WO1997008164A1 - Bicyclic herbicides - Google Patents

Bicyclic herbicides Download PDF

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Publication number
WO1997008164A1
WO1997008164A1 PCT/US1996/013347 US9613347W WO9708164A1 WO 1997008164 A1 WO1997008164 A1 WO 1997008164A1 US 9613347 W US9613347 W US 9613347W WO 9708164 A1 WO9708164 A1 WO 9708164A1
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Prior art keywords
alkyl
halogen
optionally substituted
haloalkyl
alkoxy
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PCT/US1996/013347
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French (fr)
Inventor
Stephen Kenneth Gee
Mary Ann Hanagan
Wonpyo Hong
Roman Kucharczyk
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E.I. Du Pont De Nemours And Company
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Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU67778/96A priority Critical patent/AU6777896A/en
Priority to EP96928223A priority patent/EP0846112A1/en
Publication of WO1997008164A1 publication Critical patent/WO1997008164A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
    • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/16—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
    • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
    • 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
    • C07D401/06—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 only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/06—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Definitions

  • This invention relates to certain bicyclic compounds, their 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.
  • EP 283,261 discloses cyclic diones of Formula i as herbicides:
  • X, X 1 and X 2 are independently O or S;
  • R 1 is a monocyclic or fused-bicyclic heterocyclic group containing up to ten ring atoms up to five of which may be selected from O, N and S, optionally substituted with one or more groups selected from, among others, oxo, halogen, nitro, cyano, alkyl, haloalkyl, haloalkoxy, alkoxy, alkylsulfonyl; and Y is, among others, C 2 -C 4 alkylene which is optionally substituted with one or more groups selected from, among others, halogen or alkyl.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation: wherein
  • Y is O; NR 9 ; or CH 2 optionally substituted with one or two groups independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and halogen; provided that when A is -NR 9 -(CH 2 ) n -, then Y is CH 2 ;
  • X is O or S
  • R 1 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, halogen, cyano, nitro, S(O) 2 NR 10 R 11 , C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl, C 3 -C 6 alkenylsulfonyl, C 3 -C 6 haloalkenylsulfonyl, C 3 -C 6 alkynylsulfonyl, C 3 -C 6 haloalkynylsulfonyl or C 3 -C 6 cycloalkylsulfonyl; or R 1 is phenylsulfonyl optionally substituted with C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alk
  • each R 2 is independently C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6
  • R 3 is OR 12 , C 1 -C 6 alkylthio, C 1 -C 6 haloalkylthio, C 1 -C 6 alkylsulfinyl, C 1 -C 6 haloalkylsulfinyl, C 1 -C 6 alkylsulfonyl, C 1 -C 6 haloalkylsulfonyl or halogen; each R 4 is independently C 1 -C 3 alkyl, C 1 -C 3 alkoxy, C 1 -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 H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6
  • R 5 is benzoyl or phenylsulfonyl, each optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro;
  • R 6 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 6 is phenyl or benzyl, each optionally substituted on the phenyl ring with C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, 1-2 halogen, cyano or nitro;
  • R 7 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, C 1 -C 6 haloalkoxy, halogen, cyano or nitro;
  • each R 9 is independently H; C 1 -C 6 alkyl; C 1 -C 6 haloalkyl; C 3 -C 6 alkenyl; C 3 -C 6 haloalkenyl; C 3 -C 6 alkynyl; C 3 -C 6 haloalkynyl; C 3 -C 6 cycloalkyl; C 1 -C 6 alkoxy; C 1 -C 6 haloalkoxy; C 2 -C 6 alkoxyalkyl; formyl; C 2 -C 6 alkylcarbonyl; C 2 -C 6 alkoxycarbonyl; C 2 -C 6 alkylaminocarbonyl; C 3 -C 7
  • dialkylaminocarbonyl or phenyl, benzyl or benzoyl, each optionally substituted on the phenyl ring with C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, 1-2 halogen, cyano or nitro;
  • R 10 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl or C 1 -C 6 alkoxy; or R 10 is phenyl or benzyl, each optionally substituted on the phenyl ring with C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, C 1 -C 3 alkoxy, C 1 -C 3 haloalkoxy, 1-2 halogen, cyano or nitro;
  • R 11 is H, C 1 -C 6 alkyl or C 1 -C 6 haloalkyl; or R 10 and R 11 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -,
  • R 12 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6
  • R 12 is benzoyl or phenylsulfonyl, each optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro;
  • n 1, 2 or 3;
  • n 1 or 2;
  • q 0, 1, 2, 3 or 4;
  • r 0, 1 or 2;
  • Y is CH 2 optionally substituted with one or two groups independently selected from C 1 -C 6 alkyl, C 1 -C 6 haloalkyl and halogen; then Z is O or S(O) 2 ;
  • each R 8 is independently C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 1 -C 6 alkoxy, hydroxy or halogen provided that no more than one R 8 is C 1 -C 6 alkoxy; and (vi) when A is -(CH 2 ) m - optionally substituted with one to four R 8 ; Y is CH 2
  • each R 8 is independently C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, hydroxy or halogen.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-4 alkyl indicates that one to four of the available positions for that substituent may be alkyl which are independently selected.
  • 1-4 CH 3 indicates that one to four of the available positions for that substituent may be methyl.
  • Alkenyl includes straight-chain or branched alkenes such as 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl” includes straight-chain or branched alkynes such as 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. “Alkynyl” can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • 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 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 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.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
  • alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl include F 3 C, ClCH 2 , CF 3 CH 2 and CF 3 CCl 2 .
  • haloalkenyl “haloalkynyl", “haloalkoxy", and the like, are defined analogously to the term “haloalkyl”.
  • CF 3 CH 2 CH CHCH 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CCl 3 C ⁇ C and FCH 2 C ⁇ CCH 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 CCl 3 S, CF 3 S, CCl 3 CH 2 S and ClCH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • 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 .
  • C i -C j The total number of carbon atoms in a substituent group is indicated by the "C i -C j " prefix where i and j are numbers from 1 to 7.
  • C 1 -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or
  • 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 include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R) i-j , then the number of substituents may be selected from the integers between i and j inclusive.
  • 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 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 Ia (Formula I where Q is Q-1, R 3 is OR 12 , and R 12 is H) can also exist as the tautomers of
  • 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 an enol.
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • Compounds of Formula I above, and agriculturally suitable salts are: Preferred 1.
  • X is O
  • each R 4 is independently C 1 -C 3 alkyl
  • R 6 is H, C 1 -C 6 alkyl or C 3 -C 6 alkenyl
  • R 7 is H, C 1 -C 3 alkyl or C 1 -C 3 haloalkyl
  • R 9 is H, C 1 -C 6 alkyl, C 1 -C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or
  • R 12 is H, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylaminocarbonyl, C 3 -C 7 dialkylaminocarbonyl, C 1 -C 6 alkylsulfonyl or C 1 -C 6 haloalkylsulfonyl; or R 12 is benzoyl or phenylsulfonyl, each optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro;
  • q 0, 1 or 2;
  • r is 0 or 0.
  • R 1 is H, methyl, halogen, S(O) 2 NR 10 R 11 , C 1 -C 4 alkylsulfonyl, C 1 -C 4 haloalkylsulfonyl or C 3 -C 5 cycloalkylsulfonyl;
  • R 2 is methyl, halogen or nitro
  • R 3 is OR 12 ;
  • R 10 is H, C 1 -C 4 alkyl, allyl or propargyl
  • R 11 is H or C 1 -C 4 alkyl
  • R 12 is H or C 1 -C 3 alkylsulfonyl; or R 12 is benzoyl or phenylsulfonyl, each optionally substituted with C 1 -C 3 alkyl, halogen, cyano or nitro. Most preferred are compounds of Preferred 2 selected from the group:
  • 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 1-31.
  • the definitions of Q, A, Y, Z, X, R 1 -R 12 , m, n, q and r in the compounds of Formulae 1-29 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae Ia-Ie are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ie are as defined above for Formula I.
  • Compounds of Formulae Id and Ie correspond to Formula I compounds wherein Q is Q-1 and Q-2, respectively.
  • X 1 is chlorine, bromine, fluorine, methylsulfonyloxy (OMs), trifluoromethylsulfonyloxy (OTf), p-toluenesulfonyloxy (OTs) or acetyloxy (OAc) and R 13 is as previously defined.
  • X 1 is chlorine, bromine, fluorine
  • an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, peroxytrifluoroacetic acid, potassium peroxymonosulfate or hydrogen peroxide.
  • the oxidation is carried out by methods known in the art (or by obvious modifications of these methods); for example, see S. Patai, et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons, 1988; pp 205-213, 235-253.
  • a cyanide source e.g., acetone cyanohydrin or potassium cyanide.
  • Enol esters of Formula 4 can be prepared by reacting a dione of Formula 5 with an acid chloride of Formula 6 in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such 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
  • Enol esters of Formula 4 can also be prepared by reacting a dione of Formula 5 with an acid of Formula 7 in the presence of a coupling agent such as 2-chloro-1-methylpyridinium iodide and a slight excess of 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 6A).
  • a coupling agent such as 2-chloro-1-methylpyridinium iodide and a slight excess of base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene
  • the acid chlorides of Formula 6 can be prepared by reacting an acid of Formula 7 with a halogenating reagent (e.g., oxalyl chloride or thionyl chloride) and a catalytic amount of dimethylformamide (Scheme 7).
  • a halogenating reagent e.g., oxalyl chloride or thionyl chloride
  • Scheme 7 a catalytic amount of dimethylformamide
  • Scheme 8 illustrates the preparation of acids of Formula 7 whereby a ketone of Formula 8 is reacted with an oxidizing reagent such as NaOCl, NaOBr, NaOI or NaNO 2 .
  • an oxidizing reagent such as NaOCl, NaOBr, NaOI or NaNO 2 .
  • the oxidation is carried out by methods known in the art (or by obvious modifications of these methods): for example, see T. F. Braish, et al., Org. Prep. Proced. Int., (1991), 23, 655-658 and J. A. Skorcz, et al., Heterocycl. Chem., (1973), 10, 249.
  • Scheme 9 illustrates the preparation of sulfones of Formula 8a whereby a sulfide of
  • Formula 9 is reacted with an oxidizing reagent such as peroxyacetic acid,
  • oxidation is carried out by methods known in the art (or by obvious modifications of these methods): for example, see S. Patai, et al., The
  • the functional group may be protected before the oxidation and then be deprotected after the oxidation.
  • the protection and deprotection 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., J. E. McMurry and T. Hoz, J. Org. Chem., (1975), 40, 3797 and references cited therein.
  • Scheme 10 illustrates the preparation of ketones of Formula 9 whereby a sulfide of Formula 10 is reacted with an acylating reagent 11 such as acetyl chloride or acetic anhydride in the presence of a Lewis acid such as aluminum chloride in a solvent such as carbon disulfide, methylene chloride or 1,2-dichloroethane. This conversion is carried out using methods well known in the art: for example, see R. A. Cutler, J. Amer. Chem. Soc, (1952), 74, 5475.
  • an appropriate leaving group such as a halogen, a mesylate or tosylate.
  • the reactions to prepare the mesylate or tosylate are carried with a sulfonyl chloride of Formula 13 in the presence of a base such as pyridine, sodium hydride or triethylamine in a solvent such as pyridine or methylene chloride at temperatures between 0 °C and room temperature.
  • a base such as pyridine, sodium hydride or triethylamine
  • solvent such as pyridine or methylene chloride
  • Compounds of Formula 12a can be prepared from an amide of Formula 14 by treatment with an excess of a base such as n-butyllithum and an electrophile such as an epoxide of Formula 15 in a solvent such as THF.
  • a base such as n-butyllithum
  • an electrophile such as an epoxide of Formula 15 in a solvent such as THF.
  • This conversion is carried out using methods known in the literature (or obvious modifications of these methods): for example, see R. N. Misra, et al., Bioorg. Med. Chem. Lett., (1991), 1, 295-298 and B. H. Bhide, et al., Chem. and lnd., (1975), 519.
  • Compounds of Formula 14 can be prepared from an acid chloride of Formula 16 and an amine of Formula 17 in the presence of a base such as triethylamine or excess NH 2 R 9 in a solvent such as chloroform. This conversion is carried out using methods well known in the literature (or obvious modifications of these methods): for example, see A. D. Wolf, EP 196,786.
  • a reducing reagent such as hydrogen at 345 kPa (50 psi)
  • a catalyst such as palladium on carbon in a solvent such as ethanol.
  • the reduction is carried out by methods well known in the art (or by obvious modifications of these methods): for example, R. D. Clark, et at., J. Med. Chem., (1993), 36, 2645-57 and C. Y. Cheng, J. Heterocyclic. Chem., (1995), 32, 73.
  • the reaction is carried out by methods well known in the art (or by obvious modifications of these methods): for example, see R. Singh, et. al., J. Indian Chem. Soc, (1991), 68, 276-80, M. Somei, Chem. Pharm. Bull., (1981), 29, 249, and N. Gilman, Synth. Commun., (1982), 12, 373-80.
  • This coupling is carried out by methods known in the art (or by obvious modification of these methods): for example, see K. Nakamura, et al.,
  • R 5a is the same as R 5 as described in the Summary of the Invention excluding H.
  • a cyanide source e.g., acetone cyanohydrin or potassium cyanide.
  • An ester of Formula 20 can be prepared by reacting a hydroxypyrazole of
  • the preparation of compounds of the Formula 23a can be accomplished by treatment of compounds of the Formula 23 with triethylsilane in trifluoroacetic acid (Scheme 27).
  • the reaction is best carried out at temperatures between 25 °C and 72 °C.
  • Compounds of the Formula 25a can readily be prepared by treatment of compounds of the Formula 25 with triethylsilane in refluxing trifluoroacetic acid
  • This general method is carried out by the addition of n-butyl lithium to a solution of the compound of the Formula 27 in THF or diethyl ether at temperatures from 25 °C to -70 °C. Carbon dioxide is introduced to produce the resulting acid.
  • This classical reaction is known to one skilled in the art. For a typical procedure see, R. L. Danheiser et al., J. Am. Chem. Soc, (1986), 108, 806-810.
  • protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products.
  • the use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991).
  • One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 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.
  • Step C Preparation of N-(1,1-dimethylethyl)-2-(ethylthio)-6-(2- hydroxyethyl)benzamide
  • Step D Preparation of N-(1,1-dimethylethyl)-2-(ethylthio)-6-[2- [(methylsulfonyl)oxy]ethyl]benzamide
  • Step E Preparation of 2-(1,1-dimethylethyl)-8-(ethylthio)-3,4-dihydro-1(2H)- isoquinolinone
  • Step F Preparation of 5-acetyl-2-(1,1-dimethylethyl)-8-(ethylthio)-3,4-dihydro- 1(2H)-isoquinolinone
  • Step G Preparation of 5-acetyl-2-(1,1-dimethylethyl)-8-(ethylsulfonyl)-3,4- dihydro-1(2H)-isoquinolinone
  • Step H Preparation of 2-(1,1-dimethylethyl)-8-(ethylsulfonyl)-1,2,3,4-tetrahydro- 1-oxo-5-isoquinolinecarboxylic acid
  • Step I Preparation of (1-ethyl-1H-pyrazol-5-yl)2-(1,1-dimethylethyl)-8- (ethylsulfonyl)-1,2,3,4-tetrahydro-1-oxo-5-isoquinolinecarboxylate
  • Step J Preparation of 2-(1,1-dimethylethyl)-5-[(1-ethyl-5-hydroxy-1H-pyrazol-4- yl)carbonyl]-8-(ethylsulfonyl)-3.4-dihydro-1(2H)-isoquinolinone
  • Step F Preparation of 2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene-5- carboxylic acid 1,1-dioxide
  • Step H Preparation of (2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene-5-yl)(1- ethyl-5-hydroxy-1H-pyrazol-4-yl)methanone S, S-dioxide
  • acetone cyanohydrin To a solution of 0.89 g (2.56 mmol) of the title compound of Step G in 15 mL of acetonitrile at room temperature was added 4 drops of acetone cyanohydrin followed by 0.57 mL (4.09 mmol) of triethylamine. The solution was stirred at room temperature overnight, then diluted with excess water, acidified with 1N ⁇ Cl to p ⁇ 3-5 and extracted with ethyl acetate.
  • Step A Preparation of methyl 4-[(2-ethoxy-2-oxoethyl)thio]-3-nitrobenzoate 0.36 g (9 mmol) of 60% sodium hydride was suspended in anhydrous
  • Step B Preparation of methyl 3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylate
  • Step C Preparation of methyl 4-ethyl-3,4-dihydro-3-oxo-2H- 1 ,4-benzothiazine-6- carboxylate
  • Step D Preparation of methyl 4-ethyl-3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylate 1,1 -dioxide
  • Step E Preparation of 4-ethyl-3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylic acid 1,1-dioxide
  • Step F Preparation of 3-oxo-1-cyclohexen-1-yl 4-ethyl-3,4-dihydro-3-oxo-2H- 1,4-benzothiazine-6-carboxylate 1,1-dioxide
  • Step G Preparation of 4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]- 2H-1,4-benzothiazin-3(4H)-one 1,1-dioxide
  • 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
  • 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;
  • the entire formulation of active ingredient can be encapsulated (or
  • 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
  • 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,
  • 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
  • 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
  • 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
  • flumiclorac-pentyl flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine-ammonium, glufosinate,
  • Preferred for better control of undesired vegetation e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety
  • Preferred for better control of undesired vegetation e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety
  • weeds are mixtures of a compound of this invention with a herbicide selected from the group atrazine, chlorimuron-ethyl, cyanazine, glyphosate (and its isopropylammonium, sesquisodium and trimesium salts), imazaquin (and its ammonium salt), imazethapyr (and its ammonium salt), nicosulfuron,
  • a herbicide selected from the group atrazine, chlorimuron-ethyl, cyanazine, glyphosate (and its isopropylammonium, sesquisodium and trimesium salts), imazaquin (and its ammonium salt), imazethapyr (and its ammonium salt), nicosulfuron,
  • Specifically preferred mixtures are selected from the group: compound 1 and atrazine; compound 1 and chlorimuron-ethyl;
  • 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.
  • PhSO 2 phenylsulfonyl
  • PhC(O) benzoyl.
  • the abbreviation "Ex.” stands for “Example” and is followed by a number indicating in which example the compound is prepared.
  • 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), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), 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 the
  • Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-gall ⁇ ) and Late watergrass (Echinochloa oryzicola) grown to the 2 leaf stage for testing.
  • Test compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application) and to plants that were grown for various periods of time before treatment (postemergence application).
  • a sandy loam soil was used for the preemergence test while 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 within approximately one day after planting seeds for the preemergence test.
  • Crop and weed species include American black nightshade
  • 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 D, 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.
  • alexandergrass (Brachiaria plantaginea), alfalfa (Medicago sativa), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria plantyphylla), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), cotton (Gossypium hirsutum), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), johnson grass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), peanuts (Arachis hypogaea), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trich
  • Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants.
  • Plant response ratings summarized in Table E, 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.
  • Test 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) and to plants that were in the one-to four leaf stage (postemergence application).
  • a sandy loam soil was used for the preemergence test while 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 within approximately one day after planting seeds for the preemergence test.
  • Crop and weed species include annual bluegrass (Poa annua), black nightshade (Solanum nigra), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Gahum aparine), green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), little seed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), ryegrass (Lolium multiflorum), scentless chamomile (Matricaria inodora), speedwell (Veronica pers
  • 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,
  • a dash response (-) means no test result.
  • Treated plants and untreated controls were maintained under greenhouse conditions for twenty to thirty days at which time 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. A dash response (-) indicated that no test result was recorded.

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Abstract

Compounds of Formula (I), and their agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetaion, wherein Q is (Q-1) or (Q-2); and A, Y, Z, R1-R7, q and r 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
BICYCLIC HERBICIDES BACKGROUND OF THE INVENTION
This invention relates to certain bicyclic compounds, their 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.
EP 283,261 discloses cyclic diones of Formula i as herbicides:
Figure imgf000003_0001
wherein
X, X1 and X2 are independently O or S;
R1 is a monocyclic or fused-bicyclic heterocyclic group containing up to ten ring atoms up to five of which may be selected from O, N and S, optionally substituted with one or more groups selected from, among others, oxo, halogen, nitro, cyano, alkyl, haloalkyl, haloalkoxy, alkoxy, alkylsulfonyl; and Y is, among others, C2-C4 alkylene which is optionally substituted with one or more groups selected from, among others, halogen or alkyl.
The bicyclic herbicides 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, agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
Figure imgf000004_0001
wherein
Q is
;
Figure imgf000004_0002
A is -(CH2)m-, -CH=CH-, -CH2CH=CH-, -CH=CHCH2-, -(CH2)n-NR9-,
-NR9-(CH2)n-, -(CH2)n-O- or -(CH2)n-S(O)2-, each group optionally substituted with one to four R8, and the directionality of the A linkage is defined such that the moiety depicted on the left side of the linkage is bonded to Y and the moiety on the right side of the linkage is bonded to the phenyl ring;
Y is O; NR9; or CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; provided that when A is -NR9-(CH2)n-, then Y is CH2;
Z is C(=X), O, or S(O)2; provided that when Y is O or NR9, then Z is C(=X);
X is O or S;
R1 is H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano, nitro, S(O)2NR10R11, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C6 alkenylsulfonyl, C3-C6 haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6 haloalkynylsulfonyl or C3-C6 cycloalkylsulfonyl; or R1 is phenylsulfonyl optionally substituted with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro;
each R2 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6
haloalkoxy, halogen, cyano or nitro; R3 is OR12, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl or halogen; 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 H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6
alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R5 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
R6 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl or C3-C6 alkynyl; or R6 is phenyl or benzyl, 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;
R7 is H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano or nitro;
each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, hydroxy or halogen; or two R8 groups bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O) or C(=S); provided that when two R8 groups are attached to a carbon atom which is attached to an O, NR9 or S(O)2, then no more than one of said R8 groups can be C1-C6 alkoxy, C1-C6 haloalkoxy, hydroxy or halogen;
each R9 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C3-C6 alkenyl; C3-C6 haloalkenyl; C3-C6 alkynyl; C3-C6 haloalkynyl; C3-C6 cycloalkyl; C1-C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkoxyalkyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; C2-C6 alkylaminocarbonyl; C3-C7
dialkylaminocarbonyl; or phenyl, benzyl or benzoyl, 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;
R10 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, C3-C6 cycloalkyl or C1-C6 alkoxy; or R10 is phenyl or benzyl, 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;
R11 is H, C1-C6 alkyl or C1-C6 haloalkyl; or R10 and R11 can be taken together as -CH2CH2-, -CH2CH2CH2-,
-CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-, each optionally substituted with 1-4 C1-C3 alkyl;
R12 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6
alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
m is 1, 2 or 3;
n is 1 or 2;
q is 0, 1, 2, 3 or 4; and
r is 0, 1 or 2;
provided that
(i) when Z is C(=X) or O; A is -(CH2)m- optionally substituted with one to four R8; and m is 1 or 2; then Q is Q-2;
(ii) when Z is C(=X) or O; and A is -CH=CH- optionally substituted with one to two R8; then Q is Q-2;
(iii) when Z is C(=X) or O; A is -(CH2)n-NR9-, -NR9-(CH2)n- or -(CH2)n-O- each optionally substituted with one to four R8; and n is 1 ; then Q is Q-2;
(iv) when A is -(CH2)n-NR9-, -(CH2)n-O- or -(CH2)n-S(O)2- each optionally
substituted with one to four R8; and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; then Z is O or S(O)2;
(v) when A is -(CH2)m- optionally substituted with one to four R8; Y is CH2
optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; and Z is O or S(O)2; then each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, hydroxy or halogen provided that no more than one R8 is C1-C6 alkoxy; and (vi) when A is -(CH2)m- optionally substituted with one to four R8; Y is CH2
optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; Z is S(O)2; and m is 2; then Q is Q-1 and each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, hydroxy or halogen.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different butyl, pentyl or hexyl isomers. The term "1-4 alkyl" indicates that one to four of the available positions for that substituent may be alkyl which are independently selected. The term "1-4 CH3" indicates that one to four of the available positions for that substituent may be methyl. "Alkenyl" includes straight-chain or branched alkenes such as 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as 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. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. 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, ClCH2, CF3CH2 and CF3CCl2. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (Cl)2C=CHCH2 and
CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CCl3C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CCl3S, CF3S, CCl3CH2S and ClCH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). 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 "Ci-Cj" prefix where i and j are numbers from 1 to 7. For example, C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or
CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. 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.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i-j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R1 or R12, 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 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 Ia (Formula I where Q is Q-1, R3 is OR12, and R12 is H) can also exist as the tautomers of
Formulae Ib 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.
Figure imgf000009_0001
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 an enol.
Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and agriculturally suitable salts
thereof, wherein:
the A-Y-Z moiety is selected from combinations of A, Y and Z such that (i) when A is -(CH2)m- optionally substituted with one to two R8 and Y is O or NR9, then Z is C(=X);
(ii) when A is -(CH2)m- optionally substituted with one to two R8 and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen, then Z is O; and
(iii) when A is -(CH2)m- or -(CH2)n-NR9- optionally substituted with one to two R8 and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen, then Z is S(O)2;
X is O;
each R4 is independently C1-C3 alkyl;
R6 is H, C1-C6 alkyl or C3-C6 alkenyl;
R7 is H, C1-C3 alkyl or C1-C3 haloalkyl;
R9 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl or
C3-C6 cycloalkyl;
R12 is H, formyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
q is 0, 1 or 2; and
r is 0 or 0.
Preferred 2. Compounds of Preferred 1 wherein:
R1 is H, methyl, halogen, S(O)2NR10R11, C1-C4 alkylsulfonyl, C1-C4 haloalkylsulfonyl or C3-C5 cycloalkylsulfonyl;
R2 is methyl, halogen or nitro;
R3 is OR12;
R5 is H or C1-C3 alkylsulfonyl; or R5 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro; each R8 is independently C1-C3 alkyl, C1-C3 alkoxy or halogen; or two R8 groups bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O);
R10 is H, C1-C4 alkyl, allyl or propargyl;
R11 is H or C1-C4 alkyl; and
R12 is H or C1-C3 alkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro. Most preferred are compounds of Preferred 2 selected from the group:
2-(1,1-dimethylethyl)-5-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)carbonyl]-8- (ethylsulfonyl)-3,4-dihydro-1(2H)-isoquinolinone;
(2,3-dihydro-2,4,7-trimethylbenzo[b]thiophen-5-yl)(1-ethyl-5-hydroxy-1H- pyrazol-4-yl)methanone S,S-dioxide;
(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)(2,3,4,5-tetrahydro-6,9-dimethyl-1- benzothiepin-7-yl)methanone S,S-dioxide;
4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2H-1,4-benzothiazin- 3(4H)-one 1,1-dioxide; 4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-5,8-dimethyl-2H-1,4- benzothiazin-3(4H)-one 1,1 -dioxide; and
(2,3-dihydro-2,4,7-trimethylbenzo[b]thiophen-5-yl)(5-hydroxy-1-methyl-1H- pyrazol-4-yl)methanone S,S-dioxide.
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 1-31. The definitions of Q, A, Y, Z, X, R1-R12, m, n, q and r in the compounds of Formulae 1-29 below are as defined above in the Summary of the Invention. Compounds of Formulae Ia-Ie are various subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ie are as defined above for Formula I. Compounds of Formulae Id and Ie correspond to Formula I compounds wherein Q is Q-1 and Q-2, respectively.
Figure imgf000011_0001
Scheme 1 illustrates the preparation of compounds of Formula Id (R3 = OR13 and R13 is the same as R12 as described in the Summary of the Invention excluding H) whereby a compound of Formula Id (R3 = OH) is reacted with a reagent of Formula 2 in the presence of a base wherein X1 is chlorine, bromine, fluorine, methylsulfonyloxy (OMs), trifluoromethylsulfonyloxy (OTf), p-toluenesulfonyloxy (OTs) or acetyloxy (OAc) and R13 is as previously defined. The coupling is carried out by methods known in the art (or by obvious modifications of these methods): for example, see K. Nakamura, et al., WO 95/04054. Scheme 1
Figure imgf000012_0001
Scheme 2 illustrates the preparation of compounds of Formula Id (R3 = S(O)rR14; r = 1 or 2; and R14 = C1-C6 alkyl or C1-C6 haloalkyl) whereby a compound of
Formula Id (R3 = SR14) is reacted with an oxidizing reagent such as peroxyacetic acid, m-chloroperoxybenzoic acid, peroxytrifluoroacetic acid, potassium peroxymonosulfate or hydrogen peroxide. The oxidation is carried out by methods known in the art (or by obvious modifications of these methods); for example, see S. Patai, et al., The Chemistry of Sulphones and Sulphoxides, John Wiley & Sons, 1988; pp 205-213, 235-253.
Scheme 2
Figure imgf000012_0002
Compounds of Formula Id (R3 = Nu; Nu = SR14 or OR15; R14 is as defined previously; R15 is C1-C6 alkyl, C1-C6 haloalkyl or C2-C6 alkoxyalkyl) can be prepared from a compound of Formula Id (R3 = halogen) by treatment with a nucleophile of Formula 3 (Nu = SR14 or OR15; M = Na, K or Li) as shown in Scheme 3 using methods well documented in the literature (or obvious modifications of these methods): for example, see P. H. Nelson, et al., Synthesis, (1992), 12, 1287-1291; and S. Miyano, et al., J. Chem. Soc. Perkin Trans, (1976), 1, 1146. Scheme 3
Figure imgf000013_0001
Compounds of Formula Id (R3 = halogen) can be prepared by reacting a compound of Formula Id (R3 = 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 obvious modifications of these methods): for example, see S. Muller, et al., WO 94/13619; S. Muller, et al., DE 4,241,999.
Scheme 4
Figure imgf000013_0002
Scheme 5 illustrates the preparation of compounds of Formula Id (R3 = OH) whereby an enol ester of Formula 4 is reacted with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by obvious modifications of these methods): for example, see W. J. Michaely,
EP 369,803.
Figure imgf000014_0001
Enol esters of Formula 4 can be prepared by reacting a dione of Formula 5 with an acid chloride of Formula 6 in the presence of a slight molar excess of a base such as triethylamine in an inert organic solvent such 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
Figure imgf000014_0002
Enol esters of Formula 4 can also be prepared by reacting a dione of Formula 5 with an acid of Formula 7 in the presence of a coupling agent such as 2-chloro-1-methylpyridinium iodide and a slight excess of 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 6A). This type of coupling is known in the art: for example, see T. Mukaiyama et al., Chem. Lett. (1975), 1045-1048.
Scheme 6A
Figure imgf000015_0001
The acid chlorides of Formula 6 can be prepared by reacting an acid of Formula 7 with a halogenating reagent (e.g., 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
Figure imgf000015_0002
Scheme 8 illustrates the preparation of acids of Formula 7 whereby a ketone of Formula 8 is reacted with an oxidizing reagent such as NaOCl, NaOBr, NaOI or NaNO2. The oxidation is carried out by methods known in the art (or by obvious modifications of these methods): for example, see T. F. Braish, et al., Org. Prep. Proced. Int., (1991), 23, 655-658 and J. A. Skorcz, et al., Heterocycl. Chem., (1973), 10, 249. Scheme 8
Figure imgf000016_0001
(R16=NR10R11, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl or C3-C6 cycloalkyl; or phenyl optionally substituted) Scheme 9 illustrates the preparation of sulfones of Formula 8a whereby a sulfide of
Formula 9 is reacted with an oxidizing reagent such as peroxyacetic acid,
m-chloroperoxybenzoic acid, peroxytrifluoroacetic acid, potassium peroxymonosulfate or hydrogen peroxide. The oxidation is carried out by methods known in the art (or by obvious modifications of these methods): for example, see S. Patai, et al., The
Chemistry of Sulphones and Sulphoxides, John Wiley & Sons, 1988; pp 205-213,
235-253. For some sulfides of Formula 9 containing 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 protection and deprotection 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., J. E. McMurry and T. Hoz, J. Org. Chem., (1975), 40, 3797 and references cited therein.
Scheme 9
Figure imgf000016_0002
(R16=NR10R11, C1-C6 alkyl, C1-C6 haloalkyl, C3 -C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl or C3-C6 cycloalkyl; or phenyl optionally substituted) Scheme 10 illustrates the preparation of ketones of Formula 9 whereby a sulfide of Formula 10 is reacted with an acylating reagent 11 such as acetyl chloride or acetic anhydride in the presence of a Lewis acid such as aluminum chloride in a solvent such as carbon disulfide, methylene chloride or 1,2-dichloroethane. This conversion is carried out using methods well known in the art: for example, see R. A. Cutler, J. Amer. Chem. Soc, (1952), 74, 5475.
Scheme 10
Figure imgf000017_0001
The lactam of Formula 10a (X = O, Y = NR9, A = -(CH2)m-, and m = 2) can be prepared by treating an amide of Formula 12 (Scheme 11) with a base such as potassium t-butoxide or sodium hydride in a solvent such as benzene, dimethylformamide or THF. This conversion is carried out using methods known in the art (or obvious modifications of these methods): for example, see R. N. Misra, et al., Bioorg. Med. Chem. Lett., (1991), 1, 295-298.
Scheme 11
Figure imgf000017_0002
The compounds of Formula 12 (Scheme 12) can be prepared from compounds of Formula 12a (X3 = OH) by converting the alcohol to an appropriate leaving group such as a halogen, a mesylate or tosylate. For example, the reactions to prepare the mesylate or tosylate are carried with a sulfonyl chloride of Formula 13 in the presence of a base such as pyridine, sodium hydride or triethylamine in a solvent such as pyridine or methylene chloride at temperatures between 0 °C and room temperature. This conversion is carried out using methods well known in the literature (or obvious modifications of these methods): for example, see R. N. Misra, et al., Bioorg. Med. Chem. Lett., (1991), 1, 295-298, Helv. Chim. Acta, (1947), 30, 1454 and L. F. Fieser and M. Fieser, Reagents for Organic Synthesis, Vol. 1, Wiley, New York, (1967), 1179.
Scheme 12
Figure imgf000018_0001
Compounds of Formula 12a (Scheme 13) can be prepared from an amide of Formula 14 by treatment with an excess of a base such as n-butyllithum and an electrophile such as an epoxide of Formula 15 in a solvent such as THF. This conversion is carried out using methods known in the literature (or obvious modifications of these methods): for example, see R. N. Misra, et al., Bioorg. Med. Chem. Lett., (1991), 1, 295-298 and B. H. Bhide, et al., Chem. and lnd., (1975), 519.
Scheme 13
Figure imgf000018_0002
Compounds of Formula 14 (Scheme 14) can be prepared from an acid chloride of Formula 16 and an amine of Formula 17 in the presence of a base such as triethylamine or excess NH2R9 in a solvent such as chloroform. This conversion is carried out using methods well known in the literature (or obvious modifications of these methods): for example, see A. D. Wolf, EP 196,786.
Scheme 14
Figure imgf000019_0001
Scheme 15 illustrates the preparation of compounds of Formula 10b (X = O, Y = NR9) whereby an olefin of Formula 10c is reacted with a reducing reagent such as hydrogen at 345 kPa (50 psi) in the presence of a catalyst such as palladium on carbon in a solvent such as ethanol. The reduction is carried out by methods well known in the art (or by obvious modifications of these methods): for example, R. D. Clark, et at., J. Med. Chem., (1993), 36, 2645-57 and C. Y. Cheng, J. Heterocyclic. Chem., (1995), 32, 73.
Scheme 15
Figure imgf000019_0002
Scheme 16 illustrates the preparation of compounds of Formula 10d (X = O,
Y = NR9) whereby an amide of Formula 18 is treated with an alkyllithium such as n-butyllithium in a solvent such as THF. The resulting dianion is treated with an electrophile such as DMF or an amide to give compounds of Formula 10d. The reaction is carried out by methods well known in the art (or by obvious modifications of these methods): for example, see R. D. Clark, et al., J. Med. Chem., (1993), 36, 2645-57. Scheme 16
Figure imgf000020_0001
Olefins of Formula 10e (X = O, Y = NR9, A = -CH=CH-, -CH2CH=CH- or -CH=CHCH2-) can also be prepared from the corresponding lactones 10f (Y = O) with a substituted amine of Formula 17 (Scheme 17). The reaction is carried out by methods well known in the art (or by obvious modifications of these methods): for example, see R. Singh, et. al., J. Indian Chem. Soc, (1991), 68, 276-80, M. Somei, Chem. Pharm. Bull., (1981), 29, 249, and N. Gilman, Synth. Commun., (1982), 12, 373-80.
Scheme 17
Figure imgf000020_0002
The preparation of lactones of Formula 10g (X = O, Y = O) (Scheme 18) is carried out by methods well known in the art (or by obvious modifications of these methods): for example, see R. M. Hauser, J. Org. Chem., (1988), 53, 4676-4681. Scheme 18
Figure imgf000021_0001
The preparation of compounds of Formula 10h (X = O, Y = O, A = -(CH2)m-, m = 2) is carried out by methods well known in the art (or by obvious modifications of these methods): for example, R. J. Pasteris, EP 166,516, A. D. Wolf, EP 196,786 and F. M. Hauser, J. Org. Chem., (1988), 53, 4676-4681.
Scheme 19
Figure imgf000021_0002
The preparation of compounds of Formula 10i (X = O, Y = NR9, A = -(CH2)m-, m = 1) is carried out by methods known in the art (or by obvious modifications of these methods): for example, see J. Epsztajn, et al., Tetrahedron, (1993), 49, 929-938 and R. J. Pasteris, EP 107,979 and EP 166,516. Scheme 20
Figure imgf000022_0001
The preparation of compounds of Formula 10j (X = O, Y = O, A = -(CH2)m-, m = 1) is carried out by methods known in the art (or by obvious modifications of these methods): for example, see R. Mali, et al., J. Chem. Res., Synop., (1993), 5, 184-185 and B. H. Bhide, Tetrahedron, (1971), 27, 6171.
Scheme 21
Figure imgf000022_0002
Scheme 22 illustrates the preparation of compounds of Formula Ie (R5 = R5a and
R5a is the same as R5 as described in the Summary of the Invention excluding H) whereby a compound of Formula Ie (R5 = H) is reacted with a reagent of Formula 19 in the presence of a base wherein X4 is chlorine, bromine, fluorine, OTf or OAc and R5a is as previously defined. This coupling is carried out by methods known in the art (or by obvious modification of these methods): for example, see K. Nakamura, et al.,
WO 95/04054. Scheme 22
wherein
R5a is the same as R5 as described in the Summary of the Invention excluding H.
Scheme 23 illustrates the preparation of compounds of Formula Ie (R5 = H) whereby an ester of Formula 20 is reacted with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide). This rearrangement is carried out by methods known in the art (or by obvious modification of these methods): for example, see W. J. Michaely,
EP 369,803.
Scheme 23
Figure imgf000023_0002
An ester of Formula 20 can be prepared by reacting a hydroxypyrazole of
Formula 21 with an acid chloride of Formula 6 in the presence of a slight molar 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 24). This type of coupling is carried out by methods known in the art (or by obvious modification of these methods): for example, see W. J. Michaely, EP 369,803. Scheme 24
Figure imgf000024_0001
Scheme 25 illustrates the synthesis of compounds of the Formula 23
(R8 = C1-C6 alkyl) wherein a thioether of the Formula 22 is heated either neat or in the presence of a high boiling solvent such as dimethylaniline at temperature from 150 °C to 200 °C to provide the benzothiophenes 23 (Scheme 25). For a representative example see, W. K. Anderson et al., J. Chem. Soc. Perkin Transactions 1 (1986), 1-4.
Scheme 25
Figure imgf000024_0002
Compounds of the Formula 25 which can serve as intermediates for the synthesis of compounds of the present invention can readily be prepared by acid catalyzed cyclization of an appropriately substituted carboxylic acid of the Formula 24
(Scheme 26). Acid catalysts that have been used to promote this reaction are sulfuric acid, hydrochloric acid, trifluoroacetic acid and polyphosphoric acid. For a general review see, B. Iddon and R. M. Scrowston, Advances in Heterocyclic Chemistry, Vol. 1, Academic Press, New York (1970), 177. Scheme 26
Figure imgf000025_0001
The preparation of compounds of the Formula 23a can be accomplished by treatment of compounds of the Formula 23 with triethylsilane in trifluoroacetic acid (Scheme 27). The reaction is best carried out at temperatures between 25 °C and 72 °C. For an example of this transformation see, E. N. Karaulova et al., Zur Russ. Fiz-Chim., (1960), 30, 3292.
Scheme 27
Figure imgf000025_0002
Compounds of the Formula 25a can readily be prepared by treatment of compounds of the Formula 25 with triethylsilane in refluxing trifluoroacetic acid
(Scheme 28). For a representative example, see, C. T. West et al., J. Org. Chem., (1963), 35, 2675-2681.
Schema 28
Figure imgf000025_0003
Compounds of Formula 26 (A = -(CH2)m-, Y = -CH2-) can be regioselectively brominated para to the thioether functionality giving structures of Formula 27
(Scheme 29). Typical conditions employed are the treatment of compounds of
Formula 26 with one equivalent to a slight excess of bromine in an inert solvent such as dichloromethane or chloroform at temperatures from 20 °C up to the boihng point of the solvent. For a representative example see K. Nakamura et al., WO 95/04054.
Scheme 29
Figure imgf000026_0001
Scheme 30 illustrates the preparation of carboxylic acids of the Formula 28 (A = -(CH2)m-, Y = -CH2-) via halogen metal exchange followed by quenching of the resulting anion with carbon dioxide. This general method is carried out by the addition of n-butyl lithium to a solution of the compound of the Formula 27 in THF or diethyl ether at temperatures from 25 °C to -70 °C. Carbon dioxide is introduced to produce the resulting acid. This classical reaction is known to one skilled in the art. For a typical procedure see, R. L. Danheiser et al., J. Am. Chem. Soc, (1986), 108, 806-810.
Scheme 30
Figure imgf000026_0002
Compounds of the Formula 29 (A = -(CH2)m-, Y = -CH2-) (Scheme 31) can readily be prepared by oxidation of compounds of the Formula 28 using any one of a number of oxidants. Typical reagents used for this transformation are hydrogen peroxide, peroxyacetic acid, m-chloroperoxybenzoic acid and potassium
peroxymonosulfate. The oxidations can be carried out by methods known in the art or obvious modifications. For a general review see, S. Patai e.t.a., The Chemistry of Sulphones and Sulfoxides, John Wiley & Sons, 1988, pp. 205-213. Scheme 31
Figure imgf000027_0001
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 interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula 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.
1H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, br s = broad singlet. EXAMPLE 1
Step A: Preparation of 2-(ethylthio)benzoic acid
73.5 g ( 1.84 mol) of sodium hydroxide was dissolved in 750 mL of ethanol. To this solution at 20 °C, 135 g (0.87 mol) of thiosalicylic acid and an additional 600 mL of ethanol was added. After stirring at room temperature for 1 h, the reaction mixture was cooled to 0 °C and 77 mL (0.97 mol) of ethyl iodide was added dropwise. The reaction mixture was then heated under reflux for 1 h, cooled to 10 °C and 1 N HCl added until the mixture was pH 2. The resulting precipitate was collected by filtration and washed several times with water. The solid was dried to give 148 g of the title compound of Step A. 1H NMR (CDCl3) δ 1.40 (t,3H), 3.00 (q,2H), 7.20 (t,1H), 7.38 (d,1H), 7.50 (t,1H), 8.15 (d,1H).
Step B: Preparation of N-(1,1-dimethylethyl)-2-(ethylthio)benzamide
296.4 g (1.63 mol) of the title compound of Step A, 300 mL (4.07 mol) of thionyl chloride and 600 mL of methylene chloride were heated at reflux for 4 h. After standing at room temperature overnight, an additional 25 mL of thionyl chloride was added and the reaction refluxed an additional 3 h. The reaction was concentrated under reduced pressure, chloroform was added, and the mixture was again concentrated to give 316 g of the acid chloride.
A solution of the acid chloride in 550 mL of chloroform was added dropwise to a solution of 377 mL (3.58 mol) of t-butyl amine in 550 mL of chloroform at 0 °C. After the addition was complete, the reaction was heated at 40 °C and then allowed to stand at room temperature overnight. The reaction mixture was poured into water and extracted twice with methylene chloride. The combined organic extracts were washed twice with 1 Ν HCl, dried (MgSO4) and concentrated. The crude oil was triturated with hexane to give 284 g of the title compound of Step B as a white solid (a sample prepared in a separate experiment provided material melting at 126-129 °C). An additional 44.6 g was obtained from the filtrate. 1H ΝMR (CDCl3) δ 1.29 (t,3H), 1.48 (s,9H), 2.92 (q,2H), 6.52 (br s, 1H), 7.21-7.40 (m,3H), 7.62 (dd,1H).
Step C: Preparation of N-(1,1-dimethylethyl)-2-(ethylthio)-6-(2- hydroxyethyl)benzamide
20.0 g (84.4 mmol) of the title compound of Step B was dissolved in 250 mL of dry THF and cooled to -45 °C. n-Butyl lithium (116 mL of a 1.6 M solution in hexanes, 186 mmol) was added dropwise to this mixture at -45 °C. The reaction was allowed to warm to 0 °C and kept at this temperature for 30 min. Ethylene oxide was then added rapidly at 0 °C and the reaction was kept below room temperature. After 1 h, saturated ammonium chloride was added and the reaction mixture was extracted twice with ether. The combined organic extracts were dried (Νa2SO4) and concentrated. The crude oil was triturated with w-butyl chloride to give 9.94 g of the title compound of Step C as a white solid melting at 113-117 °C. 1H NMR (Me2SO-d6) δ 1.17 (t,3H), 1.32 (s,9H), 2.67 (t,2H), 2.87 (q,2H) 3.55-3.59 (m,2H), 4.62 (t,1H), 7.00-7.21 (m,3H), 7.84
(br s.1H).
Step D: Preparation of N-(1,1-dimethylethyl)-2-(ethylthio)-6-[2- [(methylsulfonyl)oxy]ethyl]benzamide
To a mixture of 16.67 g (59.32 mmol) of the title compound of Step C in 245 mL of pyridine at 0 °C was added dropwise 14 mL (178 mmol) of mesyl chloride at 0 °C. After 1 h at 0 °C, the reaction mixture was poured into ice water and the precipitate collected by filtration. The solid was washed with water and dried to give 15.14 g of the title compound of Step D (a sample prepared in a separate experiment provided material melting at 111-113 °C). 1H ΝMR (Me2SO-d6) δ 1.20 (t,3H), 1.36 (s,9H), 2.93 (m,5H), 3.11 (s,3H), 4.38 (t,2H), 7.17 (dd,1H), 7.30 (m,2H), 8.00 (br s,1H).
Step E: Preparation of 2-(1,1-dimethylethyl)-8-(ethylthio)-3,4-dihydro-1(2H)- isoquinolinone
To a mixture of 5.67 g (50.61 mmol) of potassium t-butoxide in 100 mL of dimethylformamide at 0 °C was added a solution of 15.14 g (42.17 mmol) of the title compound of Step D in 100 mL dimethylformamide at 0 °C. The reaction was allowed to warm to room temperature over 1 h and an additional 150 mL of dimethylformamide and 1 g of potassium t-butoxide added. After an additional 30 min, the reaction mixture was poured onto ice and 10% HCl was added to adjust the pH to 2. The reaction mixture was extracted three times with ethyl acetate. The combined organic phases were washed three times with water, then saturated aqueous ΝaCl, dried (MgSO4) and concentrated to give 8.6 g of the title compound of Step E as an amber oil. 1H ΝMR (CDCl3) δ 1.40 (t,3H), 1.55 (s,9H), 2.88 (m,4H), 3.50 (m,2H), 6.85 (d,1H), 7.18 (d,1H), 7.23 (m,2H).
Step F: Preparation of 5-acetyl-2-(1,1-dimethylethyl)-8-(ethylthio)-3,4-dihydro- 1(2H)-isoquinolinone
To a solution of 2.0 g (7.6 mmol) of the title compound of Step E and 32 mL of methylene chloride was added 1.0 g (7.5 mmol) of aluminum chloride. The reaction mixture was heated under reflux for 1 h and cooled to room temperature. A solution of 1.2 g (9.12 mmol) of aluminum chloride and 0.72 g (9.12 mmol) of acetyl chloride in 20 mL of methylene chloride was added and the reaction mixture was refluxed an additional 2 h. The reaction mixture was cooled and 20 mL of 1 Ν ΗCl was added dropwise. The phases were separated and the aqueous phase was extracted two more times with methylene chloride. The combined organic phases were dried (MgSO4) and concentrated to give 2.3 g of an oil. The residue was flash chromatographed on silica gel with ethyl acetate/hexane to give 1.04 g of the title compound of Step F as a white solid (a sample prepared in a separate experiment provided material melting at 109-110 °C). 1H NMR (Me2SO-d6) δ 1.25 (t,3H), 1.45 (s,9H), 2.55 (s,3H), 2.89 (q,2H), 3.00 (t,2H), 3.40 (t,2H), 7.33 (d,1H), 7.86 (d,1H).
Step G: Preparation of 5-acetyl-2-(1,1-dimethylethyl)-8-(ethylsulfonyl)-3,4- dihydro-1(2H)-isoquinolinone
To a solution of 2.06 g (3.35 mmol) of Oxone® in 8 mL of water was added a solution of 0.41 g (1.34 mmol) of the title compound of Step Fin 3 mL of acetone. The reaction mixture was stirred at room temperature for 1.5 h and then diluted with water and ethyl acetate. The phases were separated and the aqueous phase was extracted again with ethyl acetate. The combined organic phases were dried (MgSO4) and concentrated to give 0.5 g of the title compound of Step G as a solid (a sample prepared in a separate experiment provided material melting at 139-142 °C). 1Η NMR (Me2SO-d6) δ 1.18 (t,3H), 1.47 (s,9H), 2.62 (s,3H), 3.00(t,2H), 3,48 (t,2H), 3.85 (q,2H), 7.97
(d,1H,J=8.26 Hz), 8.08 (d,1H,J=8.26 Hz).
Step H: Preparation of 2-(1,1-dimethylethyl)-8-(ethylsulfonyl)-1,2,3,4-tetrahydro- 1-oxo-5-isoquinolinecarboxylic acid
To a 5 °C solution of 0.54 g (13.5 mmol) of sodium hydroxide in 1.25 mL of water was added 0.24 mL (4.65 mmol) of bromine and the reaction mixture was stirred until a clear yellow solution was obtained. To this solution was added 0.5 g (1.48 mmol) of the title compound of Step G dissolved in 1 mL of 1,4-dioxane and the reaction mixture was stirred at room temperature for 3 h. The reaction mixture was diluted with water and adjusted to pH 2 with concentrated HCl. It was extracted three times with ethyl acetate and the combined organic extracts were dried (MgSO4) and concentrated to give 0.53 g of the title compound of Step H as an amber oil. 1H NMR (Me2SO-d6) δ 1.18 (t,3H), 1.48 (s,9H), 3.20 (t,2H), 3.51 (t,2H), 3.85 (q,2H), 7.95(d,1H,J=8.26 Hz), 8.06 (d,1H,J=8.26 Hz).
Step I: Preparation of (1-ethyl-1H-pyrazol-5-yl)2-(1,1-dimethylethyl)-8- (ethylsulfonyl)-1,2,3,4-tetrahydro-1-oxo-5-isoquinolinecarboxylate
0.5 g (1.45 mmol) of title compound of Step Η and 14 mL of thionyl chloride were combined and heated under reflux for 4 h. The reaction mixture was allowed to cool and was then concentrated. The residue was dissolved in methylene chloride and re-concentrated. The residue was dissolved in 6 mL of chloroform and 0.2 g
(1.79 mmol) of 1-ethyl-5-hydroxy-1H-pyrazole was added followed by 0.18 g
(1.78 mmol) of triethylamine. The reaction mixture was heated at reflux for 1 h and then allowed to stir at room temperature overnight. The reaction mixture was poured into ice and 1 N ΗCl and extracted three times with methylene chloride. The combined organic extracts were dried (MgSO4) and concentrated to give 0.5 g of an oil. The residue was flash chromatographed on silica gel with ethyl acetate to give 90 mg of the title compound of Step I as a solid (a sample prepared in a separate experiment provided material melting at 158-161 °C with apparent decomposition). 1H NMR (Me2SO-d6) δ 1.20 (t,3H), 1.32 (t,3H), 1.49 (s,9H), 3.25 (m,2H), 3.56 (m,2H), 3.87 (q,2H) 4.09 (q,2H), 6.24 (d,1H), 7.47 (d,1H), 8.09 (d,1H), 8.38 (d,1H).
Step J: Preparation of 2-(1,1-dimethylethyl)-5-[(1-ethyl-5-hydroxy-1H-pyrazol-4- yl)carbonyl]-8-(ethylsulfonyl)-3.4-dihydro-1(2H)-isoquinolinone
0.28 g (0.65 mmol) of the title compound of Step I, 3.4 mL of dry methylene chloride, 0.16 mL (1.15 mmol) of triethylamine and one drop of acetone cyanohydrin were combined and stirred at room temperature over the weekend. The reaction mixture was diluted with ethyl acetate and 1 N ΗCl. The organic phase was then extracted three times with saturated aqueous sodium bicarbonate. The basic aqueous phase was adjusted to pΗ 2 and extracted four times with methylene chloride. The combined methylene chloride extracts were dried (MgSO4) and concentrated to give 0.35 g.
Trituration with ether/hexane gave 0.15 g of the title compound of Step J, a compound of the invention, as a yellow solid melting at 164-167 °C. 1Η NMR (Me2SO-d6) δ 1.20 (t,3H), 1.27 (t,3H), 1.47 (s,9H), 2.82 (t,2H), 3.50 (t,2H), 3.87 (q,2H), 3.92 (q,2H), 7.48 (s,1H), 7.69 (d,1H), 7.97 (d,1H).
EXAMPLE 2
Step A: Preparation of 1-[(2-chloro-2-propenyl)thio]-2,5-dimethylbenzene
To a suspension of potassium carbonate 50.0 g (0.362 mol) in 600 mL of DMF at room temperature was added 50.0 g (0.362 mol) of 2,5-dimethylthiophenol dropwise. The temperature was allowed to rise to 29 °C with continued stirring for an additional 1 h. 40.1 g (0.362 mol) of 2,3-dichloropropene was added dropwise at room
temperature and the reaction was allowed to stir overnight. The crude reaction mixture was poured into excess ice/water and the resulting solution was extracted twice with ethyl acetate. The combined organic phase was dried (MgSO4) and concentrated to give a gold oil 76.1 g of the title compound of Step A which was used in the next step without further purification. 1H NMR (CDCl3) δ 2.30 (s,3H), 2.40 (s,3H), 3.64 (s,2H), 5.22 (d,2H), 6.95 (d,1H), 7.08 (d,1H), 7.13 (s,1H).
Step B: Preparation of 2,4,7-trimethylbenzo[b]thiophene
To 230 mL of dimethylaniline at reflux was added dropwise a solution of 50.0 g
(0.236 mol) of the title compound of Step A and 200 mL of dimethylaniline. The solution was heated overnight at reflux and then allowed to come to room temperature. The crude reaction mixture was diluted with excess ether and washed with 1N HCl until dimethylaniline could no longer be detected. The ether layer was dried over MgSO4, filtered and concentrated to yield 38.1 g of the title compound of Step B as a brown oil. The compound was used without further purification in the next reaction. 1H NMR (CDCl3) δ 2.30 (s,3H), 2.55 (s,3H), 2.61 (s,3H), 6.95 (d,1H), 7.04 (d, 1H), 7.10 (s,1H). Step C: Preparation of 2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene
A solution of 38.0 g (0.215 mol) of the title compound of step B, 98.0 mL (0.429 mol) of triethylsilane in 280 mL of trifluoroacetic acid was heated overnight at reflux. The crude reaction mixture was concentrated, diluted with excess ether, and washed with saturated sodium bicarbonate until an aqueous test extraction was neutral. The ether phase was dried over MgSO4, filtered and concentrated to yield an orange oil. Chromatography on silica gel with hexane provided 20.4 g of the title compound of Step C as a pale yellow oil. 1H NMR (CDCl3) δ 1.48 (d,3H), 2.20 (s,6H), 2.90 (dd,1H), 3.38( dd,1H), 3.95-4.09 (m,1H), 6.78 (d,1H), 6.83 (d,1H).
Step D: Preparation of 5-bromo-2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene
A solution of 10.3 g (58.0 mmol) of the title compound of Step C in 120 mL of dichloromethane was treated at room temperature with 9.3 g (58.0 mmol) of bromine dropwise. The solution was stirred an additional 3 h, diluted with excess ethyl acetate, washed with excess saturated sodium bisulfite solution and dried over MgSO4. Filtration followed by concentration provided the crude product as a yellow oil. Chromatography on silica gel in hexanes provide 10.6 g of the title compound of Step D as a clear oil. 1H NMR (CDCl3) δ 1.46 (d,3H), 2.16 (s,3H), 2.29 (s,3H), 2.95 (dd.1H), 3.40 (dd,1H), 3.93-3.99 (m,1H), 7.15 (s,1H).
Step E: Preparation of 2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene-5- carboxylic acid
To a solution of 15.1 g (58.7 mmol) of the title compound of Step D in THF at -70 °C was added dropwise a solution of n-butyl lithium (24.7 mL of a 2.5 M solution in hexanes, 61.6 mmol). During the addition, the temperature was maintained below -60 °C. The reaction mixture was stirred an additional 30 min at -70 °C and then excess carbon dioxide gas was passed into the solution (15 min). The reaction mixture was allowed to slowly warm to room temperature and stir overnight. The reaction mixture was diluted with excess water, acidified with concentrated HCl to pH 2, and extracted with ethyl acetate several times. The combined organic phase was dried over MgSO4, filtered and concentrated to provide the crude acid as a green solid. The crude product was suspended in hexanes, collected by filtration, and air dried to yield 8.5 g of the title compound of Step E as a green solid. 1H NMR (CDCl3) δ 1.48(d,3H), 2.23(s,3H), 2.51(s,3H), 3.01(dd,1H), 3.47(dd,1H), 3.98-4.03(m,1H), 7.71(s,1H).
Step F: Preparation of 2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene-5- carboxylic acid 1,1-dioxide
To a solution of 38.8 g (56.0 mmol) of Oxone® in 250 mL of water at room temperature was added dropwise a solution of 5.0 g (23.0 mmol) of the title compound of Step E in 50 mL of acetone. To the resulting solution was added portionwise 12.0 g (143 mmol) of sodium bicarbonate. The solution was stirred an additional 1.5 h at room temperature. To the solution was added 1N HCl to bring the pH to 3. The solution was extracted with ethyl acetate and the combined organic phase was washed with saturated sodium bisulfite solution, dried over MgSO4, filtered and concentrated to provide the title compound of Step F as a white solid melting at 186-189 °C. 1H NMR (CDCl3) δ 1.56 (d,3H), 2.52 (s,3H), 2.65 (s,3H), 2.82 (dd.1H), 3.40-3.61(m,2H), 7.83 (s,1H). Step G: Preparation of 1-ethyl-1-H-pyrazol-5-yl 2,3-dihydro-2,4,7- trimethylbenzo[b]thiophene-5-carboxylate 1,1-dioxide
To a solution of 1.0 g (3.94 mmol) of the title compound of Step F in 35 mL of dichloromethane at room temperature was added 0.55 mL (6.30 mmol) of oxalyl chloride and a catalytic amount of dimethylformamide. The resulting solution was heated to reflux for 3 h and then stirred at ambient temperature overnight. The reaction mixture was concentrated in vacuo. The crude reaction mass was dissolved in 20 mL of dichloromethane and treated at room temperature successively with 0.89 mL
(6.30 mmol) of triethylamine followed by 0.46 g (4.11 mmol) of 1-ethyl-5-hydroxy-1H-pyrazole. The reaction mixture was stirred at room temperature overnight. The reaction mixture was diluted with excess ethyl acetate, washed with water and dried over MgSO4. Filtration followed by concentration afforded the crude product which was chromatographed on silica gel (elution with 1:1 ethyl acetate:hexanes) to afford 0.89 g of the title compound of Step G as a white solid. 1H NMR (CDCl3) δ 1.45 (t,3Η), 1.58 (d,3H), 2.54 (s,3H), 2.69 (s,3H), 2.85 (dd,1H), 3.47-3.59 (m,2H), 4.10 (q,2H), 6.24 (d,1H), 7.50 (d,1H), 7.86 (s,1H).
Step H: Preparation of (2,3-dihydro-2,4,7-trimethylbenzo[b]thiophene-5-yl)(1- ethyl-5-hydroxy-1H-pyrazol-4-yl)methanone S, S-dioxide To a solution of 0.89 g (2.56 mmol) of the title compound of Step G in 15 mL of acetonitrile at room temperature was added 4 drops of acetone cyanohydrin followed by 0.57 mL (4.09 mmol) of triethylamine. The solution was stirred at room temperature overnight, then diluted with excess water, acidified with 1N ΗCl to pΗ 3-5 and extracted with ethyl acetate. The organic phase was dried over MgSO4, filtered and concentrated. The crude product was triturated with a 1:1 mixture of n-butyl chloride:hexanes to yield the title compound of Step Η, a compound of the invention, as a white solid melting at 152-157 °C. 1Η NMR (CDCl3) δ 1.46 (t,3H), 1.57 (d,3H), 2.29 (s,3H), 2.66 (s,3H), 2.80 (dd,1H), 3.44 (dd,1H), 3.50-3.61 (m,1H), 4.08 (q,2H), 7.28 (s,1H), 7.35 (s.1H).
EXAMPLE 3
Step A: Preparation of methyl 4-[(2-ethoxy-2-oxoethyl)thio]-3-nitrobenzoate 0.36 g (9 mmol) of 60% sodium hydride was suspended in anhydrous
dimethylformamide and cooled to 0 °C. After the dropwise addition of 0.93 mL
(8.5 mmol) of ethyl 2-mercaptoacetate, the reaction was warmed to room temperature and stirred for an additional 30 minutes. 1.8 g (8.3 mmol) of methyl 4-chloro-3- nitrobenzoate was added dropwise, keeping the reaction temperature below 10 °C. The reaction mixture was then slowly warmed to room temperature and poured into 150 mL of ice water. The precipitate was stirred vigorously for 20 minutes and then filtered. The solid was dried to give 2.3 g of the title compound of Step A as a yellow solid melting at 74-76 °C. 1H NMR (CDCl3) δ 8.88 (d,1H), 8.20 (d,1H), 7.6 (d,1H), 4.23 (q,2H), 3.97 (s,3H), 3.80 (s,2H), 1.28 (t,3H).
Step B: Preparation of methyl 3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylate
10.0 g (35 mmol) of the title compound of Step A was dissolved in 160 mL of acetic acid and 20 mL of water was added. The solution was heated to 65 °C and 11.7 g (210 mmol) of iron powder was added in small portions. Vigorous stirring was continued for 10 minutes after the end of the iron addition, after which the reaction was filtered through Celite®. The solids were washed with acetic acid and the combined filtrates concentrated. The crude mixture was partitioned between ethyl acetate and sodium bicarbonate solution. The layers were separated and the organic phase was extracted three times with more ethyl acetate. The combined ethyl acetate layers were washed with sodium bicarbonate solution and saturated aqueous NaCl, dried over magnesium sulfate, and concentrated to yield 7.0 g of the title compound of Step B as a white solid melting at 178-180 °C. 1.3 NMR (CDCl3) δ 8.68 (br s,lΗ), 7.67 (d,1H), 7.57 (s,1H), 7.38 (d,1H), 3.93 (s,3H), 3.49 (s,2H).
Step C: Preparation of methyl 4-ethyl-3,4-dihydro-3-oxo-2H- 1 ,4-benzothiazine-6- carboxylate
10.0 g (45 mmol) of the title compound of Step B was dissolved in 50 mL of anhydrous dimethylformamide. 6.0 g (54 mmol) of potassium t-butoxide was added and the reaction was stirred for 15 minutes. 4.0 mL (50 mmol) of ethyl iodide was added dropwise and the reaction was stirred for 2 h. The reaction mixture was poured into 350 mL of cold water and extracted three times with diethyl ether. The combined ether extracts were washed three times with water, twice with saturated aqueous NaCl, and were then dried over magnesium sulfate and concentrated to a crude oil.
Chromatography with ethyl acetate and hexane yielded 3.7 g of the title compound of Step C. 1Η NMR (CDCl3) δ 7.80 (s,1H), 7.70 (d,1H), 7.42 (d,1H), 4.09 (q,2H), 3.94 (s,3H), 3.41 (s,2H), 1.30 (t,3H).
Step D: Preparation of methyl 4-ethyl-3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylate 1,1 -dioxide
To a mixture of 2.0 g (8.0 mmol) of the title compound of Step C in 50 mL of methylene chloride was added 5.0 mL (24 mmol) of 32% peracetic acid dropwise over a period of 20 minutes. The reaction mixture was stirred at room temperature for 48 h, diluted further with methylene chloride, washed once with water, twice with sodium sulfite solution, and once with sodium bicarbonate solution. The organic phase was dried over magnesium sulfate and concentrated to afford 2.05 g of the title compound of Step D as a yellow solid. 1H NMR (CDCl3) δ 8.05 (d,1H), 7.99 (m,2H), 4.26 (s,2H), 4.18 (q,2H), 4.00 (s,3H), 1.37 (t,3H).
Step E: Preparation of 4-ethyl-3,4-dihydro-3-oxo-2H-1,4-benzothiazine-6- carboxylic acid 1,1-dioxide
To a mixture of 2.05 g (7.2 mmol) of the title compound of Step D in 15 mL of methanol was added dropwise a solution of 1.2 g (29 mmol) of sodium hydroxide in 5 mL of water. The reaction mixture was stirred at room temperature for 1 h, diluted with water, and cooled in an ice/water bath. Slow acidification with 1N ΗCl to pΗ 2 yielded a precipitate which was isolated by filtration to give 1.45 g of the title compound of Step E as a white solid. 1Η NMR (Me2SO-d6) δ 13.8 (s,1H), 8.02 (d,1H), 7.96 (d,1H), 7.91 (d,1H), 4.91 (s,2H), 4.11 (q,2H), 1.20 (t,3H).
Step F: Preparation of 3-oxo-1-cyclohexen-1-yl 4-ethyl-3,4-dihydro-3-oxo-2H- 1,4-benzothiazine-6-carboxylate 1,1-dioxide
To a mixture of 500 mg (1.86 mmol) of the title compound of Step E and 570 mg (2.23 mmol) of N-methyl-2-chloropyridinium iodide in 2 mL of methylene chloride was added 310 μL (2.25 mmol) of triethylamine and the reaction mixture was stirred for 15 minutes. A solution of 212 mg (1.9 mmol) of 1,3-cyclohexanedione and 310 μL (2.25 mmol) of triethylamine in 2 mL of methylene chloride was then added dropwise. After stirring overnight at room temperature, the reaction mixture was concentrated and the crude residue was chromatographed in ethyl acetate and hexane to give 210 mg of the title compound of Step F as a white solid. 1Η ΝMR (CDCl3) δ 8.1 (d,1H), 8.02 (s,1H), 8.0 (d,1H), 6.08 (s,1H), 4.28 (s,2H), 4.2 (q,2H), 2.7 (t,2H), 2.5 (t,2H), 2.2 (m,2H), 1.38 (t,3H).
Step G: Preparation of 4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]- 2H-1,4-benzothiazin-3(4H)-one 1,1-dioxide
80 mg (0.22 mmol) of the title compound of Step F, 56 μL (0.40 mmol) of triethylamine, and 1 drop of acetone cyanohydrin were dissolved in 6 mL of dry acetonitrile and stirred for 12 h. A catalytic crystal of potassium cyanide was added to the reaction mixture and stirring was continued for another 24 h. The reaction mixture was then concentrated and the residue was dissolved in water. The aqueous mixture was washed once with diethyl ether, acidified to pΗ 2 with 1N ΗCl, and extracted twice with ethyl acetate. The combined ethyl acetate extracts were dried over magnesium sulfate and concentrated to yield 60 mg of the title compound of Step G, a compound of the invention, as an oil which crystallized to a solid melting at 158-165 °C. 1Η ΝMR (CDCl3) δ 7.96 (d,1H), 7.37 (s,1H), 7.33 (d,1H), 4.26 (s,2H), 4.12 (q,2H), 2.8
(br s,2H), 2.5 (br s,2H), 2.1 (m,2H), 1.36 (t,3H). By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 30 can be prepared. The following abbreviations are used in the Tables which follow: t=tertiary, n=normal, i=iso, Me=methyl, Et=ethyl, Pr=propyl, i-Pr=isopropyl, Bu=butyl, Ph=phenyl, OMe=methoxy, OEt=ethoxy, CN=cyano, NO2=nitro, CHO=formyl, CO2Et=ethoxycarbonyl, SO2Me=methylsulfonyl, SO2Et=ethylsulfonyl, and SO2Ph = phenylsulfonyl.
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Figure imgf000046_0001
Figure imgf000046_0003
Figure imgf000046_0002
Figure imgf000047_0003
Figure imgf000047_0002
Figure imgf000048_0002
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.
Figure imgf000048_0001
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,
N,N-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-methyl-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-E.
Figure imgf000050_0001
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.
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, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butylate, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham,
chlorsulfuron, chlorthal-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-(1-methylethyl)-5-oxo-1H-imidazol-2-yl]-5-methyl-3-pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethyl α,2-dichloro-5-[4-(difluoromethyl)-4,5-dihydro-3-methyl-5-oxo-1H-1,2,4-triazol-1-yl]-4-fluorobenzenepropanoate (F8426), fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl,
fiazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam,
flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, fluridone, flurochloridone, fluroxypyr, fomesafen, fosamine-ammonium, glufosinate,
glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium,
glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox (AC 299 263), imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole (RPA 201772), lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methyl [[2-chloro-4-fluoro-5-[(tetrahydro-3-oxo-1H,3H-[1,3,4]thiadiazolo[3,4-a]pyridazin-1-ylidene)amino]phenyl]thioacetate (KIΗ 9201), methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[1-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2-methoxyethyUdene]amino]oxy]acetate (AKΗ-7088), methyl5-[[[[(4,6-d-methyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]-1-(2-pyridinyl)-1H-pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, 3-oxetanyl 2-[[[[(4,6-dimethyl-2-pyrimidinyl)amino]carbonyl]amino]sulfonyl]benzoate (CGA 277476), oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl,
quizalofop-P-tefuiyl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione
(ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390),
thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron,
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 atrazine, chlorimuron-ethyl, cyanazine, glyphosate (and its isopropylammonium, sesquisodium and trimesium salts), imazaquin (and its ammonium salt), imazethapyr (and its ammonium salt), nicosulfuron,
primisulfuron-methyl, rimsulfuron and thifensulfuron-methyl. Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-E) are selected from the group: compound 1 and atrazine; compound 1 and chlorimuron-ethyl;
compound 1 and cyanazine; compound 1 and glyphosate; compound 1 and imazaquin; compound 1 and imazethapyr; compound 1 and nicosulfuron; compound 1 and primisulfuron-methyl; compound 1 and rimsulfuron; compound 1 and thifensulfuron-methyl; compound 20 and atrazine; compound 20 and chlorimuron-ethyl; compound 20 and cyanazine; compound 20 and glyphosate; compound 20 and imazaquin; compound 20 and imazethapyr; compound 20 and nicosulfuron; compound
20 and primisulfuron-methyl; compound 20 and rimsulfuron; compound 20 and thifensulfuron-methyl; compound 21 and atrazine; compound 21 and chlorimuron-ethyl; compound 21 and cyanazine; compound 21 and glyphosate; compound 21 and imazaquin; compound 21 and imazethapyr; compound 21 and nicosulfuron; compound
21 and primisulfuron-methyl; compound 21 and rimsulfuron; compound 21 and thifensulfuron-methyl; compound 22 and atrazine; compound 22 and chlorimuron-ethyl; compound 22 and cyanazine; compound 22 and glyphosate; compound 22 and imazaquin; compound 22 and imazethapyr; compound 22 and nicosulfuron; compound
22 and primisulfuron-methyl; compound 22 and rimsulfuron; compound 22 and thifensulfuron-methyl; compound 41 and atrazine; compound 41 and chlorimuron-ethyl; compound 41 and cyanazine; compound 41 and glyphosate; compound 41 and imazaquin; compound 41 and imazethapyr; compound 41 and nicosulfuron; compound 41 and primisulfuron-methyl; compound 41 and rimsulfuron; and compound 41 and thifensulfuron-methyl.
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.
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-E for compound descriptions. The following abbreviations are used in the Index Tables which follow: t= tertiary, n = normal, i = iso, Me = methyl, Et = ethyl, Pr = propyl, Bu = butyl, Ph = phenyl, OMe = methoxy, MeSO2 = methylsulfonyl, EtSO2 = ethylsulfonyl,
PhSO2 = phenylsulfonyl, and PhC(O) = benzoyl. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
Figure imgf000054_0001
Figure imgf000055_0001
Figure imgf000055_0002
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000056_0003
Figure imgf000057_0001
BIOLOGICAL EXAMPLES OF THE INVENTION TEST A
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-galli), 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 (Setariafaberii), lambsquarters (Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrastϊ), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild oat (Avena fatua) 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.
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
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), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), 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 theophrastϊ), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), and wild oat (Avena fatua). 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), barnyardgrass (Echinochloa crus-gallϊ) 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 this 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.
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
TEST C
Seeds of barnyardgrass (Echinochloa crus-galli), bindweed (Convolvulus arvensis), black nightshade (Solanum ptycanthum dunal), cassia (Cassia obtusifolia), cocklebur (Xanthium strumarium), common ragweed (Ambrosia artemisiifolia), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria spp.), fall panicum (Panicum dichotomiflorum), giant foxtail (Setariafaberii), 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), sunflower (Helianthus annuus), velvetleaf (Abutilon theophrasti), wild proso (Panicum 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 receiving preemergence treatments were planted immediately prior to test chemical application. 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 C, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control.
Figure imgf000085_0001
Figure imgf000086_0001
TEST D
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application) and to plants that were grown for various periods of time before treatment (postemergence application). A sandy loam soil was used for the preemergence test while 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 within approximately one day after planting seeds for the preemergence 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 American black nightshade
(Solanum americanum), arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common lambsquarters (Chenopodium album), common ragweed (Ambrosia artemisiifolia), 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 D, 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.
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
TEST E
Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), alfalfa (Medicago sativa), bermudagrass (Cynodon dactylon), broadleaf signalgrass (Brachiaria plantyphylla), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), cotton (Gossypium hirsutum), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), 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), Surinam grass (Brachiaria decumbens) and texas panicum (Panicum Texas) 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 E, 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.
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
TEST F
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) and to plants that were in the one-to four leaf stage (postemergence application). A sandy loam soil was used for the preemergence test while 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 within approximately one day after planting seeds for the preemergence 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 annua), black nightshade (Solanum nigra), blackgrass (Alopecurus myosuroides), chickweed (Stellaria media), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Gahum aparine), green foxtail (Setaria viridis), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), little seed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), ryegrass (Lolium multiflorum), scentless chamomile (Matricaria inodora), speedwell (Veronica persica), spring barley (Hordeum vulgare cv. 'Klages'), spring wheat (Triticum aestivum cv. 'ERA'), sugar beet (Beta vulgaris cv. 'USl'), sunflower (Helianthus annuus cv. 'Russian Giant"), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avena fatua), windgrass (Apera spica-venti), winter barley (Hordeum vulgare cv. 'Igri') and winter wheat (Triticum aestivum cv. Talent").
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 F, 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.
Figure imgf000097_0001
Figure imgf000098_0001
Figure imgf000099_0001
Figure imgf000100_0001
TEST G
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture and applied to the surface of the water which was contained in each pot.
Individual containers of barnyardgrass (Echinochloa oryzicola), small flower umbrella sedge (Cyperus difformis), common falsepimpernel (Lindernia procumbens), monochoria (Monochoria vaginalis) and bulrush (Scirpus juncoides) were seeded and allowed to grow until the 1.5 to 2.5 leaf stage of development. A Sultama clay loam soil was used for this propagation. Japonica rice (Oryza sativa) was transplanted at 0 and 2 cm depth five days before application of the test compound to the water surface. An early and late stage of each weed species was treated, the stage of development being related to the concurrent planting of Scirpus juncoides which was then treated at the 1.5 (early) and the 2.5 (late) leaf stage.
Treated plants and untreated controls were maintained under greenhouse conditions for twenty to thirty days at which time 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. A dash response (-) indicated that no test result was recorded.
Figure imgf000101_0001
Figure imgf000102_0001

Claims

CLAIMS What is claimed is:
1. A compound selected from Formula I, and agriculturally suitable salts thereof,
Figure imgf000103_0001
wherein
Q is
or ;
Figure imgf000103_0002
Figure imgf000103_0003
A is -(CH2)m-, -CH=CH-, -CH2CH=CH-, -CH=CHCH2-, -(CH2)n-NR9-,
-NR9-(CH2)n-, -(CH2)n-O- or -(CH2)n-S(O)2-, each group optionally substituted with one to four R8, and the directionality of the A linkage is defined such that the moiety depicted on the left side of the linkage is bonded to Y and the moiety on the right side of the linkage is bonded to the phenyl ring;
Y is O; NR9; or CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; provided that when A is -NR9-(CH2)n-, then Y is CH2;
Z is C(=X), O, or S(O)2; provided that when Y is O or NR9, then Z is C(=X);
X is O or S;
R1 is H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano, nitro, S(O)2NR10R11, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl, C3-C6 alkenylsulfonyl, C3-C6 haloalkenylsulfonyl, C3-C6 alkynylsulfonyl, C3-C6 haloalkynylsulfonyl or C3-C6 cycloalkylsulfonyl; or R1 is phenylsulfonyl optionally substituted with C1-C3 alkyl, C1-C3 haloalkyl, C1-C3 alkoxy, C1-C3 haloalkoxy, 1-2 halogen, cyano or nitro;
each R2 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano or nitro;
R3 is OR12, C1-C6 alkylthio, C1-C6 haloalkylthio, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl or halogen; 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 H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6
alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R5 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
R6 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl or C3-C6 alkynyl; or R6 is phenyl or benzyl, 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;
R7 is H, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, halogen, cyano or nitro;
each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, hydroxy or halogen; or two R8 groups bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O) or C(=S); provided that when two R8 groups are attached to a carbon atom which is attached to an O, NR9 or S(O)2, then no more than one of said R8 groups can be C1-C6 alkoxy, C1-C6 haloalkoxy, hydroxy or halogen;
each R9 is independently H; C1-C6 alkyl; C1-C6 haloalkyl; C3-C6 alkenyl; C3-C6 haloalkenyl; C3-C6 alkynyl; C3-C6 haloalkynyl; C3-C6 cycloalkyl; C2 -C6 alkoxy; C1-C6 haloalkoxy; C2-C6 alkoxyalkyl; formyl; C2-C6 alkylcarbonyl; C2-C6 alkoxycarbonyl; C2-C6 alkylaminocarbonyl; C3-C7
dialkylaminocarbonyl; or phenyl, benzyl or benzoyl, 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;
R10 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C3-C6 haloalkynyl, C3-C6 cycloalkyl or C1-C6 alkoxy; or R10 is phenyl or benzyl, 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;
R11 is H, C1-C6 alkyl or C1-C6 haloalkyl; or
R10 and R11 can be taken together as -CH2CH2-, -CH2CH2CH2-,
-CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2- or -CH2CH2OCH2CH2-, each optionally substituted with 1-4 C1-C3 alkyl;
R12 is H, C1-C6 alkyl, C1-C6 haloalkyl, C2-C6 alkoxyalkyl, formyl, C2-C6
alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
m is 1, 2 or 3;
n is 1 or 2;
q is 0, 1, 2, 3 or 4; and
r is 0, 1 or 2;
provided that
(i) when Z is C(=X) or O; A is -(CH2)m- optionally substituted with one to four
R8; and m is 1 or 2; then Q is Q-2;
(ii) when Z is C(=X) or O; and A is -CH=CH- optionally substituted with one to two R8; then Q is Q-2;
(iii) when Z is C(=X) or O; A is -(CH2)n-NR9-, -NR9-(CH2)n- or -(CH2)n-O- each optionally substituted with one to four R8; and n is 1; then Q is Q-2;
(iv) when A is -(CH2)n-NR9-, -(CH2)n-O- or -(CH2)n-S(O)2- each optionally
substituted with one to four R8; and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; then Z is O or S(O)2;
(v) when A is -(CH2)m- optionally substituted with one to four R8; Y is CH2
optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; and Z is O or S(O)2; then each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, hydroxy or halogen provided that no more than one R8 is C1-C6 alkoxy; and (vi) when A is -(CH2)m- optionally substituted with one to four R8; Y is CH2
optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen; Z is S(O)2; and m is 2; then Q is Q-1 and each R8 is independently C1-C6 alkyl, C1-C6 haloalkyl, hydroxy or halogen.
2. A compound of Claim 1 wherein:
the A-Y-Z moiety is selected from combinations of A, Y and Z such that (i) when A is -(CH2)m- optionally substituted with one to two R8 and Y is O or NR9, then Z is C(=X);
(ii) when A is -(CH2)m- optionally substituted with one to two R8 and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen, then Z is O; and
(iii) when A is -(CH2)m- or -(CH2)n-NR9- optionally substituted with one to two R8 and Y is CH2 optionally substituted with one or two groups independently selected from C1-C6 alkyl, C1-C6 haloalkyl and halogen, then Z is S(O)2;
X is O;
each R4 is independently C1-C3 alkyl;
R6 is H, C1-C6 alkyl or C3-C6 alkenyl;
R7 is H, C1-C3 alkyl or C1-C3 haloalkyl;
R9 is H, C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 alkenyl, C3-C6 alkynyl or C3-C6 cycloalkyl;
R12 is H, formyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6
alkylaminocarbonyl, C3-C7 dialkylaminocarbonyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
q is 0, 1 or 2; and
r is 0 or 1.
3. A compound of Claim 2 wherein:
R1 is H, methyl, halogen, S(O)2NR10R11, C1-C4 alkylsulfonyl, C1-C4
haloalkylsulfonyl or C3-C5 cycloalkylsulfonyl;
R2 is methyl, halogen or nitro;
R3 is OR12;
R5 is H or C1-C3 alkylsulfonyl; or R5 is benzoyl or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro;
each R8 is independently C1-C3 alkyl, C1-C3 alkoxy or halogen; or two R8 groups bonded to the same carbon atom can be taken together with the carbon to which they are attached to form C(=O);
R10 is H, C1-C4 alkyl, allyl or propargyl;
R11 is H or C1-C4 alkyl; and
R12 is H or C1-C3 alkylsulfonyl; or R12 is benzoyl or phenylsulfonyl, each
optionally substituted with C1-C3 alkyl, halogen, cyano or nitro.
4. The compound of Claim 3 which is selected from the group:
2-(1,1-dimethylethyl)-5-[(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)carbonyl]-8- (ethylsulfonyl)-3,4-dihydro-1(2H)-isoquinolinone; (2,3-dihydro-2,4,7-trimethylbenzo[b]thiophen-5-yl)(1-ethyl-5-hydroxy-1H- pyrazol-4-yl)methanone S,S-dioxide;
(1-ethyl-5-hydroxy-1H-pyrazol-4-yl)(2,3,4,5-tetrahydro-6,9-dimethyl-1- benzothiepin-7-yl)methanone S,S-dioxide;
4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-2H-1,4-benzothiazin- 3(4H)-one 1,1-dioxide;
4-ethyl-6-[(2-hydroxy-6-oxo-1-cyclohexen-1-yl)carbonyl]-5,8-dimethyl-2H-1,4- benzothiazin-3(4H)-one 1,1-dioxide; and
(2,3-dihydro-2,4,7-trime-hylbenzo[b]thiophen-5-yl)(5-hydroxy-1-methyl-1H- pyrazol-4-yl)methanone 5,5-dioxide.
5. 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.
6. 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.
PCT/US1996/013347 1995-08-25 1996-08-15 Bicyclic herbicides WO1997008164A1 (en)

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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0810226A1 (en) * 1995-02-13 1997-12-03 Idemitsu Kosan Company Limited Pyrazole derivatives
WO1998012192A1 (en) * 1996-09-20 1998-03-26 Basf Aktiengesellschaft 4-hetaroylpyrazol derivatives and the use thereof as herbicides
WO1998040366A1 (en) * 1997-03-10 1998-09-17 Basf Aktiengesellschaft Saccharine-5-carbonyl-cyclohexane-1,3,5-trione derivatives, their preparation and their use as herbicides
WO1999009023A1 (en) * 1997-08-20 1999-02-25 Novartis Ag Benzothiophene derivates as herbicides
WO1999057111A1 (en) * 1998-04-30 1999-11-11 Basf Aktiengesellschaft Cyclohexenondioxothio chromanoyl derivatives
EP0970956A1 (en) * 1995-10-04 2000-01-12 Idemitsu Kosan Company Limited Pyrazole derivatives
WO2000014087A1 (en) * 1998-09-04 2000-03-16 Aventis Cropscience Gmbh Benzoyl derivatives, method for producing them and their use as herbicides and plant growth regulators
WO2000020408A1 (en) * 1998-10-06 2000-04-13 Idemitsu Kosan Co., Ltd. Triketone derivative and herbicide
US6054414A (en) * 1995-09-01 2000-04-25 Basf Aktiengesellschaft Benzoyl derivatives
WO2000055158A1 (en) * 1999-03-12 2000-09-21 Basf Aktiengesellschaft Tricyclic benzoylpyrazole derivatives used as a herbicide
WO2000068228A1 (en) * 1999-05-07 2000-11-16 Basf Aktiengesellschaft 4-(3',4'-heterocyclyl benzoyl) pyrazoles as herbicidal agents
WO2000069853A1 (en) * 1999-05-13 2000-11-23 Idemitsu Kosan Co., Ltd. Azole compounds and herbicide compositions
WO2001000584A2 (en) * 1999-06-25 2001-01-04 Basf Aktiengesellschaft Pyrazolyl derivatives of bicyclic benzoic acids for use as herbicides
WO2001000607A1 (en) * 1999-06-25 2001-01-04 Basf Aktiengesellschaft Cyclohexenone derivatives of bicyclic benzoic acids as herbicides
US6180797B1 (en) 1999-04-06 2001-01-30 American Cyanamid Co. Process for the dehalogenation of thiochroman and dihydrobenzothiophene derivatives
WO2001007422A1 (en) * 1999-07-27 2001-02-01 Aventis Cropscience Gmbh Isoxazolyl- and isoxazolinyl-substituted benzoylcyclohexanediones, production method and use thereof as herbicides and plant growth regulators
WO2001029033A2 (en) * 1999-10-22 2001-04-26 Basf Corporation Thiono-thiochroman and -dihydrobenzothiophene compounds as herbicidal agents
WO2001066522A1 (en) * 2000-03-09 2001-09-13 Syngenta Participations Ag Acylated phenyl or pyridine herbicides
WO2001079200A1 (en) * 2000-04-19 2001-10-25 Idemitsu Kosan Co., Ltd. Pyrazole derivatives and herbicides containing the same
US6316390B1 (en) 1997-12-24 2001-11-13 Idemitsu Kosan Co., Ltd. Triketone derivatives
US6326333B1 (en) 1998-05-18 2001-12-04 Basf Aktiengesellschaft Pyrazolyldioxothiochromanoyl derivatives
US6329530B1 (en) 1998-11-19 2001-12-11 Basf Aktiengesellschaft Method for the production of 1-substituted 5-hydroxypyrazoles
WO2002015695A2 (en) * 2000-08-25 2002-02-28 Basf Aktiengesellschaft Synergistic combination of a dihydrobenzothiophene herbicide and a photosystem ii inhibitor
US6392058B1 (en) 1998-11-19 2002-05-21 Basf Aktiengesellschaft Method for producing 1-substituted 5-Hydroxypyrazoles
WO2002050055A1 (en) * 2000-12-21 2002-06-27 Idemitsu Kosan Co., Ltd. Benzothiophene derivatives and herbicidal compositions containing the same
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US6472538B1 (en) 1998-11-05 2002-10-29 Basf Aktiengesellschaft Method for producing 1-substituted 5-hydroxypyrazoles
US6479436B1 (en) 1996-09-20 2002-11-12 Basf Aktiengesellschaft Hetaroyl cyclohexanedione derivatives with herbicidal effect
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US7390820B2 (en) * 2003-08-25 2008-06-24 Amgen Inc. Substituted quinolinone derivatives and methods of use
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WO2012123409A1 (en) 2011-03-15 2012-09-20 Bayer Cropscience Ag N-(1,2,5-oxadiazol-3-yl)-, n-(tetrazol-5-yl)- and n-(triazol-5-yl)bicycloarylcarboxamides and their use as herbicides
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WO2019233863A1 (en) 2018-06-04 2019-12-12 Bayer Aktiengesellschaft Herbicidally active bicyclic benzoylpyrazoles
WO2020063981A1 (en) * 2018-09-29 2020-04-02 山东先达农化股份有限公司 Triketone compound, preparation method therefor and use thereof, and herbicide
JP2021517592A (en) * 2018-04-11 2021-07-26 山▲東▼先▲達▼▲農▼▲化▼股▲ふん▼有限公司Ｓｈａｎｄｏｎｇ Ｃｙｎｄａ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ． Quinazoline dione compounds, their use and pesticide herbicides

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283261A2 (en) * 1987-03-19 1988-09-21 Zeneca Limited Herbicidal substituted cyclic diones
WO1993018031A1 (en) * 1992-03-03 1993-09-16 Idemitsu Kosan Co., Ltd. Pyrazole derivative
WO1994004524A1 (en) * 1992-08-18 1994-03-03 Idemitsu Kosan Co., Ltd. Cyclohexanedione derivative
WO1995004054A1 (en) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Pyrazole derivative

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0283261A2 (en) * 1987-03-19 1988-09-21 Zeneca Limited Herbicidal substituted cyclic diones
WO1993018031A1 (en) * 1992-03-03 1993-09-16 Idemitsu Kosan Co., Ltd. Pyrazole derivative
US5468722A (en) * 1992-03-03 1995-11-21 Idemitsu Kosan Co., Ltd. Pyrazole derivatives
WO1994004524A1 (en) * 1992-08-18 1994-03-03 Idemitsu Kosan Co., Ltd. Cyclohexanedione derivative
US5480858A (en) * 1992-08-18 1996-01-02 Idemitsu Kosan Co., Ltd. Cyclohexanedione derivatives
WO1995004054A1 (en) * 1993-08-02 1995-02-09 Idemitsu Kosan Co., Ltd. Pyrazole derivative
EP0712853A1 (en) * 1993-08-02 1996-05-22 Idemitsu Kosan Company Limited Pyrazole derivative

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US6054414A (en) * 1995-09-01 2000-04-25 Basf Aktiengesellschaft Benzoyl derivatives
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US6479436B1 (en) 1996-09-20 2002-11-12 Basf Aktiengesellschaft Hetaroyl cyclohexanedione derivatives with herbicidal effect
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CN1073093C (en) * 1997-03-10 2001-10-17 巴斯福股份公司 Saccharine-5-carbonyl-cyclohexane-1,3,5-trione derivatives,their preparation and their use as herbicides
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US6083880A (en) * 1997-03-10 2000-07-04 Basf Aktiengesellschaft Saccharine-5-carbonyl-cyclohexane-1, 3, 5-trione derivatives, their preparation and their use as herbicides
WO1999009023A1 (en) * 1997-08-20 1999-02-25 Novartis Ag Benzothiophene derivates as herbicides
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US6316390B1 (en) 1997-12-24 2001-11-13 Idemitsu Kosan Co., Ltd. Triketone derivatives
US6440899B1 (en) 1998-04-30 2002-08-27 Basf Aktiengesellschaft Cyclohexenonedioxothiochromanoyl derivatives
WO1999057111A1 (en) * 1998-04-30 1999-11-11 Basf Aktiengesellschaft Cyclohexenondioxothio chromanoyl derivatives
US6326333B1 (en) 1998-05-18 2001-12-04 Basf Aktiengesellschaft Pyrazolyldioxothiochromanoyl derivatives
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US6297196B1 (en) 1998-09-04 2001-10-02 Hoechst Schering Agrevo Gmbh Benzoyl derivatives, process for their preparation and their use as herbicides and plant growth regulators
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US6756343B1 (en) 1998-10-06 2004-06-29 Idemitsu Kosan Co., Ltd. Triketone derivatives and herbicide
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WO2012123409A1 (en) 2011-03-15 2012-09-20 Bayer Cropscience Ag N-(1,2,5-oxadiazol-3-yl)-, n-(tetrazol-5-yl)- and n-(triazol-5-yl)bicycloarylcarboxamides and their use as herbicides
CN104961704A (en) * 2015-07-09 2015-10-07 南开大学 2-(6-nitro-3-oxa-2H-benzo [1, 4] oxazine-7-hydroxy) cyclohexane-1, 3-diketone type compound and herbicidal activity
CN104961704B (en) * 2015-07-09 2017-06-09 南开大学 (the oxa- 2H benzos of 6 nitro 3 [hydroxyl of 1,4] oxazines 7) cyclohexadione compounds of hexamethylene 1,3 and activity of weeding containing 2
JP2021517592A (en) * 2018-04-11 2021-07-26 山▲東▼先▲達▼▲農▼▲化▼股▲ふん▼有限公司Ｓｈａｎｄｏｎｇ Ｃｙｎｄａ Ｃｈｅｍｉｃａｌ Ｃｏ．，Ｌｔｄ． Quinazoline dione compounds, their use and pesticide herbicides
WO2019233863A1 (en) 2018-06-04 2019-12-12 Bayer Aktiengesellschaft Herbicidally active bicyclic benzoylpyrazoles
WO2020063981A1 (en) * 2018-09-29 2020-04-02 山东先达农化股份有限公司 Triketone compound, preparation method therefor and use thereof, and herbicide

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