WO2014031971A1 - Pyridazinones herbicides - Google Patents

Pyridazinones herbicides Download PDF

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Publication number
WO2014031971A1
WO2014031971A1 PCT/US2013/056420 US2013056420W WO2014031971A1 WO 2014031971 A1 WO2014031971 A1 WO 2014031971A1 US 2013056420 W US2013056420 W US 2013056420W WO 2014031971 A1 WO2014031971 A1 WO 2014031971A1
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compound
alkyl
haloalkyl
methyl
hydroxy
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PCT/US2013/056420
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English (en)
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Thomas Martin Stevenson
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E. I. Du Pont De Nemours And Company
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain pyridazinones, their salts and compositions, and methods of their use for controlling undesirable vegetation.
  • the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, maize, potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds that are more effective, less costly, less toxic, environmentally safer or have different sites of action.
  • This invention is directed to compounds of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides:
  • A is a radical selected from the roup consisting of
  • B 1 and B 3 are each independently a radical selected from the group consisting of
  • B 2 is a radical selected from the group consisting of
  • R 1 is halogen, C j -Cg alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, -Cg alkoxy, C j -Cg haloalkoxy, C 2 -C 6 alkenyloxy, C3-Cg haloalkenyloxy, C3-C7 alkynyloxy, C 2 -Cg alkoxyalkoxy, C 2 -Cg cyanoalkoxy, C 2 -C 6 alkylthioalkoxy, C j -Cg alkylthio, C j -Cg alkylsulfinyl, C j -Cg alkylsulfonyl, -Cg haloalkylthio,
  • each R A is independently C1-C4 alkyl or C 2 -C4 haloalkyl
  • each R B is independently C 1-C4 alkyl or C 2 -C4 haloalkyl
  • R A and R B are taken together with the nitrogen atom to which they are both attached to form a 5- or 6-membered ring including ring members selected from -CH 2 -, -O- and -N-;
  • R c is C r C 4 alkyl or C 2 -C 4 haloalkyl
  • R D is C r C 3 alkylene
  • cycloalkylalkyl C 6 -C 14 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 3 -C ⁇ o alkoxyalkenyl, C 4 -C ⁇ o cycloalkoxyalkyl, C 3 -C ⁇ o alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -Cg alkylthioalkoxy, C 2 -C 8 alkylsulfinylalkyl, C 2 -C 8 alkylsulfonylalkyl, C 2 -C 8 alkylaminoalkyl, C 3 -C ⁇ o dialkylaminoalkyl,
  • dialkylaminocarbonyl C 4 -C ⁇ o cycloalkylaminocarbonyl, C 2 -C5 cyanoalkyl, C j -Cg hydroxyalkyl, C 4 -C 10 cycloalkenylalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -C 8 alkoxyhaloalkyl, C 2 -C 8 haloalkoxyhaloalkyl, C 4 -C ⁇ o halocycloalkoxyalkyl, C 4 -C 10 cycloalkenyloxyalkyl, C 4 -C 10 halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C 3 -C ⁇ o alkoxyalkylcarbonyl, C 3 -C ⁇ o alkoxycarbonylalkyl, C 2 -C 8 haloalkoxycarbonyl, C ⁇ -Cg alkoxy, C ⁇ -Cg
  • haloalkylsulfinyl -Cg alkylsulfonyl, C j -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C 3 -C 8 trialkylsilyl, C 3 -C 8 cycloalkenyloxy, C 3 -C 8 halocycloalkenyloxy, C 2 -C 8 haloalkoxyalkoxy, C 2 -C 8 alkoxyhaloalkoxy, C 2 -C 8 haloalkoxyhaloalkoxy, C 3 -C ⁇ o alkoxycarbonylalkoxy, C 2 -C 8
  • alkyl(thiocarbonyl)oxy C 2 -C 8 alkylcarbonylthio, C 2 -C 8 alkyl(thiocarbonyl)thio, C 3 -C 8 cycloalkylsulfmyl, -Cg alkylaminosulfonyl, C 2 -C 8
  • dialkylaminosulfonyl C 3 -C ⁇ o halotrialkylsilyl, C ⁇ -Cg alkylamino, C 2 -C 8 dialkylamino, C ⁇ -Cg haloalkylamino, C 2 -C 8 halodialkylamino, C 3 -C 8 cycloalkylamino, C 2 -C 8 alkylcarbonylamino, C 2 -C 8 haloalkylcarbonylamino, C ⁇ -Cg alkylsulfonylamino, C ⁇ -Cg haloalkylsulfonylamino or C 4 -C ⁇ o
  • R 2 are taken together with the atoms to which they are attached to form a 5-, 6- or 7-membered partially unsaturated or fully unsaturated ring along with ring members consisting of carbon atoms and up to 2 oxygen atoms, 2 nitrogen atoms and 2 sulfur atoms or up to two -S(O)-, -S(0) 2 - and -C(O)- groups, the ring optionally substituted on carbon atom ring members selected from halogen, cyano, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C j -Cg haloalkyl, C 3 -C 8 cycloalkyl and C 2 -C 8 alkoxyalkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, C j -Cg alkyl, C j -Cg alkoxy and
  • C ⁇ -Cg haloalkoxy the ring optionally substituted on nitrogen ring members seleced from H and C j -Cg alkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, C j -Cg alkyl, C j -Cg alkoxy and C j -Cg haloalkoxy;
  • W 1 is C j -Cg alkylene, C 2 -C 6 alkenylene, C 2 -C 6 alkynylene or C j ⁇ alkyleneoxy;
  • W 2 is C j -Cg alkylene or C j ⁇ alkyleneoxy
  • R 3 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 8
  • cycloalkylalkoxy C 2 -C 6 alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2 -C 6 alkynyloxy, C 3 -C 6 haloalkynyloxy, C 2 -C 8 alkoxyalkoxy, C 2 -C 8 alkylcarbonyloxy, C 2 -C 8 haloalkylcarbonyloxy, C 4 -C 10 cycloalkylcarbonyloxy, C 3 -C 10
  • alkylsulfonyl -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C j -Cg alkylsulfonyloxy, C j -Cg alkylamino, C 2 -C 8 dialkylamino, C j -Cg
  • haloalkylamino C 2 -C 8 halodialkylamino, C3-C 8 cycloalkylamino, C 2 -C 8 alkylcarbonylamino, C 2 -C 8 haloalkylcarbonylamino, C ⁇ -Cg alkylsulfonylamino or C ⁇ -Cg haloalkylsulfonylamino; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy, benzylsulfonyloxy, phenylthio, benzylthio, phenylsulfmyl, benzylsulfinyl, phenylsulfonyl or benzylsulfonyl, each optionally substituted on ring members with up to five substituents selected from R 21 ;
  • M + is an alkali metal cation or an ammonium cation
  • R 4 , R 5 , R 6 and R 7 are each independently H, halogen, hydroxy, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -Cg haloalkyl, C j -Cg alkoxy, C j -Cg haloalkoxy,
  • R 8 is H, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -Cg haloalkynyl, C3-C 8 cycloalkyl or C3-C 8 halocycloalkyl; or benzyl optionally substituted on ring members with up to five substituents selected from R 21 ;
  • R 9 is H, C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C r C 6 haloalkyl, C 2 -C 6
  • haloalkenyl C 2 -Cg haloalkynyl, C3-C 8 cycloalkyl, C3-C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 6 -C 14 cycloalkylcycloalkyl, C4-C10 halocycloalkylalkyl, C5-C ⁇ 2 alkylcycloalkylalkyl, C3-Cg cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10 alkoxyalkoxyalkyl or C 2 -C 8 alkylthioalkyl;
  • R 10 is H, halogen, cyano, hydroxy, amino, nitro, SH, -S0 2 NH 2 , -S0 2 NHCN,
  • R 1 1 is H, halogen, cyano, hydroxy, amino, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C j -Cg haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 4 -C 10 halocycloalkylalkyl, C5-C ⁇ 2 alkylcycloalkylalkyl, C3-C 8 cycloalkenyl, C3-C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C 4 -C 10 cycloalkoxyalkyl, C 3 -C 10
  • R 12 is H, halogen, cyano, hydroxy, amino, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C j -Cg haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 6 -C 14 cycloalkylcycloalkyl, C 4 -C ⁇ o halocycloalkylalkyl, C5-C ⁇ 2 alkylcycloalkylalkyl, C3"C 8 cycloalkenyl, C3-C 8 halocycloalkenyl or C 2 -C 8 alkoxycarbonylamino;
  • R 13 is H, halogen, cyano, hydroxy, amino, nitro or C 2 -C 8 alkoxycarbonyl
  • n 0, 1, or 2;
  • each R 14 , R 15 , R 18 and R 19 is independently H, halogen, cyano, hydroxy or C j -Cg alkyl; or
  • R 14 and R 18 is taken together as C 2 -Cg alkylene or C 2 -Cg alkenylene;
  • R 20 is H, C j -Cg haloalkyl, C 2 -C 6 haloalkenyl, C j -Cg alkoxy, C j -Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or C 3 -C 8 cycloalkyl; T is C j -Cg alkylene or C 2 -C 6 alkenylene; each G is independently a 5- or 6-membered heterocyclic ring or an 8-, 9- or
  • cycloalkylalkyl C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C 3 -C ⁇ Q alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -C 8 alkylsulfinylalkyl, C 2 -C 8 alkoxyhaloalkyl, C 2 -C5 cyanoalkyl, C j -Cg hydroxyalkyl, -Cg alkoxy, C j -Cg haloalkoxy, C 3 -C 8 cycloalkoxy, C 3 -C 8 halocycloalkoxy, C4-C10 cycloalkylalkoxy, C 2 -Cg alkenyloxy, C 2 -C 6 haloalkenyloxy, C 2
  • alkylcarbonyloxy C ⁇ -Cg alkylthio, C ⁇ -Cg haloalkylthio, C 3 -C 8 cycloalkylthio, C j -Cg alkylsulfinyl, -Cg haloalkylsulfinyl, -Cg alkylsulfonyl, -Cg haloalkylsulfonyl, C 3 -C 8 cycloalkylsulfonyl, C j -Cg alkylamino, C 2 -C 8 dialkylamino, C ⁇ -Cg haloalkylamino, C 2 -C 8 halodialkylamino or C 3 -C 8 cycloalkylamino; and
  • each R 22 is independently C j -Cg alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, -Cg
  • haloalkyl C 3 -C 8 cycloalkyl or C 2 -C 8 alkoxyalkyl.
  • this invention relates to a compound selected from Formula 1, an N-oxide, or a salt thereof.
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having,” “contains”, “containing,” “characterized by” or any other variation thereof, are intended to cover a non-exclusive inclusion, subject to any limitation explicitly indicated.
  • a composition, mixture, process or method that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, mixture, process or method.
  • a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • seedling used either alone or in a combination of words means a young plant developing from the embryo of a seed.
  • narrowleaf used either alone or in words such as “broadleaf weed” means dicot or dicotyledon, a term used to describe a group of angiosperms characterized by embryos having two cotyledons.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkylene denotes a straight-chain or branched alkanediyl.
  • alkylene examples include CH 2 , CH 2 CH 2 , CH(CH 3 ), CH 2 CH 2 CH 2 , CH 2 CH(CH 3 ) and the different butylene isomers.
  • alkenylene denotes a straight-chain or branched alkenediyl containing one olefmic bond.
  • Alkynylene denotes a straight-chain or branched alkynediyl containing one triple bond.
  • alkynylene examples include C ⁇ C, CH 2 C ⁇ C, C ⁇ CCH 2 and the different butynylene isomers.
  • alkyleneoxy dentotes a straight- chain or branched alkylen bonded through oxygen. Examples of alkyleneoxy include -CH 2 CH 2 0-, -CH(CH 3 )CH 2 0- and -CH 2 0- where the oxygen is bonded to the compound of Formula 1 , and the carbon is bonded to alkylene is bonded to the phenyl (i.e. when R 2 is W!Cphenyl)) or G (i.e. when R 2 is W 2 G).
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • Alkenyloxy includes straight-chain or branched alkenyloxy moieties.
  • Alkenyloxyalkyl denotes alkenyloxy substitution on alkyl.
  • Alkynyloxy includes straight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 0, CH 3 C ⁇ CCH 2 0 and CH 3 C ⁇ CCH 2 CH 2 0.
  • Alkynyloxyalkyl denotes alkynyloxy substitution on alkyl.
  • alkynyloxyalkyl examples include CH 3 C ⁇ CCH 2 OCH 2 and CH 3 C ⁇ CCH 2 CH 2 OCH 2 .
  • Alkoxyalkoxyalkyl denotes alkoxyalkoxy substitution on alkyl. Examples of “alkoxyalkoxyalkyl” include CH 3 OCH 2 OCH 2 , CH 3 OCH 2 OCH 2 CH 2 , CH 3 CH 2 OCH 2 OCH 2 and
  • alkoxyalkoxyalkoxyalkyl denotes alkoxyalkoxyalkoxy substitution on alkyl. Examples of “alkoxyalkoxyalkoxyalkyl” include
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfmyl includes both enantiomers of an alkylsulfmyl group.
  • alkylsulfmyl examples include CH 3 S(0)-, CH 3 CH 2 S(0)-, CH 3 CH 2 CH 2 S(0)-, (CH 3 ) 2 CHS(0)- and the different butylsulfmyl, pentylsulfmyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(0) 2 -, CH 3 CH 2 S(0) 2 -, CH 3 CH 2 CH 2 S(0) 2 -, (CH 3 ) 2 CHS(0) 2 -, and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • cycloalkylsulfinyl and “cycloalkylsulfonyl are defined analogously to the terms “alkylsulfmyl” and "alkylsulfonyl” above.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl.
  • alkylthioalkyl include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 ;
  • alkylsulfmylalkyl and “alkylsulfonylalkyl” include the corresponding sulfoxides and sulfones, respectively.
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy. Examples of “alkylthioalkoxy” include CH 3 SCH 2 CH 2 0 and CH 3 CH 2 SCH 2 0.
  • Alkylamino includes an NH radical substituted with straight-chain or branched alkyl
  • alkylamino examples include CH 3 CH 2 NH, CH 3 CH 2 CH 2 NH, and (CH 3 ) 2 CHCH 2 NH.
  • dialkylamino examples include (CH 3 ) 2 N, (CH 3 CH 2 CH 2 ) 2 N and CH 3 CH 2 (CH 3 )N.
  • Alkylaminoalkyl denotes alkylamino substitution on alkyl.
  • alkylaminoalkyl examples include CH 3 NHCH 2 , CH 3 NHCH 2 CH 2 , CH 3 CH 2 NHCH 2 , CH 3 CH 2 CH 2 CH 2 NHCH 2 and CH 3 CH 2 NHCH 2 CH 2 .
  • dialkylaminoalkyl examples include ((CH 3 ) 2 CH) 2 NCH 2 , (CH 3 CH 2 CH 2 ) 2 NCH 2 and CH 3 CH 2 (CH 3 )NCH 2 CH 2 .
  • Alkylcarbonylthio denotes a straight-chain or branched alkylcarbonyl attached to and linked through a sulfur atom.
  • alkyl(thiocarbonyl)oxy denotes an alkyl group bonded to a thiocarbonyl moiety attached to and linked through an oxygen atom.
  • alkyl(thiocarbonyl)thio refers to an alkyl group bonded to a thiocarbonyl moiety attached to and linked through a sulfur atom.
  • Trialkylsilyl includes 3 branched and/or straight-chain alkyl radicals attached to and linked through a silicon atom, such as trimethylsilyl, triethylsilyl and tert-butyldimethylsilyl.
  • Examples of “halotrialkylsilyl” include CF 3 (CH 3 ) 2 Si-, (CF 3 ) 3 Si-, and CH 2 Cl(CH 3 ) 2 Si-.
  • “Hydroxyalkyl” denotes an alkyl group substituted with one hydroxy group. Examples of “hydroxyalkyl” include HOCH 2 CH 2 , CH 3 CH 2 (OH)CH and HOCH 2 CH 2 CH 2 CH 2 .
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 . “Cyanoalkoxy” denotes an alkoxy group substituted by one cyano group. Examples of “cyanoalkoxy” include NCCH 2 CH 2 0 and CH 3 CH(CN)CH 2 0.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • cycloalkylalkyl denotes cycloalkyl substitution on an alkyl moiety. Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • cycloalkoxy denotes cycloalkyl linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety.
  • alkylcycloalkyl include methylcyclopropyl, ethylcyclopentyl and other straight-chain or branched alkyl groups bonded to cycloalkyl moiety.
  • Cycloalkylalkoxy denotes cycloalkylalkyl linked through an oxygen atom attached to the alkyl chain.
  • Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
  • halogen either alone or in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, or when used in descriptions such as “alkyl substituted with halogen” said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” or “alkyl substituted with halogen” include F 3 C-, C1CH 2 -, CF 3 CH 2 - and CF 3 CC1 2 -.
  • haloalkylcarbonyloxy is defined analogously to the term “haloalkyl”.
  • haloalkoxy includes CF 3 0-, CC1 3 CH 2 0-, HCF 2 CH 2 CH 2 0- and CF 3 CH 2 0-.
  • haloalkylthio include CC1 3 S-, CF 3 S-, CC1 3 CH 2 S- and C1CH 2 CH 2 CH 2 S-.
  • haloalkylsulfmyl include CF 3 S(0)-, CC1 3 S(0)-, CF 3 CH 2 S(0)- and CF 3 CF 2 S(0)-.
  • haloalkylsulfonyl examples include CF 3 S(0) 2 -, CC1 3 S(0) 2 -, CF 3 CH 2 S(0) 2 - and CF 3 CF 2 S(0) 2 -.
  • haloalkylsulfonylamino examples include CF 3 S(0) 2 N, and CF 3 CH 2 S(0) 2 N.
  • haloalkynyl examples include HC ⁇ CCHC1-, CF 3 C ⁇ C-, CC1 3 C ⁇ C- and FCH 2 C ⁇ CCH 2 -.
  • haloalkoxyalkoxy examples include CF 3 OCH 2 0-, C1CH 2 CH 2 0CH 2 CH 2 0-, Cl 3 CCH 2 OCH 2 0- as well as branched alkyl derivatives.
  • haloalkylamino examples include CF 3 (CH 3 )CHNH, (CF 3 ) 2 CHNH and CH 2 C1CH 2 NH.
  • halodialkyl either alone or in compound words such as “halodialkylamino" means at least one of the two alkyl groups is substituted with at least one halogen atom, and independently each halogenated alkyl group may be partially or fully substituted with halogen atoms which may be the same or different.
  • halodialkylamino examples include (BrCH 2 CH 2 ) 2 N and
  • alkoxycarbonylalkyl denotes alkoxycarbonyl substitution of alkyl.
  • alkoxycarbonylalkoxy denotes alkoxycarbonyl substitution of alkoxy.
  • haloalkylcarbonyl haloalkoxycarbonyl
  • alkoxyalkylcarbonyl alkoxyalkylcarbonyl
  • cycloalkoxycarbonyl cycloalkylalkoxycarbonyl
  • cycloalkylaminocarbonyl are defined analogously.
  • alkylcarbonylalkoxy denotes alkylcarbonyl bonded to an alkoxy moiety.
  • cycloalkylcarbonyloxy denotes a cycloalkylcarbonyl group bonded to oxygen.
  • Examples of “cycloalkylcarbonyloxy” include cyclopropyl- C(0)0- and cyclohexyl-C(0)0-.
  • Alkylsulfonylamino denotes an NH radical substituted with alkylsulfonyl.
  • alkylsulfonyloxy denotes an alkylsulfonyl group bonded to an oxygen atom.
  • cycloalkoxyalkyl denotes cycloalkoxy substitution on an alkyl moiety.
  • examples of “cycloalkoxyalkyl” include cyclopropyloxymethyl, cyclopentyloxyethyl and other cycloalkoxy moieties bonded to straight-chain or branched alkyl groups.
  • cycloalkylthio denotes cycloalkyl attached to and linked through a sulfur atom such as cyclopropylthio and cyclopentylthio;
  • cycloalkylsulfonyl includes the corresponding sulfones.
  • Alkylcycloalkylalkyl denotes an alkyl group substituted with alkylcycloalkyl.
  • alkylcycloalkylalkyl include 1-, 2-, 3- or 4-methyl or -ethyl cyclohexylmethyl.
  • cycloalkylcycloalkyl denotes cycloalkyl substitution on another cycloalkyl ring, wherein each cycloalkyl ring independently has from 3 to 7 carbon atom ring members.
  • cycloalkylcycloalkyl examples include cyclopropylcyclopropyl (such as ⁇ , ⁇ -bicyclopropyl-l-yl, 1 , l'-bicyclopropyl-2-yl), cyclohexylcyclopentyl (such as 4-cyclopentylcyclohexyl) and cyclohexylcyclohexyl (such as ⁇ , ⁇ -bicyclohexyl-l-yl), and the different cis- and trans-cycloalkylcycloalkyl isomers, (such as (lR,2S)-l,l'-bicyclopropyl- 2-yl and (li?,2i?)-l,l'-bicyclopropyl-2-yl).
  • cyclopropylcyclopropyl such as ⁇ , ⁇ -bicyclopropyl-l-yl, 1 , l'-bicyclopropyl-2-yl
  • Dialkoxyalkyl denotes two independent alkoxy groups substituted on same carbon of the alkyl group. Examples of “dialkoxyalkyl” include (CH 3 0) 2 CH- and CH 3 CH 2 0(CH 3 0)CH-.
  • Cycloalkylammo denotes an NH radical substituted with cycloalkyl. Examples of “cycloalkylammo” include cyclopropylamino and cyclohexylamino.
  • Cycloalkyl(alkyl)amino means a cycloalkylammo group where the hydrogen atom is replaced by an alkyl radical.
  • cycloalkyl(alkyl)amino examples include groups such as cyclopropyl(methyl)amino, cyclobutyl(butyl)amino, cyclopentyl(propyl)amino, cyclohexyl(methyl)amino and the like.
  • cycloalkylaminoalkyl denotes cycloalkylammo substitution on an alkyl group.
  • Examples of “cycloalkylaminoalkyl” include cyclopropylaminomethyl, cyclopentylaminoethyl, and other cycloalkylammo moieties bonded to straight-chain or branched alkyl groups.
  • Examples of “cycloalkylalkoxycarbonyl” include cyclopropylethoxycarbonyl and cyclopentylmethoxycarbonyl.
  • Cycloalkylcarbonyloxy denotes cycloalkylcarbonyl attached to and linked through an oxygen atom. Examples of “cycloalkylcarbonyloxy” include cyclohexylcarbonyloxy and cyclopentylcarbonyloxy.
  • cycloalkenylalkyl denotes cycloalkenyl substitution on an alkyl moiety.
  • cycloalkenylalkyl examples include cyclobutenylmethyl, cyclopentenylethyl, and other cycloalkenyl moieties bonded to straight-chain or branched alkyl groups.
  • cycloalkenyloxy denotes cycloalkenyl linked through an oxygen atom such as cyclopentenyloxy and cyclohexenyloxy.
  • cycloalkenyloxyalkyl denotes cycloalkenyloxy substitution on an alkyl moiety.
  • cycloalkenyloxyalkyl examples include cyclobutenyloxymethyl, cyclopentenyloxyethyl, and other cycloalkenyloxy moieties bonded to straight-chain or branched alkyl groups.
  • alkylaminosulfonyl denotes a straight-chain or branched alkylamino moiety bonded to a sulfonyl group.
  • alkylaminosulfonyl examples include CH 3 NHS(0) 2 - or CH 3 CH 2 CH 2 NHS(0) 2 -.
  • dialkylaminosulfonyl denotes a straight-chain or branched dialkylamino moiety bonded to a sulfonyl group.
  • Examples of a “dialkylaminosulfonyl” group include (CH 3 ) 2 NS(0) 2 - or (CH 3 CH 2 CH 2 ) 2 NS(0) 2 -.
  • C1-C4 alkylsulfonyl designates methylsulfonyl through butylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2 -
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 )-, CH 3 OCH 2 CH 2 - or CH 3 CH 2 OCH 2 -
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 - and CH 3 CH 2 OCH 2 CH 2 -.
  • said substituents are independently selected from the group of defined substituents, e.g., (R v ) r , r is 1, 2, 3, 4 or 5 in U-l of Exhibit 2.
  • a group contains a substituent which can be hydrogen, for example R 2 , R 3 , R 3A , R 4 , R 5 , R 6 , R?, R 8 , Hi*, RlO, R11, Rl2 ? R13 ? R 14 R15 ? R18 ? R19 or R 20 ?
  • a "ring” or “ring system” as a component of Formula 1 is carbocyclic or heterocyclic.
  • the term “ring system” denotes two or more fused rings.
  • the terms “bicyclic ring system” and “fused bicyclic ring system” denote a ring system consisting of two fused rings, in which either ring can be saturated, partially unsaturated or fully unsaturated unless otherwise indicated.
  • carbocyclic ring denotes a ring or ring system wherein the atoms forming the ring backbone are selected only from carbon.
  • a carbocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring.
  • saturated carbocyclic refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
  • heterocyclic ring denotes a ring or ring system in which at least one atom forming the ring backbone is not carbon, e.g., nitrogen, oxygen or sulfur.
  • a heterocyclic ring contains no more than 4 nitrogen atoms, no more than 2 oxygen atoms and no more than 2 sulfur atoms.
  • a heterocyclic ring can be a saturated, partially unsaturated or fully unsaturated ring. When a fully unsaturated heterocyclic ring satisfies Huckel's rule, then said ring is also called a “heteroaromatic ring” or “aromatic heterocyclic ring”.
  • heterocyclic rings and ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • Aromatic indicates that each of the ring atoms is essentially in the same plane and has a / ⁇ -orbital perpendicular to the ring plane, and that (4n + 2) ⁇ electrons, where n is a positive integer, are associated with the ring to comply with Huckel's rule.
  • aromatic ring system denotes a carbocyclic or heterocyclic ring system in which at least one ring of the ring system is aromatic. As used herein, the following definitions shall apply unless otherwise indicated.
  • the term “optionally substituted” is used interchangeably with the phrase “substituted or unsubstituted”. Unless otherwise indicated, an optionally substituted group may have a substituent at each substitutable position of the group, and each substitution is independent of the other.
  • G may be attached to the remainder of Formula 1 through any available carbon or nitrogen ring atom, unless otherwise described.
  • the ring or ring system of G may be saturated, partially saturated or fully unsaturated and is optionally substituted with up to 5 substituents selected from a group of substituents as defined in the Summary of the Invention.
  • Examples of a 5- or 6-membered unsaturated aromatic heterocyclic ring optionally substituted with from up to 5 substituents include the rings Q-l through Q-60 illustrated in Exhibit 1 wherein R v is any substituent as defined in the Summary of the Invention for R 21 on carbon ring members or R 22 on nitrogen ring members, and r is an integer from 0 to 5, limited by the number of available positions on each Q group.
  • Q-29, Q-30, Q-36, Q-37, Q-38, Q-39, Q-40, Q-41, Q-42 and Q-43 have only one available position, for these Q groups r is limited to the integers 0 or 1, and r being 0 means that the Q group is unsubstituted and a hydrogen is present at the position indicated by (R v ) r .
  • G is an optionally substituted 5- or 6-membered non-aromatic heterocyclic ring
  • one or two carbon ring members of the heterocycle can optionally be in the oxidized form of a carbonyl moiety.
  • Examples of a 5- or 6-membered non-aromatic heterocyclic ring include the rings U-l through U-36 as illustrated in Exhibit 2. Note that when the attachment point on the U group is illustrated as floating, the U group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the U group by replacement of a hydrogen atom. The optional substituents corresponding to R v can be attached to any available carbon or nitrogen by replacing a hydrogen atom.
  • r is an integer from 0 to 5, more typically 0 to 4, limited by the number of available positions on each U group.
  • G comprises a ring selected from U-29 through U-36
  • U 2 is selected from O, S or N.
  • the nitrogen atom can complete its valence by substitution with either H or the substituents corresponding to R v as defined in the Summary of the Invention for U (i.e. R 21 or R 22 ).
  • G can be (among others) an 8-, 9- or 10-membered fused bicyclic ring system optionally substituted with one or more substituents selected from a group of substituents as defined in the Summary of the Invention (i.e. R 21 or R 22 ).
  • Examples of an 8-, 9- or 10-membered fused bicyclic ring system optionally substituted with from one or more substituents include the rings Q-81 through Q-123 illustrated in Exhibit 3 wherein R v is any substituent as defined in the Summary of the Invention for G (i.e. R 21 or R 22 ), and r is an integer from 0 to 5, more typically 0 to 4.
  • R v groups are shown in the structures Q-1 through Q-60 and Q-81 through Q-123, it is noted that they do not need to be present since they are optional substituents.
  • the nitrogen atoms that require substitution to fill their valence are substituted with H or R v .
  • (R v ) r can be attached to any available carbon atom or nitrogen atom of the Q group.
  • the Q group can be attached to the remainder of Formula 1 through any available carbon or nitrogen of the Q group by replacement of a hydrogen atom.
  • some Q groups can only be substituted with less than 4 R v groups (e.g., Q-1 through Q-5, Q-7 through Q-48, and Q-52 through Q-60).
  • R 1 and R 2 may also be taken together along with the atoms to which they are attached to form a 5-, 6- or 7-membered partially unsaturated or fully unsaturated ring fused to the pyridazinone ring.
  • the fused ring includes as ring members the two atoms shared with the pyridazinone ring to which the R 1 and R 2 substituents are attached.
  • the other 3, 4 or 5 ring members of the fused ring are provided by the R 1 and R 2 substituents taken together.
  • the fused ring is optionally substituted on carbon atom ring members and on nitrogen atom ring members with groups as defined in the Summary of the Invention. Typically the total number of said substituents selected does not exceed 3.
  • Exhibit 4 provides, as illustrative examples, fused rings formed by R 1 and R 2 taken together. As these rings are fused with the pyridazinone ring of Formula 1, a portion of the pyridazinone ring is shown and the truncated lines represent the ring bonds of the pyridazinone ring. The rings depicted are fused to the two adjacent carbon atoms of the pyridazinone ring.
  • the optional substituents (R v ) r on carbon atom ring members e.g.
  • halogen, cyano, i ⁇ C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci ⁇ C 6 haloalkyl, C 3 -C 8 cycloalkyl and C 2 -C 8 alkoxyalkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 alkoxy and i ⁇ C 6 haloalkoxy) and on nitrogen atom ring members (H and Ci-C ⁇ alkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 alkoxy and Ci-C ⁇ haloalkoxy) are selected from groups as defined in the Summary of the Invention.
  • Substituents are limited by the number of available positions on each T-ring. When the attachment point between (R v ) r and the T-ring is illustrated as floating, R v may be bonded to any available T-ring carbon or nitrogen atom.
  • R v may be bonded to any available T-ring carbon or nitrogen atom.
  • r is nominally an integer from 0 to 3
  • some of the rings shown in Exhibit 4 have less than 3 available positions, and for these groups r is limited to the number of available positions.
  • “r" is 0 this means the ring is unsubstituted and hydrogen atoms are present at all available positions. If r is 0 and (R v ) r is shown attached to a particular atom, then hydrogen is attached to that atom.
  • Compounds 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). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers or as an optically active form.
  • a compound of Formula 1 when a compound of Formula 1 is identified by A being A-1, A-2 or A-3, and the R 3A variable being -SH, then said compound of Formula 1 can exist as a "di-keto thioketo" tautomer, a "di-keto thioenol” tautomer or a "keto thioketo enol” tautomer, or a combination thereof.
  • acyclic enols e.g., the fragment A-7 in the definition of the variable A
  • tautomers represent functionally equivalent species, and identification of a compound by one tautomer is to be considered reference to all possible tautomers of the compound unless otherwise indicated.
  • Non-crystalline forms include embodiments which are solids such as waxes and gums as well as embodiments which are liquids such as solutions and melts.
  • Crystalline forms include embodiments which represent essentially a single crystal type and embodiments which represent a mixture of polymorphs (i.e. different crystalline types).
  • polymorph refers to a particular crystalline form of a chemical compound that can crystallize in different crystalline forms, these forms having different arrangements and/or conformations of the molecules in the crystal lattice.
  • polymorphs can have the same chemical composition, they can also differ in composition due the presence or absence of co- crystallized water or other molecules, which can be weakly or strongly bound in the lattice. Polymorphs can differ in such chemical, physical and biological properties as crystal shape, density, hardness, color, chemical stability, melting point, hygroscopicity, suspensibility, dissolution rate and biological availability.
  • a polymorph of a compound of Formula 1 can exhibit beneficial effects (e.g., suitability for preparation of useful formulations, improved biological performance) relative to another polymorph or a mixture of polymorphs of the same compound of Formula 1.
  • Preparation and isolation of a particular polymorph of a compound of Formula 1 can be achieved by methods known to those skilled in the art including, for example, crystallization using selected solvents and temperatures.
  • nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides.
  • nitrogen-containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as tert-bvXy ⁇ hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as tert-bvXy ⁇ hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • salts of chemical compounds are in equilibrium with their corresponding nonsalt forms, salts share the biological utility of the nonsalt forms.
  • the salts of a compound of Formula 1 include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • salts also include those formed with organic or inorganic bases such as pyridine, triethylamine or ammonia, or amides, hydrides, hydroxides or carbonates of sodium, potassium, lithium, calcium, magnesium or barium. Accordingly, the present invention comprises compounds selected from Formula 1, N-oxides and agriculturally suitable salts thereof.
  • Embodiments of the present invention as described in the Summary of the Invention include (where Formula 1 as used in the following Embodiments includes N-oxides and salts thereof):
  • Embodiment 1 A compound of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides as described in the Summary of the Invention.
  • Embodiment 2 A compound of Embodiment 1 wherein A is A-l, A-3, A-5 or A-6.
  • Embodiment 3 A compound of Embodiment 2 wherein A is A-l, A-3 or A-5.
  • Embodiment 4 A compound of Embodiment 3 wherein A is A-l or A-3.
  • Embodiment 5 A compound of Embodiment 4 wherein A is A-l .
  • Embodiment 6 A compound of Embodiment 4 wherein A is A-3.
  • Embodiment 7 A compound of any one of Embodiments 1 through 5 wherein A is other than A-l .
  • Embodiment 8 A compound of any one of Embodiments 1 through 7 wherein B 1 is C-l .
  • Embodiment 9 A compound of any one of Embodiments 1 through 7 wherein B 1 is
  • Embodiment 10 A compound of any one of Embodiments 1 through 9 wherein B 2 is C-3.
  • Embodiment 1 1.
  • Embodiment 12 A compound of any one of Embodiments 1 through 1 1 wherein B 3 is C-l .
  • Embodiment 13 A compound of any one of Embodiments 1 through 1 1 wherein B 3 is
  • Embodiment 14 A compound of any one of Embodiments 1 through 13 wherein R 1 is halogen, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Ci ⁇ C 6 alkoxy, i ⁇ C 6 haloalkoxy, C 2 -C 6 alkenyloxy, C 3 -C 8 haloalkenyloxy, C3-C7 alkynyloxy, C 2 -C 6 alkoxyalkoxy, C 2 -C 6 cyanoalkoxy, C 2 -C 6 alkylthioalkoxy, i ⁇ C 6 alkylthio, i ⁇ C 6 alkylsulfinyl, Ci - C 6 alkylsulfonyl, Ci ⁇ C 6 haloalkylthio, i
  • Embodiment 15 A compound of Embodiment 14 wherein R 1 is halogen, i-C ⁇ alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, i-C ⁇ alkoxy, Ci-C ⁇ haloalkoxy or C 2 -C6 alkenyloxy.
  • R 1 is halogen, i-C ⁇ alkyl, Ci-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, i-C ⁇ alkoxy, Ci-C ⁇ haloalkoxy or C 2 -C6 alkenyloxy.
  • Embodiment 16 A compound of Embodiment 15 wherein R 1 is halogen, i-C ⁇ alkyl, C ⁇ -C6 haloalkyl, i-C ⁇ alkoxy or i-C ⁇ haloalkoxy.
  • Embodiment 17 A compound of Embodiment 16 wherein R 1 is chloro, methyl,
  • Embodiment 18 A compound of Embodiment 17 wherein R 1 is methyl.
  • Embodiment 18 A A compound of Embodiment 17 wherein R 1 is choro or methyl.
  • Embodiment 19 A compound of any one of Embodiments 1 through 14 wherein each R A is independently Ci -C4 alkyl.
  • Embodiment 20 A compound of any one of Embodiments 1 through 14 wherein each
  • R B is independently C 1 -C4 alkyl.
  • Embodiment 21 A compound of any one of Embodiments 1 through 14 wherein R A and R B are taken together with the nitrogen atom to which they are both attached to form a 6-membered ring including ring members selected from -CH 2 - and -0-.
  • Embodiment 22 A compound of Embodiment 21 wherein R A and R B are taken
  • a 6- membered ring including ring members selected from 4 -CH 2 - and 1 -O- (i.e. a morpholine moiety).
  • Embodiment 23 A compound of Embodiment 21 wherein R A and R B are taken
  • a 6- membered ring including ring members selected from 5 -CH 2 - (i.e. a piperidine ring).
  • Embodiment 24 A compound of any one of Embodiments 1 through 14 wherein R c is C 1 -C4 alkyl.
  • Embodiment 25 A compound of any one of Embodiments 1 through 14 wherein R D is Ci alkylene (i.e. -CH 2 -).
  • cycloalkylalkyl C 6 -C 14 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C 5 -C 12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -Cg alkoxyalkyl, C3-C10 alkoxyalkenyl, C 4 -C ⁇ o cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -C6 alkylthioalkoxy, C 2 -C 8 alkylsulfinylalkyl, C 2 -C 8 alkylsulfonylalkyl, C 2 -Cg alkylaminoalkyl, C3-C10 dialkylaminoalkyl, C 2 -Cg
  • dialkylaminocarbonyl C 4 -C ⁇ o cycloalkylaminocarbonyl, C 2 -C5 cyanoalkyl, Ci-Cfr hydroxyalkyl, C 4 -C 10 cycloalkenylalkyl, C 2 -C 8 haloalkoxyalkyl, C 2 -C 8 alkoxyhaloalkyl, C 2 -C 8 haloalkoxyhaloalkyl, C 4 -C ⁇ o halocycloalkoxyalkyl, C 4 -C 10 cycloalkenyloxyalkyl, C 4 -C 10 halocycloalkenyloxyalkyl, C 3 -C 10 dialkoxyalkyl, C3-C10 alkoxyalkylcarbonyl, C3-C10 alkoxycarbonylalkyl, C 2 -C 8 haloalkoxycarbonyl, i-C ⁇ alkoxy, Ci-C ⁇ haloalkoxy, C
  • Embodiment 27 A compound of Embodiment 26 wherein R 2 is phenyl or
  • -W 1 phenyl
  • phenyl each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G or -W 2 G; or Ci-C 6 alkyl, Ci ⁇ C 6 haloalkyl, C3"C 8 cycloalkyl, C 2 -C 8 alkoxyalkyl, i-C ⁇ alkoxy, i-C ⁇ haloalkoxy or C 2 -C 8 alkoxyalkoxy.
  • Embodiment 28 A compound of Embodiment 27 wherein R 2 is phenyl optionally substituted with up to five substituents selected from R 21 ; or Ci-C 6 alkyl, Ci ⁇ C 6 haloalkyl, C3-C 8 cycloalkyl, C 2 -C 8 alkoxyalkyl, i-C ⁇ alkoxy, i-C ⁇
  • Embodiment 28A A compound of Embodiment 27 wherein R 2 is Ci-C ⁇ alkyl, C3-C 8 cycloalkyl or i-C ⁇ haloalkoxy.
  • Embodiment 28B A compound of Embodiment 28A wherein R 2 is n-propyl, c-hexyl or -OCH 2 CH 2 CF 3 .
  • Embodiment 28C A compound of Embodiment 28B wherein R 2 is c-hexyl.
  • Embodiment 29 A compound of Embodiment 28 wherein R 2 is phenyl; or i-C ⁇ alkyl.
  • Embodiment 30 A compound of Embodiment 29 wherein R 2 is phenyl; or n-propyl.
  • Embodiment 31 A compound of any one of Embodiments 1 through 13 wherein R 1 and R 2 are taken together with the atoms to which they are attached to form a 6-membered partially unsaturated ring along with ring members consisting of carbon atoms and up to 2 oxygen atoms, 2 sulfur atoms or up to two -S(0) 2 - groups, the ring optionally substituted on carbon atom ring members selected from halogen, cyano, i ⁇ C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci ⁇ C 6 haloalkyl, C 3 -Cg cycloalkyl and C 2 -C ⁇ alkoxyalkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, Ci ⁇ C 6 alkyl
  • Embodiment 32 A compound of Embodiment 31 wherein R 1 and R 2 are taken
  • Ci-Cft alkyl Ci-Cft alkyl
  • Embodiment 33 A compound of Embodiment 32 wherein R 1 and R 2 are taken
  • Embodiment 35 A compound of Embodiment 34 wherein W 1 is -CH 2 -.
  • Embodiment 36 A compound of any one of Embodiments 1 through 33 wherein W 2 is
  • Embodiment 37 A compound of any one of Embodiments 1 through 36 wherin R 3 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 8 cycloalkyl, C 4 -C 10 cycloalkylalkyl, C 3 -C 8 halocycloalkyl, C j -C 4 cyanoalkyl, C 2 -C6 alkoxyalkyl or C 3 -C6 alkoxy carbonylalkyl.
  • Embodiment 38 A compound of Embodiment 37 wherein R 3 is H, C j -C 4 alkyl, C j -C 4 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 10 cycloalkylalkyl or C 3 -C 6
  • Embodiment 39 A compound of Embodiment 38 wherein R 3 is C 1 -C4 alkyl or C3-Cg cycloalkyl.
  • Embodiment 40 A compound of Embodiment 39 wherein R 3 is methyl or
  • Embodiment 41 A compound of Embodiment 40 wherein R 3 is methyl.
  • Embodiment 42 A compound of any one of Embodiments 1 through 41 wherein R 3A is H, hydroxy, -O M + , C 2 -C 8 alkylcarbonyloxy, C 2 -C 8 haloalkylcarbonyloxy, C4-C10 cycloalkylcarbonyloxy or C3-C10 alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R 21 .
  • Embodiment 43 A compound of Embodiment 42 wherein R 3A is hydroxy, -O M + or C 2 -C 8 alkylcarbonyloxy; or phenylsulfonyloxy optionally substituted with up to two substituents selected from R 21 .
  • Embodiment 44 A compound of Embodiment 43 wherein R 3A is hydroxy or C 2 -Cg alkylcarbonyloxy.
  • Embodiment 45 A compound of Embodiment 44 wherein R 3A is hydroxy or
  • Embodiment 46 A compound of Embodiment 43 wherein M + is a sodium or
  • Embodiment 47 A compound of any one of Embodiments 1 , 2, 3, 7 and 14 through 46 wherein R 9 is Ci-C ⁇ alkyl.
  • Embodiment 48 A compound of Embodiment 47 wherein R 9 is ethyl.
  • Embodiment 49 A compound of any one of Embodiments 1 , 2, 3 7 and 14 through 48 wherein R 10 is H, halogen or i-C ⁇ alkyl.
  • Embodiment 50 A compound of Embodiment 49 wherein R 10 is H or methyl.
  • Embodiment 51 A compound of Embodiment 50 wherein R 10 is methyl.
  • Embodiment 52 A compound any one of Embodiments 1 , 2 and 14 through 46
  • R 1 1 is H or i-C ⁇ alkyl.
  • Embodiment 53 A compound of any one of Embodiments 1 through 52 wherein when instances of R 14 and R 18 are taken alone (i.e. R 14 and R 18 are not taken together as alkylene or alkenylene), then independently said instances of R 14 and R 18 are
  • Embodiment 54 A compound of Embodiment 53 wherein when instances of R 14 and R 18 are taken alone, then independently said instances of each R 14 and R 18 are H or methyl.
  • Embodiment 55 A compound of Embodiment 54 wherein when instances of R 14 and R 18 are taken alone, then independently said instances of R 14 and R 18 are H.
  • Embodiment 57 A compound of any one of Embodiments 1 through 55 wherein all instances of R 14 and R 18 are taken alone.
  • Embodiment 58 A compound of any one of Embodiments 1 through 55 wherein
  • each R 15 and R 19 is H or i-C ⁇ alkyl.
  • Embodiment 59 A compound of Embodiment 58 wherein independently each R 15 and
  • R 19 is H or methyl.
  • Embodiment 60 A compound of Embodiment 59 wherein independently each R 15 and
  • R 19 is H.
  • Embodiment 61 A compound of Embodiment 57 and 59 wherein each R 14 , R 15 , R 18 and R 19 is H or methyl.
  • Embodiment 62 A compound of Embodiment 61 wherein each R 14 , R 15 , R 18 and R 19 is H.
  • Embodiment 63 A compound of any one of Embodiments 1 through 62 wherein R 20 is H, Ci-Cfr alkyl, C 2 -C 6 alkenyl or C 3 -C 8 cycloalkyl.
  • Embodiment 64 A compound of Embodiment 63 wherein R 20 is H or CH 3 .
  • Embodiment 66 A compound of Embodiment 65 wherein T is -CH 2 CH 2 -.
  • Embodiment 67 A compound of any one of Embodiments 1 through 27 and 31
  • each G is independently a 5- or 6-membered heterocyclic ring optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members.
  • Embodiment 68 A compound of Embodiment 67 wherein G is
  • G-21 r is 0, 1, 2 or 3.
  • Embodiment 69 A compound of Embodiment 68 wherein G is G-2, G-3, G-9 or G-15.
  • Embodiment 70 A compound of Embodiment 69 wherein G is G-2, G-3 or G-15.
  • Embodiment 71 A compound of Embodiment 70 wherein G is G-2 or G-3.
  • Embodiment 72 A compound of Embodiment 71 wherein G is G-2.
  • Embodiment 73 A compound of Embodiment 70 wherein G is G-3.
  • Embodiment 73 A compound of Embodiment 68 wherein G is G-21.
  • Embodiment 73B A compound of Embodiment 68 wherein G is other than G-21.
  • Embodiment 74 A compound of any one of Embodiments 68 through 73 wherein r is 0, 1 or 2.
  • Embodiment 75 A compound Embodiment 74 wherein r is 0 or 1.
  • Embodiment 76 A compound any one of Embodiments 1 through 75 wherein each R 21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, Ci-C ⁇ , alkyl, C2-C6 alkenyl, C2-C6 alkynyl, Ci-C ⁇ , haloalkyl, C2-C6 haloalkenyl, C2-C6 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C4-C10 alkylcycloalkyl, C4-C10 cycloalkylalkyl, C3-C8 cycloalkenyl, C3-C8 halocycloalkenyl, C2-Cg alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg al
  • alkylcarbonyloxy C ⁇ -C6 alkylthio, C ⁇ -C6 haloalkylthio, C3-Cg cycloalkylthio, Ci-Cfr alkylsulfmyl, Ci ⁇ C 6 haloalkylsulfinyl, Ci ⁇ C 6 alkylsulfonyl, Ci ⁇ C 6 haloalkylsulfonyl or C3-Cg cycloalkylsulfonyl.
  • Embodiment 77 A compound of Embodiment 76 wherein each R 21 is independently halogen, nitro, i ⁇ C 6 alkyl, Ci ⁇ C 6 haloalkyl, Ci ⁇ C 6 alkoxy, i ⁇ C 6 haloalkoxy or C r C 6 alkylthio.
  • Embodiment 78 A compound of Embodiment 77 wherein each R 21 is independently fluorine, chlorine, bromine, methyl, trifluoromethyl, methoxy, trifluoromethoxy or thiomethoxy.
  • Embodiment 79 A compound of Embodiments 1 through 78 wherein each R 22 is
  • Embodiment 80 A compound of Embodiment 79 wherein each R 22 is independently methyl or -CH 2 CF 3 .
  • Embodiments of the present invention as described in the Summary of the Invention and any of Embodiments 1 through 80 can be combinded in any way, and the descriptions of variables in the embodiments pertain not only to the compounds of Formula 1 but also to the starting compounds and intermediate compounds useful for preparing the compounds of Formula 1. Combined Embodiments from above can be illustrated as:
  • Embodiment A A compound of Formula 1 (including all stereoisomers), N-oxides, and salts thereof, agricultural compositions containing them and their use as herbicides as described in the Summary of the Invention wherein
  • A is A-l , A-3, A-5 or A-6;
  • R 1 is halogen, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Ci ⁇ C 6 alkoxy, i ⁇ C 6 haloalkoxy, C 2 -C 6 alkenyloxy, C3-Cg haloalkenyloxy, C3-C7 alkynyloxy, C 2 -C6 alkoxyalkoxy, C 2 -C6 cyanoalkoxy, C 2 -C6 alkylthioalkoxy, Ci-C ⁇ alkylthio, Ci-C ⁇ alkylthio, Ci-C ⁇ alkylsulfmyl,
  • Ci-Cfr alkylsulfonyl Ci ⁇ C 6 haloalkylthio, i ⁇ C 6 haloalkylsulfinyl, Ci ⁇ C 6 haloalkylsulfonyl, (R A )(R B )N-, (R A )(R B )NS0 2 -, R c S0 2 N(R D )-, nitro or cyano; each R A is independently -C4 alkyl;
  • each R B is independently Ci -C4 alkyl
  • R A and R B are taken together with the nitrogen atom to which they are both attached to form a 6-membered ring including ring members selected from -CH 2 - and -0-;
  • RC is C r C 4 alkyl
  • R D is Ci alkylene
  • cycloalkylalkyl C 6 -C 14 cycloalkylcycloalkyl, C 4 -C 10 halocycloalkylalkyl, C5-C12 alkylcycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C2-Cg alkoxyalkyl, C3-C10 alkoxyalkenyl, C 4 -C ⁇ o cycloalkoxyalkyl, C3-C10 alkoxyalkoxyalkyl, C2-C 8 alkylthioalkyl, C2-C6 alkylthioalkoxy, C2-C 8 alkylsulfinylalkyl, C2-Cg alkylsulfonylalkyl, C2-Cg alkylaminoalkyl, C3-C10 dialkylaminoalkyl, C2-Cg haloalkylaminoalkyl, C 4
  • R 1 and R 2 are taken together with the atoms to which they are attached to form a 6-membered partially unsaturated ring along with ring members consisting of carbon atoms and up to 2 oxygen atoms, 2 sulfur atoms or up to two -S(0) 2 - groups, the ring optionally substituted on carbon atom ring members selected from halogen, cyano, i ⁇ C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci ⁇ C 6 haloalkyl, C3-C 8 cycloalkyl and C2-C 8 alkoxyalkyl; and phenyl optionally substituted with up to 5 substituents selected from cyano, nitro, halogen, Ci ⁇ C 6 alkyl, i-C ⁇ alkoxy and Ci-C ⁇ haloalkoxy;
  • W 2 is -CH 2 - or -CH 2 0-;
  • R 3 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 alkynyl, C 3 -C 8
  • cycloalkyl C 4 -C 10 cycloalkylalkyl, C 3 -C 8 halocycloalkyl, C 1 -C4 cyanoalkyl, C2-C6 alkoxyalkyl or C3-C6 alkoxycarbonylalkyl;
  • R 3A is H, hydroxy, -O M + , C 2 -C 8 alkylcarbonyloxy, C 2 -C 8 haloalkylcarbonyloxy, C 4 -C ⁇ o cycloalkylcarbonyloxy or C3-C10 alkylcarbonylalkoxy; or benzyloxy, phenyloxy, benzylcarbonyloxy, phenylcarbonyloxy, phenylsulfonyloxy or benzylsulfonyloxy, each optionally substituted on ring members with up to two substituents selected from R 21 ;
  • M + is a sodium or potassium metal cation
  • R 9 is C r C 6 alkyl
  • R 10 is H, halogen or Ci ⁇ C 6 alkyl
  • R 1 1 is H or C r C 6 alkyl
  • R 14 and R 18 are H or C r C 6 alkyl
  • each R 15 and R 19 is H or C r C 6 alkyl
  • R 20 is H, C r C 6 alkyl, C 2 -C 6 alkenyl or C 3 -C 8 cycloalkyl;
  • G is independently a 5- or 6-membered heterocyclic ring optionally substituted with up to five substituents selected from R 21 on carbon ring members and R 22 on nitrogen ring members;
  • each R 21 is independently halogen, cyano, hydroxy, nitro, -CHO, -SH, Ci ⁇ C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, Ci ⁇ C 6 haloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 haloalkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 halocycloalkyl, C 4 -C 10 alkylcycloalkyl, C 4 -C 10 cycloalkylalkyl, C 3 -C 8 cycloalkenyl, C 3 -C 8 halocycloalkenyl, C 2 -C 8 alkoxyalkyl, C4-C10 cycloalkoxyalkyl, C 3 -C ⁇ Q alkoxyalkoxyalkyl, C 2 -C 8 alkylthioalkyl, C 2 -C 8 al
  • each R 22 is independently i-C ⁇ alkyl or i-C ⁇ haloalkyl.
  • Embodimenent B A compound of Embodiment A wherein
  • A is A-l , A-3 or A-5;
  • B 1 is C-l ;
  • B 2 is C-3;
  • B 3 is C-l ;
  • R 1 is halogen, Ci ⁇ C 6 alkyl, Ci ⁇ C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, Ci ⁇ C 6 alkoxy, i ⁇ C 6 haloalkoxy or C 2 -C 6 alkenyloxy;
  • R 2 is phenyl or -W 1 (phenyl), each optionally substituted on ring members with up to five substituents selected from R 21 ; or -G or -W 2 G; or Ci-C 6 alkyl, Ci ⁇ C 6 haloalkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkoxyalkyl, Ci ⁇ C 6 alkoxy, i ⁇ C 6 haloalkoxy or C 2 -C 8 alkoxyalkoxy; or
  • R 1 and R 2 are taken together with the atoms to which they are attached to form a
  • 6-membered partially unsaturated ring along with ring members consisting of carbon atoms and 2 oxygen atoms, 2 sulfur atoms or two -S(0) 2 - groups, the ring optionally substituted on carbon atom ring members selected from halogen, cyano and i ⁇ C 6 alkyl;
  • W 1 is -CH ;
  • R 3 is H, C1-C4 alkyl, C1-C4 haloalkyl, C 3 -C 8 cycloalkyl, C 4 -C 10 cycloalkylalkyl or C3-C6 alkoxycarbonylalkyl;
  • R 3A is hydroxy, -O M + or C2 ⁇ Cg alkylcarbonyloxy; or phenylsulfonyloxy optionally substituted with up to two substituents selected from R 21 ;
  • R 9 is ethyl
  • R 10 is H or methyl
  • each R 14 , R 15 , R 18 and R 19 is H or methyl
  • T is -CH 2 CH ;
  • G-21 r is 0, 1 , 2 or 3;
  • each R 21 is independently halogen, nitro, Ci-C ⁇ , alkyl, Ci-C ⁇ , haloalkyl, Ci-C ⁇ , alkoxy,
  • each R 22 is independently methyl or -CH2CF3.
  • Embodimenent C A compound of Embodiment B wherein
  • A is A-l or A-3;
  • R 1 is halogen, Ci-C ⁇ , alkyl, Ci-C ⁇ , haloalkyl, Ci-C ⁇ , alkoxy or Ci-C ⁇ , haloalkoxy;
  • R 2 is phenyl optionally substituted with up to five substituents selected from R 21 ; or C j -C6 alkyl, Ci-C ⁇ , haloalkyl, C3-C8 cycloalkyl, C2-Cg alkoxyalkyl, Ci-C ⁇ , alkoxy, C ⁇ -C6 haloalkoxy or C2-Cg alkoxyalkoxy; or
  • R 1 and R 2 are taken together with the atoms to which they are attached to form a
  • 6-membered partially unsaturated ring along with ring members consisting of carbon atoms and two -S(0)2- groups, the ring optionally substituted on carbon atom ring members selected from halogen and C ⁇ -C6 alkyl;
  • R 3 is C r C 4 alkyl or C 3 -C 8 cycloalkyl
  • R 3A is hydroxy or C2-Cg alkylcarbonyloxy
  • R 10 is methyl
  • each R 14 , R 15 , R 18 and R 19 is H;
  • each R 21 is independently fluorine, chlorine, bromine, methyl, trifluoromethyl,
  • Embodimenent D A compound of Embodiment C wherein
  • A is A-l ;
  • R 1 is chloro, methyl, methoxy or trifluoromethyl
  • R 2 is phenyl; or Ci-C ⁇ , alkyl
  • R 3 is methyl or cyclopropyl
  • Embodimenent E A compound of Embodiment D wherein
  • R 1 is methyl
  • R 2 is phenyl; or n-propyl
  • R 3 is methyl
  • Embodimenent F A compound of Embodiment C wherein
  • A is A-l ;
  • R 1 is choro or methyl
  • R 2 is /? -propyl, c-hexyl or -OCH 2 CH 2 CF3;
  • R 3 is methyl
  • A is A-l ;
  • B 1 is C-l ;
  • B 2 is C-3;
  • B 3 is C-l ;
  • R 1 is CH 3 ;
  • R 2 is -OCH 2 CH 2 CF 3 ;
  • R 3 is CH 3 ;
  • R 3A is hydroxy; each R 1 and R 15 is H; and each R 18 and R 19 is H (Compound 37).
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation a herbicidally effective amount of a compound of the invention (e.g., as a composition described herein).
  • a herbicidally effective amount of a compound of the invention e.g., as a composition described herein.
  • embodiments relating to methods of use are those involving the compounds of embodiments described above.
  • This invention also includes a herbicidal mixture comprising (a) a compound selected from Formula 1, N-oxides, and salts thereof, and (b) at least one additional active ingredient selected from (bl) photosystem II inhibitors, (b2) acetohydroxy acid synthase (AHAS) inhibitors, (b3) acetyl-CoA carboxylase (ACCase) inhibitors, (b4) auxin mimics and (b5) 5 -enol-pyruvylshikimate-3 -phosphate (EPSP) synthase inhibitors, (b6) photosystem I electron diverters, (b7) protoporphyrinogen oxidase (PPO) inhibitors, (b8) glutamine synthetase (GS) inhibitors, (b9) very long chain fatty acid (VLCFA) elongase inhibitors, (blO) auxin transport inhibitors, (bl 1) phytoene desaturase (PDS) inhibitors, (bl2) 4-hydroxyphenyl-pyruv
  • Photosystem II inhibitors are chemical compounds that bind to the D-l protein at the ( ⁇ -binding niche and thus block electron transport from Q A to Q B in the chloroplast thylakoid membranes.
  • the electrons blocked from passing through photosystem II are transferred through a series of reactions to form toxic compounds that disrupt cell membranes and cause chloroplast swelling, membrane leakage, and ultimately cellular destruction.
  • the Q B -binding niche has three different binding sites: binding site A binds the triazines such as atrazine, triazinones such as hexazinone, and uracils such as bromacil, binding site B binds the phenylureas such as diuron, and binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate.
  • triazines such as atrazine
  • triazinones such as hexazinone
  • uracils such as bromacil
  • binding site B binds the phenylureas such as diuron
  • binding site C binds benzothiadiazoles such as bentazon, nitriles such as bromoxynil and phenyl-pyridazines such as pyridate.
  • photosystem II inhibitors include ametryn, atrazine, cyanazine, desmetryne, dimethametryn, prometon, prometryne, propazine, simazine, simetryn, terbumeton, terbuthylazine, terbutryne, trietazine, hexazinone, metamitron, metribuzin, amicarbazone, bromacil, lenacil, terbacil, chloridazon, desmedipham, phenmedipham, chlorobromuron, chlorotoluron, chloroxuron, dimefuron, diuron, ethidimuron, fenuron, fluometuron, isoproturon, isouron, linuron, methabenzthiazuron, metobromuron, metoxuron, monolinuron, neburon, siduron, tebuthiuron, propanil, pentanochlor, bromof
  • AH AS inhibitors are chemical compounds that inhibit acetohydroxy acid synthase (AHAS), also known as acetolactate synthase (ALS), and thus kill plants by inhibiting the production of the branched-chain aliphatic amino acids such as valine, leucine and isoleucine, which are required for DNA synthesis and cell growth.
  • AHAS acetohydroxy acid synthase
  • ALS acetolactate synthase
  • AHAS inhibitors include amidosulfuron, azimsulfuron, bensulfuron-methyl, chlorimuron-ethyl, chlorsulfuron, cinosulfuron, cyclosulfamuron, ethametsulfuron-methyl, ethoxysulfuron, flazasulfuron, flupyrsulfuron-methyl (including sodium salt), foramsulfuron, halosulfuron-methyl, imazosulfuron, iodosulfuron-methyl (including sodium salt), mesosulfuron-methyl, metazosulfuron, metsulfuron-methyl, nicosulfuron, oxasulfuron, primisulfuron-methyl, propyrisulfuron, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl, sulfosulfuron, thifensulfuron-methyl,
  • ACCase inhibitors are chemical compounds that inhibit the acetyl-CoA carboxylase enzyme, which is responsible for catalyzing an early step in lipid and fatty acid synthesis in plants. Lipids are essential components of cell membranes, and without them, new cells cannot be produced. The inhibition of acetyl CoA carboxylase and the subsequent lack of lipid production leads to losses in cell membrane integrity, especially in regions of active growth such as meristems. Eventually shoot and rhizome growth ceases, and shoot meristems and rhizome buds begin to die back.
  • ACCase inhibitors include clodinafop, cyhalofop, diclofop, fenoxaprop, fluazifop, haloxyfop, propaquizafop, quizalofop, alloxydim, butroxydim, clethodim, cyclopyrimorate (6-chloro-3-(2-cyclopropyl- 6-methylphenoxy)-4-pyridazinyl 4-morpholinecarboxylate), cycloxydim, pinoxaden, profoxydim, sethoxydim, tepraloxydim and tralkoxydim, including resolved forms such as fenoxaprop-P, fluazifop-P, haloxyfop-P and quizalofop-P and ester forms such as clodinafop-propargyl, cyhalo fop-butyl, diclo fop-methyl and fenoxaprop-P-e
  • auxin is a plant hormone that regulates growth in many plant tissues.
  • auxin mimics are chemical compounds mimicking the plant growth hormone auxin, thus causing uncontrolled and disorganized growth leading to plant death in susceptible species.
  • auxin mimics include aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), aminopyralid benazolin-ethyl, chloramben, clomeprop, clopyralid, dicamba, 2,4-D, 2,4-DB, dichlorprop, fluroxypyr, halauxifen (4-amino-3-chloro- 6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridinecarboxylic acid) and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), mecoprop, MCPA, MCPB, 2,3,6-TBA, piclor
  • EEPSP (5 -enol-pyruvylshikimate-3 -phosphate) synthase inhibitors) are chemical compounds that inhibit the enzyme, 5 -enol-pyruvylshikimate-3 -phosphate synthase, which is involved in the synthesis of aromatic amino acids such as tyrosine, tryptophan and phenylalanine.
  • EPSP inhibitor herbicides are readily absorbed through plant foliage and translocated in the phloem to the growing points.
  • Glyphosate is a relatively nonselective postemergence herbicide that belongs to this group.
  • Glyphosate includes esters and salts such as ammonium, isopropylammonium, potassium, sodium (including sesquisodium) and trimesium (alternatively named sulfosate).
  • Photosystem I electron diverters are chemical compounds that accept electrons from Photosystem I, and after several cycles, generate hydroxyl radicals. These radicals are extremely reactive and readily destroy unsaturated lipids, including membrane fatty acids and chlorophyll. This destroys cell membrane integrity, so that cells and organelles "leak", leading to rapid leaf wilting and desiccation, and eventually to plant death. Examples of this second type of photosynthesis inhibitor include paraquat and diquat.
  • PPO inhibitors are chemical compounds that inhibit the enzyme protoporphyrinogen oxidase, quickly resulting in formation of highly reactive compounds in plants that rupture cell membranes, causing cell fluids to leak out.
  • PPO inhibitors include acifluorfen-sodium, bifenox, chlomethoxyfen, fluoroglycofen-ethyl, fomesafen, halosafen, lactofen, oxyfluorfen, fluazolate, pyraflufen-ethyl, cinidon-ethyl, flumioxazin, flumiclorac-pentyl, fluthiacet-methyl, tiafenacil (methyl N-[2-[[2-chloro-5-[3, 6- dihydro-3-methyl-2,6-dioxo-4-(trifluoromethyl)-l(2/ ⁇
  • oxopropyl]-P-alaninate thidiazimin, oxadiazon, oxadiargyl, saflufencil, azafenidin, carfentrazone carfentrazone-ethyl, sulfentrazone, pentoxazone, benzfendizone, butafenacil, pyraclonil, profluazol and flufenpyr-ethyl.
  • GS (glutamine synthase) inhibitors are chemical compounds that inhibit the activity of the glutamine synthetase enzyme, which plants use to convert ammonia into glutamine. Consequently, ammonia accumulates and glutamine levels decrease. Plant damage probably occurs due to the combined effects of ammonia toxicity and deficiency of amino acids required for other metabolic processes.
  • the GS inhibitors include glufosinate and its esters and salts such as glufosinate-ammonium and other phosphinothricin derivatives, glufosinate-P and bilanaphos.
  • VLCFA very long chain fatty acid
  • elongase inhibitors are herbicides having a wide variety of chemical structures, which inhibit the elongase.
  • Elongase is one of the enzymes located in or near chloroplasts which are involved in biosynthesis of VLCFAs.
  • very-long-chain fatty acids are the main constituents of hydrophobic polymers that prevent desiccation at the leaf surface and provide stability to pollen grains.
  • Such herbicides include acetochlor, alachlor, butachlor, dimethachlor, dimethanamid, metazachlor, metolachlor, pethoxamid, pretilachlor, propachlor, propisochlor, pyroxasulfone, thenylchlor, diphenamid, napropamide, naproanilide, fenoxasulfone, flufenacet, indanofan, mefenacet, fentrazamide, anilofos, cafenstrole, piperophos including resolved forms such as S-metolachlor and chloroacetamides and oxyacetamides.
  • auxin transport inhibitors are chemical substances that inhibit auxin transport in plants, such as by binding with an auxin-carrier protein.
  • auxin transport inhibitors include naptalam (also known as N-(l-naphthyl)phthalamic acid and 2-[(l-naphthalenylamino)carbonyl]benzoic acid) and diflufenzopyr.
  • PDS phytoene desaturase inhibitors
  • bl l are chemical compounds that inhibit carotenoid biosynthesis pathway at the phytoene desaturase step.
  • PDS inhibitors include norflurzon, diflufenican, picolinafen, beflubutamide, fluridone, flurochloridone and flurtamone.
  • HPPD (4-hydroxyphenyl-pyruvate dioxygenase) inhibitors are chemical substances that inhibit the biosynthesis of synthesis of 4-hydroxyphenyl-pyruvate dioxygenase.
  • HPPD inhibitors include fenquinotrione (2-[[8-chloro-3,4- dihydro-4-(4-methoxyphenyl)-3-oxo-2-quinoxalinyl]car-bonyl]-l,3-cyclohexanedione), mesotrione, sulcotrione, topramezone, tembotrione, tefuryltrione, isoxachlortole, isoxaflutole, benzofenap, pyrasulfatole, pyrazolynate, pyrazoxyfen, bicyclopyrone and benzobicyclon.
  • HST homogentisate solenesyltransererase inhibitors
  • HST inhibitors include haloxydine, pyriclor and the com ounds of Formulae A, B and C.
  • HST inhibitors also include com ounds of Formulae D and E.
  • Cellulose biosynthesis inhibitors inhibit the biosynthesis of cellulose in certain plants. They are most effective when using a pre-aplication or early post-application on young or rapidly growing plants. Examples of cellulose biosynthesis inhibitors include chlorthiamid, diclobenil, flupoxam, indaziflam, isoxaben and triaziflam.
  • herbicides include herbicides that act through a variety of different modes of action such as mitotic disruptors (e.g., flamprop-M-methyl and flamprop-M-isopropyl) organic arsenicals (e.g., DSMA, and MSMA), 7,8-dihydropteroate synthase inhibitors, chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors.
  • mitotic disruptors e.g., flamprop-M-methyl and flamprop-M-isopropyl
  • organic arsenicals e.g., DSMA, and MSMA
  • 7,8-dihydropteroate synthase inhibitors e.g., chloroplast isoprenoid synthesis inhibitors and cell-wall biosynthesis inhibitors.
  • Other herbicides include those herbicides having unknown modes of action or do not fall into a specific category listed in (bl) through (bl4) or act through a combination of modes of action listed above.
  • herbicides examples include aclonifen, asulam, amitrole, clomezone, fluometuron, difenzoquat, bromobutide, flurenol, cinmethylin, cumyluron, dazomet, dymron, methyldymron, methiozolon, ipfencarbazone, etobenzanid, fosamine, fosamine-ammonium, metam, oxaziclomefone, oleic acid, pelargonic acid and pyributicarb.
  • Herbicide safeners (bl6) are substances added to a herbicide formulation to eliminate or reduce phytotoxic effects of the herbicide to certain crops.
  • herbicide safeners include but are not limited to allidochlor, N-(aminocarbonyl)-2-methylbenzenesulfonamide, benoxacor, BCS (l-bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfamide, daimuron, dichlormid, 4-(dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dicyclonon, dietholate, dimepiperate, ethyl 1 ,6-dihydro- 1 -(2-methoxyphenyl)-6-oxo-2-phenyl
  • compounds of Formula 1 wherein A is A-l, A-2, A-3 or A-5 can be prepared by reacting a compound of Formula 2 which is Ai-H wherein A 1 is
  • X 1 is a nucleophilic reaction leaving group (i.e. nucleofuge), for example, halogen, alkylcarbonyloxy, haloalkyloxy, haloalkoxycarbonyloxy, 1-pyridinyl 1-imidazolyl group; in the presence of a base to form a compound of Formula 4,
  • cyanide ion e.g., acetone cyanohydrin, potassium cyanide, sodium cyanide
  • a base such as triethylamine or pyridine
  • the intermediate compound of Formula 4a, 4b, 4c or 4d is then rearranged to the corresponding compound of Formula la, lb, lc or Id.
  • a fluoride anion source such as potassium fluoride or cesium fluoride, optionally in the presence of a phase transfer catalyst (e.g., tetrabutyl ammonium bromide), can be used to cause this rearrangement.
  • reaction is conducted in a solvent such as dimethylsulfoxide, N,N-dimethylformamide, acetonitrile or dichloromethane at temperatures ranging from ambient temperature to the reflux temperature of the solvent.
  • a solvent such as dimethylsulfoxide, N,N-dimethylformamide, acetonitrile or dichloromethane
  • compounds of Formula la, lb, lc or Id can be prepared by Process 2 (in Schemes la, lb, lc and Id respectively) by reacting a compound of Formula 2a, 2b, 2c or 2d with a compound of Formula 3 in the presence of a cyanide or fluoride anion source along with a base.
  • a cyanide or fluoride anion source for reaction conditions for this general coupling methodology, see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapters 4.3 and 4.4, and references cited
  • Compounds of Formula la, lb or lc can also be prepared as shown in Scheme 2, by reacting dione 2a, 2b or 2c with intermediate 3a (i.e. Formula 3 in which X 1 is -CN) in the presence of a base or Lewis acid.
  • intermediate 3a i.e. Formula 3 in which X 1 is -CN
  • a compound of Formulae 4a, 4b, 4c or 4d is useful as an intermediate in the method of Schemes la-Id and can also be prepared by reacting a compound of Formula 2a, 2b, 2c or 2d, respectively, with a carboxylic acid of Formula 5 in the presence of a dehydrating condensation agent such as 2-chloro-l-pyridinium iodide (known as the Mukaiyama coupling agent), dicyclohexyl carbodiimide (DCC) or the like and optionally in the presence of a base.
  • a dehydrating condensation agent such as 2-chloro-l-pyridinium iodide (known as the Mukaiyama coupling agent), dicyclohexyl carbodiimide (DCC) or the like and optionally in the presence of a base.
  • an intermediate compound of Formula 4a, 4b or 4c can also be made by the palladium-catalyzed carbonylation reaction of a halo compound of Formula 6 in the presence of a compound of Formula 2a, 2b or 2c, respectively.
  • reaction conditions for this general enol ester forming methodology see Edmunds, A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 and references cited therein.
  • X 2 is CI.
  • a compound of Formula le i.e. Formula 1 in which A is A-4) wherein R 3A is hydroxy
  • a compound of Formula 7 i.e. Formula 1 in which A is A-4) wherein R 3A is hydroxy
  • a strong base such as n-butyllithium or lithium diisopropylamide in an appropriate solvent such as tetrahydrofuran or diethyl ether.
  • a strong base such as n-butyllithium or lithium diisopropylamide
  • an appropriate solvent such as tetrahydrofuran or diethyl ether.
  • a compound of Formula 1 wherein A is A-l, A-2, A-3, A-4 or A-5 and R 3A is bonded to the remainder of Formula 1 through a nitrogen, sulfur or carbon atom can be prepared by reacting a compound of Formula 1 wherein R 3 A is hydroxy with an appropriate halogenating agent to prepare a corresponding halo compound of Formula 1 wherein R 3A is halogen, followed by reacting the halo compound with an appropriate nucleophilic compound to replace the halogen with R 3A through displacement.
  • reaction conditions for this general functionalization method see Edmunds, A. or Van Almsick A. in Modern Crop Protection Compounds; Kramer, W. and Schirmer, U., Eds.; Wiley, Weinheim, 2007; Chapter 4.3 or Chapter 4.4, and references cited therein.
  • R is bonded R Jft is bonded providing R 3A bonded R is OH
  • sulfur or carbon X 2 is CI, Br or I
  • compounds of Formula lg i.e. Formula 1 in which A is A-6 and R 11 is H
  • compounds of Formula 11 can be prepared by acylation of compounds of Formula 10 with a compound of Formula 3.
  • Acylation on carbon can be achieved by using a magnesium enolate of the compound of Formula 10 produced using conditions previously described in Scheme 7.
  • Removal of the ester can be conveniently carried out by heating the reaction product with a source of acid which cleaves the tert-butyl group and results in decarboxylation producing the compound of Formula 11.
  • Acid sources such as hydrochloric acid, hydrobromic acid, sulfuric acid, trifluoroacetic acid and /?-toluenesulfonic acid as well as many others may be employed.
  • the compound of Formula 11 is then reacted with an ortho formate ester or N,N-dimethylformamide dimethylacetal (DMF-DMA) to provide an intermediate compound of Formula 12.
  • Reaction of the compound of Formula 12 with hydroxylamine hydrochloride salt in a solvent such as ethanol, acetonitrile, water or acetic acid provides the isoxazole compound of Formula lg.
  • carboxylic acids of Formula 5 can be prepared by de- esterification of esters of Formula 13.
  • the de-esterification can be accomplished by many well-known methods, for example, saponification procedures using alkali hydroxides such as LiOH, NaOH or KOH in a lower alkanol such methanol or ethanol or in mixtures of alkanols and water.
  • a dealkylating agent such as lithium iodide or trimethylsilyl iodide can be used in the presence of a base in a solvent such as pyridine or ethyl acetate.
  • boron tribromide (BBr 3 ) can be used to prepare a compound of Formula 5 from a compound of Formula 13 in a solvent such as dichloromethane, hexanes or toluene.
  • a solvent such as dichloromethane, hexanes or toluene.
  • a typical procedure using boron tribromide is disclosed in Bioorg. & Med. Chem. Lett. 2009, 19(16), 4733-4739. Additional reaction procedures for de-esterification can be found in PCT Patent Publication WO 2006/133242.
  • R 30 is C j -Cg alkyl
  • esters of Formula 13 can be prepared from the corresponding nitriles of Formula 14.
  • a nitrile is converted into the ester of the alkanol.
  • Suitable acids include, for example, hydrochloric, hydrobromic acid and sulfuric acid.
  • R 30 is C i -C 6 alkyl
  • Ci -C 6 alkanol is used.
  • Lower (i.e. C 1 -C4) alkanols are preferred, and methanol is especially preferred for this method.
  • the nitrile of Formula 14 is reacted with hydrochloric acid in the presence of methanol as a solvent.
  • the reaction temperature can be from about 0 to 200 °C depending upon the alcohol used and whether the pressure is increased above ambient atmospheric pressure.
  • An especially useful procedure to perform the reaction involves generating the hydrochloric acid by addition of thionyl chloride, trimethylsilyl chloride or acetyl chloride to methanol in the presence of the compound of Formula 14.
  • esters of Formula 13 can also be prepared from corresponding halo compounds of Formula 6.
  • the compound of Formula 6 is reacted with carbon monoxide and the appropriate Ci-C ⁇ alkanol in the presence of an acid acceptor and a transition metal catalyst.
  • an acid acceptor and a transition metal catalyst typically lower alkanols such as methanol and ethanol are preferred in this transformation.
  • Carbon monoxide can be present at pressures ranging from about 100 to 10000 kPa.
  • suitable acid acceptors include tertiary amines such as triethylamine, alkali metal carbonates such as potassium carbonate, alkali metal phosphates, alkali metal acetates and alkali metal hydrogencarbonates. Tertiary amines are most preferred.
  • Palladium catalysts are most preferred for use in this carbonylation reaction.
  • a wide variety of commercially available ligands and palladium sources can be employed.
  • the most useful catalysts are those generated from l ,3-bis(diphenylphosphino)propane (dppp) and l ,l'-bis(diphenylphosphino)ferrocene (dppf). These reactions can be performed at temperatures between about 0 and 200 °C; temperatures between about 50 and 100 °C are most commonly employed.
  • Suitable solvents include polar aprotic solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone and N,N-dimethylacetamide as well as ethers such as dioxane and tetrahydrofuran.
  • polar aprotic solvents such as N,N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidinone and N,N-dimethylacetamide
  • ethers such as dioxane and tetrahydrofuran.
  • X 2 is CI, Br or I
  • nitriles of Formula 14 can be prepared by cyanation of corresponding halo compounds of Formula 6. Cyanation reactions are well known in the art. A particularly useful cyanide source for this reaction is copper (I) cyanide. Heating a halide of Formula 6 with an excess of copper(I) cyanide in an aprotic polar solvent such as N,N-dimethylacetamide, N,N-dimethylformamide or N-methylpyrrolidinone forms the compound of Formula 14. The reaction can be perfomed at temperatures ranging from about 0 to 250 °C, but preferably at temperatures between 100 °C and 150 °C. This reaction may also be performed with the aid of a transition metal catalyst.
  • X 2 is CI, Br or I
  • Esters of Formula 13a can be prepared by reaction of hydroxypyridazinones of Formula 15 with halogenating agents as shown in Scheme 14.
  • halogenating agents such as, but not limited to, POCl 3 , PC1 5 , SOCl 2 , SOBr 2 , PBr 3 and POBr 3 will accomplish this conversion.
  • This reaction can be carried out in aprotic solvents which are compatible with the reagents for example, dichloromethane, chlorobenzene, toluene, dichloroethane and chloroform. Temperatures from 0 to 180 °C can be employed.
  • a tertiary amine base can be helpful.
  • Preferred amines for this purpose are N,N-dimethylaniline and N,N-diethylaniline.
  • the halogens may be interconverted by reaction of alkali halides in solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile or N-methylpyrrolidinone at temperatures from 80 to 200 °C.
  • R is halogen
  • Compounds of Formula 13b may be obtained by alkylation of compounds of Formula 15 with i-C ⁇ alkyl halides or sulfonates in the presence of an acid acceptor as shown in Scheme 15. The reaction may be conducted at temperatures between -20 and 150 °C.
  • Useful solvents include, but are not limited to N,N-dimethylformamide, N,N-dimethylacetamide, acetonitrile, N-methylpyrrolidinone, dioxane, tetrahydrofuran or dimethylsulfoxide.
  • Suitable acid acceptors include but are not limited to alkali carbonates, hydroxides, alkoxides and hydrides as well as cesium carbonate and alkali hexamethyldisilazides.
  • a preferred set of conditions utilizes N,N-dimethylformamide as solvent with sodium hydride as acid acceptor.
  • compounds of Formula 13c (, compounds of Formula 13 wherein R 1 is -C ⁇ alkylthio or (R A )(R B )N can be prepared by nucleophilic displacement reactions of compounds of Formula 13a with -C ⁇ alkanethiols or amines (R A )(R B )NH.
  • Useful solvents include, but are not limited to N,N-dimethylformamide, N,N- dimethylacetamide, N-methylpyrrolidinone, dioxane, tetrahydrofuran or dimethylsulfoxide.
  • the reaction may be conducted at temperatures between -20 and 150 °C.
  • compounds of Formula 13b can be prepared in similar fashion by reaction of compounds of Formula 13a with C j -C ( , alcohols in the presence of a base.
  • compounds of Formula 13e i.e. compounds of Formula 13 wherein R 1 is Ci-C ⁇ alkyl
  • transition metal catalyzed reactions of compounds of Formula 13d i.e. compounds of Formula 13 wherein R 1 is a sulfonate such as trifluoromethanesulfonate
  • R 1 is a sulfonate such as trifluoromethanesulfonate
  • Various palladium catalyzed reactions are known to introduce functional groups in this way.
  • E. Negishi Handbook of Organopalladium Chemistry for Organic Synthesis, John Wiley and Sons, Inc., New York, 2002; N. Miyaura, Cross-Coupling Reactions: A Practical Guide, Springer, New York, 2002; H. C.
  • Sulfonate precursors of formula 13d can be made from the hydroxyl precursors of Formula 15 by the well known sulfonylation reaction outlined by Maes and Lemiere in Comprehensive Heterocyclic Chemistry III, Volume 8, Katritsky, Ramsden, Scriven and Taylor editors, and references cited therein.
  • Scheme 18 shows the synthesis of compounds of Formula 15 by the cyclization of hydrazono esters of formula 16 in the presence of an acid acceptor.
  • Suitable acid acceptors for the reaction include inorganic bases, such as alkali or alkaline earth metal (such as lithium, sodium, potassium and cesium) hydrides and alkoxides or organic bases, such as triethylamine, N,N-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene.
  • solvents are suitable for the reaction, including, for example but are not limited to aromatic hydrocarbons (such as toluene and xylenes), tetrahydrofuran, dioxane, dimethoxy ethane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, and acetonitrile as well as mixtures of these solvents.
  • aromatic hydrocarbons such as toluene and xylenes
  • tetrahydrofuran dioxane
  • dimethoxy ethane dimethoxy ethane
  • N,N-dimethylformamide N,N-dimethylacetamide
  • N-methylpyrrolidinone acetonitrile
  • R 30 is -Cg alkyl
  • Compounds of Formula 16 can be synthesized by the reaction of an activated acid derivative of Formula 20 with a hydrazone of Formula 19 in the presence of an acid acceptor as shown in Scheme 19.
  • Suitable acid acceptors for the reaction include inorganic bases, such as alkali or alkaline earth metal (such as lithium, sodium, potassium, cesium) hydrides, alkoxides, carbonates, phosphates and hydroxides, and organic bases, such as triethylamine, N,N-diisopropylethylamine and l,8-diazabicyclo[5.4.0]undec-7-ene.
  • Preferred acid acceptors are trialkylamines and potassium hydroxide.
  • a wide variety of solvents are suitable for the reaction, including, for example but are not limited to tetrahydrofuran, dichloromethane, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidinone, acetonitrile and acetone, as well as mixtures of these solvents.
  • This reaction can be conducted between about -20 and 100 °C, and preferably between about 0 and 50 °C.
  • Activated acid derivatives include, for example, but are not limited to acid chlorides, acid bromides, acylimidazoles, mixed anhydrides and acylcyanides. Examples of related chemistry can be found in U.S. Pat. No. 7,517,994.
  • Hydrazones of Formula 19 can be prepared as shown in Scheme 19 by reaction of ketomalonates of Formula 17 with hydrazines of Formula 18. This reaction can be performed by methods disclosed in U.S. Pat. No. 7,517,994.
  • Preferred catalysts include palladium tetrakis-(triphenylphosphine) and bis-(triphenylphospine) palladium dichloride.
  • the zincation reaction may be carried out at temperatures from -20 to 150 °C and the coupling reaction from 0 to 120 °C.
  • Ethereal solvents such as dioxane and tetrahydrofuran are preferred for this reaction, but other solvents which do not react with the zinc reagent may also be employed.
  • the transition metal can be a copper (I) salt such as CuCl, Cul, CuBr or CuCN or a soluble version in which lithium chloride is used to increase the solubility of the salt.
  • compounds of Formula 5 can be prepared by the reaction of zincated heterocycles with carbon dioxide in the presence of a transition metal catalyst.
  • Pyridazinones of Formula 21 can be zincated as indicated in Scheme 21 and treated with carbon dioxide in the presence of palladium or nickel catalysts.
  • Conditions and catalysts which are suitable for this transformation are disclosed in J. Am. Chem. Soc. 2008, 130, 7826-7827. Preferred conditions are from -10 to 30 °C using a catalyst prepared from Pd(OAc)2 and tricyclohexylphosphine in tetrahydrofuran as solvent.
  • Mass spectra are reported as the molecular weight of the highest isotopic abundance parent ion (M+l) formed by addition of H + (molecular weight of 1) to the molecule, observed by mass spectrometry using atmospheric pressure chemical ionization (AP + ) where "amu” stands for atomic mass units. The presence of molecular ions containing one or more higher atomic weight isotopes of lower abundance (e.g., 37 C1, 81 Br) is not reported.
  • Step A Preparation of l,3-diethyl-2-(2-methylhydrazinylidene)propanedioate (2- propanone 2-methylhydrazone- 1,3 -diethyl ester)
  • Step B Preparation of ethyl l,6-dihydro-4-hydroxy-l-methyl-6-oxo-5-phenyl-3- pyridazinecarboxylate To a stirred solution of l,3-diethyl-2-(2-propanone 2-methylhydrazone)propanedioate (i.e.
  • Step A (2-propanone 2-methylhydrazone- 1,3 -diethyl ester), 3.0 g, 14.9 mmol) in tetrahydrofuran (30 mL) was added lithium hexamethyldisilazide (1M solution in tetrahydrofuran, 32.7 mL, 32.7 mmol) at 0 °C over a period of 40 min. The mixture was stirred for an additional 40 min and subsequently treated dropwise with phenylacetyl chloride (2.75 g, 17.82 mmol). The reaction mixture was stirred at room temperature for 6 h, then cooled to 0 °C and the pH adjusted to approximately 2 by slow addition of IN hydrochloric acid (40 mL).
  • IN hydrochloric acid 40 mL
  • Step C Preparation of ethyl 4-chloro-l,6-dihydro-l-methyl-6-oxo-5-phenyl-3- pyridazinecarboxylate
  • Step D Preparation of ethyl l,6-dihydro-l,4-dimethyl-6-oxo-5-phenyl-3- pyridazinecarboxylate
  • Step F Preparation of 3-oxo-l-cyclohexen-l-yl l,6-dihydro-l,4-dimethyl-6-oxo-5- phenyl-3 -pyridazinecarboxylate
  • the reaction mixture was diluted with water, acidified by slow addition of aqueous IN hydrochloric acid, and extracted with ethyl acetate. The organic layers were dried (Na 2 S04) and concentrated under reduced pressure. The crude material was purified by chromatography on silica gel eluting with 1 to 3% methanol in dichloromethane to provide the title compound (30%) as a light brown gum.
  • Step G Preparation of 6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2,5- dimethyl-4-phenyl-3(2H)-pyridazinone
  • the reaction mixture was cooled to room temperature, partitioned between water and ethyl acetate (1 : 1, 30 mL) and filtered. The layers were separated, and the aqueous layer was extracted with ethyl acetate (15 mL). The combined organic extracts were washed with water and brine, dried (Na 2 S0 4 ) and concentrated under reduced pressure. The crude material was purified by chromatography on silica gel eluting with 10 to 15% ethyl acetate in hexanes to afford the title compound (71 mg) as a light brown oil.
  • Step B Preparation of l,6-dihydro-l-methyl-6-oxo-5-phenyl-4-(trifluoromethyl)-3- pyridazinecarboxylic acid
  • Step E ethyl l,6-dihydro-l-methyl-6-oxo-5-phenyl- 4-(trifluoromethyl)-3-pyridazinecarboxylate (i.e. the product of Step A) afforded the title compound (92%>) as a light brown solid.
  • Step C Preparation of 3 -oxo-1 -cyclohexen- 1-yl l,6-dihydro-l-methyl-6-oxo-5- phenyl-4-(trifluoromethyl)-3-pyridazinecarboxylate
  • Step F l,6-dihydro-l-methyl-6-oxo-5-phenyl-4- (trifluoromethyl)-3-pyridazinecarboxylic acid (i.e. the product of Step B) afforded the title compound (88%>) as a light brown gum.
  • Step D Preparation of 6-[(2-hydroxy-6-oxo-l -cyclohexen- l-yl)carbonyl] -2-methyl-4- phenyl-4-(trifluoromethyl)-3(2H)-pyridazinone
  • Step A Preparation of 4-chloro-l,6-dihydro-l-methyl-6-oxo-5-phenyl-3- pyridazinecarboxylic acid
  • Step B Preparation of 3-oxo-l-cyclohexen-l-yl 4-chloro-l,6-dihydro-l-methyl-6- oxo-5 -phenyl-3 -pyridazinecarboxylate
  • Step F 4-chloro-l,6-dihydro-l-methyl-6-oxo-5- phenyl-3-pyridazinecarboxylic acid (i.e. the product of Step A) afforded the title compound (72%) as a clear gum.
  • Step C Preparation of 5-chloro-6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2- methyl-4-phenyl-3(2H)-pyridazinone
  • Step G 3-oxo-l-cyclohexen-l-yl 4-chloro-l,6- dihydro-l-methyl-6-oxo-5 -phenyl-3 -pyridazinecarboxylate (, the product of Step B) afforded the title compound (34%) as a light brown solid. MP 176-178 °C.
  • Step A Preparation of 1 ,6-dihydro-4-methoxy- 1 -methyl-6-oxo-5 -phenyl-3 - pyridazinecarboxylic acid
  • Step B Preparation of 3-oxo-l-cyclohexen-l-yl l,6-dihydro-4-methoxy-l-methyl-6- oxo-5 -phenyl-3 -pyridazinecarboxylate
  • Step F l,6-dihydro-4-methoxy-l-methyl-6-oxo-5- phenyl-3-pyridazinecarboxylic acid (i.e. the product of Step A) afforded he title compound (88%) as a clear gum.
  • Step C Preparation of 6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-5-methoxy-
  • Step G 3-oxo-l-cyclohexen-l-yl l,6-dihydro-4- methoxy-l-methyl-6-oxo-5 -phenyl-3 -pyridazinecarboxylate (i.e. the product of Step B) afforded the title compound (18%) as a light brown solid. MP 205-207 °C.
  • Step A Preparation of pentanoic acid l-methyl-2-(l-methylethylidene)hydrazide
  • the reaction mixture was stirred for 6 h and warmed to room temperature during this time, then water (10 mL) was added and the mixture was extracted with ethyl acetate (3 X 30 mL). The combined organic extracts were dried (Na 2 S04) and concentrated under reduced pressure. The crude material was purified by chromatography on silica gel eluting with 10 to 15% ethyl acetate in hexanes to obtain the title compound (154 mg) as a light brown oil.
  • Step B Preparation of ethyl l,6-dihydro-4-hydroxy-l-methyl-6-oxo-5-propyl-3- pyridazinecarboxylate
  • a stirred solution of 1M lithium hexamethyldisilazide in tetrahydrofuran (59 mL, 59.0 mmol) at -78 °C was added dropwise a solution of pentanoic acid l-methyl-2-(l- methylethylidene)hydrazide (i.e. the product of Step A, 2.98 g, 14.8 mmol) in tetrahydrofuran (20 mL).
  • the reaction mixture was warmed to -40 °C and stirred for 1.5 h.
  • the reaction mixture was quenched with IN hydrochloric acid and extracted with ethyl acetate (3 X 30 mL).
  • the combined organic extracts were dried (Na 2 S04) and concentrated under reduced pressure.
  • the crude material was purified by chromatography on silica gel eluting with 5 to 10% ethyl acetate in hexanes to afford the title compound (1.85 g) as a light brown oil.
  • Step C Preparation of ethyl 4-chloro- 1 ,6-dihydro- 1 -methyl-6-oxo-5-propyl-3- pyridazinecarboxylate
  • Step C ethyl l,6-dihydro-4-hydroxy-l-methyl-6-oxo- 5-propyl-3-pyridazinecarboxylate (, the product of Step B) afforded the title compound (76%>) as a light-brown oil.
  • Step D Preparation of ethyl l,6-dihydro-l,4-dimethyl-6-oxo-5-propyl-3- pyridazinecarboxylate
  • Step E Preparation of 1 ,6-dihydro- 1 ,4-dimethyl-6-oxo-5 -propyl-3- pyridazinecarboxylic acid
  • Step E ethyl l,6-dihydro-l,4-dimethyl-6-oxo-5- propyl-3 -pyridazinecarboxylate (i.e. the product of Step D) afforded the title compound (86%) as an off-white solid.
  • Step F Preparation of 3-oxo-l-cyclohexen-l-yl l,6-dihydro-l,4-dimethyl-6-oxo-5- propyl-3 -pyridazinecarboxylate
  • Step F l,6-dihydro-l,4-dimethyl-6-oxo-5-propyl-3- pyridazinecarboxylic acid (i.e. the product of Step E) afforded the title compound (77%>) as a light brown gum.
  • Step G Preparation of 6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2,5- dimethyl-4-propyl-3 (2H)-pyridazinone
  • Step G 3-oxo-l-cyclohexen-l-yl l,6-dihydro-l,4- dimethyl-6-oxo-5-propyl-3-pyridazinecarboxylate (i.e. the product of Step F) afforded the title compound (56%) as an orange yellow oil.
  • reaction mixture was then poured over 100 mL of an ice/water mixture and extracted into ethyl acetate.
  • the organic layer was washed with brine, dried (MgS0 4 ) and absorbed onto silica gel. Chromatography through silica gel eluting with a gradient of 0 to 100% ethyl acetate in hexanes provided 1.76 g of the title product as a white solid.
  • Step B Preparation of 5-chloro-6-iodo-4-(2-methoxyethoxy)-2-methyl-3(2H)- pyridazinone
  • Step D Preparation of methyl 4-chloro-l,6-dihydro-5-(2-methoxyethoxy)-l-methyl-6- oxo-3 -pyridazinecarboxylate
  • Step E Preparation of 4-chloro-l,6-dihydro-5-(2-methoxyethoxy)-l-methyl-6-oxo-3- pyridazinecarboxylic acid
  • Step F Preparation of 3-oxo-l-cyclohexen-l-yl 4-chloro-l,6-dihydro-5-(2- methoxyethoxy)- 1 -methyl-6-oxo-3 -pyridazinecarboxylate
  • Step G Preparation of 5-chloro-6[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-4-
  • Step B Preparation of ethyl l,6-dihydro-4-hydroxy-5-methoxy-l-methyl-6-oxo-3- pyridazinecarboxylate
  • Lithium hexamethyldisilazide (73.6 mL of a 1M solution in tetrahydrofuran, 73.6 mmol) was cooled to -78 °C and treated with a solution of 1,3-diethyl 2-[2-(2- methoxyacetyl)-2-methylhydrazinylidene]propanedioate (i.e. the product obtained in Step A) (12.6 g, 45.9 mmol) in tetrahydrofuran (50 mL), dropwise, over 1 h. The mixture was warmed to -45 °C and maintained at this temperature ( ⁇ 5 °C) for 1.5 h.
  • the reaction was quenched with a previously prepared aqueous HCl solution (100 mL of a 2M solution in MeOH/water: prepared by diluting concentrated aqueous HCl (12N) with methanol), diluted with ethyl acetate (200 mL) and the precipitate was dissolved with water (100 mL).
  • the separated aqueous layer was extracted with ethyl acetate (3 x 100 mL) and the combined organic extracts washed with water (100 mL), brine (100 mL), then dried (Na 2 S0 4 ), filtered and concentrated.
  • the residue was chromatographed through 120 g silica gel eluting with a gradient of 0% to 100% ethyl acetate in hexanes to give the title compound as a light tan oil (6.62 g).
  • Step C Preparation of ethyl l,6-dihydro-5-methoxy-l-methyl-6-oxo-4- [[(trifluoromethyl)sulfonyl]oxy]-3-pyridazinecarboxylate
  • Step D Preparation of ethyl l,6-dihydro-5-methoxy-l,4-dimethyl-6-oxo-3- pyridazinecarboxylate
  • Step F Preparation of ethyl l,6-dihydro-l,4-dimethyl-6-oxo-5-(2-propen-l-yloxy)-3- pyridazinecarboxylate
  • Step G Preparation of 6-[(2-Hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2,5- dimethyl-4-(2-propen-l-yloxy)-3(2H)-pyridazinone
  • aqueous fraction was acidified with HC1 (5 mL of a IN aq. soln), extracted with dichoromethane/methanol (3 x 50 mL of a 4: 1 v/v solution), dried (Na2S04), filtered and concentrated to give l,6-dihydro-l,4-dimethyl-6-oxo-5-(2-propen-l-yloxy)-3- pyridazinecarboxylic acid as a white solid (204 mg). MS (ESI+) 225 (M+H).
  • the carboxylic acid (204 mg, 0.911 mmol) obtained above was dissolved in tetrahydrofuran (5 mL), treated with 2-chloro-l-methylpyridin-l-ium iodide (349 mg, 1.37 mmol), 1,3-cyclohexanedione (112 mg, 1.00 mmol) and N,N-diisopropylethylamine (464 ⁇ , 2.73 mmol). The mixture was heated at 50 °C for 16 h, cooled to ambient temperature, diluted with water (10 mL) and extracted with ethyl acetate (3 x 50 mL).
  • Step C Preparation of 6-[(2-hydroxy-6-oxo-l-cyclohexen-l-yl)carbonyl]-2,5- dimethy l-4-(4-morpholinyl)-3 (2H)-pyridazinone
  • A is A-la and R1 is Me.
  • the present disclosure also includes Tables 2 through 100, each of which is constructed the same as Table 1 above except that the row heading in Table 1 (i.e. "A is A- la and R 1 is Me.") is replaced with the respective row headings shown below.
  • Table 2 the row heading is "A is A- la and R 1 is CL”, and R 2 is as defined in Table 1 above.
  • the first entry in Table 2 specifically discloses 5-chloro-6-[(2-hydroxy-6-oxo- 1 -cyclohexen- 1 -yl)carbonyl]-2,4-dimethyl-3(2H)-pyridazinone.
  • A- la R1 is Br. 53 A is A-3a, R 1 is SCH 2 CF 3 .
  • R 4 A is A-la, R1 is F. 54 A is A-3a, R 1 is SCHF 2 .
  • 6 A is A-la, R 1 is CF 3 . 56 A is A-3a, R 1 is S0 2 Me.
  • R 7 A is A-la
  • R 1 is OMe
  • 57 A is A-3a
  • R 1 is CH 2 OCH 2 CH 2 OMe.
  • R 8 A is A-la
  • R 1 is OCH 2 CF 3 .
  • 58 A is A-3a
  • R 1 is c-Pr.
  • 9 A is A-la, R 1 is O-allyl. 59 A is A-3a, R 1 is NMe 2 .
  • 10 A is A-la
  • R 1 is OCH 2 CH 2 OMe
  • 60 A is A-3a
  • R 1 is N0 2 .
  • 11 A is A-la, R 1 is OCH 2 CN. 61 A is A-5a, R 1 is Me.
  • R 12 A is A-la
  • R 1 is SMe
  • 62 A is A-5a
  • R 1 is CI.
  • R 14 A is A-la, R 1 is SCHF 2 .
  • 64 A is A-5a, R 1 is F.
  • 16 A is A-la
  • R 1 is S0 2 Me.
  • 66 A is A-5a
  • R 1 is CF 3 .
  • 17 A is A-la
  • R 1 is CH 2 OCH 2 CH 2 OMe.
  • 67 A is A-5a
  • R 1 is OMe.
  • 18 A is A-la
  • R1 is c-Pr.
  • 68 A is A-5a
  • R 1 is OCH 2 CF 3 .
  • 19 A is A-la
  • R 1 is NMe 2 .
  • 69 A is A-5a
  • R 1 is O-allyl.
  • 20 A is A-la
  • R 1 is N0 2 .
  • 70 A is A-5a
  • R 1 is OCH 2 CH 2 OMe. is OCH 2 CN.
  • A is A- la, R1 is Me and R 3
  • the present disclosure also includes Tables 102 through 140, each of which is constructed the same as Table 101 above except that the row heading in Table 1 (i.e. "A is A- la, R 1 is Me and R 3 is Et.") is replaced with the respective row headings shown below.
  • Table 102 the row heading is "A is A- la, RHs Me and R 3 is n-Pr.”, and R 2 is as defined in Table 1 above.
  • the first entry in Table 102 specifically discloses 6-[(2- hydroxy-6-oxo- 1 -cyclohexen- 1 -yl)carbonyl]-4,5-dimethyl-2-propyl-3 (2H)-pyridazinone.
  • 102 A is A-la
  • R 1 is Me
  • R J is n-Pr
  • 122 A is A-la
  • R is CI
  • R 3 is «-Pr.
  • 103 A is A-la, R 1 is Me, R 3 is «-Bu.
  • 123 A is A-la, R is CI, R 3 is «-Bu.
  • 104 A is A-la, R 1 is Me, R 3 is c-Pr.
  • 124 A is A-la, R is CI, R 3 is c-Pr.
  • 105 A is A-la
  • R1 is Me
  • R 3 is c-hexyl
  • 125 A is A-la
  • R is CI
  • R 3 is c-hexyl.
  • 106 A is A-la, R 1 is Me, R 3 is CH 2 CF 3 .
  • 126 A is A-la, R is C1, R 3 is CH 2 CF 3 .
  • 107 A is A-la, R 1 is Me, R 3 is CH 2 CH 2 OMe.
  • 127 A is A-la, R is CI, R 3 is CH 2 CH 2 OMe.
  • 108 A is A-la, R 1 is Me, R 3 is allyl.
  • 128 A is A-la, R is CI, R 3 is allyl.
  • 109 A is A-la, R1 is Me, R 3 is propargyl.
  • 129 A is A-la, R is CI, R 3 is propargyl.
  • 110 A is A-la
  • R 1 is Me
  • R 3 is z ' -Pr
  • 130 A is A-la
  • R is CI
  • R 3 is z ' -Pr.
  • 111 A is A-la
  • R 1 is CF 3
  • R 3 is Et.
  • 131 A is A-la
  • R is OMe
  • R 3 is Et.
  • 112 A is A-la
  • R 1 is CF 3
  • R 3 is «-Pr
  • 132 A is A-la
  • R is OMe
  • R 3 is «-Pr.
  • 113 A is A-la
  • R 1 is CF 3
  • R J is «-Bu
  • 133 A is A-la
  • R is OMe
  • R 3 is «-Bu.
  • 114 A is A-la
  • R 1 is CF 3
  • R 3 is c-Pr
  • 134 A is A-la
  • R is OMe
  • R 3 is c-Pr.
  • 115 A is A-la
  • R 1 is CF 3
  • R 3 is c-hexyl
  • 135 A is A-la
  • R is OMe
  • R 3 is c-hexyl.
  • 116 A is A-la, R 1 is CF 3 , R 3 is CH 2 CF 3 .
  • 136 A is A-la, R is OMe, R 3 is CH 2 CF 3 .
  • 117 A is A-la, R 1 is CF 3 , R 3 is CH 2 CH 2 OMe.
  • 137 A is A-la, R is OMe, R 3 is CH 2 CH 2 OMe.
  • 118 A is A-la, R 1 is CF 3 , R 3 is allyl.
  • 138 A is A-la, R is OMe, R 3 is allyl.
  • 119 A is A-la
  • R1 is CF 3
  • R 3 is propargyl
  • 139 A is A-la
  • R is OMe
  • R 3 is propargyl
  • 120 A is A-la
  • R 1 is CF 3
  • R 3 is z ' -Pr
  • 140 A is A-la
  • R is OMe
  • R 3 is z ' -Pr.
  • 121 A is A-la, R 1 is CI, R 3 is Et.
  • a compound of Formula 1 of this invention (including N-oxides and salts thereof) will generally be used as a herbicidal active ingredient in a composition, i.e. formulation, with at least one additional component selected from the group consisting of surfactants, solid diluents and liquid diluents, which serve as a carrier.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include both liquid and solid compositions.
  • Liquid compositions include solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like, which optionally can be thickened into gels.
  • aqueous liquid compositions are soluble concentrate, suspension concentrate, capsule suspension, concentrated emulsion, microemulsion and suspo-emulsion.
  • nonaqueous liquid compositions are emulsifiable concentrate, microemulsifiable concentrate, dispersible concentrate and oil dispersion.
  • compositions are dusts, powders, granules, pellets, prills, pastilles, tablets, filled films (including seed coatings) and the like, which can be water-dispersible ("wettable") or water-soluble. Films and coatings formed from film- forming solutions or flowable suspensions are particularly useful for seed treatment.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • An emulsifiable granule combines the advantages of both an emulsifiable concentrate formulation and a dry granular formulation. High-strength compositions are primarily used as intermediates for further formulation.
  • Sprayable formulations are typically extended in a suitable medium before spraying. Such liquid and solid formulations are formulated to be readily diluted in the spray medium, usually water. Spray volumes can range from about from about one to several thousand liters per hectare, but more typically are in the range from about ten to several hundred liters per hectare. Sprayable formulations can be tank mixed with water or another suitable medium for foliar treatment by aerial or ground application, or for application to the growing medium of the plant. Liquid and dry formulations can be metered directly into drip irrigation systems or metered into the furrow during planting.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, gypsum, cellulose, titanium dioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose), silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Typical solid diluents are described in Watkins et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey.
  • Liquid diluents include, for example, water, N,N-dimethylalkanamides (e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide, N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), ethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, propylene carbonate, butylene carbonate, paraffins (e.g., white mineral oils, normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes, glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons, dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy- 4-methyl-2-pentan
  • Liquid diluents also include glycerol esters of saturated and unsaturated fatty acids (typically C 6 -C 2 2), such as plant seed and fruit oils (e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil), and mixtures thereof.
  • plant seed and fruit oils e.g., oils of olive, castor, linseed, sesame, corn (maize), peanut, sunflower, grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palm kernel
  • animal-sourced fats e.g., beef tallow, pork tallow, lard, cod liver oil, fish oil
  • Liquid diluents also include alkylated fatty acids (e.g., methylated, ethylated, butylated) wherein the fatty acids may be obtained by hydrolysis of glycerol esters from plant and animal sources, and can be purified by distillation.
  • alkylated fatty acids e.g., methylated, ethylated, butylated
  • Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950.
  • the solid and liquid compositions of the present invention often include one or more surfactants.
  • surfactants also known as “surface-active agents”
  • surface-active agents generally modify, most often reduce, the surface tension of the liquid.
  • surfactants can be useful as wetting agents, dispersants, emulsifiers or defoaming agents.
  • Nonionic surfactants useful for the present compositions include, but are not limited to: alcohol alkoxylates such as alcohol alkoxylates based on natural and synthetic alcohols (which may be branched or linear) and prepared from the alcohols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof; amine ethoxylates, alkanolamides and ethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylated soybean, castor and rapeseed oils; alkylphenol alkoxylates such as octylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenol ethoxylates and dodecyl phenol ethoxylates (prepared from the phenols and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); block polymers prepared from ethylene oxide or propylene
  • Useful anionic surfactants include, but are not limited to: alkylaryl sulfonic acids and their salts; carboxylated alcohol or alkylphenol ethoxylates; diphenyl sulfonate derivatives; lignin and lignin derivatives such as lignosulfonates; maleic or succinic acids or their anhydrides; olefin sulfonates; phosphate esters such as phosphate esters of alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates and phosphate esters of styryl phenol ethoxylates; protein-based surfactants; sarcosine derivatives; styryl phenol ether sulfate; sulfates and sulfonates of oils and fatty acids; sulfates and sulfonates of ethoxylated alkylphenols; sulfates of alcohols; sulfates of e
  • Useful cationic surfactants include, but are not limited to: amides and ethoxylated amides; amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amines, ethoxylated diamines and propoxylated amines (prepared from the amines and ethylene oxide, propylene oxide, butylene oxide or mixtures thereof); amine salts such as amine acetates and diamine salts; quaternary ammonium salts such as quaternary salts, ethoxylated quaternary salts and diquaternary salts; and amine oxides such as alkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.
  • amines such as N-alkyl propanediamines, tripropylenetriamines and dipropylenetetramines, and ethoxylated amine
  • Nonionic, anionic and cationic surfactants and their recommended uses are disclosed in a variety of published references including McCutcheon 's Emulsifiers and Detergents, annual American and International Editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; and A. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition, John Wiley and Sons, New York, 1987.
  • compositions of this invention may also contain formulation auxiliaries and additives, known to those skilled in the art as formulation aids (some of which may be considered to also function as solid diluents, liquid diluents or surfactants).
  • formulation auxiliaries and additives may control: pH (buffers), foaming during processing (antifoams such polyorganosiloxanes), sedimentation of active ingredients (suspending agents), viscosity (thixotropic thickeners), in-container microbial growth (antimicrobials), product freezing (antifreezes), color (dyes/pigment dispersions), wash-off (film formers or stickers), evaporation (evaporation retardants), and other formulation attributes.
  • Film formers include, for example, polyvinyl acetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinyl acetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers and waxes.
  • formulation auxiliaries and additives include those listed in McCutcheon 's Volume 2: Functional Materials, annual International and North American editions published by McCutcheon's Division, The Manufacturing Confectioner Publishing Co.; and PCT Publication WO 03/024222.
  • the compound of Formula 1 and any other active ingredients are typically incorporated into the present compositions by dissolving the active ingredient in a solvent or by grinding in a liquid or dry diluent.
  • Solutions, including emulsifiable concentrates can be prepared by simply mixing the ingredients. If the solvent of a liquid composition intended for use as an emulsifiable concentrate is water-immiscible, an emulsifier is typically added to emulsify the active-containing solvent upon dilution with water.
  • Active ingredient slurries, with particle diameters of up to 2,000 ⁇ can be wet milled using media mills to obtain particles with average diameters below 3 ⁇ .
  • Aqueous slurries can be made into finished suspension concentrates (see, for example, U.S. 3,060,084) or further processed by spray drying to form water-dispersible granules. Dry formulations usually require dry milling processes, which produce average particle diameters in the 2 to 10 um range. Dusts and powders can be prepared by blending and usually grinding (such as with a hammer mill or fluid-energy mill). Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • 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.
  • Attapulgite granules low volatile matter, 0.71/0.30 mm;
  • These compounds generally show highest activity for early postemergence weed control (i.e. applied when the emerged weed seedlings are still young) and preemergence weed control (i.e. applied before weed seedlings emerge from the soil). Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures.
  • Compounds of this invention may show tolerance to important agronomic crops including, but not limited to, alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass).
  • important agronomic crops including, but 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
  • Compounds of the invention are particularly useful for selective control of weeds in wheat, barley, and particularly maize, soybean, cotton and perennial plantation crops such as sugarcane and citrus.
  • Compounds of this invention can be used in crops genetically transformed or bred to incorporate resistance to herbicides, express proteins toxic to invertebrate pests (such as Bacillus thuringiensis toxin), and/or express other useful traits.
  • invertebrate pests such as Bacillus thuringiensis toxin
  • the subject compounds are useful to modify plant growth.
  • the compounds of the invention have both postemergent and preemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth
  • the compounds can be usefully applied by a variety of methods involving contacting a herbicidally effective amount of a compound of the invention, or a composition comprising said compound and at least one of a surfactant, a solid diluent or a liquid diluent, to the foliage or other part of the undesired vegetation or to the environment of the undesired vegetation such as the soil or water in which the undesired vegetation is growing or which surrounds the seed or other propagule of the undesired vegetation.
  • a herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of a compound of this invention is about 0.001 to 20 kg/ha with a typical range of about 0.004 to 1 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
  • Compounds of this invention can also be mixed with one or more other biologically active compounds or agents including herbicides, herbicide safeners, fungicides, insecticides, nematocides, bactericides, acaricides, growth regulators such as insect molting inhibitors and rooting stimulants, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants, plant nutrients, other biologically active compounds or entomopathogenic bacteria, virus or fungi to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • Mixtures of the compounds of the invention with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes.
  • the present invention also pertains to a composition
  • a composition comprising a compound of Formula 1 (in a herbicidally effective amount) and at least one additional biologically active compound or agent (in a biologically effective amount) and can further comprise at least one of a surfactant, a solid diluent or a liquid diluent.
  • the other biologically active compounds or agents can be formulated in compositions comprising at least one of a surfactant, solid or liquid diluent.
  • one or more other biologically active compounds or agents can be formulated together with a compound of Formula 1, to form a premix, or one or more other biologically active compounds or agents can be formulated separately from the compound of Formula 1, and the formulations combined together before application (e.g., in a spray tank) or, alternatively, applied in succession.
  • a mixture of one or more of the following herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, ametryn, amicarbazone, amidosulfuron, aminocyclopyrachlor and its esters (e.g., methyl, ethyl) and salts (e.g., sodium, potassium), 4-amino-3-chloro-6-(4-chloro-2-fluoro-3-methoxyphenyl)-2-pyridine- carboxylic acid and its esters (e.g., methyl) and salts (e.g., sodium, potassium), aminopyralid, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azimsulfuron, beflubutamid, benazolin, benazolin-ethy
  • herbicides also include bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc, Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
  • bioherbicides such as Alternaria destruens Simmons, Colletotrichum gloeosporiodes (Penz.) Penz. & Sacc, Drechsiera monoceras (MTB-951), Myrothecium verrucaria (Albertini & Schweinitz) Ditmar: Fries, Phytophthora palmivora (Butl.) Butl. and Puccinia thlaspeos Schub.
  • Compounds of this invention can also be used in combination with plant growth regulators such as aviglycine, N-(phenylmethyl)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl, and plant growth modifying organisms such as Bacillus cereus strain BP01.
  • plant growth regulators such as aviglycine, N-(phenylmethyl)-lH-purin-6-amine, epocholeone, gibberellic acid, gibberellin A 4 and A 7 , harpin protein, mepiquat chloride, prohexadione calcium, prohydrojasmon, sodium nitrophenolate and trinexapac-methyl
  • plant growth regulators such as aviglycine, N-(phenylmethyl)-lH-purin-6-
  • the weight ratio of these various mixing partners (in total) to the compound of Formula 1 is typically between about 1 :3000 and about 3000: 1. Of note are weight ratios between about 1 :300 and about 300: 1 (for example ratios between about 1 :30 and about 30: 1).
  • weight ratios between about 1 :300 and about 300: 1 for example ratios between about 1 :30 and about 30: 1).
  • One skilled in the art can easily determine through simple experimentation the biologically effective amounts of active ingredients necessary for the desired spectrum of biological activity. It will be evident that including these additional components may expand the spectrum of weeds controlled beyond the spectrum controlled by the compound of Formula 1 alone.
  • combinations of a compound of this invention with other biologically active (particularly herbicidal) compounds or agents (i.e. active ingredients) can result in a greater-than-additive (i.e. synergistic) effect on weeds and/or a less-than-additive effect (i.e. safening) on crops or other desirable plants. Reducing the quantity of active ingredients released in the environment while ensuring effective pest control is always desirable. Ability to use greater amounts of active ingredients to provide more effective weed control without excessive crop injury is also desirable.
  • synergism of herbicidal active ingredients occurs on weeds at application rates giving agronomically satisfactory levels of weed control, such combinations can be advantageous for reducing crop production cost and decreasing environmental load.
  • safening of herbicidal active ingredients occurs on crops, such combinations can be advantageous for increasing crop protection by reducing weed competition.
  • a composition of the present invention can further comprise (in a herbicidally effective amount) at least one additional herbicidal active ingredient having a similar spectrum of control but a different site of action.
  • herbicide safeners such as allidochlor, N-(aminocarbonyl)-2-methylbenzenesulfonamide, benoxacor, BCS (1- bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cumyluron, cyometrinil, cyprosulfonamide, daimuron, dichlormid, 4-(dichloroacetyl)-l-oxa-4-azospiro[4.5]decane (MON 4660), 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), dicyclonon, dietholate, dimepiperate, ethyl 1 ,6-dihydro- 1 -(2-methoxyphenyl)-6-oxo-2-phenyl-5- pyrimidinecarboxylate, fenchlorazole-
  • herbicide safeners such as allidoch
  • Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of this invention and an antidotally effective amount of a herbicide safener. Seed treatment is particularly useful for selective weed control, because it physically restricts antidoting to the crop plants. Therefore a particularly useful embodiment of the present invention is a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of the crop with a herbicidally effective amount of a compound of this invention wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.
  • composition comprising a compound of the invention (in a herbicidally effective amount), at least one additional active ingredient selected from the group consisting of other herbicides and herbicide safeners (in an effective amount), and at least one component selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • Preferred for better control of undesired vegetation e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety
  • a herbicide selected from the group consisting of 2,4-D, ametryne, aminocyclopyrachlor, aminopyralid, atrazine, bromacil, bromoxynil, bromoxynil octanoate, carfentrazone-ethyl, chlorimuron-ethyl, chlorsulfuron, clopyralid, clopyralid-olamine, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, diflufenican, dimethenamid, dimethenamid-P, diuron, florasulam, flufenacet, flumetsulam, flumioxazin, flupyrsulfuron-
  • a herbicide selected from the group consisting of 2,4-D, a
  • Table Al lists specific combinations of a Component (a) with Component (b) illustrative of the mixtures, compositions and methods of the present invention.
  • Compound 1 in the Component (a) column is identified in Index Table A.
  • the second column of Table Al lists the specific Component (b) compound (e.g., "2,4-D" in the first line).
  • the third, fourth and fifth columns of Table Al lists ranges of weight ratios for rates at which the Component (b) compound is typically applied to a field-grown crop relative to Component (a).
  • the first line of Table Al specifically discloses the combination of Component (a) with 2,4-D is typically applied in a weight ratio between 1:192 to 6:1.
  • the remaining lines of Table Al are to be construed similarly.
  • Component (a) Component (b) Weiaht Ratio Weiaht Ratio Weiaht Ratio Weiaht Ratio
  • Compound 1 Amitrole 1:768 to 2:1 1:256 to 1:2 1:96 to 1:11
  • Compound 1 Anilofos 1:96 to 12:1 1:32 to 4:1 1:12 to 1:2
  • Component (a) Component (b) Weiaht Ratio Weiaht Ratio Weiaht Ratio Weiaht Ratio
  • Compound 1 Carfenstrole 1:192 to 6:1 1:64 to 2:1 1:24 to 1:3
  • Component (a) Component (b) Weiaht Ratio Weiaht Ratio Weiaht Ratio Weiaht Ratio
  • Compound 1 Diclosulam 1:10 to 112:1 1:3 to 38:1 1:1 to 7:1
  • Compound 1 Fenoxaprop-ethyl 1:120 to 10:1 1:40 to 4:1 1:15 to 1:2
  • Component (a) Component (b) Weiaht Ratio Weiaht Ratio Weiaht Ratio Weiaht Ratio
  • Component (a) Component (b) Weiaht Ratio Weiaht Ratio Weiaht Ratio Weiaht Ratio

Abstract

L'invention porte sur des composés de la formule 1, y compris tous les stéréo-isomères, N-oxydes et sels de ceux-ci, dans ladite formule A représentant un radical choisi dans le groupe constitué par les formules A-1, A-2, A-3, A-4, A-5, A-6 et A-7 et B1, B2, B3, T, R1, R2, R3, R3A, R4, R5, R6, R7, R8, R9, R10, R11, R12 et R13 étant tels que définis dans la description. L'invention porte également sur des compositions contenant les composés de la formule 1 et sur des procédés pour lutter contre la végétation non désirée comportant la mise en contact de la végétation non désirée ou de son environnement à l'aide d'une quantité efficace d'un composé ou d'une composition selon l'invention.
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