl Cl A-33 S02CH2CH2CH3 Cl Cl
A-24 S02N(CH3)2 CH3 CH3 A-33 S02N(CH3)2 CH3 CH3
A-24 S02N(CH3)2 Cl CH3 A-33 S02N(CH3)2 Cl CH3
A-24 S02N(CH3)2 Cl Cl A-33 S02N(CH3)2 Cl Cl
A-24 S02CF3 CH3 CH3 A-33 S02CF3 CH3 CH3
A-24 S02CF3 Cl CH3 A-33 S02CF3 Cl CH3
A-24 S02CF3 Cl Cl A-33 S02CF3 Cl Cl
A-24 S02OCH2CF CH CH3 A-33 S02OCH2CF3 CH3 CH3
A-24 S02OCH2CF Cl CH3 A-33 S02OCH2CF3 Cl CH3
A-24 S02OCH2CF3 Cl Cl A-33 S02OCH2CF3 Cl Cl
A-24 CF3 CH3 CH3 A-33 CF3 CH3 CH3
A-24 CF3 Cl CH3 A-33 CF3 Cl CH3
A-24 CF3 Cl Cl A-33 CF3 Cl Cl
A-24 OCH3 CH3 CH3 A-33 OCH3 CH3 CH3
A-24 OCH Cl CH3 A-33 OCH3 Cl CH3
A-24 OCH3 Cl Cl A-33 OCH3 Cl Cl
A-24 N02 CH3 CH3 A-33 N02 CH3 CH3
A-24 N02 Cl CH3 A-33 N02 Cl CH3
A-24 N02 Cl Cl A-33 N02 Cl Cl
A-42 S02CH3 N02 CH3 A-44 S02CH3 N02 CH3
A-42 S02CH3 Cl CH3 A-44 SO,CH3 Cl CH3
A-42 S02CH3 Cl Cl A-44 S02CH3 Cl Cl
A-42 S02CH2CH3 Cl CH3 A-44 S02CH2CH3 Cl CH3
A-42 S02CH2CH3 Cl Cl A-44 S02CH2CH3 Cl Cl
A-42 S02CH2CH2CH3 Cl CH3 A-44 S02CH2CH2CH3 Cl CH3
A-42 S02CH2CH2CH3 Cl Cl A-44 S02CH2CH2CH3 Cl Cl
A-42 S02N(CH3)2 CH3 CH3 A-44 S02N(CH3)2 CH3 CH3
A-42 S02N(CH3)2 Cl CH3 A-44 S02N(CH3)2 Cl CH3
A-42 S02N(CH3)2 Cl Cl A-44 S02N(CH3)2 Cl Cl
A-42 S02CF3 CH3 CH3 A-44 S02CF3 CH3 CH3
A-42 S02CF3 Cl CH3 A-44 S02CF3 Cl CH3
A-42 S02CF3 Cl Cl A-44 S02CF3 Cl Cl
A-42 S02OCH2CF3 CH3 CH3 A-44 S02OCH2CF3 CH3 CH3
A-42 S02OCH2CF3 Cl CH, A-44 S02OCH2CF3 Cl CH, O 97/46530
53
CH3 CH3 A-91 CF3 CH3 CH3
Cl CH3 A-91 CF3 Cl CH3
Cl Cl A-91 CF3 Cl Cl
CH3 CH3 A-91 OCH3 CH3 CH3
Cl CH3 A-91 OCH3 Cl CH3
Cl Cl A-91 OCH3 Cl Cl
CH3 CH3 A-91 N02 CH3 CH3
Cl CH3 A-91 N02 Cl CH3 Cl Cl A-91 NO, Cl Cl
TABLE 10
O 97/4653
59
TABLE 11
o
TABLE 13
lais isN
Rla is CH,, Rlb is CN, and W is N
Rla IS
Rla is Cl. Rlb is Cl. and W is CH
Rla is CH . Rlb is SO2CH?. and W is N
TABLE 14
Rϊa is CH , R b is H, and W is N
Rla IS
RiaisCl.RlbisCl.andWisN
RlaisCl.RlbisCl.andWisCH
Rla IS
TABLE 15
Rl jsCl.RlbisCl.andWisN
TABLE 16
Rla is isCH
Rlais
Rla is Cl. Rlb is Cl. and W is N
Rla is Cl. Rlb is Cl. and W is CH
TABLE 17
TABLE 18
WisCH
WisN
TABLE 19
WisCH
TABLE 20
W is N
Formulation/Utility
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. 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 liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. 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. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
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 5-90 0-94 1-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, Λ/,/V-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-mefhyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. 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 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; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989. In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-C.
Example A High Strength Concentrate Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B Wettable Powder
Compound 15 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example C
Granule Compound 25 10.0% attapulgite granules (low volatile matter,
0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example D Extruded Pellet Compound 26 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%. Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. 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. Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are 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). 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. 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 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops. 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, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorfhal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 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, 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimefhenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxy fop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]-l-(2-pyridinyl)-lH-pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamidc (BAY 1 1390), thifensulfuron-methyl, thiobencarb, tralkoxydim, iri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, and vernolate.
In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds. Preferred for better control of undesired vegetation (e.g., lower use rate, 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 nicosulfuron, rimsulfuron, nicosulfuron in combination with rimsulfuron, imazethapyr, sethoxydim, glyphosate, and glufosinate. 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 Tables A-D for compound descriptions. The abbreviation "dec." indicates that the compound appeared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared. INDEX TABLE A
*See Index Table D for Η NMR data.
INDEX TABLE B
Cmod R4a R4b R3 Rl W m.p. f°α
14 H H N 4-pyridyl oil* 15 (Ex. 3) H H N 4-pyridyl 137-145
19 H H N 4-pyridyl oil*
20 H H N 2-pyridyl 126-131
21 CH3 CH3 N 2-pyridyl oil*
22 H H N 3-pyridyl oil* 23 (Ex. 2) H H CH 3-CF3-I 7- 141-143 pyrazol- 1 -yl
24 H H OH CF3 CH 3-CF3- I//- 123- 126 ρyrazol-1-yl
*See Index Table D for lH NMR data.
INDEX TABLE C
Cmpd No. Structure m.p. (°C) 25 (Ex. 1) 93 (dec.)
*See Index Table D for *H NMR data. INDEX TABLE D Cmpd No. JH NMR Data (CDCI3 solution unless indicated otherwise)3
1 δ 9.7 (m, 2H), 7.63 (m, 2H), 7.62 (m, IH), 7.6 (s, IH), 7.37 (m, IH), 2.8 (m, 2H), 2.5 ( , 2H), 2.08 (m, 2H).
2 δ 8.65 (d, 2H), 7.6 (d, IH), 7.5 (m, 3H), 7.27 (m, IH), 3.13 (m, 6H), 2.32 (s, 4H), 1.3 (m, 9H), 1.04 (s, 6H).
3 δ 8.8 (m, 2H), 7.84 ( , 2H), 7.69 (m, 2H), 7.38 (d, IH), 2.4 (m, 2H), 1.2 (m, 2H), 1.04 (d, 6H).
4 δ 8.62 (d, 2H), 7.6 (s, IH), 7.5 (m, 3H), 7.28 (d, IH), 3.17 (m, 6H), 2.5 (d, 2H), 2.2 (d, IH), 1.7 (m, IH), 1.31 (m, 9H), 1.03 (d, 3H).
5 δ 8.72 ( , 2H), 7.65 (m, 3H), 7.5 (d. IH), 7.3 (d, IH), 2.6-2.0 (m, 4H), 1.6 (m, IH), 1.13 (d, 6H).
6 δ 7.9 (s, IH), 7.7 (s, IH), 7.5 (d, IH), 7.28 (d, lH), 6.8 (s, IH), 3.18 (m, 6H), 2.42 (m, 4H), 1.98 (m, 2H), 1.29 (m, 9H).
8 δ 8.63 (d, 2H), 7.48 (s, IH), 7.46 (m, 3H), 7.2 (d, IH), 3.15 (m, 6H), 2.43 (m, 4H), 1.98 (m, 2H), 1.29 ( , 9H).
9 δ 8.7 (m, IH), 8.0 (s, !H), 7.8 (d, lH), 7.72 (m, IH), 7.70 (m, I H), 7.26 (m, IH), 3.14 (m, 6H), 2.45 (m, 4H), 1.99 (m, 2H), 1.26 (m, 9H).
10 δ 7.8 (d, I H), 7.77 (s, IH), 7.6 (d, I H), 7.3 (m, IH), 7.18 (d, IH), 3.09 (m, 6H), 2.45 (m, 4H), 2.34 (s, 3H), 1.99 (m, 2H), 1.26 (m, 9H).
1 1 δ 7.88 (m, 2H), 7.85 (m, IH), 7.33 (s, IH), 7.16 (d, IH), 2.71 (m, 2H), 2.4 (m, 2H), 2.33 (s, 3H), 2.0 (m, 2H).
12 δ 8.8 (s, IH), 8.6 (d, IH), 7.8 (dd, IH), 7.5 (s, IH), 7.4 (d, I H), 7.35 (m, IH), 7.24 (d, IH), 3.21 (m, 6H), 2.45 (m, 4H), 1.99 (m, 2H), 1.28 (m, 9H).
14 δ 8.6 (d, IH), 8.55 (d, IH), 7.8 (d, IH), 7.5 (m, 3H), 3.0 (m, 6H), 2.33 (m,
4H), 1.8 (m, 2H), 1.16 (m, 9H). 19 δ 8.6 ( , 2H), 7.7 (m, IH), 7.65 (m, IH), 7.5 (m, IH), 7.2 (m, IH), 2.95 (m,
6H), 2.9 (m, IH), 2.3 (m, 2H), 1.6 (m, 2H), 1.13 (m, 9H), 0.95 (m, 6H).
21 δ 8.47 (m, IH), 8.44 (m, IH), 7.8 (m, IH), 7.73 (m, IH), 7.7 (m, IH), 7.25 (m, I H), 2.6 (m, IH), 2.02 (m, 2H), 0.92 (m, 6H).
22 δ 8.6 (m, 2H), 8.0 (m, IH), 7.77 (m, I H), 7.6 (m, IH), 7.4 (m, IH), 3.2-1.8 (m, 6H).
26 6 7.57 (d. lH), 7.1 (s, 1H), 6.1 (d, IH), 3.67 (s, 3H), 3.2-2.1 (m, 10H), 1.73 (s, 3H), 1.29 (t, 3H), 1.13 (d. 3H).
27 67.56 (d, IH), 7.1 (s, IH), 6.1 1 (d, IH), 3.67 (s, 3H), 3.2-3.0 (m, 2H), 2.82 (t, 2H), 2.74 (s, 3H), 2.42 (t, 2H), 2.14-2.0 (m, 2H), 1.74 (s, 3H), 1.29 (t, 3H). 29 δ 8.7 (m, 2H), 7.7-7.4 (m, 5H), 7.09 (s, IH), 3.9 (q, 2H), 3.24 (m, 6H), 1.35
(m, 12H).
a ]H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (dd)-doublet of doublets, (t)-triplet, (q)-quartet, (m)-multiplet.
BIOLOGICAL EXAMPLES OF THE INVENTION
TEST A
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-gallϊ), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), lambsquarters (Chenopodium album), morningglory (ϊpomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which includes a surfactant.
At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from two to eighteen cm (one to four leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table A, are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control. A dash (-) response means no test result.
TEST B
The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one-to-four leaf stage (postemergence application). A sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.
Plant species in the preemergence and postemergence tests consisted of barnyardgrass (Echinochloa crus-galli), barley (Hordeum vulgare), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays v. Pioneer 3394), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setaria faberii), johnsongrass (Sorghum halpense), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), pigweed (Amaranthus retroflexus), rape (Brassica napus), ryegrass (Lolium multiflorum), soybean (Glycine max), speedwell (Veronica persica), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avenafatua). Additionally, two 10.3 cm pots each containing two plant of corn (Zea mays) of the varieties M17 and B73 were treated in addition to the normal compliment of crop species.
All plant species were planted one day before application of the compound for the preemergence portion of this test. Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass2 (Echinochloa crus-galli) and Late watergrass (Echinochloa oryzicola grown to the 2 leaf stage for testing.
All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response ratings, summarized in Table B, were recorded 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 COMPOUND
Rate 31 g/ha 1 5 6 12 13 14 15 22 23 24 25 26
POSTEMERGENCE
Barley Igri
Barnyard 2
Barnyardgrass
Bedstraw
Blackgrass
Chickweed
Cocklebur
Corn
Corn (B73)
Corn (M17)
Cotton
Crabgrass
Downy Brome
Duck salad
Giant foxtail
Italn. Rygrass
Johnsongrass
Lambsquarter
Morningglory
Rape
Redroot Pigweed
Rice Japonica
Soybean
Speedwell
Sugar beet
Umbrella sedge
Velvetleaf
Wheat
Wild buckwheat
Wild oat
TEST C
Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica Rice (Oryza saliva) seed or seedlings at the 2.0 to 3.5 leaf stage; seeds, tubers or plant parts selected from arrowhead (Sagittaria rigida), barnyardgrass (Echinochloa crus- galli), ducksalad (Heteranthera limosa), early watergrass (Echinochloa oryzoides), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), redstem (Ammonia species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis) and tighthead sprangletop (Leptochloafasicularis), were planted into this soil. Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the two leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied directly to the paddy water, by pipette, or to the plant foliage, by an air-pressure assisted, calibrated belt-conveyer spray system.
Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria platyphylla), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), cotton (Gossypium hirsutum), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltatά), Johnson grass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanuts (Arachis hypogaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), and Surinam grass (Brachiaria decumbens) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm).
Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table D, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.
Table D COMPOUND
Rate 125 g/ha 22 23 25
POSTEMERGENCE
Alexandergrass 80 75 95
Bermudagrass 85 60 85
Brdlf Sgnlgrass 80 98 100
Cmn Purslane 70 30 75
Cmn Ragweed 50
Cotton 95 35 0
Dallisgrass 85 75 0
Goosegrass 85 35
Guineagrass 80 95 75
Itchgrass 5 35 0
Johnson grass 80 90 100
Large Crabgrass 70 100
Peanuts 65 50 90
Pit Morninglory 80 90 30
Purple Nutsedge 75 30 10
Sandbur 40 75 20
Sourgrass 80 60 20
Surinam grass 90 75 90
Table D COMPOUND
Rate 64 g/ha 22 23 25
POSTEMERGENCE
Alexandergrass 80 65 100
Bermudagrass 75 50 75
Brdlf Sgnlgrass 95 95 80
Cmn Purslane 65 30 75
Cmn Ragweed
Cotton 90 35 0
Dallisgrass 85 75 0
Goosegrass 70 35 90
Guineagrass 75 80 35
Itchgrass 0 0 0
Johnson grass 80 80 100
Large Crabgrass 60 50 0
Peanuts 35 65 75
Pit Morninglory 75 90 30
Purple Nutsedge 75 20 10
Sandbur 20 0 20
Sourgrass 70 40 20
Surinam grass 80 65
Large Crabgrass 65 40
Peanuts 100 5
Pit Morninglory 65 100
Purple Nutsedge - 0
Sandbur 0 0
Sourgrass 98 85 Surinam grass 0 0
Table D COMPOUND
Rate 16 g/ha 22 POSTEMERGENCE
Alexandergrass 35
Bermudagrass 50
Brdlf Sgnlgrass 40
Cmn Purslane 30 Cmn Ragweed
Cotton 70
Dallisgrass 35
Goosegrass 30
Guineagrass 35
Itchgrass 20
Johnson grass 35
Large Crabgrass 50 Peanuts 0
Pit Morninglory 65 Purple Nutsedge 5 Sandbur 0
Sourgrass 35
Surinam grass 35
Table D COMPOUND
Rate 8 g/ha 22 POSTEMERGENCE
Alexandergrass 35
Bermudagrass 40
Brdlf Sgnlgrass 70
Cmn Purslane 35 Cmn Ragweed
Cotton 0
Dallisgrass 20
Goosegrass 30
Guineagrass 35
Itchgrass 0
Johnson grass 35
Large Crabgrass 35
Peanuts 0
Pit Morninglory 35
Purple Nutsedge 0
Sandbur 0
Sourgrass 35
Surinam grass 35
TEST E
Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Concolculus arvensis), black nightshade (Solanum ptycanthum dunal), cassia (Cassia obtusifolia), cocklebur (Xanthium strumarium), common ragweed (Ambrosia artemisiifoliά), corn (Zea mays v. Pioneer 3394), corn2 (Zea mays v. IMR Ciba 4393), cotton (Gossypium hirsutam), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setaria faberii), green foxtail (Setaria viridis), jimsonweed (Datura stramonium), johnsongrass (Sorghum halepense), lambsquarter (Chenopodium album), morningglory (Ipomoea spp.), pigweed (Amaranthus retroflexus), prickly sida (Sida spinosa), shattercane (Sorghum vulgare), signalgrass (Brachiaria platyphylla), smartweed (Polygonum pensylvanicum), soybean (Glycine max v. Williams 95) and soybean2 (Glycine max v. Asgrow 3304), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Pancium miliaceum), woolly cupgrass (Eriochloa villosa), yellow foxtail (Setaria lutescens) and purple nutsedge (Cyperus rotundus) tubers were planted into a sandy loam or clay loam soil. These crops and weeds were grown in the greenhouse until the plants ranged in height from two to eighteen cm (one to four leaf stage), then treated postemergence with the test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. Pots treated in this fashion were placed in the greenhouse and maintained according to routine greenhouse procedures. Treated plants and untreated controls were maintained in the greenhouse approximately 14-21 days after application of the test compound. Visual evaluations of plant injury responses were then recorded. Plant response ratings, summarized in Table E, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.
Table E COMPOUND
TEST F
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifoliά), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common lambsquarters (Chenopodium album), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), Florida beggarweed (Desmodium purpureum), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb (Polygonum persicaria), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla).
Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table F, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.
TEST G
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Test compounds were applied 13 days after the last postemergence planting.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include bristly starbur (Acanthospermun hispidum) alexandergrass (Brachiaria plantaginea), american black nightshade (Solanum americanum), apple-of-Peru (Nicandra physaloides), arrowleaf sida (Sida rhombifolia), Brazilian sicklepod (Cassia tora Brazilian), Surinam grass (Brachiaria decumbens), capim- colchao (Digitaria horizontalis), Crist, soybean (Glycine max v. Cristalina), florida beggarweed (Desmodium purpureum), hairy beggarticks (Bidens pilosa), slender amaranth (Amaranthus viridis), southern sandbur (Cenchrus echinatus), tall morningglory (Ipomoea purpurea), tropical spiderwort (Commelina benghalensis), W20 Soybean (Glycine max v. W20), W4-4 Soybean (Glycine max v. W4-4), corn (Zea mays v. Pioneer 3394) and wild pointsettia (Eupohorbia heterophylla).
Treated plants and untreated controls were maintained in a greenhouse for approximately 13 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table G, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control.
Table G COMPOUND
Rate 70 g/ha 23 POSTEMERGENCE
Acanthospermum 100
Alexandergrass 100
Apple-of-Peru 80
Arrowleaf Sida 70
Surinam grass 100
Bl. Nightshade 100
Braz Sicklepod 65
Capim-Colch 100 Corn 15
Crist. Soybean 100 Crist. Soybean 100 Fl . Beggarweed 100 Fl. Beggarweed 85 H. Beggarticks 85 H. Beggarticks 75 Morningglory 90 Morningglory 80 SI. Amaranth 100 SI. Amaranth 90 Southern Sandur 85 Southern Sandur 80 Tr. Spiderwort 100 Tr. Spiderwort 90 Wld Pointsettia 100 Wld Pointsettia 85 W20 Soybean 100 W20 Soybean 100 W4-4 Soybean 100 W4-4 Soybean 100
Table G COMPOUND Table G COMPOUND Table G COMPOUND
Rate 35 g/ha 23 Rate 17 g/ha 23 Rate 8 g/ha 23 POSTEMERGENCE POSTEMERGENCE POSTEMERGENCE
Acanthospermum 100 Acanthospermum 100 Acanthospermum 55
Alexandergrass 100 Alexandergrass 100 Alexandergrass 85
Apple-of-Peru 80 Apple-of-Peru 75 Apple-of-Peru 65
Arrowleaf Sida 65 Arrowleaf Sida 60 Arrowleaf Sida 40
Surinam grass 100 Surinam grass 90 Surinam grass 80
Bl . Nightshade 100 Bl . Nightshade 100 Bl . Nightshade 85
Braz Sicklepod 60 Braz Sicklepod 35 Braz Sicklepod 10
Capim-Colch 100 Capim-Colch 65 Capim-Colch 60 Corn 0 Corn 0 Corn 0
Crist. Soybean 100 Crist. Soybean 90 Crist. Soybean 85
Fl. Beggarweed 85 Fl. Beggarweed 85 Fl. Beggarweed 100
H. Beggarticks 70 H. Beggarticks 80 H. Beggarticks 75
Morningglory 70 Morningglory 65 Morningglory 60
Si. Amaranth 80 SI. Amaranth 80 SI. Amaranth 75
Southern Sandur 50 Southern Sandur 45 Southern Sandur 45
Tr. Spiderwort 80 Tr. Spiderwort 70 Tr. Spiderwort 65
Wld Pointsettia 85 Wld Pointsettia 70 Wld Pointsettia 70
W20 Soybean 90 W20 Soybean 80 W20 Soybean 75
W4-4 Soybean 100 W4-4 Soybean 100 W4-4 Soybean 90
TEST H
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which includes a surfactant and applied to plants that were in the one-to four leaf stage (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include annual bluegrass (Poa annuά), blackgrass (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed
(Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Galium aparine), green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), ryegrass (Lolium multiflorum), scentless chamomile (Matricaria inodora), spring barley (Hordeum vulgare), sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell (Veronica hederaefolia), spring wheat (Triticum aestivum), winter wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avenafatua), windgrass (Apera spica-venti) and winter barley (Hordeum vulgare).
Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table H, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result.
Table H COMPOUND Table H
Rate 125 g/ha 15 Rate 62 g/ha POSTEMERGENCE POSTEMERGENCE
Annual Bluegras 0 Annual Bluegras
Blackgrass 0 Blackgrass
Blk Nightshade 75 Blk Nightshade
Chickweed 85 Chickweed
Common poppy 55 Common poppy
Deadnettle 75 Deadnettle
Downy brome 0 Downy brome
Field violet 75 Field violet
Galium 30 Galium
Green foxtail 30 Green foxtail
Jointed Goatgra 0 Jointed Goatgra
Kochia 85 Kochia
Lambsquarters 75 Lambsquarters
LS Canarygrass 0 LS Canarygrass
Rape 85 Rape
Redroot Pigweed 75 Redroot Pigweed
Russian Thistle 10 Russian Thistle
Ryegrass 0 Ryegrass
Scentless Chamo 60 Scentless Chamo
Spring Barley 0 Spring Barley
Sugar beet 100 Sugar beet
Sunflower 55 Sunflower
Veronica hedera 40 Veronica hedera
Wheat (Spring) 0 Wheat (Spring)
Wheat (Winter) 0 Wheat (Winter)
Wild buckwheat 75 Wild buckwheat
Wild mustard 95 Wild mustard
Wild oat 0 Wild oat
Windgrass 0 Windgrass
Winter Barley 0 Winter Barley Table H COMPOUND
Rate 8 g/ha 25
POSTEMERGENCE
Annual Bluegras 30
Blackgrass 10
Blk Nightshade 75
Chickweed 60
Common poppy 50
Deadnettle 60
Downy brome 15
Field violet 50
Galium 50
Green foxtail 50
Jointed Goatgra 0
Kochia 45
Lambsquarters 100
LS Canarygrass 50
Rape 60
Redroot Pigweed 70
Russian Thistle 10
Ryegrass 2
Scentless Chamo 50
Spring Barley 0
Sugar beet 50
Sunflower 60
Veronica hedera 50
Wheat (Spring) 10
Wheat (Winter) 20
Wild buckwheat 0
Wild mustard 70
Wild oat 10
Windgrass 30
Winter Barley 2

Claims

CLAIMS What is claimed is:
1. A compound selected from the formula
and N-oxides and agriculturally suitable salts thereof, wherein
Q is
A is a five- to ten-membered monocyclic or fused bicyclic ring system, which may be fully aromatic or partially saturated, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that each heterocyclic ring system contains no more than 2 oxygens and no more than 2 sulfurs, and each ring system is optionally substituted with one to three R2, provided that when a nitrogen atom of a heterocyclic ring is substituted with R2, then R2 is other than halogen;
each R1 is independently H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6
haloalkoxy, halogen, cyano, nitro, -(Y)t-S(O)nR15 or -(Y)t-C(O)R15;
W is N or CH; Y is O or NR12;
R2 is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl,
C3-C6 haloalkynyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C3-C6 alkenyloxy, C3-C6 alkynyloxy, mercapto, C1-C6 alkylthio, C1-C3 haloalkylthio, C3-C6 alkenylthio, C3-C6 haloalkenylthio, C3-C6 alkynylthio, C2-C5 alkoxyalkylthio, C3-C5 acetylalkylthio, C3-C6 alkoxycarbonylalkylthio, C2-C4 cyanoalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6
haloalkylsulfonyl, aminosulfonyl, C1-C2 alkylaminosulfonyl, C2-C4
dialkylaminosulfonyl, (CH2)rR16, NR12R13, halogen, cyano or nitro; or R2 is phenyl or benzylthio, each optionally substituted on the phenyl ring with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro;
R3 is OR14, SH, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, halogen or NR12R13; or R3 is phenylthio, phenylsulfonyl or -SCH2C(O)Ph, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
each R4 is independently C1-C3 alkyl, C1-C3 alkoxy, C1-C3 alkylthio or halogen; or when two R4 are attached to the same carbon atom, then said R4 pair can be taken together to form -OCH2CH2O-, -OCH2CH2CH2O-, -SCH2CH2S- or -SCH2CH2CH2S-, each group optionally substituted with 1 -4 CH3;
R5 is OR14, SH, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, halogen or
NR12R13; or R5 is phenylthio, phenylsulfonyl or -SCH2C(O)Ph, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
R6 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl or
-CH2CH2OR12; or R6 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
R7 is H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano or nitro;
R8 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl or C1-C6 halocycloalkyl;
R9 is H, C2-C6 alkoxycarbonyl, C2-C6 haloalkoxycarbonyl, CO2H or cyano;
R10 is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl optionally substituted with 1-4 C1-C3 alkyl or C3-C6 halocycloalkyl;
R1 1 is cyano, C2-C6 alkoxycarbonyl, C2-C6 alkylcarbonyl, S(O)nR13 or C(O)NR12R13; each R12 is independently H or C1-C6 alkyl ;
R13 is C1-C6 alkyl or C1-C6 alkoxy; or
R12 and R13 can be taken together as -CH2CH2-, -CH2CH2CH2-,
-CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-; R14 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6
alkylcarbonyl, C2-C6 alkoxycarbonyl, C(O)NR12R13, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R14 is phenyl, benzyl, benzoyl, -CH2C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
R15 is NR12R13, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl or C3-C6 cycloalkyl; or R15 is phenyl optionally substituted with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro;
R16 is C1-C3 alkoxy, C2-C4 alkoxycarbonyl, C1-C3 alkylthio, C1-C3 alkylsulfinyl or
C1-C3 alkylsulfonyl; or R16 is phenyl optionally substituted with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro; m is 0, 1, 2 or 3;
n is 0, 1 or 2;
p is 0, 1, 2, 3 or 4;
r is 1, 2 or 3; and
t is 0 or 1 ;
provided that when W is CH and A is in the meta position with respect to the group Q- C(O)- of Formula I, then m is 3 and R1 is other than H.
2. A compound of Claim 1 wherein
A is selected from the group 1H-pyrrolyl; furanyl; thienyl; 1H-pyrazolyl;
1H-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; 1H-1,2,3-triazolyl;
2H-1,2,3-triazolyl; 1H-1,2,4-triazolyl; 4H-1,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl;
1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; 1H-tetrazolyl;
2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl; pyrazinyl; 1,3,5-triazinyl;
1,2,4-triazinyl; and A may optionally be substituted by one to three R2, provided that when a nitrogen atom of a heterocyclic ring is substituted with R2, then R2 is other than halogen.
3. A compound of Claim 2 wherein
Q is Q-1.
4. A compound of Claim 3 wherein
each R1 is independently C1-C3 alkyl, C1-C3 alkoxy, halogen or nitro;
R3 is OR14; and R14 is H or C1-C4 alkylsulfonyl; or R14 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro.
5. A compound of Claim 4 wherein
A is pyridinyl, pyridazinyl, pyrimidinyl or 1H-pyrazolyl;
R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2Η or cyano;
R15 is C1-C6 alkyl;
t is 0; and
n is 2.
6. A compound of Claim 2 wherein:
Q is Q-2.
7. A compound of Claim 6 wherein:
each R1 is independently C1-C3 alkyl, C1-C3 alkoxy, halogen or nitro;
R5 is OR14;
R14 is H or C1-C4 alkylsulfonyl; or R14 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro.
R6 is H, C1-C6 alkyl, or C3-C6 alkenyl; and
R7 is H.
8. A compound of Claim 7 wherein
A is pyridinyl, pyridazinyl, pyrimidinyl or 1H-pyrazolyl;
R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2Η or cyano;
R15 is C1-C6 alkyl;
t is 0; and
n is 2.
9. A compound of Claim 2 wherein
Q is Q-3.
10. A compound of Claim 9 wherein
each R1 is independently C1-C3 alkyl, C1-C3 alkoxy, halogen or nitro;
R8 is H, C1-C3 alkyl, or cyclopropyl; and
R9 is H or C2-C3 alkoxycarbonyl.
11. A compound of Claim 10 wherein
A is pyridinyl, pyridazinyl, pyrimidinyl or 1H-pyrazolyl; R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2H or cyano;
R15 is C1-C6 alkyl;
t is 0; and
n is 2.
12. A compound of Claim 2 wherein
Q is Q-4.
13. A compound of Claim 12 wherein
each R1 is independently C1-C3 alkyl, C1-C3 alkoxy, halogen or nitro;
R10 is C3-C6 cycloalkyl or C3-C6 halocycloalkyl, each optionally substituted with 1-4 C1-C3 alkyl; and
R1 1 is cyano or C2-C6 alkoxycarbonyl.
14. A compound of Claim 13 wherein
A is pyridinyl, pyridazinyl, pyrimidinyl or 1H-pyrazolyl;
R2 is -(Y)t-S(O)nR15, CF3, OCF3, OCF2Η or cyano;
R15 is C1-C6 alkyl;
t is 0; and
n is 2.
15. The compound of Claim 5 which is selected from the group
a) 3-hydroxy-2-[[6-(trifluoromethyl)[2,4'-bipyridin]-3-yl]carbonyl]-2-cyclohexen- 1-one;
b) 2-[2-chloro-4-(4-pyridinyl)benzoyl]-3-hydroxy-2-cyclohexen-1-one; and c) 2-[2,5-dimethyl-3-(1-methyl-1H-pyrazol-3-yl)-4-(methylsulfonyl)benzoyl]-3- hydroxy-2-cyclohexen-1-one.
16. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
17. 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.
EP97928809A 1996-06-06 1997-06-02 Herbicidal pyridinyl and pyrazolylphenyl ketones Withdrawn EP0922032A1 (en)

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