WO2004035545A2 - Azolecarboxamide herbicides - Google Patents

Azolecarboxamide herbicides Download PDF

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Publication number
WO2004035545A2
WO2004035545A2 PCT/US2003/032965 US0332965W WO2004035545A2 WO 2004035545 A2 WO2004035545 A2 WO 2004035545A2 US 0332965 W US0332965 W US 0332965W WO 2004035545 A2 WO2004035545 A2 WO 2004035545A2
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WIPO (PCT)
Prior art keywords
alkyl
haloalkyl
alkenyl
compound
ethyl
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PCT/US2003/032965
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French (fr)
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WO2004035545A3 (en
Inventor
Dominic Ming-Tak Chan
Balreddy Kamireddy
Hyeong Baik Kim
Kanu Maganbhai Patel
Paula Louise Sharpe
Mark S. Casini
Ming Xu
Gregory Russell Armel
Thomas Martin Stevenson
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E.I. Du Pont De Nemours And Company
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Priority to AU2003301443A priority Critical patent/AU2003301443A1/en
Priority to PCT/US2004/010711 priority patent/WO2004106324A1/en
Publication of WO2004035545A2 publication Critical patent/WO2004035545A2/en
Publication of WO2004035545A3 publication Critical patent/WO2004035545A3/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/04—1,2,3-Triazoles; Hydrogenated 1,2,3-triazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • This invention relates to certain azolecarboxamides their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation.
  • This invention is directed to a compound of Formula I including all geometric and stereoisomers, N-oxides or agriculturally suitable salts thereof, agricultural compositions containing them and their use as herbicides:
  • T is CR 6 or N; U is CR ⁇ or N; Y is CR 8 or N; Z is CR 9 or N; R la is H, C!-C 4 alkyl, fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl,
  • R lb is halogen, Cv-C 4 alkyl, ⁇ -04 fluoroalkyl, C 2 -C alkenyl, C 2 -C 4 fluoroalkenyl,
  • R l is H;
  • R 2a is Cj-C ⁇ alkyl, C ⁇ Cg haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl,
  • R 2b is Cj-C ⁇ alkyl, C ⁇ - ⁇ haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, C 4 -C 6 alkylcycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 6 cycloalkylalkyl or C 5 -C 6 alkylcycloalkylalkyl;
  • R 3 is H, F or -O ⁇ alkyl
  • R 4 is H, Cj-C 2 alkyl, C 2 -C6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkoxyalkyl or C2-Cg alkylthioalkyl;
  • R5 is C(O)ORl 2 , COR* 3 , C(NORl4)Rl5, _ CN> 0 Rl6, S(O) m Rl7
  • R 6 is H, F, C 1 -C 2 alkyl, Cr-C 2 fluoroalkyl, alkoxy, C x -C 2 fluoroalkoxy,
  • R 5 and R 6 are taken together as a radical selected from -C(W 1 )N(R 11 )(CH2) n - and
  • R 7 is H, F, Ci-02 alkyl, fluoroalkoxy
  • R 8 and R 9 are independently selected from H, F, Ct ⁇ C 2 alkyl, Cj-C2 fluoroalkyl,
  • R 10 is H, C ⁇ . alkyl, C j -Gj. haloalkyl, C 3 -C 4 alkenyl, C 2 -C 4 alkoxymethyl or C 2 -C4 alkylthiomethyl;
  • R 11 is H, C ! -C 5 alkyl, Ci-Cs haloalkyl, C 2 -C 5 alkenyl, C 3 -C 5 haloalkenyl,
  • R 15 is C1-C3 alkyl, C ⁇ -C 3 haloalkyl or cyclopropyl
  • R 16 is C1-C4 alkyl, C1-C4 haloalkyl, C 2 -C 3 alkoxyalkyl, C 2 -C 3 alkylthioalkyl
  • R 17 is C!-C 4 alkyl, Ct-C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 4 haloalkenyl,
  • R 22 is Ct-C 3 alkyl
  • R 21 and R 22 are taken together as -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -, each optionally substituted with 1-2 methyl;
  • R 23 is C!-C 2 alkyl or C ⁇ haloalkyl;
  • R 24 is Ct-C 2 alkyl or C ⁇ haloalkyl
  • R 25 is 0 ⁇ 2 alkyl or C C ⁇ haloalkyl
  • R 27 is Ct-C 3 alkyl, ⁇ -03 haloalkyl or cyclopropyl;
  • R 28 and R 28b are independently Ct-C 2 alkyl or C ] -C2 alkoxy;
  • W is O or S
  • Y 1 and Y 2 are independently CH 2 , O, S, NH or NCH 3 ; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that
  • R la or R lb is selected from the radicals of the group consisting of Ct-C 3 alkyl, C - ⁇ fluoroalkyl, C2-C3 alkenyl, C 2 -C 3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
  • R 5 and R 6 are taken together as -C(W 1 )N(R 10 )(CH 2 ) n - and n is 1 , then R 10 is 0 ⁇ 4 alkyl, Cv-C 4 haloalkyl, C3-C4 alkenyl, C 2 -C alkoxymethyl or C 2 -C 4 alkylthiomethyl;
  • R 10 and R 11 is haloalkyl, then R la or R lb is CH 2 CH
  • this invention pertains to a compound of Formula I, including all geometric and stereoisomers, N-oxides or agriculturally suitable salts thereof.
  • This invention also relates to a herbicidal composition comprising a herbicidally effective amount of a compound of Formula I and at least one of a surfactant, a solid diluent or a liquid diluent.
  • This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula I (e.g., as a composition described herein).
  • This invention also relates to 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 Formula I and an antidotally effective amount of a safener.
  • the present invention also relates to a herbicidal mixture comprising a herbicidally effective amount of a compound of Formula Iz including all geometric and stereoisomers, N-oxides and agriculturally suitable salts thereof
  • T is CR 6 or N
  • U is CR 7 or N
  • Y is CR 8 or N;
  • Z is CR 9 or N;
  • R la is H, C]-C 4 alkyl, C!-C 4 fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl,
  • R lb is halogen, C]-C alkyl, C 1 -C 4 fluoroalkyl, C 2 -C alkenyl, C 2 -C 4 fluoroalkenyl,
  • R 2 is Ci-Cg alkyl, Cj-Cg haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl,
  • R 2b is Cj-Cg alkyl, C ⁇ Cg haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl,
  • R 3 is H, F or alkyl; or
  • R 2a or 2 b is taken together with R 3 as -C(R 26 )(R 6 b )-(Y 1 ) s -(CH 2 ) t -(Y 2 ) u - or
  • R 4 is H, C 1 -C alkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkoxyalkyl or C 2 -C6 alkylthioalkyl;
  • R5 is C(O)OR 12 , COR 13 , C(NOR 14 )R 15 , -CN, OR 16 , S(O) m R 17
  • R6 is H, F, Ct-C 2 alkyl, C]-C 2 fluoroalkyl, Ct-C 2 alkoxy, C ! -C 2 fluoroalkoxy,
  • R5 and R 6 are taken together as a radical selected from -C(W 1 )N(R 1 l )(CH 2 ) n - and
  • R 7 is H, F, Cj-C 2 alkyl, fluoroalkoxy
  • R 8 and R 9 are independently selected from H, F, Cj-C 2 alkyl, C1-C2 fluoroalkyl,
  • R 10 is H, C!-C 4 alkyl, Ci-C 4 haloalkyl, C 3 -C 4 alkenyl, C 2 -C 4 alkoxymethyl or
  • R 11 is H, C!-C 5 alkyl, C ⁇ s haloalkyl, C 2 -C 5 alkenyl, C 3 -C 5 haloalkenyl,
  • each R 12 is independently C1-C5 alkyl, C1-C5 haloalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C alkylthioalkyl, C2-C5 alkenyl, C 3 -C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C 4 -C5 cycloalkylalkyl;
  • R 13 is C1-C3 alkyl, C -C 3 haloalkyl or cyclopropyl;
  • R 14 is H, Ci-C 4 alkyl, C!-C 4 haloalkyl, C3-C4 alkenyl, C 2 -C 6 alkylcarbonyl or
  • R 15 is C2-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
  • R 16 is Ci-C 4 alkyl, CJ- J haloalkyl, C 2 -C 3 alkoxyalkyl, C 2 -C 3 alkylthioalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl;
  • R 17 is Ci-C/j. alkyl, Ct-C 4 haloalkyl, C 2 -C 4 alkenyl, C3-C4 haloalkenyl,
  • R 22 is C!-C 3 alkyl
  • R 21 and R 22 are taken together as -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -, each optionally substituted with 1-2 methyl;
  • R 23 is Ci-C ⁇ alkyl or Cj-C 2 haloalkyl;
  • R 24 is Ct-C 2 alkyl or C C 2 haloalkyl;
  • Yl and Y 2 are independently CH 2 , 0, S, NH or NCH 3 ; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that (a) when R 5 is C(W 1 )NR 10 R 11 or C(NORl )R 15 , then R 9 is other than alkoxy or alkylthio;
  • R la or R lb is selected from the radicals of the group consisting of Cj-C alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
  • R 10 is C1-C4 alkyl, haloalkyl, C3-C4 alkenyl, C 2 -C 4 alkoxymethyl or C 2 -C4 alkylthiomethyl;
  • R la or R l is CH 2 CH 3 or
  • CH 2 CF3 and R 2a or R 2b is tert-butyl, isopropyl or cyclopropyl;
  • R lb is halogen, C 2 -C 4 alkyl, Ci-C ⁇ fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl, C 2 -C 4 alkynyl or C 2 -C 4 fluoroalkynyl;
  • the present invention further relates to a herbicidal composition
  • a herbicidal composition comprising said herbicidal mixture and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the present invention also relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula Iz and effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener (e.g., in the form of the aforedescribed herbicidal mixture or herbicidal composition).
  • a herbicide safener e.g., in the form of the aforedescribed herbicidal mixture or herbicidal composition.
  • a particular aspect of the present invention relates to a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of a crop with an effective amount of a compound of Formula Iz and an antidotally effective amount of a herbicide safener (e.g., safener applied as a seed treatment).
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, rc-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl which are independently selected.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl” also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl” includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy and pentoxy 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 CH2OCH 2 CH 2 .
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio and pentylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH3CH 2 SCH2CH 2 .
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group.
  • alkylsulfinyl examples include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl isomers.
  • alkenylthio alkenylsulfinyl
  • alkenylsulfonyl alkynylthio
  • alkynylsulfinyl alkynylsulfonyl
  • cycloalkoxy includes the same groups linked through an oxygen atom such as cyclopropyloxy and cyclobutyloxy.
  • cycloalkylalkyl examples include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • Cycloalkylalkoxy includes cyclopropylmethoxy.
  • Alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclo ⁇ entyl.
  • carbocyclic ring denotes a ring wherein the atoms forming the ring backbone and selected only from carbon.
  • “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.
  • aromatic ring system denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic. Aromatic indicates that each of ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n + 2) ⁇ electrons, where n is 0 or a positive integer, are associated with the ring to comply with H ⁇ ckel's rule.
  • aromatic carbocyclic ring system includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic.
  • nonaromatic carbocyclic ring system denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles wherein none of the rings in the ring system are aromatic.
  • aromatic heterocyclic ring system and “heteroaromatic ring” include fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic.
  • nonaromatic heterocyclic ring system denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles wherein none of the rings in the ring system are aromatic.
  • the heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • 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.
  • N-oxides of heterocycles are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethydioxirane
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • CF 3 CH 2 CH CHCH 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • fluoroalkyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • fluoroalkyl fluoroalkenyl
  • fluoroalkynyl may be partially or fully substituted with fluorine atoms.
  • C1-C3 alkyl designates methyl through propyl
  • C 2 alkoxyalkyl designates CH3UCH 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 CH3CH2OCH2CH2.
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the agriculturally suitable salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the agriculturally suitable salts of the compounds of the invention also include those formed with strong bases (e.g., hydrides or hydroxides of sodium, potassium or lithium).
  • Preferred 1 A compound of Formula I wherein when J is J-1 and R la is CH3 then at least one of T and U is ⁇ or C-F. Preferred 2. A compound of Preferred 1 wherein when J is J-1 and R la is CH 3 then at least one of T and U is C-F. Preferred 3. A compound of Formula I wherein when J is J-1, R la is CH 3 and T is ⁇ then U is N or C-F. Preferred 4. A compound of Preferred 3 wherein when J is J-1, R la is CH 3 and T is N then U is C-F.
  • R la is C -C4 alkyl, Ct-C fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C fluoroalkenyl, C 2 -C 4 alkynyl or C 2 -C 4 fluoroalkynyl.
  • R la is C -C4 alkyl, Ct-C fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C fluoroalkenyl, C 2 -C 4 alkynyl or C 2 -C 4 fluoroalkynyl.
  • R la or R lb is selected from the radicals in the group consisting of C 1 -C 3 alkyl, C 1 -C 3 fluoroalkyl, C 2 -C 3 alkenyl, C 2 -C 3 fluoroalkenyl, C 2 -C 3 alkynyl or C -C 3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring.
  • R la or R lb is CH 2 CH 3 , CH 2 CH 2 F,
  • Preferred 14 A compound of Formula I wherein R 2a or R 2b is tert-butyl, isopropyl or cyclopropyl.
  • Preferred 17 A compound of Preferred 16 wherein the sum of s, t and u is 2 and the sum of v and w is 0;
  • a compound of Preferred 16 wherein R 26a is C1-C2 alkyl. Preferred 19. A compound of Preferred 18 wherein R 26a and R 26b are CH3. Preferred 20. A compound of Formula I wherein R 3 is H. Preferred 21. A compound of Formula I wherein R 4 is H. Preferred 22. A compound of Formula I wherein the carbon atom of R 12 linking to oxygen is bonded to at least one hydrogen atom. Preferred 23. A compound of Formula I wherein R 5 is CONRiOR 11 or C(O)OR 12 ;
  • Preferred 24 A compound of Preferred 23 wherein R 5 is CONRiOR 11 ; R 10 is H or
  • Preferred 25 A compound of Formula I wherein R 6 is H or F.
  • Preferred 26 A compound of Formula I wherein R 7 is H or F.
  • Preferred 27 A compound of Formula I wherein R 8 and R 9 are H or F.
  • Preferred 28 A compound of Formula I wherein T is C-F or N.
  • Preferred 29 A compound of Formula I wherein U is C-F or N.
  • J J-1 and R la is H, which is particularly useful as a synthetic intermediate. Combinations of preferred groups are illustrated by:
  • Preferred A A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5 or J-8.
  • Preferred C A compound of Preferred B wherein at most one of T, U, Y and Z is N.
  • Preferred D A compound of Preferred C wherein R 5 is CONR 10 R ⁇ or C(O)OR 12 ;
  • Preferred E A compound of Preferred D wherein R 6 is H or F and R 7 is H or F.
  • Preferred F A compound of Preferred E wherein J is J-1 , J-3 or J-5.
  • Preferred G A compound of Preferred F wherein R 5 is CONR ⁇ R 11 ; R 10 is H or
  • Preferred H A compound of Preferred G wherein R 2a is tert-butyl or isopropyl;
  • R 8 and R 9 are H or F.
  • Preferred I A compound of Formula I wherein at most one of T, U, Y and Z is N; R la or R lb is selected from the radicals in the group consisting of C ] -C 3 alkyl, C!-C 3 fluoroalkyl, C 2 -C 3 alkenyl, C -C 3 fluoroalkenyl, C 2 -C 3 alkynyl or C 2 -
  • R 6 is H or F
  • R 7 is H or F
  • R 4 is H
  • R 26a is C 1 -C 2 alkyl
  • W is O
  • Y 1 and Y 2 are independently CH2 or O
  • the sum of s, t and u is 2
  • the sum of v and w is 0.
  • Preferred J A compound of Preferred I wherein R la or R lb is CH 2 CH 3 , CH 2 CH 2 F,
  • R 2a or R 2b is tert-butyl, isopropyl or cyclopropyl, and R 3 is H.
  • Preferred K A compound of Preferred J wherein R 5 is CONR 10 R or C(O)OR 12 ;
  • Preferred L A compound of Preferred K wherein R 2a or R 2b is tert-butyl or isopropyl.
  • Preferred M A compound of Preferred L wherein J is J-1, J-2, J-3, J-4, J-5 or J-8.
  • Preferred N A compound of Preferred M wherein R 5 is CONR ⁇ R 11 ; R 10 is H or
  • Preferred O A compound of Preferred N wherein R 8 and R 9 are H or F.
  • Preferred P A compound of Preferred O wherein J is J-1, J-3 or J-5.
  • R 2a is C ⁇ -Cg alkyl, C ⁇ -Cg haloalkyl, C 2 -C6 alkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkenyl, C 2 -Cg haloalkenyl, C 2 -Cg alkynyl, C 2 -Cg haloalkynyl, C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C 4 -C 6 cycloalkylalkyl, C 5 -C 6 alkylcycloalkylalkyl, -CR 20 (OR 21 )(OR 22 ) or Sj R 23 R 24 R 25 ; R 2b is Cl -Cg alkyl, C 2 -C6 alkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -Cg alkeny
  • the preferred herbicidal compositions of the present invention are those involving the above preferred compounds.
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • This invention also relates to 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 the compounds of the invention and an antidotally effective amount of a safener.
  • the preferred methods of use are those involving the above preferred compounds.
  • Formula I is a subgenus of Formula Iz; Formulae I and Iz share the same substituent group definitions, but the scope of Formula Iz is not constrained by provisos (a) and (b) of Formula I.
  • J, W, R la , R l , R l , R 2a , R 2b , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , Ri5, Ri6, R17, R 18, R 19 R 20, R 21, R 22, R 23, R 24 ; R 25, R 26 a> R 26b ; R 27, R 28a ; R 28b , W, W 1 , T, U, Y, Z, m, n, s and v in the compounds of Formulae I through Ig, Iz and 1 through 63 below are as defined above in the Summary of the Invention unless otherwise indicated.
  • Compounds of Formulae la through Ig are various subsets of the compounds of Formulae I and Iz, compounds of Formula 2a and 2b are subsets of the compounds of Formula 2, and compounds of Formulae 17a through 17j are subsets of the compounds of Formula 17.
  • the reaction is carried out in an anhydrous aprotic solvent such as dichloromethane or tetrahydrofuran, preferably in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine, at a temperature typically between room temperature and 70 °C to provide the amide of Formula la.
  • a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine
  • R 4 is alkylcarbonyl or alkoxycarbonyl
  • a strong base such as sodium hydroxide and phase transfer conditions such as those described by M. J. Haddadin et al., Heterocycles 1984, 22, 113 may be advantageous.
  • compounds of Formula la can be prepared by coupling the appropriately substituted azole carboxylic acid of Formula 3 with appropriately substituted amino compound of Formula 2 as shown in Scheme 2.
  • This reaction is carried out in the presence of a dehydrating coupling reagent such as dicyclohexyl carbodiimide, l-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 1-propane- phosphonic acid cyclic anhydride or carbonyl diimidazole in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine in an anhydrous aprotic solvent such as dichloromethane or tetrahydrofuran at a temperature typically between room temperature and 70 °C.
  • a dehydrating coupling reagent such as dicyclohexyl carbodiimide, l-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 1-propane- phosphonic acid cyclic anhydride or carbonyl diimidazole in the
  • compounds of Formula lb (Formula I or Iz wherein W is S) can be prepared from corresponding compounds of Formula la by treatment with a thionating reagent such as P 2 S5 (see for example, E. Klingsberg et al., J. Am. Chem. Soc. 1951, 72, 4988; E. C. Taylor Jr. et al, /. Am. Chem. Soc. 1953, 75, 1904; R. Crossley et al., J. Chem. Soc. Perkin Trans. 1 1976, 977; J. Noss et al., Justus Liebigs Ann. Chem.
  • a thionating reagent such as P 2 S5
  • compounds of Formula lb can be directly prepared from the corresponding carboxylic acid of Formula 3 and amino compound of Formula 2 by treatment with (EtO)2P(S)SH according to the general procedure of ⁇ . Borthakur et al., Tetrahedron Lett. 1995, -? ⁇ 5(37), 6745.
  • compounds of Formula la or lb wherein R 4 is alkyl, alkylcarbonyl, alkoxycarbonyl, alkoxyalkyl or alkylthioalkyl can be prepared from the corresponding compounds of Formula la or lb wherein R 4 is H by treatment with the appropriate alkylating or acylating reagents in the presence of base using methods well known in the art.
  • Acyl chlorides of Formula 1 can be prepared from the carboxylic acids of Formula 3 by using methods well known in the art such as treatment with oxalyl chloride and catalytic N,N-dimethylformamide in dichloromethane or treatment with thionyl chloride. This preparation is illustrated in Step E of Example 1, Step C of Example 12, Step B of Example 13, Step D of Example 14, and Step E of Example 25.
  • compounds of Formula I can be prepared from other compounds of Formula I (or Iz).
  • a compound of Formula lc wherein R 30 is NR 10 R or OR 12 (Formula I or Iz wherein R 5 is C(O)NR 10 R 11 or C(O)OR 12 ) can be prepared from the corresponding carboxylic acid of Formula 4, which is in turn prepared from a compound of Formula lc wherein R 30 is OR 12 as shown in Scheme 4.
  • ester compound of Formula lc wherein R 30 is OR 12 is converted to the corresponding carboxylic acid of Formula 4 by general procedures well known in the art such as by treatment with aqueous lithium hydroxide in tetrahydrofuran, followed by acidification.
  • the carboxylic acid of Formula 4 is then converted to the corresponding carboxamide of Formula lc wherein R 30 is NR 10 R 12 or ester of Formula lc wherein R 30 is OR 12 by amidation or esterification procedures well known in the art.
  • One procedure illustrated in Scheme 4 involves conversion of the carboxylic acid of Formula 4 to an intermediate carbonyl chloride by treatment with oxalyl chloride preferably in the presence of N,N-dimethylformamide and an inert solvent such as dichloromethane, and then contacting the intermediate carbonyl chloride with the appropriate amine of Formula 5 or alcohol of Formula 6 to prepare the carboxamide or ester, respectively.
  • a dehydrating coupling reagent can be used analogous to the method of Scheme 2.
  • the method of Scheme 4 is illustrated in Examples 2, 3, 5, 6 and 9, Steps A and B of Example 11, and Example 23.
  • compounds of Formula I can be prepared from compounds structurally related to Formula I (or Iz).
  • compounds of Formula Id can be prepared from corresponding compounds of Formula 7 by treatment with the corresponding sulfonating reagent of Formula 8 wherein X 1 is a leaving group such as halogen or OS(O) 2 R 27 .
  • X 1 is preferably Cl.
  • the reaction is conducted in the presence of a base such as pyridine, triethylamine or 4-(dimethylarnino)pyridine in solvents such as dichloromethane or tetrahydrofuran at temperatures typically between 0 and 70 °C under an inert atmosphere.
  • a base such as pyridine, triethylamine or 4-(dimethylarnino)pyridine
  • solvents such as dichloromethane or tetrahydrofuran
  • compounds of Formula Ie can be prepared from corresponding compounds of Formula 7 by treatment with the corresponding phosphorating reagent of Formula 9 wherein X 2 is a leaving group such as halogen.
  • X 2 is preferably Cl.
  • the reaction is conducted in the presence of a base such as pyridine, triethylamine or 4-(dimethylamino)pyridine in solvents such as dichloromethane or tetrahydrofuran at temperatures typically between 0 and 70 °C under an inert atmosphere.
  • a base such as pyridine, triethylamine or 4-(dimethylamino)pyridine
  • solvents such as dichloromethane or tetrahydrofuran
  • Compounds of Formula I (or Iz) can also be prepared from other compounds of Formula I (or Iz) wherein substituents on the J groups are introduced or elaborated. For example, halogens can be attached using electrophilic addition reactions.
  • Example 21 illustrates the addition of fluorine as R 3 wherein J of Formula I (or Iz) is J-1.
  • Carboxylic acids of Formula 3 can be prepared from corresponding esters of Formula
  • R 31 is a carbon-based radical such as alkyl (e.g., methyl, ethyl), benzyl, etc. as shown in Scheme 7.
  • hydroxide such as aqueous sodium hydroxide or aqueous lithium hydroxide in tetrahydrofuran
  • acidification typically with a strong mineral acid such as hydrochloric or sulfuric acid.
  • a strong mineral acid such as hydrochloric or sulfuric acid.
  • Carboxylic esters of Formula 17a (Formula 17 wherein J is J-1 and R 31 is ethyl) can be prepared according to the general method described by J. J. Parlow et al., J. Org. Chem.
  • This method involves base-induced condensation of a ketone of Formula 18 with diethyl oxalate (19) to give a tricarbonyl compound of Formula 20, which is condensed with a hydrazine of Formula 21 to prepare the pyrazolecarboxylate of Formula 17a.
  • the condensation of the tricarbonyl compound of Formula 20 with the hydrazine of Formula 21 is typically conducted in an alcohol, ester or carbonate diester solvent.
  • the hydrazine of Formula 21 can be in the form of a salt.
  • the diketoester of Formula 20 can be alkylated or fluorinated to provide the corresponding diketoester of Formula 20 wherein R 3 is alkyl or fluorine.
  • the method of Scheme 8 is illustrated in Steps A and B of Example 1 and Steps A and B of Example 25.
  • the pyrazolecarboxylate of Formula 17a can be alkylated with the appropriate alkylating agent in the presence of a base and solvent to give a pyrazolecarboxylate of Formula 17a wherein R la is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl.
  • Appropriate alkylating agents are typically of the formula R la X (22) wherein X is a nucleophihc reaction leaving group (e.g., bromide, iodide, mesylate (OS(O) 2 CH3), triflate (OS(O) 2 CF3), tosylate (OS(O)2Ph-4-CH 3 ), etc.).
  • Typical bases include potassium tert-butoxide, potassium carbonate, sodium hydride and potassium hydroxide.
  • Typical solvents include N,N-dimethylformamide, acetonitrile and tetrahydrofuran. A particularly useful combination of base and solvent is potassium carbonate in acetonitrile. Alkylation isomers can be separated by common methods such as chromatography and crystallization. This modification is illustrated in Step C of Example 1 and Step C of Example 25.
  • R la groups can be converted to others on compounds of Formula 17a.
  • R la is 2-hydroxyethyl
  • DAST diethylaminosulfur trifluoride
  • the product compounds of Formula 17a wherein R la is 2-fluoroethyl and vinyl can then be separated by methods known in the art such as chromatography on silica gel and crystallization.
  • a compound of Formula 17a wherein R 2a is a l,l-dimethyl-2-haloethyl group can be prepared by first including R 2a in Formula 18 as a 1,1 -dimethyl -2-hydroxyethyl group protected as a tetrahydropyranyl ether (e.g., prepared from dihydropyran and pyridinyl -tosylate (PPTS) using the general procedure of M. Miyashita et al., J. Org. Chem.
  • PPTS pyridinyl -tosylate
  • Formula 17c (Formula 17 wherein J is J-3 and R 31 is ethyl) wherein R lb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can be prepared from sydnones of Formula 23 and alkynes of Formula 24 according to the general method of J. Heterocycl. Chem. 1993, 30, 365-371 and J. Heterocycl. Chem. 1996, 33, 719-726 as depicted in Scheme 9. (One skilled in the art recognizes that to prepare 17b without a substituent at the pyrazole 5-position as specified for Formula 17b (J-2), the R 3 radical in the sydnone of Formula 23 must be hydrogen.)
  • sydnones of Formula 23 are heated with alkynes of Formula 24 in higher boiling solvents (e.g., xylenes, toluene, dioxane, ethylene glycol) for typically 12-72 hours.
  • the isomers 17b and 17c then can be separated by the usual methods such as column chromatography and distillation.
  • the sydnones of Formula 23 can be prepared using the general methods described in J. Heterocycl. Chem. 1993, 30, 365-371, /. Heterocycl. Chem. 1996, 33, 719-726 and the references cited therein.
  • the method of Scheme 9 is illustrated in Step A of Example 12 and Step A of Example 14.
  • Carboxylic esters of Formula 17d (Formula 17 wherein J is J-3 but R 2c can be H as well as R 2b ; R 3 is H and R 31 is ethyl) wherein R lb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can also be prepared according to the method depicted in Scheme 10 wherein R 32 is NMe 2 or OEt when (MeO) 2 CHNMe 2 or HC(OEt) 3 , respectively, is used to prepare intermediate 26.
  • the intermediate of Formula 26 is prepared from the ketoester of Formula 25 according to the general procedures published in /. Heterocycl. Chem., 1987, 24, 693-695.
  • the starting ketoesters of Formula 25 can, in turn, be prepared according to the general procedures of J. Org. Chem. 1997, 62, 5908-5919.
  • the condensation of the ketoester of Formula 26 with the hydrazine of Formula 27 is typically conducted in an alcohol, ester or carbonate diester solvent.
  • the hydrazine of Formula 27 can be in the form of a salt.
  • the pyrazolecarboxylate of Formula 17d can be alkylated with the appropriate alkylating agent in the presence of a base and solvent to give a pyrazolecarboxylate of Formula 17d wherein R 2c is R 2b .
  • Appropriate alkylating agents are typically of the formula R 2b X (28) wherein X is a nucleophihc reaction leaving group (e.g., bromide, iodide, mesylate (OS(O) 2 CH 3 ), triflate (OS(O) 2 CF 3 ), tosylate (OS(O) 2 Ph-4-CH 3 ), etc.).
  • Typical bases include potassium tert-butoxide, potassium carbonate, sodium hydride and potassium hydroxide.
  • Typical solvents include N,N-dimethylformamide, acetonitrile and tetrahydrofuran. Alkylation isomers can be separated by common methods such as chromatography and crystallization.
  • Compounds of Formula 17b can also be prepared using methods or slight modification thereof taught in: /. Heterocycl. Chem. 1999, 36(1), 217- 220, Agric. Biol. Chem. 1984, 48(1), 45-50, Bull. Soc. Chim. Fr. 1978, (7-8, Pt. 2), 401-14, Khim. Geterotsikl. Soedin. 1968, 4(4), 685-94, European Patent Application Publication EP 419917 and Spanish Patent ES 493459 (1981).
  • Compounds of Formula 17c i.e. pyrazole isomer J-3
  • Compounds of Formula 17c i.e. pyrazole isomer J-3
  • Compounds of Formula 17c i.e. pyrazole isomer J-3
  • Compounds of Formula 17c i.e. pyrazole isomer J-3
  • Compounds of Formula 17c i.e. pyrazole isomer J-3
  • pyrazoles of Formulae 17b and 17c (wherein R lb is halogen) can be prepared from corresponding pyrazoles of Formula 17e (Formula 7 wherein J is J-2 but R lb is H; and R 31 is ethyl) and Formula 17f (Formula 17 wherein J is J-3 but R lb is H; and R 31 is ethyl), respectively.
  • One variation of method of Scheme 11 involves heating a compound of Formula 17e or 17f with N-chloro- or N-bromosuccinimide in an organic solvent such as N,N-dimethyl- formamide, at temperatures between 30 and 110 °C, preferably at about 60 °C.
  • an organic solvent such as N,N-dimethyl- formamide
  • bromine or chlorine can be added at or below room temperature to a compound of Formula 17e or 17f in a halocarbon solvent such as dichloromethane, trichloromethane or tetrachloromethane to give the corresponding compound of Formula 17b or 17c, respectively.
  • the method of Scheme 11 is illustrated in Step B of Example 14.
  • Pyrazoles of Formula 17b and 17c wherein R lb is halogen can also be prepared using the general methods taught in: Bulletin of the Korean Chemical Society 1998, 19(1), 725- 726, Izv. Akad. Nauk SSSR, Ser. Khim. 1981, (6), 1342-8, Izv. Akad. Nauk SSSR, Ser. Khim. 1980, (5), 1071-7, /. Heterocycl. Chem. 1997, 34(2), 537-540, /. Heterocycl. Chem. 1991, 28(8), 1849-52, J. Fluorine Chem. 1988, 39(3), 435-40, U.S. Patent No.
  • Thiazolecarboxylates of Formula 17g (Formula 17 wherein J is J-4) can be prepared as illustrated in Scheme 12.
  • acyl chloride of Formula 29 which can be prepared by a variety of general methods known in the art; many acyl chlorides of Formula 29 are commercially available.
  • the acyl chloride of Formula 29 is treated with an ammonia solution to prepare the carboxamide of Formula 30, which is in turn treated with a thionating reagent such as Lawesson's Reagent (2,4-bis(methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide) to prepare the thioamide of Formula 31.
  • a thionating reagent such as Lawesson's Reagent (2,4-bis(methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide
  • the thioamide of Formula 31 is then reacted with the chloro compound of Formula 32 to provide the thiazolecarboxylate of Formula 17g.
  • Carboxylic esters of Formula 17h (Formula 17 wherein J is J-5) can be prepared by the general method shown in Scheme 13.
  • an alpha-bromo ketone of Formula 33 is converted to a Wittig reagent of Formula 34 and then condensed with a 2-oxocarboxylic acid ester of Formula 35 to provide a 4-oxo-2-pentenoic ester of Formula 36 according to the general procedure of P. F. Schuda et al., Synthesis 1987 (12), 1055-7.
  • the 4-oxo-2-pentenoic ester of Formula 36 is then condensed with a hydrazine of Formula 37 to form the carboxylic ester of Formula 17h according to the general procedures of G. Westphal & H. H. Stroh, Liebigs Ann. Chem. 1968, 716, 160-163 and R. C. Moreau & P. Loiseau, Annales Pharmaceutiques Francoises 1978, 36 (1-2), 67-75.
  • This method is illustrated by Steps A through C of Example 22.
  • Carboxylic esters of Formula 17i (Formula 17 wherein J is J-6 and R 31 is ethyl) wherein R ld is H, alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can be prepared from sydnones of Formula 23 and alkenes of Formula 38 according to the general methods described in Z. Obshch. Khim. 1962, 52(5), 1446-1451 as depicted in Scheme 14.
  • sydnones of Formula 23 are heated with alkenes of Formula 38 in higher boiling solvents (e.g., xylenes, toluene, dioxane, ethylene glycol) for typically 12-72 hours.
  • the isomer 17i can then be isolated by the usual methods such as column chromatography and distillation.
  • the ester of Formula 17i can then be converted to the corresponding carboxylic acid as described for Scheme 7 and coupled to form the compound of Formula la as described for Schemes 1 and 2.
  • Most R l substituents can be introduced as R ld in the method of Scheme 14, but halogen cannot. Halogen as well as other R lb substituents can be introduced in the method shown in Scheme 15.
  • the compound of Formula If wherein Ri is R ib is prepared from the compound of Formula If wherein Rid is H.
  • the compound of Formula If wherein R id is H is then deprotonated using a strong base such as lithium diisopropylamide (LDA) and then reacted with an electrophile introducing R lb .
  • LDA lithium diisopropylamide
  • the electrophile can be elemental halogen (e.g., Cl 2 , Br 2 ) or a halogen derivative such as N-bromosuccinimide or N-chlorosuccinimide.
  • R lb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl
  • the electrophile is typically of the formula R lb X (39) wherein X is a nucleophic reaction leaving group as already described for the compound of Formula 22 in connection with the modified method of Scheme 8.
  • Carboxylic esters of Formula 17j (Formula 17 wherein J is J-7) wherein R lc is H can be prepared by the general method shown in Scheme 16.
  • a 3-oxo-carboxylic acid ester of Formula 40 is condensed with an aldehyde of Formula 41 to provide an unsaturated ester of Formula 42, which is condensed with a hydrazine of Formula 43 to provide the carboxylic ester of Formula 17j according to the general procedure of P. S. Engel et al., /. Am. Chem. Soc. 1997, 119 (26), 6059-6065.
  • the ester of Formula 17j can then be converted to the corresponding carboxylic acid as described for Scheme 7 and coupled to form the compound of Formula la as described for Schemes 1 and 2.
  • the coupling can be conducted first to prepare the amide of Formula 44, which is then condensed with the aldehyde of Formula 41 to prepare the unsaturated amide of Formula 45, which is condensed with the hydrazine of Formula 43 to prepare the compound of Formula Ig wherein R lc is H.
  • Carboxylic esters of Formula 17k (Formula 17 wherein J is J-8) can be prepared by the general method shown in Scheme 18.
  • an alkynecarboxylic acid ester of Formula 24 is heated with an excess of azidotrimethylsilane at a temperature of about 100-110 °C under an inert atomosphere.
  • the reaction is worked up by treating the cooled reaction mixture with excess methanol to consume remaining trimethylsilyl azide and desilylate the azide adduct. Evaporation leaves the 1,2,3-triazole of Formula 46.
  • the triazole of Formula 46 is then converted to the triazole of Formula ' 17k by alkylation with R 2b X 3 (47) wherein X 3 is a nucleophihc reaction leaving group such as Cl, Br, I, sulfonates such as p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, or sulfates such as -OSO 2 OR 2b .
  • X 3 is a strong leaving groups such as I.
  • the reaction is conducted in the presence of a base such as potassium carbonate in a polar aprotic solvent such as acetonitrile at a temperature commonly between 40 and 80 °C, typically about 50-60 °C.
  • the triazole of Formula 17k can be isolated and purified by the usual methods known to those skilled in the art such as chromatography and crystallization. This method is illustrated by Step B of Example 26.
  • R 2b is a tertiary alkyl group such as tert-butyl
  • alkylation with R 2b X 3 may give low yields.
  • Compounds of Formula 17k wherein R 2 is a tertiary alkyl group can be satisfactorily prepared from compounds of Formula 46 by reaction with the appropriate alcohol R 2b OH (47) in trifluoroacetic acid solution in the presence of concentrated sulfuric acid according to the general procedure of J. W. Tilley et al., J. Med Chem. 1991, 34(3), 1125-1134. This method is illustrated by Step A of Example 28.
  • esters are shown for the compounds of Formulae 24, 46 and 17k, one skilled in the art recognizes that corresponding esters wherein ethyl is replaced by other carbon-based radicals, e.g., R 31 , can be used as well for this method. Also known in the art are other methods to prepare 1,2,3-triazole rings, such as those described in PCT Patent Publication WO 02/096258.
  • Amino compounds of Formula 2 can be prepared by a wide variety of methods available to the synthetic organic chemist. Many of these methods involve converting one substitutent to another on the aromatic ring. For example, the amino function of Formula 2a (Formula 2 wherein R 4 is H, T is CR 6 , U is CR 7 , Y is CR 8 and Z is CR 9 ) can be obtained by reduction of the nitro compound of Formula 60 as shown in Scheme 19.
  • the nitro compound of Formula 60 can be reduced to the aniline of Formula 2a by a variety of reducing agents known in the art, such as iron in acetic acid, tin(II) chloride or hydrogenation over a palladium or platinum sulfide catalyst.
  • the nitro function of Formula 60 can be added by well known nitration reactions.
  • the method of Scheme 19 is illustrated in Step B of Example 4, Step C of Example 7, Step B of Example 16 and Step B of Example 17. Many compounds of Formula 60 are commercially available.
  • T, U and/or Z are N, the aryl ring of Formula 2 is activated to nucleophihc substitution facilitating introduction of amino by displacement of leaving groups such as halogen.
  • compounds of Formula 2b (Formula 2 wherein R 4 is H and R 5 is CO 2 R 12 ) wherein T is CR 6 or N; U is CR 7 or N; Y is CR 8 or N; Z is CR 9 or N; R 6 , R 7 , R 8 and R 9 are each independently H or F; and R 12 is -C5 alkyl, C 2 -C 5 haloalkyl, C 3 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C 3 -C 5 alkynyl, C 3 -C5 cycloalkyl or C4-C5 cycloalkylalkyl can be prepared as shown in Scheme 20.
  • amides of Formula 2 wherein R 5 is C(O)NR 10 R 11 can be converted to thioamides of Formula 2 wherein R 5 is C(S)NR 10 R n using the thionating reagents already described for the method of Scheme 3. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I or Iz may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, T. W. Greene, P. G. M.
  • Step A Preparation of ethyl 2-hydroxy-5,5-dimethyl-4-oxo-2-hexenoate
  • Step B Preparation of ethyl 5-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate
  • Step D Preparation of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid
  • Step E Preparation of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride
  • a solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Step D) (1.2 g, 6.11 mmol) and oxalyl chloride (2 mL) in dichloromethane (30 mL) in the presence of anhydrous DMF (0.1 mL) was stirred under nitrogen atmosphere at room temperature for 4 h. The reaction mixture was then concentrated to yield the title acid chloride as a liquid.
  • Step F Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl] aminojbenzoate A solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e.
  • Step A Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- aminojbenzoic acid
  • a solution of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] benzoate i.e. the product of Example 1, Step F
  • methanol methanol
  • Step B Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- aminojbenzoyl chloride
  • Step C Preparation of 2-fluoroethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
  • Step B Preparation of ethyl 3-amino-4-fluorobenzoate
  • Step C Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH- ⁇ yrazol-5-yl]- carbonyl] amino-4-fluorobenzoate
  • 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride i.e. the product of Example 1, Step E
  • dichloromethane 40 mL
  • Step A Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] -4-fluorobenzoic acid
  • Step B Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl]-
  • Step D Preparation of N- [5 - [(dimethylamino)carbonyl] -2-fluorophenyl] -
  • Step C Preparation of methyl 6-amino-2-pyridinecarboxylate Hydrogen chloride gas was bubbled through a suspension of 6-(acetylamino)-
  • Step D Preparation of methyl 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl]amino]-2-pyridinecarboxylate
  • 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride i.e. the product of Example 1, Step E
  • Step B Preparation of 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] -2-pyridinecarboxamide
  • a procedure analogous to that of Example 6 was used to convert 6- [ [[3 -( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5-yl] carbonyl] amino-2-pyridine- carboxylic acid (520 mg) (i.e. the product of Step A) and dimethylamine (0.5 mL, 2.0 M in T ⁇ F) to the title compound, a compound of present invention.
  • Step B was used to convert N-(4-methyl- 2-pyridinyl)acetamide (10 g) (i.e. the product of Step A) to the title acid, which was obtained as a solid (3.4 g).
  • Step C A procedure analogous to that of Example 8, Step C was used to convert 4-(acetylamino)-2-pyridinecarboxylic acid (i.e. the product of Step B) (3.4 g) to the title compound (0.92 g).
  • l ⁇ ⁇ MR (CDCI3) ⁇ 8.2 (d, 1 ⁇ ), 7.17 (d, 1 ⁇ ), 7.06 (s, 1 ⁇ ), 4.59 (br s, 2 ⁇ , ⁇ H2), 3.92 (s, 3H).
  • Step D Preparation of methyl 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl]amino]-4-pyridinecarboxylate
  • Step B was used to convert 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Example 1, Step D) (1.0 g) and methyl 4-amino-2-pyridinecarboxylate (i.e. the product of Step C) (0.78 g) to the title compound (0.85 g), a compound of present invention.
  • Step A Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-4-pyridinecarboxylic acid
  • Step A was used to convert methyl 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]-4-pyridinecarboxylate (i.e. the compound of Example 10, Step D) (1.02 g, 3.09 mmol) to the title acid as a white solid (0.9 g).
  • Step B Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino]-N,N-dimethyl-4-pyridinecarboxamide
  • Step B was used to convert 2- [[ [3-( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5 -yl] carbonyl] amino-4-pyridinecarboxylic acid (i.e. the compound of Step A) (200 mg) and dimethylamine to the title compound (110 mg), a compound of present invention.
  • Step A Preparation of ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate and ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate
  • Ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate (3.62 g) was the major isomer.
  • Ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate (0.78 g) was the minor isomer.
  • Step B Preparation of l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylic acid
  • Step A Preparation of l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid
  • Step B was used to convert ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate (i.e. the major isomer product of Example 12, Step A) (1.76 g, 7.76 mmol) to the title acid (1.08 g).
  • Step B Preparation of N-[3-[(diethylamino)carbonyl]phenyl]-l-(l,l-dimethylethyl)- 3-ethyl-lH-pyrazole-4-carboxamide
  • Step C A procedure analogous to that of Example 12, Step C was used to convert l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid (i.e. the product of Step A)
  • Step A Preparation of ethyl l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate
  • Ethyl propiolate (6.9 g, 70.3 mmol) was added to a solution of 3-(l,l-dimethylethyl)- sydnone (65 g, 35.2 mmol) in toluene (60 mL) under a nitrogen atmosphere.
  • the reaction mixture was heated to reflux for two days and cooled to room temperature.
  • the resulting white solid was removed by filtration using hexanes for rinsing.
  • the filtrate was concentrated to leave a liquid, which was applied to a silica gel flash column (eluted with 100% hexanes followed by 10:90 ethyl acetate-hexanes) to give the title product (2.61 g) as a major isomer.
  • Step C Preparation of ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylic acid
  • Step B was used to hydrolyze ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate (i.e. the product of Step B) (0.61 g, 2.18 mmol) to give the title acid (0.4 g) as a solid.
  • NMR (CDCI3) ⁇ 7.6 (s, 1 ⁇ ), 1.6 (s, 9 ⁇ ).
  • Step D Preparation of 4-bromo-l-(l,l-dimethylethyl)-N-[3-[(ethylamino)carbonyl]- phenyl] - lH-pyrazole-3-carboxamide
  • Step C was used to convert ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylic acid (i.e. product of Step C) (100 mg, 0.405 mmol) and 3-amino-N-ethylbenzamide (70 mg, 0.425 mmol) to the title compound (72 mg), a compound of present invention.
  • Step C Preparation of N-(2,3-dihydro-2-methyl-l-oxo-lH-isoindol-4-yl)- 3-(l , 1 -dimethylethyl)- l-ethyl-lH-pyrazole-5-carboxamide ⁇
  • Triethylamine (3.0 g, 29.7 mmol) was added to the reaction mixture, and then a solution of 40% aqueous solution of dimethylamine (1.52 g, 13.5 mmol) in dichloromethane (20 mL) was added dropwise to the reaction mixture at such a rate that the temperature of the reaction mixture did not exceed 5 °C.
  • the cooled reaction mixture was stirred for 15 minutes more, and then hydrochloric acid (1 ⁇ ) was added.
  • the layers were separated, and the organic layer was washed with water, saturated aqueous sodium bicarbonate solution and brine, and then dried over sodium sulfate and concentrated to give the title compound (1.87 g).
  • Step B Preparation of 3-amino-4-fluoro-N,N-dimethylbenzamide 4-Fluoro-N,N-dimethyl-3-nitrobenzamide (i.e. the product of Step A) ( 1.76 g,
  • Step C Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]- l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxamide
  • Step C was used to convert l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid (i.e. the product of Example 13, Step A) (100 mg) and 3-amino-4-fluoro-N,N-dimethylbenzamide (92 mg, 0.509 mmol) (i.e.
  • Step B A procedure analogous to that of Example 16, Step B was used to convert N-ethyl- 2-fluoro-5-nitrobenzamide (0.78 g, 3.68 mmol) and iron powder (0.62 g, 11.0 mmol) of acetic acid (10 mL) to give the title compound (0.62 g, oil).
  • Step C Preparation of l-(l,l-dimethylethyl)-3-ethyl-N-[3-[(ethylamino)carbonyl]- 4-fluorophenyl]-lH-pyrazole-4-carboxamide
  • Step C A procedure analogous to that of Example 17, Step C was used to convert 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Example 1, Step D) (200 mg, 1.0 mmol), 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 490 mg 1.5 mmol), 4-(dimethylamino)pyridine (187 mg, 1.5 mmol) and 5-amino- N,N-dimethyl-2-fluorobenzamide (195 mg, 1.0 mmol) in dichloromethane (4 mL) to the title product, a compound of the present invention, m.p.
  • Step C Preparation of methyl 5-amino-3-pyridinecarboxylate Over 30 minutes hydrogen chloride gas was bubbled through dry methanol (60 mL) cooled to 0-5 °C. Then 5-amino-3-pyridinecarboxylic acid (i.e. the product of Step B) (6.0 g, 43 mmol) was added, and the reaction mixture was heated at 75 °C for 3 h. The reaction mixture was concentrated, the residue was poured into cold water (30 mL), and the pH of the resulting mixture was increased to 4-5 by adding sodium bicarbonate.
  • 5-amino-3-pyridinecarboxylic acid i.e. the product of Step B
  • the resulting residue was diluted with dichloromethane (20 mL) and added to a mixture of methyl 5-amino-3-pyridinecarboxylate (i.e. the product of Step C) (2.98 g, 24.4 mmol) and triethylamine (4.12 g, 5.67 mL, 42.8 mmol) in dichloromethane (20 mL) at 0 °C.
  • the reaction mixture was gradually warmed to room temperature and then heated at 45 °C for 12 h.
  • the dichloromethane solvent was removed by distillation under reduced pressure, and the residue was quenched with ice water and extracted with dichloromethane (3 x 30 mL). The combined organic extracts were then washed with water and brine.
  • the solution was dried over sodium sulfate and filtered, and the solvent was removed to give the crude product.
  • the crude product was purified by column chromatography (60-120 mesh silica gel, 20% ethyl acetate-petroleum ether) to provide the title product (5.1g, 78% yield), a compound of the present invention.
  • Step A Preparation of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
  • Step B Preparation of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
  • Step A Preparation of 3, 3 -dimethyl- l-(triphenylphosphoranylidene)-2-butanone
  • Step C Preparation of butyl 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
  • Step D Preparation of 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
  • Step ⁇ Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro- lH-pyrazol-5-yl]carbonyl]amino]-4-fluorobenzoate To a stirred solution of 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
  • the solvent was removed in vacuo and partitioned between water (50 mL) and ethyl acetate (100 mL). The aqueous layer was extracted with ethyl acetate (30 mL). The organic layer was washed with aqueous saturated sodium bicarbonate (50 mL) and water (50 mL), and dried (MgSO 4 ). The solvent was removed in vacuo to provide the title product, a compound of the present invention, as an oil (1.36 g).
  • Example 22 the product of Example 22 (1.0 g, 2.7 mmol) in ethanol (10 mL) was added aqueous sodium hydroxide (10%, 2.2 g). The solution was stirred overnight at room temperature and then concentrated in vacuo. The p ⁇ of the solution was adjusted to 2 using hydrochloric acid (1 ⁇ ). Most of the water was removed in vacuo, and then the cloudy solution was extracted with ethyl acetate. The solvent was removed in vacuo from the organic extract to provide the acid in crude form (0.64 g), which was then dissolved in dichloromethane (20 mL), and oxalyl chloride (0.31 g) and N,N-dimethylformamide (one drop) were added.
  • Step B Preparation of l-(l,l-dimethylethyl)-3-ethyl-N-[5-[(ethylamino)carbonyl]-
  • Step A Preparation of ethyl 2-hydroxy-3,3-dimethyl- ⁇ -oxo-l-cyclopentene-l-acetate
  • 2,2-Dimethylcyclopentanone (9.6 g) was added to a mixture of diethyl oxalate (11.6 mL), 21% solution of sodium ethoxide in ethanol (11.6 mL) and ethanol (20 mL). The mixture was stirred at room temperature for 18 h. The mixture was then poured onto ice- cold water (200 mL) and acidified to pH 4-5 using acetic acid and extracted with diethyl ether (3 x 50 mL). The organic extracts were washed with water (3 x 50 mL) and dried (MgSO4) and concentrated to provide the title compound as an oil (17.58 g).
  • Step B Preparation of tautomeric mixture of ethyl 2,4,5,6-tetrahydro-6,6-dimethyl-
  • Step C Preparation of ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-
  • Step B) the product of Step B) (7.69 g) in N,N-dimethylformamide (50 mL), potassium carbonate (7.71 g) and tetrabutylammonium bromide (100 mg) were added.
  • Ethyl iodide (4.44 mL) was added at once, and the mixture was stirred at room temperature for 18 h. The mixture was poured into water (200 mL) and extracted with diethyl ether (3 x 100 mL).
  • the later fractions contained ethyl 1-ethyl-l ,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate. These fractions were combined and concentrated to provide 1-ethyl-l, 4,5,6-tetrahydro-6,6-dimethyl- 3-cyclopentapyrazolecarboxylate (3.5 g).
  • Step D Preparation of 2-ethyl-2,4,5 ,6-tetrahydro-6,6-dimethyl-
  • Step E Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-2-ethyl- 2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxamide
  • Step B Preparation of ethyl 5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazole-
  • Step C Preparation of ethyl 3-[[[5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazol- 4-yl]carbonyl]amino]benzoate
  • the aqueous layer was acidified with hydrochloric acid (6 N) to p ⁇ 1-2 and extracted with ethyl acetate, dried (Na 2 SO4) and concentrated to provide the carboxylic acid intermediate as a white solid (0.94 g, 5.08 mmol, 90% yield).
  • To a stirred solution of the carboxylic acid intermediate (0.78 g, 4.22 mmol) in dichloromethane (25 mL) was added oxalyl chloride (1.61 g, 12.7 mmol) dropwise at room temperature. After stirring the reaction mixture for 10 minutes, N,N-dimethylformamide (two drops) was added. The mixture was stirred for an additional 1.5 h and then concentrated to provide the acid chloride intermediate as a pale yellow oil.
  • Step A Preparation of ethyl 2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazole- 4-carboxylate and ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-l,2,3-triazole-
  • Ethyl 2-( 1 , 1 -dimethylethyl)-5-ethyl-2H- 1 ,2,3-triazole-4-carboxylate l ⁇ NMR (CDCI3): 4.41 (q, 2 ⁇ ), 2.93 (q, 2H), 1.68 (d, 9H), 1.40 (t, 3H), 1.27 (t, 3H).
  • Step B Preparation of ethyl 3-[[[2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazol-
  • 1-pyrrolyl means -N(-(CH 2 )5-)
  • 4-morpholinyl means -N(-(CH 2 ) 2 O(CH 2 ) 2 -).
  • R la is Et ;
  • R 2a is tert-Bi i ;
  • T, U, Y and Z are CH
  • R la is Et ;
  • R 2a is tert- i i ;
  • T , U and Y are CH ;
  • Z is CF
  • Rla is Et ;
  • R 2a is tert-Bx. i ;
  • T , U and Y are CH ;
  • Z is CF
  • Rl is Et ;
  • R 2a is tert-Bi ⁇ ;
  • U is CF ;
  • T, Y and Z are CH
  • Rla is Me ; R 2a is tert-B u ; U is CF ; T, Y and Z are CH
  • OS(0) 2 CH 2 CH 3 0S(0) 2 CH 2 C1 OP(0)Me(OMe) OP(0)(OMe) 2 Rla is Me ;
  • R 2a is tert-Bu ;
  • T, U, Y and Z are CH
  • R a is Et ;
  • R 2a is isopro 3yl ;
  • T, U, Y and Z are CH
  • Rla is Et ;
  • R 2a is isopro 3 yl ;
  • U is CF ;
  • T, Y and Z ar s CH
  • R la is Et ;
  • R 2a is cyclop ropyl ;
  • T, U, Y and Z are CI I
  • R ia is CH 2 CH 2 F ; R 2a 1 s tert-Bu ; T, TJ, Y and Z an ⁇ CH
  • R la is CH 2 CH 2 F ;
  • R 2a is tert-Bu ;
  • U is CF ;
  • T, Y ar d Z are CH
  • R la is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • U is CF ;
  • T, Y and Z are CH
  • Rla is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • T, U, Y and Z are CH
  • Rla is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • T, U, Y and Z are CH
  • R ia is Me ; R 2a is tert-B u ; U is N ; T, Y and Z are ( H
  • Rla is Et ; R 2a is tert-Bu ; U is N ; T, Y and Z are CH
  • R ia is Et ; R 2a is tert-Bu ; U is N ; T, Y and Z are CH
  • Rla is Et ;
  • R 2a is tert-Bi i ;
  • T is N ;
  • U, Y and Z are CH
  • Rl is Et ; R 2a is tert-B ⁇ i ; T is N ; U, Y and Z are C H
  • Rl is Et ;
  • R 2a is tert-B ⁇ 1 ;
  • T , U and Y are CH ;
  • Z is N
  • R la is CH 2 CH 3 ;
  • R 2a is Si(CH 3 ) 3 ;
  • Rlb is Et ;
  • R 2b is tert-Bu ;
  • T, U, Y and Z are CH
  • R lb is Et ;
  • R 2b is tert-Bu ;
  • T, U, Y and Z are CH

Abstract

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation, wherein J is (J-1), (J-2,(J-3), (J-4), (J-5), (J-6), (J-7), (J-8) and R1a, R1b, R1c, R2a, R2b, R3, R4, R05, T, U, W, Y and Z are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I). Also disclosed are mixtures and compositions comprising a herbicidally effective amount of a compound of Formula (Iz) wherein J, R1a, R1b, R1c, R2a, R2b, R3, R4, R05, T, U, W, Y and Z are as defined in the disclosure; and an effective amount of another herbicide or herbicide safener. Also disclosed is a method for selectively controlling undesired vegetation in a crop that involves contacting the locus of a crop with an effective amount of a compound of Formula (Iz) and a effective amount of a safener.

Description

TITLE AZOLECARBOXAMLDE HERBICIDES
FIELD OF THE INVENTION This invention relates to certain azolecarboxamides their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation.
BACKGROUND OF THE INVENTION The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
J. J. Parlow, D. A. Mischke and S. S. Woodard, J. Org. Chem. 1997, 62, 5908-5919 and J. J. Parlow, J. Heterocyclic Chem. 1998, 35, 1493-1499 disclose certain pyrazole- carbonylaminobenzene- and pyridinecarboxamides as herbicides. The present Applicants have discovered azolecarboxamides not disclosed by these two publications and which have significantly improved herbicidal utility. Additionally the present Applicants have discovered more efficacious or selective herbicidal compositions and improved methods of weed control from combination of azolecarboxamides with other herbicides and/or herbicide safeners. SUMMARY OF THE INVENTION
This invention is directed to a compound of Formula I including all geometric and stereoisomers, N-oxides or agriculturally suitable salts thereof, agricultural compositions containing them and their use as herbicides:
Figure imgf000003_0001
wherein
Figure imgf000004_0001
T is CR6 or N; U is CR^ or N; Y is CR8 or N; Z is CR9 or N; Rla is H, C!-C4 alkyl,
Figure imgf000004_0002
fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C4 fluoroalkynyl; Rlb is halogen, Cv-C4 alkyl, ^-04 fluoroalkyl, C2-C alkenyl, C2-C4 fluoroalkenyl,
C2-C alkynyl or C2-C fluoroalkynyl; Rl is H; R2a is Cj-Cβ alkyl, C^Cg haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C -C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C -C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C -C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or SiR23R24R25;
R2b is Cj-Cβ alkyl, C^-^ haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl;
R3 is H, F or -O^ alkyl; or
R2a or R 2b is taken together with R3 as -C(R 6a)(R26b).(γl)s_(CH2)r(Y2)u- or _C(R26a)(R26b)_(γi)v_CH=CH_(γ2)w. wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3; R4 is H, Cj-C2 alkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkoxyalkyl or C2-Cg alkylthioalkyl; R5 is
Figure imgf000005_0001
C(O)ORl2, COR*3, C(NORl4)Rl5, _CN> 0Rl6, S(O)mRl7
S(O)2NRl8Rl9, OS(O)2R27 or OP(O)R28aR28b; R6 is H, F, C1-C2 alkyl, Cr-C2 fluoroalkyl,
Figure imgf000005_0002
alkoxy, Cx-C2 fluoroalkoxy,
C ~C2 alkylthio or Ct-C2 fluoroalkylthio; or R5 and R6 are taken together as a radical selected from -C(W1)N(R11)(CH2)n- and
-C(NOR1 )CH2(CH2)n- wherein the right end of the radical is connected to the ring at T; R7 is H, F, Ci-02 alkyl,
Figure imgf000005_0003
fluoroalkoxy,
C1-C2 alkylthio or C1-C2 fluoroalkylthio; R8 and R9 are independently selected from H, F, Ct~C2 alkyl, Cj-C2 fluoroalkyl,
C]~C2 alkoxy, C1-C2 fluoroalkoxy, C1-C2 alkylthio and Cj-C2 fluoroalkylthio; R10 is H, C^ . alkyl, Cj-Gj. haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl;
R11 is H, C!-C5 alkyl, Ci-Cs haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl,
C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, Cr-C3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or -(CH2)2O(CH2)2-, each optionally substituted with 1-2
Figure imgf000005_0004
alkyl; each R12 is independently C1-C5 alkyl, C1-C5 haloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl; R13 is Cr-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; R14 is H, Cx-C4 alkyl, C!-C4 haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or
C2-Cg alkoxycarbonyl; R15 is C1-C3 alkyl, Cι-C3 haloalkyl or cyclopropyl; R16 is C1-C4 alkyl, C1-C4 haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl,
C2-C alkenyl, C3-C4 haloalkenyl, C3-C alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl;
R17 is C!-C4 alkyl, Ct-C4 haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl,
C -C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, Cj- alkyl, Cj- haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C alkylthiomethyl; each R19 is independently H, C^Cg alkyl, Cj-Cs haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy, C -C5 alkoxyalkyl or C2-C5 alkylthioalkyl; R20 is C1-C4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R21 is C!-C3 alkyl;
R22 is Ct-C3 alkyl; or
R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl; R23 is C!-C2 alkyl or C^ haloalkyl;
R24 is Ct-C2 alkyl or C^ haloalkyl;
R25 is 0^2 alkyl or C C^ haloalkyl;
R26a ancj R26b ^Q independently H or -C2 alkyl;
R27 is Ct-C3 alkyl, ^-03 haloalkyl or cyclopropyl; R28 and R28b are independently Ct-C2 alkyl or C]-C2 alkoxy;
W is O or S;
WMs O or S;
Y1 and Y2 are independently CH2, O, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that
(a) when J is J-1, Rla is CH3 and R5 is C(W1)NRl°R11, C(O)OR12, COR13, OR16 or S(O)mR17, then at least one of T, U, Y and Z is N or C-F;
(b) when J is J-1, Rla is CH3, R5 is C(W1)NR10R11, C(O)OR12, COR13, OR16 or S(O)mR17 and T is N, then at least one of U, Y and Z is N or C-F;
(c) when R5 is C(W1)NR10R11 or C(NOR1 )R15, then R9 is other than alkoxy or alkylthio; (d) when R5 is C(W1)NR10R11, then R6 is other than alkyl or alkoxy;
(e) when R5 is COR13, then Rla or Rlb is selected from the radicals of the group consisting of Ct-C3 alkyl, C - ^ fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring; (f) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1 , then R10 is 0^4 alkyl, Cv-C4 haloalkyl, C3-C4 alkenyl, C2-C alkoxymethyl or C2-C4 alkylthiomethyl; (g) when at least one of R10 and R11 is haloalkyl, then Rla or Rlb is CH2CH3 or CH2CF3 and R2a or R b is tert-butyl, isopropyl or cyclopropyl; (h) when J is J-2 or J-6, then R7 and R9 are H;
(i) when J is J-2 or J-6, and R2 is -C2 alkyl, then Rl is halogen, C2-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C alkynyl or C2-C fluoroalkynyl; (j) when Rla is CH3 and R5 is C(NOR )Ri5, then R7 is other than alkyl; (k) when T is N, then Z is CR9; (1) when T is N, R7 is alkoxy, then R11 is H;
(m) when R7 and R9 are F, and one of R10 and R11 is H, then the other of R10 and R1 * is other than H;
(n) when Z is N and one of R10 and R11 is H, then the other of R10 and R1 is other than trifluoroethyl; (o) when J is J-8 and R2b is C5-C6 cycloalkyl, then R5 is C(O)NR10R ; and (p) when J is J-8 and R7 is other than H, then R2b is tert-butyl and R5 is C^NRiOR11.
More particularly, this invention pertains to a compound of Formula I, including all geometric and stereoisomers, N-oxides or agriculturally suitable salts thereof. This invention also relates to a herbicidal composition comprising a herbicidally effective amount of a compound of Formula I and at least one of a surfactant, a solid diluent or a liquid diluent. This invention further relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula I (e.g., as a composition described herein). This invention also relates to 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 Formula I and an antidotally effective amount of a safener.
The present invention also relates to a herbicidal mixture comprising a herbicidally effective amount of a compound of Formula Iz including all geometric and stereoisomers, N-oxides and agriculturally suitable salts thereof
Figure imgf000007_0001
Iz wherein
Figure imgf000007_0002
Figure imgf000008_0001
J-5 J-6 J-7 J-8
T is CR6 or N;
U is CR7 or N;
Y is CR8 or N; Z is CR9 or N;
Rla is H, C]-C4 alkyl, C!-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C4 fluoroalkynyl; Rlb is halogen, C]-C alkyl, C1-C4 fluoroalkyl, C2-C alkenyl, C2-C4 fluoroalkenyl,
C2-C alkynyl or C2-C4 fluoroalkynyl; Ri is H;
R2 is Ci-Cg alkyl, Cj-Cg haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or SiR23R2 R25;
R2b is Cj-Cg alkyl, C^Cg haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-Cg haloalkynyl,
C3-C6 cycloalkyl, C -C6 alkylcycloalkyl, C3-Cg halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl; R3 is H, F or
Figure imgf000008_0002
alkyl; or
R2a or 2b is taken together with R3 as -C(R26 )(R 6b)-(Y1)s-(CH2)t-(Y2)u- or
-C(R26 )(R26b)_(γl)v_CH=CH-(Y2)w- wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3; R4 is H, C1-C alkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkoxyalkyl or C2-C6 alkylthioalkyl;
R5 is
Figure imgf000008_0003
C(O)OR12, COR13, C(NOR14)R15, -CN, OR16, S(O)mR17
S(O)2NR18R19, OS(O)2R27 or OP(O)R28aR28b; R6 is H, F, Ct-C2 alkyl, C]-C2 fluoroalkyl, Ct-C2 alkoxy, C!-C2 fluoroalkoxy,
Ct-C2 alkylthio or C1-C2 fluoroalkylthio; or R5 and R6 are taken together as a radical selected from -C(W1)N(R1 l)(CH2)n- and
-C(NOR14)CH2(CH2)n- wherein the right end of the radical is connected to the ring at T; R7 is H, F, Cj-C2 alkyl,
Figure imgf000009_0001
fluoroalkoxy,
C1-C2 alkylthio or C1-C2 fluoroalkylthio; R8 and R9 are independently selected from H, F, Cj-C2 alkyl, C1-C2 fluoroalkyl,
CJ-C2 alkoxy, C1-C2 fluoroalkoxy, C1-C2 alkylthio and C1-C2 fluoroalkylthio; R10 is H, C!-C4 alkyl, Ci-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or
C2-C4 alkylthiomethyl; R11 is H, C!-C5 alkyl, C^s haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl,
C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or
-(CH2)2O(CH2)2-, each optionally substituted with 1-2 C1-C2 alkyl; each R12 is independently C1-C5 alkyl, C1-C5 haloalkyl, C2-C4 alkoxyalkyl, C2-C alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl; R13 is C1-C3 alkyl, C -C3 haloalkyl or cyclopropyl;
R14 is H, Ci-C4 alkyl, C!-C4 haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or
C2-C6 alkoxycarbonyl; R15 is C2-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
R16 is Ci-C4 alkyl, CJ- J haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl; R17 is Ci-C/j. alkyl, Ct-C4 haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl,
C3-C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, Cj-C4 alkyl, Cr-C"4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; each R19 is independently H, Cj-Cs alkyl, Ci-Cs haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy, C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; R20 is C]_-C4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R21 is Ct-C3 alkyl;
R22 is C!-C3 alkyl; or
R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl; R23 is Ci-C^ alkyl or Cj-C2 haloalkyl; R24 is Ct-C2 alkyl or C C2 haloalkyl;
R25 is d-C2 alkyl or C^-C^ haloalkyl; R26a and R26b ^e independently H or Cj-C^ alkyl; R27 is CIL-CS alkyl, C!-C3 haloalkyl or cyclopropyl; R28a and R28b QJ-Q independently C1-C2 alkyl or Cl-C2 alkoxy; W is O or S; Ms O or S;
Yl and Y2 are independently CH2, 0, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that (a) when R5 is C(W1)NR10R11 or C(NORl )R15, then R9 is other than alkoxy or alkylthio;
(b) when R5 is C(W1)NR10R11, then R6 is other than alkyl or alkoxy;
(c) when R5 is COR13, then Rla or Rlb is selected from the radicals of the group consisting of Cj-C alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
(d) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1, then R10 is C1-C4 alkyl,
Figure imgf000010_0001
haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; (e) when at least one of R10 and R11 is haloalkyl, then Rla or Rl is CH2CH3 or
CH2CF3 and R2a or R2b is tert-butyl, isopropyl or cyclopropyl;
(f) when J is J-2 or J-6, then R7 and R9 are H;
(g) when J is J-2 or J-6, and R2b is
Figure imgf000010_0002
alkyl, then Rlb is halogen, C2-C4 alkyl, Ci-C^ fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl;
(h) when Rla is CH3 and R5 is C(NOR14)R15, then R7 is other than alkyl; (i) when T is N, then Z is CR9; (j) when T is N, R7 is alkoxy, then R11 is H;
(k) when R7 and R9 are F, and one of R10 and R11 is H, then the other of RlO and R11 is other than H;
(1) when Z is N and one of R10 and R1 *■ is H, then the other of R10 and R11 is other than trifluoroethyl; (m)when J is J-8 and R2b is C5-C6 cycloalkyl, then R5 is C(O)NR10R11; and (n) when J is J-8 and R7 is other than H, then R2b is tert-butyl and R5 is C(O)NR10Rn; and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener. The present invention further relates to a herbicidal composition comprising said herbicidal mixture and at least one of a surfactant, a solid diluent or a liquid diluent.
The present invention also relates to a method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula Iz and effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener (e.g., in the form of the aforedescribed herbicidal mixture or herbicidal composition). A particular aspect of the present invention relates to a method for selectively controlling the growth of undesired vegetation in a crop comprising contacting the locus of a crop with an effective amount of a compound of Formula Iz and an antidotally effective amount of a herbicide safener (e.g., safener applied as a seed treatment).
DETAILS OF THE INVENTION In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, rc-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy and pentoxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio and pentylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl isomers. "Alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like, are defined analogously to the above examples. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkoxy" includes the same groups linked through an oxygen atom such as cyclopropyloxy and cyclobutyloxy. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. "Cycloalkylalkoxy" includes cyclopropylmethoxy. "Alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcycloρentyl. The term "carbocyclic ring" denotes a ring wherein the atoms forming the ring backbone and selected only from carbon. "Saturated carbocyclic" refers to a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic. Aromatic indicates that each of ring atoms is essentially in the same plane and has a p-orbital perpendicular to the ring plane, and in which (4n + 2) π electrons, where n is 0 or a positive integer, are associated with the ring to comply with Hϋckel's rule. The term "aromatic carbocyclic ring system" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic. The term "nonaromatic carbocyclic ring system" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles wherein none of the rings in the ring system are aromatic. The terms "aromatic heterocyclic ring system" and "heteroaromatic ring" include fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic. The term "nonaromatic heterocyclic ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles wherein none of the rings in the ring system are aromatic. The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all nitrogen-containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen-containing heterocycles which can form N-oxides. Synthetic methods for the preparation of N-oxides of heterocycles are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and m-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. N. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "1-2 halogen" indicates that one or two of the available positions for that substituent may be halogen which are independently selected. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl", "haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and
CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. Similarly, "fluoroalkyl", "fluoroalkenyl" and "fluoroalkynyl" may be partially or fully substituted with fluorine atoms.
The total number of carbon atoms in a substituent group is indicated by the "CJ-CJ" prefix where i and j are numbers from 1 to 6. For example, C1-C3 alkyl designates methyl through propyl; C2 alkoxyalkyl designates CH3UCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R6 or R10, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. When a position on a group is said to be "not substituted" or "unsubstituted", then hydrogen atoms are attached to take up any free valency.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
The agriculturally suitable salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The agriculturally suitable salts of the compounds of the invention also include those formed with strong bases (e.g., hydrides or hydroxides of sodium, potassium or lithium). One skilled in the art recognizes that because in the environment and under physiological conditions salts of the compounds of the invention are in equibrium with their corresponding nonsalt forms, agriculturally suitable salts share the biological utility of the nonsalt forms.
Preferred for reason of cost, ease of synthesis and/or biological efficacy is:
Preferred 1. A compound of Formula I wherein when J is J-1 and Rla is CH3 then at least one of T and U is Ν or C-F. Preferred 2. A compound of Preferred 1 wherein when J is J-1 and Rla is CH3 then at least one of T and U is C-F. Preferred 3. A compound of Formula I wherein when J is J-1, Rla is CH3 and T is Ν then U is N or C-F. Preferred 4. A compound of Preferred 3 wherein when J is J-1, Rla is CH3 and T is N then U is C-F.
Preferred 5. A compound of Formula I wherein at most one of T, U, Y and Z is N. Preferred 6. A compound of Formula I wherein W is O. Preferred 7. A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5 or J-8. Preferred 8. A compound of Preferred 7 wherein J is J-1, J-3 or J-5. Preferred 9. A compound of Preferred 8 wherein J is J-1 or J-3.
Preferred 10. A compound of Formula I wherein Rla is C -C4 alkyl, Ct-C fluoroalkyl, C2-C4 alkenyl, C2-C fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl. Preferred 11. A compound of Formula I wherein Rla or Rlb is selected from the radicals in the group consisting of C1-C3 alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C -C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring. Preferred 12. A compound of Preferred 11 wherein Rla or Rlb is CH2CH3, CH2CH2F,
CH2CHF2, CH2CF3 or CH=CH2. Preferred 13. A compound of Preferred 12 wherein Rla or Rl is CH2CH3 or CH2CF3. Preferred 14. A compound of Formula I wherein R2a or R2b is tert-butyl, isopropyl or cyclopropyl.
Preferred 15. A compound of Preferred 14 wherein R2a or R2b is tert-butyl or isopropyl. Preferred 16. A compound of Formula I wherein Y1 and Y2 are independently CH2 or
O; Preferred 17. A compound of Preferred 16 wherein the sum of s, t and u is 2 and the sum of v and w is 0;
Preferred 18. A compound of Preferred 16 wherein R26a is C1-C2 alkyl. Preferred 19. A compound of Preferred 18 wherein R26a and R26b are CH3. Preferred 20. A compound of Formula I wherein R3 is H. Preferred 21. A compound of Formula I wherein R4 is H. Preferred 22. A compound of Formula I wherein the carbon atom of R12 linking to oxygen is bonded to at least one hydrogen atom. Preferred 23. A compound of Formula I wherein R5 is CONRiOR11 or C(O)OR12;
R10 is H or Ci- j. alkyl; R11 is Ct-C4 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-; and R12 is C1-C3 alkyl. Preferred 24. A compound of Preferred 23 wherein R5 is CONRiOR11 ; R10 is H or
Ct-C2 alkyl; and R11 is C1-C3 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-. Preferred 25. A compound of Formula I wherein R6 is H or F. Preferred 26. A compound of Formula I wherein R7 is H or F. Preferred 27. A compound of Formula I wherein R8 and R9 are H or F.
Preferred 28. A compound of Formula I wherein T is C-F or N. Preferred 29. A compound of Formula I wherein U is C-F or N. Of note is a compound of Formula I wherein J is J-1 and Rla is H, which is particularly useful as a synthetic intermediate. Combinations of preferred groups are illustrated by:
Preferred A. A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5 or J-8. Preferred B. A compound of Preferred A wherein Rla or Rlb is CH2CH3, CH2CH2F, CH2CHF2, CH2CF3 or CH=CH2; R2a or R2b is tert-butyl, isopropyl or cyclopropyl; R3 is H; R4 is H; and W is O. Preferred C. A compound of Preferred B wherein at most one of T, U, Y and Z is N.
Preferred D. A compound of Preferred C wherein R5 is CONR10Rπ or C(O)OR12;
R10 is H or C!-C4 alkyl; R11 is Ci-C4 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-; and R12 is Cj-Cg alkyl. Preferred E. A compound of Preferred D wherein R6 is H or F and R7 is H or F.
Preferred F. A compound of Preferred E wherein J is J-1 , J-3 or J-5.
Preferred G. A compound of Preferred F wherein R5 is CONR^R11; R10 is H or
C1-C2 alkyl; and R11 is C1-C3 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-.
Preferred H. A compound of Preferred G wherein R2a is tert-butyl or isopropyl; and
R8 and R9 are H or F. Preferred I. A compound of Formula I wherein at most one of T, U, Y and Z is N; Rla or Rlb is selected from the radicals in the group consisting of C]-C3 alkyl, C!-C3 fluoroalkyl, C2-C3 alkenyl, C -C3 fluoroalkenyl, C2-C3 alkynyl or C2-
C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring; R6 is H or F; R7 is H or F; R4 is H; R26a is C1-C2 alkyl; W is O; Y1 and Y2 are independently CH2 or O; the sum of s, t and u is 2; and the sum of v and w is 0. Preferred J. A compound of Preferred I wherein Rla or Rlb is CH2CH3, CH2CH2F,
CH2CHF2, CH2CF3 or CH=CH2, R2a or R2b is tert-butyl, isopropyl or cyclopropyl, and R3 is H. Preferred K. A compound of Preferred J wherein R5 is CONR10R or C(O)OR12;
R10 is H or Ct-C4 alkyl; R11 is Ct-C4 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-; and R12 is -C3 alkyl.
Preferred L. A compound of Preferred K wherein R2a or R2b is tert-butyl or isopropyl. Preferred M. A compound of Preferred L wherein J is J-1, J-2, J-3, J-4, J-5 or J-8. Preferred N. A compound of Preferred M wherein R5 is CONR^R11; R10 is H or
Cι~C2 alkyl; and R11 is Ct-C3 alkyl; or R10 and R11 are taken together as -CH2CH=CH2CH-.
Preferred O. A compound of Preferred N wherein R8 and R9 are H or F. Preferred P. A compound of Preferred O wherein J is J-1, J-3 or J-5.
Specifically preferred is a compound of Preferred I selected from the group:
3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl)-2-fluorophenyl]- lH-pyrazole-5-carboxamide;
N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-3-(l,l-dimethylethyl)-l-ethyl- lH-pyrazole-5-carboxamide;
2- [ [(3 -( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5-yl] carbonyl] amino] -N,N-dimethyl- 4-pyridinecarboxamide; 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]-N-ethyl-
4-pyridinecarboxamide; N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-l-ethyl-3-(l-methylethyl)- lH-pyrazole-5-carboxamide;
N- [5 - [(dimethylamino)carbonyl] -2-fluorophenyl] - 1 -( 1 , 1 -dimethylethyl)-3 -ethyl- lH-pyrazole-4-carboxamide; 3-(l,l-dimethylethyl)-l-(2-fluoroethyl)-N-[3-[(lE)-l-(hydroxyimino)ethyl]phenyl]- lH-pyrazole-5-carboxamide;
3 -( 1 , 1 -dimethylethyl)- 1 -ethyl-N- [5- [(ethylmethylamino)carbonyl] -2-fluorophenyl] - lH-pyrazole-5-carboxamide;
3 -( 1 , 1 -dimethylethyl)- 1 -ethyl-N- [3- [(ethylamino)carbonyl] -4-fluorophenyl] - lH-pyrazole-5-carboxamide;
N-[5-[(2,5-dihydro-lH-pyrrol-l-yl)carbonyl]-2-fluorophenyl]~ 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxamide; and
3-(l,l-dimethylethyl)-l-ethyl-N-[3-(trifluoromethoxy)phenyl]-lH-pyrazole- 5-carboxamide. Of note are compounds of Formula I wherein J is J-1, J-2, J-3 or J-4 wherein R2a is
C^Cg alkyl, C^-Cg haloalkyl, C2-C6 alkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-C alkynyl, C -Cg haloalkynyl, C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl. Also of note are compounds of Formula I wherein J is J-1, J-2, J-3, J-4, J-5, J-6 or J-7. Also of note are compounds of Formula I wherein R2a is C^-Cg alkyl, C^-Cg haloalkyl, C2-C6 alkoxyalkyl, C2-Cg alkylthioalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or SjR23R24R25; R2b is Cl-C6 alkyl, Ct-C6 haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C2-Cg alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-Cg cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl; R3 is Η, F or C]-C2 alkyl; and R5 is C(W1)ΝR10R11, C(O)OR12, COR13, C(NOR14)R15, -CN, ORiS, S(O)mR17 or S(O)2NR18R19.
The preferred herbicidal compositions of the present invention are those involving the above preferred compounds.
This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein). The preferred methods of use are those involving the above preferred compounds. This invention also relates to 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 the compounds of the invention and an antidotally effective amount of a safener. The preferred methods of use are those involving the above preferred compounds.
The compounds of Formulae I and Iz can be prepared by one or more of the following methods and variations as described in Schemes 1 through 20 and accompanying text. Formula I is a subgenus of Formula Iz; Formulae I and Iz share the same substituent group definitions, but the scope of Formula Iz is not constrained by provisos (a) and (b) of Formula I. The definitions of J, W, Rla, Rl , Rl , R2a, R2b, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, Ri5, Ri6, R17, R18, R19 R20, R21, R22, R23, R24; R25, R26a> R26b; R27, R28a; R28b, W, W1, T, U, Y, Z, m, n, s and v in the compounds of Formulae I through Ig, Iz and 1 through 63 below are as defined above in the Summary of the Invention unless otherwise indicated. Compounds of Formulae la through Ig are various subsets of the compounds of Formulae I and Iz, compounds of Formula 2a and 2b are subsets of the compounds of Formula 2, and compounds of Formulae 17a through 17j are subsets of the compounds of Formula 17.
Compounds of Formula la (Formula I or Iz wherein W is O) can be prepared by coupling the appropriately substitituted azole acyl chloride of Formula 1 with the appropriately substituted amino compound of Formula 2 as shown in Scheme 1.
Scheme 1
Figure imgf000018_0001
1 2 la
The reaction is carried out in an anhydrous aprotic solvent such as dichloromethane or tetrahydrofuran, preferably in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine, at a temperature typically between room temperature and 70 °C to provide the amide of Formula la. When R4 is alkylcarbonyl or alkoxycarbonyl, a strong base such as sodium hydroxide and phase transfer conditions such as those described by M. J. Haddadin et al., Heterocycles 1984, 22, 113 may be advantageous. The reaction of Scheme 1 is illustrated in Step F of Example 1, Step C of Example 4, Step D of Example 7, Step D of Example 8, Step C of Example 12, Step B of Example 13, Step D of Example 14, Step C of Example 15, Step C of Example 16, Step D of Example 19, and Step E of Example 25, which follow.
Alternatively, compounds of Formula la can be prepared by coupling the appropriately substituted azole carboxylic acid of Formula 3 with appropriately substituted amino compound of Formula 2 as shown in Scheme 2. Scheme 2
J"~-C— OH + 2 ■ ϊa
II O
This reaction is carried out in the presence of a dehydrating coupling reagent such as dicyclohexyl carbodiimide, l-(3-dimethylaminopropyl)-3-ethylcarbodiimide, 1-propane- phosphonic acid cyclic anhydride or carbonyl diimidazole in the presence of a base such as triethylamine, pyridine, 4-(dimethylamino)pyridine or N,N-diisopropylethylamine in an anhydrous aprotic solvent such as dichloromethane or tetrahydrofuran at a temperature typically between room temperature and 70 °C. The method of Scheme 2 is illustrated in Step D of Example 10, Step C of Example 17, Example 18, Step B of Example 20 and Step E of Example 22.
As shown in Scheme 3, compounds of Formula lb (Formula I or Iz wherein W is S) can be prepared from corresponding compounds of Formula la by treatment with a thionating reagent such as P2S5 (see for example, E. Klingsberg et al., J. Am. Chem. Soc. 1951, 72, 4988; E. C. Taylor Jr. et al, /. Am. Chem. Soc. 1953, 75, 1904; R. Crossley et al., J. Chem. Soc. Perkin Trans. 1 1976, 977; J. Noss et al., Justus Liebigs Ann. Chem. 1968, 716, 209) or Lawesson's Reagent (2,5-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane- 2,4-disulfide; see, for example, S. Prabhakar et al. Synthesis, 1984 (10), 829).
Scheme 3
Figure imgf000019_0001
lb Alternatively, compounds of Formula lb can be directly prepared from the corresponding carboxylic acid of Formula 3 and amino compound of Formula 2 by treatment with (EtO)2P(S)SH according to the general procedure of Ν. Borthakur et al., Tetrahedron Lett. 1995, -?<5(37), 6745. Also, compounds of Formula la or lb wherein R4 is alkyl, alkylcarbonyl, alkoxycarbonyl, alkoxyalkyl or alkylthioalkyl can be prepared from the corresponding compounds of Formula la or lb wherein R4 is H by treatment with the appropriate alkylating or acylating reagents in the presence of base using methods well known in the art.
Acyl chlorides of Formula 1 can be prepared from the carboxylic acids of Formula 3 by using methods well known in the art such as treatment with oxalyl chloride and catalytic N,N-dimethylformamide in dichloromethane or treatment with thionyl chloride. This preparation is illustrated in Step E of Example 1, Step C of Example 12, Step B of Example 13, Step D of Example 14, and Step E of Example 25.
In some instances compounds of Formula I (or Iz) can be prepared from other compounds of Formula I (or Iz). For example, a compound of Formula lc wherein R30 is NR10R or OR12 (Formula I or Iz wherein R5 is C(O)NR10R11 or C(O)OR12) can be prepared from the corresponding carboxylic acid of Formula 4, which is in turn prepared from a compound of Formula lc wherein R30 is OR12 as shown in Scheme 4.
Scheme 4
Figure imgf000020_0001
R30is OR12 RSOis NRiORii or
OR12 In this method, the ester compound of Formula lc wherein R30 is OR12 is converted to the corresponding carboxylic acid of Formula 4 by general procedures well known in the art such as by treatment with aqueous lithium hydroxide in tetrahydrofuran, followed by acidification. The carboxylic acid of Formula 4 is then converted to the corresponding carboxamide of Formula lc wherein R30 is NR10R12 or ester of Formula lc wherein R30 is OR12 by amidation or esterification procedures well known in the art. One procedure illustrated in Scheme 4 involves conversion of the carboxylic acid of Formula 4 to an intermediate carbonyl chloride by treatment with oxalyl chloride preferably in the presence of N,N-dimethylformamide and an inert solvent such as dichloromethane, and then contacting the intermediate carbonyl chloride with the appropriate amine of Formula 5 or alcohol of Formula 6 to prepare the carboxamide or ester, respectively. As an alternative to preparing the intermediate carbonyl chloride, a dehydrating coupling reagent can be used analogous to the method of Scheme 2. The method of Scheme 4 is illustrated in Examples 2, 3, 5, 6 and 9, Steps A and B of Example 11, and Example 23.
In other instances compounds of Formula I (or Iz) can be prepared from compounds structurally related to Formula I (or Iz). For example, as shown in Scheme 5, compounds of Formula Id can be prepared from corresponding compounds of Formula 7 by treatment with the corresponding sulfonating reagent of Formula 8 wherein X1 is a leaving group such as halogen or OS(O)2R27. For reason of cost, X1 is preferably Cl. Scheme 5
Figure imgf000021_0001
7 Id
The reaction is conducted in the presence of a base such as pyridine, triethylamine or 4-(dimethylarnino)pyridine in solvents such as dichloromethane or tetrahydrofuran at temperatures typically between 0 and 70 °C under an inert atmosphere. Compounds of Formula 7 can be prepared by methods analogous to Schemes 1 and 2, starting with the appropriate amino compound analogous to Formula 2 wherein R5 is replaced by a hydroxy group. Although the hydroxy group can be converted to a protecting group before the reaction with the compound of Formulae 1 or 3 and then deprotected to give the compound of Formula 7, such protection is generally unnecessary, because the amino group is more reactive than the hydroxy group.
As shown in Scheme 6, compounds of Formula Ie can be prepared from corresponding compounds of Formula 7 by treatment with the corresponding phosphorating reagent of Formula 9 wherein X2 is a leaving group such as halogen. For reason of cost, X2 is preferably Cl.
Scheme 6
Figure imgf000021_0002
Ie
The reaction is conducted in the presence of a base such as pyridine, triethylamine or 4-(dimethylamino)pyridine in solvents such as dichloromethane or tetrahydrofuran at temperatures typically between 0 and 70 °C under an inert atmosphere.
Compounds of Formula I (or Iz) can also be prepared from other compounds of Formula I (or Iz) wherein substituents on the J groups are introduced or elaborated. For example, halogens can be attached using electrophilic addition reactions. Example 21 illustrates the addition of fluorine as R3 wherein J of Formula I (or Iz) is J-1. Carboxylic acids of Formula 3 can be prepared from corresponding esters of Formula
17 wherein R31 is a carbon-based radical such as alkyl (e.g., methyl, ethyl), benzyl, etc. as shown in Scheme 7. Scheme 7
Ester cleavage conditions
J-C(0)OR31 >■ 3
17
A wide range of ester cleavage conditions known in the art can be used for this method.
Particularly suitable are conditions involving treatment with hydroxide, such as aqueous sodium hydroxide or aqueous lithium hydroxide in tetrahydrofuran, followed by acidification, typically with a strong mineral acid such as hydrochloric or sulfuric acid. For cleaving esters of Formula 17 wherein R31 is benzyl, hydrogenation over palladium catalyst according to general procedures known in the art can be particularly advantageous. The method of Scheme 7 is illustrated in Step D of Example 1, Step B of Example 12, Step A of Example 13, Step C of Example 14, and Step D of Example 22, and Step D of Example 25.
Carboxylic esters of Formula 17a (Formula 17 wherein J is J-1 and R31 is ethyl) can be prepared according to the general method described by J. J. Parlow et al., J. Org. Chem.
1997, 62, 5908-5919 and modifications thereof as discussed for Scheme 8.
Scheme 8
Figure imgf000022_0001
This method involves base-induced condensation of a ketone of Formula 18 with diethyl oxalate (19) to give a tricarbonyl compound of Formula 20, which is condensed with a hydrazine of Formula 21 to prepare the pyrazolecarboxylate of Formula 17a. The condensation of the tricarbonyl compound of Formula 20 with the hydrazine of Formula 21 is typically conducted in an alcohol, ester or carbonate diester solvent. The hydrazine of Formula 21 can be in the form of a salt. As a modification of the general method of Scheme 8, when R3 is H, the diketoester of Formula 20 can be alkylated or fluorinated to provide the corresponding diketoester of Formula 20 wherein R3 is alkyl or fluorine. The method of Scheme 8 is illustrated in Steps A and B of Example 1 and Steps A and B of Example 25. As another modification of general method of Scheme 8, when Rla is H, the pyrazolecarboxylate of Formula 17a can be alkylated with the appropriate alkylating agent in the presence of a base and solvent to give a pyrazolecarboxylate of Formula 17a wherein Rla is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl. Appropriate alkylating agents are typically of the formula RlaX (22) wherein X is a nucleophihc reaction leaving group (e.g., bromide, iodide, mesylate (OS(O)2CH3), triflate (OS(O)2CF3), tosylate (OS(O)2Ph-4-CH3), etc.). Typical bases include potassium tert-butoxide, potassium carbonate, sodium hydride and potassium hydroxide. Typical solvents include N,N-dimethylformamide, acetonitrile and tetrahydrofuran. A particularly useful combination of base and solvent is potassium carbonate in acetonitrile. Alkylation isomers can be separated by common methods such as chromatography and crystallization. This modification is illustrated in Step C of Example 1 and Step C of Example 25.
Also, some of the Rla groups can be converted to others on compounds of Formula 17a. For example, when Rla is 2-hydroxyethyl, treatment with DAST (diethylaminosulfur trifluoride) typically gives a mixture of 2-fluoroethyl and vinyl for Rla. The product compounds of Formula 17a wherein Rla is 2-fluoroethyl and vinyl can then be separated by methods known in the art such as chromatography on silica gel and crystallization.
Compounds of Formula 18 are commercially available or can be prepared by methods well known in the art. For example, compounds of Formula 18 wherein R2a is -CR20(OR21)(OR22) can be prepared according to the general procedure described by B. Tellegen, Reel. Trav. Chim. Pays-Bas 1938, 57, 133-141. Alternate approaches to construct R2a using variations of the process of Scheme 8 are feasible. For example, a compound of Formula 17a wherein R2a is a l,l-dimethyl-2-haloethyl group can be prepared by first including R2a in Formula 18 as a 1,1 -dimethyl -2-hydroxyethyl group protected as a tetrahydropyranyl ether (e.g., prepared from dihydropyran and pyridinyl -tosylate (PPTS) using the general procedure of M. Miyashita et al., J. Org. Chem. 1977, 142(23), 3772- 3774), and then after preparation of the pyrazole ring according to the process of Scheme 8, deprotecting using PPTS to give the corresponding alcohol, which can then be converted to the mesylate using methanesulfonyl chloride and base, which is then displaced using an appropriate inorganic halide salt in N,N-dimethylformamide according to the general methods disclosed by P. Sulmon et al., Organic Preparations and Procedures Int. 1989, 21(1), 91-104 and European Patent EP-25,948-Bl. Similarly, substituents can be completed after conducting the processes of other Schemes described herein as an alternative to including the substituents in final form in the starting materials for the processes. Carboxylic esters of Formula 17b (Formula 17 wherein J is J-2 and R31 is ethyl) and
Formula 17c (Formula 17 wherein J is J-3 and R31 is ethyl) wherein Rlb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can be prepared from sydnones of Formula 23 and alkynes of Formula 24 according to the general method of J. Heterocycl. Chem. 1993, 30, 365-371 and J. Heterocycl. Chem. 1996, 33, 719-726 as depicted in Scheme 9. (One skilled in the art recognizes that to prepare 17b without a substituent at the pyrazole 5-position as specified for Formula 17b (J-2), the R3 radical in the sydnone of Formula 23 must be hydrogen.)
Scheme 9
Figure imgf000024_0001
In this method, sydnones of Formula 23 are heated with alkynes of Formula 24 in higher boiling solvents (e.g., xylenes, toluene, dioxane, ethylene glycol) for typically 12-72 hours. The isomers 17b and 17c then can be separated by the usual methods such as column chromatography and distillation. The sydnones of Formula 23 can be prepared using the general methods described in J. Heterocycl. Chem. 1993, 30, 365-371, /. Heterocycl. Chem. 1996, 33, 719-726 and the references cited therein. The method of Scheme 9 is illustrated in Step A of Example 12 and Step A of Example 14.
Carboxylic esters of Formula 17d (Formula 17 wherein J is J-3 but R2c can be H as well as R2b; R3 is H and R31 is ethyl) wherein Rlb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can also be prepared according to the method depicted in Scheme 10 wherein R32 is NMe2 or OEt when (MeO)2CHNMe2 or HC(OEt)3, respectively, is used to prepare intermediate 26.
Scheme 10
Figure imgf000024_0002
In this method the intermediate of Formula 26 is prepared from the ketoester of Formula 25 according to the general procedures published in /. Heterocycl. Chem., 1987, 24, 693-695. The starting ketoesters of Formula 25 can, in turn, be prepared according to the general procedures of J. Org. Chem. 1997, 62, 5908-5919. The condensation of the ketoester of Formula 26 with the hydrazine of Formula 27 is typically conducted in an alcohol, ester or carbonate diester solvent. The hydrazine of Formula 27 can be in the form of a salt.
When R2c is H, the pyrazolecarboxylate of Formula 17d can be alkylated with the appropriate alkylating agent in the presence of a base and solvent to give a pyrazolecarboxylate of Formula 17d wherein R2c is R2b. Appropriate alkylating agents are typically of the formula R2bX (28) wherein X is a nucleophihc reaction leaving group (e.g., bromide, iodide, mesylate (OS(O)2CH3), triflate (OS(O)2CF3), tosylate (OS(O)2Ph-4-CH3), etc.). Typical bases include potassium tert-butoxide, potassium carbonate, sodium hydride and potassium hydroxide. Typical solvents include N,N-dimethylformamide, acetonitrile and tetrahydrofuran. Alkylation isomers can be separated by common methods such as chromatography and crystallization.
Compounds of Formula 17b (i.e. pyrazole isomer J-2) can also be prepared using methods or slight modification thereof taught in: /. Heterocycl. Chem. 1999, 36(1), 217- 220, Agric. Biol. Chem. 1984, 48(1), 45-50, Bull. Soc. Chim. Fr. 1978, (7-8, Pt. 2), 401-14, Khim. Geterotsikl. Soedin. 1968, 4(4), 685-94, European Patent Application Publication EP 419917 and Spanish Patent ES 493459 (1981). Compounds of Formula 17c (i.e. pyrazole isomer J-3) can also be prepared using methods or slight modification thereof taught in: /. Heterocycl. Chem. 1991, 28(6), 1545-7, /. Heterocycl Chem. 1987, 24(6), 1669-75, /. Chem. Res., Synop. 1986, (5), 166-7, Aust. J. Chem. 1983, 36(1), 135X-1, Japanese Patent Application Publications JP 01061463, JP 01106866, JP 01061463 and JP 04021671, and Japanese Patents JP 2000212166 and JP 2000044541.
As shown in Scheme 11, pyrazoles of Formulae 17b and 17c (wherein Rlb is halogen) can be prepared from corresponding pyrazoles of Formula 17e (Formula 7 wherein J is J-2 but Rlb is H; and R31 is ethyl) and Formula 17f (Formula 17 wherein J is J-3 but Rlb is H; and R31 is ethyl), respectively.
Scheme 11
Figure imgf000025_0001
Figure imgf000026_0001
17f 17c
One variation of method of Scheme 11 involves heating a compound of Formula 17e or 17f with N-chloro- or N-bromosuccinimide in an organic solvent such as N,N-dimethyl- formamide, at temperatures between 30 and 110 °C, preferably at about 60 °C. Alternatively, bromine or chlorine can be added at or below room temperature to a compound of Formula 17e or 17f in a halocarbon solvent such as dichloromethane, trichloromethane or tetrachloromethane to give the corresponding compound of Formula 17b or 17c, respectively. The method of Scheme 11 is illustrated in Step B of Example 14.
Pyrazoles of Formula 17b and 17c wherein Rlb is halogen can also be prepared using the general methods taught in: Bulletin of the Korean Chemical Society 1998, 19(1), 725- 726, Izv. Akad. Nauk SSSR, Ser. Khim. 1981, (6), 1342-8, Izv. Akad. Nauk SSSR, Ser. Khim. 1980, (5), 1071-7, /. Heterocycl. Chem. 1997, 34(2), 537-540, /. Heterocycl. Chem. 1991, 28(8), 1849-52, J. Fluorine Chem. 1988, 39(3), 435-40, U.S. Patent No. 5201938, German Patent Application Publication DE 19632945-A1, and Japanese Patent Application Publications JP 10114750, JP 06056793, JP 05339242, JP 05043553, JP 03133961 and JP 01029364.
Thiazolecarboxylates of Formula 17g (Formula 17 wherein J is J-4) can be prepared as illustrated in Scheme 12.
Scheme 12
Figure imgf000026_0002
This method starts with an acyl chloride of Formula 29, which can be prepared by a variety of general methods known in the art; many acyl chlorides of Formula 29 are commercially available. The acyl chloride of Formula 29 is treated with an ammonia solution to prepare the carboxamide of Formula 30, which is in turn treated with a thionating reagent such as Lawesson's Reagent (2,4-bis(methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide) to prepare the thioamide of Formula 31. The thioamide of Formula 31 is then reacted with the chloro compound of Formula 32 to provide the thiazolecarboxylate of Formula 17g.
Carboxylic esters of Formula 17h (Formula 17 wherein J is J-5) can be prepared by the general method shown in Scheme 13.
Scheme 13
Figure imgf000027_0001
In this method, an alpha-bromo ketone of Formula 33 is converted to a Wittig reagent of Formula 34 and then condensed with a 2-oxocarboxylic acid ester of Formula 35 to provide a 4-oxo-2-pentenoic ester of Formula 36 according to the general procedure of P. F. Schuda et al., Synthesis 1987 (12), 1055-7. The 4-oxo-2-pentenoic ester of Formula 36 is then condensed with a hydrazine of Formula 37 to form the carboxylic ester of Formula 17h according to the general procedures of G. Westphal & H. H. Stroh, Liebigs Ann. Chem. 1968, 716, 160-163 and R. C. Moreau & P. Loiseau, Annales Pharmaceutiques Francoises 1978, 36 (1-2), 67-75. This method is illustrated by Steps A through C of Example 22.
Carboxylic esters of Formula 17i (Formula 17 wherein J is J-6 and R31 is ethyl) wherein Rld is H, alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl can be prepared from sydnones of Formula 23 and alkenes of Formula 38 according to the general methods described in Z. Obshch. Khim. 1962, 52(5), 1446-1451 as depicted in Scheme 14. Scheme 14
Figure imgf000027_0002
In this method, sydnones of Formula 23 are heated with alkenes of Formula 38 in higher boiling solvents (e.g., xylenes, toluene, dioxane, ethylene glycol) for typically 12-72 hours. The isomer 17i can then be isolated by the usual methods such as column chromatography and distillation. The ester of Formula 17i can then be converted to the corresponding carboxylic acid as described for Scheme 7 and coupled to form the compound of Formula la as described for Schemes 1 and 2. Most Rl substituents can be introduced as Rld in the method of Scheme 14, but halogen cannot. Halogen as well as other Rlb substituents can be introduced in the method shown in Scheme 15. Scheme 15
Figure imgf000028_0001
Figure imgf000028_0002
electrophile
If (Rid is H) If (Rid is Rlb)
In this method, the compound of Formula If wherein Ri is Rib is prepared from the compound of Formula If wherein Rid is H. The compound of Formula If wherein Rid is H is then deprotonated using a strong base such as lithium diisopropylamide (LDA) and then reacted with an electrophile introducing Rlb. This general method is discussed by T. M. Stevenson et al., "l-Arylpyrazoline-3-carboxanilides" in Synthesis and Chemistry of Agrochemicals TV (D. R. Baker et al., Eds., American Chemical Society, Washington, D.C., 1995) Chapter 26, pp. 291-299. For halogenation, the electrophile can be elemental halogen (e.g., Cl2, Br2) or a halogen derivative such as N-bromosuccinimide or N-chlorosuccinimide. When Rlb is alkyl, fluoroalkyl, alkenyl, fluoroalkenyl, alkynyl or fluoroalkynyl the electrophile is typically of the formula RlbX (39) wherein X is a nucleophic reaction leaving group as already described for the compound of Formula 22 in connection with the modified method of Scheme 8.
Carboxylic esters of Formula 17j (Formula 17 wherein J is J-7) wherein Rlc is H can be prepared by the general method shown in Scheme 16.
Scheme 16
Figure imgf000028_0003
In this method, a 3-oxo-carboxylic acid ester of Formula 40 is condensed with an aldehyde of Formula 41 to provide an unsaturated ester of Formula 42, which is condensed with a hydrazine of Formula 43 to provide the carboxylic ester of Formula 17j according to the general procedure of P. S. Engel et al., /. Am. Chem. Soc. 1997, 119 (26), 6059-6065.
The ester of Formula 17j can then be converted to the corresponding carboxylic acid as described for Scheme 7 and coupled to form the compound of Formula la as described for Schemes 1 and 2. Alternatively as shown in Scheme 17, the coupling can be conducted first to prepare the amide of Formula 44, which is then condensed with the aldehyde of Formula 41 to prepare the unsaturated amide of Formula 45, which is condensed with the hydrazine of Formula 43 to prepare the compound of Formula Ig wherein Rlc is H.
Scheme 17
Figure imgf000029_0001
The method of Scheme 17 is illustrated in Steps A and B of Example 24.
Carboxylic esters of Formula 17k (Formula 17 wherein J is J-8) can be prepared by the general method shown in Scheme 18.
Scheme 18
Figure imgf000029_0002
In this method, an alkynecarboxylic acid ester of Formula 24 is heated with an excess of azidotrimethylsilane at a temperature of about 100-110 °C under an inert atomosphere. The reaction is worked up by treating the cooled reaction mixture with excess methanol to consume remaining trimethylsilyl azide and desilylate the azide adduct. Evaporation leaves the 1,2,3-triazole of Formula 46. These conditions are described by R. S. Klein et al., /. Heterocycl. Chem. 1976, 13, 589-592 and illustrated by Step A of Example 26. The triazole of Formula 46 is then converted to the triazole of Formula' 17k by alkylation with R2bX3 (47) wherein X3 is a nucleophihc reaction leaving group such as Cl, Br, I, sulfonates such as p-toluenesulfonate, methanesulfonate or trifluoromethanesulfonate, or sulfates such as -OSO2OR2b. Preferably, X3 is a strong leaving groups such as I. The reaction is conducted in the presence of a base such as potassium carbonate in a polar aprotic solvent such as acetonitrile at a temperature commonly between 40 and 80 °C, typically about 50-60 °C. Filtration to remove solid byproducts and evaporation of the solvent leaves a crude product containing the triazole of Formula 17k typically together with other alkylation regioisomers. The triazole of Formula 17k can be isolated and purified by the usual methods known to those skilled in the art such as chromatography and crystallization. This method is illustrated by Step B of Example 26.
When R2b is a tertiary alkyl group such as tert-butyl, alkylation with R2bX3 may give low yields. Compounds of Formula 17k wherein R2 is a tertiary alkyl group can be satisfactorily prepared from compounds of Formula 46 by reaction with the appropriate alcohol R2bOH (47) in trifluoroacetic acid solution in the presence of concentrated sulfuric acid according to the general procedure of J. W. Tilley et al., J. Med Chem. 1991, 34(3), 1125-1134. This method is illustrated by Step A of Example 28.
Although ethyl esters are shown for the compounds of Formulae 24, 46 and 17k, one skilled in the art recognizes that corresponding esters wherein ethyl is replaced by other carbon-based radicals, e.g., R31, can be used as well for this method. Also known in the art are other methods to prepare 1,2,3-triazole rings, such as those described in PCT Patent Publication WO 02/096258.
Amino compounds of Formula 2 can be prepared by a wide variety of methods available to the synthetic organic chemist. Many of these methods involve converting one substitutent to another on the aromatic ring. For example, the amino function of Formula 2a (Formula 2 wherein R4 is H, T is CR6, U is CR7, Y is CR8 and Z is CR9) can be obtained by reduction of the nitro compound of Formula 60 as shown in Scheme 19.
Scheme 19
Figure imgf000030_0001
The nitro compound of Formula 60 can be reduced to the aniline of Formula 2a by a variety of reducing agents known in the art, such as iron in acetic acid, tin(II) chloride or hydrogenation over a palladium or platinum sulfide catalyst. The nitro function of Formula 60 can be added by well known nitration reactions. The method of Scheme 19 is illustrated in Step B of Example 4, Step C of Example 7, Step B of Example 16 and Step B of Example 17. Many compounds of Formula 60 are commercially available. When T, U and/or Z are N, the aryl ring of Formula 2 is activated to nucleophihc substitution facilitating introduction of amino by displacement of leaving groups such as halogen.
As another example of conversion of one substituent to another, compounds of Formula 2b (Formula 2 wherein R4 is H and R5 is CO2R12) wherein T is CR6 or N; U is CR7 or N; Y is CR8 or N; Z is CR9 or N; R6, R7, R8 and R9 are each independently H or F; and R12 is -C5 alkyl, C2-C5 haloalkyl, C3-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl can be prepared as shown in Scheme 20.
Scheme 20
Figure imgf000031_0001
61 62 2b In the method of Scheme 20, the amino function of a compound of Formula 61 is protected as the acetamide by treatment with acetic anhydride. Treatment with potassium permanganate then oxidizes the aromatic methyl radical to a carboxylic acid function to provide the compound of Formula 62. The compound of Formula 62 is then treated with strong acid, such as hydrochloric acid and alcohol of Formula 63 to form the ester group and deprotect the amino radical. This method works particularly well for short aliphatic alcohols (e.g., R12 is Me or Et). The method of Scheme 20 is illustrated in Steps A through C of Example 8 and Steps A through C of Example 10. Other synthetic approaches to prepare compounds of Formula 2b are also feasible, as is illustrated by Steps A through C of Example 19. Compounds of Formula 2b wherein R12 is methyl or ethyl can be coupled to form compounds of Formula la wherein R4 is H and R5 is CO2R12 according to the methods of Schemes 1 and 2, and then R12 converted to other radicals or CO2R12 converted to other groups such C(O)NR10Rn according to the method of Scheme 4 and other methods known to those skilled in the art. This conversion is illustrated by Example 20.
As still another example of conversion of one substituent to another, amides of Formula 2 wherein R5 is C(O)NR10R11 can be converted to thioamides of Formula 2 wherein R5 is C(S)NR10Rn using the thionating reagents already described for the method of Scheme 3. It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I or Iz may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, T. W. Greene, P. G. M. Wuts, Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I or Iz. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I or Iz.
One skilled in the art will also recognize that compounds of Formula I (or Iz) and the intermediates described herein can be subjected to various electrophilic, nucleophihc, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. lH NMR spectra are reported in ppm downfield from tetramethylsilane; 19F NMR spectra are reported in ppm relative to CF3CC13; "s" means singlet, "d" means doublet, "t" means triplet, "q" means quartet, "m" means multiplet, "dd" means doublet of doublets, "dt" means doublet of triplets, "dq" means doublet of quartets, "br s" means broad singlet, "br d" means broad doublet.
EXAMPLE 1
Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-ρyrazol-5-yl]carbonyl]- aminojbenzoate (Compound 80)
Step A: Preparation of ethyl 2-hydroxy-5,5-dimethyl-4-oxo-2-hexenoate
To a solution of sodium ethoxide in ethanol (250 mL, 21% by weight in ethanol, 670 mmol) was added dropwise a solution of diethyl oxalate (45.2 mL, 332.5 mmol) and pinacolone (alternatively named 3,3-dimethyl-2-butanone) (41.7 mL) in ethanol (300 mL) at room temperature under nitrogen atmosphere. The reaction mixture was stirred at room temperature overnight, concentrated to its half volume and poured into ice. Concentrated hydrochloric acid was added to lower the pΗ to approximately 4, and then the mixture was extracted with ethyl acetate. The extracts were dried over magnesium sulfate and concentrated to give the title compound as an oil (60 g, yield 90%).
Step B: Preparation of ethyl 5-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate
To a solution of ethyl 2-hydroxy-5,5-dimethyl-4-oxo-2-hexenoate (i.e. the product of Step A) (45.3 g, 226 mmol) in ethanol (200 mL) and acetic acid (2 mL) was added hydrazine monohydrate (12.1 mL, 249 mmol) dropwise under nitrogen atmosphere at room temperature. The reaction mixture was stirred at room temperature overnight and concentrated to give 40.8 g of the title compound. XΗ NMR (CDCI3) δ 6.7 (s, IH), 6.60 (br s, IH), 4.40 (q, 2H), 1.40 (t, 3H), 1.32 (s, 9H). Step C: Preparation of ethyl 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylate
To a solution of ethyl 5-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate (i.e. the product of Step B) (20.0 g, 102 mmol) in anhydrous N,N-dimethylformamide (DMF)
(100 mL) was added sequentially potassium carbonate (28.2 g, 204 mmol) and iodoethane
(11.4 mL, 143 mmol) at room temperature. After stirring at room temperature in an inert atmosphere for 6 h, the reaction mixture was diluted with ethyl acetate (400 mL) and washed with water (2x50 mL). The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the desired isomer (i.e. the title compound) as a white solid (13.8 g, 64% yield) and a minor isomer (2.1 g, 10% yield). iΗ ΝMR (CDCI3) δ 6.7 (s, 1Η), 4.55 (q, 2Η), 4.32 (q, 2H), 1.40 (m, 6H), 1.32 (s, 9H). XH ΝMR (CDCI3) (minor isomer) δ 6.7 (s, IH), 4.20 (q, 2H), 4.30 (q, 2H), 1.36 (m, 6H), 1.32 (s, 9H).
Step D: Preparation of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid
A solution of ethyl 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylate (i.e. the product of Step C) (6.9 g, 30.8 mmol) in ethanol (200 mL) was stirred with an aqueous solution of sodium hydroxide (10%, 19 mL) at room temperature for 6 h. The mixture was then concentrated and acidified with 1 Ν hydrochloric acid. The precipitated solids were filtered and dried to give 6 g of the title acid as a white solid. Η ΝMR (CDCI3) δ 10.00 (s, 1Η), 6.80 (s, 1Η), 4.60 (q, 2Η), 1.40 (t, 3H), 1.32 (s, 9H).
Step E: Preparation of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride A solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Step D) (1.2 g, 6.11 mmol) and oxalyl chloride (2 mL) in dichloromethane (30 mL) in the presence of anhydrous DMF (0.1 mL) was stirred under nitrogen atmosphere at room temperature for 4 h. The reaction mixture was then concentrated to yield the title acid chloride as a liquid. Step F: Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl] aminojbenzoate A solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e. the product of Step E) (1.3 g) in dichloromethane (30 mL) was added to a solution of ethyl 3-aminobenzoate (1.21 g) in dichloromethane (10 mL) in the presence of triethylamine (2 mL) and 4-(dimethylamino)pyridine (DMAP) (0.1 g). After stirring at room temperature overnight the reaction mixture was diluted with dichloromethane (50 mL) and washed with 1 N hydrochloric acid. The organic phase was separated, dried (MgSO4) and concentrated. The residue was purified by chromatography on silica gel to give the title compound (1.7 g, 81% yield), a compound of present invention, as a solid. lΗ NMR (CDC13) δ 8.01 (m, 2Η), 7.80 (d, IH), 7.42 (t, IH), 6.53 (s, IH), 4.57 (q, 2H), 4.38 (q, 2H), 1.38 (m, 6H), 1.34 (s, 9H).
EXAMPLE 2
Preparation of 2-fluoroethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl] amino]benzoate (Compound 82)
Step A: Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- aminojbenzoic acid A solution of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] benzoate (i.e. the product of Example 1, Step F) (4.8 g, 14 mmol) in methanol (30 mL) was stirred with an aqueous solution of sodium hydroxide (10%, 17 mL) at room temperature for 6 h. The reaction mixture was then concentrated and acidified with 1 N hydrochloric acid. The precipitated solids were filtered and dried to give the title acid as a white solid (4.3 g). Η NMR (CDCI3) δ 10.6 (s, 1Η), 8.38 (s, 1Η), 8.00 (d, 1Η), 7.62 (d, 1Η), 7.40 (t, 1Η), 4.47 (q, 2Η), 1.34 (t, 3H), 1.20 (s, 9H).
Step B: Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- aminojbenzoyl chloride
A solution of the 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- benzoic acid (i.e. the product of Step A) (1.2 g, 3.80 mmol), oxalyl chloride (1.72 mL) and anhydrous DMF (0.1 mL) in dichloromethane (10 mL) was stirred under nitrogen atmosphere at room temperature for 4 h. The reaction mixture was then concentrated to yield the title acid chloride.
Step C: Preparation of 2-fluoroethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
5-yl]carbonyl]amino]benzoate To a solution of the 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino]benzoyl chloride (i.e. the product of Step B) (0.2 g) in dichloromethane (5 mL) was added a solution of 2-fluoroethanol (0.1 mL), triethylamine (0.2 mL) and DMAP (20 mg) under nitrogen atmosphere at room temperature. After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (15 mL) and washed with 1 N hydrochloric acid (5 mL). The organic phase was dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (155 mg), a compound of present invention.
!H NMR (CDC13) δ 8.05 (m, IH), 7.88 (d, IH), 7.70 (br s, IH, NH), 7.42 (t, IH), 6.50 (s, IH), 4.60 (m, 6H), 1.42 (t, 3H), 1.34 (s, 9H).
EXAMPLE 3 Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[3-[[(2,2,2-trifluoroethyl)amino]carbonyl]- phenyl]-lH-pyrazole-5-carboxamide (Compound 43) To a solution of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- benzoyl chloride (i.e. the product of Example 2, Step B) (0.2 g) in dichloromethane (5 mL) was added sequentially 2,2,2-trifluoroethylamine (0.1 mL), triethylamine (0.2 mL) and DMAP (20 mg) at room temperature. After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (15 mL) and washed with hydrochloric acid (1 Ν, 5 mL). The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (155 mg), a compound of present invention. lΗ ΝMR (CDCI3) δ 7.44 (m, 3Η), 7.12 (dd, IH), 6.76 (s, IH), 6.42 (s, IH, ΝH), 4.60 (q, 2H), 4.12 (m, 2H), 1.42 (t, 3H), 1.38 (s, 9H).
EXAMPLE 4
Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino-
4-fluorobenzoate (Compound 70) Step A: Preparation of ethyl 4-fluoro-3-nitrobenzoate
A mixture of 4-fluoro-3-nitrobenzoic acid (10 g, 54 mmol), diethyl sulfate (8.5 mL) and potassium carbonate (10 g) in anhydrous acetone (120 mL) was heated to reflux for 6 h. The reaction mixture was then filtered, and the filtrate was concentrated. The residue was purified by chromatography on silica gel to give the title compound (11.2 g) as a yellow oil. lΗ ΝMR (CDCI3) δ 8.64 (dd, 1Η), 8.32 (m, 1Η), 7.38 (t, 1Η), 4.44 (q, 2Η), 1.40 (t, 3H).
Step B: Preparation of ethyl 3-amino-4-fluorobenzoate
A solution of ethyl 4-fluoro-3-nitrobenzoate (the product of Step A) (5.7 g,
26.7 mmol) in acetic acid (50 mL) and ethyl acetate (60 mL) was added dropwise over
20 minutes to a suspension of iron powder (6.0 g) in acetic acid (5% wt, 30 mL) at 80 °C. After the addition, the reaction mixture was stirred at 80 °C for additional 20 minutes. The mixture was then cooled to room temperature. Solids were removed by filteration through Celite® diatomaceous filter aid, and the filtrate was concentrated. The residue was diluted with ethyl acetate (100 mL) and washed sequentially with water (25 mL) and aqueous sodium bicarbonate solution (5%, 25 mL). The organic layer was dried and concentrated to give the title compound (4.5 g). iH NMR (CDC13) δ 7.60 (dd, IH), 7.42 (m, IH), 7.08 (t, IH), 4.34 (q, 2H), 3.90 (br s, 2H), 1.34 (t, 3H).
Step C: Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-ρyrazol-5-yl]- carbonyl] amino-4-fluorobenzoate A solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e. the product of Example 1, Step E) (4.7 g) in dichloromethane (40 mL) was added to a solution of ethyl 3-amino-4-fluorobenzoate (i.e. the product of Step B) (4.46 g, 24.3 mmol) and N,N-diisopropylethylamine (8.5 mL) in dichloromethane (10 mL). After stirring at room temperature overnight, the reaction mixture was diluted with dichloromethane (100 mL) and washed with 1 Ν hydrochloric acid. The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (6.6 g), a compound of the present invention. lH ΝMR (CDCI3) δ 8.14 (m, 1Η), 8.00 (dd, 1Η), 7.26 (s, 1Η), 6.26 (s, 1Η), 4.34 (m, 4Η), 1.41 (m, 6H), 1.20 (s, 9H).
EXAMPLE 5 Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl]-2-fluorophenyl]- lH-pyrazole-5-carboxamide (Compound 2)
Step A: Preparation of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] -4-fluorobenzoic acid A solution of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-4-fluorobenzoate (i.e. the product of Example 4, Step C) (6.6 g, 18.3 mmol) in methanol (40 mL) and aqueous sodium hydroxide (10%, 17 mL) was stirred at room temperature for 6 h. The reaction mixture was then concentrated and acidified with 1 Ν hydrochloric acid. The precipitated solids were filtered and dried to give 5.3 g of the title acid as a white solid. iΗ ΝMR (DMSO-rf6) δ 10.54 (s, 1Η), 8.22 (dd, 1Η), 7.86 (m, 1Η), 7.40 (t, 1Η), 6.89 (s, 1Η), 4.44 (q, 2Η), 1.32 (t, 3H), 1.30 (s, 9H).
Step B: Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl]-
2-fluorophenyl]-lH-pyrazole-5-carboxamide To a solution of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]arnino]- 4-fluorobenzoic acid (i.e. the product of Step A) (200 mg) in dichloromethane (5 mL) was added sequentially 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 4 mL), ethylamine (0.3 mL) and DMAP (0.2 g) at room temperature. After stirring at room temperature overnight, the reaction mixture was diluted with dichloromethane (10 mL) and washed with 1 N hydrochloric acid (5 mL). The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound, a compound of present invention, as white solid, m.p. 188.5 °C.
EXAMPLE 6
Alternate Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl]- 2-fluorophenyl]-lH-pyrazole-5-carboxamide (Compound 2) To a solution of 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- 4-fluorobenzoic acid (i.e. the product of Example 5, Step A) (200 mg) in dichloromethane (5 mL) was added oxalyl chloride (0.5 mL) and anhydrous DMF (0.1 mL). After stirring at room temperature for 2 h, the reaction mixture was concentrated under reduced pressure. To a solution of the residue (200 mg) in dichloromethane (5 mL) at room temperature was added sequentially ethylamine (0.3 mL), triethylamine (0.5 ml) and DMAP (0.1 g). After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (10 mL) and washed with hydrochloric acid (1 Ν, 5 mL). The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound, a compound of present invention, as white solid, m.p. 188.5 °C.
EXAMPLE 7 Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-3-(l ,1-dimethylethyl)- l-ethyl-lH-pyrazole-5-carboxamide (Compound 6)
Step A: Preparation of 4-fluoro-3-nitrobenzoyl chloride
A solution of 4-fluoro-3-nitrobenzoic acid (13 g, 70 mmol), oxalyl chloride (8.5 mL) and DMF (0.5 mL) in anhydrous dichloromethane (200 mL) was stirred at room temperature under nitrogen atmosphere for 2 h. The reaction mixture was then concentrated to remove the solvent, and the crude title compound was used for the next reaction without further purification (13 g).
Step B : Preparation of 4-fluoro-N,N-dimethyl-3-nitrobenzamide
To a solution of 4-fluoro-3-nitrobenzoyl chloride (i.e. the product of Step A) (4.1 g) in dichloromethane (50 mL) was added dimethylamine hydrochloride (2.13 g) and N,N-diisopropylethylamine (4 mL) at room temperature. After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (100 mL) and washed with 1 Ν hydrochloric acid (15 mL). The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (3.4 g) as white solid. Step C: Preparation of 3-amino-4-fluoro-N,N-dimethylbenzamide
A solution of 4-fluoro-N,N-dimethyl-3-nitrobenzamide (i.e. the product of Step B) (1.8 g, 8.5 mmol) in acetic acid (9 mL) and ethyl acetate (10 mL) was added dropwise over 20 minutes to a suspension of iron powder (1.5 g) in acetic acid (5%, 5 mL) at 80 °C. After the addition, the reaction mixture was stirred at 80 °C for additional 20 minutes. The mixture was then cooled to room temperature. Solids were removed by filteration through Celite® diatomaceous filter aid, and the filtrate was concentrated. The residue was diluted with ethyl acetate (50 mL) and washed sequentially with water (10 mL) and aqueous sodium bicarbonate solution (5%, 15 mL). The organic layer was dried and concentrated to give the title compound ( 1.1 g) .
Step D : Preparation of N- [5 - [(dimethylamino)carbonyl] -2-fluorophenyl] -
3-( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazole-5 -carboxamide A solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e. the product of Example 1, Step E) (1.2 g) in dichloromethane (10 mL) was added to a solution of 3-amino-4-fluoro-N,N-dimethylbenzamide (i.e. the product of Step C) (1.1 g) and N,N-diisopropylethylamine (2.5 mL) in dichloromethane (5 mL). After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (20 mL) and washed with 1 Ν hydrochloric acid. The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (1.8 g), a compound of present invention. lΗ ΝMR (CDC13) δ 8.40 (dd, 1Η), 8.02 (br s, 1Η, ΝΗ), 7.22 (m, 2Η), 6.54 (s, IH), 4.58 (q, 2H), 3.10 (s, 3H), 3.03 (s, 3H), 1.44 (t, 3H), 1.34 (s, 9H).
EXAMPLE 8
Preparation of methyl 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- 2-pyridinecarboxylate (Compound 143)
Step A: Preparation of N-(6-methyl-2-pyridinyl)acetamide
A solution of 2-amino-6-picoline (20 g, 185 mmol) and acetic anhydride (35 mL) in anhydrous tetrahydrofuran (TΗF) (150 mL) was heated at reflux for 10 h. The reaction mixture was then cooled to room temperature and concentrated to leave a thick oily residue. The residue was dissolved in dichloromethane (400 mL) and washed sequentially with hydrochloric acid (1 Ν, 50 mL) and water (50 mL). The organic phase was dried and concentrated to give the title compound as a white solid (27.6 g, 99% yield). lΗ ΝMR (CDCI3) δ 8-02 (d> 1Η)> 8-00 (br s, IH, ΝH), 7.61 (t, IH), 6.90 (d, IH), 2.44 (s, 3H), 2.20 (s, 3H). Step B: Preparation of 6-(acetylamino)-2-pyridinecarboxylic acid
To a suspension of N-(6-methyl-2-pyridinyl)acetamide (i.e. the product of Step A) (27 g, 184 mmol) in water (250 mL) at 90 °C was added potassium permanganate (29.1 g, 184 mmol) in small portions. After the addition, the mixture was heated to 90 °C for 6 h. The mixture was then cooled and filtered through a pad of Celite® diatomaceous filter aid. The filtrate was concentrated to half of its volume and acidified with concentrated hydrochloric acid. The precipitated solids were isolated by filtration and dried to give 20 g of the title compound.
Step C: Preparation of methyl 6-amino-2-pyridinecarboxylate Hydrogen chloride gas was bubbled through a suspension of 6-(acetylamino)-
2-pyridinecarboxylic acid (i.e. the product of Step B) (20 g) in methanol (100 mL) for 1 h. The reaction mixture was then heated to reflux overnight. Concentration followed by purification on silica gel column provided the title compound (12 g). IH ΝMR (CDC13) δ 7.52 (m, 2H), 6.69 (d, IH), 4.80 (br s, 2H, ΝH2), 3.96 (s, 3H). Step D: Preparation of methyl 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl]amino]-2-pyridinecarboxylate To a solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e. the product of Example 1, Step E) (1.2 g) in dichloromethane (10 mL) was added sequentially a solution of methyl 6-amino-2-pyridinecarboxylate (i.e. the product of Step C) (1.03 g) in dichloromethane (5 mL) followed by triethylamine (2 mL) and then DMAP (0.1 g). After stirring at room temperature for 6 h, the reaction mixture was diluted with dichloromethane (20 mL) and washed with 1 N hydrochloric acid. The organic phase was separated, dried and concentrated. The residue was purified by chromatography on silica gel to give the title compound (1.24 g), a compound of the present invention. lΗ NMR (CDC13) δ 8.72 (s, 1Η, NΗ), 8.42 (m, 1Η), 7.82 (d, 2Η), 6.64 (s, IH), 4.48 (q, 2H), 4.01 (s, 3H), 1.45 (t, 3H), 1.31 (s, 9H).
EXAMPLE 9
Preparation of 6- [ [[3-(l , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5-yl]carbonyl] amino] - 2-pyridinecarboxamide (Compound 162) Step A: Preparation of 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-2-pyridinecarboxylic acid
A solution of methyl 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino]-2-pyridinecarboxylate (i.e. the product of Example 8, Step D) (1.02 g, 3.09 mmol) in methanol (50 mL) was stirred at room temperature with an aqueous solution of sodium hydroxide (10 wt%, 2 mL) for 6 h. The reaction mixture was then concentrated and acidified with 1 N hydrochloric acid. The precipitated solids were isolated by filtration and dried to give the title acid as a white solid (0.9 g).
!H NMR (DMSO--i6) δ 8.28 (d, IH), 8.00 (t, IH), 7.82 (d, 2H), 6.60 (s, IH), 4.40 (q, 2H), 1.45 (t, 3H), 1.31 (s, 9H). Step B: Preparation of 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino] -2-pyridinecarboxamide A procedure analogous to that of Example 6 was used to convert 6- [ [[3 -( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5-yl] carbonyl] amino-2-pyridine- carboxylic acid (520 mg) (i.e. the product of Step A) and dimethylamine (0.5 mL, 2.0 M in TΗF) to the title compound, a compound of present invention. lΗ NMR (CDCI3) δ 8.46 (s, 1Η, NΗ), 8.38 (d, 1Η), 7.80 (t, 1Η), 7.32 (dd, 1Η), 6.55 (s, 1Η), 4.60 (q, 2Η), 3.14 (s, 3H), 3.02 (s, 3H), 1.43 (t, 3H), 1.30 (s, 9H).
EXAMPLE 10
Preparation of methyl 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- 4-pyridinecarboxylate (Compound 151)
Step A: Preparation of N-(4-methyl-2-pyridinyl)acetamide
A solution of 2-amino-4-picoline (25 g, 231 mmol) in acetic anhydride (150 mL) was heated to reflux for 10 h. The reaction mixture was then cooled to room temperature and concentrated to give a thick oily residue. The residue was dissolved in dichloromethane (400 mL) and washed sequentially with 1 Ν hydrochloric acid (50 mL) and water (50 mL). The organic phase was dried and concentrated to give the title compound as a white solid (30 g).
Step B: Preparation of 4-(acetylamino)-2-pyridinecarboxylic acid
A procedure analogous to that of Example 8, Step B was used to convert N-(4-methyl- 2-pyridinyl)acetamide (10 g) (i.e. the product of Step A) to the title acid, which was obtained as a solid (3.4 g).
Step C: Preparation of methyl 4-amino-2-pyridinecarboxylate
A procedure analogous to that of Example 8, Step C was used to convert 4-(acetylamino)-2-pyridinecarboxylic acid (i.e. the product of Step B) (3.4 g) to the title compound (0.92 g). lΗ ΝMR (CDCI3) δ 8.2 (d, 1Η), 7.17 (d, 1Η), 7.06 (s, 1Η), 4.59 (br s, 2Η, ΝH2), 3.92 (s, 3H). Step D: Preparation of methyl 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl]amino]-4-pyridinecarboxylate A procedure analogous to that of Example 5, Step B was used to convert 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Example 1, Step D) (1.0 g) and methyl 4-amino-2-pyridinecarboxylate (i.e. the product of Step C) (0.78 g) to the title compound (0.85 g), a compound of present invention. XΗ NMR (CDC13) δ 8.60 (d, IH), 7.92 (s, IH, NH), 7.80 (d, IH), 6.28 (s, IH), 4.38 (q, 2H), 3.96 (s, 3H), 1.45 (t, 3H), 1.21 (s, 9H).
EXAMPLE 11 Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]-
N,N-dimethyl-4-pyridinecarboxamide (Compound 156)
Step A: Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-4-pyridinecarboxylic acid A procedure analogous to that of Example 9, Step A was used to convert methyl 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]-4-pyridinecarboxylate (i.e. the compound of Example 10, Step D) (1.02 g, 3.09 mmol) to the title acid as a white solid (0.9 g).
!Η ΝMR (DMSO- 6) δ 10.84 (s, 1Η) 8.64 (s, 1Η), 8.52 (d, 1Η), 7.60 (d, 1Η), 7/18 (s, 1Η), 4.40 (q, 2Η), 1.32 (t, 3H), 1.23 (s, 9H). Step B: Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino]-N,N-dimethyl-4-pyridinecarboxamide A procedure analogous to that of Example 5, Step B was used to convert 2- [[ [3-( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5 -yl] carbonyl] amino-4-pyridinecarboxylic acid (i.e. the compound of Step A) (200 mg) and dimethylamine to the title compound (110 mg), a compound of present invention. lΗ ΝMR (CDCI3) δ 8.68 (s, 1Η, ΝΗ), 8.40 (d, 2Η), 7.04 (d, IH), 6.61 (s, IH), 4.58 (q, 2H), 3.18 (s, 3H), 3.00 (s, 3H), 1.42 (t, 3H), 1.31 (s, 9H).
EXAMPLE 12
Preparation of N-[3-[(diethylamino)carbonyl]phenyl]-l-(l,l-dimethylethyl)-4-ethyl- lH-pyrazole-3-carboxamide (Compound 168)
Step A: Preparation of ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate and ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate
Ethyl 2-pentynoate (5.32 g, 42.2 mmol) was added to a solution of 3-(l,l- dimethylethyl)sydnone (6 g, 42.2 mmol) in xylenes (75 mL) under a nitrogen atmosphere. The reaction mixture was heated to reflux for three days and cooled to room temperature. The resulting white solids were removed by filtration using xylenes for rinsing. The filtrate was concentrated to leave a liquid, which was applied to a silica gel flash column (eluted with hexanes followed by 5:95 ethyl acetate-hexanes) to give the two title isomeric products as oils. Ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate (3.62 g) was the major isomer. Ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate (0.78 g) was the minor isomer. iΗNMR (CDC13) δ major isomer: 7.92 (s, 1Η), 4.2 (q, 2Η), 2.88 (q, 2H), 1.57 (s, 9H), 1.3 (t,
3H), 1.2 (t, 3H); minor isomer: 7.34 (s, IH), 4.4 (q, 2H), 2.7 (q, 2H), 1.6 (s, 9H), 1.39 (t,
3H), 1.20 (t, 3H). Step B: Preparation of l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylic acid
A solution of ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate (i.e. minor isomer product of Step A) (0.75 g, 3.34 mmol) in ethanol (13 mL) was stirred at room temperature with aqueous sodium hydroxide (3 M, 6.7 mL, 20.0 mmol) for 2 days. The reaction mixture was then concentrated, and the pΗ of the resulting residue was adjusted to 2 with 1 N hydrochloric acid. The aqueous layer was extracted with diethyl ether (3x). The combined organic extracts were washed with brine solution, dried (Na2SO4) and concentrated to leave an oil (0.82 g). The oil solidified on standing, and the resulting solids were isolated using filtration and rinsed with hexanes to yield the title acid as a solid (0.53g). !Η NMR (CDCI3) δ 7.38 (s, 1Η), 2.77 (q, 2Η), 1.6 (s, 9H), 1.21 (t, 3H). Step C: Preparation of N-[3-[(diethylamino)carbonyl]phenyl]-l-(l,l-dimethylethyl)-
4-ethyl-lH-pyrazole-3-carboxamide A solution of l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylic acid (i.e. product of Step B) (0.1 g, 0.51 mmol) in thionyl chloride (5 mL) was heated at reflux for about four hours. The reaction mixture was concentrated to yield the corresponding acid chloride as a liquid. The acid chloride was added to a solution of 3-amino- N,N-diethylbenzamide (0.117 g, 0.611 mmol) and triethylamine (107 μL, 0.764 mmol) in dichloromethane (2 mL). After stirring at room temperature overnight, the reaction mixture was concentrated and the resulting residue was partitioned between dichloromethane and 1 Ν hydrochloric acid. The dichloromethane layer was washed sequentially with 1 Ν hydrochloric acid and brine, dried and concentrated to give an oil. The oil was purified by column chromatography on silica gel to give the title compound (60 mg), a compound of present invention. iΗ ΝMR (CDCI3) δ 8.86 (br s, 1Η), 7.8 (d, 1Η), 7.6 (s, 1Η), 7.36 (t, 1Η), 7.08 (d, 1Η), 3.5 (m, 2Η), 3.3 (m, 2H), 2.87 (q, 2H), 1.6 (s, 9H), 1.3 (m, 3H), 1.24 (t, 3H), 1.1 (m, 3H). EXAMPLE 13
Preparation of N-[3-[(diethylamino)carbonyl]ρhenyl]-l-(l , l-dimethylethyl)-3-ethyl- lH-pyrazole-4-carboxamide (Compound 182)
Step A: Preparation of l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid A procedure analogous to that of Example 12, Step B was used to convert ethyl l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylate (i.e. the major isomer product of Example 12, Step A) (1.76 g, 7.76 mmol) to the title acid (1.08 g). lH ΝMR (CDC13) δ 8.0 (s, 1Η), 2.9 (q, 2Η), 1.58 (s, 9H), 1.26 (t, 3H).
Step B: Preparation of N-[3-[(diethylamino)carbonyl]phenyl]-l-(l,l-dimethylethyl)- 3-ethyl-lH-pyrazole-4-carboxamide
A procedure analogous to that of Example 12, Step C was used to convert l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid (i.e. the product of Step A)
(100 mg) and 3-amino-N,N-diethylbenzamide (0.117g, 0.611 mmol) to the title compound
(91 mg), a compound of present invention. lΗ ΝMR (CDCI3) δ 8.0 (s, 1Η), 7.7 (br s, 1Η), 7.6 (d, 1Η), 7.5 (s, 1Η), 7.3 (t, 1Η), 7.0 (d,
1Η), 3.5 (m, 2Η), 3.3 (m, 2H), 2.9 (q, 2H), 1.6 (s, 9H), 1.32 (t, 3H), 1.3 (m, 3H), 1.1 (m,
3H).
EXAMPLE 14
Preparation of 4-bromo-l-(l,l-dimethylethyl)-N-[3-[(ethylamino)carbonyl]phenyl]- lH-pyrazole-3-carboxamide (Compound 221)
Step A: Preparation of ethyl l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate
Ethyl propiolate (6.9 g, 70.3 mmol) was added to a solution of 3-(l,l-dimethylethyl)- sydnone (65 g, 35.2 mmol) in toluene (60 mL) under a nitrogen atmosphere. The reaction mixture was heated to reflux for two days and cooled to room temperature. The resulting white solid was removed by filtration using hexanes for rinsing. The filtrate was concentrated to leave a liquid, which was applied to a silica gel flash column (eluted with 100% hexanes followed by 10:90 ethyl acetate-hexanes) to give the title product (2.61 g) as a major isomer. Η ΝMR (CDCI3) δ 7.5 (s, 1Η), 6.7 (m, 1Η), 4.4 (q, 2Η), 1.63 (s, 9H), 1.39 (t, 3H). Step B : Preparation of ethyl 4-bromo- 1 -( 1 , 1 -dimethylethyl)- lH-pyrazole-
3-carboxylate
To a solution of ethyl l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate (i.e. the product of Step A) (0.1 g, 0.509 mmol) in DMF (3.0 mL) at room temperature was added
N-bromosuccinimide (0.90 mg, 0.509 mmol). After heating to 60 °C for 4 h, the reaction mixture was cooled to room temperature and partitioned between water and diethyl ether (3x50 mL). The organic extracts were washed with water (4x) and brine, dried (Na SO4) and then concentrated to give the title product as an oil (0.126 mg). :H NMR (CDC13) δ 7.6 (s, IH), 4.4 (q, 2H), 1.6 (s, 9H), 1.4 (t, 3H).
Step C: Preparation of ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylic acid
A procedure analogous to that of Example 12, Step B was used to hydrolyze ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylate (i.e. the product of Step B) (0.61 g, 2.18 mmol) to give the title acid (0.4 g) as a solid. Η NMR (CDCI3) δ 7.6 (s, 1Η), 1.6 (s, 9Η). Ste D: Preparation of 4-bromo-l-(l,l-dimethylethyl)-N-[3-[(ethylamino)carbonyl]- phenyl] - lH-pyrazole-3-carboxamide A procedure analogous to that of Example 12, Step C was used to convert ethyl 4-bromo-l-(l,l-dimethylethyl)-lH-pyrazole-3-carboxylic acid (i.e. product of Step C) (100 mg, 0.405 mmol) and 3-amino-N-ethylbenzamide (70 mg, 0.425 mmol) to the title compound (72 mg), a compound of present invention.
Η ΝMR (CDCI3) δ 8.82 (br s, 1Η), 8.18 (s, 1Η), 7.81 (d, 1Η), 7.6 (s, 1Η), 7.56 (d, 1Η), 7.42 (t, 1Η), 6.27 (br s, 1Η), 3.5 (m, 2Η), 1.6 (s, 9H), 1.27 (t, 3H).
EXAMPLE 15
Preparation of N-(2,3-dihydro-2-methyl-l-oxo-lH-isoindol-4-yl)-3-(l,l-dimethylethyl)- 1 -ethyl- lH-pyrazole-5 -carboxamide (Compound 55)
Step A: Preparation of 2,3-dihydro-2-methyl-4-nitro-lH-isoindol-l-one
To a solution of methyl 2-(bromomethyl))-3-nitrobenzoate (2.97 g, 10.8 mmol) prepared according to P. Japtap et al. (PCT Application Publication WO 01/77075 A2) in methanol (6 mL) was added a solution of methylamine in methanol (2.0 M, 20 mL). After stirring at room temperature for 3 h, the methanol was evaporated in vacuum and the residue was washed with ether and water to give the title compound as a white solid (0.98 g, 50% yield).
Η ΝMR (CDC13): δ 8.39 (d, 1Η), 8.18 (d, 1Η), 7.70 (t, 1Η), 7.27 (s, 1Η), 4.87 (s, 2Η), 3.27 (t, 3H). Step B: Preparation of 4-amino-2,3-dihydro-2-methyl-lH-isoindol-l-one
A slurry of 2,3-dihydro-2-methyl-4-nitro-lH-isoindol-l-one (i.e. product of Step A) (0.97 g, 5.1 mmol) and 10% palladium on carbon (0.24 g) in ethyl acetate (35 mL) was hydrogenated at 45 psi (310 kPa) at room temperature for 5.5 h. The mixture was then filtered through a pad of Celite® diatomaceous filter aid, and the Celite® was extracted with ethyl acetate. The filtrate was concentrated under vacuum to give the title compound (0.81 g, 97% yield). 2H NMR (CDCI3): δ 7.29 (m, 2H), 6.80 (d, IH), 4.21 (s, 2H), 3.20 (s, 3H).
Step C: Preparation of N-(2,3-dihydro-2-methyl-l-oxo-lH-isoindol-4-yl)- 3-(l , 1 -dimethylethyl)- l-ethyl-lH-pyrazole-5-carboxamide ^^
4-Amino-2,3-dihydro-2-methyl-lH-isoindol-l-one (i.e. the product of Step B) (0.15 g, 0.9 mmol) and triethylamine (0.187 g) was dissolved in dichloromethane (4 mL). 3-(l,l-Dimethylethyl)-l-ethyl-lH-pyrazole-5-carbonyl chloride (i.e. the product of Example 1, Step E) (0.318 g) was added to the reaction mixture, which was then stirred at room temperature for 2 days. Ethyl acetate (20 mL) and water (2 mL) were added, and the reaction mixture was passed through a Narian Chem Elut filter containing diatomaceous filter aid. The solvent was removed under vacuum, and the residue was triturated with 30% ethyl acetate in hexane to give the title compound, a compound of the invention, as a white solid (0.19 g, 55% yield). lΗ ΝMR (CDCI3): δ 7.74 (d, 1Η), 7.72 (s, 1Η), 7.58 (d, 1Η), 7.55 (t, 1Η), 6.52 (s, 1Η), 4.57 (q, 2Η), 4.43 (s, 2H), 3.20 (s, 3H), 1.45 (t, 3H), 1.34 (s, 9H). EXAMPLE 16
Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-l-(l,l-dimethylethyl)- 3-ethyl-lH-pyrazole-4-carboxamide (Compound 222)
Step A: Preparation of 4-fluoro-N,N-dimethyl-3-nitrobenzamide
4-Fluoro-3-nitrobenzoic acid (5 g, 27.0 mmol) was heated at reflux in thionyl chloride (20 mL) for 4 h. The reaction mixture was concentrated, diluted with dichloromethane and then reconcentrated to provide the acid chloride as a liquid. The acid chloride was then diluted with dichloromethane (50 mL). Half of the acid chloride solution was placed in a round-bottom flask and further diluted with dichloromethane to give a total volume of 50 mL. The acid chloride solution was cooled to 0 °C. Triethylamine (3.0 g, 29.7 mmol) was added to the reaction mixture, and then a solution of 40% aqueous solution of dimethylamine (1.52 g, 13.5 mmol) in dichloromethane (20 mL) was added dropwise to the reaction mixture at such a rate that the temperature of the reaction mixture did not exceed 5 °C. The cooled reaction mixture was stirred for 15 minutes more, and then hydrochloric acid (1 Ν) was added. The layers were separated, and the organic layer was washed with water, saturated aqueous sodium bicarbonate solution and brine, and then dried over sodium sulfate and concentrated to give the title compound (1.87 g).
IH ΝMR (CDCI3): δ 8.1 (m, IH), 7.7-7.8 (m, IH), 7.3-7.4 (m, IH,), 3.1(s, 3H), 3.0 (s, 3H). 19F ΝMR (CDCl3): δ -115.5.
Step B: Preparation of 3-amino-4-fluoro-N,N-dimethylbenzamide 4-Fluoro-N,N-dimethyl-3-nitrobenzamide (i.e. the product of Step A) ( 1.76 g,
8.29 mmol) was dissolved in acetic acid (22 mL). The reaction mixture was heated to 85 °C, and then iron powder (1.39 g) was added in portions. After the addition was complete, the reaction mixture was stirred at 85 °C for an additional 20 minutes. The mixture was then cooled to room temperature and concentrated. Solids were removed by filtration through Celite® diatomaceous filter aid, using ethyl acetate and water for rinsing. The layers in the filtrate were separated. The organic layer was washed sequentially with water, aqueous saturated sodium bicarbonate solution and brine, and then dried over sodium sulfate and concentrated to give the title compound (1.5 g).
JH NMR (CDC13): δ 6.9-7.0 (m, IH), 6.8 (m, IH), 6.69-7.78 (m, IH), 3.8 (br s, 2H, NH2), 3.0 (s, 3H), 2.9 (s, 3H). Step C: Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]- l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxamide A procedure analogous to that of Example 12, Step C was used to convert l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid (i.e. the product of Example 13, Step A) (100 mg) and 3-amino-4-fluoro-N,N-dimethylbenzamide (92 mg, 0.509 mmol) (i.e. the product of Step B of Example 16) to the title compound (117 mg), a compound of present invention. !Η ΝMR (CDCI3): δ 8.5 (m, 1Η), 7.9 (s, 1Η), 7.7 (br s, 1Η, ΝΗ), 7.1-7.2 (m, 2Η), 3.1(s,
3H), 3.0 (s, 3H), 2.9 (q, 2H), 1.6 (s, 9H), 1.3 (t, 3H). 19F ΝMR (CDCI3): δ -130.2. EXAMPLE 17
Preparation of l-(l,l-dimethylethyl)-3-ethyl-N-[3-[(ethylamino)carbonyl]-4-fluorophenyl]- lH-pyrazole-4-carboxamide (Compound 241)
Step A: Preparation of N-ethyl-2-fluoro-5-nitrobenzamide
A procedure analogous to that of Example 16, Step A was used to convert 2-fluoro- 5-nitrobenzoic acid (5 g, 27.0 mmol) and ethylamine (2 M in TΗF, 10 mL, 19.8 mmol) to give the title compound (1.6 g). lΗ ΝMR (CDCI3): δ 8.9-9.0 (m, 1Η), 8.3-8.4 (m, 1Η), 7.2-7.3 (m, 1Η), 6.6 (t, 1Η), 3.5 (q,
2Η), 1.2 (t, 3H). 19F ΝMR (CDCI3): δ -105.2. Step B: Preparation of 5-amino-N-ethyl-2-fluorobenzamide
A procedure analogous to that of Example 16, Step B was used to convert N-ethyl- 2-fluoro-5-nitrobenzamide (0.78 g, 3.68 mmol) and iron powder (0.62 g, 11.0 mmol) of acetic acid (10 mL) to give the title compound (0.62 g, oil). lH ΝMR (CDCI3): δ 7.3 (m, IH), 6.8-6.9 (m, IH), 6.6-6.7 (m, 2H), 3.5 (q, 2H), 1.2 (t, 3H). Step C: Preparation of l-(l,l-dimethylethyl)-3-ethyl-N-[3-[(ethylamino)carbonyl]- 4-fluorophenyl]-lH-pyrazole-4-carboxamide
To a solution of l-(l,l-dimethylethyl)-3-ethyl-lH-pyrazole-4-carboxylic acid (i.e. the product of Example 13, Step A) (150 mg, 0.76 mmol) in dichloromethane (4 mL) was added sequentially 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 365 mg, 1.14 mmol), 4-(dimethylamino)pyridine (140 mg, 1.14 mmol), 5-amino-N-ethyl-2-fluoro- benzamide (i.e. the product of Step B) (146 mg, 0.80 mmol) at room temperature. After stirring at room temperature overnight, the reaction mixture was diluted with 1 Ν hydrochloric acid (3.5 mL) and then filtered thru an Extube™ (tube containing diatomaceous earth marketed by Varian, Inc., 24201 Frampton Avenue, Harbor City, CA 90710 USA), which was rinsed well with dichloromethane. The filtrate was concentrated to leave the crude product as an oil. The crude product was purified by chromatography on silica gel to give an oil. Trituration with diethyl ethyl and hexanes provided the title product, a compound of the present invention, as a white solid, m.p. 168-169 °C. lH ΝMR (CDC13): δ 8.2-8.3 (m, IH), 7.9 (s, IH), 7.8 (m, IH), 7.7 (br s, IH, ΝH), 7.1-7.2 (m, IH), 6.7 (t, IH), 3.5 (q, 2H), 2.9 (q, 2H), 1.59 (s, 9H), 1.3 (t, 3H), 1.2 (t, 3H). 19F ΝMR (CDCI3): δ -120.2.
EXAMPLE 18
Preparation of N- [3 - [(dimethylamino)carbonyl] -4-fluorophenyl] -3 -( 1 , 1 -dimethylethyl)- l-ethyl-lH-pyrazole-5-carboxamide (Compound 236)
A procedure analogous to that of Example 17, Step C was used to convert 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Example 1, Step D) (200 mg, 1.0 mmol), 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 490 mg 1.5 mmol), 4-(dimethylamino)pyridine (187 mg, 1.5 mmol) and 5-amino- N,N-dimethyl-2-fluorobenzamide (195 mg, 1.0 mmol) in dichloromethane (4 mL) to the title product, a compound of the present invention, m.p. 93-95 °C. Η ΝMR (CDCI3): δ 8.7 (br s, 1Η, ΝΗ), 7.7-7.8 (m, 1Η), 7.4 (m, 1Η), 6.9-7.0 (m, 1Η), 6.6
(s, 1Η), 4.5 (q, 2Η), 3.1 (s, 3H), 2.9 (s, 3H), 1.42 (t, 3H), 1.4 (s, 9H). 19F ΝMR (CDCI3): δ -121.0. EXAMPLE 19
Preparation of ethyl 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino-
3-pyridinecarboxylate (Compound 255)
Step A: Preparation of 5-bromo-3-ρyridinecarboxyric acid
Thionyl chloride (96.74 g, 58.9 mL, 0.813 mol) was added to 3-pyridinecarboxylic acid (also named nicotinic acid) (20 g, 0.163 mol) and heated at reflux (-80 °C) for 3 h. The thionyl chloride was then distilled off under reduced pressure. The resulting acid chloride was cooled to 0 to -5 °C, and bromine (13 mL, 0.163 mol) was added. The reaction mixture was heated at 155 °C for 8-10 h, then cooled to room temperature and quenched with ice- cold water (200 mL) added dropwise, causing a white solid to form. The solid was collected using filtration and dried to provide the title compound (31.5 g, 94% yield). Step B: Preparation of 5-amino-3-pyridinecarboxylic acid
To a mixture of 5-biOmo-3-pyridinecarboxylic acid (i.e. the product of Step A) (25 g, 0.124 mol) in aqueous ammonia (67.32 mL) was added copper sulphate pentahydrate (8.41 g), and the reaction mixture heated in an autoclave at 120 °C for 16 h. Progress of the reaction was monitored by thin layer chromatography, using ninhydrin to visualize the product. The reaction mixture was washed with saturated solution of sodium sulfide to remove copper ions and was then acidified to a pH of about 4-5 using concentrated hydrochloric acid, causing a solid to separate as the acidified mixture cooled. The solid was collected using filtration and dried to provide the title compound (12.9 g, 74% yield).
Step C: Preparation of methyl 5-amino-3-pyridinecarboxylate Over 30 minutes hydrogen chloride gas was bubbled through dry methanol (60 mL) cooled to 0-5 °C. Then 5-amino-3-pyridinecarboxylic acid (i.e. the product of Step B) (6.0 g, 43 mmol) was added, and the reaction mixture was heated at 75 °C for 3 h. The reaction mixture was concentrated, the residue was poured into cold water (30 mL), and the pH of the resulting mixture was increased to 4-5 by adding sodium bicarbonate. The mixture was then extracted with ethyl acetate, and the ethyl acetate extract was washed with water and brine, and then dried (Na2SO4) and concentrated. The residue was triturated with ethyl acetate-petroleum ether to yield the title compound (4.2 g, 63% yield). IH NMR (CDC13): δ 8.63 (s, IH, ArH), 8.25 (s, IH, ArH), 7.57 (s, IH, ArH), 3.93 (s, 3H, CH3), 3.87 (br s, 2H, NH2). Step D: Preparation of ethyl 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
5-yl]carbonyl]amino-3-pyridinecarboxylate To a solution of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid (i.e. the product of Example 1, Step D) (4.00 g, 2.84 mmol) in dry dichloromethane (35 mL) was added oxalyl chloride (3.88 g, 2.47 mL, 30.6 mmol) followed by a few drops of N,N-dimethylformamide. The resulting solution was stirred and heated to 45 °C for 2.5 h. The dichloromethane solvent and excess oxalyl chloride were removed by distillation under reduced pressure. The resulting residue was diluted with dichloromethane (20 mL) and added to a mixture of methyl 5-amino-3-pyridinecarboxylate (i.e. the product of Step C) (2.98 g, 24.4 mmol) and triethylamine (4.12 g, 5.67 mL, 42.8 mmol) in dichloromethane (20 mL) at 0 °C. The reaction mixture was gradually warmed to room temperature and then heated at 45 °C for 12 h. The dichloromethane solvent was removed by distillation under reduced pressure, and the residue was quenched with ice water and extracted with dichloromethane (3 x 30 mL). The combined organic extracts were then washed with water and brine. The solution was dried over sodium sulfate and filtered, and the solvent was removed to give the crude product. The crude product was purified by column chromatography (60-120 mesh silica gel, 20% ethyl acetate-petroleum ether) to provide the title product (5.1g, 78% yield), a compound of the present invention.
*H NMR (CDC13): δ 9.0 (m, 2H, ArH), 8.71 (s, IH, ArH), 8.01 (s, IH, ArH), 6.58 (s, IH,
ArH), 4.58 (q, J = 7.2 Hz, 2H, CH2), 3.98 (s, 3H, CH3), 1.46 (t, J = 7.2 Hz, 3H, CH3), 1.34
(s, 9H, 3 CH3).
EXAMPLE 20 Preparation of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]-
NN-diethyl-3-pyridinecarboxamide (Compound 261)
Step A: Preparation of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
5-yl]carbonyl]amino]-3-pyridinecarboxylic acid To a solution of ethyl 5-[[[3~(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-3-pyridinecarboxylate (i.e. the product of Example 19, Step D) (3.11 g, 9.77 mmol) in tetrahydrofuran (20 mL) was added a solution of lithium hydroxide (0.938 g, 39 mmol) in water (10 mL). The reaction mixture was stirred at room temperature for 24 h. The solvent was then evaporated under reduced pressure, and the residue was diluted with water, acidified with hydrochloric acid (1.5 Ν) to a pΗ of about 4-5 and extracted with ethyl acetate (2 x 15 mL). The combined organic extracts were washed with cold water and brine, and then dried (Νa2SO4). The solvent was removed by evaporation to leave the title compound (2.4 g, 92% yield). iΗ NMR (DMSO-d6): δ 13.50 (br s, 1Η, OΗ), 10.49 (s, 1Η, NΗ), 9.10 (s, 1Η, ArΗ), 8.80 (s, 1Η, ArΗ), 8.71 (s, 1Η, ArΗ), 7.00 (s, 1Η, ArΗ), 4.46 (q, / = 6.78 Ηz, 2Η, CH2), 1.15-1.35 (m, 12H, 4 CH3).
Step B: Preparation of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
5 -yl] carbonyl] amino] -N,N-diethyl-3 -pyridinec arboxamide
To a solution of 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]amino]- 3-pyridinecarboxylic acid (i.e. the product of Step A) (250 mg, 0.793 mmol) in dichloromethane (5 mL) at room temperature under nitrogen atmosphere was added sequentially 1-propanephosphonic acid cyclic anhydride (50% in ethyl acetate, 2 mL, 3.4 mmol), diethylamine (0.5 mL, 5 mmol) and 4-(dimethylamino)pyridine (0.1 g, 0.8 mmol). The reaction mixture was stirred at room temperature for 6 h and then diluted with additional dichloromethane (10 mL) and washed with hydrochloric acid (1 Ν, 5 mL). The organic phase was separated, dried and concentrated, and the residue was purified using flash chromatography to provide the title product, a compound of the present invention, as a solid (256 mg, 84% yield).
!H NMR (CDC13): δ 8.70 (s, IH,), 8.42 (s, IH), 8.18 (m, IH,), 6.58 (s, IH), 4.57 (q, 2H), 3.60 (m, 4H), 1.46 (t, 3H), 1.34 (s, 9H), 1.26 (m, 6H). EXAMPLE 21
Preparation of N- [5- [(dimethylamino)carbonyl] -2-fluorophenyl] -3 -( 1 , 1 -dimethylethyl)- l-ethyl-4-fluoro-lH-pyrazole-5-carboxamide (Compound 276) A solution of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-3-(l,l-dimethylethyl)- 1 -ethyl- lH-pyrazole-5-carboxamide (i.e. the product of Example 7, Step D) (0.32 g, 0.88 mmol) and SELECTFLUOR™ fluorinating reagent (l-(chloromethyl-4-fluoro-l,4-diazonia- bicyclo[2.2.2]octane bis(tetrafluoroborate)) (0.72 g, 1.97 mmol) in acetonitrile (10 mL) was heated to reflux for 5 h. The mixture was cooled to room temperature and concentrated, and the residue was diluted with equal volumes of water and dichloromethane. The organic layer was separated and concentrated. The residue was purified by flash column chromatography on silica gel to provide the title product, a compound of the present invention, as a white solid (0.14 g, 42% yield).
!Η ΝMR (CDCI3): δ 8.5 (d, 1Η), 8.3 (d, 1Η), 7.2 (br s, 1Η), 7.17 (m, 1Η), 4.55 (q, 2Η), 3.1 (d, 6H), 1.43 (t, 3H), 1.37 (s, 9H).
EXAMPLE 22 Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazol-
5-yl]carbonyl]amino]-4-fluorobenzoate (Compound 267)
Step A: Preparation of 3, 3 -dimethyl- l-(triphenylphosphoranylidene)-2-butanone
To a solution of triphenylphosphine (10.74 g, 40.9 mmol) in chloroform (25 mL) was added dropwise l-bromo-3,3-dimethyl-2-butanone (7.33 g, 40.9 mmol). The cloudy solution was stirred at room temperature overnight. The solvent was removed in vacuo to give a white solid, which was then stirred overnight with saturated aqueous sodium bicarbonate (200 mL) at room temperature. The white solid was then collected by filtration and dried in a vacuum oven to a constant weight of the title compound (13.7 g). lΗ ΝMR (CDCI3): δ 7.8-7.3 (m, 15Η), 3.80 (d, IH), 1.20 (s, 9H). Step B: Preparation of butyl (2E)-5,5-dimethyl-4-oxo-2-hexenoate
A slurry of the 3,3-dimethyl-l-(triphenylphosphoranylidene)-2-butanone (i.e. the product of Step A) (12.5 g, 34.5 mmol) and butyl oxoacetate (4.5 g, 34.5 mmol) in toluene (200 mL) was stirred for 3 days at room temperature. The toluene solvent was removed in vacuo to leave an orange solid as crude product, which was then purified by column chromatography (10% ethyl acetate in hexane) to provide the title compound (5 g) as the trans isomer. *H NMR (CDCI3): δ 7.51 (d, IH), 6.77 (d, IH), 4.21 (t, 2H), 1.68 (m, 2H), 1.41 (m, 2H), 1.20 (s, 9H), 0.95 (t, 3H).
Step C: Preparation of butyl 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
5-carboxylate A slurry of butyl (2E)-5,5-dimethyl-4-oxo-2-hexenoate (i.e. the product of Step B)
(6.5 g, 30.9 mmol), ethylhydrazine ethanedioate (l:l) (5.6 g, 37.1 mmol), and N,N-diisopropylethylamine (5.2 g, 40.2 mmol) in methanol (65 mL) was stirred for 5 days at room temperature. The solvent was removed in vacuo, and the residue was purified by column chromatography (3-13% ethyl acetate in hexane) to give the title compound (4.8 g). *Η ΝMR (CDCI3): δ 4.18 (m, 2Η), 3.62 (dd, IH), 3.06 (m, 2H), 2.95 (m, 2H), 1.62 (m, 2H), 1.39 (m, 2H), 1.18 (t, 3H), 1.15 (s, 9H), 0.94 (t, 3H).
Step D: Preparation of 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
5-carboxylic acid Butyl 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-5-carboxylate (i.e. the product of Step C) (1.8 g, 7.1 mmol) was dissolved in ethanol (20 mL), and aqueous sodium hydroxide (10%, 5.7 g) was added. The solution was stirred overnight at room temperature. Most of the ethanol solvent was removed in vacuo, and then the pΗ of the residual solution was adjusted to 2 using hydrochloric acid (1 Ν). The cloudy mixture was extracted with ethyl acetate (2x). The combined organic extracts were dried (MgSO4), and the solvent was removed in vacuo to provide the title compound (0.64 g).
*Η ΝMR (CDCI3): δ 3.75 (dd, 1Η), 3.24 (m, 1Η), 3.05 (m, 1Η), 2.92 (dd, 1Η), 1.18 (t, 3Η), 1.16 (s, 9H).
Step Ε: Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro- lH-pyrazol-5-yl]carbonyl]amino]-4-fluorobenzoate To a stirred solution of 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
5-carboxylic acid (i.e. the product of Step D) (0.8 g, 4.1 mmol) in dichloromethane (5 mL) was added 1-propanephosphonic acid cyclic anhydride (50 wt % solution in ethyl acetate, 3.9 g, 6.14 mmol) followed by 4-(dimethylamino)pyridine (0.75 g, 6.14 mmol). After stirring for 1 h, ethyl 3-amino-4-fluorobenzoate (0.68 g, 3.7 mmol) was added, and the resulting solution was stirred at room temperature overnight. The solvent was removed in vacuo and partitioned between water (50 mL) and ethyl acetate (100 mL). The aqueous layer was extracted with ethyl acetate (30 mL). The organic layer was washed with aqueous saturated sodium bicarbonate (50 mL) and water (50 mL), and dried (MgSO4). The solvent was removed in vacuo to provide the title product, a compound of the present invention, as an oil (1.36 g). XH NMR (CDCI3): δ 9.3 (s, IH), 8.95 (d, IH), 7.80 (m, IH), 7.16 (t, IH), 3.70 (t, IH), 3.33 (dd, IH), 3.18 (dq, IH), 2.95 (dq, IH), 2.83 (dd, IH), 1.39 (t, 3H), 1.21 (t, 3H), 1.17 (s, 9H).
EXAMPLE 23 Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-3-(l,l-dimethylethyl)- l-ethyl-4,5-dihydro-lH-pyrazole-5-carboxamide (Compound 268) To a solution of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazol- 5-yl]carbonyl]amino]-4-fluorobenzoate (i.e. the product of Example 22) (1.0 g, 2.7 mmol) in ethanol (10 mL) was added aqueous sodium hydroxide (10%, 2.2 g). The solution was stirred overnight at room temperature and then concentrated in vacuo. The pΗ of the solution was adjusted to 2 using hydrochloric acid (1 Ν). Most of the water was removed in vacuo, and then the cloudy solution was extracted with ethyl acetate. The solvent was removed in vacuo from the organic extract to provide the acid in crude form (0.64 g), which was then dissolved in dichloromethane (20 mL), and oxalyl chloride (0.31 g) and N,N-dimethylformamide (one drop) were added. The resulting solution was stirred at room temperature overnight. The solvent was removed in vacuo, and more dichloromethane was added, and the solvent was again removed in vacuo. This process was repeated once more to provide the acid chloride in crude form (0.61 g). The acid chloride (0.3 g) was combined with a tetrahydrofuran solution of dimethylamine (2 M, 5 mL), and the reaction mixture was stirred overnight at room temperature. The solvent was removed in vacuo, and the residue was diluted with ethyl acetate and washed with water. The ethyl acetate solution was dried (MgSO4) and evaporated to leave the title product, a compound of the present invention, as an oil (0.20 g). lΗ ΝMR (CDCI3): δ 9.3 (s, 1Η), 8.42 (d, 1Η), 7.15 (m, 2Η), 4.12 (m, IH), 3.70 (t, IH), 3.30 (dd, IH), 3.15 (m, IH), 3.02 (br d, 6H), 2.95 (m, IH), 2.80 (dd, IH), 1.34-1.20 (m, 3H), 1.17 (s, 9H).
EXAMPLE 24
Preparation of 1 -( 1 , 1 -dimethylethyl)-3 -ethyl-N- [5 - [(ethylamino)carbonyl] -2-fluorophenyl] - 4,5-dihydro-lH-pyrazole-4-carboxamide (Compound 336) Step A: Preparation of 3-[(l,3-dioxopentyl)amino]-N-ethyl-4-fluorobenzamide
A solution of 3-amino-N-ethyl-4-fluorobenzamide (0.50 g, 1.8 mmol) and methyl 3-oxopentanoate (alternatively named methyl propionylacetate; 1.50 g, 11.5 mmol) was heated at 73-80 °C for 60 h. Upon cooling to room temperature, an off-white solid precipitated out; this was collected by filtration and washed successively with hexane and diethyl ether. The solid was dried under vacuum to give the title compound (0.42 g). !H NMR (CDCI3): 6 9.65 (br s, IH), 8.64 (dd, IH), 7.63 (m, IH), 7.17 (dd, IH), 6.15 (br s, IH), 3.61 (s, 2H), 3.48 (q, 2H), 2.62 (q, 2H), 1.24 (t, 3H), 1.14 (t, 3H).
Step B: Preparation of l-(l,l-dimethylethyl)-3-ethyl-N-[5-[(ethylamino)carbonyl]-
2-fluorophenyl]-4,5-dihydro-lH-ρyrazole-4-carboxamide A solution of 3-[(l,3-dioxopentyl)amino]-N-ethyl-4-fluorobenzamide (i.e. the product of Step A) (0.36 g, 1.3 mmol) in methanol (2 mL) was added dropwise to a slurry of sodium acetate (0.165 g) and aqueous formaldehyde (37%, 0.145 g) over 2 minutes. The resulting yellowish solution was stirred at room temperature for 3 h and then partitioned between ethyl acetate (40 mL) and water (10 mL). The organic layer was washed with water (10 mL) and dried (MgSO4), and the solvent was removed in vacuo to leave a gummy solid. This was then stirred with a mixture of tert-butylhydrazine hydrochloride (0.177 g) and anhydrous sodium carbonate (0.148 g) in methanol (3 mL) at room temperature for 20 h. Then the solvent was removed using a rotary evaporator, and the residue was purified by column chromatography (ethyl acetate - hexane) to provide 0.17 g of the title compound, a compound of the present invention, as a solid (0.17 g).
!Η ΝMR (CDCI3): δ 9.42 (br s, 1Η), 8.63 (dd, 1Η), 7.61 (m, 1Η), 7.13 (dd, 1Η), 6.25 (br s, 1Η), 3.64 (dd, 1Η), 3.54 (dd, 1Η), 3.46 (m, 2Η), 3.25 (t, IH), 2.41 (m, 2H), 1.23 (s, 9H), 1.23 (t, 3H), 1.17 (t, 3H).
EXAMPLE 25 Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-2-ethyl-2,4,5,6-tetrahydro- 6,6-dimethyl-3-cyclopentapyrazolecarboxamide (Compound 352)
Step A: Preparation of ethyl 2-hydroxy-3,3-dimethyl-α-oxo-l-cyclopentene-l-acetate
2,2-Dimethylcyclopentanone (9.6 g) was added to a mixture of diethyl oxalate (11.6 mL), 21% solution of sodium ethoxide in ethanol (11.6 mL) and ethanol (20 mL). The mixture was stirred at room temperature for 18 h. The mixture was then poured onto ice- cold water (200 mL) and acidified to pH 4-5 using acetic acid and extracted with diethyl ether (3 x 50 mL). The organic extracts were washed with water (3 x 50 mL) and dried (MgSO4) and concentrated to provide the title compound as an oil (17.58 g). *H ΝMR (CDCI3): 5 12.9 (br s, IH), 4.36 (q, 2H), 2.9(t, 2H), 1.83 (t, 2H), 1.4 (t, 3H), 1.13 (s, 6H).
Step B: Preparation of tautomeric mixture of ethyl 2,4,5,6-tetrahydro-6,6-dimethyl-
3-cyclopyrazolecarboxylate and ethyl l,4,5,6-tetrahydro-6,6-dimethyl-3- cyclopentapyrazolecarboxylate Hydrazine hydrate (2.5 mL) was added dropwise to ethyl 2-hydroxy-3,3-dimethyl- α-oxo-1-cyclopentene-l-acetate (i.e. the product of Step A) (10 g) dissolved in acetic acid (25 mL) at room temperature, and the mixture was stirred for a further 2 h. The reaction mixture was poured onto ice water (200 mL) and extracted with ethyl acetate (4 x 50 mL), dried (MgSO4) and concentrated to provide a yellow solid residue. The residue was chromatographed on silica gel using 6:4 hexanes-ethyl acetate as eluant to provide the title tautomeric mixture as an orange solid (7.8 g) IH NMR (CDC13): 54.36 (q, 2H), 2.8 (t, 2H), 2.29 (t, 2H), 1.4-1.2 (m, 9H).
Step C: Preparation of ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-
3-cyclopentapyrazolecarboxylate and ethyl l-ethyl-l,4,5,6-tetrahydro-6,6- dimethyl-3-cyclopentapyrazolecarboxylate To a solution of a tautomeric mixture of ethyl 2,4,5,6-tetrahydro-6,6-dimethyl- 3-cyclopyrazolecarboxylate and ethyl l,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazole- carboxylate (i.e. the product of Step B) (7.69 g) in N,N-dimethylformamide (50 mL), potassium carbonate (7.71 g) and tetrabutylammonium bromide (100 mg) were added. Ethyl iodide (4.44 mL) was added at once, and the mixture was stirred at room temperature for 18 h. The mixture was poured into water (200 mL) and extracted with diethyl ether (3 x 100 mL). The organic phase was washed with water (3 x 50 mL) and dried (MgSU4) and concentrated to provide residue containing mixture of ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6- dimethyl-3-cyclopentapyrazolecarboxylate and ethyl l-ethyl-l,4,5,6-tetrahydro-6,6- dimethyl-3-cyclopentapyrazolecarboxylate. The residue was chromatographed on silica gel using as eluant hexanes-ethyl acetate (9:1, 8:2, 7:3 and 1:1); the earlier fractions contained ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate. The fractions were combined and concentrated to provide ethyl 2-ethyl-2,4,5,6-tetrahydro- 6,6-dimethyl-3-cyclopentapyrazolecarboxylate (3.7 g). The later fractions contained ethyl 1-ethyl-l ,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate. These fractions were combined and concentrated to provide 1-ethyl-l, 4,5,6-tetrahydro-6,6-dimethyl- 3-cyclopentapyrazolecarboxylate (3.5 g).
Ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate: lH ΝMR (CDCI3): δ 4.53 (q, 2H), 4.31 (q, 2H), 2.75 (t, 2H), 2.21 (t, 2H), 1.42-1.3 (m,
12H). Ethyl l-ethyl-l,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate: IH ΝMR (CDCI3): δ 4.37 (q, 2H), 4.13 (q, 2H), 2.73 (t, 2H), 2.36 (t, 2H), 1.49 (t, 3H), 1.39(m, 9H).
Step D : Preparation of 2-ethyl-2,4,5 ,6-tetrahydro-6,6-dimethyl-
3-cyclopentapyrazolecarboxylic acid
To a solution of ethyl 2-ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazole- carboxylate (i.e. first eluted product of Step C) (3.63g) in tetrahydrofuran (25 mL), aqueous sodium hydroxide (1 Ν, 23.1 mL) was added, and the mixture was stirred at room temperature for 18 h. Then the mixture was acidified with hydrochloric acid (6 Ν) and extracted with dichloromethane (3 x 25 mL), dried (MgSU4) and concentrated to provide the title compound as a white solid (3.1 g).
*H NMR (CDC13): δ 4.56 (q, 2H), 2.84 (m, 2H), 2.24 (m, 2H), 1.42 (t, 3H), 1.32 (s, 6H).
Step E: Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-2-ethyl- 2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxamide
2-Ethyl-2,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylic acid (i.e. the product of Step D) (0.6 g) was dissolved in dichloromethane (2 mL), and one drop of
N,N-dimethylformamide was added, followed by oxalyl chloride (0.25 mL), and the mixture was stirred at room temperature for 1 h and concentrated. The residue was dissolved in dichloromethane (2 mL) and then added to solution of 3-amino-4-fluoro-N,N-dimethyl- benzamide (i.e. the product of Example 7, Step C) (0.6 g) and triethylamine (0.5 mL). The mixture was stirred at room temperature for 2 h and then chromatographed on a column containing silica gel (10 g), using dichloromethane as eluant to provide the title product, a compound of the present invention, as a white solid (0.5 g). !H ΝMR (CDCI3): 8.6 (d, IH), 7.8 (br s, IH), 7.19 (d, 2H), 4.6 (q, 2H), 3.1 (d, 6H), 2.95 (t,
2H), 2.4 (t, 2H), 1.44 (t, 3H), 1.26 (s, 6H).
EXAMPLE 26
Preparation of ethyl 3-[[[5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazol- 4-yl]carbonyl]amino]benzoate (Compound 367) Step A: Preparation of ethyl 5-ethyl-l,2,3-triazole-4-carboxylate
Ethyl 2-pentynoate (16.6 g, 0.132 mol) and trimethylsilylazide (38.0 g, 0.333 mol) were stirred at 100-110 °C under nitrogen for 70 h. After cooling and dilution with methanol (60 mL) a white solid precipitated. After evaporation of the mixture under reduced pressure, the residue was crystallized from ethyl ether to afford the title product as a white solid (15.7 g, 0.093 mol, 70% yield). iΗ ΝMR (CDCI3): 4.42 (q, 2Η), 3.07 (q, 2H), 1.37 (t, 3H), 1.32 (t, 3H).
Step B: Preparation of ethyl 5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazole-
4-carboxylate and ethyl 4-ethyl-l-(l-methylethyl)-lH-l,2,3-triazole- 5-carboxylate A mixture of ethyl 5-ethyl-l,2,3-triazole-4-carboxylate (i.e. the product of Step A)
(3.84 g, 22.7 mmol), potassium carbonate (5.64 g, 40.9 mmol) and 2-iodopropane (6.95 g, 40.9 mmol) in acetonitrile (68 mL) was stirred at 50-60 °C under nitrogen for 2 h. After cooling to room temperature, the mixture was filtered through a short pad of silica gel and rinsed with ethyl acetate. The solution was concentrated and the residue was purified by column chromatography to provide ethyl 5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazole- 4-carboxylate (2.87 g, 13.6 mmol, 60% yield), followed by its isomer ethyl 4-ethyl- l-(l-methylethyl)-lH-l,2,3-triazole-5-carboxylate (0.96 g, 4.54 mmol, 20% yield) as white solids.
Ethyl 5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazole-4-carboxylate:
*Η NMR (CDC13): 4.82 (m, 1Η), 4.42 (q, 2Η), 2.95 (q, 2H), 1.58 (d, 6H), 1.41 (t, 3H), 1.28 (t, 3H).
Ethyl 4-ethyl-l-(l-methylethyl)-lH-l ,2,3-triazole-5-carboxylate:
!Η NMR (CDC13): 5.42 (m, 1Η), 4.42 (q, 2Η), 2.94 (q, 2H), 1.58 (d, 6H), 1.39 (t, 3H), 1.28 (t, 3H).
Step C: Preparation of ethyl 3-[[[5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazol- 4-yl]carbonyl]amino]benzoate
To a stirred solution of ethyl 5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazole- 4-carboxylate (i.e. the first eluted product of Step B) (1.119 g, 5.64 mmol) in tetrahydrofuran (15 mL) was added a solution of lithium hydroxide (0.54 g, 22.56 mmol) in water (15 mL). The mixture was stirred at room temperature overnight, and then partitioned between ether and water. The aqueous layer was acidified with hydrochloric acid (6 N) to pΗ 1-2 and extracted with ethyl acetate, dried (Na2SO4) and concentrated to provide the carboxylic acid intermediate as a white solid (0.94 g, 5.08 mmol, 90% yield). To a stirred solution of the carboxylic acid intermediate (0.78 g, 4.22 mmol) in dichloromethane (25 mL) was added oxalyl chloride (1.61 g, 12.7 mmol) dropwise at room temperature. After stirring the reaction mixture for 10 minutes, N,N-dimethylformamide (two drops) was added. The mixture was stirred for an additional 1.5 h and then concentrated to provide the acid chloride intermediate as a pale yellow oil. To a stirred solution of ethyl 3-aminobenzoate (0.70 g, 4.22 mmol), N,N-diisopropylethylamine (1.09 g, 8.44 mmol) in dichloromethane (15 mL) was added a solution of the acid chloride intermediate in dichloromethane (5 mL). The reaction mixture was stirred at room temperature for 2 h and then concentrated. The residue was chromatographed to afford the title product, a compound of the present invention, as a white solid (1.36 g, 4.10 mmol, 97% yield).
!Η ΝMR (CDCI3): 8.62 (br s, 1Η), 8.14 (d, 1Η), 8.10 (s, 1Η), 7.81 (d, 1Η), 7.43 (t, 1Η), 4.80 (m, 1Η), 4.40 (q, 2Η), 3.04 (q, 2H), 1.61 (d, 6H), 1.41 (t, 3H), 1.32 (t, 3H). EXAMPLE 27
Preparation of N-[3-[(dimethylamino)carbonyl)phenyl]-5-ethyl-2-(l-methylethyl)-
2H-l,2,3-triazole-4-carboxamide (Compound 358)
To a stirred solution of ethyl 3-[[[5-ethyl-2-(l-methylethyl)-2H-l,2,3-triazol-
4-yl]carbonyl]amino]benzoate (i.e. the product of Example 26, Step C) (1.34 g, 4.04 mmol) in tetrahydrofuran (15 mL) was added a solution of lithium hydroxide (0.48 g, 20.2 mmol) in water (15 mL). The mixture was stirred at room temperature overnight, then partitioned between ether and water. The aqueous layer was acidified with hydrochloric acid (6 Ν) to pΗ 1-2 and extracted with ethyl acetate, dried (Na2SO ) and concentrated to provide the carboxylic acid intermediate as a white solid (1.10 g, 3.62 mmol, 90% yield). A mixture of the carboxylic acid intermediate (130 mg, 0.43 mmol), 4-(dimethylamino)pyridine (78 mg, 0.64 mmol), 1-propanephosphonic acid cyclic anhydride (50 wt % in EtOAc, 423 mg, 0.66 mmol), and dimethylamine (2.0 M in THF, 0.66 mL, 1.32 mmol) in dichloromethane (3 mL) was stirred at room temperature overnight. The mixture was concentrated and the residue was purified by column chromatography to afford the title product, a compound of the present invention, as a white solid (130 mg, 0.40 mmol, 92% yield). lU NMR (CDC13): 8.62 (br s, IH), 7.77 (s, IH), 7.71 (d, IH), 7.39 (t, IH), 7.18 (d, IH), 4.80 (m, IH), 2.98-3.10 (m, 8H), 1.60 (d, 6H), 1.32 (t, 3H).
EXAMPLE 28
Preparation of ethyl 3-[[[2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazol- 4-yl]carbonyl]amino]benzoate (Compound 360)
Step A: Preparation of ethyl 2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazole- 4-carboxylate and ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-l,2,3-triazole-
5-carboxylate To a stirred solution of 5-ethyl-l,2,3-triazole-4-carboxylic acid ethyl ester (i.e. product of Step A of Example 26) (1.05 g, 6.25 mmol) and tert-butyl alcohol (0.93 g, 12.5 mmol) in trifluoroacetic acid (6 mL) was added concentrated sulfuric acid (0.61 g, 6.25 mmol). After stirring at room temperature for 14 h, the reaction mixture was partitioned between ethyl acetate and water. The organic layer was washed with water, saturated aqueous sodium carbonate and brine, and then dried (Na SO4). After concentration, the residue was purified by column chromatography to afford ethyl 2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazole- 4-carboxylate (0.74 g, 3.76 mmol, 64% yield), followed by its isomer ethyl l-(l,l-dimethyl- ethyl)-4-ethyl-lH-l,2,3-triazole-5-carboxylate (0.24 g, 1.22 mmol, 21% yield) as colorless oils.
Ethyl 2-( 1 , 1 -dimethylethyl)-5-ethyl-2H- 1 ,2,3-triazole-4-carboxylate: lΗ NMR (CDCI3): 4.41 (q, 2Η), 2.93 (q, 2H), 1.68 (d, 9H), 1.40 (t, 3H), 1.27 (t, 3H). Ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-l,2,3-triazole-5-carboxylate: lΗ NMR (CDCI3): 4.40 (q, 2Η). 2.87 (q, 2H), 1.77 (d, 6H), 1.42 (t, 3H), 1.29 (t, 3H).
Step B: Preparation of ethyl 3-[[[2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazol-
4-yl] carbonyl] amino]benzoate The title product, a compound of the present invention, was prepared from ethyl 2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazole-4-carboxylate (i.e. the first eluted product of Step A) following a procedure analogous to Step C of Example 26.
*Η NMR (CDC13): 8.62 (br s, IH), 8.14 (d, IH), 8.09 (s, IH), 7.81 (d, IH), 7.44 (t, IH), 4.80 (m, IH), 4.40 (q, 2H), 3.04 (q, 2H), 1.70 (s, 9H), 1.41 (t, 3H), 1.31 (t, 3H). EXAMPLE 29 Preparation of 2-(l,l-dimethylethyl)-5-ethyl-N-[3-[(ethylamino)carbonyl]phenyl]-
2H-l,2,3-triazole-4-carboxamide (Compound 365) The title product, a compound of the present invention, was prepared from ethyl 3-[[[2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazol-4-yl]carbonyl]amino]benzoate (i.e. the product of Step B of Example 28) following a procedure analogous to Example 27. *Η ΝMR (CDC13): 8.72 (br s, IH), 8.06 (s, IH), 7.88 (d, IH), 7.53 (d, IH), 7.36 (t, IH), 6.71 (br s, IH), 3.47 (q, 2H), 3.02 (q, 2H), 1.68 (s, 9H), 1.31 (t, 3H), 1.23 (t, 3H).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 15 can be prepared. The following abbreviations are used in the Tables which follow: t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, Z-Pr means isopropyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN means cyano, NO2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl. Furthermore, 1-pyrrolyl means -N(-(CH2)5-), 3-pyrrolin-l-yl means -N(-CH2CH=CHCH -), and 4-morpholinyl means -N(-(CH2)2O(CH2)2-).
TABLE 1
Figure imgf000058_0001
Rla is Et ; R2a is tert-Bi i ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
Cθ2(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 0CH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl Rla is Et ; R2a is tert-Bv i ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0) CH3
OS(0)2CH2CH3 OS(0)2CH2Cl OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is tert- i i ; T , U and Y are CH ; Z is CF
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 OCH2CH2Cl S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl) Rla is Et ; R2a is tert-Bx. i ; T , U and Y are CH ; Z is CF
Bl Bl Bl Bl
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(N0H)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
0S(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rl is Et ; R2a is tert-Bi ι ; U is CF ; T, Y and Z are CH
Bl R5 Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 0CH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C0 -cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)N eCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2 Rla is Et ; R2a is tert-Bu ; T is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
Cθ2(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rla is Me ; R2a is tert-B u ; U is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH20CH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2 Rla is Me ; R2a is tert-Bu ; T, U, Y and Z are CH
Bl Bl Bl Bl
C(NOH)CH3 C(N0CH3)CH2CH3 S(0)2NHMe S(0)2NEt2
C(NOH)CH2CH3 C(N0H)CH2CH2C1 S(0)2NMe2 S(0)2NH(CH2)2CH3
C(NOH)CH2Cl CN S(0)2NHEt S(0)2NH(CH2)3CH3
C(NOH)CH2Br C(0)-(3-pyrrolin-l-yl) C(0)-(l-pyrrolyl)
R a is Et ; R2a is isopro 3yl ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
Cθ2(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is isopro 3yl ; U is CF ; T, Y and Z ar s CH
Bl Bl Bl gl
CQ2Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2 Rla is Et ; R2a is isopropyl ; U is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0) NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is cyclop ropyl ; T, U, Y and Z are CI I
Bl Bl ≠ Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F 0CH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
Cθ2CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1 Rla is Et ; Rza is cyclopropyl ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Ria is CH2CH2F ; R2a 1 s tert-Bu ; T, TJ, Y and Z an ϊ CH
Bl Bl R5 Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
Cθ2(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rla is CH2CH2F ; R2a is tert-Bu ; U is CF ; T, Y ar d Z are CH
Bl gl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) Rla is CH2CF3 ; R2a is tert-Bu ; U is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 OCH2CH2Cl S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is CH2CF3 ; R2a is tert-Bu ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(NOH)CH2CH2Cl S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2) CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3 fi-1
Rla is CH2CF3 ; R2a is tert-Bu ; T, U, Y and Z are CH
Bl E! Bl Bl
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cycloρropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cycloρentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 0P(O)Me(OMe) OP(0)(OMe)2
Ria is Me ; R2a is tert-B u ; U is N ; T, Y and Z are ( H
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cycloρropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cycloρentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2 Rla is Me ; R2a is tert- -Bu ; U is N ; T, Y and Z are CH
Bl Bl Bl Bl
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrτolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is tert-Bu ; U is N ; T, Y and Z are CH
Bl
C02Et
C02CH3
C02(CH2)2CH3
C02(CH2)2CH2C1
C02(CH2)2CH2F
C02CH2CH2F
C02CH2CH2C1
C02(CH2)3CH3
C02CH2CH=CH2
C02CH2C≡CH
C02-cyclopropyl
C02-cyclopentyl
C02CH2OCH3
C02CH2SCH3
C(0)CH3
C(0)CH2CH3
C(NOH)CH3
C(NOH)CH2CH3
C(0)CH2C1
C(0)CH2Br
C(NOH)CH2Cl
C(NOH)CH2Br
C(0)CF2H
Figure imgf000067_0001
Ria is Et ; R2a is tert-Bu ; U is N ; T, Y and Z are CH
Bl Bl El Ε
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is tert-Bi i ; T is N ; U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(NOH)CH2CH2Cl S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
Cθ2(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cycloρropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rl is Et ; R2a is tert-B\ i ; T is N ; U, Y and Z are C H
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1 Rla is Et ; R2a is tert-Bu ; T is N ; U, Y and Z are CH
R5 Bl Bl Bl
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cycloρentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rl is Et ; R2a is tert-Bι 1 ; T , U and Y are CH ; Z is N
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rla is CH2CH3 ; R2a is Si(CH3)3 ; T, U, Y and Z a] re CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH Rla is CH2CH3 ; R2a is Si(CH3)3 ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
TABLE 2
Figure imgf000070_0001
3 Bl w Bl 1 u Y Z
F H 0 C(0)NMe2 CH CH CH CH
Me H o C(0)NHEt CH CF CH CH
Et H o C(0)NMe2 CH N CH CH
H Me o C(0)NMe2 CH CH CH CH
H Et 0 C(0)NHEt CH CF CH CH
H C(0)Et 0 C(0)NMe2 CH CH CH CH
H C(0)0-«-Pr o C(0)NHEt CH N CH CH
H CH2OMe 0 C(0)NMe2 CH CH CH CH
H CH2S-n-Bu o C(0)NHEt CH CF CH CH
H H s C(0)NMe2 CH CH CH CH
H H s C(0)NHEt CH CF CH CH
H H o C(0)NMe2 N N CH CH
H H 0 C(0)NHEt CH N CH N
H H o C(0)NMe2 CH N N CH
H H 0 C(0)NHEt N N CH N
H H o C(0)NMe2 CH CCF3 CH CH
H H o C(0)NHEt CH COEt CH CH
H H 0 C(0)NMe2 CH COCF2H CH CH
H H o C(0)NHEt CH CMe CH CH
H H o C(0)NMe2 CH CEt CH CH
H H 0 C(0)NHEt CH CSMe CH CH
H H o O CC((00))NNMMee92 CH CSEt CH CH Bl Bl w gl T U Y Z
H H O C(0)NHEt CH COMe CH CH
H H C(0)NMe2 CH CH CF CH
H H C(0)NHEt CH CH CCH3 CH
H H C(0)OEt CCF3 CH CH CH
H H C(0)OMe CSMe CH CH CH
H H C(0)OEt COCF2H CH CH CH
H H C(0)OMe CMe CH CH CH
H H C(0)OEt COMe CH CH CH
H H C(0)OMe CH CH CH COMe
H H C(0)OEt CH CH CH COCF2H
H H C(0)OMe CH CH CH CMe
H H C(0)OEt CH CH CH CCF3
H H C(0)OMe CH CH CH CSMe
H H -C(0)NHCH2- CH CH CH
H H -C(0)NMeCH2- CH CH CH
H H -C(0)NEtCH2- CH CH CH
H H -C(0)N(cyclo-Pr)CH2- CH CH CH
H H -C(0)N(i-Pr)CH2- CH CH CH
H H -C(0)NMeCH2- N CH CH
H H -C(0)NEtCH2- CF CH CH
H H -C(0)NMeCH2CH2- CH CH CH
TABLE 3
Figure imgf000071_0001
TABLE 4
Figure imgf000072_0001
R26 R27 γi U RlO RU R26 R27 γi U RlO RU
Me Me CH2 CH Me Me Me H CH2 CF H Et
Me Me o CF H Et Et H CH2 N Me Me
Me Me s N Me Me Et Me CH2 CH H Et
Me Me NH CH H Et Et Et CH2 CF Me Me
Me Me NCH3 CF Me Me Me Me CH CH H Et
TABLE 5
Figure imgf000072_0002
R26 R27 U R10 RU R26 R27 U RlO RU
Me Me CH Me Me Me H CF H Et
Me Me CF H Et Et H N Me Me
Me Me N Me Me Et Me CH H Et
Me Me CH H Et Et Et CF Me Me
Me Me CF Me Me Me Me N H Et
TABLE 6
Figure imgf000072_0003
Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
Cθ2(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Me ; R2b is tert-l \u ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) 7?
Rlb is Et ; R2b is tert-Bu ; U is N ; T, Y and Z are CH
B! Bl Bl Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 OCH2CH2Cl S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cycloρentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0) NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-morpholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 OS(0)2CH2Cl OP(0)Me(OMe) OP(0)(OMe)2
Rl is Et ; R2b is tert-B, j ; T is N ; U, Y and Z are C H
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NHMe(CH2)2CH3 C(0)-(1 -pyrrolyl) TABLE 7
Figure imgf000075_0001
Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
El gl Bl El
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(NOH)CH2CH2Cl S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CB=CH2 OCH2CH2Cl S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(N0H)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 OS(0)2CH2Cl OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Et ; R2b is tert-B\ α ; U is CF ; T, Y and Z are CH
El gl El Bl
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F Rl is Et ; R2b is tert-Bu ; U is CF ; T, Y and Z are ( :H
Bl El El El
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Me ; R2b is tert-l 5u ; T, U, Y and Z are CH
El Bl El Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(N0H)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) Rl is Me ; R2b is tert-Bu ; U is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-B\ i ; U is N ; T, Y and Z are CH
El Bl El El
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH20CH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2 Rlb is Et ; R2b is tert-Bu ; T is N ; U, Y and Z are CH
Bl El • El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 G(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 • C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 . C(0)NMeCH2CH2Cl C(0)-(3-pyrroHn-l-yl)
C(NOH)CH2CH3 ' C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
TABLE 8
Figure imgf000078_0001
El El w Ei I u Y Z
F H 0 C(0)NMe2 CH CH CH CH
Me H 0 C(0)NHEt CH CF CH CH
Et H o C(0)NMe2 CH N CH CH
H Me 0 C(0)NMe2 CH CH CH CH
H C(0)Me 0 C(0)NMe2 CH CH CH CH
H C(0)OEt 0 C(0)NHEt CH N CH CH
H CH2OMe o C(0)NMe2 CH CH CH CH
H H s C(0)NMe2 CH CH CH CH
H H s C(0)NHEt CH CF CH CH
H H 0 C(0)NMe2 N N CH CH
H H 0 C(0)NMe2 CH CCF3 CH CH
H H o C(0)NHEt CH CMe CH CH
H H 0 C(0)NMe2 CH CH CF CH
H H 0 C(0)NHEt CH CH CCH3 CH
H H o C(0)OMe CMe CH CH CH
H H 0 C(0)OEt COMe CH CH CH
H H 0 C(0)OMe CH CH CH COMe
H H o C(0)OMe CH CH CH CMe ^BLE 9
Figure imgf000079_0001
Rl is Et ; R2a is tert-Bi i ; T, U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 0CH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rl is Et ; R2a is tert-B\ 1 ; U is CF ; T, Y and Z are ( CH gl El Bl Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F 7δ
Rlb is Et ; R2a is tert-Bi i ; U is CF ; T, Y and Z are CH
Bl Bl Bl Bl
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 • S(0)2NMe C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0) NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Me ; R2a is tert-Ε Su ; T, U, Y and Z are CH
El Bl El Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) Rl is Me ; R2a is tert-. Bu ; U is CF ; T, Y and Z are CH
Bl Bl Bl El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(N0H)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rl is Et ; R a is tert- Bu ; U is N ; T, Y and Z are CH
R5 E! Bl El
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(NOH)CH2CH2Cl S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2 Rlb is Et ; R2a is tert-Bu ; T is N ; U, Y and Z are CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(O)-d-pyrrolyl)
TABLE 10
Figure imgf000082_0001
Rla is Et ; R2a is .ert-Bι i ; T, U, Y and Z are CH
Bl El Bl El
C02Et C(NOCH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
C02-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
C02-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3 Rla is Et ; R2a is tert-Bu ; T, U, Y and Z are CH
El El El Bl
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(N0H)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rla is Et ; R2a is tert-Bu ; U is CF ; T, Y and Z are CH
Bl El El Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(1 -pyrrolyl)
Rla is Et ; R2a is tert-Bu ; U is N ; T, Y and Z are CH
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rla is Et ; R2a is tert-Bu ; T is N ; U, Y and Z are CH
Bl Bl El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2) CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) TABLE 11
Figure imgf000084_0001
Rlc g Bl W Bl 1 u Y z
H F H 0 C(0)NMe2 CH CH CH CH
H Me H o C(0)NHEt CH CF CH CH
H Et H 0 C(0)NMe2 CH N CH CH
H H Me 0 C(0)NMe2 CH CH CH CH
H H C(0)Me 0 C(0)NMe2 CH CH CH CH
H H C(0)OEt o C(0)NHEt CH N CH CH
H H CH2OMe 0 C(0)NMe2 CH CH CH CH
H H H s C(0)NMe2 CH CH CH CH
H H H s C(0)NHEt CH CF CH CH
H H H 0 C(0)NMe2 N N CH CH
H H H o C(0)NMe CH CCF3 CH CH
H H H 0 C(0)NHEt CH CMe CH CH
H H H o C(0)NMe2 CH CH CF CH
H H H 0 C(0)NHEt CH CH CCH3 CH
H H H 0 C(0)OMe CMe CH CH CH
H H H o C(0)OEt COMe CH CH CH
H H H o C(0)OMe CH CH CH COMe
H H H 0 C(0)OMe CH CH CH CMe
TABLE 12
Figure imgf000084_0002
Rlb is Et ; R2b is tert-B j ; T, U, Y and Z are CH
Bl Bl El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C ≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2 Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
El El R5 Bl
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl) C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-Bu ; U is N ; T, Y and Z are CH
El El Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rl is Et ; R2b is tert -- Bu ; T is N ; U, Y and Z are CH
Bl Bl El E
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(N0H)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(O)-Cl-pyrrolyl)
TABLE 13
Figure imgf000085_0001
Rlb is Et ; R2b is tø?- Bu ; T, U, Y and Z are CH gl Bl El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2 Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
El El R5 Bl
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl) C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-Bu ; U is CF ; T, Y and Z are CH
Bl Bl Bl El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-Bu ; U is N ; T, Y and Z are CH
E Bl El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-Bu ; T is N ; U, Y and Z are CH
El gl El El
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl) TABLE 14
Figure imgf000087_0001
glc El El W gl 1 U Y Z
H F H 0 C(0)NMe2 CH CH CH CH
H Me H o C(0)NHEt CH CF CH CH
H H Me 0 C(0)NMe2 CH CH CH CH
H H C(0)Me 0 C(0)NMe2 CH CH CH CH
H H H s C(0)NMe2 CH CH CH CH
H H H 0 C(0)NMe2 N N CH CH
H H H o C(0)NMe2 CH CCF3 CH CH
H H H o C(0)NHEt CH CMe CH CH
H H H 0 C(0)NMe2 CH CH CF CH
H H H 0 C(0)NHEt CH CH CCH3 CH
H H H 0 C(0)OMe CMe CH CH CH
H H H 0 C(0)OMe CH CH CH CMe
H Me H 0 C(0)-(3-pyrrolin-3 ι-yi) CH CH CH CH
H H C(0)OEt 0 C(0)-(l-pyrrolyl) CH CF CH CH
TABLE 15
Figure imgf000087_0002
Rlb is Et ; R2b is tert-Bu ; T, U, Y and Z are CH
Bl El El Bl
C02Et C(NOCH3)CH CH3 SCH2CH2F C(0)NEt2
C02CH3 C(NOH)CH2CH2Cl S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F Rlb is Et ; R2b is tert-Bv i ; T, U, Y and Z are CH
El El Bl Bl
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cycloproρyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(N0H)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(NOH)CH2Cl SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 0S(0)2CH2C1 OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Me ; R2b is tert-Ε »u ; T, U, Y and Z are CH
El Bl El Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
Cθ2(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NMeOMe C(0)-(l-pyrrolyl)
Rlb is Et ; R2b is tert-B\ α ; U is N ; T, Y and Z are C H
El El El Bl
C02Et C(N0CH3)CH2CH3 SCH2CH2F C(0)NEt2
C02CH3 C(N0H)CH2CH2C1 S(CH2)2CH3 C(0)NHCH2CH2F
C02(CH2)2CH3 CN S(CH2)2CH2F C(0)NHCH2CH2C1
C02(CH2)2CH2C1 OCH3 S(CH2)2CH2C1 C(0)NH(CH2)2CH3
C02(CH2)2CH2F OCH2CH3 S(0)CH2CH3 C(0)NH(CH2)2CH2F
C02CH2CH2F 0(CH2)2CH3 S(0)2CH2CH3 C(0)NH(CH2)2CH2C1 ST
Rlb is Et ; R2b is tert-Bi i ; U is N ; T, Y and Z are CH
El Bl Bl Bl
C02CH2CH2C1 0(CH2)3CH3 S(0)(CH2)2CH3 C(0)NH(CH2)3CH3
C02(CH2)3CH3 OCH2CH2F S(0)2(CH2)2CH3 C(0)NH(CH2)3CH2F
C02CH2CH=CH2 0CH2CH2C1 S(0)(CH2)2CH2C1 C(0)NH(CH2)3CH2C1
C02CH2C≡CH 0(CH2)2CH2F S(0)2(CH2)2CH2C1 C(0)NMeCH2CH2F
Cθ2-cyclopropyl 0(CH2)2CH2C1 S(0)CH2CH2F C(0)NMeCH2CH2Cl
Cθ2-cyclopentyl 0(CH2)3CH2C1 S(0)2CH2CH2F C(0)NMeOMe
C02CH2OCH3 0(CH2)3CH2F S(0)CH2CH2C1 C(0)NHCH2C≡CH
C02CH2SCH3 O-cyclopentyl S(0)2CH2CH2C1 C(0)NMeCH2C≡CH
C(0)CH3 O-cyclopropyl S(0)2NHMe C(0)NHCH2CH=CH2
C(0)CH2CH3 OCH2OCH3 S(0)2NMe2 C(0)NMeCH2CH=CH2
C(NOH)CH3 OCH2SCH3 S(0)2NHEt C(0)NMeEt
C(NOH)CH2CH3 SCH3 S(0)2NEt2 C(0)-(3-pyrrolin-l-yl)
C(0)CH2C1 S(0)CH3 S(0)2NH(CH2)2CH3 C(0)-(4-moφholinyl)
C(0)CH2Br S(0)2CH3 S(0)2NH(CH2)3CH3 C(0)NMe(CH2)2CH3
C(N0H)CH2C1 SCF3 C(0)NHEt C(0)-(l-pyrrolyl)
C(NOH)CH2Br S(0)CF3 C(0)NH2 C(S)NHEt
C(0)CF2H S(0)2CF3 C(0)NHMe C(S)NMe2
C(0)CH2CH2C1 SCH2CH3 C(0)NMe2 OS(0)2CH3
OS(0)2CH2CH3 OS(0)2CH2Cl OP(0)Me(OMe) OP(0)(OMe)2
Rlb is Et ; R2b is tert-B 11 ; T is N ; U, Y and Z are C H
Bl Bl Bl Bl
C02Et C(0)NHEt C(0)NH(CH2)2CH2F C(0)NHCH2C≡CH
C02CH3 C(0)NH2 C(0)NH(CH2)2CH2C1 C(0)NMeCH2C≡CH
C02(CH2)2CH3 C(0)NHMe C(0)NH(CH2)3CH3 C(0)NHCH2CH=CH2
C02CH2CH=CH2 C(0)NMe2 C(0)NH(CH2)3CH2F C(0)NMeCH2CH=CH2
C02CH2C≡CH C(0)NEt2 C(0)NH(CH2)3CH2C1 C(0)NMeEt
C(NOH)CH3 C(0)NHCH2CH2C1 C(0)NMeCH2CH2Cl C(0)-(3-pyrrolin-l-yl)
C(NOH)CH2CH3 C(0)NH(CH2)2CH3 C(0)NHMe(CH2)2CH3 C(0)-(l-pyrrolyl)
Formulation/Utilitv
Compounds of Formula I or Iz will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active Ingredient Diluent Surfactant
Water-Dispersible and Water- 5-90 0-94 1-15 soluble Granules, Tablets and Powders.
Suspensions, Emulsions, 5-50 40-95 0-15 Solutions (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, N,N-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxy- ethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, propylene carbonate, dibasic esters, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol, benzyl and tetrahydrofurfuryl alcohol.
Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see T. S. Woods, "The Formulator's Toolbox - Product Forms for Modern Agriculture" in Pesticide Chemistry and Bioscience, Tlie Food-Environment Challenge, T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th International Congress on Pesticide Chemistry, The Royal Society of Chemistry, Cambridge, 1999, pp. 120-133. See also U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A- K. Example A High Strength Concentrate Compound 2 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
Example B Wettable Powder Compound 6 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example C
Granule
Compound 156 10.0% attapulgite granules (low volatile matter,
0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example D Aqueous Suspension Compound 2 25.0% hydrated attapulgite 3.0% crude calcium ligninsulfonate 10.0% sodium dihydrogen phosphate 0.5% water 61.5%.
Example E
Extruded Pellet
Compound 6 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. Many of the compounds of this invention, by virtue of selective metabolism in crops versus weeds, or by selective activity at the locus of physiological inhibition in crops and weeds, or by selective placement on or within the environment of a mixture of crops and weeds, are useful for the selective control of grass and/or broadleaf weeds within a crop/weed mixture. 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, sunflower, rice, oats, peanuts, vegetables, tomato, potato and perennial plantation crops. Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Compounds of the invention are particularly useful for selective control of weeds in perennial plantation crops, transplanted rice, maize and cool-season cereal crops. Of particular note is the use of compounds of the invention for selective weed control in perennial plantation crops (also known as permanent crops) including: fruit trees such as citrus (e.g., orange, lemon, lime, grapefruit, tangerine), pome fruits (e.g., apple, pear, quince) and stone fruits (e.g., peach, nectarine, apricot, plum, cherry), nut trees (e.g., almond, hickory, pecan, walnut, cashew, chestnut, filbert, macademia, pistachio), forest trees such as hardwoods (e.g., eucalyptus, oak, maple, birch, ash) and softwoods (i.e. conifers such as fir, redwood, spruce, cedar, cypress, larch, hemlock, loblolly and other pines), banana, plantain, pineapple, hops, coffee, tea, cocoa, oilseed palm, rubber, sugarcane, grapes (e.g., Vitus vinifera, V. labrusca, V. rotundifolia), and perennial turf grasses (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue, Bermuda grass). Alternatively, the subject compounds are useful to modify plant growth. The formulated compounds can be applied to the soil, for example, as a treatment spray mixture, mixed with solid fertilizer or included in irrigation water.
Many of the compounds 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. One skilled in the art will recognize that the preferred combination of these selectivity factors within a compound or group of compounds can readily be determined by performing routine biological and/or biochemical assays.
As the compounds of the invention have both preemergent and postemergent herbicidal activity, to control undesired vegetation by killing or injuring the vegetation or reducing its growth, the compounds can be usefully applied by a variety of methods which can include banding, directed sprays, or broadcast applications that involve 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 Formula I or Iz is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is about 0.1 g/ha to 20 kg/ha, with a preferred range of about 1 g ha to about 5000 g/ha and a more preferred range of about 4 to about 3000 g/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
The compounds of Formula Iz (including Formula I) may be used in combination with other herbicides, insecticides, or fungicides, and other agricultural chemicals such as fertilizers. Other herbicides, insecticides and fungicides can include biological agents such as the herbicidal microbes Alternaria destruens, Colletotrichum gloesporiodes, Drechsiera monoceras (MTB-951) and Puccinia thlaspeos. Mixtures of compounds of Formula Iz (or I) with other herbicides can broaden the spectrum of activity against additional weed species, and suppress the proliferation of any resistant biotypes. Mixtures of compounds of Formula Iz (or I) with other herbicides can also provide greater than expected (i.e. synergistic) control of weeds and/or less than expected (i.e. safening) effect on crops. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a herbicidally effective amount of a compound of Formula Iz and an effective amount of another herbicide. Of note is said herbicidal mixture wherein the compound of Formula Iz is a compound of Formula I. A mixture of one or more of the following other herbicides with a compound of Formula Iz may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, alloxydim, Alternaria destruens, ametryn, amicarbazone, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, beflubutamid, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, benzfendizone, benzobicyclon, benzofenap, bifenox, bilanafos, bispyribac and its sodium salt, bromacil, bromobutide, bromoxynil, bromoxynil octanoate, butachlor, butafenacil, butamifos, butralin, butroxydim butylate, cafenstrole, caloxydim (BAS 620H), carbetamide, carfentrazone-ethyl, catechin, chlomethoxyfen, chloramben, chlorbromuron, chlorflurenol-methyl, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, chlorthiamid, cinidon-ethyl, cinmethylin, cinosulfuron, clethodim, clodinafop-propargyl, clomazone, clomeprop, clopyralid, clopyralid-olamine, cloransulam- methyl, Colletotrichum gloesporiodes, cumyluron, cyanazine, cycloate, cyclosulfamuron, cycloxydim, cyhalof op-butyl, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclof op-methyl, diclosulam, difenzoquat metilsulfate, diflufenican, diflufenzopyr, dimefuron, dimepiperate, dimethachlor, dimethametryn, dimethenamid, dimethipin, dimethylarsinic acid and its sodium salt, dinitramine, dinoterb, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, Drechsiera monoceras, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, etobenzanid, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fentrazamide, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, flamprop-M-methyl, flazasulfuron, florasulam, fluazifop-butyl, fluazifop-P-butyl, fluazolate, flucarbazone, fluchloralin, flufenacet, flufenpyr-ethyl, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, flurtamone, fluthiacet-methyl, fomesafen, foramsulfuron, fosamine-ammonium, furilazole, glufosinate and its salts such as particularly glufosinate- ammonium, glyphosate and its salts such as particularly glyphosate-ammonium, glyphosate-isopropylammonium, glyphosate-sodium, glyphosate-potassium and glyphosate- trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxyfop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapic, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, indanofan, iodosulfuron-methyl, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, MCPB and its sodium salt, MCPB-ethyl, mecoprop, mecoprop-P, mefenacet, mefluidide, mesosulfuron-methyl, mesotrione, metam-sodium, metamifop, metamitron, metazachlor, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyldymron, methyl [[[l-[5- [2-chloro-4-(trifluoromethyl)phenoxy]-2-nitxophenyl]-2-methoxyethylidene]amino]oxy]- acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2-pyrirmdinyl)amino]carbonyl]amino]- sulfonyl]-l-(2-pyridinyl)-lH-pyrazole-4-carboxylate (NC-330), metobenzuron, metobromuron, metolachlor, S-metholachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, naproanilide, napropamide, naptalam, neburon, nicosulfuron, norflurazon, orbencarb, oryzalin, oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, penoxsulam, pentanochlor, pentoxazone, perfluidone, pethoxamid, phenmedipham, picloram, picloram-potassium, picolinafen, piperofos, pretilachlor, primisulfuron-methyl, prodiamine, profoxydim (BAS625Η, 2-[l-[[2-(4-chlorophenoxy)propoxy]imino]butyl]-3-hydroxy- 5-(tetrahydro-2H-thiopyran-3-yl)-2-cyclohexen-l-one), prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propisochlor, propoxycarbazone, propyzamide, prosulfocarb, prosulfuron, Puccinia thlaspeos, pyraflufen-ethyl, pyrazolynate, pyrazoxyfen, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyridate, pyriftalid, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quinmerac, quinoclamine, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, simetryn, sulcotrione, sulfentrazone, sulfometuron-methyl, sulfosulfuron, 2,3,6-TBA, TCA, TCA-sodium, tebutam, tebuthiuron, tepraloxydim, terbacil, terbumeton, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thiazopyr, thifensulfuron-methyl, thiobencarb, tiocarbazil, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trietazine, trifloxysulfuron, trifluralin, triflusulfuron-methyl, tritosulfuron and vernolate. Combinations of compounds of the invention with other herbicides 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. For example, combination of a sulfonylurea herbicide such as thifensulfuron-methyl and tribenuron-methyl with a compound of the invention can reduce phytotoxicity to certain crops. In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds.
Preferred for better control of undesired vegetation (e.g., lower use rate such as from synergism, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds is a herbicidal mixture of a compound of Formula Iz (including Formula I) with an other herbicide selected from the group consisting of atrazine, bromacil, diuron, hexazinone, terbacil, glyphosate (particularly glyphosate-ammonium, glyphosate-isopropylammonium, glyphosate-sodium, glyphosate-potassium, glyphosate- trimesium), glufosinate (particularly glufosinate-ammonium), rimsulfuron, metsulfuron- methyl, sulfometuron-methyl, ametryn and paraquat. Specifically preferred mixtures (wherein compound A is N-[3-[(dimethylamino)carbonyl]phenyl]-3-(l,l-dimethylethyl)- l-methyl-lH-pyrazole-5-carboxamide (Formula Iz wherein J is J-1, Rla is Me, R2a is t-Bu, R3 is Η, W is O, R4 is Η, T, U, Y and Z are CΗ, and R5 is C(O)ΝMe2); other compound numbers refer to compounds in Index Tables A-K) are selected from the group: compound 2 and atrazine; compound 6 and atrazine; compound 14 and atrazine; compound 115 and atrazine; compound 152 and atrazine; compound 156 and atrazine; compound 162 and atrazine; compound 193 and atrazine; compound 222 and atrazine; compound A and atrazine, compound 2 and bromacil; compound 6 and bromacil; compound 14 and bromacil; compound 115 and bromacil; compound 152 and bromacil; compound 156 and bromacil; compound 162 and bromacil; compound 193 and bromacil; compound 222 and bromacil; compound A and bromacil; compound 2 and diuron; compound 6 and diuron; compound 14 and diuron; compound 115 and diuron; compound 152 and diuron; compound 156 and diuron; compound 162 and diuron; compound 193 and diuron; compound 222 and diuron; compound A and diuron; compound 2 and hexazinone; compound 6 and hexazinone; compound 14 and hexazinone; compound 115 and hexazinone; compound 152 and hexazinone; compound 156 and hexazinone; compound 162 and hexazinone; compound 193 and hexazinone; compound 222 and hexazinone; compound A and hexazinone; compound 2 and terbacil; compound 6 and terbacil; compound 14 and terbacil; compound 115 and terbacil; compound 152 and terbacil; compound 156 and terbacil; compound 162 and terbacil; compound 193 and terbacil; compound 222 and terbacil; compound A and terbacil; compound 2 and glyphosate; compound 6 and glyphosate; compound 14 and glyphosate; compound 115 and glyphosate; compound 152 and glyphosate; compound 156 and glyphosate; compound 162 and glyphosate; compound 193 and glyphosate; compound 222 and glyphosate; compound A and glyphosate; compound 2 and glufosinate; compound 6 and glufosinate; compound 14 and glufosinate; compound 115 and glufosinate; compound 152 and glufosinate; compound 156 and glufosinate; compound 162 and glufosinate; compound 193 and glufosinate; compound 222 and glufosinate; compound A and glufosinate; compound 2 and rimsulfuron; compound 6 and rimsulfuron; compound 14 and rimsulfuron; compound 115 and rimsulfuron; compound 152 and rimsulfuron; compound 156 and rimsulfuron; compound 162 and rimsulfuron; compound 193 and rimsulfuron; compound 222 and rimsulfuron; compound A and rimsulfuron; compound 2 and metsulfuron-methyl; compound 6 and metsulfuron- methyl; compound 14 and metsulfuron-methyl; compound 115 and metsulfuron-methyl; compound 152 and metsulfuron-methyl; compound 156 and metsulfuron-methyl; compound 162 and metsulfuron-methyl; compound 193 and metsulfuron-methyl; compound 222 and metsulfuron-methyl; compound A and metsulfuron-methyl; compound 2 and sulfometuron- methyl; compound 6 and sulfometuron-methyl; compound 14 and sulfometuron-methyl; compound 115 and sulfometuron-methyl; compound 152 and sulfometuron-methyl; compound 156 and sulfometuron-methyl; compound 162 and sulfometuron-methyl; compound 193 and sulfometuron-methyl; compound 222 and sulfometuron-methyl; compound A and sulfometuron-methyl; compound 2 and ametryn; compound 6 and ametryn; compound 14 and ametryn; compound 115 and ametryn; compound 152 and ametryn; compound 156 and ametryn; compound 162 and ametryn; compound 193 and ametryn; compound 222 and ametryn; compound A and ametryn; compound 2 and paraquat; compound 6 and paraquat; compound 14 and paraquat; compound 115 and paraquat; compound 152 and paraquat; compound 156 and paraquat; compound 162 and paraquat; compound 193 and paraquat; compound 222 and paraquat; compound A and paraquat. Particularly preferred because of greater than additive (i.e. synergistic) efficacy on certain weeds are mixtures of compound 2 and diuron; compound 2 and terbacil; compound 6 and atrazine; compound 6 and diuron; compound 6 and hexazinone; and compound 6 and terbacil. Herbicidally effective amounts of compounds of Formula Iz (including Formula I) as well as herbicidally effective amounts of other herbicides can be easily determined by one skilled in the art through simple experimentation. Synergistically effective amounts of these herbicidal compounds can likewise be easily determined.
Mixtures of compound 6 with diuron and hexazinone are especially notable for their synergistic activity in controlling Urochloa species (previously classified in genus Brachiaria) such as Urochloa decumbens (Staph) R. D. Webster, which is commonly known as Surinam grass or signal grass. U. decumbens is native to central Africa, but because it grows satisfactorily on poor soils, it has been planted in other tropical and subtropical regions for use as cattle forage. Unfortunately this species has subsquently become widespread and troublesome in many crops. As reported by R. A. Pitelli et al., "Brachiaria decumbens, a major exotic invasive plant in Brazil", Weed Science Society of America Abstracts 2003, 43, 23, this species has become a major weed in forestry, citrus, sugarcane, horse pastures and roadsides as well as soybean, maize and cotton crops. Therefore a preferred embodiment of the present invention is a method for controlling the growth of undesired vegetation comprising Urochloa decumbens (Staph) R. D. Webster comprising contacting the vegetation or its environment with herbicidally effective amounts of the compound of Formula I (or Iz) which is N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]- 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxamide (compound 6) and at least one other herbicide selected from the group consisting of diuron and hexazinone. In said method compound 6 is typically applied at an application rate between about 60 and 600 g/ha, preferably between about 120 and 450 g/ha, and more preferably between about 240 and 360 g/ha; diuron is typically applied between about 250 and 2500 g/ha, preferably between about 500 and 2000 g/ha, and more preferably between about 960 and 1440 g/ha; and hexazinone is typically applied between about 100 and 600 g/ha, preferably between about 200 and 450 g/ha, more preferably between about 240 and 360 g/ha. Typical use rate ratios by weight for compound 6 to diuron (compound 6 : diuron) are in the range of about 1:40 to 2:1, preferably about 1:17 to 1:1, and more preferably about 1:6 to about 1:3. Typical use rate ratios by weight for compound 6 to hexazinone are in the range of about 1:10 to 6:1, preferably about 1:4 to 2:1, and more preferably about 2:3 to 3:2. Compounds of Formula Iz (including Formula I) can also be used in combination with herbicide safeners such as benoxacor, BCS (l-bromo-4-[(chloromethyl)sulfonyl]benzene), cloquintocet-mexyl, cyometrinil, dichlormid, 2-(dichloromethyl)-2-methyl-l,3-dioxolane (MG 191), fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-ethyl, methoxyphenone ((4-methoxy-3-methylphenyl)(3-methylphenyl)- methanone), naphthalic anhydride (1,8-naphthalic anhydride) and oxabetrinil to increase safety to certain crops. Antidotally effective amounts of the herbicide safeners can be applied at the same time as the compounds of this invention, or applied as seed treatments. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a compound of Formula Iz 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 Formula Iz wherein seed from which the crop is grown is treated with an antidotally effective amount of safener. Seed treatment with 1,8-naphthalic anhydride works well in a wide variety of crops such as maize, wheat, barley and sugarbeets. Of note is said method wherein the compound of Formula Iz is a compound of Formula I. Antidotally effective amounts of safeners can be easily determined by one skilled in the art through simple experimentation.
A compound of Formula Iz can thus be applied in admixture with other herbicides and/or herbicide safeners, in binary or multiple combinations in order to achieve optimal weed control spectrum and duration of weed control, suppress proliferation of resistant biotypes, benefit from synergy against particularly troublesome weeds and/or reduce injury to crops. Therefore an aspect of the present invention relates to a herbicidal mixture comprising a herbicidally effective amount of a compound of Formula Iz, an N-oxide or an agriculturally suitable salt thereof, and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener. Typically the herbicidal mixture is applied in the form of a herbicidal composition comprising the herbicidal mixture and at least one of a surfactant, a solid diluent or liquid diluent. Related to this herbicidal mixture and herbicidal composition is a method for controlling the growth of undesired vegetation by applying a herbicidally effective amount of said herbicidal mixture or herbicidal composition to the locus of the undesired vegetation. Of note are said herbicidal mixture, herbicidal composition and method wherein the compound of Formula Iz is a compound of Formula I. Also of note are said herbicidal mixture, herbicidal composition and method wherein the compound of Formula Iz is selected from Formula Iz wherein: J is J-1, Ria is Me, R2a is t-Bu, R3 is H, W is O, R4 is H, T, U, Y and Z are CH, and R5 is C(O)ΝMe2; J is J-1, Rla is Me, R2a is t-Bu, R3 is H, W is O, R4 is H, T, U, Y and Z are CH, and R5 is C(O)NHMe; J is J-1, Rla is Me, R2a is t-Bu, R3 is H, W is O, R4 is H, T, U, Y and Z are CH, and R5 is C(O)NH-n-Pr; J is J-1, Ria is Me, R2a is t-Bu, R3 is H, W is O, R4 is H, T, U, Y and Z are CH, and R5 is C(O)NEt2; or J is J-1, Rla is Me, R2a is t-Bu, R3 is H, W is O, R4 is H, U, Y and Z are CH, T is N, and R5 is C(O)NEt2 (or the pyridine N-oxide thereof, i.e. T is N(O)). The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A-K for compound descriptions. The following abbreviations are used in the Index Tables which follow: t means tertiary, -? means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, z-Pr means isopropyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN means cyano, NO2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O)2Me means methylsulfonyl. The abbreviation "dec" indicates that the compound appeared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
Figure imgf000100_0001
R can be one or more substituents; a dash ("-") indicates no substituents.
Compound Rla g2a El Bl E El m.p. (°C)
1 Et t-Bu H H 6-F C(0)N4CH2CH=CHCH2} *
2 (Ex. 5, 6) Et t-Bu H H 6-F C(0)NHCH2CH3 188.5
3 Et t-Bu H H 6-F C(0)NHCH2CH2F *
4 Et *-Bu H H 6-F C(0)N(CH2CH3)2 *
5 Et t-Bu H H 6-F C(0)NHCH2CF3 *
6 (Ex. 7) Et *-Bu H H 6-F C(0)N(CH3)2 *
7 Et t-Bu H H 6-F C(0)NHCH3 250-252
8 Et t-Bu H H 2,4,5-tri-F C(0)NHCH2CH3 *
9 Et t-Bu H H 6-F C(0)N(CH3)CH2CH=CH2 *
10 Et t-Bu H H 6-F C(0)N(CH3)CH2C≡CH *
11 Et t-Bu H H 6-F C(0)NHCH2CH2OCH3 *
12 Et t-Bu H H 6-F C(0)N(CH3)CH2CH(CH3)2 *
13 Et -Pr H H 6-F C(0)NHCH2CH3 *
14 Et /-Pr H H 6-F C(0)N(CH3)2 *
15 Et -Pr H H 6-F C(0)N(CH2CH3)2 *
16 Et t-Bu H H 6-F C(0)N(CH3)CH2CH3 *
17 Et t-Bu H H 6-F C(0)N(CH3)CH2CH2CH3 *
18 Et c-Pr H H 6-F C(0)N(CH3)2 *
19 Et c-Pr H H 6-F C(0)N(CH2CH3)2 *
20 Et c-Pr H H 6-F C(0)NHCH2CH3 *
21 Et c-Pr H H 6-F C(0)N(CH3)CH2CH=CH2 *
22 Et /-Bu H H 6-F C(0)N(CH3)2 *
23 Et /-Bu H H 6-F C(0)N(CH2CH3)2 *
24 Et /-Bu H H 6-F C(0)NHCH2CH3 *
25 Et /-Bu H H 6-F C(0)N(CH3)CH2CH=CH2 * Compound Rla g2a El Bl g Bl m.p. (°C)
26 Et t-Bu H H - C(0)NtCH(CH3)(CH2)4} 197-198
27 Et t-Bu H H - C(0)NHCH2CH3 176-179
28 Et ■ t-Bu H H - C(0)N(CH2CH3)2 153-155
29 Et t-Bu H H - C(0)NHCH3 195-197
30 CH2CF3 t-Bu H H - C(0)NHCH3 204-206
31 CH2CF3 t-Bu H H - C(0)NHCH2CH3 *
32 CH2CF3 t-Bu H H - C(0)N(CH2CH3)2 *
33 CH=CH2 t-Bu H H - C(0)NHCH2CH3 *
34 CH=CH2 t-Bu H H - C(0)N(CH2CH3)2 *
35 CH2CH2F t-Bu H H - C(0)NHCH2CH3 *
36 CH2CH2F t-Bu H H - C(0)N(CH2CH3)2 *
37 CH=CH2 t-Bu H H - C(0)NHCH2CF3 *
38 CH=CH2 t-Bu H H - C(0)NHCH2CH2C1 *
39 CH=CH2 t-Bu H H - C(0)NH(c-Pr) *
40 n-Bu t-Bu H H - C(0)N(CH2CH3)2 154-156
41 n-Bu t-Bu H H - C(0)NHCH2CH3 139-141
42 /-Bu t-Bu H H - C(0)NHCH2CH3 *
43 (Ex. 3) Et t-Bu H H - C(0)NHCH2CF3 #*
44 Et t-Bu H H - C(0)NH(c-Pr) *
45 Et t-Bu H H - C(0)NHCH2CH2F *
46 Et t-Bu H H - C(0)NHCH2CH=CH2 *
47 Et t-Bu H H - C(0)NHCH2C≡CH *
48 Et t-Bu H H - C(0)N(CH3)CH2CH3 *
49 Et t-Bu H H - C(0)N(CH3)2 *
50 CH2C≡CH t-Bu H H - C(0)NHCH2CH3 *
51 Et t-Bu H H - C(0)NH(/-Pr) *
52 Et t-Bu H H 2-f(CH2)2TNHC(0)- *
53 Me t-Bu H H 2-KCH2)2}NHC(0)- *
54 Me t-Bu H H 2-KCH2)2ΪNMeC(0)- *
55 (Ex. 15) Et t-Bu H H 2-f(CH2)2TNMeC(0)- **
56 CH2CH=CH t-Bu H H - C(0)NHCH2CH3 *
57 ra-Pr t-Bu H H - C(0)NHCH2CH3 162-163
58 Et t-Bu H H 4-F C(0)NHCH2CH3 *
59 Et t-Bu H H 4-F C(0)N(CH2CH3)2 *
60 Et t-Bu H H 4-F C(0)NHCH2CH2F *
61 Et t-Bu H H - C(0)NH(/-Bu) *
62 Et t-Bu H H - C(0)NHCH2(c-Pr) * Compound Rla R2a Bl Bl E El m.p. (DC
63 Et t-Bu H H 2- 4jCH2)2}NEtC(0)- *
64 Et t-Bu H H 2-KCH2)2}N(c-Pr)C(0)- *
65 Et t-Bu H H 2-KCH2)2TN(«-Pr)C(0)- *
66 Et t-Bu H H 2-KCH2)2TN(c-pentyl)C(0)- *
67 Et t-Bu H H - C(0)NHOCH3 *
68 Et t-Bu H H 4-CH3 C(0)NHCH2CH3 *
69 Et t-Bu H H 4-CH3 C(0)N(CH2CH3)2 *
70 (Ex. 4) Et t-Bu H H 6-F C02CH2CH3 **
71 Et t-Bu H H 6-F C02(t-Bu) *
72 Et /-Bu H H 6-F C02CH2CH3 *
73 Et /-Pr H H 6-F C02CH2CH3 *
74 Et c-Pr H H 6-F C02CH2CH3 *
75 Et t-Bu H H 6-F, 4-OCH3 C02CH3 *
76 Et t-Bu H H 6-F, 4-OCH3 C02CH2CH3 *
77 Et t-Bu H H 6-F, 4-OCH3 C02(/-Pr) *
78 CH=CH2 t-Bu H H - C02CH2CH3 *
79 CH2CH2F t-Bu H H - C02CH2CH3 *
80 (Ex. 1) Et t-Bu H H - C02CH2CH3 **
81 Et t-Bu H H - C02CH3 *
82 (Ex. 2) Et t-Bu H H - C02CH2CH2F **
83 Et t-Bu H H - C02CH2CF3 *
84 Et t-Bu H H - C02CH2C≡CH *
85 Et t-Bu H H - C02CH2CH=CH2 *
86 Et t-Bu H H - C02(CH2)3CH3 *
87 Et t-Bu H H 2-CH3 C02CH3 *
88 Et t-Bu H H 2-CH3 C02CH2CH3 #
89 Et t-Bu H H 4-F C02CH2CH3 *
90 Et t-Bu H H 2-CH3 C02(CH2)2CH3 *
91 Et t-Bu H H 2-CH3 C02CH2CH2F *
92 Et t-Bu H H 2-CH3 C02(/-Pr) *
93 Et t-Bu H H 2-CH3 C02CH2(c-Pr) *
94 Et t-Bu H H 2-CH3 C02CH2CH=CH2 *
95 Et t-Bu H H 4-OEt C02CH2CH3 *
96 Et t-Bu H H 4-OMe C02CH2CH3 *
97 Et f-Bu H H 2-OMe C02CH2CH3 *
98 Et t-Bu H H - C02(t-Bu) *
99 Et t-Bu H H 4-CH3 C02CH2CH3 * Compound Rla R2a E3 El E El m.π. (°C)
100 Et t-Bu H H 4-CH3 C02(/-Pr) *
101 Et t-Bu H H 4-OMe C02(/-Pr) *
102 Me t-Bu H H - C(=N0H)CH3 189-191
103 Me CF3 H H - C(=NOH)CH3 189-191
104 Me t-Bu H H 6-OMe C(=NOH)CH3 196-197
105 Me t-Bu H H - C(=NOCH2CH3)CH3 94-95
106 Me t-Bu H H - C(=NOCH3)CH3 125-126
107 Me t-Bu H H - C(=NOH)CH3 *
108 Et t-Bu H H - C(=NOH)CH3 172-174
109 Me t-Bu H H 4-F C(=NOH)CH3 165-167
110 /-Pr t-Bu H H - C(=NOH)CH3 *
111 Me t-Bu H H 2-KCH2)2TC(=NOH)- *
112 CH2CF3 t-Bu H H - C(=NOH)CH3 145-147
113 n-Pτ t-Bu H H - C(=NOH)CH3 173-175
114 CH=CH2 t-Bu H H - C(=NOH)CH3 *
115 CH2CH2F t-Bu H H - C(=NOH)CH3 *
116 Me t-Bu H H 2-KCH2)3TC(=NOH)- *
117 CH2CH=CH2 t-Bu H H - C(=NOH)CH3 *
118 Me t-Bu H H - C(=NOH)CH2CH3 188-190
119 n-Bu t-Bu H H - C(=NOH)CH3 161-163
120 Me s-Bu H H - C(=NOH)CH3 139-141
121 Me t-Bu H H - CN 95-99
122 Et t-Bu H H - C(0)CH3 106-108
123 Me t-Bu H H 4-F C(0)CH3 124-127
124 Me t-Bu H H - S(0)2NH(/-Pr) *
125 Me t-Bu H H - S(0)2NH(CH2)3CH3 *
126 CH2CF3 t-Bu H H - C(0)CH3 108-109
127 CH=CH2 t-Bu H H - C(0)CH3 *
128 CH2CH2F t-Bu H H - C(0)CH3 *
129 CH2CH=CH2 t-Bu H H - C(0)CH3 *
130 Et t-Bu H H - SCF3 *
131 Et t-Bu H H - SCH3 *
132 CH2CH2F t-Bu H H - SCF3 *
133 Et t-Bu H H - S(0)2CH3 *
134 Et t-Bu H H - S(0)2CF3 *
135 Et t-Bu H H - S(0)CF3 *
136 Et t-Bu H H - OCH2CH3 * Compound Rla g2a El El g El m.p. (°C)
137 Et t-Bu H H - 0(CH2)3CH3 *
138 Et t-Bu H H - 0(CH2)2CH2F *
139 Et t-Bu H H - CN *
140 Et t-Bu H H 6-F CN 153-154
141 Et t-Bu H C(0)Me 4-Me C02CH2CH3 *
236 (Ex. 18) Et t-Bu H H 4-F C(0)N(CH3)2 #*
242 Et t-Bu H H 6-F C(0)NJCH2CH2CH2CH2} *
243 Et t-Bu H H 6-F C(0)NtCH2CH20CH2CH2T *
244 Et t-Bu H H 6-F C(0)N(CH3)OCH3 *
248 Et t-Bu H H 4,6-di-F C02(/-Pr) *
249 Et t-Bu H H 4,6-di-F C02CH2CH2CH3 *
250 Et t-Bu H H 4,6-di-F C02CH2CH3 *
251 Et t-Bu H H 4,6-di-F C(0)NHCH3 *
252 Et t-Bu H H 4,6-di-F C(0)NHCH2CH3 *
253 Et t-Bu H H 4,6-di-F C(0)N(CH2CH3)2 *
254 Et t-Bu H H 4,6-di-F C(0)N(CH3)CH2CH3 *
270 Et t-Bu H H 4,6-di-F C(0)N(CH3)2 *
271 Et t-Bu H H 6-F C(0)NH2 *
272 Et t-Bu H H - OCF3 *
273 Et t-Bu H H - OCH(CH3)2 *
275 Et t-Bu F H 6-F C(0)NHCH2CH3 *
276 (Ex. 21) Et t-Bu F H 6-F C(0)N(CH3)2 **
285 Et t-Bu H H - C(0)N(CH3)CH2CH=CH2 *
286 Et t-Bu H H - C(0)NJCH2CH=CHCH2} *
294 Et t-Bu H H 6-F C(S)N(CH3)2 *
295 Et 1-Me-c-] Pr H H - C02CH2CH3 *
296 Et 1-Me-c-] Pr H H 6-F C02CH2CH3 *
297 Et t-Bu H H 6-OCH3 OCH3 *
298 Et t-Bu H H 4-OCH3 OCH3 *
299 Et 1-Me-c-] Pr H H 6-F C(0)N(CH3)2 *
300 Et 1-Me-c-] Pr H H 6-F C(0)NHCH2CH3 *
301 Et 1-Me-c-] Pr H H 6-F C(0)NtCH2CH=CHCH2T *
302 Et 1-Me-c-] Pr H H 6-F C(0)NHCH2C≡CH *
303 Et 1-Me-c-] Pr H H - C(0)N(CH3)2 *
304 Et 1-Me-c-] Pr H H - C(0)NfCH2CH=CHCH2} *
306 Et 1-Me-c-] Pr H H - C(0)NHCH2CH3 *
311 H t-Bu H H - C(=NOH)CH3 * Compound Rl R2a Bl Bl B Bl m.p. (°C)
329 Et t-Bu H H - C(0)NHCH2SCH2CH3 *
332 Et t-Bu H H - OCHF2 *
333 Et t-Bu H H - OCF2CHF2 *
338 Et t-Bu H H 6-F OCF3 *
347 Et t-Bu H H 6-F OCH3 *
348 Et t-Bu H H 6-F OCH2CH3 *
349 Et t-Bu H H 6-F C(S)NHCH2CH3 *
350 Et t-Bu H H 6-F OCH2CH2F *
351 H t-Bu H H - C(0)NHCH2CH3 *
* See Index Table K for !H NMR data. ** See synthesis example for 1H NMR data.
INDEX TABLE B
Figure imgf000105_0001
R can be one or more substituents; a dash ("-") indicates no substituents.
Compound Ria R2a Bl El E El m.p. (°C
352 (Ex. 25) Et -(CH3)2CKCH2)2T- H 6-F C(0)N(CH3)2 **
353 Et -(CH3)2C CH2)2ir- H 6-F C(0)NHCH2CH3 *
* See Index Table K for XH NMR data. ** See synthesis example for 1H NMR data.
INDEX TABLE C
Figure imgf000105_0002
Compound Rla g2a El T u Y z gl m.D. CO
142 Et t-Bu H CH N CH CH C(0)NfCH2CH=CHCH2T *
143 (Ex. 8) Et t-Bu H N CH CH CH C02CH3 ** Compound Rla R2a El 1 U Y Z El m.p. (°C
144 Et t-Bu H N CH CH CH C(0)NHCH2CH3 *
145 Et t-Bu H N CH CH CH C(0)N(CH2CH3)2 *
146 Et t-Bu H N CH CH CH C(0)NH(c-Pr) *
147 Et t-Bu H N CH CH CH C(0)NHCH2C≡CH *
148 Et t-Bu H CH N CCH3 CH C02CH3 *
149 Et t-Bu H CH N CCH3 CH C(0)NHCH2CH3 *
150 Et t-Bu H N CH CCH3 CH C(0)NHCH2CH3 *
151 (Ex. 10) Et t-Bu H CH N CH CH C02CH3 **
152 Et t-Bu H CH N CH CH C(0)NHCH2CH3 *
153 Et t-Bu H CH N CH CH C(0)N(CH2CH3)2 *
154 Et t-Bu H CH N CH CH C(0)NH(/-Bu) *
155 Et t-Bu H CH N CH CH C(0)NHCH2(c-Pr) *
156 (Ex. 11) Et t-Bu H CH N CH CH C(0)N(CH3)2 **
157 Et t-Bu H CH N CH CH C02CH2CH3 *
158 Et t-Bu H N CH CH CH C(0)N(CH3)CH2CN *
159 Et t-Bu H CH N CH CH C(0)N(CH3)CH2CH=CH2 *
160 Et t-Bu H CH N CH CH C(0)N(CH3)CH2C≡CH *
161 Et t-Bu H CH N CH CH C(0)NH(CH2)2OCH3 *
162 (Ex. 9) Et t-Bu H N CH CH CH C(0)N(CH3)2 **
163 Et t-Bu H N CH CH CH C(0)N(CH3)CH2CH=CH2 *
164 Me t-Bu H N N CH CH C(=NOH)CH3 196-197
165 Et t-Bu H N N CH CH OCH3 *
166 Et t-Bu H N N COCH3 CH OCH3 *
167 Et t-Bu H N N COCH3 CH SCH2F *
245 Et t-Bu H N CH CH CH C(0)NτCH2CH2CH2CH2} *
246 Et t-Bu H N CH CH CH C(0)N(CH3)OCH3 *
247 Et t-Bu H N CH CH CH C(0)N{CH2CH2OCH2CH2} *
255 (Ex. 19) Et t-Bu H CH CH N CH C02CH2CH3 **
256 Et t-Bu H CH CH CH N C(0)N(CH3)2 *
257 Et t-Bu H CH CH CH N C(0)NHCH2CH3 *
258 Et t-Bu H CH CH N CH C(0)N(CH3)2 *
259 Et t-Bu H CH CH N CH C(0)NHCH CH3 *
260 Et t-Bu H CH CH N CH C(0)N{CH2CH=CHCH2T, *
261 (Ex. 20) Et t-Bu H CH CH N CH C(0)N(CH2CH3)2 **
262 Et t-Bu H CH CH N CH C(0)N(CH2CH=CH2)2 *
263 Et t-Bu H CH CH N CH C(0)N(CH3)CH2CH3 *
264 Et t-Bu H CH CH N CH C(0)NHCH2C≡CH * Compound Rla g2a Bl ϊ U Y Z El m.D. (°C)
265 Et t-Bu H N COCH3 CH CH C02CH3 *
266 Et t-Bu H N COCH3 CH CH C(0)NHCH2CH3 *
274 Et t-Bu F N CH CH CH C(0)N(CH3)2 *
277 Et t-Bu H N CF CH CH C(0)N(CH3)2 *
278 Et t-Bu H N CF CH CH C(0)NHCH2CH3 *
279 Et t-Bu H N CF CH CH C(0)NHCH2C≡CH *
280 Et t-Bu H N CF CH CH C(0)N(CH3)CH2CH3 *
281 Et t-Bu H N CF CH CH C(0)N£CH2CH=CHCH2} *
282 Et t-Bu H CH CH CH N C(0)NrCH2CH=CHCH2} *
283 Et t-Bu H CH CH CH N C(0)NHCH2C≡CH *
284 Et t-Bu H CH CH CH N C(0)NHCH2CH2F *
287 Et t-Bu H N CH N CH C(0)N(CH3)2 *
288 Et t-Bu H N CH N CH C(0)NHCH2CH3 *
289 Et t-Bu H N CH N CH C(0)NHCH2C≡CH *
290 Et t-Bu H N CH N CH C(0)NJCH2CH=CHCH2} *
291 Et t-Bu H N CH N CH C(0)NHCH2CF3 *
312 Me t-Bu H N CH CH CH C02CH3 *
313 Me t-Bu H N CH CH CH C02CH2CH3 *
314 Me t-Bu H N CH CH CH C(0)N(CH2CH3)2 *
315 Me t-Bu H N CH CH CH C(0)NH(c-Pr) *
316 Me t-Bu H N CH CH CH C(0)NHCH2C≡CH *
317 Me t-Bu H N CH CH CH C02CH2C≡CH *
318 Me t-Bu H N CH CH CH C(0)NHCH2CH=CH2 *
334 Et t-Bu H CH N CH CH C(S)N(CH3)2 170-172
* See Index Table K for H NMR data.
*# See synthesis example for H NMR data.
INDEX TABLE D
Figure imgf000107_0001
R can be one or more substituents; a dash ("-") indicates no substituents. Compound Rla g2a E El m. . (°C)
305 Et t-Bu 6-F C(S)N(CH3)2 90-92
346 Et t-Bu 6-F C02CH2CH3
* See Index Table K for lR NMR data.
INDEX TABLE E
Figure imgf000108_0001
Compound Rlb R2b ϊ U El m.p. (°C)
168 (Ex. I ) Et t-Bu CH CH C(0)N(CH2CH3)2 **
169 CF3 t-Bu CH CH C(0)N(CH2CH3)2 *
170 CF3 t-Bu CH CH C(0)NHCH2CH3 *
171 CF3 t-Bu CH CH C(=NOH)CH3 *
218 Cl t-Bu CH CH C(0)N(CH2CH3)2 *
219 Cl t-Bu CH CH C(0)NHCH2CH3 *
220 Br t-Bu CH CH C(0)N(CH2CH3)2 *
221 (Ex. 14) Br t-Bu CH CH C(0)NHCH2CH3 **
232 Et t-Bu CH N C(0)N(CH3)2 163-165
233 Et t-Bu CH N C(0)NHCH2CH3 141-143
234 Et t-Bu CH N C(0)N(CH2CH3)2 90-91
235 Et t-Bu CH N C(0)N(CH3)CH2CH3 103-105
330 Et t-Bu N CH C(0)N(CH3)2 159-160
* See Index Table K for XH NMR data. ** See synthesis example for 1H NMR data.
INDEX TABLE F
Figure imgf000108_0002
R can be one or more substituents; a dash ("-") indicates no substituents. Compound Rlb g2b T U R gl m.p. (°Q
172 CF3 Et CH CH - C(0)NHCH2CH3 Compound Rlb R2b T U R Bl m.p. (°C)
179 Me /-Pr CH CH - C(0)CH3 116-118
180 Me /-Pr CH CH - C(=NOH)CH3 192-193
181 Et t-Bu CH CH - C(0)NHCH2CH3 160-163
182 (Ex. 13) Et t-Bu CH CH - C(0)N(CH2CH3)2 **
183 Me t-Bu CH CH - C(0)NHCH2CH3 *
184 Me t-Bu CH CH - C(0)N(CH2CH3)2 *
185 n-Pr t-Bu CH CH - C(0)N(CH2CH3)2 *
186 Et t-Bu CH CH - C02CH2CH3 *
187 Et t-Bu CH CH - C(0)CH3 *
188 Et t-Bu CH CH - C(=NOH)CH3 *
189 Me t-Bu CH CH - O(ZPr) *
190 Me t-Bu CH CH - OCH2CH3 *
191 CF3 t-Bu CH CH - C(0)N(CH2CH3)2 *
192 CF3 t-Bu CH CH - C(0)NHCH2CH3 *
193 Et t-Bu CH CF - C(0)NHCH2CH3 *
194 Et t-Bu CH CF - C(0)NHCH3 *
222 (Ex. 16) Et t-Bu CH CF - C(0)N(CH3)2 **
223 Et t-Bu CH CF - C(0)N(CH2CH3)2 179-180
224 Et t-Bu CH CF - C(0)N(CH3)CH2CH3 138-139
238 Et t-Bu CH N - C02CH2CH3 *
239 Et t-Bu CH CH 4-F C(0)N(CH3)2 170-171
240 Et t-Bu CH CH 4-F C(0)N(CH2CH3)2 163-165
241 (Ex. 17) Et t-Bu CH CH 4-F C(0)NHCH2CH3 **
292 Et t-Bu N CH - C(0)N(CH3)2 148-149
293 Et t-Bu CH N - C(0)N(CH3)2 150-151
344 Me t-Bu CH CH 6-F C(0)N(CH3)2 201-202
345 Me t-Bu CH CH 6-F C(0)NHCH2CH3 203-204
* See Index Table K for IH NMR data.
** See synthesi s example ; for IH NMR data.
INDEX TABLE G
Figure imgf000109_0001
R can be one or more substituents; a dash ("-") indicates no substituents.
Compound Rlb R2a I g El m.p. (°C)
195 Me t-Bu CH - C(=NOH)CH3 *
196 Me t-Bu CH - C(0)CH3 *
197 Me t-Bu CH - C02CH3 *
198 Me t-Bu CH - C(0)NHCH2CH3 #
199 Me t-Bu CH - C(0)N(CH2CH3)2 *
200 Me t-Bu CH - C(0)NHCH2CH2F *
201 Me t-Bu CH - C(0)NHCH2CF3 *
202 Me t-Bu CH - C(0)NHCH2CH=CH2 *
203 Me t-Bu CH - C(0)NHCH2C≡CH *
204 Et t-Bu CH - C02CH2CH3 *
205 Et t-Bu CH - C(0)N(CH2CH3)2 *
206 Et t-Bu CH - C(0)NHCH2CF3 *
207 Et t-Bu CH - C(0)NHCH2CH=CH2 *
209 Et t-Bu CH - C(0)NHCH2CH2F *
210 Et t-Bu CH - C(0)NHCH2CH3 *
211 Et t-Bu CH - C(0)NH(/-Bu) *
212 Et t-Bu CH - C(0)NHCH2(c-Pr) *
213 Et t-Bu N - C(0)NHCH2CH3 *
214 Et t-Bu N - C(0)N(CH2CH3)2 *
215 Et t-Bu N - C(0)NHCH2(c-Pr) *
216 Et t-Bu N - C(0)NH(t-Bu) *
217 Et t-Bu N - C(0)NHCH2C≡CH *
225 Et t-Bu CH 6-F C(0)N(CH3)2 *
226 Et t-Bu CH 6-F C(0)NHCH2CH3 *
227 Me t-Bu CH - C(0)N(CH3)CH2CH3 *
228 Et t-Bu CH - C(0)N(CH3)2 *
229 Et t-Bu CH - C(0)N(CH3)CH2CH3 *
230 Et t-Bu CH 6-F C(0)N(CH2CH3)2 *
231 Et t-Bu CH 6-F C(0)N(CH3)CH2CH3 *
237 t-Bu Et CH 6-F C(0)NHCH2CH=CH2 *
319 Et t-Bu CH - C(0)NHCH2C≡CH *
326 Me t-Bu CH - C(0)N(CH3)2 *
327 t-Bu Et CH 6-F C(0)N(CH2CH=CH2)2 *
See Index Table K for :H NMR data. INDEX TABLE H
Figure imgf000111_0001
R can be one or more substituents; a dash ("-") indicates no substituents.
Compound Rla g2a RIC E El m.p. PC)
267 (Ex. 22) Et t-Bu H 6-F C02CH2CH3 *#
268 (Ex. 23) Et t-Bu H 6-F C(0)N(CH3)2 **
269 Et t-Bu H 6-F C(0)NHCH2CH3 *
307 Et t-Bu H 6-F C(0)N(CH3)CH2CH3 *
308 Et t-Bu H 6-F C(0)N(CH2CH3)2 *
309 Et t-Bu H 6-F C(0)N{CH2CH2CH2CH2} *
310 Et t-Bu H 6-F C(0)N{CH2CH=CHCH2} *
331 Et t-Bu H 6-F C(0)N4 H2CH2CH2CH2CH2} *
* See Index Table K for 2H NMR data. ** See synthesis example for 1H NMR data.
INDEX TABLE I
Figure imgf000111_0002
R can be one or more substituents; a dash ("-") indicates no substituents.
Compound Rlb R2b IC g Bl m.p. TO
335 Et t-Bu H 6-F C02CH2CH3 *
336 (Ex. 24) Et t-Bu H 6-F C(0)NHCH2CH3 **
340 Et t-Bu H 6-F C(0)NrCH2CH=CHCH2} *
341 Et t-Bu H 6-F C(0)N{CH2CH2CH2CH2T *
342 Et t-Bu H 6-F C(0)N(CH3)CH2CH3 *
343 Et t-Bu H 6-F C(0)N(CH3)2 *
* See Index Table K for :H NMR data. ** See synthesis example for 1H NMR data. INDEX TABLE J
Figure imgf000112_0001
R can be one or more substituents; a dash ( "-") indicates no substituents.
Compound Rlb R2b g R5 m.υ. (°C)
354 Et c-pentyl - C(0)N{CH2CH=CHCH2} *
355 Et c-pentyl - C(0)N(CH3)2 *
356 Et c-pentyl - C(0)NHCH2CH3 *
357 Et -Pr - C(0)NHCH2CH3 *
358 (Ex. 27) Et -Pr - C(0)N(CH3)2 **
359 Et -Pr - C(0)NfCH2CH=CHCH2} *
360 (Ex. 28) Et t-Bu - C02CH2CH3 **
361 Et t-Bu 6-F C(0)N(CH3)2 *
362 Et t-Bu 6-F C(0)NCH2CH3 *
363 Et t-Bu 6-F C(0)N{CH2CH=CHCH2} *
364 Et t-Bu - C(0)N(CH3)2 *
365 (Ex. 29) Et t-Bu - C(0)NCH2CH3 **
366 Et t-Bu - C(0)N4CH2CH=CHCH2T *
367 (Ex. 26) Et /-Pr - C02CH2CH3 φϊj;
* See Index Table K for !H NMR data. ** See synthesis example for NMR data.
INDEX TABLE K
Cmpd
IH NMR Data (CDCI3 solution unless indicated otherwise)21 No. δ 8.56 (dd, IH), 8.00 (br s, IH, NH), 7.24 (m, 2H), 6.54 (s, IH), 5.92 (m, IH), 5.82 (m, IH), 4.57
(q, 2H), 4.42 (m, 2H), 4.20 (m, 2H), 1.42 (t, 3H), 1.28 (s, 9H). δ 8.82 (m, IH), 7.92 (br s, IH, NH), 7.62 (m, IH), 7.24 (s, IH), 6.56 (br s, IH, NH), 6.42 (s, IH),
4.56 (m, 4H), 3.78 (m, 2H), 1.46 (t, 3H), 1.33 (s, 9H). δ 8.42 (m, IH), 7.92 (br s, IH, NH), 7.24 (m, 2H), 6.42 (s, IH), 4.52 (q, 2H), 3.42 (m, 4H), 1.46
(m, 6H), 1.30 (s, 9H). δ 8.80 (m, IH), 7.92 (br s, IH, NH), 7.64 (m, IH), 7.24 (m, IH), 6.56 (t, IH, NH), 6.51 (s, IH),
4.56 (q, 2H), 4.06 (m, 2H), 1.46 (t, 3H), 1.33 (s, 9H). δ 8.20 (m, IH), 8.12 (s, IH), 8.08 (br s, IH), 6.57 (s, IH), 6.30 (s, IH), 3.50 (m, 2H), 1.51 (t, 3H),
1.43 (t, 3H), 1.33 (s, 9H), 1.25 (t, 3H). C™pd IH NMR Data (CDCI3 solution unless indicated otherwise)a
9 δ 8.40 (dd, IH), 8.14 (br s, IH, NH), 7.22 (m, 2H), 6.56 (s, IH), 5.86 (m, IH), 5.28 (m, 2H), 4.58
(q, 2H), 3.08 (s, 3H), 1.44 (t, 3H), 1.34 (s, 9H).
10 δ 8.52 (dd, IH), 7.92 (br s, IH, NH), 7.22 (m, 2H), 6.58 (s, IH), 4.60 (q, 2H), 4.02 (m, 2H), 3.20
(s, 3H), 2.40 (s, IH), 1.44 (t, 3H), 1.34 (s, 9H).
11 δ 8.68 (dd, IH), 7.84 (br s, IH, NH), 7.62 (m, IH), 7.24 (m, IH), 6.60 (s, IH, NH), 6.49 (s, IH),
4.60 (q, 2H), 3.62 (m, 4H), 3.39 (s, 3H), 1.44 (t, 3H), 1.34 (s, 9H).
12 δ 8.40 (dd, IH), 8.00 (br s, IH, NH), 7.24 (m, 2H), 6.56 (s, IH), 4.60 (q, 2H), 3.42 (m, 2H), 3.00
(s, 3H), 1.44 (t, 3H), 1.34 (m, IH), 1.28 (s, 9H), 1.00 (d, 6H).
13 δ 8.62 (dd, IH), 7. 92 (br s, IH, NH), 7.66 (m, IH), 7.24 (m, IH), 6.48 (s, IH), 6.32 (br s, IH,
NH), 4.56 (q, 4H), 3.48 (q, 2H), 3.00 (m, IH), 1.31 (t, 3H), 1.28 (t, 3H), 1.24 (d, 6H).
14 δ 8.40 (dd, IH), 8.00 (br s, IH, NH), 7.18(m, 2H), 6.51 (s, IH), 4.56 (q, 2H), 3.10 (s, 3H), 3.08
(m, IH), 3.03 (s, 3H), 1.41 (t, 3H), 1.24 (d, 6H).
15 δ 9.00 (s, IH, NH), 8.60 (dd, IH), 7.12 (m, 2H), 6.55 (s, IH), 4.16 (q, 2H), 3.42 (m, 4H), 3.03 (m,
IH), 1.41 (t, 3H), 1.24 (d, 6H).
16 δ 8.40 (br s, IH), 8.20 (m, IH), 7.20 (dd, 2H), 6.52 (s, IH), 4.57 (q, 2H), 3.40 (m, 2H), 3.00 (s,
3H), 1.44 (t, 6H), 1.34 (s, 9H).
17 δ 8.38 (dd, IH), 8.02 (br s, IH, NH), 7.12 (m, 2H), 6.60 (s, IH), 4.57 (q, 2H), 3.60 (t, 2H), 3.20
(t, 3H), 3.00 (s, 3H), 1.60 (m, 2H) 1.44 (t, 6H), 1.34 (s, 9H).
18 δ 8.40 (dd, IH), 8.04 (br s, IH, NH), 7.18(m, 2H), 6.41 (s, IH), 4.56 (q, 2H), 3.10 (s, 3H), 3.08
(m, IH), 3.03 (s, 3H), 1.96 (m, IH) 1.34 (t, 3H), 0.94 (m, 4H).
19 δ 8.34 (dd, IH), 8.06 (br s, IH, NH), 7.18(m, 2H), 6.41 (s, IH), 4.56 (q, 2H), 3.40 (m, 4H), 1.96
(m, IH) 1.34 (t, 3H), 1.24 (m, 6H) 0.94 (m, 4H).
20 δ 8.82 (dd, IH), 8.00 (br s, IH, NH), 7.18(m, 2H), 6.41 (s, IH), 6.24 (br s, IH, NH) 4.56 (q, 2H),
3.42 (q, 2H), 1.96 (m, IH) 1.34 (t, 3H), 1.26 (t, 3H), 0.98 (m, 2H), 0.80 (m, 2H).
21 δ 8.36 (br s, IH, NH), 8.20 (dd, IH), 7.12(m, 2H), 6.42 (s, IH), 5.80 (m, IH), 5.24 (m, 2H), 4.56
(q, 2H), 4.16 (m, 2H), 3.10 (s, 3H), 1.98 (m, IH) 1.42 (t, 3H), 1.26 (t, 3H) 0.94 (m, 2H), 0.80 (m, 2H).
22 δ 9.00 (br s, IH, NH), 8.62 (dd, IH), 7.18(m, 2H), 6.56 (s, IH), 4.18 (q, 2H), 3.10 (s, 3H), 3.06 (s,
3H), 2.42 (d, 2H), 1.98 (m, IH) 1.46 (t, 3H), 0.98 (d, 6H).
23 δ 9.00 (br s, IH, NH), 8.60 (dd, IH), 7.18(m, 2H), 6.52 (s, IH), 4.14 (q, 2H), 3.40 (m, 4H), 2.44
(d, 2H), 1.98 (m, IH) 1.46 (t, 3H), 1.20 (t, 6H), 0.98 (d, 6H).
24 δ 9.04 (br s, IH, NH), 8.78 (dd, IH), 7.62 (m, IH), 7.20 (t, IH), 6.60 (s, IH), 6.42 (br s, IH, NH),
4.18 (q, 2H), 3.62 (q, 2H), 2.46 (d, 2H), 1.98 (m, IH) 1.48 (t, 3H), 1.22 (t, 3H), 1.02 (d, 6H).
25 δ 9.00 (br s, IH, NH), 8.60 (dd, IH), 7.62 (m, IH), 7.20 (m, 2H), 6.60 (s, IH), 5.82 (m, IH), 5.28
(m, 2H), 4.12 (q, 2H), 3.00 (s, 3H), 2.52 (d, 2H), 1.98 (m, IH) 1.48 (t, 3H), 1.00 (d, 6H).
31 δ 8.60 (IH, NH), 8.00 (d, IH), 7.90 (dd, IH), 7.40 (m, 2H), 6.71 (s, IH), 6.20 (t, IH, NH), 5.22
(m, 2H), 3.42 (m, 2H), 1.35 (s, 9H), 1.22 (t, 3H).
32 δ 9.23 (IH, NH), 7.64 (dd, IH), 7.30 (m, 2H), 7.23 (dd, IH), 6.91 (s, IH), 5.33 (m, 2H), 3.62 (q,
2H), 3.20 (q, 2H), 1.35 (s, 9H), 1.22 (t, 3H), 1.10 (t, 3H). ™p 1H NMR Data (CDCI3 solution unless indicated otherwise)3
33 δ 9.00 (IH, NH), 8.00 (m, 2H), 7.45 (m, 2H), 6.71 (s, IH), 6.42 (t, IH, NH), 5.82 (d, IH), 3.46 (q,
2H), 1.36 (t, 3H), 1.28 (s, 9H).
34 δ 9.20 (IH, NH), 8.00 (m, IH), 7.60 (dd, IH), 7.20 (m, 2H), 6.91 (dd, IH), 6.87 (s, IH), 5.82 (d,
IH), 3.56 (q, 2H), 3.20 (q, 2H), 1.35 (s, 9H), 1.22 (t, 6H).
35 δ 8.80 (s, IH, NH), 8.00 (d, IH), 7.90 (d, IH), 7.42 (m, 2H), 6.70 (s, IH), 6.40 (br s, IH, NH),
4.82 (m, 4H), 4.18 (m, 2H), 1.31 (s, 9H), 1,18 (t, 3H).
36 δ 9.20 (s, IH, NH), 7.70 (dd, IH), 7.32 (m, 2H), 6.92 (dd, IH), 6.80 (s, IH), 4.82 (m, 4H), 3.48
(m, 4H), 1.31 (s, 9H), 1,25 (t, 6H).
37 δ 8.20 (br s, IH, NH), 7.86 (m, 3H), 7.45 (dd, IH), 7.40 (t, IH), 6.45 (s, IH), 5.82 (d, IH), 5.00
(d, IH), 4.06 (m, 2H), 1.28 (s, 9H).
38 δ 8.06 (m, 3H), 7.45 (m, 2H), 6.55 (s, IH), 5.87 (d, IH), 5.00 (d, IH), 3.86 (m, 4H), 1.28 (s, 9H).
39 δ 8.26 (br s, IH, NH), 7.86 (m, 3H), 7.45 (m, 2H), 6.65 (s, IH), 6.40 (br s, IH, NH), 5.82 (d, IH),
5.00 (d, IH), 2.80 (m, IH), 1.28 (s, 9H), 0.90 (m, 2H), 0.60 (m, 2H).
44 δ 7.44 (m, 3H), 7.12 (dd, IH), 6.76 (s, IH), 4.60 (q, 2H), 2.86 (m, IH), 1.42 (t, 3H), 1.38 (s, 9H),
0.86 (m, 2H), 0.68 (m, 2H).
45 δ 7.44 (m, 3H), 7.12 (dd, IH), 6.70 (s, IH), 4.60 (m, 4H), 3.82 (m, 2H), 1.42 (t, 3H), 1.38 (s, 9H).
46 δ 7.42 (m, 3H), 7.10 (dd, IH), 6.80 (s, IH), 6.52 (s, IH, NH), 5.92 (m, IH), 5.20 (m, 2H), 4.60
(m, 2H), 4.02 (m, 2H), 1.42 (t, 3H), 1.38 (s, 9H).
47 δ 7.42 (m, 3H), 7.10 (dd, IH), 6.80 (s, IH), 6.52 (s, IH, NH), 4.60 (m, 2H), 4.20 (m, 2H), 2.20
(m, IH), 1.42 (t, 3H), 1.38 (s, 9H).
48 (Acetone--^) δ 1.18 (t, 3H), 1.3 (s, 9H), 1.4 (t, 3H), 3.0 (s, 3H), 3.4 (m, 2H), 4.5 (q, 2H), 6.9 (s,
IH), 7.1 (t, IH), 7.4 (d, IH), 7.8 (d, IH), 7.9 (s, IH), 9.5 (br s, IH).
49 (Acetone-- ) δ 1.29 (s, 9H), 1.39 (t, 3H), 3.0 (m, 6H), 4.5 (q, 2H), 6.8 (s, IH), 7.1 (d, IH), 7.4 (t,
IH), 7.8 (d, IH), 7.9 (s, IH), 9.5 (br s, IH).
50 DMSO-d6) δ 1.13 (t, 3H), 1.29 (s, 9H), 3.3 (q, 2H), 5.31 (d, 2H), 7.0 (s, IH), 7.4 (t, IH), 7.59 (d,
IH), 7.89 (d, IH), 8.16 (s, IH), 8.47 (t, IH), 10.3 (br s, IH).
51 δ 7.82 (s, IH), 7.80 (dd, IH), 7.62 (s, IH, NH), 7.40 (m, 2H), 6.48 (s, IH), 6.00 (s, IH, NH), 4.58
(q, 2H), 4.24 (m, IH), 1.42 (t, 3H), 1.38 (s, 9H), 1.26 (d, 3H), 1.20 (d, 3H).
52 δ 8.02 (d, IH), 7.72 (d, IH), 7.50 (s, IH), 7.42 (t, IH), 6.45 (s, IH), 6.05 (s, IH), 4.56 (q, 2H),
3.58 (m, 2H), 2.95 (t, 2H), 1.44 (t, 3H), 1.34 (s, 9H).
53 δ 8.02 (d, IH), 7.68 (d, IH), 7.65 (s, IH), 7.40 (t, IH), 6.54 (s, IH), 6.28 (s, IH), 4.15 (s, 3H),
3.56 (d of t, IH), 2.94 (t, 2H), 1.34 (s, 9H).
54 δ 7.85 (d, IH), 7.57 (t, IH), 7.39 (d, IH), 6.22 (s, IH), 4.29 (s, IH), 3.99 (s, 3H), 3.18 (s, 2H),
1.22 (s, 9H). 56 (Acetone--t6) δ 1.2 (t, 3H), 1.30 (s, 9H), 3.4 (q, 2H), 5.0-5.1 (m, IH), 5.17 (dd, 2H), 6.0-6.1 (m,
IH), 6.96 (s, IH), 7.4 (t, IH), 7.6 (d, IH), 7.7 (br s, IH), 7.9 (d, IH), 8.2 (s, IH), 9.5 (br s, IH). 58 δ 8.20 (m, IH), 7.96 (m, IH), 7.80 (br s, IH, NH), 7.20 (m, IH), 6.49 (s, IH), 4.62 (q, 2H), 3.50
(q, 2H), 1.42 (t, 3H), 1.32 (s, 9H), 1.26 (t, 3H). N P IH NMR Data (CDCI3 solution unless indicated otherwise)3
59 δ 9.32 (br s, IH, NH), 7.66 (m, IH), 7.18 (dd, IH), 7.00 (t, IH), 6.69 (s, IH), 4.62 (q, 2H), 3.60
(q, 2H), 3.34(q, 2H), 1.42 (t, 6H), 1.32 (s, 9H), 1.26 (t, 3H).
60 δ 8.30 (br s, IH, NH), 8.16 (m, IH), 7.90 (m, IH), 7.20 (t, IH), 6.59 (s, IH), 4.62 (m, 4H), 3.80
(m, 2H), 1.42 (t, 3H), 1.32 (s, 9H).
61 δ 8.32 (s, IH, NH), 7.86 (m, 2H), 7.58 (m, 2H), 6.58 (s, IH), 6.30 (s, IH, NH), 4.58 (q, 2H), 3.24
(t, 2H), 1.92 (m, IH), 1.42 (t, 3H), 1.31 (s, 9H), 0.96 (d, 6H).
62 δ 8.38 (s, IH, NH), 7.86 (m, 2H), 7.58 (m, 2H), 6.58 (s, IH), 6.30 (s, IH, NH), 4.58 (q, 2H), 3.28
(m, 2H), 1.92 (m, IH), 1.42 (t, 3H), 1.31 (s, 9H), 1.00 (m, IH), 0.66 (m, 2H), 0.32 (m, 2H).
63 δ 7.78 (s, IH), 7.73 (d, IH), 7.58 (d, IH), 7.58 (t, IH), 6.53 (s, IH), 4.57 (q, 2H), 4.43 (s, 2H),
3.67 (d, 2H), 1.45 (t, 3H), 1.34 (s, 9H) 1.27 (t, 3H).
64 δ 7.72 (d, IH), 7.69 (s, IH), 7.57 (d, IH), 7.58 (t, IH), 6.53 (s, IH), 4.57 (q, 2H), 4.37 (s, 2H),
2.94 (m, IH), 1.45 (t, 3H), 1.34 (s, 9H) 0.97 (m, 2H).
65 δ 7.80 (s, IH), 7.73 (d, IH), 7.71 (d, IH), 7.47 (t, IH), 6.54 (s, IH), 4.59 (q, 2H), 4.42 (s, 2H),
3.58 (t, 2H), 1.66 (m, 2H), 1.45 (t, 3H), 1.35 (s, 9H), 0.95 (t, 3H).
66 δ 7.75 (d, IH), 7.66 (s, IH), 7.55 (d, IH), 7.48 (t, IH), 6.52 (s, IH), 4.76 (m, IH), 4.57 (q, 2H),
4.39 (s, 2H), 2.00 (m, 2H), 2.70 (m, 6H), 1.45 (t, 3H), 1.35 (s, 9H).
67 δ 9.58 (s, IH), 7.87 (s, IH), 7.86 (d, IH), 7.15 (t, IH), 6.71 (s, IH), 4.34 (q, 2H), 3.62 (s, 3H),
1.12 (t,3H), 1.11 (s,9H).
68 δ 9.24 (s, IH), 7.57 (s, IH), 7.55 (d, IH), 7.04 (d, IH), 6.70 (s, IH), 6.70 (br s, IH), 4.45 (q, 2H),
3.33 (q, 2H), 2.28 (s, 3H), 1.30 (t, 3H), 1.22 (t, 3H), 1.12 (s, 9H).
69 δ 8.23 (s, IH), 7.58 (d, IH), 7.22 (s, IH), 7.17 (d, IH), 6.62 (s, IH), 4.56 (q, 2H), 3.8-3.6 (br m,
2H), 3.16 (br q, 2H), 2.20 (s, 3H), 1.43 (t, 3H), 1.33 (s, 9H), 1.25 (t, 3H), 1.06 (t, 3H).
71 δ 8.86 (dd, IH), 7.80 (m, IH), 7.16 (m, IH), 6.42 (s, IH), 4.58 (q, 2H), 1.51 (s, 9H), 1.42 (t, 3H),
1.32 (s,9H).
72 δ 9.04 (br s, IH, NH), 8.78 (dd, IH), 7.62 (m, IH), 7.20 (t, IH), 6.60 (s, IH), 4.18 (q, 2H), 2.46
(d, 2H), 1.98 (m, IH) 1.48 (t, 3H), 1.02 (d, 6H).
73 δ 8.62 (dd, IH), 7.92 (br s, IH, NH), 7.66 (m, IH), 7.24 (m, IH), 6.48 (s, IH), 4.56 (q, 4H), 4.18
(q, 2H), 3.00 (m, IH), 1.31 (t, 3H), 1.28 (t, 3H), 1.24 (d, 6H).
74 δ 8.52 (dd, IH), 7.80 (br s, IH, NH), 7.62 (m, IH), 7.28 (m, IH), 6.48 (s, IH,), 4.56 (q, 4H), 4.20
(q, 2H), 3.00 (m, IH), 1.31 (t, 3H), 1.28 (t, 3H), 1.24 (d, 6H).
75 δ 8.66 (d, IH), 7.26 (s, IH), 6.78 (d, IH), 6.47 (s, IH), 4.57 (q, 2H), 3.90 (s, 3H), 3.89 (s, 3H),
1.44 (t, 3H), 1.33 (s, 9H).
76 δ 8.57 (d, IH), 7.60 (s, IH), 6.78 (d, IH), 6.47 (s, IH), 4.56 (q, 2H), 4.36 (q, 2H), 3.89 (s, 3H),
1.44 (t, 3H), 1.38 (t, 3H), 1.33 (s, 9H).
77 δ 8.55 (d, IH), 7.57 (s, IH), 6.78 (d, IH), 6.47 (s, IH), 5.22 (septet, IH), 4.56 (q, 2H), 4.36 (q,
2H), 3.89 (s, 3H), 1.47 (t, 3H), 1.34 (d, 6H), 1.33 (s, 9H).
78 δ 8.00 (m, 4H), 7.45 (t, IH), 6.61 (s, IH), 5.86 (d, IH), 4.92 (d, IH), 4.40 (q, 2H), 1.36 (t, 3H),
1.28 (s,9H). N p 1H NMR Data (CDCI3 solution unless indicated otherwise)
79 δ 8.00 (s, IH), 8.00 (dd, IH), 7.90 (d, IH), 7.42 (t, IH), 6.54 (s, IH), 6.40 (br s, 4.92 (m, 4H)
4.40 (q, 2H), 1.36 (t, 3H), 1.28 (s, 9H). 81 (DMSO--i6) δ 1.29 (s, 9H), 1.3 (t, 3H), 3.88 (s, 3H), 4.4 (q, 2H), 7.0 (s, IH), 7.5 (t, IH), 7.7 (d
IH), 8.0 (d, IH), 8.4 (s, IH), 10.3 (br s, IH).
83 δ 8.04 (d, IH), 7.80 (d, IH), 7.42 (t, IH), 6.52 (s, IH), 4.73 (q, 2H), 4.58 (m, 2H), 1.42 (t, 3H)
1.38 (s, 9H).
84 δ 8.34 (s, IH), 8.04 (d, IH), 7.82 (d, IH), 7.42 (t, IH), 6.62 (s, IH), 4.90 (d, 2H), 4.62 (q, 2H)
2.52 (t, IH), 1.42 (t, 3H), 1.38 (s, 9H).
85 δ 8.24 (s, IH), 8.06 (d, IH), 7.82 (dd, IH), 7.42 (t, IH), 6.58 (s, IH), 6.00 (m, IH), 5.32 (m, 2H)
4.80 (d, 2H), 4.60 (q, 2H), 2.52 (t, IH), 1.42 (t, 3H), 1.38 (s, 9H).
86 δ 8.24 (s, IH), 8.06 (d, IH), 7.82 (dd, IH), 7.42 (t, IH), 6.58 (s, IH), 4.60 (d, 2H), 4.32 (t, 2H)
1.76 (m, 2H), 1.42 (t, 3H), 1.38 (s, 9H).
87 δ 7.90 (d, IH), 7.72 (d, 2H), 7.55 (s, IH), 7.30 (t, IH), 6.50 (s, IH), 4.56 (q, 2H), 3.91 (s, 3H)
2.52 (s, 3H), 1.44 (t, 3H), 1.34 (s, 9H).
88 δ 7.92 (d, IH), 7.71 (d, 2H), 7.52 (s, IH), 7.30 (t, IH), 6.47 (s, IH), 4.57 (q, 2H), 4.37 (q, 2H)
2.52 (s, 3H), 1.42 (t, 3H), 1.40 (t, 3H), 1.34 (s, 9H).
89 δ 8.00 (m, 2H), 7. 70 (br s, IH, NH), 7.18 (t, IH), 6.48 (s, IH,), 4.56 (q, 4H), 4.42 (q, 2H),1.31
(m, 6H), 1.24 (s, 9H).
90 δ 7.93 (d, IH), 7.73 (d, IH), 7.53 (s, IH), 7.30 (t, IH), 6.47 (s, IH), 4.57 (q, 2H), 4.27 (t, 2H),
2.53 (s, 3H), 1.80 (m, 2H), 1.44 (t, 2H), 1.35 (s, 9H), 1.04 (t, 3H).
91 δ 7.95 (d, IH), 7.75 (d, IH), 7.75 (s, IH), 7.32 (t, IH), 6.48 (s, IH), 4.80 (m, IH), 4.65-4.50 (m,
5H), 4.59 (q, 2H), 2.53 (s, 3H), 1.45 (t, 3H), 1.35 (s, 9H).
92 δ 7.90 (d, IH), 7.68 (d, IH), 7.52 (s, IH), 7.30 (t, IH), 6.47 (s, IH), 5.23 (septet, IH), 4.57 (q,
2H), 2.52 (s, 3H), 1.42 (t, 2H), 1.37 (d, 6H), 1.35 (s, 9H).
93 δ 7.92 (d, IH), 7.73 (d, IH), 7.54 (s, IH), 7.31 (t, IH), 4.57 (q, 2H), 4.15 (d, 2H), 2.53 (s, 3H),
1.44 (t, 2H), 1.35 (s, 9H), 1.29 (m, IH), 0.64 (m, 2H), 0.36 (m, 2H).
94 δ 7.93 (d, IH), 7.75 (d, IH), 7.53 (s, IH), 7.31 (t, IH), 6.47 (s, IH), 6.05 (dd of t, IH), 5.42 (d,
IH), 5.25 (d, IH), 4.82 (m, 2H), 4.57 (q, 2H), 2.53 (s, 3H), 1.44 (t, 2H), 1.35 (s, 9H).
95 δ 7.86 (d, IH), 7.78 (d, IH), 7.63 (s, IH), 6.97 (d, IH), 6.45 (s, IH), 4.56 (q, 2H), 4.36 (q, 2H),
4.11 (q, 2H), 1.40 (m, 9H), 1.32 (s, 9H).
96 δ 7.86 (dd, IH), 7.59 (s, IH), 6.97 (d, IH), 6.45 (s, IH), 4.56 (q, 2H), 4.36 (q, 2H), 3.91 (s, 3H),
1.44 (t, 3H), 1.39 (t, 3H), 1.33 (s, 9H).
97 δ 8.60 (d, IH), 8.43 (s, IH), 7.62 (d, IH), 7.20 (t, IH), 6.44 (s, IH), 4.60 (q, 2H), 4.42 (q, 2H),
3.94 (s, 3H), 1.46 (t, 3H), 1.42 (t, 3H), 1.34 (s, 9H).
98 δ 8.04 (d, IH), 7. 94 (br s, IH, NH), 7.80 (m, 2H), 7.40 (t, IH), 6.48 (s, IH), 4.58 (q, 4H), 1.61 (s,
9H), 1.44 (t, 3H), 1.33 (s, 9H).
99 δ 7.92 (s, IH), 7.80 (d, IH), 7.65 (s, IH), 7.24 (d, IH), 6.47 (s, IH), 4.56 (q, 2H), 4.37 (q, 2H),
2.57 (s, 3H), 1.44 (t, 3H), 1.40 (t, 3H), 1.33 (s, 9H). ™p NMR Data (CDCI3 solution unless indicated otherwise)3
100 δ 7.85 (d, IH), 7.83 (s, IH), 7.64 (s, IH), 7.24 (d, IH), 6.47 (s, IH), 5.25 (septet, IH), 4.56 (q,
2H), 2.57 (s, 3H), 1.44 (t, 3H), 1.38 (d, 6H), 1.33 (s, 9H).
101 δ 8.30 (s, IH), 7.87 (d, IH), 7.77 (s, IH), 6.92 (d, IH), 6.58 (s, IH), 5.21 (septet, IH), 4.56 (q,
2H), 3.84 (s, 3H), 1.42 (t, 3H), 1.32 (d, 6H), 1.28 (s, 9H). 107 (DMSO---6) δ 1.0 (s, 9H), 2.0 (s, 3H), 3.38 (s, 3H), 3.8 (s, 3H), 5.4 (s, IH), 7.2 (d, IH), 7.3 (t, IH), 7.4 (s, IH), 7.5 (d, IH), 11.3 (s, IH).
110 δ 8.7 (br s, IH), 7.83-7.88 (m, 2H), 7.36-7.38 (m, 2H), 6.6 (s, IH), 4.7 (m, IH), 2.3 (s, IH), 1.55
(s, 3H), 1.53 (s, 3H), 1.4 (s, 9H).
111 δ 7.96 (d, IH), 7.55 (d, IH), 7.47 (s, IH), 7.34 (t, IH), 6.45 (s, IH), 4.16 (s, IH), 3.04 (m, 4H),
3.18 (s, 2H), 1.34 (s, 9H).
114 δ 11.20 (s, IH), 10.30 (s, IH), 8.14 (s, IH), 7. 94 (m, IH), 7.74 (m, IH), 7.40 (m, 2H), 7.11 (s,
IH), 5.68 (d, IH), 4.90 (d, IH), 2.15 (s, 3H), 1.32 (s, 9H).
115 δ 8.00 (m, 2H), 7. 64 (s, IH), 7.40 (m, 2H), 6.54 (s, IH), 4.91 (m, 4H), 2.28 (s, 3H), 1.32 (s, 9H)
116 δ 7.88 (d, IH), 7.65 (d, IH), 7.47 (s, IH), 7.27 (t, IH), 6.48 (s, IH), 4.16 (s, IH), 2.81 (t, 2H)
2.71 (t, 2H), 1.90 (m, 2H), 3.18 (s, 2H), 1.34 (s, 9H).
117 (DMSO-- ) δ 11.2 (s, IH), 10.2 (br s, IH), 8.0 (s, IH), 7.7 (d, IH), 7.35-7.38 (m, 3H), 7.0 (s
IH), 6.0 (m, IH), 5.1 (d, 2H), 4.9 (d, IH), 2.51 (s, 3H), 1.29 (s, 9H).
124 δ 8.04 (m, 2H), 7. 60 (dd, IH), 7.46 (t, 2H), 6.64 (s, IH), 4.16 (s, 3H), 3.40 (m, IH), 1.32 (s, 9H)
1.13 (d, 6H).
125 δ 8.36 (s, IH), 8.16 (dd, IH), 7. 94 (s, IH), 7.60 (m, IH), 7.52 (t, IH), 6.54 (s, IH) 4.15 (s, 3H)
3.00 (m, 2H), 1.35 (m, 4H), 1.28 (s, 9H), 0.90 (t, 3H).
127 δ 8.14 (s, IH), 7. 94 (m, 3H), 7.64 (m, IH), 7.44 (t, IH), 6.61 (s, IH), 5.88 (d, IH), 4.93 (d, IH)
2.65 (s, 3H), 1.32 (s, 9H).
128 δ 8.10 (m, IH), 8.00 (m, IH), 7. 90 (br s, IH), 7.60 (dd, IH), 7.42 (t, IH), 6.56 (s, IH), 4.71 (m
4H), 2.62 (s, 3H), 1.32 (s, 9H).
129 (DMSO-rf6) δ 10.3 (br s, IH), 8.0 (d, IH), 7.7 (d, IH), 7.5 (t, IH), 7.0 (s, IH), 6.0 (m, IH), 5.1 (d:
2H), 4.9 (d, IH), 2.58 (s, 3H), 1.29 (s, 9H).
130 δ 7.82 (s, IH), 7.80 (dd, IH), 7.62 (s, IH, NH), 7.40 (d, 2H), 6.48 (s, IH), 4.58 (q, 2H), 1.42 (t
3H), 1.38 (s, 9H).
131 δ 8.42 (s, IH, NH), 8.20 (dd, IH), 8.00 (s, IH, NH), 7.74 (d, IH), 7.40 (t, IH), 6.68 (s, IH), 4.58
(q, 2H), 2.92 (s, 3H), 1.42 (t, 3H), 1.38 (s, 9H).
132 δ 8.40 (s, IH, NH), 8.20 (dd, IH), 7.80 (s, IH, NH), 7.74 (d, IH), 7.40 (t, IH), 6.68 (s, IH), 4.40
(m, 4H), 1.38 (s, 9H).
133 δ 8.42 (s, IH, NH), 8.20 (dd, IH), 8.00 (s, IH, NH), 7.74 (d, IH), 7.40 (t, IH), 6.68 (s, IH), 4.58
(q, 2H), 3.22 (s, 3H), 1.42 (t, 3H), 1.38 (s, 9H).
134 δ 8.22 (s, IH, NH), 8.20 (dd, IH), 8.00 (s, IH, NH), 7.74 (d, IH), 7.40 (t, IH), 6.68 (s, IH), 4.58
(q, 2H), 1.42 (t, 3H), 1.38 (s, 9H).
135 δ 7.86 (s, IH), 7.80 (dd, IH), 7.60 (s, IH, NH), 7.40 (d, 2H), 6.48 (s, IH), 4.58 (q, 2H), 1.42 (t,
3H), 1.38 (s, 9H). C™pd IH NMR Data (CDCI3 solution unless indicated otherwise)3
136 δ 7.62 (s, IH, NH), 7.36 (m, 2H), 7.08 (dd, IH,), 6.86 (dd, IH), 6.60 (dd, IH), 6.42 (s, IH), 4.58
(q, 2H), 4.00 (q, ZH), 1.42 (m, 6H), 1.31 (s, 9H).
137 δ 7.60 (s, IH, NH), 7.364(m, 2H), 7.08 (dd, IH,), 6.86 (dd, IH), 6.60 (dd, IH), 6.40 (s, IH), 4.58
(q, 2H), 4.00 (t, 2H), 1.90 (m, 2H), 1.52 (m, 2H), 1.42 (t, 3H), 1.31 (s, 9H), 0.97 (s, 3H).
138 δ 7.62 (s, IH, NH), 7.36 (m, IH), 7.28 (m, IH,), 7.00 (m, IH), 6.60 (dd, IH), 6.40 (s, IH), 4.58
(q, 2H), 4.24 (t, 2H), 2.20 (m, 2H), 1.52 (m, 2H), 1.42 (t, 3H), 1.31 (s, 9H).
139 δ 8.01 (s, IH), 7.80 (m, 2H), 7.22 (m, 2H), 7.20 (t, IH), 6.52 (s, IH), 4.56 (q, 2H), 1.43 (t, 3H),
1.33 (s, 9H).
141 δ 7.92 (s, IH), 7.80 (d, IH), 7.65 (s, IH), 7.24 (d, IH), 6.47 (s, IH), 4.56 (q, 2H), 4.37 (q, 2H),
2.57 (s, 3H), 1.44 (t, 3H), 1.40 (t, 3H), 1.33 (s, 9H).
142 δ 8.60 (s, IH, NH), 8.46 (s, IH), 8.40 (d, IH), 7.20 (d, IH), 6.60 (s IH), 5.90 (m, IH), 5.80 (m,
IH), 4.54 (q, 2H), 4.40 (m, 2H), 4.20 (m, 2H), 1.42 (t, 3H), 1.31 (s, 9H).
144 δ 8.42 (d, IH), 7.92 (m, 2H), 7.80 (s, IH, NH), 6.60 (s, IH), 4.60 (q, 2H), 3.40 (q, 2H), 1.40 (t,
3H), 1.31 (s, 9H).
145 δ 8.50 (s, IH, NH), 8.22 (d, IH), 7.80 (t, IH), 7.30 (d, IH), 6.60 (s, IH), 4.60 (q, 2H), 3.56 (q,
2H), 3.32 (q, 2H), 1.43 (s, 9H), 1.30 (t, 3H), 1.15 (t, 3H).
146 δ 8.39 (d, IH), 8.20 (s, IH, NH), 7.92 (d, IH), 7.84 (t, IH), 7.80 (s, IH), 6.60 (s, IH), 4.60 (q,
2H), 2.96 (m, IH), 1.40 (t, 3H), 1.31 (s, 9H), 0.88 (m, 2H), 0.68 (m, 2H).
147 δ 8.42 (m, 2H), 7.92 (m, 3H, NH), 6.60 (s, IH), 4.60 (q, 2H), 4.20 (m, 2H), 2.22 (m, IH), 1.46 (t,
3H), 1.31 (s, 9H).
148 δ 8.62 (s, IH), 8.32 (s, IH), 7.42 (s, IH), 6.60 (s, IH), 4.60 (q, 2H), 3.96 (s, 3H), 2.52 (s, 3H),
1.46 (t, 3H), 1.31 (s, 9H).
149 δ 8.52 (s, IH), 8.32 (s, IH), 7.42 (s, IH), 6.60 (s, IH), 6.42 (t, IH, NH), 4.60 (q, 2H), 3.40 (q,
2H), 2.52 (s, 3H), 1.46 (t, 3H), 1.31 (s, 9H).
150 δ 8.22 (s, IH), 8.18 (s, IH), 7.82 (s, IH), 7.64 (t, IH), 6.57 (s, IH), 4.60 (q, 2H), 3.40 (q, 2H),
2.52 (s, 3H), 1.46 (t, 3H), 1.31 (s, 9H).
152 δ 8.60 (s, IH, NH), 8.38 (d, 2H), 7.60 (d, IH), 6.58 (s, IH), 6.40 (t, IH, NH), 4.58 (q, 2H), 3.60
(q, 2H), 1.45 (t, 3H), 1.31 (s, 9H), 1.28 (t, 3H).
153 δ 8.60 (s, IH, NH), 8.38 (d, 2H), 7.04 (d, IH), 6.58 (s, IH), 4.58 (q,. 2H), 3.60 (q, 2H), 3.28 (q,
2H), 1.40 (t, 3H), 1.31 (s, 9H), 1.28 (t, 3H).
154 δ 8.60 (s, IH, NH), 8.40 (d, 2H), 7.60 (d, IH), 6.58 (s, IH), 6.40 (t, IH, NH), 4.58 (q, 2H), 3.40
(t, 2H), 1.96 (m, IH), 1.31 (s, 9H), 1.28 (t, 3H), 1.4 (d, 6H).
155 δ 8.60 (s, IH, NH), 8.40 (d, 2H), 7.60 (d, IH), 6.58 (s, IH), 6.50 (t, IH, NH), 4.58 (q, 2H), 3.36
(t, 2H), 1.90 (m, IH), 1.31 (s, 9H), 1.30 (t, 3H), 1.28 (t, 3H), 0.62 (m, 2H), 0.36 (m, 2H).
157 δ 8.80 (s, IH), 8.42 (d, IH), 7.64 (d, IH), 6.58 (s, IH), 4.58 (q, 2H), 4.26 (q, 2H), 1.45 (m, 6H),
1.21 (s, 9H).
158 δ 8.42 (m, 2H), 7.92 (m, 3H, NH & aromatic), 6.60 (s, IH), 4.60 (q, 2H), 4.20 (m, 2H), 3.12 (s,
3H), 2.22 (m, IH), 1.46 (t, 3H), 1.31 (s, 9H). N P NMR Data (CDCI3 solution unless indicated otherwise)3
159 δ 8.68 (s, IH, NH), 8.40 (d, 2H), 7.04 (d, IH), 6.61 (s, IH), 5.86 (m, IH), 5.22 (m, 2H), 4.58 (q,
2H), 4.20 (d, IH), 3.80 (d, IH), 3.08 (s, 3H), 1.42 (t, 3H), 1.31 (s, 9H).
160 δ 8.80 (s, IH, NH), 8.40 (d, IH), 7.14 (dd, IH), 6.61 (s, IH), 4.58 (q, 2H), 4.40 (d, IH), 4.00 (d,
IH), 3.17 & 3.06 (2xs, 3H), 2.20 (m, IH), 1.42 (t, 3H), 1.31 (s, 9H).
161 δ 8.68 (s, IH, NH), 8.52 (s, IH), 8.40 (d, IH), 7.46 (d, IH), 6.80 (t, IH, NH), 6.61 (s, IH), 4.58
(q, 2H), 3.60 (m, 4H), 3.40 (s, IH), 1.48 (t, 3H), 1.31 (s, 9H). 163 δ 8.46 (m, 2H, NH and 1 aromatic), 7.80 (m, IH), 7.32 (dd, IH), 6.55 (s, IH), 5.82 (m, IH), 5.34 (m, 2H), 4.60 (q, 2H), 4.20 (d, IH), 3.92 (d, IH), 3.09 (2 s, 3H), 1.43 (t, 3H), 1.30 (s, 9H).
165 δ 8.40 (d, IH), 8.36 (br s, IH), 6.58 (s, IH), 6.48 (d, IH), 4.60 (q, 2H), 3.99 (s, 3H), 1.45 (q, 3H),
1.30 (s,9H).
166 δ 8.20 (br s, IH), 6.51 (s, IH), 5.80 (s, IH), 4.60 (q, 2H), 3.96 (s, 6H), 1.45 (q, 3H), 1.30 (s, 9H).
167 δ 8.16 (br s, IH), 6.56 (s, IH), 6.02 (s, IH), 5.00 (br s, IH), 4.54 (q, 2H), 3.90 (s, 3H), 1.30 (s,
9H), 1.26 (t,3H).
169 δ 8.74 (br s, IH), 7.87 (s, IH), 7.82 (d, IH), 7.82 (d, IH), 7.6 (m, IH), 7.3 (t, IH), 7.1 (d, IH) 3.5
(m, 2H), 3.3 (m, 2H), 1.66 (s, 9H), 1.2 (m, 3H), 1.1 (m, 3H).
170 δ 8.83 (br s, IH), 8.14 (s, IH), 7.84-7.88 (m, 2H), 7.56 (d, IH), 7.42 (t, IH), 6.28 (br s, IH), 3.4
(q, 2H), 1.6 (s, 9H), 1.27 (t, 3H).
171 δ 8.75 (br s, IH), 7.86-7.89 (m, 3H), 7.36-7.39 (m, 2H), 2.3 (s, 3H), 1.66 (s, 9H).
172 δ 8.0 (s, IH), 7.99 (s, IH), 7.92 (br s, IH), 7.7 (d, IH), 7.5 (d, IH), 7.4 (t, IH), 6.2 (m, IH), 4.2
(q, 2H), 3.5 (m, 2H), 1.5 (t, 3H), 1.2 (t, 3H).
183 δ 7.99 (s, IH), 7.96 (s, IH), 7.78 (d, IH), 7.7 (br s, IH), 7.47 (d, IH) 7.4 (t, IH), 6.2 (br s, IH),
3.4 (q, 2H), 2.56 (s, 3H), 1.59 (s, 9H), 1.2 (t, 3H).
184 δ 8.0 (s, IH), 7.88 (br s, IH), 7.6 (d, IH), 7.4 (s, IH), 7.3 (t, IH), 7.0 (d, IH), 3.5 (m, 2H), 3.3 (m,
2H), 2.55 (s, 3H), 1.6 (s, 9H), 1.3 (m, 3H), 1.1 (m, 3H).
185 δ 8.0 (s, IH), 7.9 (br s, IH), 7.6 (d, IH), 7.4 (s, IH), 7.3 (t, IH), 7.0 (d, IH), 3.5 (m, 2H), 3.3 (m,
2H), 2.89 (t, 2H), 1.7 (q, 2H), 1.6 (s, 9H), 1.3 (m, 3H), 1.1 (m, 3H), 0.99 (t, 3H).
186 δ 8.0 (dd, IH), 798 (s, IH), 7.94 (s, IH), 7.79 (dd, IH), 7.55 (br s, IH), 7.4 (t, IH), 4.38 (q, 2H),
2.96 (q, 2H), 1.59 (s, 9H), 1.4 (t, 3H), 1.33 (t, 3H).
187 δ 8.02 (d, IH), 8.0 (s, IH), 7.96 (s, IH), 7.7 (d, IH), 7.6 (br s, IH), 7.4 (t, IH), 2.9 (q, 2H), 2.62
(s, 3H), 1.6 (s, 9H), 1.34 (t, 3H).
188 (DMSO--i6) δ 11.2 (s, IH), 9.6 (br s, IH), 8.5 (s, IH), 8.0 (d, IH), 7.0-7.7 (m, IH), 7.29-7.36 (m,
2H), 2.8 (q, 2H), 2.15 (s, 3H), 1.54 (s, 9H), 1.16 (t, 3H).
189 δ 7.9 (s, IH), 7.34-7.36 (m, 2H), 7.2 (t, IH), 7.0 (dd, IH), 6.6 (dd, IH), 4.5 (m, IH), 2.55 (s, 3H),
1.59 (s, 9H), 1.35 (s, 3H), 1.33 (s, 3H).
190 δ 7.93 (s, IH), 7.36-7.37 (m, 2H), 7.22 (t, IH), 7.0 (dd, IH), 6.6 (dd, IH), 4.0 (q, 2H), 2.56 (s,
3H), 1.59 (s,9H), 1.41 (t,3H).
191 δ 8.2 (s, IH), 7.8 (br s, IH), 7.59-7.62 (m, 2H), 7.39 (t, IH), 7.15 (d, IH), 3.5 (m, 2H), 3.3 (m,
2H), 1.6 (s, 9H), 1.2 (m, 3H), 1.1 (m, 3H). J?P IH NMR Data (CDCI3 solution unless indicated otherwise)3
192 δ 8.18 (s, IH), 8.0 (s, IH), 7.8 (br s, IH), 7.7 (d, IH), 7.57 (d, IH), 7.4 (t, IH), 6.2 (br s, IH), 3.5
(m, IH), 1.6 (s, 9H), 1.26 (t, 3H).
193 δ 8.7 (dd, IH), 7.94 (s, IH), 7.65-7.7 (m, 2H), 7.15-7.22 (m, IH), 6.2 (br s, IH), 3.4 (m, 2H), 2.9
(q, 2H), 1.6 (s, 9H), 1.35 (t, 3H), 1.25 (t, 3H).
194 δ 8.79 (dd, IH), 7.93 (s, IH), 7.66-7.7 (m, IH), 7.16-7.23 (m, IH), 6.3 (br s, IH), 3.0 (d, 3H), 1.6
(s, 9H), 1.35 (t, 3H).
195 δ 11.20 (s, IH), 8.00 (s, IH), 7.84 (d, IH), 7.60 (s, IH, NH), 7.46 (d, IH), 7.40 (t, IH), 2.73 (s,
3H), 2.16 (s, 3H), 1.45 (s, 9H).
196 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (s, IH, NH), 7.46 (d, IH), 7.40 (t, IH), 2.73 (s, 3H), 2.24 (s,
3H), 1.45 (s, 9H).
197 δ 7.97 (s, IH), 7.74 (d, IH), 7.62 (s, IH, NH), 7.46 (d, IH), 7.40 (t, IH), 3.40 (s, 3H), 2.73 (s,
3H), 1.45 (s, 9H).
198 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (s, IH, NH), 7.46 (d, IH), 7.40 (t, IH), 6.26 (br s, IH, NH), 3.50
(q, 2H), 2.73 (s, 3H), 1.45 (s, 9H), 1.20 (t, 3H).
199 δ 8.00 (s, IH, NH), 7.64 (dd, IH), 7.52 (d, IH), 7.32 (t, IH), 7.02 (dd, IH), 3.50 (m, 2H), 3.28
(m, 2H), 2.71 (s, 3H), 1.45 (s, 9H), 1.22 (m, 6H).
200 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (m, 2H, NH & aromatic), 7.40 (t, IH), 6.56 (br s, IH, NH), 4.69
(t, IH), 4.53 (t, IH), 3.80 (m, 2H), 2.73 (s, 3H), 1.45 (s, 9H).
201 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (d, IH, aromatic), 7.46 (s, IH, NH), 7.36 (t, IH), 6.46 (br s, IH,
NH), 4.18 (m, 2H), 2.73 (s, 3H), 1.45 (s, 9H).
202 δ 8.00 (s, IH), 7.84 (d, IH), 7.80 (s, IH, NH), 7.60 (d, IH), 7.36 (t, IH), 6.46 (br s, IH, NH), 5.88 m, IH), 5.24 (m, 2H), 4.06 (t, 2H), 2.73 (s, 3H), 1.45 (s, 9H).
203 δ 8.00 (s, IH), 7.84 (d, IH), 7.80 (s, IH, NH), 7.60 (d, IH), 7.36 (t, IH), 6.46 (br s, IH, NH), 4.26
(m, 2H), 2.73 (s, 3H), 1.45 (s, 9H).
204 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (s, IH, NH), 7.46 (d, IH), 7.40 (t, IH), 4.20 (q, 2H), 3.50 (q,
2H), 1.45 (s, 9H), 1.20 (m, 6H).
205 δ 8.20 (s, IH, NH), 7.64 (dd, IH), 7.52 (d, IH), 7.32 (t, IH), 7.02 (dd, IH), 3.50 (m, 2H), 3.28
(m, 2H), 3.18 (q, 2H), 1.42 (s, 9H), 1.22 (m, 9H).
206 δ 8.00 (s, IH), 7.84 (d, IH), 7.60 (s, IH, NH), 7.56 (d, IH), 7.40 (t, IH), 6.56 (br s, IH, NH), 4.08
(m, 2H), 3.20 (q, 2H), 1.45 (s, 9H), 1.20 (t, 3H).
207 δ 8.00 (s, IH), 7.86 (s, IH, NH), 7.80 (dd, IH), 7.52 (d, IH), 7.42 (t, IH), 6.40 (t, IH, NH), 5.92
(m, IH), 5.24 (m, 2H), 4.04 (m, 2H), 3.18 (q, 2H), 1.42 (s, 9H), 1.22 (t, 3H).
209 δ 8.00 (s, IH,), 7.80 (dd, IH), 7.66 (s, IH, NH), 7.62 (d, IH,), 7.42 (t, IH), 6.60 (t, IH, NH), 4.64
(m, IH), 4.52 (m, IH), 3.80 (m, 2H), 3.04 (q, 2H), 1.42 (s, 9H), 1.22 (t, 3H).
210 δ 8.00 (s, IH,), 7.80 (dd, IH), 7.66 (s, IH, NH), 7.62 (d, IH,), 7.42 (t, IH), 6.20 (t, IH, NH), 3.50
(q, 2H), 3.04 (q, 2H), 1.42 (s, 9H), 1.22 (t, 3H).
211 δ 8.00 (s, IH,), 7.90 (s, IH, NH), 7.80 (dd, IH), 7.62 (d, IH,), 7.42 (t, IH), 6.40 (t, IH, NH), 3.20
(m, 2H), 3.04 (q, 2H), 1.80 (m, IH), 1.42 (s, 9H), 1.22 (t, 3H). ™P 1H NMR Data (CDCI3 solution unless indicated otherwise)3
212 δ 8.00 (s, IH,), 7.90 (s, IH, NH), 7.80 (dd, IH), 7.62 (d, IH,), 7.40 (t, IH), 6.40 (t, IH, NH), 3.20
(m, 2H), 3.04 (q, 2H), 1.35 (s, 9H), 1.22 (t, 3H), 1.00 (m, IH), 0.58 (m, 2H), 0.30 (m, 2H).
213 δ 8.40 (d, IH), 8.04 (s, IH, NH), 8.00 (d, IH), 7.82 (t, IH), 7.60 (t IH, NH), 3.54 (q, 2H), 3.06 (q,
2H), 1.42 (s, 9H), 1.32 (m, 6H).
214 δ 8.34 (d, IH), 8.04 (s, IH, NH), 7.82 (t, IH), 7.22 (d, IH), 3.54 (q, ZH), 3.36 (q, ZH), 3.06 (q,
2H), 1.42 (s, 9H), 1.32 (m, 9H).
215 δ 8.40 (d, IH), 8.04 (s, IH, NH), 8.00 (m, 2H), 3.34 (q, 2H), 3.06 (q, 2H), 1.42 (s, 9H), 1.32 (t,
3H), 1.00 (m, IH), 0.56 (m, 2H), 0.36 (m, 2H).
216 δ 8.40 (d, IH), 8.04 (s, IH, NH), 7.96 (d, IH), 7.84 (t, IH), 7.60 (br s, IH, NH), 3.30 (t, ZH), 3.06
(q, ZH), 1.90 9m, IH), 1.4Z (s, 9H), 1.3Z (t, 3H), 1.00 (d, 6H). Z17 δ 8.40 (d, IH), 8.04 (s, IH, NH), 7.96 (m, 3H, NH & aromatic), 4.Z2 (m, ZH), 3.06 (q, ZH), Z.ZZ
(m, IH), 1.4Z (s, 9H), 1.3Z (t, 3H). Z18 δ 8.8 (br s, IH), 7.75 (d, IH), 7.70 (s, IH), 7.59 (s, IH), 7.38 (t, IH), 7.11 (d, IH), 3.5 (m, 2H),
3.3 (m, ZH), 1.6 (s, 9H), 1.3 (m, 3H), 1.1 (m, 3H). Z19 δ 8.77 (br s, IH), 8.18 (s, IH), 7.81 (d, IH), 7.6 (s, IH), 7.56 (d, IH), 7.42 (t, IH), 6.27 (br s, IH),
3.5 (m, 2H), 1.6 (s, 9H), 1.26 (t, 3H).
220 δ 8.74 (br s, IH), 7.78 (d, IH), 7.70 (s, IH), 7.6 (s, IH), 7.6 (s, IH), 7.37 (t, IH), 7.1 (d, IH), 3.5 (m, 2H), 3.3 (m, 2H), 1.6 (s, 9H), 1.3 (m, 3H), 1.1 (m, 3H).
225 δ 8.42 (dd, IH), 7.74 (s, IH), 7.19 (m, 2H), 3.12 (q, 3H), 3.03 (s, 3H), 3.00 (s, 3H), 1.37 (s, 9H),
1.30 (t, 6H).
226 δ 8.70 (dd, IH), 7.74 (s, IH), 7.70 (m, IH,), 7.20 (t, IH), 3.42 q, 2H), 3.08 (q, 2H), 1.28 (s, 9H),
1.26 (t, 3H), 1.20 (t, 3H).
227 δ 8.45 (s, IH), 7.64 (dd, IH), 7.58 (s, IH), 7.36 (t, IH), 7.08 (d, IH), 3.20 (m, 2H), 2.99 (s, 3H),
2.70 (s, 3H), 1.44 (s, 9H), 1.05 (t, 3H).
228 δ 8.34 (s, IH), 7.74 (d, IH), 7.60 (s, IH), 7.34 (t, IH), 7.16 (s, IH), 3.12 (q, 2H), 3.06 (s, 3H),
3.00 (s, 3H), 1.42 (s, 9H), 1.25 (t, 3H).
229 δ 8.20 (s, IH,), 7.68 (dd, IH), 7.60 (s, IH,), 7.32 (t, IH), 7.02 (dd, IH), 3.32 (m, 2H), 3.28 (m,
2H), 3.10 (s, 3H), 1.45 (s, 9H), 1.22 (m, 6H).
230 δ 8.40 (d, IH), 7.80 (d, IH), 7.22 (dd, IH), 3.50 (m, 4H), 3.18 (q, 2H), 1.42 (s, 9H), 1.22 (m, 6H).
231 δ 8.40 (d, IH), 7.74 (s, IH), 7.18 (m, 2H), 3.28 (m, 2H), 3.08 (q, 2H), 3.02 (s, 3H), 1.45 (s, 9H),
1.32 (t, 3H), 1.26 (t, 3H).
237 δ 8.80 (dd, IH), 7.72 (m, IH,), 7.20 (m, IH), 6.36 (s, IH), 5.86 (m, IH,), 5.22 (m, 2H), 4.10 (m,
2H), 3.08 (q, 2H), 1.35 (s, 9H), 1.32 (t, 3H).
238 δ 1.3 (t, 3H), 1.4 (t, 3H), 1.6 (s, 9H), 3.0 (q, 2H), 4.4 (q, 2H), 7.6 (d, IH), 8.0 (s, IH), 8.3 (d, IH),
8.6 (br s, IH, NH), 8.8 (s, IH).
242 δ 8.6 (dd, IH), 7.95 (br s, 1H,NH), 7.3 (m, 2H), 7.2 (m, IH), 6.48 (s, IH), 4.6 (m, 2H), 3.63 (m,
2H), 3.49 (m, 2H), 1.95 (m, 4H), 1.44 (t, 3H), 1.34 (s, 9H).
243 δ 8.5 (dd, IH), 7.9 (br s, IH, NH), 7.18 (m, 2H), 6.48 (s, IH), 4.57 (m, 2H), 3.7 (m, 8H), 1.44 (t,
3H), 1.33 (s, 9H). ™p H NMR Data (CDCI3 solution unless indicated otherwise)3
244 δ 8.75 (dd, IH), 7.8 (br s, IH, NH), 7.45 (m, IH), 7.2 (m, IH), 6.49 (s, IH), 4.59 (m, ZH), 3.63 (s,
3H), 3.36 (s, 3H), 1.4Z (t, 3H), 1.Z6 (s, 9H). Z45 δ 8.35 (d, IH), 8.33 (br s, IH, NH), 7.8 (t, 3H), 7.43(d, IH), 6.54 (s, IH), 4.6 (q, ZH), 3.6Z (m,
4H), Z.00 (m, 4H), 1.4 (t, 3H), 1.29 (s, 9H). Z46 δ 8.4 (d, IH), 8.37 (br s, IH, NH), 7.8 (t, IH), 7.4 (d, IH), 6.55 (s, IH), 4.6 (q, ZH), 3.66 (s, 3H),
3.4 (s, 3H), 1.5 (t, 3H), 1.31 (s, 9H).
Z47 δ 8.4 (d, IH), 8.39 (br s, IH, NH), 7.85 (t, IH), 7.Z9 (d, IH), 6.55 (s, IH), 4.6 (q, ZH), 3.3^1.00
(m, 8H), 1.33 (t, 3H), 1.Z6 (s, 9H). 248 δ 8.88 (t, IH), 7.65 (s, IH), 6.98 (t, IH), 6.48 (s, IH), 5.22 (m, IH), 4.57 (q, ZH), 1.46 (t, ZH),
1.40 (d, 6H), 1.33 (s, 9H).
Z49 δ 8.83 (t, IH), 7.65 (s, IH), 6.99 (t, IH), 6.48 (s, IH), 4.56 (q, ZH), 4.30 (t, ZH), 1.80 (m, ZH),
1.47 (t, ZH), 1.33 (s, 9H), 1.03 (t, 3H). 250 δ 8.83 (t, IH), 7.64 (s, IH), 6.98 (t, IH), 6.45 (s, IH), 4.58 (q, ZH), 4.40 (q, ZH), 1.45 (t, 3H),
1.41 (t, ZH), 1.33 (s, 9H).
Z51 δ 8.83 (m, IH), 7.6Z (s, IH), 6.98 (t, IH), 6.55 (br s, IH), 6.45 (s, IH), 4.56 (q, ZH), 3.03 (d, 3H),
1.43 (t, 3H), 1.33 (s, 9H). Z52 δ 8.83 (m, IH), 7.62 (s, IH), 6.98 (t, IH), 6.55 (br s, IH), 6.49 (s, IH), 4.56 (q, 2H), 3.52 (m,
2H), 1.43 (t, 3H), 1.33 (s, 9H), 1.25 (t, 3H).
253 δ 8.23 (m, IH), 7.92 (s, IH), 6.97 (t, IH), 6.53 (s, IH), 4.56 (q, 2H), 3.55 (q, 2H), 3.22 (q, 2H),
1.43 (t, 3H), 1.33 (s, 9H), 1.27 (t, 3H), 1.14 (t, 3H).
254 δ 8.23 (m, IH), 8.02 (s, IH), 6.97 (m, IH), 6.53 (s, IH), 4.54 (q, 2H), 3.50 and 3.35 (q, 2H, amide isomers), 3.09 and 2.93 (s, 3H, amide isomers), 1.43 (t, 3H), 1.33 (s, 9H), 1.25 and 1.16 (t, 3H, amide isomers).
256 δ 8.82 (s, IH), 8.52 (d, IH), 8.00 (m, IH), 7.72 (s, IH), 6.66 (s, IH), 4.62 (q, 2H), 3.10 (s, 3H),
3.09 (s, 3H), 1.42 (t, 3H), 1.33 (s, 9H).
257 δ 8.78 (s, IH), 8.42 (d, IH), 8.10 (m, IH), 7.82 (s, IH), 7.72 (s, IH), 6.66 (s, IH), 4.62 (q, ZH),
3.8Z (q, ZH), 1.4Z (t, 3H), 1.33 (s, 9H), 1.30 (t, 3H). Z58 δ 8.72 (s, IH), 8.41 (s, IH), 8.26 (s, IH), 8.12 (s, IH), 6.59 (s, IH), 4.57 (q, 2H), 3.14 (s, 3H),
3.05 (s, 3H), 1.45 (t, 3H), 1.34 (s, 9H).
259 δ 8.90 (s, IH), 8.78 (s, IH), 8.50 (s, IH), 8.04 (s, IH), 6.56 (s, IH), 6.20 (s, IH), 4.58 (q, 2H),
3.52 (q, ZH), 1.48 (t, 3H), 1.32 (s, 9H), 1.26 (t, 3H).
260 δ 8.70 (s, IH), 8.58 (s, IH), 8.40 (s, IH), 7.80 (s, IH), 6.54 (s, IH), 6.0 (m, IH), 5.80 (m, IH),
4.57 (q, 2H), 4.51 (m, 2H), 4.30 (m, 2H), 1.47 (t, 3H), 1.34 (s, 9H).
262 δ 10.50 (s, IH), 9.00 (s, IH,), 8.40 (s, IH), 8.20 (s, IH), 6.96 (s, IH,), 5.92 (m, 2H), 5.30 (m, 4H),
4.32 (q, 2H), 4.12(m, 2H), 3.80 (m, 2H), 1.32 (t, 3H), 1.30 (s, 9H).
263 δ 8.70 (s, IH,), 8.42 (s, IH), 8.18 (m, IH,), 8.08 (s, IH), 6.58 (s, IH), 4.57 (q, 2H), 3.60 (q, 2H),
3.10 (s, 3H), 1.46 (t, 3H), 1.34 (s, 9H), 1.26 (m, 3H).
264 δ 8.68 (s, IH), 8.41 (s, IH), 8.26 (s, IH), 8.12 (s, IH), 6.59 (s, IH), 4.57 (q, ZH), 3.86 (s, ZH),
Z.12 (m, IH), 1.45 (t, 3H), 1.34 (s, 9H). ™P IH NMR Data (CDCI3 solution unless indicated otherwise)3
265 δ 8.78 (d, IH,), 8.12 (d, IH,), 6.47 (s, IH), 4.42 (q, ZH), 3.8Z (s, 3H), 3.76 (s, 3H), 1.36 (t, 3H),
1.Z9 (s, 9H). Z66 δ 8.80 (d, IH,), 8.08 (s, IH), 8.0Z (d, IH,), 6.47 (s, IH), 4.4Z (q, ZH), 4.02 (q, ZH), 1.36 (m, 6H),
1.Z9 (s, 9H). Z69 δ 9.3 (s, IH), 8.70 (d, IH), 8.65 (m, IH), 7.15 (t, IH), 6.20 (br s, IH), 4.12 (m, IH), 3.70 (t, IH),
3.50 (m, 2H), 3.30 (dd, IH), 3.15 (m, IH), 2.95 (m, IH), 2.80 (dd, IH), 1.34-1.20 (m, 6H),
1.17 (s, 9H).
270 δ 8.37 (t, IH), 7.90 (s, IH), 6.93 (t, IH), 6.52 (s, IH), 4.55 (q, ZH), 3.12 (s, 3H), 2.97 (s, 3H),
1.43 (t, 3H), 1.33 (s, 9H).
271 δ 8.90 and 8.75 (d, IH, amide isomers), 8.18 and 8.13 (s, IH, amide isomers), 7.88 and 7.70 (m,
IH), 7.22 and 7.19 (t, IH, amide isomers), 4.58 (q, 2H), 1.45 (t, 3H), 1.34 (s, 9H).
272 δ 7.82 (s, IH), 7.60 (s, IH), 7.45 (d, IH), 7.36 (t, IH), 7.00 (d, IH), 6.50 (s, IH), 4.55 (q, ZH),
1.43 (t,3H), 1.32 (s,9H).
273 δ 7.65 (s, IH), 7.28 (s, IH), 7.21 (t, IH), 7.02 (d, IH), 7.72 (d, IH), 6.45 (s, IH), 4.45 (m, 3H),
1.42 (t, 3H), 1.33 (d, 6H), 1.32 (s, 9H).
274 δ 8.8 (br m IH, NH), 8.3 (d, IH), 7.8 (m, IH), 7.4 (d, IH), 4.6 (q, 2H), 3.14 (s, 3H), 3.06 (s, 3H),
1.42 (t,3H), 1,36 (s,9H).
275 δ 8.8 (dd, IH), 8.33 (br m, IH, NH), 7.7 (m, IH), 7.2 (m, IH), 6.2 (br s, IH), 4.6 (q, 2H), 3.5 (q,
2H), 1.37 (t, 3H), 1.29 (s, 9H), 1.24 (t, 3H).
276 δ 8.26 (dd, IH), 8.3 (br m, IH, NH), 7.2 (br s, IH), 7.17 (m, IH), 4.55 (q, ZH), 3.1 (s, 3H), 3.03
(s, 3H), 1.43 (t, 3H), 1.37 (s, 9H).
277 δ 8.78 (s, IH), 8.52 (m, IH), 7.60 (t, IH), 6.52 (s, IH), 4.59 (q, 2H), 3.42 (q, 2H), 1.37 (t, 3H),
1.34 (s,9H), 1.28 (t,3H).
278 δ 8.46 (dd, IH), 8.32 (s, IH), 7.62 (t, IH), 6.60 (s, IH), 4.59 (q, 2H), 4.28 (d, 2H), 2.30 (t, IH),
1.42 (t, 3H), 1.34 (s, 9H).
279 δ 8.40 (s, IH), 8.36 (m, IH), 7.42 (t, IH), 6.46 (s, IH), 4.50 (q, 2H), 3.28 (q, 2H), 3.13 (s, 3H),
1.42 (t, 3H), 1.34 (s, 9H), 1.30 (t, 3H).
280 δ 8.40 (s, IH), 8.38 (dd, IH), 7.60 (t, IH), 6.53 (s, IH), 5.90 (m, IH), 5.80 (m, IH), 4.56 (q, 2H),
4.46 (m, 2H), 4.20 (m, 2H), 1.42 (t, 3H), 1.34 (s, 9H).
281 δ 9.24 (s, IH), 8.58 (d, IH), 8.22 (dd, IH), 8.00 (d, IH), 6.68 (s, IH), 5.81 (m, ZH), 4.60 (m, 2H),
4.46 (m, 2H), 4.28 (m, 2H), 1.46 (t, 3H), 1.30 (s, 9H).
282 δ 8.56 (d, IH), 8.32 (dd, IH), 8.22 (t, IH), 8.00 (d, IH), 6.63 (s, IH), 4.59 (q, 2H), 4.28 (d, 2H),
2.30 (t, IH), 1.42 (t, 3H), 1.34 (s, 9H).
283 δ 8.51 (d, IH), 8.42 (t, IH), 8.38 (s, IH), 8.22 (dd, IH), 6.63 (s, IH), 4.59 (q, 2H), 4.00 (m, 2H),
1.45 (t, 3H), 1.36 (s, 9H).
284 δ 9.00 (s, IH), 8.48 (d, IH), 8.40 (t, IH), 8.36 (dd, IH), 8.00 (s, IH), 6.74 (s, IH), 4.58 (m, 2H),
4.40 (t, 2H), 3.60 (m, 2H), 1.46 (t, 3H), 1.32 (s, 9H).
285 δ 8.80 (s, IH), 7.84 (dd, IH), 7.60 (s, IH), 7.32 (m, IH), 7.02 (m, IH), 6.53 (s, IH), 5.82 (m, IH),
5.20 (m, 2H), 4.56 (q, 2H), 4.20 (m, 2H), 3.00 (s, 3H), 1.42 (t, 3H), 1.24 (s, 9H). ™P IH NMR Data (CDC13 solution unless indicated otherwise)3
286 δ 8.40 (s, IH), 7.68 (m, ZH), 7.40 (m, ZH), 6.53 (s, IH), 5.80 (m, ZH), 4.56 (q, ZH), 4.40 (m, ZH),
4.30 (m, ZH), 1.4Z (t, 3H), 1.Z4 (s, 9H).
287 δ 9.60 (s, IH), 8.60 (s, IH), 8.40 (s, IH), 6.59 (s, IH), 4.58 (m, ZH), 3.16 (s, 3H), 3.08 (s, 3H),
1.44 (t, 3H), 1.3Z (s, 9H).
288 δ 9.80 (s, IH), 9.Z0 (s, IH), 9.00 (s, IH), 8.Z0 (s, IH), 6.59 (s, IH), 4.58 (m, ZH), 3.36 (q, 2H),
1.34 (t, 3H), 1.32 (s, 9H), 1.26 (t, 3H).
289 δ 9.78 (s, IH), 9.18 (s, IH), 8.40 (s, IH), 7.72 (s, IH), 6.64 (s, IH), 4.58 (m, 2H), 4.26 (q, 2H),
2.24 (t, IH), 1.34 (t, 3H), 1.32 (s, 9H).
290 δ 9.68 (s, IH), 8.80 (s, IH), 8.20 (s, IH), 7.72 (s, IH), 6.56 (s, IH), 5.88 (m, 2H), 4.56 (q, 2H),
4.48 (m, 4H), 1.34 (t, 3H), 1.32 (s, 9H).
291 δ 9.82 (s, IH), 9.20 (s, IH), 8.40 (s, IH), 7.82 (t, IH), 6.66 (s, IH), 4.58 (m, 2H), 4.06 (m, 2H),
1.34 (t, 3H), 1.32 (s, 9H), 1.26 (t, 3H).
294 δ 8.4 (d, IH), 7.85 (br s, IH), 7.1 (m, 2H), 6.5 (s, IH), 4.5 (q, 2H), 3.6 (s, 3H), 3.2 (s, 3H), 1.4 (t,
3H), 1.3 (s, 9H).
295 δ 8.40 (s, IH), 8.16 (s, IH), 8.02 (d, IH), 7.80 (dd, IH), 7.40 (t, IH), 6.56 (s, IH), 4.54 (q, 2H),
4.40 (m, 2H), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.80 (m, 2H).
296 δ 9.00 (dd, IH), 7.80 (m, IH), 7.76 (s, IH), 7.20 (t, IH), 6.42 (s, IH), 4.54 (q, 2H), 4.40 (m, 2H),
1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.80 (m, 2H).
297 δ 8.40 (s, IH), 8.20 (d, IH), 6.80 (d, IH), 6.60 (dd, IH), 6.42 (s, 2H), 4.56 (q, 2H), 3.92 (s,3H),
3.80 (s, 3H), 1.42 (t, 3H), 1.24 (s, 9H).
298 δ 7.80 (s, IH), 7.60 (d, IH), 7.00 (d, IH), 6.80 (dd, IH), 6.42 (s, 2H), 4.56 (q, 2H), 3.82 (s, 6H),
1.42 (t, 3H), 1.24 (s, 9H).
299 δ 8.40 (dd, IH), 7.90 (s, IH), 7.20 (m, 2H), 6.42 (s, IH), 4.54 (q, 2H), 3.10 (s, 3H), 3.08 (s, 3H),
1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
300 δ 8.48 (d, IH), 8.00 (s, IH), 7.90 (s, IH), 7.62 (m, 2H), 6.42 (s, IH), 4.54 (q, 2H), 3.40 (q, 2H),
1.45 (s, 3H), 1.42 (t, 3H), 1.20 (t, 3H), 1.00 (m, 2H), 0.84 (m, 2H).
301 δ 8.60 (dd, IH), 7.90 (s, IH), 7.20 (m, 2H), 6.42 (s, IH), 5.84 (m, 2H), 4.51 (q, 2H), 4.30 (m,
4H), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
302 δ 8.80 (m, IH), 7.90 (s, IH), 7.60 (m, IH), 7.20 (m, IH), 6.60 (s, IH), 6.42 (s, IH), 4.50 (q, 2H),
4.20 (m, 2H), 2.30 (m, IH), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
303 δ 8.20 (s, IH), 7.70 (d, IH), 7.60 (s, 2H), 7.40 (t, IH), 7.20 (d, IH), 6.42 (s, IH), 4.54 (q, 2H),
3.10 (s, 3H), 3.00 (s, 3H), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
304 δ 7.90 (s, IH), 7.82 (s, IH), 7.62 (dd, IH), 7.40 (t, IH), 7.30 (d, IH), 6.42 (s, IH), 5.80 (m, 2H),
4.54 (q, 2H), 4.40 (m, 4H), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
306 δ 8.08 (s, IH), 8.00 (s, IH), 7.82 (dd, IH), 7.40 (m, 2H), 6.42 (s, IH), 6.20 (br s, IH), 4.54 (q,
2H), 3.44 (q, 2H), 1.45 (s, 3H), 1.42 (m, 6H), 1.00 (m, 2H), 0.84 (m, 2H).
307 δ 9.32 (s, IH), 8.58 (d, IH), 7.15 (m, 2H), 3.68 (t, IH), 3.57 and 3.33 (br m, 2H), 3.32 (dd, IH),
3.18 (dq, IH), 3.50 and 2.95 (br s, 3H, amide isomers), 2.94 (dq, IH), 2.81 (d d, IH), 1.23 (t, 3H), 1.17 (s, 9H). N P NMR Data (CDCI3 solution unless indicated otherwise)3
308 δ 9.32 (s, IH), 8.42 (d, IH), 7.12 (d, ZH), 3.68 (t, IH), 3.5 (br s, ZH), 3.3 (br s, ZH), 3.3 (dd, IH),
3.18 (m, IH), Z.95 (m, IH), Z.80 (dd, IH), 1.34-1.17 (m, 18H).
309 δ 9.3Z (s, IH), 8.55 (d, IH), 7.Z8 (m, IH), 7.13 (dd, IH), 3.68 (t, IH), 3.6Z (br m, ZH), 3.48 (br m, ZH), 3.31 (dd, IH), 3.17 (dq, IH), Z.95 (dq, IH), 2.81 (dd, IH), 1.9 (m, 4H), 1.23 (t, 3H), 1.17 (s,9H).
310 δ 9.32 (s, IH), 8.58 (d, IH), 7.28 (m, IH), 7.17 (dd, IH), 5.92 (br s, IH), 5.75 (br s, IH), 4.43 (br s, ZH), 4.Z9 (br s, ZH), 3.69 (t, IH), 3.31 (dd, IH), 3.17 (dq, IH), Z.95 (dq, IH), Z.81 (dd, IH), l.Z3(t,3H), 1.17 (s,9H).
311 δ 7.7 (m, IH), 7.6 (m, IH), 7.33-7.36 (m, 3H), 2.2 (s, 3H), 1.3 (s, 9H).
312 δ 8.70 (s, IH, NH), 8.42 (m, IH), 7.82 (d, ZH), 6.64 (s, IH), 4.1Z (s, 3H), 4.01 (s, 3H), 1.31 (s,
9H).
313 δ 8.4Z (d, IH), 7.9Z (m, ZH), 7.80 (s, IH, NH), 6.60 (s, IH), 4.04 (s, 3H), 3.40 (q, ZH), 1.31 (s,
9H).
314 δ 8.50 (s, IH, NH), 8.22 (d, IH), 7.80 (t, IH), 7.30 (d, IH), 6.60 (s, IH), 4.04 (s, 3H), 3.56 (q,
2H), 3.32 (q, 2H), 1.43 (s, 9H), 1.30 (t, 3H), 1.15 (t, 3H).
315 δ 8.39 (d, IH), 8.20 (s, IH, NH), 7.92 (d, IH), 7.84 (t, IH), 7.80 (s, IH), 6.60 (s, IH), 4.02 (s,
3H), 2.96 (m, IH), 1.31 (s, 9H), 0.88 (m, 2H), 0.68 (m, 2H).
316 δ 8.42 (m, 2H), 7.92 (m, IH, NH), 7.80 (s, IH), 6.60 (s, IH), 4.12 (m, 2H), 4.00 (s, 3H), 2.22 (m,
IH), 1.31 (s,9H).
317 δ 8.42 (m, 2H), 7.92 (m, IH, NH), 7.80 (s, IH), 6.60 (s, IH), 4.12 (m, 2H), 4.00 (s, 3H), 2.22 (m,
IH), 1.31 (s,9H).
318 δ 8.46 (m, 2H, NH and 1 aromatic), 7.80 (m, IH), 7.32 (dd, IH), 6.55 (s, IH), 5.82 (m, IH), 5.34
(m, 2H), 4.20 (d, 2H), 4.02 (s, 3H), 1.30 (s, 9H).
319 δ 8.34 (s, IH), 7.74 (d, IH), 7.60 (s, IH), 7.34 (t, IH), 7.16 (s, IH), 4.10 (m, 2H), 3.12 (q, 2H),
2.20 (m, IH), 1.42 (s, 9H), 1.25 (t, 3H).
326 δ 8.45 (s, IH), 7.72 (dd, IH), 7.60 (s, IH), 7.32 (t, IH), 7.08 (d, IH), 3.05 (s, 3H), 2.99 (s, 3H),
2.70 (s, 3H), 1.44 (s, 9H).
327 δ 8.80 (dd, IH), 7.72 (m, IH,), 7.20 (m, IH), 5.86 (m, 2H,), 5.22 (m, 4H), 4.10 (m, 4H), 3.08 (q,
2H), 1.35 (s, 9H), 1.32 (t, 3H).
329 δ 7.42 (m, 3H), 7.10 (dd, IH), 6.80 (s, IH), 6.52 (s, IH, NH), 4.50 (q, 2H), 4.20 (t, 2H), 2.28 (t, 2H), 2.20 (q, 2H), 1.42 (m, 6H), 1.38 (s, 9H).
331 δ 9.36 (br s, IH), 8.42 (dd, IH), 7.27 (m, 2H), 3.68 (t, IH), 3.68 (br s, 2H), 3.38 (br s, 2H), 3.30
(dd, IH), 3.18 (d of q, IH), 2.95 (d of q, IH), 2.80 (dd, IH), 1.58-1.70 (m, 6H), 1.25 (t, 3H), 1.17 (s, 9H).
332 δ 7.62 (br s, IH), 7.54 (br s, IH), 7.36 (m, 2H), 6.90 (m, IH), 6.47 (s, IH), 4.56 (q, 2H), 1.45 (t,
3H), 1.32 (s, 9H).
333 δ 7.70 (br s, IH), 7.60 (br s, IH), 7.44 (d, IH), 7.39 (t, IH), 7.02 (d, IH), 6.47 (s, IH), 4.56 (q,
2H), 1.45 (t, 3H), 1.31 (s, 9H). -j 1H NMR Data (CDCI3 solution unless indicated otherwise)3
335 δ 9.38 (br s, IH), 8.93 (dd, IH), 7.67 (m, IH), 7.13 (dd, IH), 4.36 (q, ZH), 3.64 (dd, IH), 3.53 (dd, IH), 3.23 (t, IH), 2.41 (m, ZH), 1.38 (t, 3H), 1.Z5 (s, 9H), 1.17 (t, 3H).
338 δ 8.41 (m, IH), 7.83 (br s, IH), 7.16 (dd, IH), 6.9Z (m, ZH), 7.47 (s, IH), 4.56 (q, ZH), 1.45 (t, 3H), 1.3Z (s, 9H).
340 δ 9.38 (br s, IH), 8.47 (dd, IH), 7.Z6 (m, IH), 7.13 (dd, IH), 5.90 (m, IH), 5.73 (m, IH), 4.43 (m,
ZH), 4.3Z (m, ZH), 3.64 (dd, IH), 3.53 (dd, IH), 3.Z4 (t, IH), Z.41 (m, ZH), 1.Z5 (s, 9H), 1.17 (t, 3H).
341 δ 9.38 (br s, IH), 8.45 (dd, IH), 7.Z6 (m, IH), 7.13 (dd, IH), 3.6Z (m, 3H), 3.43 (m, 3H), 3.Z3 (t,
IH), Z.41 (m, ZH), 1.90 (m, ZH), 1.Z3 (s, 9H), 1.16 (t, 3H). 34Z δ 9.38 (br s, IH); 8.38 (d, IH), 7.13 (m, ZH); 3.6Z (dd, IH); 3.58 (br s, IH); 3.53 (dd; IH); 3.Z5
(br s, IH); 3.Z3 (t, IH); 3.0Z, Z.98 (br s, 3H); Z.41 (m, ZH); 1.Z3 (s, 9H); 1.16 (t, 3H); 1.14 (t,
3H). 343 δ 9.38 (br s, IH); 8.38 (dd, IH), 7.13 (m, ZH); 3.6Z (dd, IH); 3.5Z (d of d; IH); 3.Z3 (t, IH); 3.09
(br s, 3H), Z.99 (br s, 3H); 2.41 (m, ZH); 1.23 (s, 9H); 1.16 (t, 3H).
346 δ 9.0 (br s 2H), 8.0 (m, IH), 7.25 (m, IH), 6.4 (s, IH), 4.6 (q, 2H), 4.4 (q, 2H), 1.45 (t, 3H), 1.4
(t, 3H), 1.3 (s, 9H).
347 δ 8.56 (dd, IH), 8.00 (br s, IH, NH), 7.24 (m, 2H), 6.54 (s, IH), 4.57 (q, 2H), 3.92 (s, 2H), 1.42
(t, 3H), 1.28 (s, 9H).
348 δ 8.14 (m, IH), 8.00 (dd, IH), 7.26 (s, IH), 6.26 (s, IH), 4.54 (q, 2H), 4.12 (q, 2H), 1.41 (m, 6H),
1.20 (s, 9H).
349 δ 8.65 (dd, IH), 7.85 (br s, IH), 7.65 (m, IH), 7.6 (br s, IH), 7.15 (dd, IH), 6.5 (s, IH), 4.6 (q,
2H), 3.85 (m, 2H), 1.4 (m, 3H), 1.3 (m, 3H), 1.25.
350 δ 8.56 (dd, IH), 8.00 (br s, IH, NH), 7.24 (m, 2H), 6.54 (s, IH), 4.57 (q, 2H), 3.92 (m, 2H), 3.10
(m, 2H), 1.42 (t, 3H), 1.28 (s, 9H).
351 (OMSO-d6) δ 13.1 (br s, NH), 10.0 (br s, NH), 8.4 (s, IH), 8.2 (s, IH), 7.9 (d, IH), 7.5 (d, IH),
7.3 (t, IH), 6.5 (s, IH) 3.2 (m, 2H), 1.3 (s, 9H), 1.1 (t, 3H).
353 δ 8.8 (m, IH), 7.8(m, IH), 7.7(m, IH), 7.2(m, IH), 6.2(br s, IH), 4.63(q, 2H), 3.5(m, 2H), 2.9(t,
2H), 2.63 (t, 2H), 148(t, 3H), 1.35(s, 6H), 1.29(t, 3H).
354 δ 8.64 (br s. IH), 7.91 (s, IH), 7.71 (d, IH), 7.40 (t, IH), 7.28 (d, IH), 5.90 (m, IH), 5.76 (m,
IH), 4.96 (m, IH), 4.45 (m, 2H), 4.28 (m, 2H), 3.03 (q, 2H), 2.20 (m, 4H), 1.93 (m, 2H), 1.74 (m, 2H), 1.31 (t, 3H).
355 δ 8.63 (br s. IH), 7.76 (s, IH), 7.72 (d, IH), 7.38 (t, IH), 7.16 (d, IH), 4.96 (m, IH), 3.06-3.16
(m, 8H), 2.20 (m, 4H), 1.93 (m, 2H), 1.74 (m, 2H), 1.31 (t, 3H).
356 δ 8.66 (br s. IH), 8.06 (s, IH), 7.83 (d, IH), 7.54 (d, IH), 7.39 (t, IH), 6.41 (br s. IH), 4.96 (m,
IH), 3.49 (m, 2H), 3.02 (q, 2H), 2.20 (m, 4H), 1.93 (m, 2H), 1.74 (m, 2H), 1.31 (t, 3H), 1.25 (t, 3H).
357 δ 8.62 (br slH), 8.10 (s, IH), 7.83 (d, IH), 7.55 (d, IH), 7.38 (t, IH), 6.60 (br s IH), 4.80 (m,
IH), 3.50 (m, 2H), 3.02 (q, 2H), 1.60 (d, 6H), 1.32 (t, 3H), 1.25 (t, 3H). p 1H NMR Data (CDCI3 solution unless indicated otherwise)3
359 δ 8.64 (br s IH), 7.92 (s, IH), 7.71 (d, IH), 7.41 (t, IH), 7.28 (d, IH), 5.91 (m, IH), 5.76 (m, IH), 4.79 (m, IH), 4.45 (m, ZH), 4.Z8 (m, ZH), 3.03 (q, ZH), 1.60 (d, 6H), 1.31 (t, 3H).
361 δ 8.88 (br slH), 8.58 (d, IH), 7.18 (m, ZH), 3.40 (m, 8H), 1.70 (s, 9H), 1.3Z (t, 3H).
36Z δ 8.88 (br s IH), 8.81 (dd, IH), 7.67 (m, IH), 7.18 (t, IH), 6.60 (br s IH), 3.48 (m, ZH), 3.01 (q, 2H), 1.70 (s, 9H), 1.31 (t, 3H), 1.25 (t, 3H).
363 δ 8.80 (br s IH), 8.72 (dd, IH), 7.30 (m, IH), 7.19 (dd, IH), 5.91 (m, IH), 5.76 (m, IH), 4.45 (m,
ZH), 4.31 (m, ZH), 3.03 (q, ZH), 1.70 (s, 9H), 1.31 (t, 3H).
364 δ 8.67 (br s IH), 7.75 (s, IH), 7.74 (d, IH), 7.38 (t, IH), 7.16 (d, IH), 3.04 (m, 8H), 1.70 (s, 9H),
1.31 (t, 3H). 366 δ 8.67 (br s IH), 7.90 (s, IH), 7.74 (d, IH), 7.40 (t, IH), 7.28 (d, IH), 5.91 (m, IH), 5.76 (m, IH), 4.45 (m, 2H), 4.28 (m, 2H), 3.04 (q, 2H), 1.69 (s, 9H), 1.31 (t, 3H).
3 H NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (dq)-doublet of quartets, (br s)-broad singlet, (br d)-broad d, (br m)-broad multiplet
BIOLOGICAL EXAMPLES OF THE INVENTION TEST A
Seeds of plant species selected from barnyardgrass (Echinochloa crus-galli (L.) Beauv.), downy bromegrass (Bromus tectorum L.), large crabgrass (Digitaria sanguinalis (L.) Scop.), giant foxtail (Setaria faberi Herrm.), morningglory (Ipomoea spp.), redroot pigweed (Amaranthus retroflexus L.) and velvetleaf (Abutilon theophrasti Medik.) were planted into a sandy loam soil and treated preemergence with a directed soil spray using test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time plants selected from these species were also treated postemergence by spraying to runoff with test chemicals formulated.
Plants ranged in height from 2 to 10 cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately ten days, after which time all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table A, are based on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test results.
Table A Compounds
2000 g ai/ha 2 3 4 5 6 8 27 28 30 33 34 35 36 40
Postemergence
Barnyardgrass 100 100 100 90 90 0 75 65 70 90 80 85 80 0
Crabgrass, Large 100 95 70 50 90 0 70 20 25 85 50 60 10 0
Foxtail, Giant 100 100 80 45 70 0 70 25 55 85 40 70 35 0 Morningglory 80 20 35 15 30 0 100 25 0 25 20 10 10 0
Pigweed 100 100 100 90 100 45 90 80 65 85 90 95 85 0
Velvetleaf 75 60 45 20 95 5 45 25 20 40 30 40 20 0
Table A Compounds 2000 g ai/ha 41 43 44 45 46 47 52 53 54 55 58 59 60 61 Postemergence Barnyardgrass 60 100 100 100 100 100 55 0 10 100 80 30 70 90 Crabgrass , Large 60 90 80 90 90 100 20 0 15 100 75 20 55 45 Foxtail, Giant 35 70 90 95 100 85 25 0 5 80 60 20 60 85 Morningglory 10 30 45 25 65 25 0 0 10 25 0 10 20 20 Pigweed 60 100 100 100 100 100 35 0 20 100 90 75 95 95 Velvetleaf 25 30 65 65 75 40 20 0 5 40 40 20 20 15
Table A Compounds 2000 g ai/ha 62 63 64 65 66 67 70 71 78 79 80 82 83 84 Postemergence Barnyardgrass 100 90 75 75 0 25 30 0 40 40 90 20 20 10 Crabgrass, Large 60 80 60 60 0 20 30 0 35 55 90 30 25 20 Foxtail, Giant 85 80 55 55 0 20 20 0 60 40 90 20 20 10 Morningglory 20 15 10 10 0 20 30 0 25 25 50 10 10 10 Pigweed 100 100 95 70 10 85 75 0 90 85 100 50 55 45
Velvetleaf 20 55 30 25 0 15 30 0 50 50 75 30 20 20
Table A Compounds 2000 g ai/ha 85 86 87 58 89 90 91 92 93 94 95 96 97 98 Postemergence Barnyardgrass 25 20 55 100 20 20 0 0 25 35 55 80 10 0
Crabgrass, Large 30 25 60 95 25 25 20 10 15 30 60 70 10 0 Foxtail, Giant 30 20 50 60 20 20 0 0 10 15 50 80 10 0 Morningglory 25 35 20 40 15 10 0 0 10 20 15 15 0 0 Pigweed 70 95 35 100 30 40 20 0 30 30 100 100 25 10 Velvetleaf 20 30 25 55 20 30 10 0 15 25 50 70 10 5
Table A Compounds 2000 g ai/ha 102 103 107 108 109 111 112 114 115 116 117 120 121 122 Postemergence Barnyardgrass 75 75 55 100 90 0 45 40 80 25 75 65 35 85 Crabgrass, Large 80 30 40 85 55 10 30 60 80 10 65 65 10 65 Foxtail, Giant 65 30 35 100 90 0 35 55 80 0 55 20 25 80 Morningglory 55 35 40 40 40 0 15 25 30 0 70 40 20 65 Pigweed 100 100 100 100 100 10 60 100 100 0 95 85 100 100 Velvetleaf 20 45 0 100 45 0 35 20 40 0 65 30 15 70
Table A Compounds 2000 g ai/ha 123 124 125 127 128 130 136 137 138 139 143 144 145 146 Postemergence Barnyardgrass 20 0 0 50 80 20 60 25 30 60 25 100 100 75 Crabgrass, Large 10 10 0 35 70 20 70 60 30 30 30 90 85 55 Foxtail, Giant 10 0 0 30 60 10 50 30 35 40 15 100 60 40 Morningglory 10 0 0 20 15 25 40 40 40 35 25 35 30 0 Pigweed 15 40 20 50 80 65 85 100 100 100 35 100 100 100
Velvetleaf 10 10 0 35 20 75 70 60 40 15 75 55 35
Table A Compounds 2000 g ai/ha 147 148 149 150 151 153 154 164 165 166 167 172 179 180 Postemergence Barnyardgrass 95 25 65 65 10 100 90 10 0 10 0 0 10 30
Crabgrass, Large 90 10 75 50 10 20 30 10 0 0 5 0 10 35 Foxtail, Giant 90 15 65 25 10 90 20 0 0 20 0 0 10 20 Morningglory 30 10 60 10 20 85 40 5 5 10 10 10 30 15 Pigweed 100 15 90 75 70 100 100 0 5 25 0 60 10 95 Velvetleaf 50 15 40 15 60 65 30 0 20 30 20 15 5 15
Table A Compounds 2000 g ai/ha 189 190 195 196 197 198 199 200 201 202 203 204 205 206 Postemergence Barnyardgrass 10 0 50 30 0 80 80 35 20 80 30 30 65 10 Crabgrass, Large 10 15 25 0 10 65 50 25 20 65 15 30 20 5 Foxtail, Giant 0 0 0 0 5 65 65 20 10 50 20 25 25 0 Morningglory 10 25 10 0 0 75 70 45 30 75 55 15 20 0 Pigweed 45 20 25 0 5 75 80 60 55 90 80 60 65 20 Velvetleaf 5 15 15 0 5 35 35 10 10 30 10 60 30 20 Table A Compounds
2000 g ai/ha 207 209 210 211 212 213 214 215 216 217 222 223 255 267 Postemergence Barnyardgrass 70 70 80 55 90 45 15 25 15 0 90 55 70 65 Crabgrass, Large 65 40 65 30 60 30 10 30 20 20 85 25 40 75 Foxtail, Giant 50 25 75 30 80 25 40 40 20 0 85 10 55 55 Morningglory 15 15 25 15 20 10 10 35 20 25 95 60 25 45 Pigweed 45 50 80 25 90 40 50 80 55 25 100 55 100 60 Velvetleaf 25 20 65 25 35 25 20 30 35 30 100 35 50 35
Table A Compounds 2000 g ai/ha 268 269 270 271 272 273 277 278 279 280 281 282 283 284 Postemergence Barnyardgrass 80 80 30 30 90 75 50 60 40 25 65 80 35 60
Crabgrass, Large 75 80 10 10 90 65 0 5 20 0 10 25 10 20 Foxtail, Giant 80 65 0 20 95 70 0 15 20 0 25 25 25 35 Morningglory 40 35 20 30 100 75 0 5 5 10 15 15 0 15 Pigweed 85 50 0 90 100 100 35 70 60 70 70 100 100 100 Velvetleaf 45 30 25 40 100 95 30 25 20 30 40 50 35 35
Table A Compounds 2000 g ai/ha 285 286 287 288 289 290 291 300 312 313 314 315 316 317 Postemergence Barnyardgrass 80 80 90 65 40 70 40 90 0 95 75 20 45 0 Crabgrass, Large 35 25 60 15 20 10 25 90 0 100 60 20 45 10 Foxtail, Giant 55 75 90 10 70 70 75 90 0 80 70 0 30 Morningglory 50 35 15 20 20 30 10 95 0 55 50 0 30 Pigweed 100 85 80 40 50 60 30 100 0 100 100 20 80 10 Velvetleaf 75 50 65 20 5 30 10 80 0 50 30 0 20 Table A Compounds
2000 g ai/ha 318 319 329 338 347 348 354 355 356 Postemergence Barnyardgrass 90 60 20 35 0 0 70 75 40 Crabgrass, Large 70 50 5 45 0 0 20 30 15 Foxtail, Giant 90 40 20 30 0 0 50 45 10 Morningglory 55 25 20 70 0 0 85 75 20 Pigweed 100 40 45 95 0 0 80 90 70 Velvetleaf 50 30 25 60 0 0 70 65 10
Table A Compounds 1000 g ai/ha 31 32 39 131 132 133 134 135 Postemergence Barnyardgrass 75 0 55 60 30 55 70 50 Crabgrass, Large 40 0 35 40 25 20 35 30 Foxtail, Giant 70 0 45 15 20 20 35 30 Morningglory 20 0 0 15 20 20 20 10 Pigweed 80 0 75 75 65 75 100 85 Velvetleaf 30 0 10 10 30 15 20 25 Table A Compounds 500 g ai/ha 2 3 4 5 6 I 27 28 30 33 34 35 36 3! Postemergence Barnyardgrass 100 100 80 30 80 0 80 65 70 75 45 70 35 55 Crabgrass, Large 85 75 20 20 80 0 50 30 25 65, 30 55 10 60 Foxtail, Giant 95 95 20 25 70 0 60 20 20 70 30 50 20 60 Morningglory 45 25 15 10 10 0 35 5 0 10 10 10 10 0 Pigweed 100 100 95 25 100 20 90 70 60 85 90 85 80 70 Velvetleaf 40 40 20 10 90 5 25 25 25 30 20 25 15 20 Table A Compounds
500 g ai/ha 40 41 43 44 45 46 47 51 52 53 54 55 58 59 Postemergence Barnyardgrass 0 30 90 90 100 100 90 75 25 0 10 90 70 20 Crabgrass, Large 15 20 65 55 80 75 85 30 0 5 10 25 40 15 Foxtail, Giant 0 20 70 50 90 80 90 40 25 0 10 30 45 15 Morningglory 0 10 20 15 25 40 20 35 0 0 0 20 10 10 Pigweed 0 40 100 100 100 100 100 85 30 0 20 90 70 40 Velvetleaf 0 25 15 45 40 45 25 40 10 0 0 35 20 15
Table A Compounds 500 g ai/ha 60 61 62 63 64 65 66 67 70 71 78 79 80 82
Postemergence Barnyardgrass 35 35 65 60 30 45 0 0 25 0 30 40 90 20 Crabgrass, Large 20 30 25 40 30 30 0 20 25 0 20 20 70 20 Foxtail, Giant 30 20 55 50 30 30 0 10 20 0 20 30 80 20 Morningglory 10 10 10 15 10 10 0 5 25 0 15 15 40 20 Pigweed 40 85 100 95 65 70 10 50 60 0 85 95 100 50 Velvetleaf 20 15 10 40 20 25 0 20 20 0 45 45 60 20
Table A Compounds 500 g ai/ha 83 84 85 86 37 88 89 90 91 92 93 94 95 96 Postemergence Barnyardgrass 5 15 20 20 15 85 20 20 0 0 20 20 30 60 Crabgrass, Large 30 20 20 20 20 85 20 15 10 0 10 10 25 30 Foxtail, Giant 20 15 20 20 20 20 20 20 0 0 10 10 20 60 Morningglory 10 5 20 20 15 35 20 10 0 0 5 20 10 10 Pigweed 45 50 75 55 10 90 20 20 0 0 20 25 85 95
Velvetleaf 20 20 30 40 10 40 20 10 5 0 10 20 45 70 Table A Compounds 500 g ai/ha 97 98 102 103 107 108 109 110 111 112 114 115 116 117 Postemergence Barnyardgrass 5 0 55 45 20 85 75 30 0 35 30 70 0 45 Crabgrass , Large 10 0 60 15 25 65 20 30 10 25 40 75 0 40 Foxtail, Giant 5 0 45 10 20 90 55 25 0 20 50 60 0 35 Morningglory 0 0 35 25 30 40 25 10 5 20 10 35 0 20 Pigweed 0 5 95 85 95 100 100 50 5 40 85 95 0 80 Velvetleaf 5 0 10 10 0 90 25 10 0 25 20 40 0 50 Table A Compounds
500 g ai/ha 120 121 122 123 124 125 127 128 130 136 137 138 139 143 Postemergence Barnyardgrass 45 10 75 5 0 0 30 70 20 55 20 15 35 10 Crabgrass, Large 50 10 35 10 10 0 15 60 20 35 30 20 0 20 Foxtail, Giant 20 15 80 0 0 0 30 45 10 25 20 20 20 10 Morningglory 20 20 30 0 5 0 10 10 20 20 25 15 20 10 Pigweed 50 90 60 0 30 20 40 50 50 65 90 60 75 20 Velvetleaf 25 10 45 0 10 0 0 20 20 55 60 20 25 0
Table A Compounds 500 g ai/ha 144 145 146 147 148 149 150 151 153 154 164 165 166 167
Postemergence Barnyardgrass 85 40 50 55 20 45 30 10 75 50 10 0 0 0 Crabgrass, Large 55 30 15 40 5 40 15 5 10 20 10 0 0 0 Foxtail, Giant 80 40 15 45 15 40 20 10 20 20 0 0 0 0 Morningglory 25 15 5 20 15 30 0 10 35 20 10 5 0 0 Pigweed 100 90 85 90 0 65 80 35 95 90 0 0 20 0 Velvetleaf 55 30 20 30 20 30 25 35 40 10 5 10 20 10
Table A Compounds 500 g ai/ha 172 179 180 189 190 195 196 197 198 199 200 201 202 203 Postemergence Barnyardgrass 0 5 20 0 0 15 0 10 45 10 10 10 45 10 Crabgrass, Large 0 10 20 10 10 10 0 5 20 15 10 10 30 10 Foxtail, Giant 0 0 15 0 0 5 0 0 30 25 0 0 30 10 Morningglory 10 10 10 10 10 10 5 0 60 45 35 25 75 50 Pigweed 25 0 30 30 10 5 0 0 55 80 50 40 50 35
Velvetleaf 5 0 10 5 0 0 0 5 30 30 10 10 30 10 Table A Compounds 500 g ai/ha 204 205 206 207 209 210 211 212 213 214 215 216 217 222 Postemergence Barnyardgrass 25 45 5 40 30 80 25 50 25 0 0 0 0 75 Crabgrass, Large 30 10 0 20 20 40 20 45 20 5 20 20 0 80 Foxtail, Giant 25 10 0 10 15 40 20 45 20 15 25 20 0 65 Morningglory 20 25 0 20 0 20 20 15 20 0 25 20 15 80 Pigweed 50 50 15 30 40 60 25 75 30 20 70 30 10 75 Velvetleaf 40 20 5 20 10 40 15 35 30 15 30 25 5 80 Table A Compounds
500 g ai/ha 223 255 267 268 269 270 271 272 273 277 278 279 280 281 Postemergence Barnyardgrass 10 40 40 80 70 0 10 55 55 0 30 20 0 30 Crabgrass, Large 20 20 45 50 35 0 10 55 25 0 10 10 5 5 Foxtail, Giant 10 30 30 55 35 0 10 45 50 0 5 10 0 0 Morningglory 50 10 30 20 20 20 10 100 70 0 10 5 0 10 Pigweed 50 70 40 35 35 20 45 100 100 10 60 70 55 70 Velvetleaf 40 35 30 45 25 15 10 100 90 25 20 20 20 35
Table A Compounds 500 g ai/ha 282 283 284 285 286 287 288 289 290 291 300 311 312 313
Postemergence Barnyardgrass 40 10 30 55 60 70 5 10 55 25 75 10 0 80 Crabgrass, Large 10 10 20 15 20 10 0 20 10 5 55 10 0 70 Foxtail, Giant 20 10 20 25 35 40 0 10 15 30 55 0 0 70 Morningglory 15 0 10 40 20 20 20 10 20 5 80 0 0 30 Pigweed 75 80 95 80 55 50 20 20 30 20 90 0 0 100 Velvetleaf 50 15 30 60 30 55 20 0 20 5 60 10 0 40
Table A Compounds 500 g ai/ha 314 315 316 317 318 319 329 338 347 348 354 355 356 Postemergence Barnyardgrass 35 20 20 0 65 10 15 20 0 0 20 40 25 Crabgrass, Large 20 20 25 10 30 10 10 20 0 0 10 10 10 Foxtail, Giant 30 0 20 0 50 0 10 20 0 0 10 10 10 Morningglory 30 0 20 0 50 15 10 25 0 0 20 15 10 Pigweed 80 10 25 0 95 40 10 70 0 0 70 40 65
Velvetleaf 20 0 15 0 40 20 10 40 0 0 50 15 10 Table A Compounds 250 g ai/ha 31 32 39 131 132 133 134 135 Postemergence Barnyardgrass 65 0 10 25 20 20 30 30 Crabgrass , Large 30 0 10 20 20 10 20 20 Foxtail , Giant 45 0 10 10 15 10 15 20 Morningglory 5 0 0 15 10 10 10 10 Pigweed 55 0 70 45 75 30 85 80 Velvetleaf 20 0 10 15 20 10 20 15 Table A Compounds
125 g ai/ha 38 51 110 311 Postemergence Barnyardgrass 40 50 30 Crabgrass, Large 30 30 25 Foxtail, Giant 50 20 20 Morningglory 0 10 0 Pigweed 50 50 40 Velvetleaf 10 40 10
Table A Compounds 2000 g ai/ha 2 3 4 5 6 8 27 28 30 33 34 35 36 40 Preemergence Barnyardgrass 100 90 95 95 100 10 90 65 75 80 80 90 75 15 Crabgrass, Large 100 90 95 95 100 10 90 55 60 95 100 100 70 15 Foxtail, Giant 100 100 95 80 100 5 100 45 65 95 85 100 85 5 Morningglory 100 90 60 20 80 - 80 30 50 70 50 85 70 10 Pigweed 100 100 100 100 100 75 100 90 100 100 100 100 100 15 Velvetleaf 100 90 100 75 100 25 100 75 55 80 25 95 90 15
Table A Compounds 2000 g ai/ha 41 43 44 45 46 47 52 53 54 55 58 59 60 61 Preemergence Barnyardgrass 75 90 90 95 100 95 90 10 25 95 75 60 85 75 Crabgrass, Large 80 90 90 75 90 90 90 40 35 100 95 45 95 90 Foxtail, Giant 70 100 100 100 100 100 60 0 15 100 95 65 90 75 Morningglory 45 40 30 75 65 30 10 0 15 20 40 40 40 50 Pigweed 85 100 100 100 100 100 90 40 65 100 100 100 100 65
Velvetleaf 40 60 35 65 85 95 50 0 0 70 65 55 95 85 Table A Compounds 2000 g ai/ha 62 63 64 65 66 67 70 71 78 79 80 82 83 84 Preemergence Barnyardgrass 95 100 85 70 20 30 20 0 45 35 35 0 0 0 Crabgrass, Large 85 100 100 100 0 55 45 0 90 55 30 0 0 0 Foxtail, Giant 100 100 90 80 0 30 55 0 70 40 70 0 0 0 Morningglory 75 70 5 5 0 30 10 0 40 60 30 15 10 - Pigweed 100 100 100 100 0 90 5 0 90 90 90 35 0 0 Velvetleaf 95 70 35 30 0 75 20 0 50 70 10 0 0 0 Table A Compounds
2000 g ai/ha 85 86 87 88 89 90 91 92 93 94 95 96 97 98 Preemergence Barnyardgrass 0 0 90 90 0 50 15 0 40 65 50 90 0 0 Crabgrass, Large 5 0 95 100 0 75 35 0 70 60 90 100 0 0 Foxtail, Giant 0 0 90 90 0 60 30 0 60 65 90 95 0 0 Morningglory 5 1 155 1 155 4 400 10 30 10 0 20 10 55 70 0 0 Pigweed 5 5 555 9 955 1 10000 10 70 55 35 70 85 100 100 0 0 Velvetleaf 0 10 65 70 10 35 20 0 25 25 80 100 0 0
Table A Compounds 2000 g ai/ha 102 103 107 108 109 111 112 114 115 116 117 120 121 122 Preemergence Barnyardgrass 85 85 35 90 90 10 50 40 85 70 70 85 40 95 Brorαegrass, Downy 60 - - - - - - - - - - - - - Crabgrass, Large 100 55 90 100 95 30 55 85 100 80 75 75 75 95 Foxtail, Giant 85 15 80 100 90 75 50 45 80 35 60 55 75 85 Morningglory 90 10 100 75 45 0 45 70 90 10 75 55 20 30 Pigweed 90 95 95 100 100 10 90 90 100 0 90 50 100 90 Velvetleaf 60 20 0 90 25 0 50 60 95 0 65 40 30 70
Table A Compounds 2000 g ai/ha 123 124 125 127 128 130 136 137 138 139 143 144 145 146 Preemergence Barnyardgrass 50 10 0 30 85 30 85 60 80 60 0 100 100 80 Crabgrass , Large 0 15 0 85 100 60 90 90 90 75 15 90 90 80 Foxtail, Giant 0 0 0 35 65 55 70 80 90 75 0 100 100 45 Morningglory 0 15 0 30 85 15 45 35 45 85 0 75 25 50 Pigweed 0 75 0 50 95 65 80 90 95 100 0 100 100 95 Velvetleaf 0 15 0 30 85 30 30 35 50 80 0 90 90 25 Table A Compounds
2000 g ai/ha 147 148 149 150 151 153 154 164 165 166 167 172 179 180
Preemergence
Barnyardgrass 95 20 90 80 0 90 95 0 0 10 0 0 40 0
Crabgrass, Large 90 15 100 50 0 25 85 0 0 30 5 0 50 50
Foxtail, Giant 95 10 100 55 0 60 70 0 0 10 10 0 10 10
Morningglory 45 5 65 35 0 55 30 0 0 5 5 0 5 10
Pigweed 100 25 95 100 0 100 100 0 20 10 50 40 35 90
Velvetleaf 85 10 25 50 10 80 60 0 5 5 10 0 0 15
Table A Compounds
2000 g ai/ha 189 190 195 196 197 198 199 200 201 202 203 204 205 206
Preemergence
Barnyardgrass 65 40 45 55 0 90 95 45 50 80 60 5 90 60
Crabgrass, Large 75 70 95 50 0 90 100 75 70 100 75 10 95 20
Foxtail, Giant 20 10 45 20 0 95 100 60 15 80 75 10 100 20
Morningglory 30 25 10 10 5 85 55 60 5 70 15 25 45 25
Pigweed 40 85 0 15 0 100 100 95 95 100 90 10 100 60
Velvetleaf 25 15 15 0 10 85 90 35 35 85 35 25 100 10
Table A Compounds
2000 g ai/ha 207 209 210 211 212 213 214 215 216 217 222 223 255 267
Preemergence
Barnyardgrass 80 80 90 70 85 70 30 35 35 0 100 80 75 80
Crabgrass, Large 90 95 100 85 95 95 65 55 55 10 95 90 55 90
Foxtail, Giant 90 90 100 70 95 85 55 75 70 10 100 90 60 85
Morningglory 85 40 100 25 65 60 30 55 15 0 100 55 70 45
Pigweed 100 100 100 40 100 95 95 85 70 40 90 90 100 80
Velvetleaf 100 75 95 65 100 35 20 30 30 5 100 85 50 60
Table A Compounds
2000 g ai/ha 268 269 270 271 272 273 277 278 279 280 281 282 283 284
Preemergence
Barnyardgrass 100 100 90 75 100 95 70 80 55 45 75 75 30 85
Crabgrass, Large 100 100 35 15 100 100 25 60 70 25 65 65 90 80
Foxtail, Giant 100 100 70 70 100 100 55 85 60 45 75 40 50 55
Morningglory 25 30 30 0 55 80 0 25 20 15 25 40 10 5
Pigweed 100 100 85 60 100 100 70 95 100 90 95 90 90 100
Velvetleaf 100 100 55 5 60 75 45 35 30 30 35 45 15 40 Table A Compounds 2000 g ai/ha 285 286 287 288 289 290 291 300 312 313 314 315 316 317 Preemergence Barnyardgrass 90 85 100 75 50 90 25 100 0 90 90 5 10 0 Crabgrass, Large 85 70 100 10 55 25 10 100 0 95 90 15 35 10 Foxtail, Giant 90 100 100 75 40 90 0 100 0 90 90 10 0 0 Morningglory 45 40 50 30 15 40 0 100 0 55 30 10 0 0 Pigweed 100 95 100 70 75 95 35 100 0 100 90 45 65 30 Velvetleaf 40 70 100 40 20 30 0 100 0 80 80 30 15 30 Table A Compounds
2000 g ai/ha 318 319 329 338 347 348 354 355 356 Preemergence Barnyardgrass 95 80 5 95 0 0 55 80 45 Crabgrass, Large 70 100 0 100 0 0 20 50 20 Foxtail, Giant 85 80 5 100 0 0 80 60 45 Morningglory 50 60 10 40 0 0 20 40 15 Pigweed 100 100 10 90 0 0 70 50 80 Velvetleaf 80 45 10 50 0 0 45 55 20
Table A Compounds 1000 g ai/ha 31 32 39 131 132 133 134 135 Preemergence Barnyardgrass 80 0 25 50 10 45 45 65 Crabgrass, Large 45 0 85 85 35 80 95 90 Foxtail, Giant 50 0 40 75 40 30 45 50 Morningglory 55 0 20 35 10 0 30 25 Pigweed 80 0 100 90 40 65 100 85 Velvetleaf 35 0 20 60 20 35 40 50
Table A Compounds 500 g ai/ha 2 3 4 5 6 8 27 28 30 33 34 35 36 38 Preemergence Barnyardgrass 100 90 90 50 100 0 75 45 45 55 55 70 45 5 Crabgrass, Large 100 95 90 80 100 10 85 75 50 90 60 95 10 10 Foxtail, Giant 100 100 90 40 100 10 90 30 30 80 40 80 5 0 Morningglory 80 55 15 10 45 0 55 45 25 35 35 25 20 10 Pigweed 100 100 100 80 100 40 100 95 90 100 100 100 95 0
Velvetleaf 100 95 80 25 100 0 75 60 50 20 20 35 20 5 Table A Compounds
500 g ai/ha 40 41 43 44 45 46 47 51 52 53 54 55 58 59
Preemergence
Barnyardgr ss 0 40 60 75 80 90 90 85 25 0 5 80 65 25
Crabgrass, Large 5 40 75 45 55 65 55 80 70 0 25 75 70 25
Foxtail, Giant 0 30 55 65 75 90 90 100 20 0 0 60 85 5
Morningglory 5 20 10 10 15 40 20 15 0 0 0 5 20 10
Pigweed 0 65 100 100 95 100 100 100 90 30 10 100 100 90
Velvetleaf 5 25 5 20 25 30 20 100 15 0 0 20 70 15
Table A Compounds
500 g ai/ha 60 61 62 63 64 65 66 67 70 71 78 79 80 82
Preemergence
Barnyardgrass 50 40 50 70 55 55 0 0 20 0 20 20 10 0
Crabgrass, Large 75 75 70 90 70 95 0 15 35 0 60 50 10 0
Foxtail, Giant 55 20 75 95 40 40 0 0 40 0 55 10 20 0
Morningglory 10 20 20 10 0 5 0 0 20 0 25 20 15 0
Pigweed 95 95 100 100 100 100 0 0 0 0 80 45 70 5
Velvetleaf 65 55 70 20 10 10 0 30 10 0 30 20 10 0
Table A Compounds
500 g ai/ha 83 84 85 86 87 88 89 90 91 92 93 94 95 96
Preemergence
Barnyardgrass 0 0 0 0 55 75 0 20 0 0 25 20 30 70
Crabgrass, Large 0 0 0 0 90 45 0 35 0 0 35 35 50 80
Foxtail, Giant 0 0 0 0 35 55 0 25 0 0 35 45 70 75
Morningglory 30 0 0 0 15 10 0 0 0 0 5 10 30 25
Pigweed 0 0 0 0 60 90 0 25 0 0 40 35 100 100
Velvetleaf 0 0 0 0 25 45 0 20 5 0 10 5 50 95
Table A Clompounds
500 g ai/ha 97 98 102 103 107 108 109 no : 111 112 114 115 116 117
Preemergence
Barnyardgrass 0 0 70 55 0 85 85 5 0 25 25 70 35 30
Bromegrass, Downy - - 60 - - - - - - - - - - -
Crabgrass, Large 0 0 95 35 65 85 80 20 25 45 40 100 45 45
Foxtail, Giant 0 0 60 0 10 95 80 0 45 25 30 50 20 25
Morningglory 0 0 65 0 95 30 35 20 0 20 35 70 0 45
Pigweed 0 0 80 80 35 100 75 10 10 65 85 95 0 55
Velvetleaf 0 0 30 20 0 55 15 10 0 25 35 85 0 50 Table A Compounds 500 g ai/ha 120 121 122 123 124 125 127 128 130 136 137 138 139 143 Preemergence Barnyardgrass 30 15 90 5 0 0 20 55 40 65 30 30 40 0 Crabgrass, Large 45 10 70 15 30 0 75 90 45 85 55 70 45 0 Foxtail, Giant 25 25 65 0 0 0 20 15 50 60 50 30 60 0 Morningglory 20 5 25 0 5 0 30 45 10 20 20 15 30 0 Pigweed 20 95 85 0 20 0 40 60 35 70 60 80 100 0 Velvetleaf 20 10 40 0 0 0 10 75 20 25 20 20 50 0 Table A Compounds
500 g ai/ha 144 145 146 147 148 149 150 151 153 154 164 165 166 167 Preemergence Barnyardgrass 100 95 70 40 0 70 50 0 80 30 0 0 0 0 Crabgrass, Large 90 70 70 85 0 95 25 0 25 25 0 0 0 0 Foxtail, Giant 90 85 45 60 0 70 15 0 15 20 0 0 0 0 Morningglory 20 20 5 20 0 30 10 0 10 10 0 0 0 0 Pigweed 100 95 85 85 0 90 75 0 100 85 0 0 0 0 Velvetleaf 70 75 20 25 0 0 20 0 15 15 0 0 0 5
Table A Compounds 500 g ai/ha 172 179 180 189 190 195 196 197 198 199 200 201 202 203 Preemergence Barnyardgrass 0 0 35 20 20 15 0 55 55 35 0 45 10 Crabgrass, Large 0 10 55 40 75 25 0 80 70 70 35 85 50 Foxtail, Giant 0 0 5 0 30 0 0 90 80 35 0 55 30 Morningglory 0 15 10 0 45 15 15 0 15 10 Pigweed 0 25 25 0 95 100 80 40 100 90 Velvetleaf 0 10 0 0 45 35 20 0 35 15
Table A Compounds 500 g ai/ha 204 205 206 207 209 210 211 212 213 214 215 216 217 222 Preemergence Barnyardgrass 0 80 10 70 60 85 55 80 40 0 15 15 0 95 Crabgrass, Large 0 80 20 95 75 90 75 90 55 55 30 15 0 100 Foxtail, Giant 0 85 0 75 50 100 45 70 60 60 50 25 0 95 Morningglory 10 30 5 35 20 55 10 30 25 5 20 0 0 75 Pigweed 0 100 25 100 75 100 30 100 75 20 30 0 0 90
Velvetleaf 5 70 15 30 10 70 25 65 15 5 15 10 0 95 Table A Compounds 500 g ai/ha 223 255 267 268 269 270 271 272 273 277 278 279 280 281 Preemergence Barnyardgrass 55 55 70 100 95 60 5 70 70 0 50 5 0 60 Crabgrass, Large 90 35 15 85 65 5 0 85 75 0 25 70 0 20 Foxtail, Giant 75 45 75 100 100 20 0 90 85 0 60 25 5 60 Morningglory 35 30 20 5 20 0 0 20 45 0 10 10 0 5 Pigweed 95 90 5 100 100 15 60 100 100 40 85 95 15 90 Velvetleaf 55 30 25 95 40 30 0 15 60 5 20 10 0 10 Table A Compounds
500 g ai/ha 282 283 284 285 286 287 288 289 290 291 300 311 312 313 Preemergence Barnyardgrass 30 0 10 70 75 95 20 0 40 0 90 0 0 80 Crabgrass, Large 40 15 15 60 15 75 0 0 5 0 90 0 0 85 Foxtail, Giant 10 10 20 60 60 65 15 10 50 0 95 0 0 75 Morningglory 10 0 0 25 30 10 5 0 10 0 90 0 0 20 Pigweed 90 60 85 100 85 100 25 0 10 0 95 0 0 95 Velvetleaf 20 0 10 35 20 50 10 0 15 0 85 0 0 65
Table A Compounds 500 g ai/ha 314 315 316 317 318 319 329 338 347 348 354 355 356 Preemergence Barnyardgrass 50 5 0 0 65 55 0 60 0 0 0 50 5 Crabgrass, Large 55 5 10 0 55 85 0 65 0 0 10 20 10 Foxtail, Giant 60 0 0 0 40 55 0 80 0 0 15 20 20 Morningglory 10 5 0 0 20 20 0 10 0 0 15 10 5 Pigweed 80 15 0 20 75 100 5 55 0 0 60 10 25 Velvetleaf 40 10 5 0 30 35 0 20 0 0 5 25 0
Table A Compounds 250 g ai/ha 31 32 39 131 132 133 134 135 Preemergence Barnyardgrass 40 0 15 45 0 25 35 Crabgrass, Large 20 0 35 20 20 25 35 40 Foxtail, Giant 20 0 20 10 25 0 20 10 Morningglory 0 0 0 15 5 0 5 0 Pigweed 45 0 55 40 30 10 35 55
Velvetleaf 10 0 10 10 15 5 15 5 Table A Compounds
125 g ai/ha 38 51 110 311
Preemergence
Barnyardgrass 0 60 10 0
Crabgrass, Large 0 80 15 0
Foxtail, Giant 0 70 0 0
Morningglory 5 10 10 0
Pigweed 0 100 10 0
Velvetleaf 0 20 10 0
TESTB
Seeds selected from barnyardgrass (Echinochloa crus-galli (L.) Beauv.), Surinam grass (Urochloa decumbens (Staph) R. D. Webster, previously named Brachiaria decumbens Stapf), cocklebur (Xanthium strumarium L.), corn (Zea mays L.), large crabgrass (Digitaria sanguinalis (L.) Scop.), giant foxtail (Setaria faberi Herrm.), lambsquarters (Chenopodium album L.), morningglory (Ipomoea coccinea L.), pigweed (Amaranthus retroflexus L.), rice (Oryza sativa L.) and velvetleaf (Abutilon theophrasti Medik.) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these crop and weed species and also blackgrass (Alopecurus myosuroides Huds.), wheat (Triticum aestivum L.) and wild oat (Avenafatua L.) were treated with postemergence applications of test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Plant species in the flooded paddy test consisted of rice (Oryza sativa L.), small flower umbrella sedge (Cyperus difformis L.), ducksalad (Heteranthera limosa (Sw.) Willd.) and barnyardgrass (Echinochloa crus-galli (L.) Beauv.) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for 13 to 15 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table B, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table B Compounds
1000 g ai/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Flooded Paddy
Barnyardgrass 80 90 80 80 50 90 80 0 70 80 80 10 80 90
Ducksalad 90 90 80 90 80 90 90 0 80 90 70 80 90 90
Rice 80 70 80 70 40 80 70 20 80 80 90 50 70 80
Sedge, Umbrella 90 90 90 90 80 90 90 0 80 70 70 30 70 50 Table B Compounds 1000 g ai/ha 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Flooded Paddy Barnyardgrass 60 80 70 80 20 40 70 0 0 0 0 0 80 80 Ducksalad 90 90 90 90 70 90 90 0 0 0 0 0 90 80 Rice 60 90 80 80 0 70 60 0 0 0 0 0 80 80 Sedge, Umbrella 80 70 70 70 60 80 60 0 0 50 0 0 90 80
Table B Compounds 1000 g ai/ha 29 30 31 32 33 34 35 36 37 40 41 42 43 44 Flooded Paddy Barnyardgrass 90 60 80 0 90 80 90 70 30 0 50 0 80 70 Ducksalad 80 80 80 0 90 80 80 90 60 0 60 50 70 70 Rice 70 60 80 0 60 50 60 40 50 0 20 0 50 70 Sedge, Umbrella 80 70 50 20 90 80 90 60 90 30 70 50 70 70 Table B Compounds
1000 g ai/ha 45 46 47 48 49 50 51 52 54 55 56 57 58 59 Flooded Paddy Barnyardgrass 80 90 90 50 70 70 90 20 0 90 80 60 80 0 Ducksalad 80 90 80 50 80 70 80 20 0 80 80 50 80 0 Rice 70 70 70 50 30 60 70 0 0 70 70 60 60 0
Sedge, Umbrella 70 80 80 50 80 80 80 40 0 80 80 60 80 0
Table B Compounds 1000 g ai/ha 60 61 62 63 64 65 66 67 68 69 70 71 72 73 Flooded Paddy Barnyardgrass 60 30 70 80 30 80 10 60 0 0 10 0 0 30 Ducksalad 70 80 80 90 90 90 0 80 0 0 0 0 0 10 Rice 50 0 30 60 50 50 0 60 0 0 10 0 0 50 Sedge, Umbrella 60 60 80 100 90 90 10 80 0 0 30 0 0 80
Table B Compounds 1000 g ai/ha 74 75 76 77 78 79 80 81 82 2 8 833 8 844 85 86 87
Flooded Paddy
Barnyardgrass 0 80 70 40 30 60 80 50 30 10 10 40 30 20
Ducksalad 0 90 100 40 30 80 90 80 20 30 20 20 20 20
Rice 0 90 60 70 40 70 60 60 40 10 0 40 50 10 Sedge, Umbrella 70 70 60 80 80 90 80 80 40 50 70 60 70 80 Table B Compounds 1000 g ai/ha 88 89 90 91 92 93 94 95 96 97 98 99 100 101 Flooded Paddy Barnyardgrass 70 10 10 0 0 0 20 50 80 0 0 0 0 70 Ducksalad 80 0 30 30 0 10 30 80 90 50 0 0 0 90 Rice 40 10 10 10 0 20 10 60 70 0 0 0 0 80 Sedge, Umbrella 80 60 50 60 0 70 50 80 90 70 0 40 0 80
Table B Compounds 1000 g ai/ha 102 104 105 106 107 108 109 110 112 113 114 115 117 118 Flooded Paddy Barnyardgrass 80 0 20 0 0 80 80 30 50 70 70 90 70 50 Ducksalad 90 60 70 80 60 90 90 0 80 90 80 90 80 80 Rice 50 0 0 0 0 70 70 20 70 60 50 60 50 80 Sedge, Umbrella 100 70 70 90 60 90 60 20 80 90 90 90 90 80 Table B Compounds
1000 g ai/ha 119 120 121 122 123 124 125 126 127 128 129 130 131 132 Flooded Paddy Barnyardgrass 0 30 0 60 0 0 0 10 50 70 30 40 70 30 Ducksalad 0 70 0 80 50 70 0 80 90 90 70 10 80 10 Rice 0 0 0 70 0 0 0 20 50 60 10 0 60 0
Sedge, Umbrella 0 10 0 80 30 0 0 80 100 90 80 0 80 40
Table B Compounds 1000 g ai/ha 133 134 135 136 137 138 139 140 141 142 143 144 145 146 Flooded Paddy Barnyardgrass 20 60 60 60 20 10 70 70 10 90 0 80 70 60 Ducksalad 50 90 80 90 30 80 80 80 80 90 0 90 70 80 Rice 0 60 60 30 20 50 50 30 0 70 0 70 40 40 Sedge, Umbrella 40 80 70 90 90 80 80 80 90 80 0 90 90 90
Table B Compounds 1000 g ai/ha 147 148 149 150 151 152 153 154 155 156 157 158 159 160
Flooded Paddy
Barnyardgrass 60 20 70 70 0 80 40 50 70 100 20 70 80 70
Ducksalad 80 0 90 20 0 80 80 80 100 100 0 90 90 90
Rice 50 0 50 40 0 70 60 20 20 90 30 60 60 90 Sedge, Umbrella 90 70 60 50 60 90 70 20 90 90 40 80 70 80 Table B C.'ompc>unds
1000 g ai/ha 161 162 163 164 165 166 167 168 169 170 171 179 180 181
Flooded Paddy
Barnyardgrass 80 80 70 0 0 0 0 50 0 10 0 0 20 80
Ducksalad 80 80 80 0 0 0 0 70 0 0 0 0 20 90
Rice 40 80 60 0 0 0 0 40 0 20 0 0 0 80
Sedge, Umbrella 60 80 70 0 0 30 0 90 0 20 0 0 0 80
Table B Compounds
1000 g ai/ha 182 183 184 185 186 187 188 189 190 191 192 193 194 195
Flooded Paddy
Barnyardgrass 40 60 0 0 30 60 60 60 20 20 80 80 50 60
Ducksalad 60 70 0 0 90 90 80 70 60 20 80 90 90 40
Rice 0 0 0 0 30 30 70 40 0 0 70 80 60 30
Sedge, Umbrella 80 80 30 60 90 80 80 70 60 90 80 80 80 50
Table B Compounds
1000 g ai/ha 196 197 198 199 200 201 202 203 204 205 206 207 209 210
Flooded Paddy
Barnyardgrass 20 0 20 10 0 0 40 0 20 70 10 80 60 80
Ducksalad 30 0 70 0 0 0 60 0 40 50 40 90 80 80
Rice 0 0 20 20 0 0 30 0 30 60 30 60 50 70
Sedge, Umbrella 30 0 70 10 50 0 50 0 80 60 50 80 90 80
Table B Compounds
1000 g ai/ha 211 212 213 214 215 216 217 218 219 220 221 222 223 224
Flooded Paddy
Barnyardgrass 20 50 60 0 30 20 0 0 0 0 40 90 40 90
Ducksalad 80 80 70 30 90 80 0 0 80 40 50 80 90 80
Rice 20 70 40 0 30 30 0 0 0 0 20 90 70 90
Sedge, Umbrella 30 70 80 50 90 90 0 20 80 80 80 70 80 80
Table B Compounds
1000 g ai/ha 225 226 227 228 229 230 231 232 233 234 235 236 237 238
Flooded Paddy
Barnyardgrass 90 80 70 90 90 50 80 40 0 0 40 80 60 10
Ducksalad 90 70 80 90 90 60 90 80 50 0 90 90 80 0
Rice 90 80 70 90 90 60 80 50 30 0 40 70 50 30
Sedge, Umbrella 90 80 50 80 80 70 90 90 80 0 80 80 40 80 Table B Compounds 1000 g ai/ha 239 240 241 242 243 244 245 246 247 248 249 250 251 252 Flooded Paddy Barnyardgrass 0 0 80 90 90 90 90 50 70 40 0 0 0 70 Ducksalad 0 0 70 90 90 90 80 50 80 30 0 40 30 90 Rice 30 0 70 90 90 90 80 60 80 50 0 50 40 80 Sedge, Umbrella 70 60 80 90 80 80 50 50 70 50 30 70 40 80
Table B Compounds 1000 g ai/ha 253 254 255 256 257 258 259 260 261 262 263 264 265 266 Flooded Paddy Barnyardgrass 0 30 70 30 0 70 30 60 0 0 60 0 0 80 Ducksalad 60 90 80 90 50 90 90 90 80 0 90 90 0 90 Rice 50 80 70 50 30 80 70 70 60 0 70 0 0 80 Sedge, Umbrella 20 60 80 70 0 70 70 70 30 0 80 50 0 80 Table B Compounds
1000 g ai/ha 267 268 269 270 271 272 273 274 275 276 277 278 279 280 Flooded Paddy Barnyardgrass 60 90 90 50 0 50 60 70 20 70 0 60 10 0 Ducksalad 0 90 80 70 40 80 90 70 60 80 0 80 60 20 Rice 70 90 80 70 20 40 40 60 20 70 0 60 40 0
Sedge, Umbrella 70 80 80 60 40 80 80 80 80 80 0 70 60 30
Table B Compounds 1000 g ai/ha 281 282 283 284 285 286 287 288 289 290 291 292 293 294 Flooded Paddy Barnyardgrass 70 20 20 30 90 90 80 0 0 70 0 20 90 90 Ducksalad 80 80 70 70 90 90 80 0 0 70 0 0 80 90 Rice 70 20 10 10 80 70 70 0 0 60 0 30 90 90 Sedge, Umbrella 70 0 80 0 90 80 80 60 0 0 70 0 60 80 80
Table B Compounds 1000 g ai/ha 295 296 297 298 299 300 301 302 303 304 305 306 307 308
Flooded Paddy
Barnyardgrass 60 80 30 90 90 90 90 70 90 80 90 80 90 90
Ducksalad 70 80 30 90 90 90 90 90 90 90 80 80 80 90
Rice 50 60 20 80 90 90 90 70 90 90 70 60 90 70 Sedge, Umbrella 80 80 80 70 90 90 90 80 90 90 90 80 90 90 Table B Compounds
1000 g ai/ha 309 310 311 312 313 314 315 316 317 318 319 329 330 331
Flooded Paddy
Barnyardgrass 90 90 50 0 70 30 0 0 0 70 10 0 0 80
Ducksalad 90 90 60 0 80 0 0 0 0 70 90 0 0 90
Rice 80 80 60 0 80 0 0 0 0 40 70 0 0 60
Sedge, Umbrella 80 80 30 0 80 60 0 0 0 80 80 0 0 90
Table B Compounds
1000 g ai/ha 332 333 334 335 336 338 340 341 342 343 344 345 346 347
Flooded Paddy
Barnyardgrass 60 50 90 60 90 40 90 90 90 90 60 30 40 0
Ducksalad 90 80 90 90 90 60 90 90 80 90 80 70 60 0
Rice 50 20 80 70 80 30 80 70 70 80 70 40 40 0
Sedge, Umbrella 90 80 80 80 80 80 80 80 70 90 80 80 80 0
Table B Compounds
1000 g ai/ha 348 349 350 351 352 353 354 355 356 357 358 359 360 361
Flooded Paddy
Barnyardgrass 0 80 0 0 90 70 40 50 50 70 80 70 40 80
Ducksalad 0 90 0 0 90 80 50 70 60 80 90 70 70 90
Rice 0 70 0 0 70 40 50 50 50 70 70 70 50 90
Sedge, Umbrella 0 80 0 0 80 90 50 70 70 80 80 80 90 90
Table B Compounds
1000 g ai/ha 362 363 364 365 366
Flooded Paddy
Barnyardgrass 50 60 90 90 80
Ducksalad 90 90 100 90 100
Rice 60 60 90 90 70
Sedge, Umbrella 90 80 100 90 90
Table B Compounds
500 g ai/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Postemergence
Barnyardgrass 30 70 20 30 20 80 0 0 40 10 0 0 10 20
Blackgrass 40 30 20 10 0 90 0 0 50 50 40 30 30 60
Cocklebur 90 80 70 70 70 80 0 0 70 80 10 - 50 20
Corn 20 20 20 20 20 60 10 0 10 0 0 0 0 0
Crabgrass, Large 0 30 10 30 20 30 0 0 20 20 10 0 30 30
Foxtail, Giant 30 30 20 30 30 20 0 0 30 20 30 30 30 40 Lambsquarters 80 90 60 100 80 100 20 10 80 90 70 70 70 70 Morningglory 60 70 50 50 20 0 0 0 0 20 10 10 10 20 Oat, Wild 50 30 20 20 20 70 0 0 50 30 20 10 30 40 Pigweed 70 70 40 80 60 70 0 10 80 90 20 30 70 60 Surinam Grass 20 50 10 30 20 60 0 0 0 30 10 20 20 20 Velvetleaf 80 50 10 20 20 60 0 0 70 70 20 20 50 50 Wheat 10 20 10 10 10 40 0 0 20 20 10 10 10 20
Table B Compounds
500 g ai/ha 15 16 17 18 19 20 21 22 23 24 25 26 27 28 Postemergence
Barnyardgrass 10 60 10 10 0 10 0 0 0 0 0 10 60 40
Blackgrass 20 70 50 30 40 40 30 30 30 30 40 0 80 30
Cocklebur 20 20 70 20 50 50 - - 10 40 0 0 50 80
Corn 0 30 30 20 20 20 0 0 20 0 10 40 20 Crabgrass, Large 10 10 10 10 10 10 10 10 0 10 10 80 30
Foxtail, Giant 40 30 40 30 20 20 20 20 0 20 10 100 50
Lambsquarters 70 70 90 50 50 40 40 60 20 10 10 100 90
Morningglory 0 20 10 20 10 40 20 30 30 20 20 0 50 40
Oat, Wild 30 40 30 30 30 40 30 10 20 30 30 0 60 30 Pigweed 30 60 60 40 60 60 30 20 20 30 10 50 100 100
Surinam Grass 10 20 20 10 20 10 10 0 10 20 0 10 80 30
Velvetleaf 30 60 60 20 10 30 20 30 0 10 0 0 70 60
Wheat 10 20 30 20 10 20 20 0 0 20 10 0 20 20
Table B Compounds 500 g ai/ha 29 30 31 32 33 34 35 36 37 40 41 42 43 44
Postemergence Barnyardgrass 50 10 50 10 30 30 20 20 20 10 20 20 70 60 Blackgrass 20 30 50 0 20 20 30 20 10 20 20 10 20 20 Cocklebur 80 70 90 20 100 90 100 50 80 50 40 20 90 80 Corn 20 20 30 10 - - - - - - - 20 30 30
Crabgrass, Large 70 10 30 10 30 20 20 20 20 20 30 70 90 90 Foxtail, Giant 40 20 30 10 30 30 20 30 20 20 20 10 50 30 Lambsquarters 100 90 90 90 90 90 90 90 90 70 70 70 90 90 Morningglory 70 60 70 0 - - - - - - - 50 100 90 Oat, Wild 40 30 30 20 10 10 10 20 20 10 10 20 30 20 Pigweed 100 100 90 50 90 90 100 90 90 60 70 70 100 100 Surinam Grass 30 40 60 10 30 50 40 10 20 20 20 20 80 20 Velvetleaf 70 50 50 30 60 50 50 40 40 20 20 60 90 80
Wheat 10 10 10 10 30 30 20 30 20 30 10 20 30 20
Table B Compounds
500 g ai/ha 45 46 47 48 50 51 52 55 56 57 58 59 60 61
Postemergence
Barnyardgrass 30 50 40 60 70 80 0 10 20 20 60 20 10 30
Blackgrass 20 20 10 10 30 0 0 10 10 10 30 0 0 0
Cocklebur 80 90 100 70 90 80 40 40 80 60 100 40 70 100
Corn 30 30 30 30 40 0 40 30 30 20 20 20 20 40
Crabgrass, Large 30 90 70 20 30 50 10 10 20 20 30 20 20 30
Foxtail, Giant 30 40 30 30 30 0 10 10 20 30 20 20 20 30
Lambsquarters 90 90 90 90 90 90 80 70 90 90 90 90 90 100
Morningglory 90 90 100 50 70 0 0 10 20 10 30 20 20 50
Oat, Wild 20 10 30 30 20 10 10 20 20 30 30 20 20 20
Pigweed 100 90 100 70 100 100 10 40 90 80 90 80 70 60
Surinam Grass 30 40 40 50 40 20 0 10 30 20 30 20 20 30
Velvetleaf 70 80 70 80 60 70 20 40 50 30 70 20 60 70
Wheat 30 30 30 20 30 20 0 10 20 10 20 10 0 10
Table B Compounds
500 g ai/ha 62 63 64 65 66 67 68 69 70 71 75 76 77 78
Postemergence
Barnyardgrass 50 20 10 10 10 10 0 0 20 10 20 20 0 30
Blackgrass 70 20 10 10 20 10 20 30 20 0 30 50 30 30
Cocklebur 100 70 50 80 30 70 10 0 100 0 30 90 0 100
Corn 20 20 20 20 20 10 0 0 20 10 20 30 10 -
Crabgrass, Large 20 20 10 20 10 10 0 0 20 10 10 20 40 30
Foxtail, Giant 30 20 10 20 20 10 0 0 30 10 20 40 40 30
Lambsquarters 90 80 70 70 70 60 10 10 80 20 40 60 90 80
Morningglory 60 20 20 20 20 10 0 0 30 0 50 10 70 -
Oat, Wild 30 30 20 20 10 30 20 20 20 0 40 40 40 20
Pigweed 90 70 50 60 30 20 30 20 50 20 70 100 90 90
Surinam Grass 70 20 10 20 10 10 0 0 20 10 20 20 20 20
Velvetleaf 70 50 10 10 10 10 0 0 60 0 20 40 30 80
Wheat 10 10 10 10 10 10 0 0 20 0 20 30 20 30 Table B Compounds
500 g ai/ha 79 80 81 82 83 84 85 86 87 88 89 90 91 92
Postemergence
Barnyardgrass 40 90 90 20 50 40 80 80 0 60 20 30 0 0 Blackgrass 30 40 20 10 0 10 20 20 0 0 10 10 0 0
Cocklebur 80 100 90 100 20 100 100 100 0 50 90 60 10 0
Corn - 50 30 30 30 20 30 30 0 70 20 10 10 10
Crabgrass, Large 30 100 20 20 30 50 80 90 60 60 20 10 10 10
Foxtail, Giant 40 90 50 10 10 10 50 60 0 40 20 10 0 0 Lambsquarters 80 80 50 50 60 60 60 90 0 100 60 50 30 20
Morningglory - 100 30 70 30 60 100 100 0 0 50 40 0 0
Oat, Wild 30 50 30 30 20 20 50 60 0 0 30 30 10 0
Pigweed 100 100 90 100 100 100 100 100 0 60 40 40 10 10
Surinam Grass 40 90 60 60 40 60 70 100 0 0 20 10 10 10 Velvetleaf 80 100 90 90 70 100 80 70 0 70 50 30 10 0
Wheat 40 30 40 20 30 30 60 40 0 0 20 10 10 0
Table B Compounds
500 g ai/ha 93 94 95 96 97 98 99 100 101 102 104 105 106 107
Postemergence Barnyardgrass 10 10 20 50 0 10 0 0 20 40 0 0 0 0
Blackgrass 10 10 0 20 0 0 40 30 40 20 0 0 0 0
Cocklebur 50 50 70 100 70 20 30 0 80 50 0 30 50 0
Corn 20 20 10 20 0 10 20 0 40 40 0 0 10 0
Crabgrass, Large 10 10 50 50 0 20 10 0 20 70 0 0 10 0 Foxtail, Giant 10 10 30 50 0 10 30 0 30 30 0 0 0 0
Lambsquarters 90 80 100 100 70 30 90 50 90 20 20 80 90 20
Morningglory 40 10 60 0 0 20 20 0 10 30 0 10 10 0
Oat, Wild 10 10 20 20 0 10 40 40 50 40 0 10 20 0
Pigweed 30 30 100 100 0 30 70 60 90 100 10 80 20 10 Surinam Grass 10 10 20 30 0 20 10 20 20 100 10 10 10 10
Velvetleaf 10 20 60 80 60 10 40 0 30 20 0 0 20 0
Wheat 10 10 10 20 0 0 20 10 20 20 0 0 0 0
Table B Compounds 500 g ai/ha 108 109 110 112 113 114 115 117 118 119 120 121 122 123 Postemergence Barnyardgrass 70 20 20 70 80 30 50 30 30 10 10 0 20 0 Blackgrass 20 20 0 20 20 30 20 10 10 10 10 0 10 0 Cocklebur 90 70 40 100 100 90 90 90 90 60 60 20 90 Corn 20 20 20 40 30 40 30 - 10 10
Crabgrass, Large 70 10 20 30 80 40 30 30 30 20 20 10 10 Foxtail, Giant 30 20 10 30 40 30 30 20 20 10 10 10 20 Lambsquarters 100 20 60 100 100 90 100 90 20 60 50 80 0 Morningglory 100 10 30 30 100 Oat, Wild 50 30 0 40 60 10 30 20 20 20 10 30 40 Pigweed 100 70 50 100 100 100 100 90 100 30 70 50 10 Surinam Grass 10 20 30 20 60 20 60 40 40 10 50 30 10 Velvetleaf 70 20 40 70 60 60 80 50 40 50 30 20 20 Wheat 20 20 30 30 30 20 30 20 10 0 10 0 10
Table B Compounds
500 g ai/ha 124 125 126 127 128 129 130 131 132 133 134 135 136 137
Postemergence Barnyardgrass 0 0 30 20 30 0 80 50 60 40 40 40 90 40
Blackgrass 0 0 0 10 10 0 60 20 40 10 20 0 60 20
Cocklebur 10 0 100 80 100 60 100 100 90 60 100 90 100 100
Corn 10 0 20 - - - 40 20 20 20 30 30 30 20
Crabgrass, Large 10 0 40 30 20 10 90 30 40 30 30 30 70 30 Foxtail, Giant 10 0 30 30 20 10 60 30 40 20 40 40 10 20
Lambsquarters 70 20 60 80 60 10 100 90 100 70 90 80 100 80
Morningglory 10 0 30 - - - 100 60 70 20 40 50 100 60
Oat, Wild 10 0 50 10 10 0 60 20 20 20 30 20 60 70
Pigweed 70 0 40 60 60 10 100 60 90 50 90 90 90 100 Surinam Grass 20 10 20 10 20 20 90 60 60 50 40 40 70 70
Velvetleaf 10 0 40 10 60 20 70 40 60 50 40 30 70 60
Wheat 0 0 0 10 20 0 40 20 20 0 20 20 40 20
Table B Compounds
500 g ai/ha 138 139 140 141 142 143 144 145 146 147 148 149 150 151 Postemergence
Barny rdgrass 20 10 0 10 10 0 80 40 60 30 20 30 50 10
Blackgrass 20 10 0 20 40 0 60 10 20 20 0 40 10 30
Cocklebur 90 100 20 20 40 0 100 30 80 80 70 100 80 0
Corn 30 20 10 10 0 10 30 20 30 30 10 30 50 10 Crabgrass, Large 20 20 0 30 10 0 100 10 20 70 10 30 10 0
Foxtail, Giant 30 20 0 20 30 0 90 40 20 40 10 10 10 20
Lambsquarters 90 90 80 90 50 20 90 70 90 90 10 60 70 50 Morningglory 60 100 0 30 50 0 80 20 20 30 10 40 40 30 Oat, Wild 30 10 0 20 20 20 50 30 20 30 10 30 20 30 Pigweed 90 90 0 80 60 20 100 100 90 90 20 70 90 30 Surinam Grass 30 20 0 20 20 10 90 20 30 30 10 20 40 10 Velvetleaf 50 60 0 80 60 20 100 60 60 60 10 50 60 20 Wheat 30 10 0 20 10 0 30 20 10 20 30 10 10 20
Table B Compounds
500 g ai/ha 153 154 155 156 157 158 159 160 161 162 163 164 165 166
Postemergence Barnyardgrass 30 50 20 40 20 0 0 10 10 30 0 0 0 0
Blackgrass 10 10 50 60 20 30 - 50 40 50 50 0 0 0
Cocklebur 100 70 80 80 90 70 80 90 30 60 60 0 0 0
Corn 20 20 20 10 0 10 0 0 0 0 0 10 0 0
Crabgrass, Large 20 20 40 10 20 30 0 0 10 40 40 0 0 0 Foxtail, Giant 20 20 30 40 40 30 50 30 30 30 40 0 0 0
Lambsquarters 80 90 90 80 70 80 90 80 70 90 80 10 0 0
Morningglory 70 70 60 50 30 50 10 70 20 60 0 0 0 0
Oat, Wild 50 30 50 40 40 40 - 30 40 40 30 0 0 0
Pigweed 70 80 100 60 80 70 80 80 60 80 80 0 0 0 Surinam Grass 30 60 30 20 20 0 20 10 20 40 40 10 0 0
Velvetleaf 60 60 70 90 80 50 70 70 50 80 80 0 0 0
Wheat 10 10 20 20 20 10 - 10 10 10 10 0 0 0
Table B Compounds
500 g ai/ha 167 169 170 171 179 180 181 182 183 184 185 186 187 18- Postemergence
Barnyardgrass 0 10 10 10 0 0 10 50 0 0 50 50 10 20
Blackgrass 0 10 0 0 0 0 10 0 10 0 0 30 0 10
Cocklebur 0 0 0 0 0 0 70 60 90 60 50 90 70 90
Corn 0 10 10 10 0 0 20 30 20 30 30 20 20 20 Crabgrass, Large 0 10 10 10 0 0 20 30 30 30 40 10 10 10
Foxtail, Giant 0 0 10 20 0 0 20 20 30 40 30 20 10 10
Lambsquarters 0 60 70 20 0 0 90 70 80 70 70 30 0 70
Morningglory 0 70 80 0 0 0 20 70 70 60 70 30 20 60
Oat, Wild 0 10 10 0 0 0 30 30 20 30 30 20 20 20 Pigweed 0 40 50 20 0 0 90 70 80 60 80 60 20 70
Surinam Grass 0 10 10 10 0 0 20 20 20 20 30 30 10 10
Velvetleaf 0 0 20 0 0 0 20 60 60 60 50 60 10 20 Wheat 0 0 0 0 0 0 0 10 0 0 10 20 0 10
Table B Compounds
500 g ai/ha 189 190 193 194 195 196 197 198 199 200 201 202 203 204
Postemergence Barnyardgrass 10 10 10 10 90 30 10 30 10 10 0 0 0 10
Blackgrass 0 0 20 0 10 0 0 10 10 10 0 0 0 20
Cocklebur 10 10 70 10 60 20 10 90 60 20 10 40 10 90
Corn 10 10 20 0 30 10 20 70 20 30 20 10 10 20
Crabgrass, Large 20 20 10 10 50 30 0 20 10 10 10 10 10 10 Foxtail, Giant 10 10 20 0 20 0 0 30 10 10 0 10 10 20
Lambsquarters 50 80 90 30 60 30 0 70 70 60 40 50 50 50
Morningglory 90 90 70 10 60 0 0 80 60 40 30 40 30 40
Oat, Wild 10 20 0 0 20 0 30 30 10 10 10 10 10 20
Pigweed 60 70 60 30 80 30 10 50 40 40 40 40 10 70 Surinam Grass 20 20 10 10 30 40 20 20 20 20 10 10 20 50
Velvetleaf 20 40 70 10 40 0 20 20 30 30 0 30 10 70
Wheat 0 0 10 0 20 0 10 10 10 0 0 0 0 30
Table B Compounds
500 g ai/ha 205 206 207 209 210 211 212 213 214 215 216 217 218 219 Postemergence
Barnyardgrass 20 10 20 20 40 10 20 50 0 20 10 0 0 0
Blackgrass 20 20 10 20 30 10 20 40 0 0 0 0 0 0
Cocklebur 80 40 80 40 90 60 90 70 0 80 70 0 0 20
Corn 20 20 20 30 60 10 40 20 20 10 10 0 10 10 Crabgrass, Large 20 30 20 20 20 10 10 30 0 0 0 0 10 10
Foxtail, Giant 30 20 20 30 30 10 40 30 20 20 20 0 0 10
Lambsquarters 70 80 80 40 80 70 100 40 0 0 0 0 10 10
Morningglory 50 20 20 20 70 30 50 30 0 40 0 10 10 60
Oat, Wild 30 20 20 20 20 10 20 20 0 20 0 0 0 0 Pigweed 50 40 60 40 70 30 90 20 0 70 20 0 20 20
Surinam Grass 20 20 20 20 30 10 60 20 10 10 20 10 10 10
Velvetleaf 40 20 30 20 70 30 70 60 10 60 60 10 0 10
Wheat 20 20 20 20 20 10 20 30 0 20 10 0 0 0
Table B Compounds 500 g ai/ha 220 221 222 223 224 225 226 227 228 229 230 231 232 233
Postemergence Barnyardgrass 0 10 20 20 30 30 20 - 70 50 20 40 Blackgrass 0 0 20 0 10 40 20 30 40 30 30 30 0 10 Cocklebur 10 20 60 30 40 20 20 30 80 70 10 40 30 20 Corn 10 10 20 20 20 20 40 40 30 20 20 20 20 30
Crabgrass, Large 10 10 20 20 20 20 20 30 40 20 20 20 20 10 Foxtail , Giant 10 10 30 20 30 20 20 60 50 50 20 30 30 30 Lambsquarters 20 20 70 80 70 70 60 70 80 80 60 70 60 70 Morningglory 0 0 80 80 70 40 80 60 80 70 70 70 70 80 Oat, Wild 10 10 20 30 30 30 30 0 50 50 40 40 0 20 Pigweed 10 20 60 70 60 70 60 - 80 80 60 70 40 70 Surinam Grass 10 10 30 10 20 20 20 30 40 20 10 30 20 20 Velvetleaf 0 0 60 20 60 40 20 70 80 70 30 50 40 50 Wheat 0 10 20 0 30 30 30 10 40 40 20 40 0 10
Table B Compounds
500 g ai/ha 234 235 236 237 238 239 240 241 242 243 244 245 246 247 Postemergence
Barnyardgrass 0 0 0 0 60 20 50 70 70 10
Blackgrass 0 20 10 10 10 0 10 10 20 0 20 0 0 0
Cocklebur 20 30 40 40 20 20 20 30 90 30 80 80 30 30
Corn 20 40 40 40 0 20 10 10 40 10 30 30 10 20 Crabgrass, Large 20 20 20 20 0 20 20 10 50 10 30 50 20 10
Foxtail, Giant 30 30 40 20 0 0 0 0 30 20 30 60 30 20
Lambsquarters 40 50 70 70 0 30 50 50 90 80 70 90 70 70
Morningglory 70 70 60 60 0 10 30 70 40 20 20 60 10 30
Oat, Wild 20 20 20 20 10 0 0 20 30 20 50 30 20 10 Pigweed 30 40 70 60 0 50 50 50 80 60 70 80 60 60
Surinam Grass 10 10 20 20 0 30 20 20 60 20 30 60 20 20
Velvetleaf 30 30 50 50 10 10 10 10 60 60 60 80 60 70
Wheat 10 20 20 20 20 0 20 10 10 0 20 20 30 0
Table B Compounds 500 g ai/ha 248 249 250 252 253 254 256 257 258 259 260 261 262 263
Postemergence
Barnyardgrass 40 20 20 10 10 10 60 0 0 0 0 0 10 10
Blackgrass 30 30 40 20 20 10 20 10 10 20 10 20 20 20
Cocklebur 50 30 40 40 20 20 0 70 30 20 20 10 10 10 Corn 30 20 30 10 0 10 10 0 10 20 0 20 20 10
Crabgrass, Large 20 30 20 10 0 10 20 10 0 20 10 10 20 20
Foxtail, Giant 30 30 30 30 0 0 50 0 0 0 0 0 20 20 Lambsquarters 70 20 40 30 30 20 60 50 70 30 30 60 80 80 Morningglory 50 30 30 20 30 30 10 0 10 0 10 0 0 20 Oat , Wild 60 40 40 20 30 20 30 30 30 20 30 20 0 20 Pigweed 80 80 70 30 30 30 60 80 60 90 70 70 80 90 Surinam Grass 20 30 20 20 0 10 20 20 10 20 20 20 20 10 Velvetleaf 30 20 30 30 10 10 30 10 0 0 20 0 20 20 Wheat 40 30 40 20 30 20 30 20 20 20 40 20 10 20
Table B Compounds
500 g ai/ha 264 265 266 267 268 269 270 271 272 273 274 275 276 277 Postemergence
Barnyardgrass 0 90 30 30 0 80 70 10 20 10
Blackgrass 20 10 20 40 50 50 20 20 100 70 30 40 40 20
Cocklebur 0 0 0 90 50 50 0 90 80 10 10 10
Corn 0 10 0 40 30 30 10 20 40 20 20 0 20 10 Crabgrass, Large 0 0 0 40 20 20 0 0 70 50 0 10 20 0
Foxtail, Giant 0 0 0 50 20 30 0 0 30 20 50 0 40 0
Lambsquarters 0 0 100 50 70 70 10 60 100 90 70 70 60 30
Morningglory 0 10 50 40 20 40 10 0 100 70 60 10 30 20
Oat, Wild 20 10 20 40 50 30 0 30 90 50 40 40 40 20 Pigweed 0 20 100 90 50 60 0 80 100 90 60 70 70 10
Surinam Grass 0 0 20 50 50 20 10 0 60 40 30 30 20 0
Velvetleaf 0 10 0 70 60 20 0 0 100 70 10 30 40 20
Wheat 10 10 30 30 30 30 0 30 30 40 20 30 30 20
Table B Compounds 500 g ai/ha 278 279 280 281 282 283 284 285 286 287 288 289 290 291
Postemergence Barnyardgrass 10 10 0 0 20 0 0 10 0 20 0 0 0 30 Blackgrass 30 30 20 30 30 40 40 30 20 30 20 10 30 10 Cocklebur 30 20 30 20 20 0 0 30 20 10 0 0 10 10 Corn 20 10 10 10 20 10 10 10 10 70 0 0 10 60
Crabgrass , Large 10 10 0 10 10 10 10 20 10 0 0 0 0 30 Foxtail, Giant 10 0 0 10 20 0 0 50 50 80 30 60 60 80 Lambsquarters 30 20 20 30 60 30 50 70 70 20 30 30 20 60 Morningglory 20 20 10 10 20 30 0 30 0 20 0 0 0 40 Oat, Wild 30 20 20 20 20 10 30 50 40 40 40 30 40 20 Pigweed 40 30 20 30 60 20 70 80 100 30 20 20 10 30 Surinam Grass 10 10 10 20 10 10 20 30 20 10 0 0 30 60 Velvetleaf 10 10 20 20 20 0 0 40 60 60 20 10 10 60
Wheat 30 30 30 30 30 20 30 40 30 30 30 20 30 0
Table B Compounds
500 g ai/ha 292 293 294 295 296 297 298 299 300 301 302 303 304 305
Postemergence
Barnyardgrass 0 10 60 50 80 20 50 90 50 60 40 40 20 0
Blackgrass 20 30 60 40 40 20 50 50 30 40 20 40 40 30
Cocklebur 10 30 30 90 60 0 50 70 50 50 10 30 100 10
Corn 20 30 50 20 70 100 10 20 30 50 50 70 80 70
Crabgrass, Large 10 20 20 60 60 30 70 90 30 60 10 60 10 0
Foxtail, Giant 20 30 50 70 60 30 50 80 30 20 20 50 30 20
Lambsquarters 70 70 80 60 70 20 90 100 80 80 70 90 90 80
Morningglory 20 70 20 100 80 30 70 80 90 90 60 90 100 0
Oat, Wild 40 50 50 50 40 20 40 40 30 40 10 40 40 30
Pigweed 30 40 70 100 100 40 90 100 90 90 90 90 90 70
Surinam Grass 20 20 40 60 50 30 50 80 10 30 10 20 10 20
Velvetleaf 10 30 80 100 100 10 60 100 70 100 10 70 60 20
Wheat 20 30 40 30 30 10 30 30 20 20 10 20 20 10
Table B Compounds
500 g ai/ha 306 307 308 309 310 311 312 313 314 315 316 317 318 319
Postemergence
Barnyardgrass 10 10 10 40 20 0 0 50 30 20 40 0 70 20
Blackgrass 30 30 30 30 30 0 0 10 20 0 0 0 10 0
Cocklebur 70 30 40 70 20 0 0 90 30 20 20 0 80 40
Corn 30 10 10 60 20 0 0 20 20 20 20 0 20 20
Crabgrass, Large 50 30 10 40 30 0 0 20 20 10 10 0 60 20
Foxtail, Giant 40 30 20 40 40 0 0 50 20 10 20 0 10 30
Lambsquarters 80 80 60 80 80 0 20 90 60 60 70 50 80 60
Morningglory 70 0 20 40 50 0 20 80 80 20 10 0 80 20
Oat, Wild 30 20 20 40 40 0 0 30 30 10 20 0 30 20
Pigweed 100 60 70 70 70 0 20 70 70 50 50 0 100 40
Surinam Grass 30 30 20 40 20 0 0 20 20 20 10 0 20 20
Velvetleaf 60 60 20 40 50 0 0 70 30 20 40 0 80 20
Wheat 20 20 20 30 20 0 0 10 10 0 0 0 10 30 Table B Clompcιunds
500 g ai/ha 329 330 331 332 333 334 335 336 338 340 341 342 343 344
Postemergence
Barnyardgrass 10 0 20 60 40 60 50 30 40 20 20 20 50 10
Blackgrass 20 0 20 80 70 70 30 20 40 30 20 30 10 0
Cocklebur 30 0 30 70 80 70 70 50 10 20 20 20 20 10
Corn 20 0 0 10 10 20 20 20 20 20 10 30 30 10
Crabgrass, Large 10 0 10 80 100 50 40 50 60 20 20 20 50 10
Foxtail, Giant 30 0 30 50 40 60 40 40 30 40 30 50 50 10
Lambsquarters 70 10 70 100 100 90 30 90 50 70 100 100 100 40
Morningglory 20 10 10 70 60 80 40 70 100 40 40 80 80 50
Oat, Wild 30 20 30 60 60 30 40 20 40 30 30 30 10 0
Pigweed 80 0 50 100 100 70 70 70 80 80 60 80 90 50
Surinam Grass 20 0 20 40 30 50 30 20 40 20 20 20 40 10
Velvetleaf 30 10 20 90 60 60 60 30 50 40 30 50 50 30
Wheat 30 0 20 30 30 20 20 10 10 10 20 10 0 10
Table B Compounds
500 g ai/ha 345 347 348 349 350 351 352 353 354 355 356 357 358 359
Postemergence
Barnyardgrass 0 0 0 10 0 0 10 10 0 10 0 10 20 10
Blackgrass 0 30 40 80 0 0 30 40 20 20 10 30 40 50
Cocklebur 0 0 0 20 20 0 10 20 20 10 0 20 20 30
Corn 0 0 0 10 20 10 10 20 0 0 0 20 0 10
Crabgrass, Large 0 0 0 20 10 10 20 10 10 10 30 10 10 20
Foxtail, Giant 0 0 0 30 30 0 30 30 20 30 30 40 30 20
Lambsquarters 20 10 0 80 10 10 60 40 50 70 50 60 50 50
Morningglory 10 10 0 50 - 0 60 - 60 40 10 30 50 10
Oat, Wild 10 20 30 40 0 0 20 40 20 30 20 30 30 30
Pigweed 20 10 0 70 60 50 60 70 50 50 70 40 40 50
Surinam Grass 0 0 0 20 10 0 40 10 20 20 20 20 10 10
Velvetleaf 10 0 0 40 10 0 60 20 10 50 0 20 20 20
Wheat 0 0 20 10 0 0 20 10 20 20 10 0 10 20
Table B Compounds
500 g ai/ha 360 361 362 363 364 365 366
Postemergence
Barnyardgrass 30 10 0 0 70 10 10
Blackgrass 50 40 20 70 80 90 50 Cocklebur 20 20 30 30 50 60 50
Corn 20 0 0 0 40 20 20
Crabgrass, Large 20 10 0 10 70 80 20
Foxtail, Giant 50 30 10 10 50 70 40
Lambsquarters 20 70 30 70 90 100 90
Morningglory 10 80 80 70 80 - 100
Oat, Wild 60 20 40 40 50 50 50
Pigweed 40 40 50 30 90 - 80
Surinam Grass 30 10 10 20 70 20 20
Velvetleaf 50 30 0 20 50 40 60
Wheat 40 0 10 20 30 30 20
Table B Compounds
250 g ai/ha 54 72 73 74 152 191 192
Postemergence
Barnyardgrass 0 0 10 0 40 10 10
Blackgrass 0 50 30 50 20 10 0
Cocklebur 10 0 20 0 90 10 60
Corn - 0 30 0 30 10 10
Crabgrass, Large 0 0 10 10 20 20 20
Foxtail, Giant 0 0 30 10 20 20 20
Lambsquarters 40 10 10 10 80 80 80
Morningglory - 0 10 10 60 90 100
Oat, Wild 0 30 40 40 20 20 20
Pigweed 10 0 20 20 90 70 60
Surinam Grass - 0 10 10 40 10 10
Velvetleaf 0 0 50 30 50 20 50
Wheat 0 10 30 20 10 0 0
Table B Compounds
125 g ai/ha 6 7 8 10 11 12 13 14 Postemergence
Barnyardgrass 0 30 10 10 10 0 0 0 0 0 0 0 10 10
Blackgrass 20 10 0 0 0 20 0 0 30 40 40 10 10 20
Cocklebur 60 50 30 30 20 0 0 0 50 20 10 10 10 10
Corn 0 20 20 20 20 0 0 0 0 0 0 0 0 0 Crabgrass, Large 0 20 0 20 20 20 0 0 0 10 0 0 20 10
Foxtail, Giant 20 30 20 20 20 10 0 0 0 20 20 0 30 20
Lambsquarters 60 80 60 80 60 30 0 0 70 80 60 20 50 50 Morningglory 0 30 20 40 0 0 0 0 0 20 0 0 10 0 Oat, Wild 40 20 20 20 20 10 0 0 40 20 20 10 10 10 Pigweed 50 60 30 40 30 20 0 0 70 80 20 0 30 30 Surinam Grass 0 20 10 10 20 10 0 0 0 20 10 0 10 10 Velvetleaf 40 20 10 20 20 0 0 0 20 70 10 0 20 40 Wheat 10 20 0 10 0 0 0 0 10 10 10 10 0
Table B Compounds
125 g ai/ha 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Postemergence Barnyardgrass 0 10 0 10 0 0 0 0 0 0 0 0 0 10
Blackgrass 10 50 20 20 10 30 20 10 20 30 30 0 60 10
Cocklebur 0 10 10 0 0 0 0 0 10 0 0 0 30
Corn 0 10 10 0 0 0 0 0 0 0 0 0 30 0
Crabgrass, Large 10 10 0 0 10 10 10 0 0 0 0 0 70 10 Foxtail, Giant 20 10 10 10 0 10 10 0 0 0 0 0 30 20
Lambsquarters 20 60 60 10 10 30 10 0 0 10 0 0 90 80
Morningglory 0 0 0 10 10 10 0 10 0 10 0 0 20 0
Oat, Wild 10 30 30 20 10 30 10 10 0 20 30 0 50 20
Pigweed 20 40 30 10 10 10 30 10 10 20 0 0 90 90 Surinam Grass 10 10 10 10 10 10 10 0 0 0 0 0 40 20
Velvetleaf 10 40 10 20 0 20 10 0 10 0 0 30 30
Wheat 10 20 20 0 0 20 10 0 20 10 0 10 10
Table B Compounds
125 g ai/ha 29 30 31 32 33 34 35 36 37 40 41 43 44 45 Postemergence
Barnyardgrass 0 10 10 0 20 20 10 20 20 10 10 20 20 20
Blackgrass 0 10 0 0 20 10 20 10 10 10 10 20 10 10
Cocklebur 50 70 80 10 80 40 50 30 60 10 10 10 40 20
Corn 10 10 30 10 - - - - - - - 20 20 20 Crabgrass, Large 20 10 20 0 20 20 20 20 10 10 20 90 20 30
Foxtail, Giant 10 10 20 0 30 30 20 20 20 0 10 30 20 20
Lambsquarters 70 80 90 70 90 80 80 80 80 40 60 90 80 80
Morningglory 0 10 30 0 - - - - - - - 80 30 40
Oat, Wild 10 20 20 10 10 10 0 20 10 0 10 10 20 0 Pigweed 100 30 60 40 80 90 80 80 60 20 50 100 90 90
Surinam Grass 20 20 30 10 10 20 20 10 10 10 10 40 20 20
Velvetleaf 60 20 30 10 50 40 30 20 20 10 10 80 50 60 Wheat 0 10 0 20 30 20 10 20 10 0 20 20 20
Table B Compounds
125 g ai/ha 46 47 48 49 50 51 52 55 56 57 58 59 60 61
Postemergence
Barnyardgrass 10 20 40 30 50 60 0 10 20 10 30 0 10 20
Blackgrass 10 10 0 0 20 0 0 - 0 0 10 0 0 0
Cocklebur 30 10 0 20 90 70 20 10 80 30 80 10 40 60
Corn 20 10 0 20 30 0 10 20 20 20 10 10 10 20
Crabgrass, Large 30 10 10 10 10 20 0 10 10 10 20 10 10 20
Foxtail, Giant 30 30 20 10 30 0 10 0 20 20 20 0 10 20
Lambsquarters 80 80 60 50 80 80 0 70 80 70 90 80 80 90
Morningglory 0 30 0 0 70 0 0 10 0 10 20 20 10 20
Oat, Wild 0 10 10 10 20 0 0 10 20 30 20 10 20 20
Pigweed 90 90 50 30 80 80 0 10 60 70 60 70 70 20
Surinam Grass 30 20 30 10 30 10 0 10 20 10 10 10 10 20
Velvetleaf 60 60 10 30 40 60 10 20 40 20 50 20 20 30
Wheat 20 20 0 0 30 20 0 10 10 10 0 0 0 10
Table B Compounds
125 g ai/ha 62 63 64 65 66 67 68 69 70 71 75 76 77 78
Postemergence
Barnyardgrass 20 10 10 10 0 10 0 0 20 0 10 10 0 30
Blackgrass 10 10 0 10 0 10 10 10 10 0 10 10 20 20
Cocklebur 70 60 30 60 20 0 10 0 50 0 10 40 0 80
Corn 10 20 10 20 10 10 0 0 20 0 10 10 10 -
Crabgrass, Large 10 10 10 10 0 10 0 0 20 0 10 10 0 20
Foxtail, Giant 10 10 10 10 0 10 0 0 20 0 20 20 0 30
Lambsquarters 80 80 70 70 60 40 0 0 80 0 40 30 50 70
Morningglory 20 20 0 10 20 0 0 0 20 0 20 10 0 -
Oat, Wild 10 20 20 10 10 10 10 10 20 0 10 30 40 10
Pigweed 80 40 20 40 20 0 10 10 30 0 50 100 70 80
Surinam Grass 50 10 10 20 10 10 0 0 20 0 10 20 0 20
Velvetleaf 60 40 10 10 10 10 0 0 20 0 20 40 20 70
Wheat 0 10 0 0 0 10 0 0 10 0 10 20 10 30
Table B Compounds
125 g ai/ha 79 80 81 82 83 84 85 86 87 88 89 90 91 92
Postemergence
Barnyardgrass 30 80 70 10 10 20 60 50 0 30 10 0 0 0 Blackgrass 20 20 0 0 0 0 10 10 0 0 0 0 0 0 Cocklebur 80 70 70 80 0 20 90 20 0 10 70 10 0 0 Corn - 20 10 20 10 10 20 20 0 10 10 10 10 10
Crabgrass, Large 20 100 10 10 30 20 50 60 0 30 10 10 0 0 Foxtail, Giant 30 50 20 10 10 20 40 0 30 20 10 0 0 Lambsquarters 70 70 0 20 0 50 80 0 70 30 50 20 20 Morningglory - 100 0 10 30 50 60 0 0 20 10 0 0 Oat, Wild 20 30 20 10 10 20 20 30 0 0 20 10 0 0 Pigweed 70 100 50 80 70 80 100 100 0 50 20 30 10 0 Surinam Grass 30 90 40 30 20 50 60 70 0 0 10 10 10 0 Velvetleaf 70 90 80 80 50 60 60 60 0 30 30 10 0 0 Wheat 30 20 20 20 20 20 50 30 0 0 20 10 0 0
Table B Compounds
125 g ai/ha 93 94 95 96 97 98 99 100 101 102 104 105 106 107 Postemergence
Barnyardgrass 10 10 0 0 0 10 0 0 10 0 0 0 0 0
Blackgrass 10 0 0 0 0 0 20 10 20 0 0 0 0 0
Cocklebur 50 20 60 90 0 0 0 0 20 30 0 30 20 0
Corn 10 20 10 10 0 10 10 0 10 20 0 0 10 0 Crabgrass, Large 10 10 0 40 0 20 10 0 10 10 0 0 0 0
Foxtail, Giant 10 10 10 30 0 10 10 0 20 10 0 0 0 0
Lambsquarters 60 50 100 100 50 20 70 0 80 10 0 50 50 10
Morningglory 10 10 0 0 0 0 0 0 10 10 0 0 10 0
Oat, Wild 10 10 10 20 0 0 20 20 30 20 0 0 10 0 Pigweed 10 10 90 70 0 10 20 0 80 80 0 0 10 0
Surinam Grass 10 10 20 20 0 10 10 0 10 70 0 0 10 10
Velvetleaf 10 10 50 70 0 10 20 0 20 0 0 0 0 0
Wheat 10 0 10 10 0 0 20 10 10 0 0 0 0 0
Table B Compounds 125 g ai/ha 108 109 110 112 113 114 115 117 118 119 120 121 122 123
Postemergence
Barnyardgrass 10 10 10 50 30 20 10 20 10 0 10 0 0 0
Blackgrass 0 0 0 20 10 10 10 0 0 0 0 0 0 0
Cocklebur 70 30 10 60 100 80 80 30 70 0 30 10 70 0 Corn 10 10 10 40 30 - - - 20 10 - 0 10 0
Crabgrass, Large 20 10 10 20 30 30 10 10 20 20 10 10 10 0
Foxtail, Giant 10 20 10 20 30 30 20 10 10 10 10 0 10 0 Lambsquarters 90 10 40 90 90 80 80 60 0 0 80 Morningglory 30 0 20 20 20 20 0 Oat, Wild 20 20 0 40 40 10 10 10 20 10 10 10 10 Pigweed 80 20 20 90 90 90 80 50 60 0 10 30 Surinam Grass 10 10 20 20 40 10 60 30 40 10 20 10 10 Velvetleaf 50 10 30 30 20 50 60 20 20 0 10 10 10 Wheat 10 10 10 20 10 20 30 10 10 0 10 0 0
Table B Compounds
125 g ai/ha 124 125 126 127 128 130 131 132 133 134 135 136 137 138 Postemergence
Barnyardgrass 0 0 0 10 20 50 10 50 0 20 20 50 30 10
Blackgrass 0 0 0 10 10 20 10 10 0 0 0 30 10 0
Cocklebur 0 0 50 10 90 100 70 90 10 80 40 100 50 40
Corn 0 0 0 - - 20 20 20 10 20 20 10 10 20 Crabgrass, Large 10 0 40 20 20 70 20 30 10 30 20 10 10 20
Foxtail, Giant 0 0 20 20 20 20 20 30 0 30 30 10 10 20
Lambsquarters 30 0 0 70 0 90 80 100 60 80 70 100 80 80
Morningglory 0 0 0 - - 100 20 60 10 20 30 20 0 20
Oat, Wild 0 0 30 10 10 40 20 20 20 30 20 50 30 20 Pigweed 20 0 40 30 20 100 30 70 20 80 80 60 90 60
Surinam Grass 10 0 20 10 10 50 20 40 0 20 30 20 20 20
Velvetleaf 0 0 0 0 50 70 10 60 10 30 20 60 40 20
Wheat 0 0 0 0 0 20 10 10 0 10 20 20 10 20
Table B Compounds 125 g ai/ha 139 140 141 142 143 144 145 146 147 148 149 150 151 153
Postemergence Barnyardgrass 10 0 0 0 0 70 0 20 20 0 0 10 0 30 Blackgrass 0 0 20 40 0 20 10 10 10 0 10 0 10 10 Cocklebur 20 0 0 40 0 30 0 20 0 20 20 60 0 50 Corn 10 0 0 0 0 20 10 10 10 10 10 10 10 10
Crabgrass, Large 10 0 10 0 0 30 10 10 20 10 10 10 0 10 Foxtail, Giant 10 0 20 30 0 40 30 20 30 10 10 0 10 10 Lambsquarters 80 20 60 60 0 90 60 80 80 10 20 50 0 80 Morningglory 10 0 20 0 0 50 0 0 0 10 20 20 10 10 Oat, Wild 10 0 10 20 0 20 10 10 0 10 10 20 10 20 Pigweed 60 0 30 50 0 100 90 80 80 10 50 70 10 20 Surinam Grass 10 0 10 10 10 60 20 10 20 10 10 10 10 30 Velvetleaf 20 0 20 10 0 80 50 50 60 10 10 20 10 50
Wheat 10 0 20 10 0 20 0 0 0 10 10 10 10 10
Table B Compounds
125 g ai/ha 154 155 156 157 158 159 160 161 162 163 164 165 166 167
Postemergence
Barnyardgrass 20 10 10 0 0 0 0 10 0 0 0 0 0 0
Blackgrass 10 40 30 10 20 - - 40 20 10 0 0 0 0
Cocklebur 60 60 40 10 20 80 20 20 10 10 0 0 0 0
Corn 10 10 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 10 20 10 0 30 0 0 0 20 20 0 0 0 0
Foxtail, Giant 10 20 20 30 0 40 30 20 20 0 0 0 0 0
Lambsquarters 80 70 60 20 80 90 70 70 80 50 0 0 0 0
Morningglory 60 30 20 0 0 10 0 20 0 0 0 0 0 0
Oat, Wild 10 40 40 10 30 - 10 30 20 10 0 0 0 0
Pigweed 20 60 30 40 50 80 40 20 40 60 0 0 0 0
Surinam Grass 30 20 10 20 0 0 10 20 0 0 0 0 0 0
Velvetleaf 20 20 60 50 50 20 70 20 60 40 0 0 0 0
Wheat 10 20 20 10 10 - - 10 10 0 0 0 0 0
Table B Compounds
125 g ai/ha 168 169 170 171 179 180 181 182 183 184 185 186 187 188
Postemergence
Barnyardgrass 50 0 0 0 0 0 0 30 0 0 30 10 10 10
Blackgrass 10 0 0 0 0 0 0 0 0 0 0 10 0 10
Cocklebur 70 0 0 0 0 0 20 50 50 30 20 60 30 20
Corn 50 10 0 0 0 0 20 30 20 20 20 20 0 10
Crabgrass, Large 20 10 10 0 0 0 10 20 20 20 20 10 10 10
Foxtail, Giant 20 0 0 10 0 0 20 0 20 30 20 10 10 10
Lambsquarters 70 40 60 10 0 0 70 60 70 60 60 10 0 60
Morningglory 70 20 30 0 0 0 20 50 60 0 40 20 20 20
Oat, Wild 20 10 10 0 0 0 20 20 10 20 10 10 10 20
Pigweed 70 20 30 10 0 0 40 50 70 20 60 60 20 50
Surinam Grass 20 0 10 10 0 0 20 10 0 10 20 10 10 10
Velvetleaf 20 0 10 0 0 0 10 0 40 30 30 60 0 10
Wheat 20 0 0 0 0 0 0 0 0 0 0 10 0 0 Table B C!ompoiunds
125 g ai/ha 189 190 193 194 195 196 197 198 199 200 201 202 203 204
Postemergence
Barnyardgrass 0 0 0 0 40 0 0 0 0 0 0 0 0 10
Blackgrass 0 0 0 0 0 0 0 0 0 0 0 0 0 20
Cocklebur 0 0 20 10 30 0 0 60 10 10 10 30 0 90
Corn 10 10 10 0 20 0 10 20 10 10 10 10 0 20
Crabgrass, Large 10 10 10 10 20 30 0 10 10 0 0 0 0 10
Foxtail, Giant 0 10 10 0 20 0 0 20 10 10 0 10 0 10
Lambsquarters 50 30 90 - 0 0 0 70 60 60 40 50 10 30
Morningglory 80 50 30 10 0 0 0 60 40 0 0 20 0 20
Oat, Wild 10 10 0 0 10 0 10 20 10 0 10 10 0 10
Pigweed 30 30 20 20 70 10 0 50 10 10 10 30 0 50
Surinam Grass 10 10 10 10 10 0 10 20 10 10 0 10 10 20
Velvetleaf 20 20 50 10 20 0 0 20 20 10 0 10 0 60
Wheat 0 0 10 0 10 0 0 0 0 0 0 0 0 10
Table B Compounds
125 g ai/ha 205 206 207 209 210 211 212 213 214 215 216 217 218 219
Postemergence
Barnyardgrass 10 0 20 10 20 10 10 0 0 0 0 0 0 0
Blackgrass 0 0 0 0 10 10 10 20 0 0 0 0 0 0
Cocklebur 40 20 40 30 60 30 80 0 0 20 0 0 0 0
Corn 20 20 20 20 20 10 20 0 0 0 0 0 0 0
Crabgrass, Large 10 10 20 20 20 10 10 0 0 0 0 0 0 0
Foxtail, Giant 20 20 20 20 20 10 10 0 0 0 0 0 0 0
Lambsquarters 60 30 50 40 70 60 90 0 0 0 0 0 0 0
Morningglory 30 20 10 20 30 10 10 10 0 0 0 0 0 0
Oat, Wild 20 20 20 20 20 10 20 10 0 10 0 0 0 0
Pigweed 40 30 30 30 40 10 60 0 0 20 0 0 0 10
Surinam Grass 20 10 20 20 20 10 30 10 0 0 0 0 0 0
Velvetleaf 20 20 20 20 30 30 50 0 0 40 0 0 0 0
Wheat 10 20 20 10 20 10 10 0 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 220 221 222 223 224 225 226 227 228 229 230 231 232 233
Postemergence
Barnyardgrass 0 0 10 10 10 10 10 - 30 20 0 10 - -
Blackgrass 0 0 0 0 0 20 20 20 30 30 30 20 0 0 Cocklebur 0 0 20 10 10 20 10 20 30 20 0 10 10 20 Corn 10 10 0 10 10 10 10 30 10 10 10 10 10 10
Crabgrass, Large 10 0 10 10 10 10 20 30 20 10 10 20 10 10 Foxtail, Giant 0 10 10 10 20 10 20 10 30 30 10 20 10 0 Lambsquarters 10 0 50 60 60 50 40 50 70 70 50 60 50 50 Morningglory 0 0 40 40 30 10 30 50 70 10 20 20 30 50 Oat, Wild 0 0 0 0 0 0 30 0 40 30 20 20 0 0 Pigweed 10 10 40 60 40 40 30 20 50 60 40 50 - 60 Surinam Grass 0 0 10 10 10 10 10 10 20 10 10 10 10 10 Velvetleaf 0 0 50 20 20 30 20 20 60 60 20 30 30 30 Wheat 0 0 0 0 0 10 20 0 30 30 10 20 0 0
Table B Compounds
125 g ai/ha 234 235 236 237 238 239 240 241 242 243 244 245 246 247
Postemergenee Barnyardgrass 0 0 0 50 10 10 40 30 0
Blackgrass 0 0 0 0 0 0 0 10 0 10 0 0 0
Cocklebur 10 0 20 10 0 0 20 40 10 30 40 20 0
Corn 0 20 20 20 0 0 0 10 10 10 10 0 0
Crabgrass, Large 10 10 0 10 0 0 0 30 10 10 10 10 10 Foxtail, Giant 0 10 10 10 0 0 0 20 10 20 30 30 10
Lambsquarters 20 40 60 60 0 0 20 30 90 70 40 80 50 60
Morningglory 20 - 10 20 0 0 20 20 20 0 10 10 0 20
Oat, Wild 20 10 20 0 0 0 0 0 10 0 30 20 10 0
Pigweed 30 30 60 30 0 20 0 30 60 20 50 60 50 60 Surinam Grass 0 10 0 20 0 0 0 10 30 10 20 30 20 10
Velvetleaf 20 20 20 30 0 0 0 10 50 50 40 70 30 30
Wheat 0 0 10 10 0 0 0 0 10 0 10 10 0 0
Table B Compounds
125 g ai/ha 248 249 250 252 253 254 256 257 258 259 260 261 262 263 Postemergence
Barnyardgrass 10 10 20 0 0 0 0 0 0 0 0 0 0 0
Blackgrass 20 20 10 10 20 0 0 0 10 10 10 0 0 10
Cocklebur 30 30 30 20 10 20 0 0 20 0 10 0 0 0
Corn 20 10 20 10 0 0 0 0 0 10 0 10 0 0 Crabgrass, Large 10 10 20 0 0 10 0 0 0 0 0 0 0 10
Foxtail, Giant 20 20 20 20 0 0 0 0 0 0 0 0 10 0
Lambsquarters 60 10 0 30 20 10 30 20 30 10 10 10 50 70 Morningglory 20 20 20 20 0 20 0 0 0 0 0 0 0 0 Oat, Wild 30 30 20 20 20 20 10 10 20 10 20 0 0 10 Pigweed 60 20 30 20 20 10 30 60 50 30 20 20 70 60 Surinam Grass 10 10 10 10 0 10 0 0 0 10 0 0 0 10 Velvetleaf 20 10 20 30 10 10 10 0 0 0 0 0 20 20 Wheat 30 30 20 20 20 10 10 0 20 10 20 0 0 10
Table B Compounds
125 g ai/ha 264 265 266 267 268 269 270 271 272 273 274 275 276 277
Postemergence Barnyardgrass 0 0 0 40 0 10 0 0 20 20 0 0 0 0
Blackgrass 0 0 20 20 30 20 0 10 60 50 30 40 30 10
Cocklebur 0 0 0 30 20 20 0 0 40 20 0 0 10 0
Corn 0 0 0 20 20 10 0 0 30 10 0 0 0 0
Crabgrass, Large 0 0 0 20 0 10 0 0 10 30 0 0 10 0 Foxtail, Giant 0 0 0 40 10 30 0 0 10 10 20 0 10 0
Lambsquarters 0 0 60 30 60 50 0 10 100 60 40 50 20 20
Morningglory 0 0 30 30 10 20 0 0 90 20 0 0 10 0
Oat, Wild 0 0 10 30 30 20 0 20 60 30 20 30 30 10
Pigweed 0 0 20 60 20 60 0 50 100 80 40 60 40 0 Surinam Grass 0 0 10 30 10 10 0 0 10 20 20 10 10 0
Velvetleaf 0 0 0 50 20 10 0 0 50 40 10 0 10 20
Wheat 0 0 20 20 30 20 0 30 20 30 20 20 20 20
Table B Compounds
125 g ai/ha 278 279 280 281 282 283 284 285 286 287 288 289 290 291 Postemergence
Barnyardgrass 0 0 0 0 0 0 o o o o o o o o
Blackgrass 20 10 20 20 20 20 20 30 10 10 20 10 20 0
Cocklebur 10 0 0 20 10 0 10 10 10 0 0 0 0
Corn 10 10 0 0 10 0 10 0 0 0 0 0 0 Crabgrass, Large 0 0 0 10 10 o o o o 0 0 0 0
Foxtail, Giant 0 0 0 10 20 0 30 20 20 0 20 20 10
Lambsquarters 20 10 10 20 10 0 50 40 10 10 0 0 10 20
Morningglory 0 0 0 0 10 0 0 20 0 0 0 0 0 0
Oat, Wild 20 20 10 10 0 0 10 40 30 20 20 20 20 10 Pigweed 10 30 10 20 20 0 60 70 60 20 10 10 10 0
Surinam Grass 10 10 0 10 10 0 0 10 10 0 0 0 0 0
Velvetleaf 10 10 10 0 10 0 0 10 10 0 10 0 0 0 Wheat 30 30 20 30 30 20 20 30 20 10 20 20 20 0
Table B Compounds
125 g ai/ha 292 293 294 295 296 297 298 299 300 301 302 303 304 305
Postemergence Barnyardgrass 0 0 20 30 30 10 10 10 30 20 10 40 20 0
Blackgrass 10 30 20 30 30 10 20 20 10 10 10 20 10 20
Cocklebur 0 20 30 40 50 0 20 20 10 10 10 10 0 10
Corn 10 10 10 10 30 10 0 0 30 50 10 70 40 70
Crabgrass, Large 0 0 10 30 30 20 20 10 10 20 0 10 10 0 Foxtail, Giant 0 20 30 60 60 20 10 10 30 10 0 50 30 20
Lambsquarters 30 50 70 40 50 10 40 40 70 70 60 80 80 50
Morningglory 0 30 10 50 50 0 60 70 90 60 30 80 100 0
Oat, Wild 10 30 40 40 30 0 30 20 30 20 0 30 30 10
Pigweed 20 10 30 100 80 0 80 90 80 80 80 70 90 0 Surinam Grass 0 10 20 50 40 20 20 20 10 10 0 10 0 0
Velvetleaf 10 10 40 70 90 0 60 60 40 30 10 30 10 20
Wheat 0 20 30 20 20 0 20 20 10 10 0 10 10 0
Table B Compounds
125 g ai/ha 306 307 308 309 310 311 312 313 314 315 316 317 318 319 Postemergence
Barnyardgrass 10 0 0 20 0 0 0 30 10 10 0 0 40 0
Blackgrass 10 10 10 10 10 0 0 0 10 0 0 0 10 0
Cocklebur 30 20 0 40 0 0 0 0 10 20 0 0 10 20
Corn 30 - 0 20 0 0 0 10 10 10 10 0 20 20 Crabgrass, Large 10 10 0 0 10 0 0 10 10 0 10 0 10 20
Foxtail, Giant 10 20 10 20 10 0 0 20 20 0 0 0 10 20
Lambsquarters 70 60 50 40 60 0 10 60 30 50 40 0 80 50
Morningglory 0 0 0 0 0 0 0 20 0 10 0 0 10
Oat, Wild 20 0 10 20 30 0 0 20 10 0 0 0 0 20 Pigweed 70 50 60 50 50 0 0 60 60 10 10 0 70 30
Surinam Grass 10 10 10 10 10 0 0 10 20 20 10 0 10 10
Velvetleaf 40 10 10 20 20 0 0 60 20 20 0 0 40 10
Wheat 10 0 10 20 10 0 0 0 0 0 0 0 0 10
Table B Compounds 125 g ai/ha 329 330 331 332 333 334 335 336 338 340 341 342 343 344
Postemergence Barnyardgrass 0 10 20 10 0 10 20 10 10 10 10 Blackgrass 20 0 10 40 30 30 10 10 20 20 10 20 0 0
Cocklebur 0 0 10 30 20 20 10 0 10 0 10 10 0 0
Corn 0 0 0 0 10 0 10 10 10 0 0 10 10 10
Crabgrass, Large 0 0 10 50 40 10 10 20 20 10 10 10 20 0
Foxtail, Giant 10 0 0 30 30 10 20 20 20 20 30 20 30 10
Lambsquarters 30 0 60 80 90 70 10 60 10 30 30 60 40 20
Morningglory 0 10 0 40 30 50 10 40 60 10 20 30 30 10
Oat, Wild 20 0 10 40 40 20 20 10 0 20 0 20 10 0
Pigweed 50 0 10 100 90 40 20 60 60 50 30 40 40 20
Surinam Grass 10 0 10 20 20 20 10 20 20 10 10 10 10 0
Velvetleaf 10 0 10 60 50 50 30 20 20 20 20 20 20 20
Wheat 20 0 20 20 20 10 10 0 0 0 10 0 0 0
Table B Compounds
125 g ai/ha 345 346 347 348 349 350 351 352 353 354 355 356 357 358
Postemergence
Barnyardgrass 0 20 0 0 0 0 0 0 10 0 0 0 0 10
Blackgrass 0 40 30 20 20 0 0 10 10 10 0 0 0 10
Cocklebur 0 30 0 0 0 0 0 0 10 10 0 - 10 0
Corn 0 0 0 0 0 0 0 0 10 0 0 0 0 0
Crabgrass, Large 0 0 0 0 20 0 0 20 10 0 10 10 0 10
Foxtail, Giant 0 20 0 0 0 0 0 10 20 10 20 30 30 10
Lambsquarters 20 30 10 0 0 0 0 10 20 10 10 10 30 30
Morningglory 10 10 0 0 0 0 0 10 10 30 10 0 10 20
Oat, Wild 0 40 0 20 10 0 0 0 10 0 0 0 0 20
Pigweed 20 70 0 0 0 0 0 10 30 40 20 30 20 20
Surinam Grass 0 10 0 0 0 0 0 10 0 0 10 10 10 10
Velvetleaf 10 10 0 0 0 0 0 10 20 - 30 - 20 10
Wheat 0 20 0 20 0 0 0 10 0 0 0 0 0 0
Table B Compounds
125 g ai/ha 359 360 361 362 363 364 365 366
Postemergence
Barnyardgrass 10 0 0 0 0 10 0 10
Blackgrass 20 30 10 10 20 30 40 40
Cocklebur 10 10 10 10 20 40 20 30
Corn 10 10 0 0 0 10 0 10
Crabgrass, Large 10 10 10 0 10 30 0 10
Foxtail, Giant 20 30 20 10 10 10 20 20 Lambsquarters 40 0 70 10 30 70 90 80
Morningglory 10 0 10 10 50 20 80 -
Oat, Wild 20 40 0 20 20 20 30 40
Pigweed 20 30 20 20 20 40 40 50
Surinam Grass 10 10 10 10 10 30 10 10
Velvetleaf 20 40 10 0 10 20 10 10
Wheat 0 30 0 0 10 10 20 20
Table B Compounds
62 g ai/ha 54 72 73 74 129 152 191 ; 192 251
Postemergence
Barnyardgrass 0 0 0 0 0 30 0 0 0
Blackgrass 0 40 30 30 0 20 0 0 50
Cocklebur 10 0 20 0 60 60 0 0 0
Corn 10 0 0 0 - 20 10 10 0
Crabgrass , Large 0 0 0 0 0 10 20 10 0
Foxtail, Giant 0 0 10 10 10 10 10 10 0
Lambsquarters 40 0 0 0 0 70 60 70 10
Morningglory 10 0 10 0 - 50 40 60 0
Oat, Wild 0 20 20 30 0 10 10 10 20
Pigweed 0 0 10 20 0 50 30 30 10
Surinam Grass 0 0 10 0 0 30 10 10 0
Velvetleaf 0 0 30 0 0 50 10 20 10
Wheat 0 10 20 20 0 10 0 0 20
Table B Compounds Table B Compound
31 g ai/ha 49 168 346 16 g ai/ha 251
Postemergence Postemergence
Barnyardgrass 10 0 0 Barnyardgrass 0
Blackgrass 0 0 30 Blackgrass 10
Cocklebur 10 30 10 Cocklebur 0
Corn 10 10 0 Corn 0
Crabgrass, Large 10 10 0 Crabgrass , Large 0
Foxtail, Giant 0 0 0 Foxtail, Giant 0
Lambsquarters 20 50 0 Lambsquarters 0
Morningglory 0 20 0 Morningglory 0
Oat, Wild 0 10 30 Oat, Wild 20
Pigweed 10 50 60 Pigweed 0
Surinam Grass 10 10 0 Surinam Grass 0 Velvetleaf 10 10 0 Velvetleaf 0
Wheat 0 0 10 Wheat 20
Table B Compounds
500 g ai/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Preemergence
Barnyardgrass 100 100 100 100 90 100 90 0 100 100 100 40 100 100
Cocklebur 100 90 50 0 0 100 70 0 80 100 50 0 - 80
Corn 70 80 60 60 0 90 70 0 60 50 80 0 70 90
Crabgrass, Large 100 100 100 90 100 100 100 0 100 100 100 10 100 100
Foxtail, Giant 100 100 100 100 100 100 100 0 100 100 100 20 100 100
Lambsquarters 100 100 100 100 90 100 100 80 100 100 100 0 100 100
Morningglory 70 90 60 30 0 - 90 0 30 30 10 30 100 100
Pigweed 100 100 100 100 100 100 100 30 100 100 100 0 100 100
Rice 80 90 90 60 20 100 80 10 90 80 80 0 90 100
Surinam Grass 90 100 90 90 50 100 60 0 90 90 100 10 100 100
Velvetleaf 100 100 100 100 eo 100 70 0 100 100 80 10 100 100
Wheat
Table B Compounds
500 g ai/ha 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Preemergence
Barnyardgrass 100 100 100 90 70 70 80 0 0 30 0 0 100 90
Cocklebur 0 100 100 60 100 20 0 0 0 0 - 0 60 0
Corn 30 70 60 50 0 10 0 0 0 0 0 0 90 10
Crabgrass, Large 100 100 90 100 100 100 100 10 10 60 0 0 100 50
Foxtail, Giant 100 100 90 100 90 70 40 10 0 80 0 0 100 60
Lambsquarters 100 100 100 100 90 90 80 0 0 0 0 - 100 100
Morningglory 10 50 10 100 60 80 20 10 0 0 0 0 40 30
Pigweed 100 100 100 100 100 100 80 0 0 100 0 0 100 100
Rice 50 90 70 90 40 50 30 0 0 0 0 0 - -
Surinam Grass 90 90 70 70 70 60 50 0 0 10 0 0 90 70
Velvetleaf 80 100 100 100 100 30 30 0 0 0 0 0 100 100
Table B Compounds
500 g ai/ha 29 30 31 32 33 34 35 36 37 40 41 42 43 44
Preemergence
Barnyardgrass 100 90 90 60 90 80 100 80 60 40 80 30 100 100
Cocklebur 90 10 40 0 30 10 30 0 0 0 0 0 10 20
Corn 50 10 20 0 30 0 40 10 10 0 0 0 10 0 Crabgrass, Large 100 60 50 60 100 100 90 20 90 70 100 70 100 100 Foxtail, Giant 100 80 90 10 100 90 100 30 60 10 70 10 80 70 Lambsquarters 90 100 100 100 100 100 100 100 100 80 100 80 100 100 Morningglory 100 60 80 60 - 20 10 10 0 10 10 10 10 10 Pigweed 100 100 100 70 100 100 100 100 100 60 70 40 100 100
Surinam Grass 80 20 60 30 80 80 80 50 40 10 60 20 50 40 Velvetleaf 90 70 90 70 80 60 60 50 20 10 10 10 100 100
Table B Compounds
500 g ai/ha 45 46 47 48 50 51 52 55 56 57 58 59 60 61 Preemergence
Barnyardgrass 100 100 90 90 80 100 60 100 80 70 100 70 100 60
Cocklebur 80 30 40 50 0 50 10 10 20 10 100 0 0 0
Corn 30 10 10 0 10 50 0 20 20 0 30 0 0 10
Crabgrass, Large 90 100 100 80 90 100 90 100 100 100 100 20 100 100 Foxtail, Giant 100 100 90 90 100 100 60 100 100 100 100 40 100 80
Lambsquarters 100 100 100 90 100 100 90 100 100 100 100 100 90 100
Morningglory 30 20 30 40 40 0 0 10 20 0 30 10 20 20
Pigweed 100 100 100 100 100 100 90 100 100 100 100 100 100 100
Rice - 60 50 50 80 70 70 - 80 0 50 0 Surinam Grass 50 70 70 80 50 80 30 80 60 40 60 10 50 30
Velvetleaf 100 100 100 100 50 100 20 30 100 0 100 40 90 90
Table B Compounds
500 g ai/ha 62 63 64 65 66 67 68 69 70 71 75 76 77 78
Preemergence Barnyardgrass 80 100 90 90 30 80 10 0 50 0 90 100 70 0
Cocklebur 10 10 0 0 0 0 0 - 0 0 10 40 0 0
Corn 10 30 0 10 0 - 0 0 20 0 30 50 40 0
Crabgrass, Large 100 100 100 80 10 20 0 0 100 0 70 90 80 10
Foxtail, Giant 90 100 100 80 10 10 0 0 100 0 90 100 60 30 Lambsquarters 100 100 100 100 50 10 90 40 0 0 80 90 90 0
Morningglory 10 10 0 10 0 0 30 20 20 0 10 80 0 10
Pigweed 100 100 100 100 30 60 90 0 50 0 90 100 100 30
Rice 10 80 60 50 0 50 0 0 10 0 70 60 60
Surinam Grass 40 80 50 50 10 50 0 0 40 0 70 90 40 10 Velvetleaf 100 70 40 60 0 20 10 0 70 0 70 90 30 10 Table B Compounds
500 g ai/ha 79 80 81 82 83 84 85 86 87 88 89 90 91 92
Preemergence
Barnyardgrass 10 20 60 0 0 0 0 0 70 90 0 20 10 0
Cocklebur 0 0 0 0 0 - 0 0 0 0 0 0 - 0
Corn 0 10 0 0 0 0 0 0 0 60 0 20 10 0
Crabgrass , Large 0 0 10 0 0 0 0 0 100 100 80 70 - 10
Foxtail, Giant 10 70 60 0 0 0 0 0 80 90 0 60 10 10
Lambsquarters 0 0 0 0 0 0 0 0 100 100 0 90 30 0
Morningglory 0 20 60 0 0 0 0 - 0 0 0 10 10 0
Pigweed 0 0 80 0 0 0 0 0 90 100 0 80 0 0
Rice - - 0 0 0 0 0 0 60 60 0 0 10 0
Surinam Grass 10 10 10 0 0 0 0 0 20 80 0 20 - 0
Velvetleaf 10 20 80 0 0 0 0 0 40 60 0 20 - 0
Table B Compounds
500 g ai/ha 93 94 95 96 97 98 99 100 101 102 104 105 106 107
Preemergence
Barnyardgrass 20 20 80 90 0 0 30 0 70 90 80 30 70 0
Cocklebur 0 0 0 0 0 0 0 0 90 0 0 0 0 0
Corn 10 0 60 70 0 0 0 0 40 50 0 0 0 0
Crabgrass , Large 20 20 90 100 0 0 70 0 90 100 90 90 100 10
Foxtail, Giant 30 30 100 90 0 0 20 0 60 80 20 10 40 0
Lambsquarters 70 0 100 100 0 0 20 0 100 100 80 80 100 30
Morningglory 10 0 - 10 0 0 0 0 10 100 20 10 10 10
Pigweed 70 20 100 100 0 0 - 0 100 100 70 80 70 0
Rice 0 0 50 70 0 0 0 0 40 - - - - -
Surinam Grass 0 0 70 80 0 0 30 0 30 40 20 10 20 10
Velvetleaf 10 0 60 90 0 0 20 0 50 70 0 0 0 0
Table B Compounds
500 g ai/ha 108 109 110 112 113 114 115 117 118 119 120 121 122 123
Preemergence
Barnyardgrass 90 100 10 70 90 80 100 90 90 10 90 80 90 0
Cocklebur 30 20 10 0 20 10 40 30 10 0 0 0 70 0
Corn 30 10 0 0 0 10 30 30 10 0 0 0 30 0
Crabgrass, Large 100 100 100 90 100 100 100 100 100 80 90 50 100 0
Foxtail, Giant 100 100 20 20 30 90 100 80 70 0 70 70 80 0
Lambsquarters 100 90 90 90 100 100 100 100 0 0 20 100 100 0 Morningglory 70 100 60 60 50 - 90 60 60 10 - 20 70 0 Pigweed 100 100 10 90 100 100 100 90 90 0 30 100 80 0 Surinam Grass 80 80 10 20 10 30 70 60 50 10 0 20 70 0 Velvetleaf 100 eθ 10 50 20 60 100 70 10 10 40 20 60 0 Table B Compounds
500 g ai/ha 124 125 126 127 128 129 130 131 132 133 134 135 136 137 Preemergence Barnyardgrass 10 0 60 70 90 60 70 90 50 60 80 50 100 70 Cocklebur 0 0 0 20 20 20 0 10 0 0 0 0 10 0 Corn 0 0 0 0 20 0 20 0 10 0 10 0 30 10
Crabgrass, Large 0 0 30 100 100 90 100 100 100 80 100 90 100 100 Foxtail, Giant 10 0 0 70 60 20 70 70 80 40 70 20 100 80 Lambsquarters 80 0 90 70 70 20 70 100 90 100 100 100 100 80 Morningglory 0 - 20 - 30 0 10 30 20 10 20 - 70 20 Pigweed 90 0 70 70 80 30 100 100 100 100 100 100 100 100 Rice 0 50 0 40 50 30 50 10
Surinam Grass 10 0 20 60 60 10 80 60 70 20 50 30 90 80 Velvetleaf 0 0 20 20 80 10 90 100 70 70 90 50 100 60
Table B Compounds 500 g ai/ha 138 139 140 141 142 143 144 145 146 147 148 149 150 151
Preemergence
Barnyardgrass 70 90 80 0 100 0 100 100 90 90 10 90 80 10
Cocklebur 10 10 80 10 40 0 20 20 0 10 0 0 0 0
Corn 10 40 0 0 0 0 10 10 0 10 0 50 20 0 Crabgrass, Large 100 100 100 20 100 0 100 100 100 100 0 100 10 10
Foxtail, Giant 70 100 80 20 100 0 100 100 90 100 20 100 60 10
Lambsquarters 100 100 100 0 100 0 100 100 100 100 - 100 100 0
Morningglory 20 30 - 30 30 0 100 40 10 30 0 40 20 0
Pigweed 100 100 80 30 100 0 100 100 100 100 0 100 100 0 Rice 40 60 70 0 80 - 30 20 40 10 10 30 40 0
Surinam Grass 30 90 60 10 60 0 100 80 30 80 0 80 10 10
Velvetleaf 40 80 20 20 100 0 100 100 90 80 0 40 10 0
Table B Compounds 500 g ai/ha 153 154 155 156 157 158 159 160 161 162 163 164 165 166 Preemergence Barnyardgrass 90 80 90 100 0 100 90 100 100 100 90 0 0 0 Cocklebur 0 10 30 100 20 40 100 70 0 90 70 0 0 0 Corn 20 0 30 80 0 60 0 20 10 80 40 0 0 0
Crabgrass, Large 80 80 100 100 20 100 70 80 100 100 90 0 0 0 Foxtail, Giant 50 30 90 100 0 100 60 70 100 100 80 0 0 0 Lambsquarters 100 90 100 100 30 100 100 100 100 100 100 0 0 0 Morningglory 10 0 40 100 40 50 40 90 40 80 70 0 0 0 Pigweed 100 100 100 100 40 100 100 100 100 100 100 0 0 0 Rice 20 0 50 100 0 90 70 80 40 90 80 - 0 0
Surinam Grass 70 10 50 100 0 90 70 70 60 100 70 0 0 0 Velvetleaf 100 70 70 100 0 80 90 80 70 100 90 0 0 0 Table B Compounds
500 g ai/ha 167 169 170 171 179 180 181 182 183 184 185 186 187 188 Preemergence Barnyardgrass 0 10 30 0 0 90 80 70 60 70 10 90 100 Cocklebur - 0 0 0 0 20 0 0 0 0 0 0 0 Corn 0 0 0 0 0 40 0 0 0 0 10 60 50
Crabgrass, Large 0 40 80 30 0 100 100 90 100 50 10 100 100 Foxtail, Giant 0 10 20 0 0 100 100 80 70 70 10 70 100 Lambsquarters 0 60 80 0 100 100 100 80 80 0 40 100 Morningglory 0 10 10 0 20 30 10 50 50 0 30 Pigweed 0 100 90 0 0 100 100 100 100 100 0 60 70 Rice 0 0 0 0 - 70 50 80 0 0 20 80 70
Surinam Grass 0 10 30 0 0 70 60 50 30 20 10 70 70 Velvetleaf 0 0 20 20 0 10 70 50 50 50 20 20 100
Table B Compounds 500 g ai/ha 189 190 193 194 195 196 197 198 199 200 201 202 203 204
Preemergence
Barnyardgrass 30 30 100 90 90 40 10 90 90 20 10 90 10
Cocklebur 0 0 70 20 0 0 0 20 0 0 0 10 10
Corn 0 0 100 50 0 0 0 40 10 0 0 20 0 Crabgrass, Large 60 80 100 100 100 100 0 100 100 90 60 100 80
Foxtail, Giant 10 10 100 80 60 0 0 100 100 10 0 90 10
Lambsquarters 30 50 100 - 80 0 100 90 80 30 100 30
Morningglory 20 0 100 50 40 0 80 60 10 10 30 10 10
Pigweed 100 90 100 100 90 0 100 100 90 20 90 90 10 Rice 50 30 100 70 20 0 80 20 10 0 30 0 0
Surinam Grass 20 10 100 60 30 0 20 50 70 10 0 60 0 0
Velvetleaf 20 10 100 60 20 20 0 60 60 20 10 20 20 0 Table B Compounds 500 g ai/ha 205 206 207 209 210 211 212 213 214 215 216 217 218 219 Preemergence Barnyardgrass 90 70 90 90 90 50 90 80 20 60 40 0 0 20 Cocklebur 20 0 20 30 40 0 50 0 0 0 0 0 0 0 Corn 40 40 50 50 70 10 30 10 0 0 0 0 0 0
Crabgrass, Large 90 60 100 60 90 70 100 70 70 80 40 0 20 100 Foxtail, Giant 100 20 90 60 100 50 100 90 90 80 60 0 0 0 Lambsquarters 100 30 100 100 100 80 100 100 80 100 100 0 0 Morningglory 30 20 40 20 30 10 60 20 0 20 0 0 Pigweed 100 80 100 100 100 30 100 100 100 100 90 0 80 Rice 70 30 70 70 80 10 20 40 0 0 70 0 0
Surinam Grass 80 20 60 50 70 30 70 40 30 70 70 0 0 Velvetleaf 80 10 60 50 70 10 80 80 0 60 0 0 10 Table B Compounds
500 g ai/ha 220 221 222 223 224 225 226 227 228 229 230 231 232 233 Preemergence Barnyardgrass 0 90 100 80 90 90 60 60 100 90 50 80 60 10 Cocklebur 0 0 80 20 50 40 0 0 80 40 0 30 0 0 Corn 0 0 90 80 70 70 20 50 80 40 10 50 0 0
Crabgrass, Large 100 100 100 100 100 100 100 100 100 100 70 90 100 90 Foxtail, Giant 10 70 90 80 70 100 70 70 100 80 80 90 30 0 Lambsquarters 70 100 100 100 100 - 90 90 100 100 90 100 90 30 Morningglory 0 0 100 30 30 10 10 20 40 20 10 10 20 0 Pigweed 100 100 100 100 100 100 70 100 100 100 80 100 90 60 Rice 0 20 100 30 80 90 30 70 90 70 0 50 50 0
Surinam Grass 10 30 100 90 100 90 40 70 100 80 10 60 30 20 Velvetleaf 0 50 100 100 100 100 50 100 100 100 30 90 40 10
Table B Compounds 500 g ai/ha 234 235 236 237 238 239 240 241 242 243 244 245 246 247
Preemergence
Barnyardgrass 0 50 90 50 0 60 70 80 100 90 90 100 90 80
Cocklebur 0 0 20 0 0 0 0 0 40 20 20 0 0 0
Corn - 20 10 20 0 0 0 30 60 50 60 10 20 30 Crabgrass, Large 40 90 70 90 0 100 100 100 100 100 100 100 100 80
Foxtail, Giant 10 50 50 40 0 0 80 90 90 80 90 90 90 70
Lambsquarters 50 90 100 90 0 70 80 100 100 100 100 100 100 100 Morningglory 0 10 20 20 0 0 0 0 10 0 20 20 10 10 Pigweed 40 100 90 70 0 70 100 100 100 100 100 100 100 100 Rice 0 20 60 30 0 0 0 80 80 80 80 50 70 40
Surinam Grass 0 60 60 30 0 0 20 90 90 80 90 80 80 50 Velvetleaf 0 30 80 60 0 0 - 100 100 100 100 90 90 100
Table B Compounds 500 g ai/ha 248 249 250 252 253 254 256 257 258 259 260 251 262 263 Preemergence Barnyardgrass 20 0 10 70 10 40 70 20 90 70 70 20 10 40 Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 - - Corn 0 0 0 60 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 40 0 10 100 - 100 100 - 50 50 - 50 30 50 Foxtail, Giant 60 0 10 90 30 30 60 50 20 70 30 0 0 20 Lambsquarters - - - 100 - 100 100 - 100 - 100 - 90 100 Morningglory 0 10 0 0 0 10 0 0 10 90 0 0 0 0 Pigweed 0 - 100 - 100 100 - 100 100 100 - 100 100 Rice 0 0 10 50 0 20 80 0 90 0 30 60 0 10
Surinam Grass 60 20 30 70 30 40 60 0 30 30 10 0 10 30 Velvetleaf 20 0 20 60 20 20 80 0 60 0 10 20 80 90 Table B Compounds
500 g ai/ha 264 265 266 267 268 269 270 271 272 273 274 275 276 277 Preemergence Barnyardgrass 10 0 80 70 100 100 50 0 90 90 100 60 80 0 Cocklebur 0 0 10 0 90 70 0 0 0 0 0 0 30 10 Corn 0 0 90 20 90 80 50 10 10 30 80 20 60 0
Crabgrass, Large 50 - 100 100 100 100 20 0 100 100 100 0 70 0 Foxtail, Giant 10 50 100 80 100 100 50 0 90 90 90 20 90 0 Lambsquarters 100 0 100 - 100 100 60 100 100 100 100 100 80 Morningglory 0 0 10 30 20 20 0 0 30 10 10 40 10 0 pigweed 100 0 100 - 100 100 20 100 100 100 40 100 100 Rice 0 0 80 40 90 90 60 0 20 40 80 60 80 20
Surinam Grass 10 40 90 50 100 100 20 0 70 50 80 10 60 0 Velvetleaf 10 10 100 50 100 100 70 0 50 40 70 0 50 40
Table B Compounds 500 g ai/ha 278 279 280 281 282 283 284 285 286 287 288 289 290 291 Preemergence Barnyardgrass 80 40 10 90 50 10 80 90 90 100 70 0 80 0 Cocklebur 0 0 0 0 0 0 0 0 0 60 0 0 0 0 Corn 20 0 0 0 0 0 0 40 50 30 0 0 0 0
Crabgrass, Large 80 80 10 70 80 50 90 70 100 100 0 20 90 0 Foxtail, Giant 80 30 10 60 20 10 10 80 90 90 10 0 80 0 Lambsquarters 100 100 80 100 100 100 100 100 100 100 90 100 100 0 Morningglory 10 0 0 20 0 0 0 10 0 10 0 0 0 0 Pigweed 100 100 100 100 100 100 100 100 100 100 90 100 100 0 Rice 80 50 10 60 40 0 20 80 80 90 70 0 80 0
Surinam Grass 60 40 10 40 20 0 10 70 60 80 0 0 10 0 Velvetleaf 60 20 20 70 30 0 60 100 60 100 0 0 0 0
Table B Compounds 500 g ai/ha 292 293 294 295 296 297 298 299 300 301 302 303 304 305 Preemergence Barnyardgrass 90 100 100 20 60 20 90 100 90 100 60 90 70 90 Cocklebur 40 90 100 0 0 0 0 60 20 0 0 20 0 70 Corn 80 100 100 10 40 0 70 90 70 10 10 70 - 60
Crabgrass, Large 100 100 100 80 100 80 100 100 100 100 100 100 100 100 Foxtail, Giant 70 100 100 70 90 60 100 100 100 90 30 100 90 100 Lambsquarters 100 100 100 - 100 80 100 100 100 100 100 100 100 100 Morningglory 30 100 20 20 20 10 40 100 60 80 10 50 10 0 Pigweed 100 100 100 - 80 40 100 100 100 100 100 100 100 100 Rice 90 100 100 20 40 10 60 90 70 70 10 80 20 80
Surinam Grass 100 100 100 20 60 20 100 100 100 100 30 100 70 100 Velvetleaf 70 100 100 60 80 10 60 100 100 100 80 100 100 100 Table B Compounds
500 g ai/ha 306 307 308 309 310 311 312 313 314 315 316 317 318 319 Preemergence Barnyardgrass 90 100 80 100 90 0 0 90 90 20 0 0 90 80 Cocklebur 50 100 0 80 50 0 0 10 0 0 0 0 0 10 Corn 100 80 70 90 70 0 0 30 10 0 0 0 0 40
Crabgrass, Large 100 100 70 100 100 0 0 90 30 20 20 0 90 100 Foxtail, Giant 100 90 90 100 100 0 0 100 100 20 0 0 80 50 Lambsquarters 100 100 100 90 100 0 0 100 80 80 60 0 100 100 Morningglory 10 10 10 0 10 0 0 40 20 0 0 0 30 20 Pigweed 100 100 100 100 100 0 0 100 100 100 90 0 100 100 Rice 80 90 50 90 80 - - 40 10 0 0 0 50 70 Surinam Grass 90 90 60 100 70 0 0 80 80 10 0 0 40 60 Velvetleaf 100 100 100 100 100 0 100 100 20 20 0 30
Table B Compounds
500 g ai/ha 329 330 331 332 333 334 335 336 338 340 341 342 343 344
Preemergence Barnyardgrass 0 0 70 60 20 100 60 100 80 100 100 100 100 70
Cocklebur 0 0 0 0 0 100 10 40 0 50 100 90 90 70
Corn 0 0 40 0 0 70 50 100 10 - - - - 90
Crabgrass, Large 0 0 80 100 70 100 100 100 100 100 100 100 100
Foxtail, Giant 0 0 80 60 20 100 90 100 100 100 90 90 100 60 Lambsquarters 0 100 100 100 100 10 100 100 100 100 100 100 100
Morningglory 0 0 0 30 10 70 10 70 10 - 30 70 100 80
Pigweed 0 0 50 100 100 100 10 100 100 100 100 100 100 90
Rice 0 0 40 40 0 - - - - - - - - -
Surinam Grass 0 0 60 20 20 100 40 100 60 100 100 100 100 100 Velvetleaf 0 0 80 80 80 100 70 100 80 100 100 100 100 100
Wheat - 90 30 100 20 100 100 100 100 80
Table B Compounds
500 g ai/ha 345 347 348 349 350 351 352 353 354 355 356 357 358 359
Preemergence Barnyardgrass 30 0 0 100 0 0 90 90 60 90 80 80 100 90
Cocklebur 10 0 0 80 0 0 0 20 0 10 20 30 90 30
Corn 10 0 0 80 0 0 80 - 20 60 50 80 100 60
Crabgrass, Large 90 0 0 100 0 0 100 80 80 100 90 100 100 100
Foxtail, Giant 30 0 0 100 0 0 100 50 70 90 80 100 100 100 Lambsquarters 100 0 0 100 0 0 100 - 100 100 100 100 100 100
Morningglory 50 0 0 30 0 0 0 20 0 10 10 70 100 50
Pigweed 100 0 0 100 0 0 70 - 90 100 100 100 100 100
Rice
Surinam Grass 70 0 0 90 0 0 100 30 20 80 60 80 100 70 Velvetleaf 40 0 0 100 0 0 100 60 50 0 70 60 100 50
Wheat 20 0 0 90 0 - 70 20 10 30 20 90 90 70
Table B Compounds 500 g ai/ha 360 361 362 353 364 365 366 Preemergence Barnyardgrass 40 100 70 50 100 100 90 Cocklebur 0 50 10 10 100 60 20 Corn 40 70 60 30 100 100 70 Crabgrass, Large 80 100 100 90 100 100 100 Foxtail, Giant 90 100 80 90 100 100 90 Lambsquarters 40 100 70 80 100 100 90 Morningglory 10 60 10 0 100 90 50 Pigweed 50 100 100 60 100 100 100
Surinam Grass 50 90 50 60 100 100 80
Velvetleaf 40 80 20 30 100 100 60
Wheat 40 80 30 30 100 100 90
Table B Compounds 250 g ai/ha 54 72 73 74 152 191 192
Preemergence
Barnyardgrass 10 0 10 0 90 10 70
Cocklebur 0 0 10 10 0 0
Corn 0 0 20 0 50 0 40 Crabgrass, Large 40 0 10 0 100 40 90
Foxtail, Giant 10 0 20 10 100 10 60
Lambsquarters 0 0 10 0 100 80 100
Morningglory 10 0 10 10 60 10 20
Pigweed 0 0 0 0 100 90 100 Rice 0 0 20 0 60 0 30
Surinam Grass 0 0 10 0 90 20 50
Velvetleaf 0 0 20 0 100 0 10
Table B Compounds
125 g ai/ha 6 7 8 10 11 12 13 14 Preemergence
Barnyardgrass 80 90 90 70 30 100 60 0 90 100 80 10 80 100
Cocklebur 30 - 20 0 0 90 0 0 40 60 0 0 0
Corn 50 80 20 0 0 70 0 0 20 0 0 0 0 30
Crabgrass, Large 100 100 100 80 70 100 90 0 70 80 100 0 90 100 Foxtail, Giant 100 100 100 60 20 100 80 0 80 70 90 10 60 100
Lambsquarters 100 100 90 100 60 100 100 0 100 100 100 0 90 100
Morningglory 60 30 20 0 0 40 10 0 - 10 0 0 20 20
Pigweed 100 100 100 100 90 100 100 0 100 100 90 0 100 100
Rice 70 70 40 30 0 90 70 0 70 60 50 0 50 90 Surinam Grass 70 90 80 50 20 100 30 0 70 50 50 0 70 100
Velvetleaf 60 100 90 90 50 100 60 0 70 100 10 0 50 90 Table B Compounds
125 g ai/ha 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Preemergence
Barnyardgrass 30 100 80 50 10 10 10 0 0 0 0 0 100 80
Cocklebur - 100 100 - 0 0 - 0 0 0 0 0 0 -
Corn 0 50 30 0 0 0 0 0 0 0 0 0 eo 0
Crabgrass, Large 70 100 60 100 0 20 20 0 0 10 0 0 100 -
Foxtail, Giant 10 go- 70 20 0 0 0 0 0 0 0 0 100 10
Lambsquarters 70 100 100 80 10 20 0 0 0 0 0 0 100 90
Morningglory 0 0 0 100 0 10 10 0 0 0 0 0 - 20
Pigweed go 100 80 80 0 30 0 0 0 0 0 0 100 go
Rice 10 70 40 30 0 10 10 0 0 0 0 0 - -
Surinam Grass 10 go 60 30 0 10 0 0 0 0 0 0 60 30
Velvetleaf 20 100 30 40 20 0 0 0 0 0 0 0 100 60
Table B Compounds
125 g ai/ha 29 30 31 32 33 34 35 36 37 40 41 43 44 45
Preemergence
Barnyardgrass 70 80 80 20 60 50 40 30 10 0 40 100 100 100
Cocklebur - 0 10 0 20 0 20 0 0 0 0 0 0 0
Corn 0 10 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 100 20 10 30 90 80 70 10 30 0 70 40 0 40
Foxtail, Giant 80 30 60 0 80 30 80 0 20 0 10 10 0 10
Lambsquarters 90 go 90 100 100 80 90 80 10 40 80 90 80 100
Morningglory 10 0 - 50 10 0 10 10 0 - 0 0 0 10
Pigweed 100 80 70 0 100 100 100 90 80 30 70 100 100 100
Surinam Grass 60 0 30 0 30 20 40 10 10 0 10 30 0 20
Velvetleaf 50 10 80 0 40 20 50 20 20 0 0 30 20 20
Table B Compounds
125 g ai/ha 46 47 48 49 50 51 52 55 56 57 58 59 60 61
Preemergence
Barnyardgrass 60 70 70 30 40 80 10 80 50 50 90 10 50 20
Cocklebur 20 0 10 0 0 0 0 0 0 0 0 0 0 0
Corn 10 0 0 0 0 0 0 0 0 0 20 0 0 0
Crabgrass, Large go 80 20 20 30 90 20 90 70 40 100 10 90 50
Foxtail, Giant 60 40 70 0 20 100 10 60 60 20 100 0 40 20
Lambsquarters 100 100 90 70 90 100 0 70 ; 100 100 100 90 90 100
Morningglory 10 20 10 0 10 0 0 0 20 0 - 0 10 - Pigweed 100 100 100 90 100 100 0 80 30 90 100 100 90 80
Rice - 10 40 10 0 0 50 40 30 60 0 30 0
Surinam Grass 20 20 10 10 20 30 0 50 30 20 30 0 10 10
Velvetleaf 50 30 90 0 20 50 0 0 0 0 60 10 10 70 Table B Compounds
125 g ai/ha 62 63 64 65 66 67 68 69 70 71 75 76 77 Preemergence Barnyardgrass 20 60 50 50 0 0 0 0 40 0 50 80 0 0 Cocklebur 0 0 0 0 0 0 0 0 0 0 0 - 0 0 Corn 0 0 0 0 0 0 0 0 10 0 0 30 0 0
Crabgrass, Large 80 70 20 20 0 0 0 0 100 0 10 80 0 0 Foxtail, Giant 70 60 10 20 0 0 0 0 90 0 30 90 0 10 Lambsquarters 100 90 60 80 0 0 20 0 - 0 20 50 60 0 Morningglory 10 0 0 0 0 0 20 0 10 0 0 10 0 0 Pigweed 100 100 100 90 0 0 70 0 30 0 50 100 90 0 Rice 0 50 0 10 0 0 0 0 0 0 40 50 0 -
Surinam Grass 10 20 10 10 0 0 0 0 40 0 30 70 0 0 Velvetleaf 80 10 0 10 0 0 0 0 30 0 20 30 0 10
Table B Compounds 125 g ai/ha 79 80 81 82 83 84 85 86 87 58 89 90 91 92
Preemergence
Barnyardgrass 0 0 10 0 0 20 70 0 10 0
Cocklebur 0 0 0 0 0 0 0 0 0 -
Corn 0 0 0 0 0 0 0 0 0 0 Crabgrass, Large 0 0 0 0 0 90 90 0 10 -
Foxtail, Giant 10 20 10 0 0 10 70 0 10 10
Lambsquarters 0 0 0 0 0 70 100 0 0
Morningglory 0 10 0 0 0 0 0
Pigweed 0 20 0 0 40 100 10 Rice 0 0 0 0 20 0
Surinam Grass 0 0 0 0 0 20 0
Velvetleaf 10 20 0 0 0 0 40 0
Table B Compounds 125 g ai/ha 93 94 95 96 97 98 99 100 101 102 104 105 106 107 Preemergence Barnyardgrass 0 10 50 70 0 0 0 0 40 80 0 0 Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 Corn 10 0 60 40 0 0 0 0 20 0 0 0 0 0
Crabgrass, Large 10 10 60 20 0 0 20 0 50 100 80 0 90 0
Foxtail, Giant 10 10 50 60 0 0 10 0 20 30 0 0 10 0
Lambsquarters 0 0 100 100 0 0 0 0 100 100 60 0 0 0
Morningglory 0 0 10 0 0 0 0 0 10 50 0 0 - 0
Pigweed 0 0 100 100 0 0 0 0 100 90 60 0 0 0
Rice 0 0 30 60 0 0 0 0 30 - - - - -
Surinam Grass 0 0 20 20 0 0 10 0 10 20 0 0 0 0
Velvetleaf 0 0 0 50 0 0 10 0 20 0 0 0 0 0
Table B Compounds
125 g ai/ha 108 109 110 112 113 114 115 117 118 119 120 121 122 123
Preemergence
Barnyardgrass 80 80 10 50 60 50 80 60 10 0 0 0 80 0
Cocklebur 10 0 0 0 0 10 20 20 0 0 0 0 20 0
Corn 10 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 100 80 80 20 100 90 90 90 90 20 70 0 90 0
Foxtail, Giant 90 70 10 10 10 50 80 20 10 0 0 0 50 0
Lambsquarters 100 20 20 0 80 100 100 90 0 0 0 70 80 0
Morningglory 50 10 20 0 0 10 30 - 10 0 10 0 20 0
Pigweed 90 30 0 0 0 80 80 60 60 0 0 80 70 0
Surinam Grass 50 60 10 20 10 20 70 30 10 0 0 0 20 0
Velvetleaf 80 20 0 0 20 40 80 60 0 0 20 0 40 0
Table B Compounds
125 g ai/ha 124 125 126 127 128 130 131 132 133 134 135 136 137 138
Preemergence
Barnyardgrass 0 0 40 20 80 10 70 10 10 50 40 90 10 10
Cocklebur 0 0 0 10 20 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 10 0 10 0 0 0 10 10 0
Crabgrass , Large 0 0 0 90 90 90 50 90 20 80 50 100 80 40
Foxtail, Giant 0 0 0 30 40 20 10 30 0 20 10 80 40 30
Lambsquarters 0 0 0 0 0 0 100 60 50 100 30 100 10 0
Morningglory 0 0 0 0 20 10 10 10 10 10 10 50 0 0
Pigweed 30 0 0 40 50 20 100 100 100 100 60 100 80 60
Rice - - - - - 0 20 0 0 0 0 20 0 0
Surinam Grass 0 0 0 50 40 60 10 40 0 30 10 40 20 0
Velvetleaf 0 0 0 10 70 10 50 30 20 30 30 50 10 0 Table B Compounds 125 g ai/ha 139 140 141 142 143 144 145 146 147 148 149 150 151 153 Preemergence Barnyardgrass 80 20 0 70 0 go 70 40 70 0 80 30 0 60 Cocklebur 0 - 0 30 0 10 0 0 0 0 0 0 0 0 Corn 10 0 0 0 0 10 0 0 10 0 10 0 0 0
Crabgrass, Large 60 0 10 80 0 80 - 10 90 0 90 0 0 50 Foxtail, Giant 70 0 10 60 0 100 80 10 70 0 60 0 0 0 Lambsquarters 100 0 0 100 0 100 80 80 90 0 60 0 0 100 Morningglory 10 - 20 - 0 100 30 0 0 0 20 0 0 0 Pigweed 90 0 0 100 0 100 100 100 100 0 100 70 0 100 Rice 30 0 0 30 - 20 0 10 0 0 20 0 0 10
Surinam Grass 30 0 0 10 0 60 30 10 20 0 40 10 0 10 Velvetleaf 50 0 0 80 0 100 80 20 30 0 0 0 0 40
Table B Compounds 125 g ai/ha 154 155 156 157 158 159 160 161 162 163 164 165 166 167 Preemergence Barnyardgrass 10 60 100 0 70 70 70 50 100 60 0 0 0 Cocklebur 0 0 100 0 40 90 40 0 30 70 0 0 0 Corn 0 0 40 0 0 0 0 0 30 0 0 0 0
Crabgrass, Large 50 60 90 0 80 40 20 80 100 60 0 0 0 Foxtail, Giant 0 20 100 0 50 50 10 20 100 20 0 0 0 Lambsquarters 70 100 100 0 70 100 100 100 100 80 0 0 0 Morningglory 0 20 60 0 50 30 20 10 20 60 0 0 0 Pigweed 90 100 100 0 100 100 100 100 100 90 0 0 0 Rice 0 20 90 0 80 - - 0 90 80 0 0
Surinam Grass 0 10 90 0 30 60 20 10 90 50 0 0 Velvetleaf 70 20 100 0 50 80 60 20 90 70 0 0 Table B Compounds
125 g ai/ha 168 169 170 171 179 180 181 182 183 184 185 186 187 188 Preemergence Barnyardgrass 70 0 0 0 0 0 30 20 20 0 0 0 70 80 Cocklebur 0 0 0 0 0 0 10 0 0 0 0 0 0 0 Corn 0 0 0 0 0 0 0 0 0 0 0 0 20 10
Crabgrass , Large 100 0 20 0 0 0 50 70 10 30 0 0 70 100 Foxtail, Giant 90 0 0 - 0 0 20 30 0 0 0 0 10 50 Lambsquarters go 0 0 0 50 20 50 50 20 0 20 go
Morningglory 0 0 0 0 0 10 10 10 0 0 20 10
Pigweed 100 0 0 0 30 100 100 100 0 0 20 40
Rice 0 0 - 40 0 0 0 0 0 30 50
Surinam Grass 50 0 0 30 20 20 0 10 0 30 30
Velvetleaf 60 0 0 0 10 10 10 10 10 70
Table B Compounds
125 g ai/ha 118899 190 193 194 195 196 197 198 199 200 201 202 203 204
Preemergence
Barnyardgrass 0 0 0 90 0 40 0 40 20 0 20 0
Cocklebur 00 0 10 0 0 0 0 0 0 0 0
Corn 00 0 70 0 0 0 0 0 0 0 0
Crabgrass, Large 30 30 100 100 80 0 80 90 50 0 60 30
Foxtail, Giant 0 0 100 10 20 0 20 10 0 0 10 0
Lambsquarters 0 0 100 30 0 0 100 80 20 0 30 10
Morningglory - 0 40 20 10 0 10 0 0 0 0 0
Pigweed 9g0o 30 loo o go 0 90 90 10 0 10 10
Rice 0 0 0 80 0 10 0 30 0 0 0 10 0
Surinam Grass 0 0 0 80 0 10 0 10 10 0 0 0 0
Velvetleaf 0 0 0 70 20 10 0 0 0 0 0 10 0
Table B Compounds
125 g ai/ha 220055 206 207 20g 210 211 212 213 214 215 216 217 218 219
Preemergence
Barnyardgrass 5 500 10 80 50 70 10 80 10 0 10
Cocklebur 1 100 0 10 10 10 0 0 0 0 0
Corn 1 100 0 10 0 20 0 10 0 0 0
Crabgrass, Large 6 600 10 70 40 90 10 60 10 0 0
Foxtail, Giant 50 0 50 30 80 10 70 20 0 0
Lambsquarters 80 0 80 60 100 10 100 30 o 90 go
Morningglory 0 0 20 10 20 0 0 0 0 10
Pigweed 100 o go 70 loo 0 100 30 0 80
Rice 10 0 50 30 60 0 10 0 0
Surinam Grass 20 0 40 20 60 0 50 0 0
Velvetleaf 30 0 20 10 10 0 10 0 0 Table B Clompcmnds
125 g ai/ha 220 221 222 223 224 225 226 227 228 229 230 231 232 233
Preemergence
Barnyardgrass 0 0 go 20 30 60 10 0 80 50 10 50 20 10
Cocklebur 0 0 30 0 20 0 0 0 30 0 0 0 0 0
Corn 0 0 60 10 20 30 0 0 60 10 0 0 0 0
Crabgrass , Large 20 80 go 50 30 10 20 40 60 40 20 30 60 20
Foxtail, Giant 0 0 60 10 10 60 20 10 70 50 10 60 0 0
Lambsquarters 0 20 100 80 100 80 - 0 100 90 20 80 80 0
Morningglory 0 0 - 10 - 0 0 0 10 10 10 10 10 0
Pigweed 0 50 go 90 80 70 40 0 go 100 40 60 go 0
Rice 0 0 90 0 30 60 20 10 80 30 0 20 10 0
Surinam Grass 0 0 90 20 60 20 10 30 60 40 0 20 0 0
Velvetleaf 0 0 100 30 70 30 10 30 100 40 10 30 20 10
Table B Compounds
125 g ai/ha 234 235 236 237 238 239 240 241 242 243 244 245 246 247
Preemergence
Barnyardgrass 0 10 50 20 0 0 0 0 80 70 80 70 60 30
Cocklebur 0 0 0 0 0 0 0 0 10 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 30 20 30 0 0 0
Crabgrass, Large 0 40 30 30 0 0 20 90 90 60 go 60 70 20
Foxtail, Giant 0 0 10 0 0 0 0 10 80 50 80 60 30 10
Lambsquarters 0 50 50 70 0 20 0 80 100 go 90 go 70 80
Morningglory 0 10 0 0 0 0 0 0 0 0 0 10 0 0
Pigweed 0 30 30 20 0 0 0 100 100 60 90 100 100 100
Rice 0 0 40 0 0 0 0 0 50 20 60 20 40 10
Surinam Grass 0 10 20 10 0 0 0 10 70 60 70 40 30 20
Velvetleaf 0 10 20 30 0 0 0 20 50 40 70 40 60 20
Table B Compounds
125 g ai/ha 248 24g 250 252 253 254 256 257 258 25g 260 261 262 263
Preemergence
Barnyardgrass 0 0 0 0 0 0 0 0 70 0 0 0 0 10
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 -
Corn 0 0 0 0 0 0 0 0 0 0 0 - 0 0
Crabgrass, Large 20 0 0 80 20 10 10 0 10 0 0 50 0 10
Foxtail, Giant 20 0 0 10 0 0 0 0 0 0 0 0 0 0
Lambsquarters 0 0 0 - 0 - - 0 - 0 - - 40 70 Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Pigweed 0 0 0 - - 0 - 0 0 0 - 0 50 80
Rice 0 0 0 30 0 0 30 0 20 0 0 0 0 0
Surinam Grass 20 0 10 10 10 0 60 0 0 0 0 0 0 10
Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 10
Table B Compounds
125 g ai/ha 264 265 266 267 268 269 270 271 272 273 274 275 276 277
Preemergence
Barnyardgrass 0 0 60 20 100 80 0 0 10 30 60 0 60 0
Cocklebur 0 0 0 0 80 20 0 0 0 0 0 0 0 0
Corn 0 0 0 0 80 60 0 0 0 0 0 0 20 0
Crabgrass, Large 10 - 50 40 100 100 0 0 80 80 10 0 10 0
Foxtail, Giant 0 0 80 30 100 80 0 0 30 50 10 0 30 0
Lambsquarters 0 - 100 0 100 100 - 0 100 70 70 - 40 40
Morningglory 0 0 0 20 0 10 0 0 0 0 0 0 0 0
Pigweed 0 0 100 - 100 100 0 0 go 70 30 0 30 60
Rice 0 0 70 20 90 70 0 0 0 0 30 0 50 0
Surinam Grass 0 0 60 10 80 50 0 0 10 20 50 0 10 0
Velvetleaf 0 0 20 20 100 60 50 0 10 10 20 0 0 0
Table B Compounds
125 g ai/ha 278 279 280 281 282 283 284 285 286 287 288 28g 2go 291
Preemergence
Barnyardgrass 30 20 0 20 30 0 0 30 30 80 0 0 0 0
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 - 0 0 0 0 0 0 0 0
Crabgrass, Large 20 10 0 10 10 0 0 20 0 70 0 0 0 0
Foxtail, Giant 20 10 0 10 10 0 0 10 10 10 0 0 10 0
Lambsquarters 100 100 - 90 100 0 90 100 100 100 0 0 100 0
Morningglory 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Pigweed 100 90 70 100 100 0 go 100 100 go 0 0 0 0
Rice 30 20 0 20 10 0 0 40 30 80 0 0 0 0
Surinam Grass 20 0 0 10 0 0 0 10 10 50 0 0 0 0
Velvetleaf 0 0 10 10 10 0 0 30 0 70 0 0 0 0
Table B Compounds
125 g ai/ha 292 293 294 2g5 296 297 2g8 2gg 300 301 302 303 304 305
Preemergence
Barnyardgrass 10 90 100 10 30 0 70 go 70 60 0 70 10 80 Cocklebur 0 60 90 0 0 0 0 20 10 0 0 0 0 50 Corn 0 70 80 0 30 0 30 50 0 0 0 - 0 10
Crabgrass, Large 80 100 100 10 40 20 100 100 100 100 70 100 10 90 Foxtail, Giant 0 60 90 10 70 10 80 100 80 70 0 50 10 80 Lambsquarters 70 80 100 0 90 0 100 100 100 100 0 100 100 100 Morningglory 0 40 0 0 10 10 10 40 10 10 0 10 10 0 Pigweed 40 10 100 0 70 0 100 100 100 100 100 100 100 100 Rice 0 90 90 10 - 0 40 80 40 10 0 70 0 70
Surinam Grass 20 90 100 0 20 10 80 100 80 90 10 50 10 80 Velvetleaf 30 100 100 50 70 0 10 100 90 100 0 10 90 80
Table B Compounds 125 g ai/ha 306 307 308 30g 310 311 312 313 314 315 316 317 318 319 Preemergence Barnyardgrass 60 80 20 80 60 0 0 80 10 0 0 40 50 Cocklebur 0 80 0 30 10 0 0 0 0 0 0 0 0 Corn 70 70 20 60 40 0 0 10 0 0 0 0 10
Crabgrass, Large 100 90 40 60 90 0 0 30 20 0 0 10 50 Foxtail, Giant 40 90 10 80 50 0 0 40 30 0 0 0 20 Lambsquarters 100 100 100 90 100 0 0 100 20 0 0 90 20 Morningglory 10 0 0 0 0 0 0 10 0 0 0 0 10 Pigweed 100 100 80 70 80 0 0 100 go 20 0 90 60 Rice 60 80 20 70 40 - - 20 0 0 0 0 30
Surinam Grass 30 70 20 60 30 0 0 30 20 0 0 0 0 20 Velvetleaf 30 100 50 80 60 0 0 30 20 1100 0 20 0 Table B Compounds
125 g ai/ha 329 330 331 332 333 334 335 336 338 340 341 342 343 344 Preemergence Barnyardgrass 0 0 60 10 0 90 50 100 20 80 80 70 70 20 Cocklebur 0 0 0 0 0 60 0 10 0 20 40 40 - 20 Corn 0 0 20 0 0 20 30 50 10 - - - - 10
Crabgrass, Large 0 0 60 40 40 go 50 o 80 80 90 40 40 60 Foxtail, Giant 0 0 20 20 10 90 60 60 30 60 50 40 30 10 Lambsquarters o o - 90 40 loo o 90 60 go loo so go go Morningglory 0 0 0 10 0 0 0 20 0 30 - 10 50 10 Pigweed 0 0 40 100 o 60 0 100 70 100 90 80 90 90 Rice 0 0 30 20 0 - - - - - - - - - Surinam Grass 0 0 40 10 10 80 30 go 20 80 100 50 50 30 Velvetleaf 0 0 20 30 10 100 40 30 - 70 60 70 100 40
Wheat - - - - - 90 0 40 0 90 100 80 100 10
Table B Compounds
125 g ai/ha 345 346 347 348 34g 350 351 352 353 354 355 356 357 358
Preemergence
Barnyardgrass 20 0 0 0 80 0 0 70 40 0 70 60 30 70
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 40
Corn 0 0 0 0 70 0 0 60 - 20 20 10 0 60
Crabgrass, Large 30 60 0 0 100 0 0 go 20 20 70 40 70 100
Foxtail , Giant 10 50 0 0 70 0 0 70 0 10 10 10 20 60
Lambsquarters 70 0 0 0 100 0 0 go - - 80 40 90 100
Morningglory 20 0 0 0 0 0 0 0 - 0 10 0 10 50
Pigweed 60 0 0 0 100 0 0 50 0 0 50 70 100 70
Rice - - - - - - 0 - - - - - - -
Surinam Grass 20 10 0 0 50 0 0 go 0 0 40 10 30 50
Velvetleaf 30 0 0 0 30 0 0 30 10 0 0 0 0 50
Wheat 0 - 0 0 80 0 - 10 0 0 10 0 40 40
Table B Compounds
125 g ai/ha 359 360 361 362 363 364 365 366
Preemergence
Barnyardgrass 0 10 80 10 0 100 90 70
Cocklebur 0 0 0 0 0 70 10 0
Corn 0 10 30 0 0 80 90 40
Crabgrass, Large go 40 80 20 20 100 100 40
Foxtail, Giant 60 50 50 10 20 100 100 50
Lambsquarters 0 0 80 0 0 100 100 -
Morningglory 0 0 10 0 0 70 50 30
Pigweed 0 20 80 0 0 100 100 70
Surinam Grass 20 20 50 10 0 100 70 30
Velvetleaf 0 20 20 0 0 100 50 0
Wheat 10 30 10 0 10 100 70 30
Table B Compounds
62 g ai/ha 54 72 73 74 129 152 191 192 251
Preemergence
Barnyardgrass 0 0 0 0 10 50 0 20 0
Cocklebur 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 Crabgrass, Large 0 0 0 0 40 90 10 30 0
Foxtail, Giant 0 0 10 0 0 90 0 10 0
Lambsquarters 0 0 0 0 0 100 50 60 -
Morningglory 0 0 0 0 - 0 0 0
Pigweed 0 0 0 0 0 100 10 30 -
Rice 0 0 20 0 - 10 0 0 0
Surinam Grass 0 0 0 0 10 40 0 10 0
Velvetleaf 0 0 0 0 0 80 0 0 0
Table B Compounds Table B Compound
31 g ai/ha 49 168 346 16 g ai/ha 251
Preemergence Preemergence
Barnyardgrass 0 0 0 Barnyardgrass 0
Cocklebur 0 0 0 Cocklebur 0
Corn 0 0 0 Corn 0
Crabgrass, Large - 90 0 Crabgrass , Large 0
Foxtail, Giant 0 0 0 Foxtail, Giant 0
Lambsquarters 0 50 0 Lambsquarters 0
Morningglory 0 0 0 Morningglory 0
Pigweed 60 90 0 Pigweed 0
Rice 10 0 - Rice 0
Surinam Grass 0 0 0 Surinam Grass 0
Velvetleaf 0 10 0 Velvetleaf 0
Wheat - - 0
TESTC Seeds of plant species selected from bermudagrass (Cynodon dactylon (L.) Pers.),
Surinam grass (Urochloa decumbens (Staph) R. D. Webster, previously named Brachiaria decumbens Stapf), cocklebur (Xanthium strumarium L.), corn (Zea mays L.), large crabgrass (Digitaria sanguinalis (L.) Scop.), woolly cupgrass (Eriochloa villosa (Thunb.) Kunth), giant foxtail (Setaria faberi Herrrn.), goosegrass (Eleusine indica (L.) Gaertn.), johnsongrass (Sorghum halepense (L.) Pers.), kochia (Kochia scoparia (L.) Schrad.), lambsquarters (Chenopodium album L.), morningglory (Ipomoea coccinea L.), eastern black nightshade (Solanum ptycanthum Dunal), yellow nutsedge (Cyperus esculentus L.), pigweed (Amaranthus retroflexus L.), common ragweed (Ambrosia elatiorL,.), soybean (Glycine max (L.) Merr.), common (oilseed) sunflower (Helianthus annuus L.) and velvetleaf (Abutilon theophrasti Medik.) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, plants selected from these crop and weed species and also winter barley (Hordeum vulgare L.), blackgrass (Alopecurus myosuroides Huds.), canarygrass (Phalaris minor Retz.), chickweed (Stellaria media (L.) Vill.), downy bromegrass (Bromus tectorum L.), green foxtail (Setaria viridis (L.) Beauv.), Italian ryegrass (Lolium multiflorum Lam.), wheat (Triticum aestivum L.), wild oat (Avenafatua L.) and windgrass (Apera spica- venti (L.) Beauv.) were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4- leaf stage) for postemergence treatments. Plant species in the flooded paddy test consisted of rice (Oryza sativa), smallflower umbrella sedge (Cyperus difformis L.), ducksalad {Heteranthera limosa (Sw.) Willd.) and barnyardgrass (Echinochloa crus-galli (L.) Beauv.) grown to the 2-leaf stage for testing. Treated plants and controls were maintained in a greenhouse for 12 to 14 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table C, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table C Compounds 500 g ai/ha 1 2 3 4 5 6 7 9 10 11 13 14 15 16 Flooded Paddy Barnyardgrass 75 90 eo so lo go go 70 so go go gs 75 s Ducksalad g5 g5 90 go 70 IOO 80 95 90 80 85 85 30 90 Rice 95 85 70 75 0 90 75 80 90 80 70 85 50 90 Sedge, Umbrella - 95 90 95 70 o 80 - 85 80 90 95 70 90
Table C Compounds 500 g ai/ha 17 18 20 21 27 28 29 31 34 43 45 47 49 51 Flooded Paddy Barnyardgras s 80 85 15 70 85 60 85 75 65 50 80 40 80 75 Ducksalad 85 70 25 65 80 70 85 60 75 70 60 80 80 85 Rice 80 80 30 45 80 35 80 50 55 20 65 50 90 50 Sedge, Umbrella 85 85 80 50 80 25 90 55 90 80 80 80 80 80 Table C Compounds
500 g ai/ha 55 56 58 62 63 64 65 67 75 7£ 79 80 81 Flooded Paddy Barnyardgr ss 75 80 85 55 50 35 60 25 70 90 80 60 30 45 Ducksalad 80 75 60 90 85 40 85 40 70 80 55 40 20 75 Rice 60 35 75 65 50 15 30 30 65 90 30 40 40 45
Sedge, Umbrella 80 90 65 85 90 75 80 75 85 90 85 70 80 80 Table C Compounds 500 g ai/ha 5 g6 101 102 106 108 112 115 117 118 122 126 127 128 Flooded Paddy Barnyardgrass 60 80 50 70 0 70 30 75 50 50 80 25 55 65 Ducksalad go go 75 go o 90 100 90 eo 50 so 30 so 95 Rice 65 75 25 60 20 50 30 75 65 50 50 0 25 70 Sedge Umbrella 95 95 90 80 80 80 50 95 80 50 80 50 85 95
Table C Compounds 500 g ai/ha 131 134 136 138 139 140 141 142 144 146 152 155 158 159 Flooded Paddy Barnyardgrass 30 50 80 30 65 15 10 90 60 20 85 65 35 80 Ducksalad 80 gθ 90 70 90 20 0 100 80 20 85 90 50 100 Rice 10 60 70 40 60 0 0 70 30 20 80 35 60 go Sedge , Umbrella 80 85 85 g5 85 65 45 go gθ go 85 75 80 80 Table C Compounds
500 g ai/ha 160 161 162 181 183 186 187 188 192 193 194 207 209 210 Flooded Paddy Barnyardgrass 85 75 90 0 0 70 75 85 70 90 25 85 80 85 Ducksalad 90 90 100 80 20 80 90 85 60 go 40 85 80 o Rice g5 65 75 0 0 65 65 75 70 75 45 60 65 75
Sedge, Umbrella 85 40 - 85 50 85 85 85 90 85 75 90 80 90
Table C Compounds 500 g ai/ha 215 216 219 222 223 225 226 227 228 22g 231 232 235 236 Flooded Paddy Barnyardgrass 50 30 0 95 45 90 60 0 95 80 80 15 0 40 Ducksalad 80 40 0 95 55 85 65 55 90 85 80 80 75 80 Rice 20 30 0 85 75 80 70 55 85 90 80 60 35 70 Sedge, Umbrella 90 50 20 90 85 50 70 15 80 75 85 80 55
Table C Compounds 500 g ai/ha 241 242 243 244 245 247 252 255 256 258 259 260 263 266
Flooded Paddy
Barnyardgrass 30 95 85 80 70 0 45 35 0 45 0 35 0 70
Ducksalad 15 95 90 95 75 80 80 40 65 90 75 85 90 g5
Rice 65 o go 75 70 75 60 50 15 70 0 15 25 80 Sedge, Umbrella 85 85 80 85 70 75 75 45 60 80 70 65 50 80 Table C Compounds 500 g ai/ha 268 26g 272 273 274 275 278 281 283 285 286 287 2gθ 2g3 Flooded Paddy Barnyardgrass g5 go 30 70 60 70 25 55 10 75 80 25 40 80 Ducksalad go 85 85 75 20 85 20 85 0 90 90 45 70 95 Rice o 80 20 60 45 70 30 50 0 65 75 55 45 80 Sedge, Umbrella 95 85 75 75 75 85 75 90 0 65 go 75 70 go
Table C Compounds 500 g ai/ha 2g4 2g5 2 6 2gs 2 300 301 302 303 304 305 306 307 308 Flooded Paddy Barnyardgrass 100 40 65 go g5 5 g5 35 95 95 IOO 70 95 65 Ducksalad 95 30 70 90 95 90 95 85 85 95 0 o 90 75 Rice 90 40 60 75 85 75 85 55 85 75 85 70 80 70 Sedge, Umbrella 90 80 85 so gs go gs 85 go gs go 90 85 80 Table C Compounds
500 g ai/ha 309 310 319 331 332 333 334 335 336 340 341 342 343 344 Flooded Paddy Barnyardgrass 90 90 65 65 60 20 95 65 80 70 60 60 80 0 Ducksalad gθ go 85 85 95 25 90 70 o go 60 80 go 45 Rice 75 80 70 65 70 20 85 55 75 80 70 80 80 15
Sedge, Umbrella so 85 80 65 85 so gs gs go go 60 so go 85 Table C Compounds 500 g ai/ha 34g 352 353 357 358 35g Flooded Paddy Barnyardgrass g5 o 20 55 85 75 Ducksalad gs gs 30 gs s 90 Rice 70 70 40 70 85 80 Sedge, Umbrella gs gs so s 85 95
Table C Compounds 250 g ai/ha 6 7 9 10 11 13 14 15 16
Flooded Paddy
Barnyardgrass 65 75 20 65 0 90 75 65 70 70 80 90 25 90
Ducksalad 95 85 80 90 50 90 80 95 90 80 75 80 20 85
Rice 75 65 10 65 0 80 65 60 70 80 65 75 25 80 Sedge, Umbrella - 85 80 85 60 90 80 - 75 70 80 90 55 90 Table C Compounds 250 g ai/ha 17 18 20 21 27 28 29 31 34 43 45 47 49 51 Flooded Paddy Barnyardgrass 75 65 0 15 60 35 60 70 45 40 60 40 70 20 Ducksalad 80 65 20 40 80 40 75 40 25 60 60 80 80 75 Rice 80 50 0 20 65 0 60 40 50 20 35 20 70 15 Sedge, Umbrella 80 80 50 30 80 20 60 40 80 70 80 80 80 65
Table C Compounds 250 g ai/ha 55 56 58 62 63 64 65 67 75 76 79 50 81 85 Flooded Paddy Barnyardgrass 25 65 35 30 20 0 30 10 65 80 25 40 0 15 Ducksalad 55 70 20 90 70 25 75 40 65 75 15 20 20 40 Rice 15 25 35 45 15 0 25 0 55 85 20 40 30 20 Sedge, Umbrella 75 90 50 80 80 35 75 75 80 85 80 70 80 80 Table C Compounds
250 g ai/ha 95 96 101 102 106 108 112 115 117 118 122 126 127 128 Flooded Paddy Barnyardgrass 55 70 30 50 0 60 10 65 50 20 60 20 30 60 Ducksalad 75 75 40 o 0 80 0 85 0 50 80 25 20 g5 Rice 55 70 0 40 0 20 10 75 45 40 10 0 25 70
Sedge, Umbrella g5 90 80 70 30 80 25 90 75 50 70 20 80 g5
Table C Compounds 250 g ai/ha 131 134 136 138 139 140 141 142 144 146 152 155 158 159 Flooded Paddy Barnyardgrass 10 50 40 15 55 0 0 80 50 0 75 50 15 70 Ducksalad 45 90 45 55 85 0 0 95 70 20 85 85 20 o Rice 0 55 50 5 45 0 0 70 30 0 75 0 35 80 Sedge, Umbrella 70 85 85 75 85 45 30 80 80 go 85 65 70 60
Table C Compounds 250 g ai/ha 160 161 162 181 183 186 187 188 192 193 194 207 209 210
Flooded Paddy
Barnyardgrass 70 30 75 0 0 45 60 75 0 85 0 75 70 85
Ducksalad 90 80 95 0 10 65 85 75 25 90 0 80 65 85
Rice 75 60 70 0 0 60 50 65 45 70 25 50 45 75 Sedge, Umbrella 80 25 75 80 10 80 80 80 85 80 35 75 65 85 Table C Compounds 250 g ai/ha 215 216 219 222 223 225 226 227 228 229 231 232 235 236 Flooded Paddy Barnyardgrass 40 0 0 90 0 80 50 0 95 75 75 0 0 15 Ducksalad 60 30 0 85 25 85 40 0 90 80 70 30 0 55 Rice 0 0 0 85 45 75 45 25 80 80 75 35 25 60 Sedge, Umbrella 70 30 0 85 65 75 40 0 80 80 65 55 55 45
Table C Compounds 250 g ai/ha 241 242 243 244 245 247 252 255 256 258 259 260 263 266 Flooded Paddy Barnyardgrass 0 90 75 75 45 0 15 25 0 15 0 20 0 50 Ducksalad 0 95 90 85 75 0 15 35 15 70 65 75 75 75 Rice 30 90 80 75 70 20 55 45 0 5 0 0 0 65 Sedge, Umbrella 55 85 80 70 70 15 50 35 60 70 55 65 30 55 Table C Compounds
250 g ai/ha 268 26g 272 273 274 276 278 281 283 285 286 287 2 θ 2g3 Flooded Paddy Barnyardgrass 95 75 10 60 30 50 0 30 0 55 70 0 25 70 Ducksalad 85 80 40 75 0 70 0 70 0 90 90 40 45 80 Rice 90 75 15 50 15 50 15 15 0 45 65 25 15 65
Sedge, Umbrella 80 80 75 75 70 80 65 40 0 50 90 70 65 80
Table C Compounds 250 g ai/ha 294 2 5 2g6 2 8 2gg 300 301 302 303 304 305 306 307 308 Flooded Paddy Barnyardgrass 5 25 50 65 g5 90 90 10 80 85 95 55 80 25 Ducksalad g5 25 40 80 g5 85 90 30 80 95 0 80 90 15 Rice 85 40 40 65 80 70 75 0 80 70 85 55 65 65 Sedge, Umbrella 90 80 75 70 g5 85 go 75 85 g5 90 90 80 70
Table C Compounds 250 g ai/ha 309 310 319 331 332 333 334 335 336 340 341 342 343 344
Flooded Paddy
Barnyardgrass 85 70 50 40 50 10 95 40 60 60 50 50 60 0
Ducksalad go 80 45 65 95 0 85 50 75 70 60 80 90 20
Rice 75 70 35 50 45 15 80 55 75 70 60 60 70 0 Sedge, Umbrella 80 85 70 25 85 30 90 90 85 70 60 70 80 75 Table C Compounds 250 g ai/ha 34g 352 353 357 358 35g Flooded Paddy Barnyardgrass go 65 20 30 75 75 Ducksalad 85 85 30 45 go 85 Rice 60 60 20 45 70 65 Sedge, Umbrella 90 90 50 90 85 go
Table C Compounds 125 g ai/ha 5 7 9 10 11 13 14 15 16 Flooded Paddy Barnyardgrass 60 75 0 50 0 90 50 50 65 20 55 80 0 80 Ducksalad 90 80 65 75 15 90 60 95 90 80 35 75 0 80 Rice 70 50 5 50 0 80 55 55 60 40 50 70 0 75 Sedge, Umbrella 80 75 55 75 15 go 80 - 70 60 75 80 10 85 Table C Compounds
125 g ai/ha 17 18 20 21 27 28 2g 31 34 43 45 47 48 4 Flooded Paddy Barnyardgrass 65 20 0 0 35 0 25 30 35 0 30 0 0 60 Ducksalad 80 40 10 40 60 0 45 20 25 0 0 70 40 50 Rice 70 40 0 0 20 0 25 10 0 0 30 20 20 25
Sedge, Umbrella 45 60 15 25 70 15 60 35 80 50 60 70 60 45
Table C Compounds 125 g ai/ha 51 55 56 58 62 63 64 65 67 75 76 7g 80 81 Flooded Paddy Barnyardgrass 0 0 20 10 10 0 0 0 0 25 70 25 20 0 Ducksalad 55 0 55 15 35 50 10 45 30 30 50 0 20 0 Rice 0 0 15 35 25 0 0 0 0 25 80 20 40 20 Sedge, Umbrella 50 20 85 20 60 70 25 20 50 75 85 75 70 70
Table C Compounds 125 g ai/ha 88 g5 g6 101 102 106 108 112 115 117 118 122 126 127
Flooded Paddy
Barnyardgrass 0 45 45 20 50 0 40 0 45 20 20 50 0 30
Ducksalad 15 25 45 0 80 0 70 0 75 0 50 80 10 15
Rice 0 10 45 0 30 0 0 0 65 15 30 10 0 25 Sedge, Umbrella 50 go 90 75 70 0 80 0 85 55 50 60 20 80 Table C Compounds 125 g ai/ha 128 131 134 136 138 139 140 141 142 144 146 147 152 155 Flooded Paddy Barnyardgrass 35 0 25 25 0 40 0 0 65 20 0 0 75 25 Ducksalad g5 20 70 0 20 70 0 0 go 50 0 0 85 80 Rice 40 0 45 35 5 35 0 0 70 20 0 0 75 0 Sedge , Umbrella go 65 75 80 40 80 20 0 80 80 80 50 80 30
Table C Compounds 125 g ai/ha 158 159 160 161 162 181 183 186 187 188 192 193 194 207 Flooded Paddy Barnyardgrass 0 50 60 0 65 0 0 30 25 55 0 55 0 65 Ducksalad 0 go 85 65 85 0 0 40 40 65 0 70 0 80 Rice 0 60 70 10 60 0 0 55 30 45 15 50 25 45 Sedge , Umbrella 45 40 70 0 - 20 0 80 65 75 75 75 0 75 Table C Compounds
125 g ai/ha 20g 210 215 216 219 222 223 225 226 227 228 229 231 232 Flooded Paddy Barnyardgrass 55 70 0 0 0 75 0 60 0 0 85 45 45 0 Ducksalad 65 55 40 20 0 75 0 75 0 0 85 0 60 0 Rice 45 55 0 0 0 70 0 70 25 0 80 35 55 20
Sedge, Umbrella 55 80 40 30 0 75 0 75 10 0 80 40 55 35
Table C Compounds 125 g ai/ha 235 236 241 242 243 244 245 247 252 255 256 258 259 260 Flooded Paddy Barnyardgrass 0 0 0 75 65 70 35 0 0 10 0 0 0 0 Ducksalad 0 40 0 95 85 85 75 0 0 10 0 45 60 70 Rice 0 30 0 85 75 70 65 0 45 0 0 0 0 0 Sedge, Umbrella 50 20 0 75 80 65 70 0 40 20 0 20 35 40
Table C Compounds 125 g ai/ha 263 266 268 269 272 273 274 276 278 281 283 285 286 287
Flooded Paddy
Barnyardgrass 0 25 go 65 0 40 10 15 0 20 0 25 55 0
Ducksalad 0 15 70 80 20 50 0 20 0 0 0 80 75 30
Rice 0 10 85 50 10 40 0 15 0 0 0 40 55 20 Sedge , Umbrella 0 20 70 80 65 75 50 75 25 20 0 35 70 35 Table C Clompo'unds
125 g ai/ha 290 293 294 2g5 296 2 8 299 300 301 302 303 304 305 306
Flooded Paddy
Barnyardgrass 0 20 90 15 25 50 85 50 75 0 45 50 85 45
Ducksalad 0 65 95 0 0 40 95 80 90 25 75 85 0 80
Rice 0 30 75 10 20 60 80 55 55 0 65 60 80 40
Sedge, Umbrella 25 75 85 80 75 0 gs 80 go 50 85 go go go
Table C Compounds
125 g ai/ha 307 308 3og 310 313 319 331 332 333 334 335 336 340 341
Flooded Paddy
Barnyardgrass 65 0 60 50 0 25 10 25 0 go 25 0 50 30
Ducksalad 70 0 go 75 30 0 50 90 0 85 35 55 70 50
Rice 60 25 70 60 20 35 15 0 0 75 25 45 40 50
Sedge, Umbrella 70 25 80 85 70 35 20 80 15 go 85 80 70 50
Table C Compounds
125 g ai/ha 342 343 344 349 352 353 357 358 35
Flooded Paddy
Barnyardgrass 20 20 0 70 45 0 0 60 55
Ducksalad 50 80 0 85 65 0 30 80 80
Rice 30 50 0 55 45 0 0 65 45
Sedge, Umbrella 50 40 75 85 75 0 85 85 go
Table C Compounds
62 g ai/ha 1 2 3 4 5 6 7 9 10 11 13 14 15 15
Flooded Paddy
Barnyardgrass 50 15 0 20 0 60 10 35 25 0 25 65 0 80
Ducksalad 90 80 15 50 15 80 20 95 80 50 25 60 0 75
Rice 65 50 0 25 0 40 15 50 60 15 10 25 0 75
Sedge, Umbrella 60 75 45 75 0 70 55 - 45 20 50 65 0 80
Table C Compounds
62 g ai/ha 17 18 20 21 27 28 29 31 34 43 45 47 48 4g
Flooded Paddy
Barnyardgrass 50 0 0 0 30 0 10 0 0 0 25 0 0 45
Ducksalad 75 20 0 0 45 0 0 10 15 0 0 0 20 0
Rice 60 0 0 0 0 0 0 0 0 0 30 0 0 15
Sedge, Umbrella 40 15 0 0 50 0 20 0 50 30 55 30 60 45 Table C Compounds 62 g ai/ha 51 55 56 58 62 63 64 65 67 75 76 79 80 81 Flooded Paddy Barnyardgrass 0 0 0 0 5 0 0 0 0 0 50 10 0 0 Ducksalad 0 0 15 0 25 0 0 15 30 0 45 0 20 0 Rice 0 0 0 0 15 0 0 0 75 20 20 20 Sedge, Umbrella 45 0 45 0 45 0 50 70 80 75 70 70
Table C Compounds 62 g ai/ha 58 95 96 101 102 106 108 112 115 117 118 122 126 127 Flooded Paddy Barnyardgrass 0 20 45 0 10 0 30 0 30 10 0 20 0 20 Ducksalad 0 10 45 0 20 0 50 0 30 0 0 50 0 0 Rice 0 10 40 0 20 0 0 0 55 0 20 0 0 20 Sedge, Umbrella 0 85 90 20 50 0 eo 0 80 40 0 50 0 80 Table C Compounds
62 g ai/ha 128 131 134 136 138 139 140 141 142 144 146 147 152 155 Flooded Paddy Barnyardgrass 30 0 10 20 0 15 0 0 50 20 0 0 40 0 Ducksalad 80 0 45 0 0 0 0 0 75 20 0 0 85 45 Rice 25 0 35 30 5 0 0 0 70 0 0 0 50 0
Sedge, Umbrella 80 55 55 65 0 75 0 0 75 80 60 30 80 0
Table C Compounds 62 g ai/ha 158 159 160 161 162 181 183 186 187 188 192 193 194 207 Flooded Paddy Barnyardgrass 0 30 20 0 45 0 0 20 0 35 0 30 0 45 Ducksalad 0 80 75 30 70 0 0 15 20 20 0 55 0 55 Rice 0 60 60 0 55 0 0 40 15 35 0 25 0 30 Sedge, Umbrella 15 10 50 0 70 10 0 80 20 30 70 75 0 70
Table C Compounds 62 g ai/ha 209 210 215 216 219 222 223 225 226 227 228 229 231 232
Flooded Paddy
Barnyardgrass 0 50 0 0 0 15 0 35 0 0 80 40 40 0
Ducksalad 65 40 40 0 - 70 0 10 0 0 80 0 10 0
Rice 0 35 0 0 0 30 0 55 0 0 75 35 30 0 Sedge, Umbrella 55 75 40 20 0 65 0 65 10 0 80 30 10 0 Table C Compounds 62 g ai/ha 235 236 241 242 243 244 245 247 252 255 256 258 25g 260 Flooded Paddy Barnyardgrass 0 0 0 15 0 0 0 0 0 0 0 0 0 0 Ducksalad 0 0 0 65 75 25 60 0 0 0 0 15 0 0 Rice 0 0 0 50 15 40 25 0 0 0 0 0 0 0 Sedge, Umbrella 0 0 0 45 75 20 55 0 0 0 0 0 0 0
Table C Compounds 62 g ai/ha 263 266 268 269 272 273 274 276 278 281 283 285 286 287 Flooded Paddy Barnyardgrass 0 0 65 45 0 20 0 0 0 0 0 10 40 0 Ducksalad 0 0 60 55 10 20 0 0 0 0 0 45 50 0 Rice 0 0 75 45 0 10 0 0 0 0 0 25 45 0 Sedge , Umbrella 0 0 55 45 30 70 0 45 0 15 0 25 30 0 Table C Compounds
62 g ai/ha 290 293 2g4 2g5 2 6 2 8 2g9 300 301 302 303 304 305 306 Flooded Paddy Barnyardgrass 0 0 75 0 15 15 85 35 50 0 30 40 70 0 Ducksalad 0 0 90 0 0 35 95 75 85 0 55 65 0 50 Rice 0 0 70 5 20 45 70 40 50 0 30 45 75 30
Sedge, Umbrella 0 20 80 80 75 0 85 80 80 15 75 75 85 85
Table C Compounds 62 g ai/ha 307 308 309 310 313 319 331 332 333 334 335 336 340 341 Flooded Paddy Barnyardgrass 30 0 50 35 0 0 0 5 0 70 10 0 20 30 Ducksalad 60 0 85 45 0 0 0 20 0 75 0 45 50 20 Rice 55 15 60 35 0 0 0 0 0 70 25 10 20 20 Sedge, Umbrella 40 0 80 35 0 20 0 65 0 80 45 25 50 20
Table C Compounds 62 g ai/ha 342 343 344 349 352 353 357 358 35g
Flooded Paddy
Barnyardgrass 20 20 0 45 25 0 0 0 15
Ducksalad 50 40 0 80 20 0 30 0 40
Rice 20 20 0 50 20 0 0 20 20 Sedge, Umbrella 40 20 0 80 50 0 40 15 80 Table C Compounds rrablei c Compounds
31 g ai/ha 48 147 313 16 g ai/ha 48 147 313
Flooded Paddy ] Flooded Paddy
Barnyardgrass 0 0 0 ] Barnyardgrass 0 0 0
Ducksalad 0 0 0 ] Ducksalad 0 0 0
Rice 0 0 0 ] Rice 0 0 0
Sedge, Umbrella 0 20 0 Sedge, Umbrella 0 0 0
Table C Compounds
500 g ai/ha 28 31 34 46 47 50 58 82 84 85 86 96 108 112
Postemergence
Bermudagrass 40 40 50 - 60 40 10 10 - 70 100 5 80 30
Chickweed 100 - 100 100 100 0 85 100 70 100 100 100 - 100
Cocklebur 80 60 70 go 90 10 50 20 0 100 100 gs 100 70
Corn 60 50 70 80 80 85 15 45 0 45 30 45 60 30
Crabgrass, Large 60 70 60 go 90 0 30 60 50 40 40 5 100 30
Cupgrass, Woolly - 60 go 70 80 0 20 80 0 85 85 50 40 70
Foxtail, Giant 40 40 40 70 70 0 40 30 0 70 70 60 70 50
Goosegrass 50 40 40 80 80 - 30 10 10 60 85 5 70 30
Johnsongrass 70 30 80 90 90 0 10 10 0 80 30 50 go 60
Kochia 80 70 go 100 100 10 85 70 80 go gs go go 80
Lambsquarters 100 go 100 100 100 0 90 100 50 100 100 100 100 100
Morningglory 60 70 40 80 90 10 20 50 0 80 85 50 - 100
Nutsedge, Yellow 20 30 20 40 30 - 5 5 0 40 30 5 30 20
Pigweed 100 100 100 100 100 100 85 loo ; 100 100 100 100 100 100
Ragweed 50 70 40 80 90 85 85 30 0 60 70 85 - 70
Soybean 80 80 80 100 100 100 go 40 20 gs gs 100 60 60
Surinam Grass 60 50 70 50 70 - 25 40 10 80 85 60 50 60
Velvetleaf 80 70 70 80 90 100 60 75 0 85 85 gs go go
Table C Compounds
500 g ai/ha 115 130 137 144 146 147 212 272 : 301 304 318 332 333 338
Postemergence
Barley, Winter - - 30 40 - - - 35 40 45 - 40 - 40
Bermudagrass 100 go - - - - 50 100 - - 80 70 5 5
Blackgrass - - 60 40 - - - 65 45 gs - 70 55 65
Bromegrass, Downy - - 40 40 - - - 65 40 50 - 65 45 45
Canarygrass - - 40 50 - - - 55 50 45 - 70 45 50
Chickweed 100 100 - 100 - 100 100 100 - - 80 100 - - Cocklebur 100 100 - 70 20 20 70 95 - - 100 15 - 5
Corn 40 50 - 30 30 15 40 20 - - 25 5 5 10
Crabgrass, Large 90 90 - 100 85 60 20 95 - - 50 70 10 15
Cupgrass, Woolly 70 80 - 50 30 30 40 65 - - 20 10 10 0
Foxtail, Giant 80 30 - 70 10 45 60 75 - - 10 20 10 10
Foxtail, Green - - 50 60 - - - 60 65 60 - 70 65 50
Goosegrass 70 60 - 20 0 5 30 80 - - 5 60 15 10
Johnsongrass 100 40 - - 0 10 35 55 - - 0 5 0 0
Kochia go 85 - 85 - 80 90 100 - - eo 100 100 90
Lambsquarters 100 100 - 100 100 100 100 100 - - 100 100 100 75
Morningglory 100 100 - 80 0 0 70 100 - - 0 - 10 50
Nutsedge, Yellow 30 0 - 0 0 0 20 0 - - 0 0 0 0
Oat, Wild - - 50 50 - - - 65 60 70 - 70 55 60
Pigweed 100 100 - 100 100 100 go 100 - - 100 95 100 80
Ragweed go 85 - 80 0 10 - 95 - - 0 60 50 10
Ryegrass, Italian - - 60 50 - - - 60 65 50 - 70 55 60
Soybean go 70 - 90 80 70 85 95 - - 90 go 45 60
Surinam Grass 60 60 - 40 20 60 50 60 - - 10 30 10 30
Velvetleaf go 85 - 50 40 40 70 100 - - 60 go 80 80
Wheat - - 40 30 - - - 35 40 40 - 35 55 45
Windgrass - - 60 70 - - - 85 40 45 - 75 80 -
Table C Compound Table C Compound
500 g ai/ha 353 500 g ai/ha 353
Postemergence Postemergence
Barley, Winter 25 Oat, 1 Wild 60
Blackgrass 70 Ryegrass, Ita-L .ian 20
Bromegrass, Downy 35 Wheat 35
Canarygrass 20 Windgrass 10
Foxtail, Green 30
Table C Compounds
250 g ai/ha 27 28 31 34 44 46 47 50 58 60 62 80 81 82
Postemergence
Barley, Winter 10 - - - - - - - - - 10 - - -
Bermudagrass 30 30 20 50 - - - 30 10 5 - 100 20 0
Blackgrass 20 - - - - - - - - - 40 - - -
Bromegrass , Downy 20 - - - - - - - - - 30 - - -
Canarygrass 30 - - - - - - - - - 40 - - - Chickweed 100 100 100 60 go so go o so 10 - 100 100 100
Cocklebur 80 60 40 50 70 70 70 10 20 10 - 100 60 5
Corn 50 40 40 50 80 80 80 85 5 0 - 70 40 10
Crabgrass, Large 40 40 60 60 go go - o is 5 - go 30 0 Cupgrass, Woolly 70 40 40 80 60 70 70 0 20 5 - go 5 80
Foxtail, Giant 40 30 30 40 50 60 60 0 20 5 - 80 20 10
Foxtail, Green 40 - - - - 50 - - -
Goosegrass 50 50 40 40 50 so 60 go 10 5 - 80 10 10
Johnsongrass 40 60 30 70 40 - go 0 5 0 - go 5 5 Kochia 100 80 70 go go loo loo 10 so 20 - 100 70 50
Lambsquarters 100 go go 100 go loo loo o go 70 - 100 5 80
Morningglory 40 40 60 10 80 60 70 0 10 10 - go 10 50
Nutsedge, Yellow 20 20 30 0 20 20 30 - 5 0 - 40 0 5
Oat, Wild 20 - - - - 50 - - - Pigweed 100 100 100 100 100 100 100 100 70 60 - 100 40 100
Ragweed 60 40 40 40 90 80 80 85 5 5 - 70 60 10
Ryegrass, Italian 20 - - - - 40 - - -
Soybean go 80 70 80 100 100 100 100 80 50 - 100 30 40
Surinam Grass 50 60 50 50 40 50 60 50 5 - 80 80 20 Velvetleaf 70 70 70 70 - 80 80 100 35 30 - 100 60 70
Wheat 20 - - - - 10 - - -
Windgrass 30 - - - -- 50 _ _ _
Table C Compounds
250 g ai/ha 84 85 86 9( 108 112 114 115 130 137 139 144 146 147 Postemergence
Barley, Winter 20 - 30 - -
Bermudagrass 30 5 60 30 90 60 go - 0 - 0 70
Blackgrass 40 - 40 - -
Bromegrass, Downy 20 - 40 - - Canarygrass 40 - 40 - -
Chickweed 70 100 100 100 - 100 100 100 100 - 80 100 100 90
Cocklebur o loo loo go loo 60 30 loo go - 10 70 10 5
Corn 0 35 20 35 50 - 40 - 45 - 10 20 10 10
Crabgrass, Large 0 10 10 5 70 30 100 70 20 - 0 100 50 10 Cupgrass, Woolly 0 80 80 30 40 60 70 70 60 - 5 50 30 10
Foxtail, Giant 0 50 50 45 - 50 10 60 15 - 10 50 0 0
Foxtail, Green 50 - 60 - -
Goosegrass 5 60 80 5 70 30 70 70 60 - 5 10 0 5 Johnsongrass 0 20 10 50 70 50 70 80 30 - 0 10 0 10
Kochia 10 go s 85 90 - 100 go 70 - 50 70 20 50
Lambsquarters 0 50 100 95 100 100 100 100 100 - - 100 100 100
Morningglory 0 60 85 30 - 70 - - 80 - 60 20 0 0
Nutsedge, Yellow 0 20 10 5 30 20 10 30 0 - 0 0 0 0
Oat, Wild - - - - - - - - - 40 - 50 - -
Pigweed 100 100 100 100 100 100 100 100 100 - 80 100 100 100
Ragweed 0 40 70 80 - 70 90 70 85 - 45 50 0 10
Ryegrass, Italian - - - - - - - - - 40 - 40 - -
Soybean 20 80 go 100 60 50 70 80 40 - 35 90 30 40
Surinam Grass 0 80 70 40 40 40 20 60 30 - 0 40 0 30
Velvetleaf 0 80 80 70 80 80 80 go 40 - 50 50 40 -
Wheat - - - - - - - - - 30 - 30 - -
Windgrass - - - - - - - - - 50 - eo - -
Table C Compounds
250 g ai/ha 212 268 272 295 296 301 304 318 332 333 334 338 353
Postemergence
Barley, Winter - 30 35 35 45 30 35 - 40 55 30 35 20
Bermudagrass 10 - 100 0 - - - - 50 5 - 0 -
Blackgrass - 60 45 65 75 90 70 - 100 50 95 50 60
Bromegrass, Downy - 40 60 45 45 40 40 - 50 45 45 40 30
Canarygrass - 50 40 35 55 50 45 - 60 40 45 40 10
Chickweed 80 - 100 100 - - - 10 100 - - - -
Cocklebur 70 - 60 10 - - - 10 10 80 - 5 -
Corn 40 - 15 15 - - - 10 5 5 - 10 -
Crabgrass, Large 20 - 80 35 - - - 30 50 5 - 10 -
Cupgrass, Woolly 30 - 60 15 - - - 10 10 5 - 0 -
Foxtail, Giant 50 - 60 40 - - - 5 15 10 - 10 -
Foxtail, Green - 50 45 60 60 60 50 - 50 50 45 40 20
Goosegrass 25 - 75 50 - - - 5 15 10 - 10 -
Johnsongrass 35 - 45 5 - - - 0 5 0 - 0 -
Kochia 90 - 100 90- - - - 60 95 100 - 90 -
Lambsquarters 90 - 100 50 - - - 100 100 80 - 75 -
Morningglory 70 - 100 30 - - - 0 80 10 - 40 -
Nutsedge, Yellow 20 - 0 5 - - - 0 0 0 - 0 -
Oat, Wild - 65 55 50 60 75 60 - 70 60 95 50 40
Pigweed 70 - 100 95 - - - 100 gs 100 - 80 -
Ragweed 80 - 80 40 - - - 0 40 50 - 5 _ Ryegrass, Italian - 40 45 65 65 45 50 - 70 50 45 50 15 Soybean 70 - 85 55 80 60 40 - 35 Surinam Grass 20 - 35 15 0 10 5 - 0 Velvetleaf 50 - 100 70 40 85 50 - 40 Wheat - 25 35 45 40 55 40 - 35 50 75 35 30
Windgrass - 100 - 65 65 35 40 - 65 50 75 - 10
Table C Compounds
125 g ai/ha 27 28 31 33 34 35 44 46 47 50 58 60 62 80
Postemergence Barley, Winter 10 - - - - - - - - - - - 10 -
Bermudagrass 30 10 20 30 40 20 o 100 - 30 5 0 100
Blackgrass 20 - - - - - - - - - - - 40 -
Bromegrass, Downy 20 - - - - - - - - - - - 20 -
Canarygrass 30 - - - - - - - - - - - 30 - Chickweed 100 100 90 100 50 90 90 70 90 0 20 10 - 100
Cocklebur 70 60 40 70 20 70 70 70 70 10 20 10 - 90
Corn 40 40 40 40 30 40 70 80 70 80 5 0 - 70
Crabgrass, Large 30 30 60 50 40 40 90 90 - 0 5 0
Cupgrass, Woolly 60 30 30 60 60 60 60 60 60 0 5 5 - 90 Foxtail, Giant 40 20 30 30 40 40 30 60 60 0 5 5 - 80
Foxtail, Green 40 - - - - - - - - - - - 50 -
Goosegrass 30 30 30 40 40 50 40 50 60 30 5 0 - 80
Johnsongrass 40 60 20 90 70 70 30 60 30 0 0 0 - 90
Kochia 60 40 70 90 90 90 90 - 100 10 80 20 - 100 Lambsquarters 80 70 80 90 80 90 90 100 100 0 70 30 - 100
Morningglory 40 0 50 30 10 40 50 60 50 0 10 10 - 90
Nutsedge, Yellow 20 0 0 10 0 0 20 20 20 - 5 0 - 40
Oat, Wild 20 - - - - - - - - - - - 40 -
Pigweed 100 90 90 100 100 100 100 100 100 100 60 40 - 100 Ragweed 50 40 40 70 30 50 50 70 80 85 5 5 - 70
Ryegrass, Italian 10 - - - - - - - - - - - 20 -
Soybean 80 80 50 90 80 90 100 100 - 100 75 40 - 90
Surinam Grass 30 20 40 50 30 60 40 40 30 50 - 5 - 80
Velvetleaf 60 60 50 - 70 80 80 80 80 100 10 20 - 100 Wheat 20 - - - - - - - - - - - 10 -
Windgrass 30 - - - - - - - - - - - 40 - Table C Compounds
125 g ai/ha 81 82 84 85 86 g6 108 112 114 115 130 137 139 144
Postemergence
Barley, Winter _ _ _ _ _ _ _ _ _ 20 - 20 Bermudagrass 0 0 - 65 - 0 30 0 90 60 85 0 0
Blackgrass _ _ _ _ _ _ _ _ - - - 40 - 30
Bromegrass, Downy _ _ _ _ _ _ _ _ _ _ _ 20 - 40
Canarygrass _ _ _ _ _ _ _ - - _ - 30 - 40
Chickweed 95 g5 50 100 100 100 - 10 - 100 100 70 100 Cocklebur 55 5 0 80 5 10 80 30 30 go 30 10 40
Corn 40 10 0 30 20 30 50 20 30 40 45 10 20
Crabgrass, Large 10 0 0 5 - 0 70 10 100 70 0 10
Cupgrass, Woolly 5 eθ 0 50 70 30 40 30 70 70 50 0 30
Foxtail, Giant 10 0 0 20 20 20 50 50 - 40 10 0 10 Foxtail, Green _ _ _ _ _ _ _ _ _ _ _ 50 - 60
Goosegrass 5 10 0 40 60 5 40 20 60 60 20 0 5
Johnsongrass 0 0 0 10 - 50 50 20 70 50 10 0 0
Kochia 20 40 0 60 85 80 80 20 80 go 30 50 65
Lambsquarters 5 50 0 30 100 80 100 20 o 100 100 - 100 Morningglory 10 10 0 40 75 5 60 20 30 80 40 50 0
Nutsedge, Yellow 0 5 0 20 5 0 30 0 0 10 0 - 0 0
Oat, Wild _ _ _ _ - - _ - - - - 40 - 50
Pigweed 10 100 100 100 100 100 100 60 100 100 100 65 100
Ragweed 60 0 0 10 65 50 - 0 80 70 40 45 0 Ryegrass, Italian _ _ _ _ _ _ _ _ _ _ _ 40 - 20
Soybean 30 30 0 60 70 100 60 0 70 70 40 30 85
Surinam Grass 50 10 0 30 60 40 40 40 10 40 10 0 0
Velvetleaf 55 10 0 75 60 70 60 0 70 go 30 50 20
Wheat _ 30 - 30 Windgrass _ _ _ _ _ _ _ _ _ _ _ so - 60
Table C Compounds 125 g ai/ha 146 147 212 268 272 2g5 296 301 304 318 332 333 334 338 Postemergence Barley, Winter - 15 35 35 40 30 35 - 35 45 30 30 Bermudagrass 0 - 80 0 - - - - 10 0 - 0 Blackgrass - 45 45 65 65 75 50 - 70 40 95 45 Bromegrass, Downy - 30 55 45 35 40 40 - 40 - 35 35 Canarygrass - 30 35 35 40 45 40 - 45 35 35 25 Chickweed 80 30 80 - 100 100 - - - 0 100 - - -
Cocklebur 5 5 60 - 60 5 - - - 5 10 5 - 0
Corn 5 5 35 - 15 10 - - - 10 0 5 - 0
Crabgrass, Large 0 0 10 - 80 30 - - - 0 - 5 - 5
Cupgrass, Woolly 10 0 5 - 40 15 - - - 0 5 0 - 0
Foxtail, Giant 0 0 20 - 45 35 - - - 0 10 5 - 5
Foxtail, Green - - - 45 40 50 50 45 45 - 40 40 35 40
Goosegrass 0 0 10 - 65 20 - - - 0 15 10 - 5
Johnsongrass 0 - 30 - 40 5 - - - 0 5 0 - 0
Kochia - 10 80 - 100 85 - - - 10 go 100 - 60
Lambsquarters 80 100 90 - 100 5 - - - 70 65 80 - 5
Morningglory 0 0 10 - 100 10 - - - 0 10 0 - 0
Nutsedge, Yellow 0 0 10 - 0 5 - - - 0 0 0 - 0
Oat, Wild - - - 35 45 50 60 65 60 - 65 60 75 45
Pigweed 90 90 - - 100 - - - - 100 go 100 - 5
Ragweed 0 0 60 - 65 30 - - - 0 30 30 - 5
Ryegrass, Italian - - - 30 45 40 45 45 50 - 60 35 35 30
Soybean 20 35 eo - 80 50 - - - 70 50 30 - 30
Surinam Grass 0 0 5 - 10 5 - - - 0 5 5 - 0
Velvetleaf 35 30 - - 95 65 - - - 35 60 50 - 0
Wheat - - - 0 35 45 35 45 40 - 30 50 75 25
Windgrass - - - 60 70 60 50 35 35 - 60 25 60 15
Table C Compound Table C Compound
125 g ai/ha 353 125 g ai/ha 353
Postemergence Postemergence
Barley, Winter 15 Oat, Wild 30
Blackgrass 20 Ryegrass , Ital .ian 15
Bromegrass, Downy 20 Wheat 15
Canarygrass 10 Windgrass 10
Foxtail, Green 20
Table C Compounds
62 g ai/ha 27 28 31 33 34 35 44 46 47 50 58 60 62 80
Postemergence
Barley, Winter 10 10 -
Bermudagrass 30 10 10 20 10 0 - - 60 0 0 0 - -
Blackgrass 10 40 -
Bromegrass, Downy 10 20 - Canarygrass 20 _ _ _ _ _ _ _ - - - 0 -
Chickweed 70 90 go go - so 90 70 go o 20 5 - 100
Cocklebur 50 40 40 50 20 60 50 60 50 10 15 10 - go
Corn 30 20 40 40 20 30 70 80 70 20 0 0 - 70
Crabgrass, Large 20 30 50 - 20 40 60 - θ 0 5 0 - 90
Cupgrass, Woolly 60 30 30 60 40 40 50 40 60 0 5 0 - 80
Foxtail, Giant 20 20 20 30 20 40 30 40 60 0 0 0 - 70
Foxtail, Green 30 _ 40
Goosegrass 30 20 30 40 30 40 40 40 50 30 0 0 - 80
Johnsongrass 40 20 20 90 70 70 30 60 30 0 0 0 - 80
Kochia 60 40 70 90 80 90 90 90 100 0 75 10 - 100
Lambsquarters 70 70 so 90 40 90 90 so go o 60 lo - go
Morningglory 40 0 50 20 10 20 50 60 50 0 10 10 - go
Nutsedge, Yellow 20 0 0 0 0 0 20 20 20 - 0 0 - 40
Oat, Wild 20 _ _ _ _ _ _ _ _ _ _ 30 -
Pigweed 90 90 go loo loo loo 100 100 100 50 eo 40 - 100
Ragweed 30 30 30 60 20 50 50 70 70 80 0 0 - 70
Ryegrass, Italian 10 - - - - - - - - - 20 -
Soybean 80 70 30 80 70 gθ 100 100 100 100 15 20 - 90
Surinam Grass 20 - 30 50 20 40 40 40 30 10 - 5 - 80
Velvetleaf 60 50 50 90 20 70 60 50 80 100 10 20 - 100
Wheat 10 _ _ _ _ _ ιo
Windgrass 20 _ _ _ _ _ _ _ _ _ _ 30 -
Table C Compounds
62 g ai/ha 81 82 84 85 86 96 108 112 114 115 137 139 144 146
Postemergence
Barley, Winter - - 10 - 0 -
Bermudagrass 0 0 0 10 0 30 0 60 10 0 0 -
Blackgrass - - 40 - 30
Bromegrass, Downy - - 10 - 20
Canarygrass - - 20 - 40
Chickweed 95 70 0 100 100 100 - 0 100 100 0 100 10
Cocklebur 55 5 0 20 85 5 70 0 30 90 5 10 5
Corn 40 10 0 30 15 30 50 10 30 40 0 10 5
Crabgrass, Large 5 0 0 0 10 0 10 0 20 60 0 0 0
Cupgrass, Woolly 5 - 0 40 50 5 20 0 70 50 0 0 10
Foxtail, Giant 10 0 0 10 10 10 30 30 10 40 0 0 0
Foxtail , Green - - 30 - 40 Goosegrass 0 0 0 35 50 5 20 20 60 40 - 0 5 0
Johnsongrass 0 0 0 10 10 0 20 20 70 30 - 0 0 0
Kochia 0 10 0 20 80 80 60 0 80 80 - 50 - 5
Lambsquarters 5 30 0 10 100 60 70 20 90 100 - - 100 40
Morningglory 10 10 0 10 10 0 30 0 10 50 - 0 0 0
Nutsedge, Yellow 0 0 0 10 0 0 20 0 0 0 - 0 0 0
Oat, Wild - - - - - - - - - - 20 - 30 -
Pigweed 5 85 100 100 100 70 60 10 100 100 - 50 100 80
Ragweed 40 0 0 10 10 50 - 0 60 70 - 0 0 0
Ryegrass, Italian - - - - - - - - - - 20 - 20 -
Soybean 10 20 0 55 45 100 50 0 70 60 - 20 70 20
Surinam Grass 50 10 0 25 10 0 20 20 10 30 - 0 0 0
Velvetleaf 55 5 0 60 40 40 40 0 60 60 - 30 0 30
Wheat - - - - - - - - - - 30 - 20 -
Windgrass - - - - - - - - - - 30 - 50 -
Table C Compounds
62 g ai/ha 147 212 268 272 295 296 301 304 318 332 333 334 338 353
Postemergence
Barley, Winter - - 0 35 35 35 30 35 - 35 40 20 20 5
Bermudagrass - 0 - 50 0 - - - - 5 0 - 0 -
Blackgrass - - 30 35 45 60 55 60 - 60 30 90 40 0
Bromegrass, Downy - - 10 30 45 35 40 40 - 35 40 30 30 10
Canarygrass - - 10 35 30 30 35 40 - 35 35 25 20 0
Chickweed 5 60 - gs 100 - - - 0 60 - - - -
Cocklebur 0 10 - 15 5 - - - 0 5 0 - 0 -
Corn 0 15 - 10 5 - - - 0 0 5 - 0 -
Crabgrass, Large 0 0 - 40 - - - - 0 30 0 - 0 -
Cupgrass, Woolly 0 5 - 25 10 - - - 0 5 0 - 0 -
Foxtail, Giant 0 10 - 15 30 - - - 0 10 5 - 5 -
Foxtail, Green - - 40 35 45 40 40 40 - 35 30 35 30 15
Goosegrass 0 10 - 20 20 - - - 0 10 5 - 0 -
Johnsongrass 0 0 - 10 5 - - - 0 0 0 - 0 -
Kochia 5 80 - gs 80 - - - 0 80 90 - 50 -
Lambsquarters 90 80 - 100 0 - - - 60 50 60 - 0 -
Morningglory 0 10 - 80 10 - - - 0 5 0 - 0 -
Nutsedge, Yellow 0 0 - 0 5 - - - 0 0 0 - 0 -
Oat, Wild - - 20 40 50 35 45 60 - 50 50 55 40 10
Pigweed 90 50 - 100 80 - - - 100 85 65 - 0 - Ragweed 0 60 - 60 25 - - - 0 5 5 - 0
Ryegrass, Italian - - 10 30 40 35 35 50 - 60 35 30 25 10
Soybean 10 50 - 60 50 - - - 65 45 30 - 10
Surinam Grass 0 0 - 5 5 - - - 0 5 5 - 0
Velvetleaf 0 0 - 85 60 - - - 0 40 - - 0
Wheat - - 0 30 45 35 40 35 - 30 40 65 25 10
Windgrass - - 30 60 50 45 35 35 - 35 20 60 10 0
Table C Compounds
31 g ai/ha 27 33 35 60 62 80 81 114 139 268 295 296 334
Postemergence
Barley, Winter 0 - - - 0 - - - - 0 35 30 20
Bermudagrass 20 20 - 0 - - 0 20 0 - 0 - -
Blackgrass 10 - - - 20 - - - - 0 45 45 75
Bromegrass, Downy 10 - - - 10 - - - - 0 45 25 20
Canarygrass 10 - - - 0 - - - - 10 25 30 20
Chickweed 70 40 70 5 - go go 80 0 - 85 - -
Cocklebur 40 - 20 10 - 70 50 30 5 - 5 - -
Corn 30 40 30 0 - 70 15 30 0 - 5 - -
Crabgrass, Large 20 40 0 0 - go 5 20 0 - 20 - -
Cupgrass, Woolly 0 50 30 0 - 80 5 40 0 - 10 - -
Foxtail, Giant 20 30 10 0 - 70 10 0 0 - 30 - -
Foxtail, Green 30 - - - 40 - - - - 35 40 40 30
Goosegrass 30 40 30 0 - 80 0 50 0 - 5 - -
Johnsongrass 30 70 60 0 - 80 0 70 0 - 0 - -
Kochia 50 60 - 5 - 100 0 30 20 - 50 - -
Lambsquarters 60 90 70 10 - 90 0 80 - - 0 - -
Morningglory 30 20 10 10 - 80 5 0 0 - 5 - -
Nutsedge, Yellow 20 0 0 0 - 40 0 0 0 - 0 - -
Oat, Wild 20 - - - 20 - - - - 20 45 35 40
Pigweed 80 go 100 20 - 100 0 go 50 - 60 - -
Ragweed 30 - 20 0 - 70 0 60 0 - 20 - -
Ryegrass, Italian 10 - - - 0 - - - - 0 40 25 20
Soybean 80 80 go 20 - go 5 20 20 - 35 - -
Surinam Grass 20 50 10 0 - 80 50 10 0 - 5 - -
Velvetleaf 50 60 50 15 - 100 5 30 0 - 60 - -
Wheat 10 - - - 0 - - - - 0 40 30 35
Windgrass 20 - - - 0 - _ _ - 20 50 45 60 Table C Compounds Table C Compounds
16 g ai/ha 33 35 16 g ai/ha : 33 35
Postemergence Postemergence
Bermudagrass 0 0 Kochia 60 : 20
Chickweed 30 70 Lambsquarters ' 70 50
Cocklebur 20 20 Morningglory 0 0
Corn 40 30 Nutsedge, , Yellow 0 0
Crabgrass, Large - 0 Pigweed 90 ' 70
Cupgrass, Woolly 30 20 Ragweed 50 20
Foxtail, Giant 30 0 Soybean 70 60
Goosegrass 30 0 Surinam Grass : 20 0
Johnsongrass 70 50 Velvetleaf 40 40
Table C Compounds
500 g ai/ha 1 2 3 6 7 g 10 11 13 14 16 28 30 31
Preemergence
Bermudagrass 100 95 95 90 100 go 100 90 100 100 100 100 go 100
Cocklebur 100 80 40 100 - 100 - - 20 90 75 30 20 -
Corn 80 60 35 80 80 65 60 80 75 95 80 0 - -
Crabgrass, Large 100 100 gs 100 100 gs 100 100 100 100 100 100 100 100
Cupgrass, Woolly 65 80 70 75 - 30 85 70 70 100 85 20 60 60
Foxtail, Giant 80 100 100 100 100 75 100 go 100 100 100 100 go 100
Goosegrass gs 100 gs 100 go 85 85 90 100 100 95 100 80 go
Johnsongrass 90 100 100 100 100 80 100 95 100 100 100 100 go go
Kochia 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Lambsquarters 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Morningglory 100 100 60 70 0 35 60 15 100 100 70 60 80 40
Nightshade 100 100 gs 100 100 100 100 100 100 100 100 100 100 100
Nutsedge, Yellow 80 - 70 85 60 60 60 eo 75 90 go 20 - 0
Pigweed 100 100 gs 100 100 100 100 100 100 100 100 100 100 100
Ragweed 100 100 100 100 100 100 100 100 100 100 100 90 20 80
Soybean 65 100 85 100 80 55 70 90 75 95 95 80 30 20
Sunflower 35 0 0 100 0 20 40 10 80 100 90 0 30 20
Surinam Grass 100 100 100 100 80 80 go 100 100 100 100 90 50 60
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56 S6 εε 06 56 06 ooτ S8 ooτ se 06 ooτ ooτ ooτ _τqoo;a
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60
-96-C0/£00.Sfl/13<I -t.SCO/tOO- OΛV Goosegrass 90 100 50 100 100 100 100 100 100 100 100 100 100 100 Johnsongrass 80 85 80 100 - 100 100 100 100 gs 100 100 90 100 Kochia 100 100 100 100 100 - - 100 100 100 100 100 100 100
Lambsquarters 100 100 100 100 100 - - 100 100 100 100 100 100 100 Morningglory 0 40 0 100 100 15 55 5 40 - - 50 45 100 Nightshade 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Nutsedge, Yellow 0 0 0 60 0 25 0 70 60 85 20 90 30 80 Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Ragweed 0 100 60 100 100 100 100 100 90 100 100 100 0 100 Soybean 0 0 20 100 90 75 15 g5 60 gs 100 100 60 95
Sunflower 0 0 30 30 30 gs 20 go 15 100 - 100 0 100 Surinam Grass 60 50 45 100 85 loo loo loo gs gs 100 100 70 100 Velvetleaf 0 100 80 100 100 100 100 100 80 100 100 100 100 100
Table C Compounds 500 g ai/ha 301 304 305 306 307 30 310 314 318 332 333 336 340 341
Preemergence
Bermudagrass 95 100 100 100 100 100 100 90 gs 100 100 100 100 100
Cocklebur 60 0 go 5 75 60 30 20 0 0 5 50 40 100
Corn 45 30 45 50 45 60 10 0 40 5 0 85 50 90 Crabgrass, Large 100 100 100 100 100 100 100 60 100 100 100 100 100 100
Cupgrass, Woolly go 80 70 50 85 100 - 20 10 10 30 85 75 100
Foxtail, Giant 100 90 100 100 100 100 100 70 80 80 75 go 85 80
Goosegrass 100 100 gs 100 100 100 95 85 go 100 100 100 go go
Johnsongrass gs 80 gs - 100 100 80 90 gs 80 5 100 90 100 Kochia 100 100 100 100 100 100 100 70 100 100 100 100 100 100
Lambsquarters 100 100 100 100 100 100 100 85 100 100 100 100 100 100
Morningglory 60 10 10 20 15 40 10 40 85 0 10 100 50 50
Nightshade 100 100 100 100 100 100 100 100 gs 100 100 100 100 100
Nutsedge, Yellow 20 5 50 40 50 60 15 0 0 0 0 60 60 60 Pigweed 100 100 100 100 100 100 100 90 100 100 100 100 100 100
Ragweed 70 70 100 100 100 100 80 60 70 70 65 100 75 100
Soybean 45 20 100 40 100 80 - 40 40 10 0 100 10 100
Sunflower 0 5 50 0 60 60 0 45 0 0 0 45 5 100
Surinam Grass 90 85 60 95 90 100 50 20 60 15 20 100 85 100 Velvetleaf 100 60 100 10 100 100 100 85 100 70 55 100 100 100 Table C Compounds Tabl< 3 C 1Compounds
500 g ai/ha 342 343 352 500 <g ai /ha 342 343 352
Preemergence Preemergence
Bermudagrass 90 go 100 Morningglory 100 100 60
Cocklebur 100 100 30 Nightshade 85 : 95 100
Corn 90 80 50 Nutsedge , Yellow 60 : 90 50
Crabgrass, Large 85 100 100 Pigweed 100 100 100
Cupgrass, Woolly 70 100 85 Ragweed 100 100 ' 60
Foxtail, Giant 70 80 100 Soybi 3an 100 100 ' 70
Goosegrass 90 85 100 Sunflower 100 100 0
Johnsongrass 100 100 100 Surinam Grass 100 100 100
Kochia 100 100 100 Velvetleaf 100 100 100
Lambsquarters 100 100 100
Table C Compounds
250 g ai/ha 1 2 3 6 7 g 10 11 13 14 16 27 28 29
Preemergence
Ber udagrass 90 gs 90 90 85 85 100 50 go 85 95 100 100 100
Cocklebur - 65 10 100 0 100 - 20 0 70 40 20 0 40
Corn 65 35 35 80 40 55 60 80 60 75 70 20 0 0
Crabgrass, Large gs 100 95 95 100 95 100 85 100 100 100 100 100 100
Cupgrass, Woolly - 60 65 75 80 25 85 55 55 95 65 40 20 60
Foxtail, Giant 75 100 100 85 80 70 80 80 95 95 90 100 50 100
Goosegrass go gs 90 100 90 85 - 80 100 100 go 100 go 90
Johnsongrass 80 100 90 90 80 75 100 go 75 100 100 100 go 90
Kochia 100 100 100 100 100 100 100 100 95 100 100 100 90 100
Lambsquarters 100 100 90 100 100 100 100 100 100 100 95 100 100 100
Morningglory 15 45 25 30 0 15 60 0 100 70 0 100 20 -
Nightshade 100 100 95 100 gs 85 100 85 100 95 100 100 100 100
Nutsedge, Yellow 60 90 65 80 40 55 50 50 65 70 80 20 20 0
Pigweed 100 95 95 100 100 100 100 100 100 100 100 100 100 100
Ragweed 100 100 100 100 100 100 100 100 100 100 100 0 60 100
Soybean 25 100 40 100 10 40 40 0 15 85 gs 30 30 30
Sunflower 25 0 0 100 0 0 0 0 65 100 75 20 0 60
Surinam Grass 100 100 100 100 80 65 go 100 gs 95 go 60 50 60
Velvetleaf 85 100 85 100 50 100 _ 50 100 100 100 100 100 80 Table C Compounds
250 g ai/ha 30 31 34 41 44 46 47 48 50 55 56 57 58 60
Preemergence
Bermudagrass 90 100 90 100 20 100 100 90 0 100 95 95 100 100
Cocklebur 20 40 0 10 0 go 0 0 80 0 - 0 10 5
Corn 60 - 0 0 0 10 0 0 0 0 0 0 0 0
Crabgrass, Large 100 100 100 100 20 100 100 70 20 gs 100 100 gs gs
Cupgrass, Woolly 30 30 70 30 10 30 60 5 30 55 35 25 60 70
Foxtail, Giant 70 70 90 30 10 100 80 10 0 75 100 100 100 80
Goosegrass 50 40 100 40 50 100 100 90 100 75 90 90 95 gs
Johnsongrass 60 70 100 20 50 go 100 50 0 gs 85 80 90 60
Kochia 90 100 - 30 10 100 10 80 100 100 95 100 gs go
Lambsquarters 100 100 100 100 100 100 100 gs 100 100 100 100 100 100
Morningglory 70 - 0 20 0 go go 0 0 20 55 25 50 10
Nightshade 100 100 go go 100 100 100 s 80 go 95 100 100 go
Nutsedge, Yellow 20 0 0 0 0 0 0 10 40 0 0 0 50 5
Pigweed 100 100 100 100 go 100 100 100 gs 95 100 100 100 100
Ragweed 0 eo 0 10 70 go 100 70 80 0 95 100 100 gs
Soybean 10 10 0 10 10 10 10 0 0 0 10 0 25 0
Sunflower 30 20 0 0 0 10 10 0 0 0 0 0 0 0
Surinam Grass 20 30 60 20 10 60 60 30 80 65 60 35 80 50
Velvetleaf 80 100 go 100 70 100 100 10 5 15 50 100 100 85
Table C Compounds
250 g ai/ha 61 62 63 64 65 80 88 gs ge 102 108 114 115 130
Preemergence
Bermudagrass 80 95 90 85 95 10 s 100 85 100 100 100 100 100
Cocklebur - 0 0 0 0 10 0 10 20 20 30 30 50 70
Corn 0 0 5 0 10 20 5 20 30 10 50 10 20 5
Crabgrass, Large 100 90 90 70 80 10 95 100 100 100 100 100 100 gs
Cupgrass, Woolly 0 20 0 0 10 10 80 30 20 20 50 30 80 40
Foxtail, Giant 40 85 10 10 20 50 85 100 100 80 100 40 100 65
Goosegrass 70 85 60 50 60 10 95 85 gs 100 100 100 100 30
Johnsongrass 50 70 75 40 65 10 50 60 85 90 100 70 100 30
Kochia 100 100 90 60 85 10 90 100 100 40 100 100 100 20
Lambsquarters 100 100 100 85 100 60 100 - - 100 100 100 100 80
Morningglory 5 10 40 0 0 50 0 70 80 80 50 - 80 -
Nightshade 40 95 gs gs 100 10 95 gs gs 100 100 90 100 -
Nutsedge, Yellow 10 40 0 0 0 0 0 0 0 30 80 0 0 0 Pigweed gs 95 100 100 100 100 100 100 100 100 100 100 100 100
Ragweed 80 85 10 0 0 10 5 100 100 go 20 30 100 60
Soybean 0 30 10 10 20 0 0 10 45 0 0 - 0 5
Sunflower 0 0 0 0 0 10 0 0 20 20 20 30 10 0
Surinam Grass 5 50 45 20 0 10 50 60 40 40 90 40 70 20
Velvetleaf 80 70 30 50 5 100 10 80 100 20 100 30 100 100
Table C Compounds
250 g ai/ha 131 134 137 139 140 144 145 146 147 149 152 153 156 162
Preemergence
Bermudagrass gs gs 100 95 60 80 80 70 go 90 100 95 gs 20
Cocklebur 25 0 0 0 0 0 0 0 - 0 65 0 100 55
Corn 0 0 5 15 0 40 5 10 0 10 50 0 40 75
Crabgrass, Large go gs 100 100 75 85 80 - go 100 100 0 go 80
Cupgrass, Woolly 15 20 5 55 0 5 0 0 10 20 100 0 80 0
Foxtail, Giant 45 0 60 95 65 100 50 60 30 60 100 0 85 50
Goosegrass 80 85 100 90 70 75 75 30 60 90 100 85 90 75
Johnsongrass 45 50 35 50 60 80 80 40 60 80 100 45 100 80
Kochia 100 100 100 100 95 100 60 85 60 60 100 100 100 100
Lambsquarters 100 100 100 100 gs 100 90 90 100 95 100 100 100 100
Morningglory 0 0 0 60 0 - 0 40 0 5 100 15 100 100
Nightshade 100 gs 90 100 65 100 80 100 90 80 100 100 100 100
Nutsedge, Yellow 0 0 0 5 0 10 0 0 0 0 40 0 85 55
Pigweed 100 100 100 100 100 100 90 95 go 100 100 100 100 100
Ragweed 90 90 70 95 70 50 0 50 0 5 100 15 100 100
Soybean 15 0 0 30 0 60 30 0 0 0 50 0 85 90
Sunflower 0 0 0 20 0 0 0 0 0 0 60 0 80 70
Surinam Grass 15 50 30 30 65 60 65 40 10 40 100 75 85 80
Velvetleaf 20 100 70 100 0 100 100 100 70 0 100 75 100 100
Table C Compounds
250 g ai/ha 182 188 193 195 198 199 202 205 207 210 212 213 215 221
Preemergence
Bermudagrass 90 100 85 30 100 100 95 100 100 100 80 80 85 85
Cocklebur 0 0 - 0 0 0 10 0 0 0 5 100 0 0
Corn 0 0 95 0 0 0 0 0 5 20 30 30 20 0
Crabgrass, Large 75 95 85 5 95 90 95 100 100 95 85 100 85 100
Cupgrass, Woolly 0 70 60 10 10 40 20 10 5 5 20 0 40 0
Foxtail, Giant 60 70 80 0 60 80 80 80 10 10 20 gs 70 40 Goosegrass 50 85 80 100 95 90 90 80 80 gs gs 80 80 0
Johnsongrass 50 35 90 0 60 60 70 60 40 50 50 60 50 10
Kochia 65 0 100 10 100 90 85 90 90 go 90 100 100 65
Lambsquarters s 100 100 10 100 100 100 90 gs 100 100 100 100 go
Morningglory 65 60 100 0 85 70 80 10 0 5 5 0 0 0
Nightshade 85 100 85 0 100 100 100 100 100 100 100 100 100 70
Nutsedge, Yellow 0 0 10 0 0 0 0 0 20 5 0 0 0 0
Pigweed gs gs 100 90 100 100 100 gs 100 100 100 100 100 100
Ragweed 60 75 100 80 95 80 95 50 60 go 30 0 100 -
Soybean 0 0 50 0 0 5 0 20 0 0 0 0 0 0
Sunflower 0 0 0 0 10 0 10 0 0 0 0 0 0 0
Surinam Grass 25 75 95 85 30 30 40 50 0 10 5 20 30 10
Velvetleaf 20 45 70 55 80 85 100 60 40 60 100 0 40 60
Table C Compounds
250 g ai/ha 222 223 242 244 268 269 287 2 3 2 2 8 299 300 301 304
Preemergence
Bermudagrass 100 100 100 100 100 100 95 100 go 80 100 100 go 100
Cocklebur 70 0 35 0 70 5 10 20 80 0 80 5 0 0
Corn 60 5 20 10 60 40 50 80 60 15 60 35 40 15
Crabgrass, Large 100 100 100 100 100 100 95 100 100 100 100 100 100 100
Cupgrass, Woolly 100 - 95 85 95 60 10 s 80 30 90 60 70 60
Foxtail, Giant gs 100 100 95 95 100 85 100 go 70 100 100 gs 60
Goosegrass 100 80 100 100 100 gs 100 95 85 100 100 100 100 go
Johnsongrass 100 - 100 95 100 100 95 100 100 60 100 gs 85 70
Kochia 100 100 - - 100 100 100 100 100 100 100 100 100 85
Lambsquarters 100 100 - - 100 100 100 100 100 100 100 100 100 100
Morningglory 30 5 0 20 5 10 - 100 50 20 100 40 10 10
Nightshade 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Nutsedge, Yellow 20 0 15 0 60 40 60 0 80 20 60 60 10 0
Pigweed 100 100 100 100 100 100 100 95 100 100 100 100 100 100
Ragweed 100 100 100 100 100 90 100 100 100 0 100 10 65 70
Soybean 100 80 65 10 90 50 85 go 100 5 90 70 20 20
Sunflower 30 0 50 15 60 5 100 65 100 0 100 5 0 0
Surinam Grass 100 70 95 100 95 85 65 100 100 40 100 100 80 40
Velvetleaf 100 100 100 100 100 75 100 100 100 100 100 5 100 _ Table C Compounds
250 g ai/ha 305 306 307 309 310 314 318 332 333 334 336 340 341 342
Preemergence
Bermudagrass 100 go 100 95 100 60 go 100 100 100 100 85 100 go
Cocklebur 65 0 35 60 5 0 0 0 0 70 30 0 50 60
Corn 45 20 30 40 5 0 10 0 0 50 85 45 85 70
Crabgrass, Large 100 100 100 100 100 40 60 100 100 100 100 100 90 70
Cupgrass, Woolly 60 30 70 90 70 0 0 5 0 85 60 45 100 50
Foxtail, Giant 100 90 100 90 85 20 50 60 50 100 90 60 55 55
Goosegrass gs 100 100 100 gs 65 80 100 85 100 100 85 85 65
Johnsongrass gs 80 90 gs 20 70 60 50 5 100 100 50 100 100
Kochia 100 100 100 100 100 30 85 100 100 100 100 90 100 100
Lambsquarters 100 100 100 100 100 30 100 100 100 100 100 100 100 100
Morningglory 5 10 10 5 5 30 0 0 0 40 100 10 5 70
Nightshade 100 100 100 100 100 go 95 95 98 100 100 100 100 80
Nutsedge, Yellow 25 10 50 45 0 0 0 0 0 55 20 0 30 40
Pigweed 100 100 100 100 100 go 100 100 100 100 100 100 100 100
Ragweed 85 - 100 70 50 40 70 5 50 100 80 20 100 100
Soybean go 15 80 80 30 40 10 0 0 80 50 0 70 100
Sunflower 0 0 60 5 0 20 0 0 0 55 30 0 50 75
Surinam Grass 60 40 90 go 30 0 50 10 5 95 100 65 100 100
Velvetleaf 100 - 100 75 10 80 100 45 50 85 100 95 100 100
Table C Compounds Table C Compounds
250 g ai/ha 343 352 250 g ai, /ha 343 352
Preemergence Preemergence
Bermudagrass go 100 Morningglory 100 40
Cocklebur 80 0 Nightshade go 50
Corn 70 30 Nutsedge , Yellow 60 10
Crabgrass, Large 80 100 Pigweed 100 100
Cupgrass, Woolly 70 60 Ragweed go 50
Foxtail, Giant 70 100 Soybean 100 50
Goosegrass 80 100 Sunflower 80 0
Johnsongrass 100 90 Surinam Grass 100 100
Kochia 100 100 Velvetleaf 100 ' 70
Lambsquarters 100 100 0 oτ 0 0 0 0 0 0 0 0 0 0 - 0 Λoχχa;c 'a as-i N
09 s 08 ooτ ooτ 06 oτ 06 06 ooτ 06 06 ooτ ooτ a _qs-}q τ
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06 0 oε ooτ ooτ oz ooτ oε ooτ ooτ ooτ 06 ooτ ooτ aβ_ι_1 'ss_α:βq'B-io
Figure imgf000218_0001
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0 ooτ ooτ ooτ ooτ ooτ ooτ oε ooτ S6 08 se ooτ ooτ aa_5_ ooτ ooτ ooτ ooτ ooτ ooτ se ooτ ooτ 56 se 56 S6 ooτ aaMβτa oε SΔ εs sz 0 oε sz oε OΔ 0 sε oε εg εz -4oχχ_λ 'aβpasαnja ooτ ooτ 06 06 08 ooτ SΔ 09 ooτ ooτ S6 S6 ooτ ooτ a eqs q τN ξl ooτ 0 S9 06 0 oτ 0 0 0 ot oε oz oz 0 A_ιoχββuτu-ιo]Λ[ ooτ εε ooτ ooτ ooτ ooτ ooτ εs ooτ 09 ooτ 06 ooτ ooτ
Figure imgf000218_0002
ooτ ooτ ooτ 06 ooτ ooτ ooτ 08 ooτ oτ - 08 ooτ ooτ _τqooϋ
06 08 58 og sg 06 ss OS 06 oε 59 OΔ 06 εΔ ss-jr uosu of
06 08 S6 06 OΔ 08 08 OΔ ooτ 05 58 06 εε S8 ss_-ιβasoo£) 01 ooτ OΔ 56 oz og OΔ og OΔ 08 5 OΔ 06 ooτ sg -ιu_τo 'χτ_-ixθj3; oε εt og oz ss 0 sτ oε εε 0 OZ oε 09 sε χχooM 'sse-iβdno ooτ εε ooτ ooτ 08 06 08 S8 εε OΔ 08 08 6 08 aβ„"_rr 'ss_α:βq_α:o
0 εε OΔ os OΔ ot εz oε 09 0 0 0 oε εt u-ioo oτ 0 sg 0 oτ 0 0 0 ooτ 0 09 s s - -mqa 3[DθQ ooτ SΔ εs 08 oε OS sg OΔ 06 oτ S6 06 06 εs ss_χβ_pra-traa aouaB-iauiaa- :
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91-
_96-εθ/εθO.SflΛLO<I si7..εo/i7θθ- OΛV Pigweed 100 100 100 100 100 100 100 go 70 100 100 100 90 95
Ragweed 20 0 0 0 10 0 80 0 30 40 80 5 40 0
Soybean 0 30 0 0 0 0 0 0 10 0 0 0 0 0
Sunflower 0 60 10 20 0 0 10 0 0 10 0 0 0 0
Surinam Grass 20 30 20 20 30 20 20 20 10 30 10 5 10 25
Velvetleaf 70 80 30 70 70 60 100 40 70 100 40 0 5 0
Table C Cimpounds
125 g ai/ha 56 57 58 60 61 62 63 64 65 80 88 95 96 102
Preemergence
Bermudagrass 90 95 100 100 70 90 90 30 85 10 95 100 80 100
Cocklebur 0 0 5 0 0 0 0 0 0 10 0 5 5 20
Corn 0 0 0 0 0 0 0 0 0 10 5 10 15 0
Crabgrass, Large 100 100 95 90 75 90 85 40 50 10 95 100 100 100
Cupgrass, Woolly 0 0 40 10 0 0 0 0 0 10 30 10 10 10
Foxtail, Giant 85 95 100 15 20 65 5 0 0 40 50 100 100 50
Goosegrass 85 75 95 85 40 70 45 10 30 10 90 50 80 100
Johnsongrass 70 65 80 50 30 40 60 20 40 10 20 40 60 80
Kochia 90 100 95 90 100 100 80 20 70 10 85 100 95 30
Lambsquarters 100 100 100 100 100 100 95 0 gs 10 95 - - 70
Morningglory 0 0 20 5 0 0 40 0 0 - 0 10 50 70
Nightshade 95 95 100 90 20 90 90 50 90 10 90 95 95 100
Nutsedge, Yellow 0 0 20 0 0 10 0 0 0 0 0 0 0 0
Pigweed 100 100 100 100 95 95 100 70 100 100 100 100 100 100
Ragweed 95 100 85 80 0 20 0 0 0 0 0 80 90 20
Soybean 0 0 5 0 0 0 0 0 0 0 0 0 5 0
Sunflower 0 0 0 0 0 0 0 0 0 0 0 0 0 20
Surinam Grass 15 15 55 0 0 10 5 5 0 10 20 10 10 -
Velvetleaf 35 0 100 70 45 - 10 30 0 100 0 60 50 20
Table C Compounds
125 g ai/ha 108 114 115 118 128 130 131 134 137 139 140 144 145 146
Preemergence
Bermudagrass 100 90 100 100 100 90 90 gs 100 90 0 80 60 60
Cocklebur 30 20 40 20 10 - 20 0 0 0 0 0 0 0
Corn 40 10 10 10 20 5 0 0 5 0 0 30 0 0
Crabgrass, Large 100 100 100 100 100 90 90 gs 70 100 65 70 50 -
Cupgrass, Woolly 50 10 30 0 20 10 0 0 0 10 0 5 0 0
Foxtail, Giant 100 30 90 10 10 45 20 0 50 80 25 70 0 10 Goosegrass 100 80 80 80 90 20 65 65 85 85 0 60 70 0
Johnsongrass 100 30 100 100 90 - 40 40 5 30 45 0 65 30
Kochia 100 go 100 20 0 0 85 100 90 100 75 80 60 50
Lambsquarters 100 100 100 60 30 30 100 100 100 100 85 95 60 go
Morningglory - 60 30 30 30 0 0 0 0 10 0 30 0 5
Nightshade 100 go 100 100 90 - 95 gs 85 100 0 100 70 60
Nutsedge, Yellow 70 0 0 0 70 0 0 0 0 0 0 0 0 0
Pigweed 100 100 100 90 60 go 100 gs 100 100 100 go 90 95
Ragweed 20 10 80 10 20 10 50 25 0 50 0 30 0 0
Soybean 0 - 0 10 20 0 0 0 0 10 - 40 10 0
Sunflower 20 30 - 20 50 0 0 0 0 10 0 0 0 0
Surinam Grass 40 10 40 20 60 5 0 15 10 20 0 40 50 0
Velvetleaf go 30 100 40 100 10 15 go 10 30 0 100 20 40
Table C Compounds
125 g ai/ha 147 149 152 153 156 162 182 188 193 195 198 199 202 205
Preemergence
Bermudagrass 70 90 90 95 93 0 75 100 80 0 85 85 85 100
Cocklebur - 0 65 0 98 - 0 0 - 0 0 0 0 0
Corn 0 0 45 0 38 70 0 0 60 0 0 0 0 0
Crabgrass , Large 50 90 100 0 85 40 25 95 85 0 85 90 gs 80
Cupgrass, Woolly 10 5 50 0 70 0 0 60 40 0 5 0 10 10
Foxtail, Giant 0 50 100 0 83 60 0 55 50 0 10 10 40 10
Goosegrass 20 70 100 75 90 60 25 70 80 100 80 70 85 70
Johnsongrass 40 60 100 15 85 80 35 20 85 0 30 30 40 10
Kochia 40 10 100 95 95 75 60 0 85 0 80 85 85 90
Lambsquarters go 95 100 100 100 95 95 100 100 0 100 gs go 90
Morningglory 0 5 80 0 60 100 15 - 20 0 70 50 55 0
Nightshade 70 80 90 100 93 100 80 95 50 0 95 95 gs 100
Nutsedge, Yellow 0 0 30 0 60 20 0 0 0 0 0 0 0 0
Pigweed go 100 100 100 gs 100 95 95 100 60 100 100 100 95
Ragweed 0 0 85 0 100 95 20 65 100 40 80 60 80 20
Soybean 0 0 10 0 50 75 0 0 30 0 0 0 0 20
Sunflower 0 0 10 0 45 15 0 0 0 0 0 0 0 0
Surinam Grass 10 5 60 0 88 75 20 30 80 0 10 0 20 20
Velvetleaf 20 0 100 20 63 75 0 0 0 50 80 70 10 40 Table C Compounds
125 g ai/ha 207 210 212 213 215 221 222 223 242 244 268 269 287 293
Preemergence
Bermudagrass 80 80 75 60 70 10 100 80 100 100 100 100 95 95
Cocklebur 0 0 0 - 0 0 20 0 0 0 60 0 0 -
Corn 0 10 0 0 20 0 20 0 0 10 45 20 - 10
Crabgrass, Large 90 80 80 50 70 100 100 100 100 100 95 100 gs gs
Cupgrass, Woolly 0 0 0 0 10 0 100 10 80 65 70 40 0 70
Foxtail, Giant 0 10 20 50 50 0 85 70 100 95 95 90 70 70
Goosegrass 60 80 60 60 40 0 100 80 100 95 go 85 100 85
Johnsongrass 10 20 0 55 20 0 100 80 95 95 go 60 85 gs
Kochia 90 90 85 85 100 0 100 90 - - 100 100 100 100
Lambsquarters 95 100 100 95 100 20 100 100 - - 100 100 100 100
Morningglory 0 0 0 0 0 0 20 0 0 15 0 5 - -
Nigh shade 75 100 100 100 100 50 100 100 100 100 100 100 100 100
Nutsedge, Yellow 0 0 0 0 0 0 0 0 0 0 50 10 15 0
Pigweed 100 100 100 100 100 100 100 100 100 100 100 100 100 85
Ragweed 50 0 0 0 0 0 100 80 100 100 go 10 100 100
Soybean 0 0 0 0 0 0 70 30 65 0 75 10 60 85
Sunflower 0 0 0 0 0 0 0 0 0 0 5 0 100 -
Surinam Grass 0 5 0 0 0 0 100 65 gs 100 70 70 50 80
Velvetleaf 10 0 100 0 0 0 50 0 100 100 100 70 gs 100
Table C Compounds
125 g ai/ha 294 298 299 300 301 304 305 305 307 309 310 314 318 332
Preemergence
Bermudagrass 80 55 100 100 go 70 85 85 100 90 85 60 70 100
Cocklebur 40 0 40 5 0 0 15 0 30 10 0 0 0 0
Corn 60 10 25 30 10 0 40 10 20 20 0 0 0 0
Crabgrass, Large 95 95 100 100 100 100 100 100 100 80 70 0 50 100
Cupgrass, Woolly 75 10 70 50 50 10 60 15 40 70 10 0 0 0
Foxtail, Giant 80 70 100 65 60 50 85 40 85 80 40 0 10 20
Goosegrass 80 95 100 100 go 85 85 70 gs 85 80 40 10 85
Johnsongrass 100 40 100 85 - 60 90 60 80 80 10 20 0 10
Kochia 100 95 100 100 100 80 100 80 100 100 100 0 60 100
Lambsquarters 100 100 100 100 100 100 100 100 100 100 100 10 95 100
Morningglory 30 5 75 40 5 10 0 5 10 5 5 10 0 0
Nightshade 100 100 100 100 95 100 go 95 100 80 35 85 90 go
Nutsedge, Yellow 55 0 50 20 5 0 20 0 20 30 0 0 0 0 Pigweed loo loo loo loo loo loo loo loo loo loo loo 60 gs 100 Ragweed 100 0 100 5 60 0 85 70 100 - 0 0 40 5 Soybean 5 0 80 30 20 0 60 10 60 40 0 10 0 0 Sunflower 50 0 85 0 0 0 0 0 10 0 0 0 0 0 Surinam Grass 5 5 o 65 30 5 55 10 85 70 10 0 20 5 Velvetleaf 100 60 80 5 70 0 100 5 100 70 10 0 70 45
Table C Compounds
125 g ai/ha 333 334 336 340 341 342 343 352
Preemergence Bermudagrass 85 100 100 70 80 60 70 100
Cocklebur 0 60 5 0 10 30 80 0
Corn 0 20 35 45 60 50 70 15
Crabgrass, Large 70 100 100 70 80 60 80 85
Cupgrass, Woolly 0 60 10 20 80 40 65 50 Foxtail, Giant 10 80 5 10 50 40 50 60
Goosegrass 30 100 100 60 85 65 75 85
Johnsongrass ' 0 100 95 50 85 100 80 go
Kochia 100 100 70 20 100 100 100 85
Lambsquarters loo loo loo 80 loo go 100 100 Morningglory 0 20 70 5 5 5 60 5
Nightshade 20 100 95 90 55 80 60 0
Nutsedge, Yellow 0 40 5 0 0 0 10 0
Pigweed loo loo loo 85 gs go go 85
Ragweed 0 100 55 0 100 5 o 40 Soybean 0 80 25 0 20 60 80 15
Sunflower 0 35 10 0 0 20 75 0
Surinam Grass 0 70 85 60 95 90 85 50
Velvetleaf 0 50 30 60 60 60 80 5
Table C Compounds 62 g ai/ha 1 2 3 4 5 6 7 9 10 11 13 14 16 27
Preemergence
Bermudagrass 80 85 60 85 0 80 60 65 50 0 0 45 70 90
Cocklebur 5 0 50 o eo 0 0 - - 0 0 0 0
Corn 25 0 0 0 0 60 0 15 35 25 0 60 20 0 Crabgrass, Large 65 95 70 60 30 75 60 40 10 80 100 95 80 100
Cupgrass, Woolly - 40 0 0 0 50 0 0 0 10 0 20 15 10
Foxtail, Giant 55 80 10 20 0 60 0 45 40 5 0 65 25 50 Goosegrass 80 90 60 60 0 85 0 65 60 50 85 gs 75 30
Johnsongrass 70 70 50 30 0 70 10 45 60 50 0 70 50 60
Kochia s 100 50 - 0 100 30 gs 80 85 50 100 gs go
Lambsquarters 100 100 90 go 40 100 20 gs 95 95 gs 100 gs 100
Morningglory 0 5 - - 0 0 0 0 0 0 75 45 0 100
Nightshade 100 100 90 gs 90 100 50 0 80 50 55 75 gs 100
Nutsedge, Yellow 15 30 0 10 0 50 0 0 10 0 0 20 40 0
Pigweed 100 gs 90 gs 80 100 30 gs 100 80 100 100 100 100
Ragweed 100 80 85 60 0 100 50 0 100 0 gs 100 85 0
Soybean 0 30 10 20 0 70 0 0 0 0 0 15 0 0
Sunflower 0 0 0 0 0 0 0 0 0 0 0 60 0 10
Surinam Grass 50 go 60 50 0 85 0 0 - - 45 90 55 20
Velvetleaf 70 60 80 80 30 40 0 25 0 10 85 90 100 40
Table C Compounds
62 g ai/ha 28 29 30 31 33 34 35 41 44 46 47 48 50 55
Preemergence
Bermudagrass go 90 10 20 80 20 go 30 0 90 go 80 0 60
Cocklebur 0 30 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass, Large 100 100 go 90 100 80 10 go 0 100 100 0 0 15
Cupgrass, Woolly 20 0 10 0 20 10 10 0 0 10 10 0 0 0
Foxtail, Giant 0 20 20 20 20 10 20 20 10 10 40 0 0 0
Goosegrass 30 30 20 30 60 20 30 20 10 60 80 20 40 0
Johnsongrass 20 go 0 0 20 50 50 0 30 50 20 10 0 0
Kochia 0 20 0 0 100 go 10 20 0 0 10 10 30 25
Lambsquarters 90 90 go 90 100 go go 50 90 100 100 85 85 80
Morningglory 20 100 0 - 0 0 100 0 0 0 0 0 0 0
Nightshade 100 100 80 90 60 10 - 0 80 90 100 50 0 15
Nutsedge, Yellow 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Pigweed 100 100 go 100 50 100 go 0 10 20 100 100 go gs
Ragweed 0 - 0 0 0 0 10 0 0 10 80 0 10 0
Soybean 0 30 0 0 0 0 0 0 0 0 0 0 0 0
Sunflower 0 50 10 0 0 0 10 0 0 0 0 0 0 0
Surinam Grass 20 10 0 10 20 10 10 20 10 10 0 0 0 0
Velvetleaf 20 80 0 20 _ 0 100 40 70 go 40 0 0 0 Table C Compounds
62 g ai/ha 56 57 58 60 61 62 63 64 65 80 88 95 96 102
Preemergence
Bermudagrass 85 55 90 80 10 10 50 0 40 10 90 70 40 100
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 10
Corn 0 0 0 0 0 0 0 0 0 0 0 0 15 0
Crabgrass, Large gs 95 go 90 50 40 10 0 50 0 90 80 85 100
Cupgrass, Woolly 0 0 0 0 0 0 0 0 0 0 20 5 5 0
Foxtail, Giant 45 20 70 0 0 15 0 0 0 10 0 60 70 10
Goosegrass 60 45 90 55 0 10 10 0 0 10 60 0 30 90
Johnsongrass 55 20 70 10 10 40 30 0 10 10 0 0 40 50
Kochia 75 100 95 80 10 100 30 0 10 10 0 100 90 0
Lambsquarters 85 100 100 100 100 100 30 0 20 0 95 - - 0
Morningglory 0 0 10 0 0 - 0 0 0 20 0 5 0 30
Nightshade 90 85 95 30 0 80 70 0 50 10 40 95 90 go
Nutsedge, Yellow 0 0 10 0 0 0 0 0 0 0 0 0 0 0
Pigweed 100 100 100 100 0 gs 100 30 70 40 100 100 100 go
Ragweed 60 65 60 10 0 10 0 0 0 0 0 50 50 10
Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sunflower 0 0 0 0 0 0 0 0 0 - 0 0 0 0
Surinam Grass 10 0 10 0 0 5 0 0 0 0 10 0 0 0
Velvetleaf 20 0 80 5 0 40 10 0 0 20 0 0 50 0
Table C Compounds
62 g ai/ha 108 114 115 118 128 130 131 134 137 139 140 144 145 146
Preemergence
Bermudagrass 100 50 100 90 100 60 15 80 50 60 0 70 20 10
Cocklebur 20 20 20 20 10 0 0 0 0 0 0 0 0 0
Corn 30 10 10 0 20 0 0 0 0 0 0 0 0 0
Crabgrass, Large 100 100 100 70 100 - 45 65 40 40 0 50 - 20
Cupgrass, Woolly 30 - 20 0 10 5 0 0 0 0 0 0 0 0
Foxtail, Giant 100 20 40 0 10 40 20 0 10 40 0 40 0 0
Goosegrass 90 40 70 20 80 10 15 20 40 60 0 30 50 0
Johnsongrass 60 20 70 40 90 - 15 0 0 20 0 0 50 -
Kochia 100 90 100 20 0 0 85 85 80 100 70 75 20 50
Lambsquarters 100 80 100 50 - 10 gs 100 40 100 75 95 20 85
Morningglory 40 - - 20 30 0 0 0 0 0 0 0 0 0
Nightshade 100 70 100 100 90 30 55 go 60 95 0 90 60 50
Nutsedge, Yellow 50 0 0 0 - 0 0 0 0 0 0 0 0 0 Pigweed 100 100 100 70 - 80 95 95 100 100 100 go 85 80
Ragweed 20 10 70 0 10 0 40 0 0 50 0 0 0 0
Soybean - 70 0 0 20 0 0 0 0 - 0 0 - 0
Sunflower 20 30 0 0 - 0 0 0 0 0 0 0 0 0
Surinam Grass 30 10 20 - 30 5 0 0 0 0 0 20 '! 0 0
Velvetleaf 60 30 20 0 30 0 0 20 0 - 0 20 0 0
Table C Compounds
62 g ai/ha 147 149 152 153 156 162 182 188 193 195 198 199 202 205
Preemergence
Bermudagrass 40 30 85 70 88 0 20 75 60 0 60 55 20 go
Cocklebur 0 0 - 0 63 - 0 0 0 0 0 0 0 0
Corn 0 0 40 0 15 20 0 0 10 0 0 0 0 0
Crabgrass, Large 0 20 100 0 60 35 0 gs 40 0 80 10 80 60
Cupgrass, Woolly 0 0 40 0 33 0 0 0 10 0 0 0 0 0
Foxtail, Giant 0 0 70 0 75 55 0 0 40 0 0 0 0 0
Goosegrass 0 10 80 55 83 60 0 15 60 100 20 5 20 50
Johnsongrass 0 10 80 0 80 65 0 0 60 0 0 0 0 0
Kochia - 0 100 65 95 65 0 0 85 0 50 80 60 go
Lambsquarters 70 75 100 95 100 80 25 gs 50 0 85 80 40 85
Morningglory 0 0 20 0 8 45 0 0 20 0 10 - 0 0
Nightshade 40 80 80 90 75 80 70 80 0 0 90 85 20 80
Nutsedge, Yellow 0 0 10 0 35 0 0 0 0 0 0 0 0 0
Pigweed 20 20 85 95 gs 100 95 gs 100 55 100 100 gs go
Ragweed 0 0 85 0 go gs 20 0 0 20 50 55 0 0
Soybean 0 0 0 0 33 15 0 0 30 0 0 0 0 -
Sunflower 0 0 0 0 25 0 0 0 0 0 0 0 0 0
Surinam Grass 0 0 40 0 75 0 0 20 50 0 0 0 10 0
Velvetleaf 5 0 0 0 43 70 0 0 0 0 5 10 5 10
Table C Compounds
62 g ai/ha 207 210 212 213 215 221 222 223 242 244 268 269 287 2g3
Preemergence
Bermudagrass 50 80 60 50 40 0 85 80 95 95 100 100 85 go
Cocklebur 0 0 0 - 0 0 0 0 0 0 10 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 10 - - -
Crabgrass, Large 80 80 60 0 0 0 100 100 100 100 90 gs 65 gs
Cupgrass, Woolly 0 0 0 0 0 0 20 0 75 65 50 10 0 45
Foxtail, Giant 0 0 0 30 0 0 20 40 85 80 80 50 0 10 Goosegrass 1100 5500 1100 0 0 0 80 60 100 70 85 70 70 65
Johnsongrass 0 0 5 5 00 0 0 0 85 80 65 60 70 40 55 65
Kochia ggoo 0 0 8855 - 100 0 o 85 - - 100 70 85 100
Lambsquarters ggoo 1 10000 110000 80 100 0 100 95 - - 100 5 100 100
Morningglory 0 0 0 0 00 0 0 0 0 0 0 0 0 0 - -
Nightshade 6 600 8 800 7700 100 100 30 85 loo loo loo loo go gs 65
Nutsedge, Yellow 0 0 0 0 00 0 0 0 0 0 0 0 30 5 0 0
Pigweed 1 10000 1 10000 110000 80 80 go loo loo loo 100 100 100 100 20
Ragweed 4 400 0 0 00 0 0 0 80 - 95 95 70 5 100 85
Soybean 0 0 0 0 00 0 0 0 40 0 0 0 60 0 0 0
Sunflower 0 0 0 0 00 0 0 0 0 0 0 0 0 0 90 10
Surinam Grass 0 0 0 0 00 0 0 0 80 50 85 100 70 5 - -
Velvetleaf 0 0 0 0 2200 0 0 0 50 0 100 15 60 5 40 80
Table C Compounds
62 g ai/ha 229944 229988 22gggg 300 301 304 305 306 307 30g 310 314 318 332
Preemergence
Bermudagrass 70 50 1l0o0o gs so 5 so 40 go go 50 10 10 80
Cocklebur 30 0 0 0 5 0 0 10 0 0 0 0 0 0 0
Corn 55 0 - 30 10 0 0 5 0 5 - 0 0
Crabgrass, Large 70 85 1 10000 100 go 35 70 100 80 - 30 0 75
Cupgrass, Woolly 55 5 5 500 20 10 5 20 5 5 40 5 0 0
Foxtail, Giant - 20 1 10000 30 35 5 35 5 70 70 5 0 0
Goosegrass 80 85 1 10000 85 50 45 80 50 gθ 85 70 0 0 80
Johnsongrass 80 20 8 855 60 30 0 65 40 60 75 0 0 0 0
Kochia 100 80 1 10000 60 100 - 100 0 100 100 s 0 10 100
Lambsquarters 100 100 1l0o0o loo loo o loo loo loo loo gs 0 80 100
Morningglory 30 5 5 5 5 0 0 5 0 0 0 0 0 0
Nightshade 100 100 1l0o0o loo go so eo go 100 70 30 60 80 20
Nutsedge, Yellow 50 0 4 400 0 0 0 10 0 5 5 0 0 0 0
Pigweed 100 100 1 10000 100 100 100 100 100 100 80 100 30 80 100
Ragweed 100 0 1 10000 5 10 0 10 0 80 50 0 0 0 0
Soybean 70 0 5 555 0 15 0 0 5 40 20 0 0 0 0
Sunflower 30 0 1 100 0 0 0 0 0 0 0 0 0 0 0
Surinam Grass 85 5 7 755 30 0 0 50 - 70 50 5 0 10 5
Velvetleaf 100 60 5 5 5 20 0 40 5 70 5 0 0 60 40 Table C Compounds
62 g ai/ha 333 334 336 340 341 342 343 352
Preemergence
Bermudagrass 40 100 gs 20 80 45 60 gs
Cocklebur 0 30 0 0 0 10 30 0
Corn 0 0 10 5 10 10 40 0
Crabgrass, Large 20 85 100 50 50 60 50 55
Cupgrass, Woolly 0 25 5 0 80 10 40 5
Foxtail, Giant 0 60 0 0 0 0 40 5
Goosegrass 0 100 gs 5 70 60 60 80
Johnsongrass 0 90 80 15 15 55 70 50
Kochia 80 100 5 10 80 50 90 80
Lambsquarters gs 100 100 70 100 70 100 85
Morningglory 0 5 5 0 0 0 5 5
Nightshade - 100 85 60 50 60 60 0
Nutsedge, Yellow 0 10 0 0 0 0 5 0
Pigweed 100 100 100 70 95 80 80 40
Ragweed 0 75 30 0 50 55 70 0
Soybean 0 15 0 0 0 10 40 0
Sunflower 0 5 0 0 0 5 10 0
Surinam Grass - 55 50 0 60 40 60 10
Velvetleaf 0 5 5 0 30 50 60 0
Table C Compounds
31 g ai/ha 4 5 27 29 33 35 41 60 62 80 gs 114 118 128
Preemergence
Bermudagrass 30 0 20 40 50 30 30 30 0 0 10 10 30 90
Cocklebur 0 0 0 30 0 0 0 0 0 - 0 0 0 10
Corn 0 0 0 0 0 0 - 0 0 0 0 10 0 20
Crabgrass, Large 40 0 100 90 90 0 0 80 5 0 10 100 10 10
Cupgrass, Woolly 0 0 0 0 20 10 0 0 0 0 0 0 0 10
Foxtail, Giant 0 0 10 0 10 0 0 0 5 10 0 20 0 0
Goosegrass 10 0 20 20 20 20 10 10 0 10 0 20 20 20
Johnsongrass 5 0 20 20 20 10 0 5 0 0 0 0 30 80
Kochia 10 0 20 0 80 0 0 80 100 10 80 go 10 0
Lambsquarters go 0 90 80 80 0 0 go 100 0 - 40 50 10
Morningglory - 0 90 90 0 0 0 0 - 0 0 40 0 30
Nightshade 90 80 90 90 10 70 0 10 80 0 go 20 60 70
Nutsedge, Yellow 0 0 0 0 0 0 0 0 0 0 0 0 0 70 Pigweed go 40 100 80 30 0 0o loo go 30 loo o 20 50
Ragweed 50 0 0 0 0 0 0 0 0 0 10 10 0 0
Soybean 0 0 0 30 0 0 0 0 0 0 0 60 0 20
Sunflower 0 0 0 30 0 10 0 0 0 0 0 30 0 50
Surinam Grass 0 0 20 0 20 0 10 0 0 0 0 10 20 20
Velvetleaf 5 0 0 10 0 0 0 5 0 20 0 0 0 30
Table C Compounds
31 g ai/ha 131 139 156 300 334
Preemergence
Bermudagrass 0 10 60 80 100
Cocklebur 0 0 40 0 5
Corn 0 0 0 0 0
Crabgrass, Large 0 20 60 100 70
Cupgrass, Woolly 0 0 20 5 20
Foxtail, Giant 0 0 40 10 30
Goosegrass 0 0 70 70 85
Johnsongrass 0 0 70 40 80
Kochia 85 70 90 60 100
Lambsquarters 95 100 100 80 100
Morningglory 0 0 0 5 0
Nightshade 0 70 - 90 100
Nutsedge, Yellow 0 0 10 0 5
Pigweed 95 100 80 100 85
Ragweed 0 0 - 5 75
Soybean 0 0 20 0 10
Sunflower 0 0 0 0 0
Surinam Grass 0 0 40 5 50
Velvetleaf 0 0 20 5 0
Table C Compounds
16 g ai/ha 4 5 33 35 118 128 156
Preemergence
Bermudagrass 0 0 30 0 0 30 0
Cocklebur 0 0 0 0 0 10 -
Corn 0 0 0 0 0 20 0
Crabgrass, Large 0 0 0 0 0 10 30
Cupgrass, Woolly 0 0 20 10 0 0 0
Foxtail, Giant 0 0 0 0 0 0 0 Goosegrass 5 0 10 0 20 10 50
Johnsongrass 0 0 20 10 30 0 5
Kochia 0 0 70 0 10 0 80
Lambsquarters 50 0 0 0 40 0 85
Morningglory - - 0 0 0 20 0
Nightshade - 80 10 20 20 50 30
Nutsedge, Yellow 0 0 0 0 0 10 0
Pigweed go 0 10 0 20 0 80
Ragweed 0 0 0 0 0 0 0
Soybean 0 0 0 0 0 20 0
Sunflower 0 0 0 10 0 50 0
Surinam Grass 0 0 20 0 20 0 0
Velvetleaf 0 0 0 0 0 20 0
TESTD Three plastic pots (ca. 16-cm diameter) per rate were partially filled with sterilized
Tama silt loam soil comprising a 35:50:15 ratio of sand, silt and clay and 2.6% organic matter. Separate plantings for each of the three pots were as follows. Seeds from the U.S. of ducksalad (Heteranthera limosa (Sw.) Willd.), smallflower umbrella sedge (Cyperus dijformis L.) and purple redstem (Ammannia coccinea Rottb.), were planted into one 16-cm pot for each rate. Seeds from the U.S. of rice flatsedge (Cyperus iria L.), bearded sprangletop (Leptochloa fascicularis (Lam.) Gray), one stand of 9 or 10 water seeded rice seedlings (Oryza sativa L. cv. 'Japonica - M202'), and one stand of 6 transplanted rice seedlings (Oryza sativa L. cv. 'Japonica - M202') were planted into one 16-cm pot for each rate. Seeds from the U.S. of barnyardgrass (Echinochloa crus-galli (L.) Beauv.), late watergrass (Echinochloa oryzicola Vasinger), early watergrass (Echinochloa oryzoides (Ard.) Fritsch) and junglerice (Echinochloa colona (L.) Link) were planted into one 16-cm pot for each rate. Plantings were sequential so that crop and weed species were at the 2.0 to 2.5-leaf stage at time of treatment.
Potted plants were grown in a greenhouse with day/night temperature settings of 29.5/26.7 °C, and supplemental balanced lighting was provided to maintain a 16-hour photoperiod. Test pots were maintained in the greenhouse until test completion.
At time of treatment, test pots were flooded to 3 cm above the soil surface, treated by application of test compounds directly to the paddy water, and then maintained at that water depth for the duration of the test. Effects of treatments on rice and weeds were visually evaluated by comparison to untreated controls after 21 days. Plant response ratings are reported on a 0 to 100 scale; where 0 is no effect and 100 is complete control. A dash (-) response means no test result. Table D Compounds Table D Compounds
Rate 1000 g ai/ha 3 215 Rate 750 g ai/ha 3 215
Flooded Paddy Flooded Paddy
Barnyardgrass 90 40 Barnyardgrass 60 30
Ducksalad 100 75 Ducksalad 100 20
Flatsedge, Rice 100 90 Flatsedge, Rice 100 80
Junglerice 100 25 Junglerice 100 25
Redstern 100 100 Redstem 100 100
Rice, Transplanted 60 35 Rice, Transplanted 60 20
Rice, Water Seeded 80 45 Rice, Water Seeded 70 45
Sedge, Umbrella 100 100 Sedge, Umbrella 100 gs
Sprangletop, Bearded 85 20 Sprangletop, Bearded 85 20
Watergrass, Early 60 40 Watergrass, Early 45 25
Watergrass, Late 80 20 Watergrass, Late 60 20
Table D Compounds Table D Compounds
Rate 500 g ai/ha 3 155 215 Rate 250 g ai/ha 3 155 215
Flooded Paddy Flooded Paddy
Barnyardgrass 20 80 0 Barnyardgrass 0 35 0
Ducksalad 95 60 20 Ducksalad 85 60 0
Flatsedge, Rice 100 70 60 Flatsedge, Rice 100 60 60
Junglerice 70 65 20 Junglerice 30 40 0
Redstem 100 95 100 Redstem 85 gs 100
Rice, Transplanted 50 30 20 Rice, Transplanted 30 30 10
Rice, Water Seeded 60 40 45 Rice, Water Seeded 45 35 35
Sedge, Umbrella 100 80 gs Sedge, Umbrella gs 75 s
Sprangletop, Bearded 60 75 20 Sprangletop, Bearded 20 40 20
Watergrass, Early 40 70 20 Watergrass, Early 20 35 0
Watergrass, Late 60 60 20 Watergrass, Late 20 30 0
Table D Compounds
Rate 125 g ai/ha 3 152 155 215
Flooded Paddy
Barnyardgrass 0 35 20 0
Ducksalad 30 90 0 0
Flatsedge, Rice 70 95 30 0
Junglerice 20 30 40 0
Redstem 40 90 0 0
Rice, Transplanted 20 45 20 0 Rice, Water Seeded 40 45 25 20
Sedge, Umbrella 80 gs 75 20
Sprangletop, Bearded 0 40 30 20
Watergrass , Early 20 45 25 0
Watergrass , Late 0 40 20 0
Table D Table D
Rate 64 g ai/ha 152 155 Rate 32 g ai/ha 152 155
Flooded Paddy Flooded Paddy
Barnyardgrass 10 0 Barnyardgrass 0 0
Ducksalad 80 0 Ducksalad 75 0
Flatsedge, Rice go 0 Flatsedge, Rice 75 0
Junglerice 0 40 Junglerice 0 20
Redstem 85 0 Redstem 60 0
Rice, Transplanted 40 0 Rice, Transplanted 25 0
Rice, Water Seeded 40 0 Rice, Water Seeded 30 0
Sedge, Umbrella 85 65 Sedge, Umbrella 75 30
Sprangletop, Bearded 35 30 Sprangletop, Bearded 30 30
Watergrass , Early 0 0 Watergrass, Early 0 0
Watergrass , Late 20 0 Watergrass, Late 15 0
Table D Compound Table D Compound
Rate 16 g ai/ha 152 Rate 8 g ai/ha 152
Flooded Paddy Flooded Paddy
Barnyardgras s 0 Barnyardgrass 0
Ducksalad 70 Ducksalad 0
Flatsedge, Rice 75 Flatsedge, Rice 75
Junglerice 0 Junglerice 0
Redstem 0 Redstem 0
Rice, Transplanted 20 Rice, Transplanted 0
Rice, Water Seeded 20 Rice, Water Seeded 0
Sedge, Umbrella 70 Sedge, Umbrella 0
Sprangletop, Bearded 30 Sprangletop, Bearded 30
Watergrass , Early 0 Watergrass, Early 0
Watergrass , Late 0 Watergrass, Late 0
TEST E
Seeds of plant species selected from bipinnate beggarticks (Bidens bipinnata L.), hairy beggarticks (Bidens radiata Thuill.), bermudagrass (Cynodon dactylon (L.) Pers.), Surinam grass (Urochloa decumbens (Staph) R. D. Webster, previously named Brachiaria decumbens Stapf), large crabgrass (Digitaria sanguinalis (L.) Scop.), green foxtail (Setaria viridis (L.) P.Beauv.), goosegrass (Eleusine indica (L.) Gaertn.), johnsongrass (Sorghum halepense (L.) Pers.), kochia (Kochia scoparia (L.) Schrad.), pitted morningglory (Ipomoea lacunosa L.), purple nutsedge (Cyperus rotundus L.), common ragweed (Ambrosia elatior L.), mustard (Brassica nigra (L.) W.DJ. Koch), guineagrass (Panicum maximum Jacq.), dallisgrass (Paspalum dilatatum Poir.), barnyardgrass (Echinochloa crus-galli (L). P.Beauv.), southern sandbur (Cenchrus echinatus L.), common sowthistle (Sonchus oleraceous L.), prickly sida (Sida spinosa L.), Italian ryegrass (Lolium multiflorum Lam.), common purslane (Portulaca oleracea L.), broadleaf signalgrass (Brachiaria platyphylla (Griseb.) Nash), common groundsel (Senecio vulgaris L.), common chickweed (Stellaria media (L.) Vill/Cyr.), tropical spiderwort (Commelina benghalensis L.), annual bluegrass (Poa annua L.), downy bromegrass (Bromus tectorum L.), itchgrass (Rottboellia cochinchinensis (L.) L.f.), quackgrass (Elytrigia repens (L.) Nevski), Canada horseweed (Erigeron Canadensis L.), field bindweed (Convolvulus arvensis L.), spotted spurge (Euphorbia maculata L.), common mallow (Malva sylvestris (=s silvestris) L.), and Russian thistle (Salsola kali L. ssp. Ruthenica (Iljin) Soo) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these weed species were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for 12 to 14 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table E, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table E Compound-;
500 g ai/ha 6 14 16 152 156 162 ιg3 222 2g4 2g9
Postemergence
Barnyardgrass gs 75 80 75 gδ 95 go - 80 80
Beggarticks, Bip. 75 80
Bermudagrass gs 85 80 75 gs 80 gs 80 75 80
Bindweed, Field 100 60 40 50 100 98 50 - 70 gs
Black Mustard 100 100 100 100 100 95 100 gs gs 100
Bluegrass gs go 100 85 gs gs 85 go gs 100
Bromegrass, Downy 100 - 100 80 100 100 80 - gs 95
Chickweed 100 - 100 100 100 - 100 100 - -
Crabgrass, Large gs 80 75 80 gs 100 100 80 95
Dallisgrass go 70 85 75 go 85 go 85 70 85
Foxtail, Green gs 80 85 85 100 gs go - 85 100 Goosegrass gs 80 80 75 gδ gδ 85 90 δ5 65
Groundsel 100 100 75 gs 100 100 100 100 - -
Guineagrass 98 100 70 80 gδ gβ 100 - 85 85
Horseweed 100 - - - 100 100 90 100 - -
Itchgrass 95 70 95 75 gs 95 75 - 80 80
Johnsongrass gs 70 100 gs 100 100 80 - go 85
Kochia 100 - - - 100 - - - - -
Mallow 100 - 70 50 100 100 90 - 100 100
Morningglory 80 40 30 30 go 90 75 90 20 60
Nutsedge, Purple - 70 75 75 - - 70 - go 85
Prickly Sida - 75 100 85 - - gs 100 100 95
Purslane 100 - - - 100 - 85 - go 100
Quackgrass gs 60 100 80 gs 95 80 85 65 100
Ragweed gs 70 80 75 gs 90 75 - δO go
Ryegrass, Italian gs 100 100 go gs 100 95 85 95 δ5
Sandbur 100 50 75 100 gβ 90 20 80 80 80
Signalgrass gs 75 70 70 gβ 90 80 65 70 80
Sowthistle 100 100 95 100 100 100 95 100 δO -
Spiderwort gs 80 30 80 65 65 70 - 90 go
Spurge, Spotted - 100 - gs - - - - - -
Surinam Grass gs 80 75 80 100 100 90 - 85 go
Thistle - 60 75 80 - _ - - δO go
Table E Compounds 250 g ai/ha 13 14 16 152 156 162 193 222 294 29g Postemergence Barnyardgrass g5 g5 70 50 70 75 g8 90 80 70 75 70 Beggarticks, Bip. - - - - - - - - - - 70 60 Bermudagrass 90 90 90 50 80 75 95 70 90 80 75 70 Bindweed, Field 70 100 30 50 30 30 80 95 50 g5 50 80 Black Mustard loo loo go 80 loo 100 loo go 95 95 go 100 Bluegrass 100 g8 60 75 80 85 g8 9δ 70 90 95 80 Bromegrass, Downy gδ 100 30 30 100 75 100 gδ 70 δO 85 80 Chickweed - 100 s 75 gs - 100 100 95 100 Crabgrass, Large gs gs go 70 60 75 gs go 100 go 75 95 Dallisgrass go 80 70 50 60 75 go 70 go 85 60 75 Foxtail, Green g5 gδ 60 50 60 65 100 85 50 80 80 65 Goosegrass gs s so 60 70 60 gδ gs so go so so Groundsel δO loo δ5 - 75 gs loo δo 70 gs go 100 Guineagrass gs gs 70 85 50 70 95 90 70 100 80 75
Horseweed - 100 100 gs - - 100 100 70 90 - -
Itchgrass go gs 75 50 60 75 95 95 60 70 75 75
Johnsongrass 100 gs 30 50 70 80 100 100 70 60 80 85
Kochia - 100 - - - - 100 - - - - -
Mallow 80 100 50 70 40 50 95 80 go 60 50 50
Morningglory go 60 60 30 10 20 80 80 60 60 20 40
Nutsedge, Purple - - 40 40 75 60 go 75 40 30 80 80
Prickly Sida - - δ5 60 70 60 - - 75 100 80 gs
Purslane - 100 70 - - - 100 - 60 60 90 80
Quackgrass gs 95 60 50 gs 80 gs go 80 80 85 85
Ragweed - 95 60 60 60 60 go 80 70 70 70 70
Ryegrass, Italian gs gβ 75 60 95 90 s gs gs 85 gs 85
Sandbur 95 100 10 10 60 40 80 80 10 50 75 70
Signalgrass 85 gs 50 50 40 60 gs 80 75 80 50 70
Sowthistle 95 100 100 go 95 90 100 75 gs 100 - gs
Spiderwort 70 go 30 30 - 10 50 60 50 60 70 80
Spurge, Spotted - - - - 95 - - - - - - -
Surinam Grass 100 gs 80 20 60 60 gs gs 85 80 80 75
Thistle _ _ _ _ 70 80 80 _ _ _ 80 70
Table E Compounds 125 g ai/ha 13 14 16 152 156 162 193 222 294 29g Postemergence Barnyardgrass go 90 70 30 60 50 gs 80 75 50 60 70 Beggarticks, Bip. 60 60 Bermudagrass 85 δO 50 30 40 40 gs 30 90 δO 50 50 Bindweed, Field 70 95 20 30 10 30 65 δO - 75 50 70 Black Mustard gs 100 80 - 100 - 100 75 gs go go 100 Bluegrass gs gs 30 50 20 60 95 95 50 δO gs 70 Bromegrass, Downy 75 gs 20 10 - - 100 95 30 50 75 70 Chickweed 100 100 gs - - - 100 100 - 100 - - Crabgrass, Large gs go 70 30 50 60 80 50 80 δO 70 85 Dallisgrass δO 75 40 10 50 30 85 40 40 60 40 70 Foxtail, Green go go 20 20 40 40 95 50 20 40 60 70 Goosegrass gs gs - 40 50 50 98 80 70 75 60 80 Groundsel - gs 50 - 75 go 100 30 40 70 - 70 Guineagrass 75 go 40 30 50 - 90 75 60 70 70 70 Horseweed _ 100 40 __ _ _ 70 50 40 - _ Itchgrass go go 50 20 50 60 95 85 60 60 70 70
Johnsongrass go s 20 20 50 70 95 80 70 60 70 80
Kochia 100 100 - - - - 100 - - - - -
Mallow 75 gs 20 - - - 90 60 60 60 40 30
Morningglory 60 10 50 10 10 10 65 70 60 40 10 20
Nutsedge, Purple - gs 20 30 50 30 75 - 20 10 70 75
Prickly Sida - - 70 60 60 - - - 60 100 70 gs
Purslane - go 70 - - - 100 - 60 30 60 75
Quackgrass go go 30 20 50 70 95 70 70 75 80 75
Ragweed 80 go 30 20 20 50 90 75 30 60 60 60
Ryegrass, Italian go 95 40 50 80 go 95 gs 60 80 80 80
Sandbur 75 95 10 10 30 20 75 50 0 10 50 40
Signalgrass 80 90 10 10 20 20 85 70 50 40 30 60
Sowthistle go 95 60 go 70 - go 75 60 60 60 65
Spiderwort - 75 30 - - - 30 10 20 40 30 80
Spurge, Spotted - - - 20 gs
Surinam Grass go go 30 20 60 30 gs go 70 80 70 75
Thistle - - - 10 60 70 80 - - - 60 70
Table E Compounds
62 g ai/ha 2 6 13 156 162 193 222 2g4 2g
Postemergence
Barnyardgrass 80 80 10 go 60 10 50 40 40
Beggarticks, Bip. 40 40
Bermudagrass 20 35 50 65 0 eo 60 20 40
Bindweed, Field 50 10 10 65 50 20 60 10 30
Black Mustard go gs 70 gs 60 60 go 70 100
Bluegrass go gs 10 go go 20 60 gs 60
Bromegrass, Downy 65 gs 10 go 50 20 10 60 50
Chickweed - 100 50 100 80 40 80 - -
Crabgrass, Large go 75 50 35 30 10 60 40 75
Dallisgrass 75 60 10 75 20 10 30 10 50
Foxtail, Green eo 80 10 75 30 10 10 40 30
Goosegrass gs go 50 gs 50 20 60 50 60
Groundsel - 20 30 80 20 20 40 50 -
Guineagrass 30 80 40 60 35 20 70 50 60
Horseweed - 75 - - 70 50 20 - -
Itchgrass 70 go 50 80 75 30 60 50 30
Johnsongrass 80 go 0 85 65 40 10 40 60 Kochia - 100
Mallow 50 65 10 80 40 20 50 20 10
Morningglory - 0 20 10 30 30 20 0 10
Nutsedge, Purple - 75 0 - - 0 10 50 40
Prickly Sida - - 60 - - 60 90 50 60
Purslane - 75 30 75 - 20 10 10 70
Quackgrass 70 80 0 75 50 0 30 60 20
Ragweed 60 75 20 80 50 10 20 30 30
Ryegrass, Italian 80 80 10 90 50 30 50 70 60
Sandbur 65 85 0 0 20 0 10 10 30
Signalgrass 30 35 10 40 30 10 10 30 20
Sowthistle 90 75 50 90 75 10 20 60 30
Spiderwort 20 60 - 20 0 - - 20 10
Surinam Grass 75 75 20 80 50 10 50 30 70
Thistle 30 40
Table Ξ Compound Table E Compound Table E Compound
31 g ai/ha 13 31 g ai/ha 13 31 g ai/ha 13
Postemergence Goosegrass 10 Purslane 20
Barnyardgrass 0 Groundsel 20 Quackgrass 0
Bermudagrass 20 Guineagras ■s 40 Ragweed 20
Bindweed, Field 10 Horseweed 10 Ryegrass, Italian 0
Black Mustard 70 Itchgrass 30 Sandbur 0
Bluegrass 10 Johnsongrass 0 Signalgrass 10
Bromegrass, Downy 0 Mallow 0 Sowthistle 10
Crabgrass, Large 30 Morningglory 10 Spiderwort 10
Dallisgrass 0 Nutsedge, Purple 0 Surinam Grass 20
Foxtail, Green 10 Prickly Sida 40
Table Ξ Compounds
500 g ai/ha 2 6 7 14 16 144 152 156 162 193 222 268 293 294
Preemergence
Barnyardgrass 100 100 70 g5 g5 go o 100 100 95 100 100 100 100 Beggarticks, Hairy - - 40 - - - - - - - -- 100 100 100
Bermudagrass 100 100 80 g5 100 o 5 100 100 100 100 100 5 5
Bindweed, Field 80 100 30 100 75 80 go 100 100 85 g5 70 g5 100
Black Mustard 100 100 100 100 100 100 100 100 100 100 100 100 100 100
Bluegrass 100 100 80 100 100 100 g5 100 100 100 100 g5 100 100 Bromegrass, Downy go 100 60 gO 5 80 go 100 100 90 100 100 80 100 Chickweed gs 100 - 95 100 gs 100 100 95 100 100 - - -
Crabgrass , Large 100 100 100 100 100 60 100 gs 100 100 100 95 100 100
Dallisgrass 95 100 85 95 95 80 95 100 95 100 100 85 100 95
Foxtail, Green 100 100 50 100 100 90 100 100 100 100 100 100 100 100
Goosegrass 95 100 70 95 85 80 go 100 95 95 gs 95 100 100
Groundsel 100 100 - 100 100 100 100 100 100 100 100 - - -
Guineagrass 100 100 100 95 80 80 100 100 100 100 100 100 100 100
Horseweed 100 100 - - - 100 - 100 100 100 100 - - -
Itchgrass 95 95 70 95 85 75 80 100 100 100 gs 95 100 100
Johnsongrass 100 100 70 95 80 60 85 100 100 95 100 80 85 85
Kochia 100 100 85 100 100 90 gs 100 95 100 100 - - -
Mallow 80 100 70 95 gs 95 90 100 100 gs gs go 85 80
Morningglory 80 100 10 70 40 100 40 100 100 70 gs 60 90 70
Nutsedge, Purple gs 100 100 75 80 50 60 gs - δo 80 85 60 90
Prickly Sida - - 20 100 gs gs 95 - - gs 100 100 100 100
Purslane 100 100 20 100 gs 100 100 100 100 100 100 - - -
Quackgrass 80 100 50 95 go 80 60 100 90 gs 100 95 gs gs
Ragweed 85 95 50 95 gs 40 80 100 gs gs gs 100 100 100
Ryegrass, Italian gs 100 40 95 s 95 95 100 gs 100 100 95 100 100
Sandbur 100 100 40 80 85 60 80 80 80 60 gs 100 100 100
Signalgrass go 95 40 gs 70 50 80 s 100 gs gs 80 100 80
Sowthistle gs 100 95 gs gs 95 95 100 gs gs gs 100 100 100
Spiderwort 100 95 eo 90 70 100 80 80 75 95 95 90 go gs
Spurge, Spotted - - - 100 100 - 100
Surinam Grass 90 100 60 100 go 70 80 95 100 100 100 100 100 100
Thistle 80 80 10 100 80 - 100 100 70 - - 100 100 100
Table Ξ Compound Table E Compounds
500 g ai/ha 29g 375 g ai, /ha 293 294
Preemergence Preemergence
Barnyardgrass 100 Barnyardgrass 100 100
Beggarticks, Hairy 100 Beggarticks, Hairy 100 100
Bermudagrass 100 Bermudagrass ( 35 ! 35
Bindweed, Field gs Bindweed, , Field ( 35 95
Black Mustard 100 Black Mustard 100 100
Bluegrass 95 Bluegrass t 35 95
Bromegrass, Downy 100 Bromegrass, Downy - 100
Crabgrass, Large 100 Crabgrass, Large 100 100
Dallisgrass 100 Dallisgrass ( 35 i 35 Foxtail, Green 100 Foxtail, Green 95 100
Goosegrass 100 Goosegrass gs 100
Guineagrass 100 Guineagrass 100 100
Itchgrass 100 Itchgrass 100 gs
Johnsongrass 100 Johnsongrass 70 85
Mallow 100 Mallow 80 -
Prickly Sida 100 Morningglory 50 40
Quackgrass 100 Nutsedge, Purple 50 80
Ragweed 100 Prickly Sida 100 100
Ryegrass, Italian 100 Quackgrass gs gs
Sandbur 100 Ragweed 100 100
Signalgrass 100 Ryegrass, Italian gs 100
Sowthistle 100 Sandbur 100 gs
Spiderwort 95 Signalgrass gs 80
Surinam Grass 100 Sowthistle gs 100
Thistle 100 Spiderwort 80 go
Surinam Grass 100 100
Thistle gs 100
Table Ξ Compounds 250 g ai/ha 7 13 14 16 144 152 156 162 193 222 268 293 Preemergence
Barnyardgrass 100 gs 60 go 35 80 80 85 100 100 δ5 100 100 100
Beggarticks, Hairy - - 20 - - - - 100 100
Bermudagrass 100 95 80 100 95 90 85 95 100 90 100 100 gs gs
Bindweed, Field 70 - 10 60 75 50 50 60 100 100 80 gs 40 60
Black Mustard 100 100 50 100 100 85 75 95 100 80 100 100 100 100
Bluegrass 100 - 75 go 95 gs loo gs 100 100 100 100 gs gs
Bromegrass, Downy go 95 60 50 80 85 60 60 100 90 80 go 60 80
Chickweed gs 95 - gs gs gs gs 100 100 95 100 100 - -
Crabgrass, Large 100 - 75 100 loo go so loo gs gs 100 100 gs gs
Dallisgrass gs gs 80 80 95 90 60 85 100 gs gs 100 85 gs
Foxtail, Green 100 - 30 gs 100 80 80 85 100 100 δO 100 100 gs
Goosegrass gs - 40 go go 85 80 60 100 gs go go gs go
Groundsel 100 - - 100 100 100 100 100 100 δO 100 100 - -
Guineagrass 100 gs 60 go 95 80 60 80 100 100 100 100 100 100
Horseweed 100 100 - 100 - 100 - 100 100 100 100 - -
Itchgrass go - 40 60 85 75 70 75 100 gs δO gs 75 go Johnsongrass 100 90 20 80 95 75 60 80 100 100 85 go 50 60
Kochia 100 100 80 75 95 70 go 85 loo gs loo lo o
Mallow 50 - 60 50 95 85 70 go loo lo o gs gs s o so
Morningglory 60 - 10 50 60 30 20 40 100 85 50 40 40 40
Nutsedge, Purple - 100 30 50 60 70 30 50 - 50 70 85 40
Prickly Sida - - 0 - 85 90 go 60 - 70 100 100 80
Purslane 100 100 0 100 100 95 go 50 100 100 100 100
Quackgrass 70 - 30 60 90 60 70 50 g5 75 70 100 95 80
Ragweed 70 - 20 80 95 70 40 80 95 75 80 95 100 70
Ryegrass, Italian gs - 40 60 85 95 60 80 loo gs loo loo gs s
Sandbur 80 - 30 20 40 δO 30 70 75 80 20 70 100 100
Signalgrass 75 - 30 70 95 60 30 70 90 100 70 95 80 95
Sowthistle gs 100 95 95 95 90 go gs 100 80 95 90 100 95
Spiderwort 70 80 20 50 80 60 60 75 50 75 90 - 85 80
Spurge, Spotted - - - - 100 100 - 100
Surinam Grass 80 - 30 90 95 60 50 70 g5 95 90 100 100 100
Thistle 60 70 10 _. 60 50 _ 40 100 60 - - 100 80
Table E Compounds Table E Compounds
250 g ai/ha 2g4 2g9 250 g ai/ha 294 29g
Preemergence Preemergence
Barnyardgrass gs 95 Kochia - -
Beggarticks, Hairy ■ 100 100 Mallow 40 gs
Bermudagrass gs 100 Morningglory 10 go
Bindweed, Field go gs Nutsedge, Purple 80 80
Black Mustard 100 100 Prickly Sida 100 100
Bluegrass gs gs Purslane - -
Bromegrass, Downy 100 100 Quackgrass 80 gs
Chickweed - - Ragweed 85 go
Crabgrass, Large gs 100 Ryegrass, Italian 100 100
Dallisgrass 80 100 Sandbur 80 100
Foxtail, Green 100 100 Signalgrass 70 100
Goosegrass 95 100 Sowthistle 95 100
Groundsel - - Spiderwort 85 gs
Guineagrass 100 100 Spurge, Spotted - -
Horseweed - - Surinam Grass 100 gs
Itchgrass 75 go Thistle 100 100
Johnsongrass 75 80 Table E Compounds
125 g ai/ha 2 6 7 13 14 16 144 152 156 162 193 222 268 2g3
Preemergence
Barnyardgrass 80 gs 30 80 δO 80 60 75 100 100 75 90 85 60
Beggarticks, Hairy - - 10 - - - - - - - - - gs 100
Bermudagrass gs gs 50 gs 95 go 80 90 100 80 100 100 go go
Bindweed, Field - 60 10 30 75 50 - 20 go 80 50 40 20 40
Black Mustard 100 100 30 100 75 85 70 90 100 50 100 100 100 gs
Bluegrass 100 100 60 60 95 gs go 80 gs 100 100 100 s gs
Bromegrass, Downy go gs 10 30 30 70 50 30 80 80 30 90 80 -
Chickweed 90 gs - go gs gs go 95 100 95 100 100 - -
Crabgrass, Large 80 go 60 δo gs 50 40 70 go 90 80 100 80 gs
Dallisgrass 90 gs 40 75 65 80 30 80 gs 95 95 80 80 60
Foxtail, Green 80 gs 10 30 75 60 50 70 100 85 30 50 gs 50
Goosegrass 90 gs 40 60 go 80 50 70 gs 90 80 75 80 go
Groundsel 70 100 - 100 80 20 100 100 100 40 100 100 - -
Guineagrass 80 gs 40 60 go 60 20 50 100 100 70 95 85 100
Horseweed 100 100 - 100 - - 100 - 100 100 100 100 - -
Itchgrass 70 gs 30 50 70 50 70 60 100 95 70 95 60 10
Johnsongrass 90 90 10 50 70 70 50 50 100 100 75 80 50 10
Kochia 100 100 0 70 gs 70 60 85 100 70 100 100 - -
Mallow - 100 60 50 85 60 60 80 100 70 95 80 50 40
Morningglory 50 70 10 50 30 20 20 10 100 60 20 30 10 10
Nutsedge, Purple - 100 0 20 50 70. 30 20 - - 30 40 70 -
Prickly Sida - - 0 - 75 go 90 20 - - 70 70 80 -
Purslane 100 100 0 60 100 gs 20 0 100 100 60 100 - -
Quackgrass 60 100 20 20 50 70 30 20 go 60 60 80 85 70
Ragweed 60 80 20 20 60 50 30 60 go 60 50 85 60 50
Ryegrass, Italian 80 95 40 40 70 go 60 50 95 gs 90 100 gs 60
Sandbur 70 100 20 0 40 70 30 30 60 70 10 40 70 10
Signalgrass 70 75 20 30 60 60 20 40 - 70 60 60 60 50
Sowthistle s gs 60 go go 60 50 80 100 60 95 go 100 75
Spiderwort 60 75 10 50 60 10 60 20 50 40 80 - 70 60
Spurge, Spotted - - - - 100 100 - 100 - - - - - -
Surinam Grass 80 go - 60 go 75 50 50 75 75 80 go go 80
Thistle 60 70 10 - 60 50 _ 20 100 50 - - 60 60 Table E Compounds Table E Compounds
125 g ai/ha 2g4 2gg 125 g ai/ha 2 4 2g9 Preemergence Preemergence
Barnyardgrass g5 85 Kochia - - Beggarticks, Hairy 100 100 Mallow 40 75
Bermudagrass go 100 Morningglory 10 75
Bindweed, Field 10 60 Nutsedge, Purple 80 -
Black Mustard 100 100 Prickly Sida 100 85
Bluegrass gs gs Purslane - -
Bromegrass, Downy 80 - Quackgrass 80 80
Chickweed - - Ragweed 75 δ5
Crabgrass, Large 75 100 Ryegrass, Italian 80 95
Dallisgrass 75 δ5 Sandbur 70 60
Foxtail, Green δO 100 Signalgrass 50 80
Goosegrass gs 100 Sowthistle 80 100
Groundsel - - Spiderwort - 85
Guineagrass go 65 Spurge, Spo11ed - -
Horseweed - - Surinam Grass gs 95
Itchgrass - 75 Thistle 50 100
Johnsongrass 30 60
Table E Compounds 62 g ai/ha 13 14 16 144 152 156 162 193 222 268 29g Preemergence Barnyardgrass 60 go 0 30 60 70 30 60 100 60 20 50 60 60 Beggarticks, Hairy - - 0 - - - - - - - - - 40 50 Bermudagrass go 90 10 80 90 80 50 70 95 70 δ5 80 60 80 Bindweed, Field 10 30 0 30 60 0 0 10 60 30 50 - 0 10 Black Mustard 60 100 10 70 60 δO 20 go 100 20 80 90 90 100 Bluegrass gs 100 0 50 50 go δO 60 gs 100 80 90 80 85 Bromegrass, Downy 50 90 0 0 20 10 20 0 60 40 10 30 - - Chickweed go 90 - 90 go 70 50 go δO - 80 80 - - Crabgrass, Large 70 80 20 60 gs 20 0 40 - 50 60 70 70 90 Dallisgrass 60 90 40 50 40 50 0 50 go 70 40 50 70 75 Foxtail, Green 40 95 0 10 30 60 10 20 100 30 10 10 70 50 Goosegrass 80 85 0 50 70 60 20 30 gs 60 30 60 70 100 Groundsel 60 100 - 70 80 - 10 95 100 10 20 30 - - Guineagrass 70 95 0 20 60 20 10 20 90 50 60 90 70 70 Horseweed 80 100 - 80 - - 70 - 95 100 80 100
Itchgrass 60 90 0 20 10 50 20 20 100 40 20 75 50 60
Johnsongrass 90 90 0 0 30 40 30 30 95 60 20 70 30 40
Kochia 90 100 0 30 10 60 0 0 100 60 100 30
Mallow 30 70 0 50 60 60 60 40 70 50 60 70 50 50
Morningglory 30 20 0 0 10 0 0 10 30 30 0 10 10
Nutsedge , Purple - 60 0 0 20 60 0 0 - 0 0 10 50 50
Prickly Sida - - 0 - 30 40 10 20 - - 20 20 60 85
Purslane - 100 0 40 100 0 0 0 100 100 - 70
Quackgrass 30 gs 20 0 30 40 10 10 50 20 10 10 40 80
Ragweed 20 50 0 10 30 20 0 20 50 20 50 30 50 20
Ryegrass, Italian 60 go 0 10 30 60 10 20 60 50 20 50 95 70
Sandbur 60 85 0 0 10 10 10 10 50 20 0 0 10 10
Signalgrass 50 75 0 10 20 10 10 10 85 10 10 20 60
Sowthistle 90 gs 0 80 30 60 10 80 60 40 60 75 80 100
Spiderwort 20 70 0 10 60 10 60 10 30 20 10 60 50 75
Spurge, Spotted - - - - go 100
Surinam Grass 6 600 δ855 _ 20 40 60 10 20 50 60 10 50 60 50
Thistle 50 50 - 10 10 - 20 80 50 - 60 100
Table E C Coommep ?oouunnd Table Ξ Compound Table Ξ Compound
31 g ai/ha 1 133 31 g ai/ha 13 31 g ai/ha 13
Preemergenee Foxtail, Green 0 Quackgrass 0
Barnyardgrass 0 Goosegrass 10 Ragweed 0
Bermudagrass 40 Guineagrass 0 Ryegrass, Italian 0
Bindweed, Field 0 Itchgrass 0 Sandbur 0
Black Mustard 30 Johnsongrass 0 Signalgrass 10
Bluegrass 0 Kochia 10 Sowthistle 30
Bromegrass, Downy 0 Mallow 40 Spiderwort 0
Chickweed 40 Morningglory 0 Surinam Grass 0
Crabgrass, Large 0 Nutsedge, Purple 0
Dallisgrass 0 Purslane 40
TEST F
Seeds of plant species selected from annual blugrass (Poa annua L.), blackgrass (Alopecurus myosuroides Huds.), catchweed bedstraw (Gallium aparine L.), common chickweed (Stellaria media (L.) Vill./Cyr.), downy bromegrass (Bromus tectorum L.), green foxtail (Setaria viridis (L.) Beauv.), Italian ryegrass (Lolium multiflorum Lam.), kochia (Kochia scoparia (L.) Schrad.), lambsquarters (Chenopodium album L.), littleseed canarygrass (Phalaris minor Retz.), pigweed (Amaranthus retroflexus L.), Russian thistle (Salsola kali L. ssp. Ruthenica (Iljin) Soo), wild buckwheat (Polygonum convolvulus L.), wild mustard (Sinapis arvensis L.), wild oat (Avenafatua L.), windgrass (Apera spica-venti (L.) Beauv.), winter barley (Hordeum vulgare L.), and wheat (Triticum aestivum L.) were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
At the same time, plants selected from these crop and weed species were treated with postemergence applications of some of the test chemicals formulated in the same manner. Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. Treated plants and controls were maintained in a greenhouse for 12 to 14 days, after which time all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table F, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table F Compound Table F Compounds
500 g ai/ha 162 250 g ai/ha g 162 248
Postemergence Postemergence
Barley, Winter 80 Barley, Winter 75 80 40
Blackgrass 100 Blackgrass 85 100 60
Bluegrass 100 Bluegrass 80 90 70
Bromegrass, Downy 90 Bromegrass, Downy 65 80 40
Canarygrass 100 Buckwheat, Wild 60 - 60
Chickweed 100 Canarygrass 65 100 45
Foxtail, Green 100 Chickweed 60 100 100
Kochia 100 Foxtail, Green 50 60 65
Lambsquarters 100 Galium 65 - 60
Mustard, Wild 100 Kochia go 100 65
Oat, Wild 100 Lambsquarters go 100 60
Pigweed 100 Mustard, Wild 90 100 60
Ryegrass, Italian 100 Oat, Wild 65 100 65
Wheat 70 Pigweed 95 100 70
Ryegrass, Italian 80 90 65
Thistle 65 - 40
Wheat 65 50 20
Windgrass 80 _ 50 Table F Compounds Table F Compounds
125 g ai/ha g 162 223 248 52 g ai/ha 9 162 248
Postemergence Postemergence
Barley, Winter 30 50 0 30 Barley, Winter 20 40 30
Blackgrass 70 80 60 60 Blackgrass 40 70 50
Bluegrass 70 60 50 60 Bluegrass 50 60 50
Bromegrass, Downy 60 50 20 40 Bromegrass, Downy 30 50 40
Buckwheat, Wild 60 - 40 50 Buckwheat, Wild 60 - 50
Canarygrass 40 70 40 40 Canarygrass 0 70 40
Chickweed 60 80 60 g8 Chickweed 30 70 65
Foxtail, Green 40 50 60 60 Foxtail, Green 40 50 60
Galium 45 - 60 60 Galium 40 - 50
Kochia 65 100 75 65 Kochia 65 100 60
Lambsquarters o 100 65 60 Lambsquarters 80 100 60
Mustard, Wild 90 80 65 60 Mustard, Wild 65 60 40
Oat, Wild 45 80 35 60 Oat, Wild 35 70 45
Pigweed 90 90 65 70 Pigweed 65 70 65
Ryegrass, Italian 65 80 45 60 Ryegrass, Italian eo 70 55
Thistle 60 - 60 30 Thistle 30 - 30
Wheat 0 40 0 5 Wheat 0 20 5
Windgrass 50 - 50 50 Windgrass 30 - 50
Table F Compound Table F Compound
31 g ai/ha 248 500 g ai/ha 162
Postemergence Preemergence
Barley, Winter 25 Barley, Winter 100
Blackgrass 45 Blackgrass 100
Bluegrass 50 Bluegrass 100
Bromegrass, Downy 40 Bromegrass, Downy 100
Buckwheat, Wild 50 Canarygrass 100
Canarygrass 35 Chickweed 100
Chickweed 65 Foxtail, Green 100
Foxtail, Green 50 Galium 100
Galium 50 Kochia 100
Kochia 60 Lambsquarters 100
Lambsquarters 35 Mustard, Wild 100
Mustard, Wild 30 Oat, Wild 100
Oat, Wild 45 Pigweed 100 Pigweed 65 Ryegrass, Italian 100
Ryegrass, Italian 45 Wheat 100
Thistle 25
Wheat 0
Windgrass 50
Table F Compounds Table F Compounds
250 g ai/ha g 162 248 125 g ai/ha g 162 223 248
Preemergence Preemergence
Barley, Winter 75 100 35 Barley, Winter 65 100 25 0
Blackgrass 100 100 65 Blackgrass 100 100 70 65
Bluegrass 100 100 100 Bluegrass 100 100 100 100
Bromegrass, Downy 75 100 65 Bromegrass, Downy 70 100 50 50
Buckwheat, Wild 100 - 60 Buckwheat, Wild 100 - 55 45
Canarygrass 75 100 75 Canarygrass 60 100 50 -
Chickweed 100 100 100 Chickweed 100 100 100 100
Foxtail, Green 100 100 100 Foxtail, Green 100 100 55 100
Galium 30 100 60 Galium 30 70 50 50
Kochia 100 100 100 Kochia 100 100 75 65
Lambsquarters 100 100 100 Lambsquarters 100 100 gs 100
Mustard, Wild 100 100 50 Mustard, Wild 100 80 100 50
Oat, Wild 75 100 65 Oat, Wild 65 100 70 50
Pigweed 100 100 gs Pigweed 100 100 100 gs
Ryegrass, Italian 100 100 60 Ryegrass, Italian gs 100 65 50
Thistle 100 - 45 Thistle 65 - 60 30
Wheat 65 100 10 Wheat 60 100 0 0
Windgrass 100 - 100 Windgrass 100 - 100 100
Table F Compounds Table F Compound
62 g ai/ha g 162 248 31 g ai/ha 248
Preemergence Preemergence
Barley, Winter 0 70 0 Barley, Winter 0
Blackgrass 70 go 50 Blackgrass 50
Bluegrass 85 100 70 Bluegrass 70
Bromegrass, Downy 60 70 45 Bromegrass, Downy 35
Buckwheat, Wild 60 - 40 Buckwheat, Wild 30
Canarygrass 50 100 45 Canarygrass 40
Chickweed 100 100 100 Chickweed 100
Foxtail, Green 70 70 65 Foxtail, Green 65 Galium 30 60 50 Galium 30
Kochia 60 60 60 Kochia 50
Lambsquarters 100 100 40 Lambsquarters 40
Mustard, Wild 100 80 50 Mustard, Wild 40
Oat, Wild 45 100 45 Oat, Wild 40
Pigweed 100 go 75 Pigweed 70
Ryegrass, Italian 65 100 50 Ryegrass, Italian 30
Thistle 45 - 30 Thistle 30
Wheat 0 60 0 Wheat 0
Windgrass 80 - 70 Windgrass 70
TESTG
This test evaluated the safening of compounds of the invention on corn (maize; Zea mays L.) cv. 'Pioneer 33G26' by seed treatment with naphthalic anhydride (1,8-naphthalic anhydride). All corn seed had been first treated with fludioxonil and metaxyl applied at the manufacturer's recommended rate as per the Pioneer 33G26 label. Some of the corn seed were subsequently also treated with naphthalic anhydride as a 1% by weight seed dressing. The corn seed were planted in pots containing pasteurized Sassafras sandy loam soil, and then treatments were applied preemergence the same day. Treatments were applied by spraying the test compounds formulated in a non-phytotoxic solvent mixture, using a flat fan nozzle and a spray volume of 280 L/ha. The treatments were triply replicated and the results subsequently averaged. The pots were placed on a greenhouse bench using a complete randomized block design except for the first replicate, which was unrandomized. The plants were grown in the greenhouse and watered as needed with a dilute nutrient solution containing 200 ppm of N. Illumination was daylight supplemented by artificial sources to maintain a photoperiod of 16 hours. The temperature was maintained at 28 ± 2 °C during the day and 23 ± 2 °C at night. The plant response was visually rated 25 days after treatment in comparison to untreated controls using a scale of 0 to 100, with 0 representing no effect and 100 representing complete plant death. The results are listed in Table G.
Table G - Results from using naphthalic anhydride to safen compounds of the invention on corn
Figure imgf000247_0001
TEST H
This test evaluated the safening of compounds of the invention on wheat (Triticum aestivum L.) cv. 'Recital' by seed treatment with naphthalic anhydride. Some of the wheat seed was treated with naphthalic anhydride as a 1% by weight seed dressing. The wheat seed were planted in pots containing pasteurized Sassafras sandy loam soil. For postemergence testing the plants were grown 8 days to the 2-leaf stage at time of treatment. Preemergence treatments were applied the same day that the seeds were planted. Treatments were applied by spraying the test compounds formulated in a non-phytotoxic solvent mixture, using a flat fan nozzle and a spray volume of 280 L/ha. The preemergence treatments were triply replicated and the results subsequently averaged. The pots were placed on a growth chamber bench using a complete randomized block design for the preemergence test except for the first replicate, which was unrandomized. The plants were grown in the growth chamber and watered as needed with a dilute nutrient solution containing 200 ppm of N. Illumination was provided by fluorescent lamps giving 200-300 μE/m /S of photosynthetically active radiation over a 14-hour photoperiod. The temperature was maintained at 23 ± 2 °C during the day and 17 ± 2 °C at night. The effects of the treatments were rated 25 days after preemergence treatment and 14 days after postemergence treatment. The plant response was visually rated in comparison to untreated controls using a scale of 0 to 100, with 0 representing no effect and 100 representing complete plant death. The results for the compounds tested preemergence are listed in Table HI, and the results for the compounds tested postemergence are listed in Table H2.
Table HI - Results from using naphthalic anhydride to safen compounds of the invention applied preemergence to wheat
Figure imgf000248_0001
Table H2 - Results from using naphthalic anhydride to safen compounds of the invention applied postemergence to wheat
Figure imgf000248_0002
TEST I
This test evaluated the safening of Compound 6 on barley (Hordeum vulgare L.) cv.
'Boone' and wheat (Triticum aestivum L.) cv. 'Recital' by Harmony® Extra Herbicide, which comprises 50 wt% thifensulfuron-methyl and 25 wt% tribenuron-methyl. Barley and wheat seeds were planted in pots containing a pasteurized blend of Matapeake soil and sand.
For postemergence testing the plants were grown 10 days so the barley seedlings were at the
2-leaf stage and the wheat seedlings were at the 2-3-leaf stage at time of treatment.
Preemergence treatments were applied the day after the seeds were planted. Treatments were applied by spraying Compound 6 and/or Harmony® Express in a non-phytotoxic solvent mixture, using flat fan nozzle and a spray volume of 280 L/ha. The treatments were triply replicated and the results subsequently averaged. The pots were placed on a greenhouse bench using a complete randomized block design except for the first replicate, which was unrandomized. The plants were grown in the greenhouse and watered as needed with a dilute nutrient solution containing 200 ppm of N. Illumination was daylight supplemented by artificial sources to maintain a photoperiod of 14 hours. The temperature was maintained at 23 ± 2 °C during the day and 17 ± 2 °C at night. The effects of the treatments were rated 25 days after preemergence treatment and 15 days after postemergence treatment. The plant response was visually rated in comparison to untreated controls using a scale of 0 to 100, with 0 representing no effect and 100 representing complete plant death. Colby's Equation was used to calculate the expected additive herbicidal effect of the mixtures of Compound 6 with Harmony® Extra (i.e. a 2:1 mixture by weight of thifensulfuron-methyl and tribenuron-methyl). Colby's Equation (Colby, S. R. "Calculating
Synergistic and Antagonistic Responses of Herbicide Combinations," Weeds, 15(1), pp 20-
22 (1967)) calculates the expected additive effect of herbicidal mixtures, and for two active ingredients is of the form:
Pa+b = Pa + Pb - (PaPb / 100) wherein Pa+b is the percentage effect of the mixture expected from additive contribution of the individual components,
Pa is the observed percentage effect of the first active ingredient at the same use rate as in the mixture, and
Pb is the observed percentage effect of the second active ingredient at the same use rate as in the mixture. The results and additive effects expected from Colby's Equation for the preemergence test are listed in Table II, and the results and additive effects expected from Colby's Equation for the postemergence test are listed in Table 12. Table II - Results from using Harmony® Extra Herbicide to safen Compound 6 applied preemergence to barley and wheat
Figure imgf000250_0001
: Effects expected from Colby's Equation.
Table 12 - Results from using Harmony® Extra Herbicide to safen Compound 6 applied postemergence to barley and wheat
Figure imgf000250_0002
* Effects expected from Colby's Equation.
TEST J
Seeds of test plants consisting of barnyardgrass (ECHCG; Echinochloa crus-galli (L.) Beauv.), blackgrass (ALOMY; Alopecurus myosuroides Huds.), Surinam grass (BRADC; Urochloa decumbens (Staph) R. D. Webster, previously named Brachiaria decumbens Stapf), cocklebur (XANST, Xanthium strumarium L.), corn (ZEAMD, Zea mays L. cv. 'Pioneer 33G26'), large crabgrass (DIGS A, Digitaria sanguinalis (L.) Scop.), giant foxtail (SETFA, Setaria faberi Herrm.), lambsquarters (CHEAL, Chenopodium album L.), morningglory (IPOCO, Ipomoea coccinea L.), pigweed (AMARE, Amaranthus retroflexus L.), velvetleaf (ABUTH, Abutilon theophrasti Medik.) wheat (TRZAS, Triticum aestivum L. cv. 'Recital') and wild oat (ANEFA, Avenafatua L.) were planted in Redi-Earth® planting medium (Scotts Company, 14111 Scottslawn Road, Marysville, Ohio 43041) comprising spaghnum peat moss and vermiculite. Seeds of small-seeded species were planted about 1 cm deep; larger seeds were planted about 2.5 cm deep. Plants were grown in a greenhouse using supplemental lighting to maintain a photoperiod of about 14 hours; daytime and nighttime temperatures were about 24-30 °C and 22-25 °C, respectively. Balanced fertilizer was applied through the watering system. The plants were grown for 7 to 11 days so that at time of treatment the plants ranged in height from 2 to 18 cm (1- to 4-leaf stage). Treatments consisted of Compounds 2 and 6 (technical material), atrazine (90DF), terbacil (Sinbar® 80DF), hexazinone (Velpar® 75WG), diuron (Karmex® 80WP) and paraquat (Gramoxone® Extra, 37%) alone and in combination, suspended or dissolved in an aqueous solvent comprising a nonionic surfactant and applied as a foliage spray using a volume of 541 L ha. Each treatment was triply replicated. The application solvent was observed to have no effect compared to untreated check plants. Treated plants and controls were maintained in the greenhouse and watered as needed with care to not wet the foliage for the first 24 hours after treatment. The effects on the plants 15 days after treatment were visually compared to untreated controls. Plant response ratings, listed in Table J as the means of the three replicates, are based on a scale of 0 to 100 where 0 is no effect and 100 is complete control. Also listed in Table J are the expected effects for the mixtures calculated using Colby's Equation.
Table J- Observed and Expected Results from Compounds 2 and 6 Alone and in Combination with Atrazine, Diuron, Hexazinone, Terbacil and Paraquat*
Figure imgf000251_0001
Figure imgf000252_0001
Figure imgf000253_0001
Figure imgf000253_0002
Figure imgf000254_0001
* Application rates are grams of active ingredient per hectare (g a.i./ha). "Obsd." is observed effect. "Exp." is expected effect calculated from Colby's Equation.
As can be seen from the results listed in Table J, many of the effects observed were close to additive, but some combinations showed considerably greater than additive (i.e. synergistic) effects or less than additive (i.e. safening) on certain plant species. Particularly noteworthy greater than additive effects were observed for mixtures of Compound 2 with diuron and particularly terbacil on crabgrass, mixtures of Compound 6 with diuron, hexazinone and terbacil on Surinam grass, mixtures of Compound 6 with atrazine on pigweed, and mixtures of Compound 6 with terbacil on barnyardgrass. Some of the mixtures also showed a less than additive effect on wheat and particularly corn.

Claims

CLAIMSWhat is claimed is:
1. A compound selected from Formula I, an N-oxide or an agriculturally suitable salt thereof,
Figure imgf000256_0001
wherein
Figure imgf000256_0002
T is CR6 or Ν; U is CR7 or Ν; Y is CR8 or N; Z is CR9 or N; Rla is H, Cj-C4 alkyl, Cγ-C^ fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C alkynyl or C2-C4 fluoroalkynyl; Rlb is halogen, C1-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C4 fluoroalkynyl; Rl is H; R2a is Cx-C6 alkyl, Cγ-C^ haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or
SiR23R24R25; R2b is Cι-C6 alkyl, Cj- haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, C3-C6 cycloalkyl, C4-C5 alkylcycloalkyl, Cβ-Cg halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl; R3 is H, F or C1-C2 alkyl; or R2a or R2b is taken together with R3 as -C(R26a)(R26b)-(Y1)s-(CH2)t-(Y2)u- or
-C(R26a)(R26b)-(Y1)v-CH=CH-(Y2)w- wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3;
R4 is H, Cj-C2 alkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkoxyalkyl or C2-C6 alkylthioalkyl; R5 is
Figure imgf000257_0001
C(O)ORl2, COR13, C(NOR*4)Rl5, -CN, OR16, S(O)mRl7
S(O)2NR18R19, OS(O)2R27 or OP(O)R28 R28b; R6 is H, F, C!-C2 alkyl, -^ fluoroalkyl, Cι-C2 alkoxy, Cι-C2 fluoroalkoxy,
C]-C2 alkylthio or C]-C2 fluoroalkylthio; or R5 and R6 are taken together as a radical selected from -C(W1)N(R11)(CH2)n- and
-C(NOR14)CH2(CH2)n- wherein the right end of the radical is connected to the ring at T; R7 is H, F, Cr-C2 alkyl, C^^ fluoroalkyl, C^^ alkoxy, C]-^ fluoroalkoxy,
C -C2 alkylthio or Cι-C fluoroalkylthio; R8 and R9 are independently selected from H, F, Cι-C2 alkyl, Ct~C fluoroalkyl,
C]-C2 alkoxy, Cι~C fluoroalkoxy, Ct-C2 alkylthio and C1-C2 fluoroalkylthio; R10 is H, C1-C4 alkyl, Cx-C^ haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl;
R11 is H, Ci-Cs alkyl, Ci-Cs haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl,
C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or -(CH2)2θ(CH2)2-, each optionally substituted with 1-2 Cι-C2 alkyl; each R12 is independently Ct-Cs alkyl, Cj-C5 haloalkyl, C2-C alkoxyalkyl, C2-C alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl; R13 is C!-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; Rl4 is H, C!-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or
C2-C6 alkoxycarbonyl; R15 is C -C3 alkyl, C1-C3 haloalkyl or cyclopropyl; R16 is Cj-04 alkyl, C1-C4 haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl,
C -C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl; R17 is C!-C4 alkyl, C -0^ haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; each R19 is independently H, C1-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy, C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl;
R20 is C1-C4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R21 is C2-C3 alkyl; R22 is Cr-C3 alkyl; or
R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl;
R23 is C!-C2 alkyl or C^ haloalkyl; R24 is C!-C2 alkyl or Cι-C2 haloalkyl;
R25 is C!-C2 al yl or cl-c2 haloalkyl;
R26a and R26b are independently H or Cj-C^ alkyl; R27 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
R28a and R28b are independently
Figure imgf000258_0001
alkyl or C1-C2 alkoxy;
W is O or S;
Wi is O or S;
Y1 and Y2 are independently CH2, O, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that (a) when J is J-1, Rl is CH3 and R5 is C(W1)NR10R11, C(O)OR12, COR13, ORi6 or
S(O)mR17, then at least one of T, U, Y and Z is N or C-F;
(b) when J is J-1, Rla is CH3, R5 is C(W1)NR1θR11, C(O)OR12, COR13, OR^ or S(O)mR17 and T is N, then at least one of U, Y and Z is N or C-F;
(c) when R5 is C(W1)NR10R11 or C(NOR14)R15, then R9 is other than alkoxy or alkylthio;
(d) when R5 is C(W1)NR10R11, then R6 is other than alkyl or alkoxy;
(e) when R5 is COR13, then Rla or Rlb is selected from the radicals of the group consisting of C1-C3 alkyl, Cv-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
(f) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1, then R10 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl;
(g) when at least one of R10 and R11 is haloalkyl, then Rla or Rlb is CH2CH3 or CH2CF3 and R2a or R2b is tert-butyl, isopropyl or cyclopropyl;
(h) when J is J-2 or J-6, then R7 and R9 are H;
(i) when J is J-2 or J-6, and R2b is C1-C2 alkyl, then Rlb is halogen, C2-C4 alkyl, C]_-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl; (j) when Rla is CH3 and R5 is C(NOR14)R15, then R7 is other than alkyl; (k) when T is N, then Z is CR9; (1) when T is N, R7 is alkoxy, then R11 is H; (m) when R7 and R9 are F, and one of R10 and R11 is H, then the other of R10 and R1 x is other than H; (n) when Z is N and one of R10 and R1 ! is H, then the other of R10 and R11 is other than trifluoroethyl; (o) when J is J-8 andR2b is C5-C6 cycloalkyl, then R5 is C(O)NR10R11; and (p) when J is J-8 and R7 is other than H, then R2b is tert-butyl and R5 is
C^NRiOR11.
2. The compound of Claim 1 wherein J is J-1, J-2, J-3, J-4, J-5 or J-8.
3. The compound of Claim 2 wherein:
Rla or Rlb is CH2CH3, CH2CH2F, CH2CHF2, CH2CF3 or CH=CH2; R2a or R2b is tert-butyl, isopropyl or cyclopropyl;
R3 is H; R4 is H; and W is O.
4. The compound of Claim 3 wherein at most one of T, U, Y and Z is N.
5. The compound of Claim 4 wherein
R5 is CONRiOR11 or C(O)OR12;
R6 is H or F; and R7 is H or F;
R10 is H or Cj- alkyl;
R11 is C1-C4 alkyl; or R10 and R11 are taken together as -CH2CH=CHCH2-; and
R12 is C!-C3 alkyl.
6. The compound of Claim 5 wherein J is J-1, J-3 or J-5.
7. The compound of Claim 6 wherein RS is CONR^R11;
R10 is H or C!-C2 alkyl; and R11 is 0^3 alkyl; or
R10 and R11 are taken together as -CH2CH=CHCH2-.
8. The compound of Claim 7 wherein R2a is tert-butyl or isopropyl; and
R8 and R9 are H or F.
9. The compound of Claim 8 which is selected from the group consisting of:
3-(l,l-dimethylethyl)-l-ethyl-N-[5-[(ethylamino)carbonyl)-2-fluorophenyl]- lH-pyrazole-5-carboxamide;
N- [5- [(dimethylamino)carbonyl]-2-fluorophenyl]-3-( 1 , 1 -dimethylethyl)- 1-ethyl- lH-pyrazole-5-carboxamide; 2-[[(3-(l,l -dimethylethyl)- 1 -ethyl- lH-pyrazol-5 -yl] carbonyl] amino] -N,N-dimethyl-
4-pyridinecarboxamide;
2- [ [ [3-( 1 , 1 -dimethylethyl)- 1 -ethyl- lH-pyrazol-5-yl] carbonyl] amino] -N-ethyl- 4-pyridinecarboxamide;
N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-l-ethyl-3-(l-methylethyl)- lH-pyrazole-5-carboxamide;
N- [5 - [(dimethylamino)carbonyl] -2-fluorophenyl] - 1 -( 1 , 1 -dimethylethyl)-3-ethyl- lH-pyrazole-4-carboxamide;
3-(l,l-dimethylethyl)-l-(2-fluoroethyl)-N-[3-[(lE)-l-(hydroxyimino)ethyl]phenyl]- lH-pyrazole-5-carboxamide; 3 -( 1 , 1 -dimethylethyl)- 1 -ethyl-N- [5 - [(ethylmethylamino)carbonyl] -2-fluorophenyl] - lH-pyrazole-5-carboxamide;
3-( 1 , 1 -dimethylethyl)- 1 -ethyl-N- [3 - [(ethylamino)carbonyl] -4-fluorophenyl] - lH-pyrazole-5-carboxamide;
N- [5 - [(2,5 -dihydro- lH-pyrrol- 1 -yl)carbonyl] -2-fluorophenyl] - 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxamide; and
3-(l,l-dimethylethyl)-l-ethyl-N-[3-(trifluoromethoxy)phenyl]-lH-pyrazole- 5-carboxamide.
10. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
11. A method for controlling the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Claim 1.
12. A method for controlling the growth of undesired vegetation comprising Urochloa decumbens (Staph) R. D. Webster comprising contacting the vegetation or its environment with herbicidally effective amounts of the compound of Claim 1 which is N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-3-(l,l-dimethylethyl)-l-ethyl- lH-pyrazole-5-carboxamide and at least one other herbicide selected from the group consisting of diuron and hexazinone.
13. A herbicidal mixture comprising a herbicidally effective amount of a compound of Formula Iz, an N-oxide or an agriculturally suitable salt thereof,
Figure imgf000261_0001
Iz wherein
Figure imgf000261_0002
J-1 J-2 J-3 J-4
Figure imgf000261_0003
T is CR6 or Ν; U is CR7 or N; Y is CR8 or N; Z is CR9 orN;
Rl is H, C1-C4 alkyl, Cj-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl;
Rlb is halogen, Cj-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl;
Rlc is H;
R2a is Ci-Cg alkyl, Cι-C6 haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or
SiR23R24R25;
R2b is Cι-C6 alkyl, Cx-C6 haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-Cg alkenyl, C2-Cg haloalkenyl, C2-C6 alkynyl, C -Cg haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl;
R3 is H, F or C C2 alkyl; or R2a or R2b is taken together with R3 as -C(R26a)(R26 )-(Y1)s-(CH2)t-(Y2)u- or
-C(R26a)(R 6b)-(Y1)v-CH=CH-(Y2)w- wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3; R4 is H, C1-C2 alkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkoxyalkyl or C2-C6 alkylthioalkyl; R5 is
Figure imgf000262_0001
C(O)OR12, COR13, C(NOR14)R15, -CN, OR16, S(O)mR17
S(O)2NR18R19, OS(O)2R27 or OP(O)R28aR28 ; R6 is H, F, Cι-C2 alkyl, C]-C- fluoroalkyl, C1-C2 alkoxy, C1-C fluoroalkoxy, Cj-C2 alkylthio or Cι-C2 fluoroalkylthio; or
R5 and R6 are taken together as a radical selected from -C(W1)N(R11)(CH2)n- and
-C(NOR14)CH2(CH2)n- wherein the right end of the radical is connected to the ring at T; R7 is H, F, C!-C2 alkyl, C!-^ fluoroalkyl, Cι-C2 alkoxy, CpC^ fluoroalkoxy, Cx-C2 alkylthio or Cx-C2 fluoroalkylthio;
R8 and R9 are independently selected from H, F, C1-C2 alkyl, Cr-C2 fluoroalkyl,
C1-C alkoxy, C1-C2 fluoroalkoxy, Cι-C2 alkylthio and Cι-C2 fluoroalkylthio; R10 is H, C!-C4 alkyl, Ci-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or
C2-C4 alkylthiomethyl; R11 is H, Ci-Cs alkyl, C!-C5 haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl,
C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C!-C3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or
-(CH2)2O(CH2)2-, each optionally substituted with 1-2 Cι-C2 alkyl; each R12 is independently Cr-C5 alkyl, Cι-C5 haloalkyl, C2-C4 alkoxyalkyl, C2-C alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl;
R13 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
R14 is H, CJ-C4 alkyl, Ct-C4 haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or
C -Cg alkoxycarbonyl; R15 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; R16 is C!-C4 alkyl, Ci- j. haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl,
C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl ; R17 is Cv-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl,
C3-C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, C1-C4 alkyl, Cι-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; each R19 is independently H, C]-C5 alkyl, C^Cs haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy, C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; R20 is Cι-C4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl;
R21 is C!-C3 alkyl; R22 is Ct-C3 alkyl; or R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl; R23 is Ci-Cz alkyl or Cι-C2 haloalkyl;
R24 is C!-C2 alkyl or Cχ-0, haloalkyl; R25 is Ct-C2 alkyl or C,-^ haloalkyl; R26a and R26b are independently H or C1-C2 alkyl; R27 is C1-C3 alkyl, CJ-C3 haloalkyl or cyclopropyl; R28a and R28b are independently C^^ alkyl or Ct-C2 alkoxy;
W is O or S; Wi is O or S;
Y1 and Y2 are independently CH2, O, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1 ; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that (a) when R5 is
Figure imgf000264_0001
or C(NOR1 )R15, then R9 is other than alkoxy or alkylthio;
(b) when R5 is C(W1)NR10R11, then R6 is other than alkyl or alkoxy;
(c) when R5 is COR13, then Rla or Rlb is selected from the radicals of the group consisting of Ct-C3 alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
(d) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1, then R10 is Cj-C4 alkyl, Cι-C4 haloalkyl, C3- 4. alkenyl, C -C4 alkoxymethyl or C2-C4 alkylthiomethyl;
(e) when at least one of R10 and R11 is haloalkyl, then Rla or Rlb is CH2CH3 or CH2CF3 and R2a or R2b is tert-butyl, isopropyl or cyclopropyl;
(f) when J is J-2 or J-6, then R7 and R9 are H;
(g) when J is J-2 or J-6, and R2b is Cj-C2 alkyl, then Rlb is halogen, C2-C4 alkyl, C^-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl; (h) when Rla is CH3 and R5 is C(NOR14)R15, then R7 is other than alkyl; (i) when T is N, then Z is CR9; (j) when T is N, R7 is alkoxy, then R11 is H; (k) when R7 and R9 are F, and one of R10 and R1 is H, then the other of R10 and R1 is other than H; (1) when Z is N and one of R10 and R11 is H, then the other of R10 and R11 is other than trifluoroethyl; (m)when J is J-8 and R2b is C5-C6 cycloalkyl, then R5 is C(O)NR10Rn; and (n) when J is J-8 and R7 is other than H, then R2b is tert-butyl and R5 is
C(O)NR10Rn; and an effective amount of at least one additional active ingredient selected from the group consisting of an other herbicide and a herbicide safener.
14. A herbicidal composition comprising the herbicidal mixture of Claim 13 and at least one of a surfactant, a solid diluent or a liquid diluent.
15. A herbicidal mixture of Claim 13 wherein the other herbicide is selected from atrazine, bromacil, diuron, hexazinone, terbacil, glyphosate, glufosinate, rimsulfuron, metsulfuron-methyl, sulfometuron-methyl, ametryn and paraquat.
16. A herbicidal mixture of Claim 13 wherein the safener is selected from 1-bromo- 4-[(chloromethyl)sulfonyl]benzene, cloquintocet-mexyl, cyometrinil, dichlormid,
2-(dichloromethyl)-2-methyl-l,3-dioxolane, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, isoxadifen-ethyl, mefenpyr-ethyl, (4-methoxy-3-methylphenyl)- (3-methylphenyl)methanone, 1,8-naphthalic anhydride and oxabetrinil.
17. A herbicidal mixture of Claim 13 wherein the compound of Formula Iz is a compound of Claim 1.
18. 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 Formula Iz, an N-oxide or an agriculturally suitable salt thereof,
Figure imgf000265_0001
Iz wherein
Figure imgf000265_0002
T is CR6 or Ν; U is CR7 or N; Y is CR8 or N; Z is CR9 or N; Rl is H, Cj- alkyl, C\-C^ fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C4 fluoroalkynyl; Rlb is halogen, C1-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C fluoroalkynyl; Rlc is H; R2a is Ct-Cg alkyl, Cj-Ce haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3~C6 halocycloalkyl, C4-Cg cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or SiR23R2 R25;
R2b is Cι-C6 alkyl, Ct-Cg haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-Cg haloalkenyl, C2-C6 alkynyl, C2-Cg haloalkynyl,
C3-C6 cycloalkyl, Qψ-Cg alkylcycloalkyl, C3-C6 halocycloalkyl, C4-Cg cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl; R3 is H, F or C^^ alkyl; or
R2a or R2b is taken together with R3 as -C(R26a)(R26b)-(Y1)s-(CH2)t-(Y2)u- or
-C(R26a)(R26b)-(Y1)v-CH=CH-(Y2)w- wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3; R4 is H, Cι-C2 alkyl, C -Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkoxyalkyl or C2-C6 alkylthioalkyl;
R5 is
Figure imgf000266_0001
C(O)OR12, COR13, C(NOR14)R15, -CN, OR16, S(O)mR17
S(O)2NR18R19, OS(O)2R27 or OP(O)R28aR28b; R6 is H, F, Ct-C2 alkyl, Ci-C2 fluoroalkyl, Cj-Cs alkoxy, 0^2 fluoroalkoxy,
C -C alkylthio or Cι-C2 fluoroalkylthio; or R5 and R6 are taken together as a radical selected from -C(W1)N(R1 l)(CE2)n and
-C(NOR14)CH2(CH2)n- wherein the right end of the radical is connected to the
R7 is H, F, Cj-C alkyl, Cr-C2 fluoroalkyl, Cι-C2 alkoxy, Cv-C2 fluoroalkoxy,
Ct~C2 alkylthio or C1-C2 fluoroalkylthio; R8 and R9 are independently selected from H, F, Cj-C alkyl, Cv-C fluoroalkyl,
Cι~C2 alkoxy, Ct-C2 fluoroalkoxy, Cr-C2 alkylthio and C1-C2 fluoroalkylthio; R10 is H,
Figure imgf000266_0002
alkyl, Ct-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or
C2-C4 alkylthiomethyl; R11 is H, Ct-C5 alkyl, C^ haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, 0^3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or
-(CH2)2O(CH2)2-, each optionally substituted with 1-2 Cι-C2 alkyl; each R12 is independently Cj-Cs alkyl, C1-C5 haloalkyl, C2-C4 alkoxyalkyl, C2-C4 alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl; R13 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; R14 is H, C!-C4 alkyl, CJ- J. haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or
C2-Cg alkoxycarbonyl; R15 is Ct-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
R16 is Cj-C^ alkyl, Ci-C4 haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl ; R17 is C!-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl,
C3-C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, C]_-C4 alkyl, C1-C haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; each R19 is independently H, Cj_-C5 alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy, C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; R20 is C1-C4 alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R21 is C1-C3 alkyl;
R22 is C!-C3 alkyl; or
R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl; R23 is Ct-Ca alkyl or -^ haloalkyl; R24 is Ci-02 alkyl or -^ haloalkyl;
R25 is C:-C2 alkyl or Ci-C haloalkyl; R26a an(χ R26b are independently H or Cj-C2 alkyl; R27 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; R28a and R28b are independently C1-C2 alkyl or Cι-C2 alkoxy; W is O or S;
W1 is O or S; c
Y1 and Y2 are independently CH2, O, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that
(a) when R5 is C(W1)NR1θRll or C(NOR14)R15, then R9 is other than alkoxy or alkylthio; (b) when R5 is C(W1)NR θR11 , then R6 is other than alkyl or alkoxy;
(c) when R5 is COR13, then Rla or Rlb is selected from the radicals of the group consisting of C1-C3 alkyl, Cv-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C -C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring; d) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1, then R10 is Ct-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C alkylthiomethyl; e) when at least one of R10 and R11 is haloalkyl, then Rla or Rlb is CH2CH3 or CH2CF3 and R2a or R2b is tert-butyl, isopropyl or cyclopropyl; f) when J is J-2 or J-6, then R7 and R9 are H; g) when J is J-2 or J-6, and R2b is Cι-C2 alkyl, then Rlb is halogen, C2-C4 alkyl, C1-C4. fluoroalkyl, C2-C4 alkenyl, C -C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl; h) when Rla is CH3 and R5 is C(NOR14)R15, then R7 is other than alkyl; i) when T is N, then Z is CR9; (j) when T is N, R7 is alkoxy, then R11 is H; (k) when R7 and R9 are F, and one of R10 and R11 is H, then the other of R10 and R11 is other than H; 1) when Z is N and one of R10 and R1 x is H, then the other of R10 and R11 is other than trifluoroethyl; m)when J is J-8 and R2b is C5-C6 cycloalkyl, then R5 is C(O)NR10R11; and (n) when J is J-8 and R7 is other than H, then R b is tert-butyl and R5 is
C^NRiOR11; and an antidotally effective amount of a safener.
19. 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 Formula Iz, an N-oxide or an agriculturally suitable salt thereof,
Figure imgf000268_0001
Iz wherein
Figure imgf000268_0002
J-1 J-2 J-3 J-4
Figure imgf000269_0001
J-5 J-6 J-7 J-8
T is CR6 or N; U is CR7 or N; Y is CR8 or N; Z is CR9 or N; Rla is H, Ci-C4 alkyl, Ci-C^ fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C4 fluoroalkynyl; Rlb is halogen, C1-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl,
C2-C4 alkynyl or C2-C fluoroalkynyl; Rlc is H; R2a is Cι-C6 alkyl, C C6 haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-Cg alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl,
C3-C6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C5-C6 alkylcycloalkylalkyl, -CR20(OR21)(OR22) or
SiR2 R24R25; R2b is Ct-C6 alkyl, C^Cg haloalkyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl,
C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C -C6 haloalkynyl,
C3-Cg cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl; R3 is H, F or Cι-C2 alkyl; or R2a or R2b is taken together with R3 as -C(R26a)(R26b)-(Y1)s-(CH2)t-(Y2)u- or
-C(R26a)(R26b)-(Y1)v-CH=CH-(Y2)w- wherein the left end of the radical is connected as R2a or R2b, and the right end of the radical is connected as R3; R4 is H, Ct-C2 alkyl, C2-C6 alkylcarbonyl, C2-C6 alkoxycarbonyl, C2-C6 alkoxyalkyl or C2-C6 alkylthioalkyl; R5 is C(W1)NR10R11, C(O)OR12, COR13, C(NOR14)R15, -CN, OR16, S(O)mR17
S(O)2NR18R19, OS(O)2R27 or OP(O)R28aR28b; R6 is H, F, Cι-C2 alkyl, Ct-C2 fluoroalkyl, Ct-C2 alkoxy, Cr-C2 fluoroalkoxy,
Ct-C2 alkylthio or ^^2 fluoroalkylthio; or R5 and R6 are taken together as a radical selected from -C(W1)N(R11)(CH2)n- and
-C(NOR14)CH2(CH2)n- wherein the right end of the radical is connected to the ring at T; R7 is H, F, Cι-C2 alkyl, Cι-C2 fluoroalkyl, Cχ-02 alkoxy, Cι-C2 fluoroalkoxy, Cι-C2 alkylthio or Cι-C2 fluoroalkylthio;
R8 and R9 are independently selected from H, F, Cj-C2 alkyl, Cj-C^ fluoroalkyl,
Cι-C2 alkoxy, C1-C2 fluoroalkoxy, C1-C2 alkylthio and Cj-C2 fluoroalkylthio; R10 is H, Ct-C4 alkyl, Cr-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or
C2-C4 alkylthiomethyl; R11 is H, Ct-Cs alkyl, C1-C5 haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl,
C3-C5 alkynyl, C3-C5 cycloalkyl, C4.-C5 cycloalkylalkyl, C1-C3 alkoxy,
C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; or R10 and R11 are taken together as -(CH2)4-, -(CH2)5-, -CH2CH=CHCH2- or
-(CH2)2O(CH2)2-, each optionally substituted with 1-2 Ci-C^ alkyl; each R12 is independently Ct-C5 alkyl, Cj-C5 haloalkyl, C2-C4 alkoxyalkyl, C2-C alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl; R13 is C1-C3 alkyl, C]~C3 haloalkyl or cyclopropyl;
R14 is H, Ct-C4 alkyl, Cj- i haloalkyl, C3-C4 alkenyl, C2-C6 alkylcarbonyl or C2-Cg alkoxycarbonyl;
R15 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
R16 is Cj-C4 alkyl, Cι-C4 haloalkyl, C2-C3 alkoxyalkyl, C2-C3 alkylthioalkyl,
C2-C4 alkenyl, C3-C4 haloalkenyl, C3-C4 alkynyl, C3-C5 cycloalkyl or cyclopropylmethyl ; R17 is C1-C4 alkyl, -C4 haloalkyl, C2-C4 alkenyl, C3-C4 haloalkenyl,
C3-C4 alkynyl, C3-C4 cycloalkyl or cyclopropylmethyl; each R18 is independently H, Cj_-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or C2-C4 alkylthiomethyl; each R19 is independently H, Ci-Cs alkyl, C!-C5 haloalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C]_-C3 alkoxy, C2-C5 alkoxyalkyl or C2-C5 alkylthioalkyl; R20 is Ct-C alkyl, cyclopropyl, cyclopropylmethyl or methylcyclopropyl; R21 is C!-C3 alkyl; R22 is Ct-C3 alkyl; or R21 and R22 are taken together as -CH2CH2- or -CH2CH2CH2-, each optionally substituted with 1-2 methyl; R23 is C!-C2 alkyl or C^^ haloalkyl; R24 is Ct-C2 alkyl or C!-C2 haloalkyl; R25 is C!-C2 alkyl or C]-C2 haloalkyl; R26a an£i R26b are independently H or C1-C2 alkyl; R27 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl; 28a and R28 are independently Cι-C2 alkyl or Cj-^ alkoxy; W is O or S;
W1 is O or S;
Y1 and Y2 are independently CH2, O, S, NH or NCH3; m is 0, 1 or 2; n is 1 or 2; s is 0 or 1; t is 1 or 2; and u is 0 or 1; provided that the sum of s, t and u is 2 or 3; and v is 0 or 1; w is 0 or 1; provided that the sum of v and w is 0 or 1; provided that (a) when R5 is
Figure imgf000271_0001
or C(NOR14)R15, then R9 is other than alkoxy or alkylthio; (b) when R5 is C(W1)NR10R1 x, then R6 is other than alkyl or alkoxy;
(c) when R5 is COR13, then Rla or Rl is selected from the radicals of the group consisting of C1-C3 alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C2-C3 fluoroalkenyl, C2-C3 alkynyl or C2-C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring; (d) when R5 and R6 are taken together as -C(W1)N(R10)(CH2)n- and n is 1, then R10 is Cj-C4 alkyl, Cι-C4 haloalkyl, C3-C4 alkenyl, C2-C4 alkoxymethyl or
C2-C4 alkylthiomethyl; (e) when at least one of R10 and R11 is haloalkyl, then Rla or Rlb is CH2CH3 or
CH2CF3 and R2a or R2b is tert-butyl, isopropyl or cyclopropyl; (f) when J is J-2 or J-6, then R7 and R9 are H;
(g) when J is J-2 or J-6, and R2b is C]-C2 alkyl, then Rlb is halogen, C2-C4 alkyl,
C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl; (h) when Rla is CH3 and R5 is C(NOR14)R15, then R7 is other than alkyl; (i) when T is N, then Z is CR9;
(j) when T is N, R7 is alkoxy, then R11 is H;
(k) when R7 and R9 are F, and one of R10 and R11 is H, then the other of R10 and R11 is other than H; (1) when Z is N and one of R10 and R11 is H, then the other of R10 and R11 is other than trifluoroethyl;
(m)when J is J-8 and R2b is C5-C6 cycloalkyl, then R5 is C(O)NR1θR11; and (n) when J is J-8 and R7 is other than H, then R2b is tert-butyl and R5 is
C OjNRTOR11; wherein seed from which the crop is grown is treated with an antidotally effective amount of a safener.
20. The method of Claim 19 wherein the safener comprises 1,8-naphthalic anhydride.
21. The method of Claim 19 wherein the compound of Formula Iz is a compound of
Claim 1.
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