WO2004106324A1 - Herbicides a base d'azolecarboxamide - Google Patents

Herbicides a base d'azolecarboxamide Download PDF

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Publication number
WO2004106324A1
WO2004106324A1 PCT/US2004/010711 US2004010711W WO2004106324A1 WO 2004106324 A1 WO2004106324 A1 WO 2004106324A1 US 2004010711 W US2004010711 W US 2004010711W WO 2004106324 A1 WO2004106324 A1 WO 2004106324A1
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Prior art keywords
alkyl
haloalkyl
compound
alkenyl
formula
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PCT/US2004/010711
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English (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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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority claimed from PCT/US2003/032965 external-priority patent/WO2004035545A2/fr
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of WO2004106324A1 publication Critical patent/WO2004106324A1/fr
Priority to US11/096,104 priority Critical patent/US20060069132A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—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:
  • R la is H, C1-C4 alkyl, C j - ⁇ fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl;
  • R lb is halogen, C1-C4 alkyl, Cj-04 fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl, C2-C4 alkynyl or C2-C4 fluoroalkynyl;
  • R lc is H
  • R 2a is C ⁇ -C 6 alkyl, C ⁇ -C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C 2 -C6 alkenyl, C 2 -Cg haloalkenyl, C 2 -C6 alkynyl, C2 ⁇ C 6 haloalkynyl, C3-C5 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C4-C6 cycloalkylalkyl, C 5 -C 6 alkylcycloalkylalkyl, -CR 20 (OR 2 1)(OR 22 ) or SiR 2 3R 2 R 5 ;
  • R 2b is C ⁇ -C 6 alkyl, C ⁇ -C 6 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, C3 ⁇ C 6 cycloalkyl, C4-C6 alkylcycloalkyl, C3-C6 halocycloalkyl, C 4 -C 6 cycloalkylalkyl or C5-C6 alkylcycloalkylalkyl;
  • R 3 is H, F or C ⁇ -C 2 alkyl; or
  • R 4 is H, C 1 -C2 alkyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C 2 -C6 alkoxyalkyl or C2-Cg alkylthioalkyl;
  • R 5 is C(Wl)NRl ⁇ Rll, C(O)ORl 2 , COR* 3 , C(NORl 4 )Rl5, _ CNj 0 R 6, S(O) m
  • R 6 is H, F, C!-C 2 alkyl, alkoxy, C]-C 2 fluoroalkoxy,
  • R 5 and R 6 are taken together as a radical selected from -C(Wl)N(RH)(CH 2 ) n - and
  • R 7 is H, F, C ⁇ -C 2 alkyl, C ⁇ -C 2 fluoroalkyl, C]-C 2 alkoxy, C j -C 2 fluoroalkoxy,
  • R 8 and R 9 are independently selected from H, F, C ⁇ C 2 alkyl, C ⁇ C 2 fluoroalkyl,
  • Rl° is H, C1-C4 alkyl, 0 ⁇ 4 haloalkyl, C3-C4 alkenyl, C 2 -C 4 alkoxymethyl or
  • RH is H, C!-C 5 alkyl, C1-C5 haloalkyl, C 2 -C 5 alkenyl, C3-C5 haloalkenyl,
  • each Rl 2 is independently C1-C5 alkyl, C ⁇ -C ⁇ haloalkyl, C -C4 alkoxyalkyl, C 2 -C4 alkylthioalkyl, C2-C5 alkenyl, C3-C5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl or C4-C5 cycloalkylalkyl;
  • R 13 is C1-C3 alkyl, 0 ⁇ 03 haloalkyl or cyclopropyl;
  • RI 4 is H, C2-C4 alkyl, C!-C 4 haloalkyl, C3-C4 alkenyl, C 2 -C 6 alkylcarbonyl or
  • Rl 5 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl
  • R i6 is C1-C4 alkyl, C1-C4 haloalkyl, C 2 -C 3 alkoxyalkyl, C 2 -C 3 alkylthioalkyl
  • Rl 7 is C!-C 4 alkyl, C!-C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 4 haloalkenyl,
  • R 2 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 ⁇ -C 2 haloalkyl;
  • R 24 is C!-C 2 alkyl or CJ-CJ haloalkyl;
  • R 25 is Ci-02 alkyl or C ⁇ -C 2 haloalkyl;
  • R 26a and R 26b are independently H or C!-C 2 alkyl;
  • R 27 is Ci-03 alkyl, C1-C3 haloalkyl or cyclopropyl;
  • R 28a an( j R 28b ⁇ Q independently C j -C 2 alkyl or C ⁇ -C 2 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 ib is selected from the radicals of the group consisting of C1-C3 alkyl, C1-C3 fluoroalkyl, C -C3 alkenyl, C 2 -C 3 fluoroalkenyl, C 2 -C3 alkynyl or C -C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring; (j) when R 5 and R 6 are taken together as -C(Wl)N(Rl°)(CH 2 ) n - and n is 1, then R 10 is C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C 2 -C4 alkoxymethyl or
  • R la or R ib is CH 2 CH 3 or
  • 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 ⁇ ; UisCR 7 or ⁇ ; YisCR 8 orN; ZisCR 9 orN; R la is H, C1-C4 alkyl, C1-C4 fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C 4 fluoroalkenyl,
  • R lh is halogen, C1-C4 alkyl, C 1 -C 4 fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C fluoroalkenyl,
  • R 2a is C ⁇ -C 6 alkyl, Ci-Cg haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl,
  • R 2b is Cj-Cg alkyl, C!-C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl,
  • R 3 is H, F or C ⁇ -C 2 alkyl
  • R 2a or R 2b is ta k en together with R 3 as -C(R 26a )(R 26b )-(Yl) s -(CH 2 ) t -(Y 2 ) u - or
  • R 4 is H, C ⁇ -C 2 alkyl, C -C6 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -C6 alkoxyalkyl or C 2 -C 6 alkylthioalkyl;
  • R5 is C(O)OR 12 , CORI 3 , C(NORl 4 )Rl 5 , -CN, OR16, S(O) m Rl 7
  • R 6 is H, F, C ⁇ -C 2 alkyl, C ⁇ 2 fluoroalkyl, C ⁇ -C 2 alkoxy, C ⁇ -C 2 fluoroalkoxy,
  • R 5 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, C ⁇ -C 2 alkyl, C ⁇ -C 2 fluoroalkyl, C ⁇ -C 2 alkoxy, C 1 -C 2 fluoroalkoxy,
  • R 8 and R 9 are independently selected from H, F, C j -C 2 alkyl, C 1 -C 2 fluoroalkyl,
  • Rl° is H, C!-C 4 alkyl, 0 ⁇ 04 haloalkyl, C3-C4 alkenyl, C 2 -C 4 alkoxymethyl or
  • RH is H, C!-C 5 alkyl, C!-C 5 haloalkyl, C 2 -C 5 alkenyl, C 3 -C 5 haloalkenyl, C3-C5 alkynyl, C3-C5 cycloalkyl, C4-C5 cycloalkylalkyl, C1-C3 alkoxy,
  • C2-C5 alkoxyalkyl, C2-C5 alkylthioalkyl, C 2 -C 6 alkylcarbonyl or C 2 -C 6 alkoxycarbonyl; or Rl° and RH are taken together as -(CH 2 ) 4 -, -(CH 2 ) 5 -, -CH 2 CH CHCH 2 - or
  • each Rl 2 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;
  • Rl 3 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl;
  • Rl 4 is H, C1-C4 alkyl, Ci-C ⁇ haloalkyl, C3-C4 alkenyl, C 2 -C 6 alkylcarbonyl or
  • Rl 5 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl
  • R 16 is C!-C 4 alkyl, C!-C 4 haloalkyl, C 2 -C 3 alkoxyalkyl, C 2 -C 3 alkylthioalkyl
  • R 17 is C1-C4 alkyl, Cj-C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 4 haloalkenyl,
  • R 21 is C1-C3 alkyl
  • R 22 is C1-C3 alkyl
  • R 21 and R 22 are taken together as -CH 2 CH 2 - or -CH2CH 2 CH 2 -, each optionally substituted with 1-2 methyl
  • R 23 is C ⁇ -C 2 alkyl or C ⁇ -C 2 haloalkyl
  • R 24 is C ⁇ -C 2 alkyl or C ⁇ C ⁇ haloalkyl
  • R 25 is C ⁇ -C 2 alkyl or C ⁇ -C 2 haloalkyl
  • R 27 is C1-C3 alkyl, C1-C3 haloalkyl or cyclopropyl
  • R 28a and R 28b are independently C ⁇ -C 2 alkyl or 0 ⁇ 02 alkoxy;
  • Yl 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 (a) when R 5 is or C(NOR 1 )R!5, then R 9 is other than alkoxy or alkylthio;
  • R 5 when R 5 is C(Wl)NRl°RH, then R 6 is other than alkyl or alkoxy;
  • R la or R lb is selected from the radicals of the group consisting of C1-C3 alkyl, C1-C3 fluoroalkyl, C 2 -C 3 alkenyl, C 2 -C 3 fluoroalkenyl, C 2 -C3 alkynyl or C 2 -C 3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
  • RTM is C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C 2 -C alkoxymethyl or C 2 -C 4 alkylthiomethyl;
  • R ia or R ib is CH 2 CH 3 or CH2CF3 and R 2a or R 2b is tert-butyl, isopropyl or cyclopropyl;
  • R ib is halogen, C 2 -C 4 alkyl, C1-C4 fluoroalkyl, C 2 -C 4 alkenyl, C 2 -C4 fluoroalkenyl, C 2 -C 4 alkynyl or C 2 -C fluoroalkynyl; (h) when R ia is CH 3 and R 5 is C(NORl 4 )Rl5, then R 7 is other than alkyl; (i) when T is N, then Z is CR 9 ; (j) when T is N and R 7 is alkoxy, then Rl 1 is H; (k) when R 7 and R 9 are F, and one of R 10 and R 1 1 is H, then the other of Rl° and R 11 is other than H; (1) when Z is N and one of R 10 and R 1 1 is H, then the other of R 10 and Rl 1 is other than trifluoro
  • 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).
  • compositions comprising, “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z-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.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH3CH 2 OCH 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.
  • alkylthioalkyl examples include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CT ⁇ 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
  • 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-ethylcyclopentyl.
  • 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 -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.
  • N-oxides 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.
  • 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 .
  • 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 fluoroalkenyl
  • fluoroalkynyl may be partially or fully substituted with fluorine atoms.
  • C j -C j The total number of carbon atoms in a substituent group is indicated by the "C j -C j " prefix where i and j are numbers from 1 to 6.
  • C 1 -C 3 alkyl designates methyl through propyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • 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).
  • Embodiments of the present invention include:
  • Embodiment 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.
  • Embodiment 2 A compound of Embodiment 1 wherein when J is J-1 and R la is CH3 then at least one of T and U is C-F.
  • Embodiment 3 A compound of Formula I wherein when J is J-1, R la is CH3 and T is ⁇ then U is N or C-F.
  • Embodiment 4 A compound of Embodiment 3 wherein when J is J-1, R la is CH 3 and T is N then U is C-F.
  • Embodiment 5. A compound of Formula I wherein at most one of T, U, Y and Z is N.
  • Embodiment 6 A compound of Formula I wherein W is O.
  • Embodiment 7 A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5, J-8 or J-9.
  • Embodiment 8 A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5 or J-8.
  • Embodiment 9 A compound of Formula I wherein J is J-1, J-3, J-5, J-8 or J-9.
  • Embodiment 10 A compound of Formula I wherein J is J-1 , J-3, J-5 or J-8.
  • Embodiment 11 A compound of Formula I wherein J is J-1, J-3, J-8 or J-9.
  • Embodiment 12 A compound of Formula I wherein J is J-1, J-3 or J-5.
  • Embodiment 13 A compound of Formula I wherein J is J-1 or J-3.
  • Embodiment 14 A compound of Formula I wherein R la is C1-C4 alkyl, C1-C4 fluoroalkyl, C2-C4 alkenyl, C2-C4 fluoroalkenyl, C 2 -C alkynyl or C 2 -C 4 fluoroalkynyl.
  • a compound of Formula I wherein R la or R lb is selected from the radicals in the group consisting of C1-C3 alkyl, C1-C3 fluoroalkyl, C2-C3 alkenyl, C 2 -C3 fluoroalkenyl, C -C3 alkynyl or C 2 -C 3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring.
  • Embodiment 17 A compound of Embodiment 16 wherein R la is CH 2 CH 3 , CH 2 CH 2 F,
  • Embodiment 18 A compound of Embodiment 17 wherein R la is CH 2 CH3 or CH CF3.
  • Embodiment 20 A compound of Embodiment 19 wherein R ib is CH 2 CH 3 , CH 2 CH 2 F,
  • Embodiment 21 A compound of Embodiment 20 wherein R ib is CH2CH3 or CH 2 CF 3 .
  • Embodiment 22 A compound of Embodiment 21 wherein Rl b is CH3, CH CH3 or CH 2 CF 3 .
  • Embodiment 23 A compound of Formula I wherein R 2a or R 2b is tert-butyl, isopropyl or cyclopropyl.
  • Embodiment 24 A compound of Embodiment 23 wherein R 2a or R 2b is tert-butyl or isopropyl.
  • Embodiment 25 A compound of Formula I wherein Y 1 and Y 2 are independently CH 2 or O;
  • Embodiment 26. A compound of Embodiment 25 wherein the sum of s, t and u is 2 and the sum of v and w is 0;
  • Embodiment 27 A compound of Embodiment 25 wherein R 26a is C ⁇ C alkyl.
  • Embodiment 28 A compound of Embodiment 27 wherein R 26a and R 26 are CH 3 .
  • Embodiment 29 A compound of Formula I wherein R 3 is H.
  • Embodiment 30 A compound of Formula I wherein R 4 is H.
  • Embodiment 31 A compound of Formula I wherein the carbon atom of R 12 linking to oxygen is bonded to at least one hydrogen atom.
  • Embodiment 32 A compound of Formula I wherein R 5 is CONRl°Rl 1 or C(O)ORl 2 ;
  • Embodiment 34. A compound of Formula I wherein R 5 is CONR l °RH or C(O)ORl 2 .
  • Embodiment 35 A compound of Formula I wherein R 5 is CONRl°RH.
  • Embodiment 38 A compound of Formula I wherein R 10 is C 1 -C 4 alkyl and R 11 is H or
  • a compound of Formula I wherem R 10 is C 1 -C 3 alkyl and R 11 is H or C ⁇ -C 2 alkyl; or R l ° and R 11 are taken together as -CH 2 CH CH 2 CH-.
  • Embodiment 40 A compound of Formula I wherein R 5 is C(O)OR 12 .
  • Embodiment 41. A comound of Formula I wherein R 12 is C 1 -C 3 alkyl.
  • Embodiment 42. A compound of Formula I wherein R 6 is H or F.
  • Embodiment 43. A compound of Formula I wherein R 7 is H or F.
  • Embodiment 44. A compound of Formula I wherein R 8 and R 9 are H or F.
  • Embodiment 45 A compound of Formula I wherein T is C-F or N.
  • Embodiment 46 A compound of Formula I wherein U is C-F or N.
  • Embodiment 47 A compound of Formula I wherein J is J-1.
  • Embodiment 48 A compound of Formula I wherein J is J-2.
  • Embodiment 49 A compound of Formula I wherein J is J-3.
  • Embodiment 50 A compound of Formula I wherein J is J-4.
  • Embodiment 51 A compound of Formula I wherein J is J-5.
  • Embodiment 52 A compound of Formula I wherein J is J-6.
  • Embodiment 53 A compound of Formula I wherein J is J-7.
  • Embodiment 54 A compound of Formula I wherein J is J-8.
  • Embodiment 55 A compound of Formula I wherein J is J-9.
  • Embodiment 56 A compound of Formula I wherein when J is J-1, then R la is other than CH 3 .
  • Embodiment 58 A compound of Formula I wherein when J is J-1, then R la is CH 2 CH 3 or CH 2 CF 3 .
  • Embodiment 59 A compound of Formula I wherein when J is J-5, then R la is
  • Embodiment 60 A compound of Formula I wherein when J is J-5, then R la is CH 2 CH3 or CH 2 CF 3 .
  • Embodiment 61 A compound of Formula I wherein when J is J-1, then R 2a is other than CF 3 .
  • Embodiment 62 A compound of Formula I wherein when J is J-1, then R 2a is other than haloalkyl.
  • Embodiment 63 A compound of Formula I wherein when J is J-3, then R lb is other than CF 3 .
  • Embodiment 64 A compound of Formula I wherein when J is J-3, then R lb is other than fluoroalkyl.
  • Embodiment 65 A compound of Formula I wherein when J is J-1 and R 5 is OR 16 , then
  • R 2a is other than Cj-C 2 alkyl; Embodiment 66. A compound of Formula I wherein when J is J-1, then R 5 is other than
  • Embodiment 67 A compound of Formula I wherein when J is J-3 and R 5 is OR 16 , then
  • R 2b is other than Cj-02 alkyl; Embodiment 68.
  • Embodiment 69 A compound of Formula I wherein when J is J-4 and R 5 is ORl 6 , then
  • R 2a is other than C ] - ⁇ alkyl; Embodiment 70.
  • Embodiment 71 A compound of Formula I wherein when J is J-4 and R 5 is ORl 6 , then
  • Rl b is other than 1-fluoroethyl.
  • Embodiment 72 A compound of Formula I wherein when J is J-4, then R b is other than 1-fluoroethyl.
  • Embodiment 74 A compound of Formula I wherein when J is J-4 and R 5 is ORl 6 , then
  • R ib is CH 2 CH 3 or CH 2 CF 3 .
  • Embodiment 75 A compound of Formula I wherein R 5 is other than OR i6 .
  • Embodiment 76 A compound of Formula I wherein R 9 is other than fluoroalkyl.
  • Embodiment 77 A compound of Formula I wherein when J is J-3, then R 5 is other than
  • Embodiment 78 A compound of Formula I wherein when J is J-4, then R 5 is other than
  • Embodiment 79 A compound of Formula I wherein R 5 is other than -CN.
  • Embodiment 80 A compound of Formula I wherein when J is J-3 and R 5 is -CN, then
  • R 9 is other than alkoxy.
  • Embodiment 81 A compound of Formula I wherein when J is J-3 then R 9 is other than alkoxy.
  • Embodiment 82 A compound of Formula I wherein R 9 is other than alkoxy.
  • Embodiment 83 A compound of Formula I wherein R 9 is H.
  • Embodiment 84 A compound of Formula I wherein Z is CR 9 .
  • Embodiment 85 A compound of Formula I wherein R 11 is other than 1-ethylpropyl.
  • Embodiment 86 A compound of Formula I wherem when J is J-9, R 5 is
  • Embodiment A A compound of Formula I wherein J is J-1, J-2, J-3, J-4, J-5, J-8 or J-9.
  • Embodiment C A compound of Embodiment B wherein at most one of T, U, Y and Z is N.
  • Embodiment D A compound of Embodiment C wherein R 5 is CONR ⁇ R 11 or
  • Embodiment E A compound of Embodiment D wherein R 6 is H or F and R 7 is H or F.
  • Embodiment F A compound of Embodiment E wherein J is J-1, J-3, J-5 or J-8.
  • Embodiment H A compound of Embodiment G wherein R 2a is tert-butyl or isopropyl; and R 8 and R 9 are H or F.
  • Embodiment I A compound of Embodiment I.
  • R la or R ib is selected from the radicals in the group consisting of C ] _-C 3 alkyl, C1-C3 fluoroalkyl, C 2 -C 3 alkenyl, C 2 -C 3 fluoroalkenyl, C 2 -C 3 alkynyl or C 2 - C3 fluoroalkynyl, each radical unbranched and connected through a terminal end carbon atom to the azole ring;
  • R 6 is H or F;
  • R 7 is H or F;
  • R 4 is H;
  • R 26a is C1-C2 alkyl;
  • W is O;
  • Y 1 and Y 2 are independently CH 2 or O; the sum of s, t and u is 2; and the sum of v and w is 0.
  • Embodiment K A compound of Embodiment J wherein R 5 is CONR ⁇ R 1 * or
  • Rl° is H or C1-C4 alkyl
  • R 11 is C ⁇ alkyl
  • Rl 2 is C j A ⁇ alkyl.
  • Embodiment L A compound of Embodiment K wherein R 2a or R 2b is tert-butyl or isopropyl.
  • Embodiment M A compound of Embodiment L wherein J is J-1, J-2, J-3, J-4, J-5, J-8 or J-9.
  • Embodiment O A compound of Embodiment N wherein R 8 and R 9 are H or F.
  • Embodiment P A compound of Embodiment O wherein J is J-1, J-3, J-5 or J-8.
  • R 2a is C ⁇ -Cg alkyl, C j - C 6 haloalkyl, C 2 -C6 alkoxyalkyl, C 2 -Cg alkylthioalkyl, C 2 -C 6 alkenyl, C 2 -Cg haloalkenyl, C 2 -Cg alkynyl, C 2 -C6 haloalkynyl, C 3 -C6 cycloalkyl, C4-C6 alkylcycloalkyl, C -Cg halocycloalkyl, C 4 -C 6 cycloalkylalkyl, C 5 -C 6 alkylcycloalkylalkyl, -CR 20 (OR 2 l)(OR 22 ) or SiR23 R 24 R 25 ; R 2b is Cl -C 6 alkyl, C!-C 6 haloalkyl, C 2 -C 6 alkoxyal
  • R 11 is ⁇ , C1-C5 alkyl, C1-C5 haloalkyl, C 2 -C5 alkenyl, C 3 -C5 haloalkenyl, C 3 -C5 alkynyl, C 3 -C5 cycloalkyl, C4-C5 cycloalkylalkyl, C ⁇ - C 3 alkoxy, C 2 -C5 alkoxyalkyl or C2-C5 alkylthioalkyl.
  • herbicidal compositions of the present invention comprising the compounds of embodiments described above.
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
  • the compounds of the invention e.g., as a composition described herein.
  • 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.
  • a herbicidally effective amount of the compounds of the invention and an antidotally effective amount of a safener.
  • 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 22 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.
  • 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
  • compounds of Formulae 17a through 171 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, 773 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
  • an ester of a carboxylic acid of Formula 3 (identified as Formula 17 below) can be condensed with a substituted amino compound of Formula 2 to provide the compound of Formula la by heating in a high-boiling inert solvent such as ⁇ , ⁇ , ⁇ -trifluorotoluene.
  • a high-boiling inert solvent such as ⁇ , ⁇ , ⁇ -trifluorotoluene.
  • Step C of Example 30 illustrates in Step C of Example 30.
  • 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.
  • 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, 56(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
  • compounds of Formula I can be prepared from other compounds of Formula I (or Iz).
  • a compound of Formula Ic wherein R 30 is ⁇ R lO R 11 or OR 12 (Formula I or Iz wherein R 5 is C(O) ⁇ R 10 R ⁇ 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 Ic wherein R 30 is OR 12 as shown in Scheme 4.
  • R 30 is ORl 2 RSOjs NRlO ll or
  • ester compound of Formula Ic wherein R 30 is OR l2 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 Ic wherein R 30 is NR l °R l2 or ester of Formula Ic wherein R 30 is OR l2 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 ⁇ l is a leaving group such as halogen or OS(O) 2 R 27 .
  • ⁇ l is preferably Cl.
  • 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 le 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 17 wherein R 3 1 is a carbon-based radical such as alkyl (e.g., methyl, ethyl), benzyl, etc. as shown in Scheme 7.
  • 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.
  • 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.
  • 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 R 3l 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.
  • 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 ia X (22) wherein X is a nucleophilic 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. 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 R ia groups can be converted to others on compounds of Formula
  • 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., /. Org. Chem.
  • PPTS pyridinyl -tosylate
  • 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, J. 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 3i 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 J. 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 nucleophilic reaction leaving group (e.g., bromide, iodide, mesylate (OS(O) 2 CH 3 ), inflate (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 can also be prepared using methods or slight modification thereof taught in: J. Heterocycl. Chem.
  • 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.
  • Scheme 11
  • 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(7), 725- 726, Izv. Akad. Nauk SSSR, Ser. Khim. 1981, (6), 1342-8, Izv. Akad. Nauk SSSR, Ser. Khim. 1980, (5), 1071-7, J. Heterocycl. Chem. 1997, 34(2), 537-540, J. Heterocycl. Chem. 1991, 25(8), 1849-52, J. Fluorine Chem. 1988, 59(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.
  • solvents e.g., xylenes, toluene, dioxane, ethylene glycol
  • 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 lb 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 Rl d is R lb is prepared from the compound of Formula If wherein Rl d is H.
  • the compound of Formula If wherein Rl d 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 Rl b 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., J. 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 Rl° 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 nucleophilic 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 b 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 2b is a tertiary alkyl group can be satisfactorily prepared from compounds of Formula 46 by reaction with the appropriate alcohol R 2b OH (48) 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, 54(3), 1125-1134. This method is illustrated by Step A of Example 28.
  • Scheme 19 describes another method for preparing carboxylic ester intermediates of Formula 17k (Formula 17 wherein J is J-8).
  • bromine is added to an aqueous solution of 1,2,3-triazole (49), and 4,5-dibromo-l,2,3-triazole (50) is collected by filtration.
  • This is then alkylated with R 2b using either an alkylating agent of Formula 47 or an alcohol of Formula 48 to provide the compound of Formula 51 using methods analogous to those already described for conversion of Formula 46 to Formula 17k in Scheme 18.
  • the compound of Formula 51 is lithiated using ⁇ -butyllithium in an ether solvent such as ethyl ether or tetrahydrofuran at -70 to -100 °C, optionally magnesium bromide is added, followed by ethyl chloroformate to give the compound of Formula 17k where Rl b is Br.
  • ether solvent such as ethyl ether or tetrahydrofuran at -70 to -100 °C
  • magnesium bromide is added
  • ethyl chloroformate to give the compound of Formula 17k where Rl b is Br.
  • Lithiation using rc-butyllithium in tetrahydrofuran at -78 °C, followed by addition of ethyl chloroformate works well.
  • the compound of Formula 17k where Rl b is Br is useful for preparing compounds of Formula I where J is J-8 and R l is Br.
  • Br can be replaced by other R lb groups such as vinyl by a variety of coupling methods known in the art.
  • the bromine can be replaced by a 1 -alkenyl group through mediation of a palladium catalyst in the Heck Reaction (for reviews, see R. A. Abramovitch et al., Tetrahedron 1988, 44(11), 3039-3071; W. Cabri and I. Candiani, Synthesis 1995, 2S(1), 2- 7; and R. F. Heck, "Palladium-catalyzed Vinylation of Organic Halides", Chapter 2 in Organic Reactions, Vol. 27, Wiley: New York, 1982, pp. 345-390).
  • 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.
  • Carboxylic esters of Formula 171 (Formula 17 wherein J is J-9) can be prepared by the general method shown in Scheme 20.
  • a iminoacetate of Formula 52 is reacted with a carboxylic acid hydrazide of Formula 53 in a suitable solvent such as dichloromethane to give the adduct of Formula 54.
  • a suitable solvent such as dichloromethane
  • the compound of Formula 54 is then cyclized to give the triazole of Formula 55 by heating to a sufficiently high temperature, typically around 200 °C.
  • a sufficiently high temperature typically around 200 °C.
  • the triazole of Formula 55 is then alkylated using R ia X (22) in the presence of a base and solvent, analogous to the alkylation of pyrazoles already described as a modification of the method of Scheme 8.
  • This method is further illustrated by Steps A and B of Example 30 below.
  • 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 21.
  • Scheme 21
  • 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 nucleophilic substitution facilitating introduction of amino by displacement of leaving groups such as halogen.
  • Formula 2b (Formula 2 wherein R 4 is H and R 5 is CO 2 R l2 ) 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 C1-C5 alkyl, C 2 -C 5 haloalkyl, C 3 -C5 alkenyl, C 3 -C 5 haloalkenyl, C 3 -C 5 alkynyl, C 3 -C5 cycloalkyl or C 4 -C5 cycloalkylalkyl can be prepared as shown in Scheme 22.
  • 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 11 using the thionating reagents already described for the method of Scheme 3.
  • Step A Preparation of ethyl 2-hydroxy-5,5-dimethyl-4-oxo-2-hexenoate
  • Step B Preparation of ethyl 5 -(1,1 -dimethylethyl)-lH-pyrazole-3-carboxylate
  • Step C Preparation of ethyl 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylate
  • Step D Preparation of 3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazole-5-carboxylic acid
  • Step F Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-ylj- carbonyl]amino]benzoate 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]- amino]benzoic acid
  • Step C Preparation of 2-fluoroethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
  • 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. l ⁇ NMR (CDC1 3 ) ⁇ 8.64 (dd, 1 ⁇ ), 8.32 (m, 1 ⁇ ), 7.38 (t, 1 ⁇ ), 4.44 (q, 2 ⁇ ), 1.40 (t, 3H). Step B: Preparation of ethyl 3-amino-4-fluorobenzoate
  • Step C Preparation of ethyl 3-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-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.
  • 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]- 2-fluorophenyl] - lH-pyrazole-5 -carboxamide
  • 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
  • Step D Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-
  • Step B Preparation of 6-(acetylamino)-2-pyridinecarboxylic acid
  • Step A 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
  • Step D Preparation of methyl 6-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]- carbonyl]amino]-2-pyridinecarboxylate
  • 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- ⁇ yrazol-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 Preparation of 4-(acetylamino)-2-pyridinecarboxylic acid
  • 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-(acetylarnino)-2-pyridinecarboxylic acid (i.e. the product of Step B) (3.4 g) to the title compound (0.92 g).
  • 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
  • Step A Preparation of 2-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-5-yl]carbonyl]- amino-4-pyridinecarboxylic acid
  • Step A A procedure analogous to that of Example 9, Step A was used to convert methyl 2- [ [[3 -( 1 , 1 -dimethylethyl)- 1 -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-(l,l-dimethylethyl)-l-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 2- ⁇ entynoate (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.
  • Ethyl l-(l,l-dimethylethyl)-4-ethyl-lH-pyrazole-3-carboxylate (0.78 g) was the minor isomer.
  • l ⁇ ⁇ MR (CDCI3) ⁇ major isomer: 7.92 (s, 1 ⁇ ), 4.2 (q, 2 ⁇ ), 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 1 -( 1 , 1 -dimethylethyl)-4-ethyl- lH-pyrazole-3-carboxylic acid
  • Step C Preparation of N-[3-[(diethylamino)carbonyl]phenyl]-l-(l,l-dimethylethyl)-
  • 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- ⁇ yrazole-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.
  • l H 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)-
  • 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
  • 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 N) 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 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-
  • 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]-
  • Step B Preparation of 5-amino-3-pyridinecarboxylic acid To a mixture of 5-bromo-3-pyridinecarboxylic acid (i.e. the product of Step A) (25 g,
  • Step D Preparation of ethyl 5-[[[3-(l,l-dimethylethyl)-l-ethyl-lH-pyrazol-
  • 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-ethy ⁇ -lH-pyrazol- 5-yl]carbonyl]amino]-N,N-diethyl-3- ⁇ yridinecarboxamide
  • Step A Preparation of 3, 3 -dimethyl- l-(triphenylphosphoranylidene)-2-butanone
  • triphenylphosphine 10.74 g, 40.9 mmol
  • chloroform 25 mL
  • 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).
  • Step B Preparation of butyl (2E)-5,5-dimethyl-4-oxo-2-hexenoate
  • Step C Preparation of butyl 3-(l,l-dimethylethyl)-l-ethyl-4,5-dihydro-lH-pyrazole-
  • 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 p ⁇ of the residual solution was adjusted to 2 using hydrochloric acid (1 ⁇ ). The cloudy mixture was extracted with ethyl acetate (2x).
  • 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.
  • 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).
  • 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 (MgSO 4 ) 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- 3-cyclopentapyrazolecarboxylate and ethyl 1 -ethyl- 1 ,4,5 ,6-tetrahydro-6,6- dimethyl-3-cyclopentapyrazolecarboxylate
  • 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.
  • 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 l-ethyl-l,4,5,6-tetrahydro-6,6-dimethyl-3-cyclopentapyrazolecarboxylate. These fractions were combined and concentrated to provide l-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- 3-cyclopentapyrazolecarboxylic acid
  • Step E Preparation of N-[5-[(dimethylamino)carbonyl]-2-fluorophenyl]-2-ethyl-
  • Step A Preparation of ethyl 5-ethyl-l,2,3-triazole-4-carboxylate
  • Ethyl 2-pentynoate (16.6 g, 0.132 mol) and xrimethylsilylazide (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).
  • 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
  • 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-xriazole-
  • Ethyl 2-(l,l-dimethylethyl)-5-ethyl-2H-l,2,3-triazole-4-carboxylate i ⁇ NMR (CDC1 3 ) ⁇ 4.41 (q, 2 ⁇ ), 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 i ⁇ NMR (CDCI3) ⁇ 4.40 (q, 2 ⁇ ), 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-
  • Step A Preparation of ethyl 5-(l,l-dimethylethyl)-lH-l,2,4-triazole-3-carboxylate
  • ethyl ethoxyiminoacetate (15.3 g, 106 mmol)
  • 2,2-dimethylpropanoic acid hydrazide (11.7 g, 101 mmol)
  • dichloromethane 320 mL
  • the reaction mixture was concentrated in vacuo to leave a residue (about 75 mL), which was diluted with hexane (75 mL) to form a white solid precipitate.
  • Step B Preparation of ethyl 3-(l,l-dimethylethyl)-l-ethyl-lH-l,2,4-triazo ⁇ e-
  • Step C Preparation of 3-(l,l-dimethylethyl)-l-ethyl-N-[3-[(ethylamino)carbonyl]- phenyl]-lH-l,2,4-triazole-5-carboxamide
  • t means tertiary, s means secondary, n means normal, i means iso, c means cyclo, Me means methyl, Et means ethyl, Pr means propyl, ⁇ ' -Pr means isopropyl, Bu means butyl, Ph means phenyl, OMe means methoxy, OEt means ethoxy, SMe means methylthio, SEt means ethylthio, CN means cyano, NO 2 means nitro, TMS means trimethylsilyl, S(O)Me means methylsulfinyl, and S(O) 2 Me means methylsulfonyl.
  • 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- u ;
  • T, U, Y and Z are CH
  • R la is Et ;
  • R 2a is tert-Bi l ;
  • T , U and Y are CH ;
  • Z is CF si B ⁇ Bl Bl
  • R la is Et ;
  • R 2a is tert-Bi i ;
  • T is CF ;
  • R la is Me ;
  • R 2a is tert-Bu ;
  • U is CF ;
  • T, Y and Z are CH
  • R la is Me ;
  • R 2a is terf-B u ;
  • T, U, Y and Z are CH
  • R la is Et ;
  • R 2a is isopro] jyl ;
  • T, U, Y and Z are CH
  • R ia is Et ;
  • R 2a is isopro Dyl ;
  • U is CF ;
  • Rl a is Et ;
  • R 2a is cyclop ropyl ;
  • T, TJ, Y and Z are Ci I
  • R ia is CH 2 CH 2 F ; R 2a i s tert-Bu ; T, TJ, Y and Z are CH g5.
  • Bl Bl El
  • R ia is CH 2 CH 2 F ; R 2a i s tert-Bu ; TJ is CF ; T, Y an d Z are CH
  • R la is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • TJ is CF ;
  • T, Y and Z are CH
  • Rl a is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • U is CF ;
  • T, Y and Z are CH
  • R 1 ⁇ is CH 2 CF 3 ;
  • R 2a is tert-Bu ;
  • T, TJ, Y and Z are ( :H
  • R ia is Me ; R 2a is tert-Bu ; U is N ; T, Y and Z are CH
  • R la is Et ;
  • R 2a is tert-Bi ⁇ ;
  • U is N ;
  • T, Y and Z are CH
  • R la is Et ;
  • R 2a is ferr-B ⁇ i ;
  • T is N ;
  • U, Y and Z are Cl 3
  • R ia is Et ;
  • R 2a is tert-Bu ;
  • T is N ;
  • U, Y and Z are CH
  • R ia is Et ; R 2a is tert-Bi 1 ; T is N ; TJ, Y and Z are C] H
  • R ia is Et ;
  • R 2a is terr-Bi i ;
  • T , U and Y are CH ;
  • Z is N
  • Rl a is CH 2 CH 3 ;
  • R 2a is Si(CH 3 ) 3 ;

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

La présente invention concerne des composés représentés par la formule générale (I), et leurs N-oxydes et certains de leurs sels admis pour l'agriculture, ces produits convenant à la lutte contre les végétaux parasites. Dans la formule générale (I), le 'J' se détaille selon les formules J-1 à J-9. Pour l'ensemble de la formulation, les R1a, R1b, R1c, R2a, R2b, R3, R4, R5, T, U, W, Y et Z sont tels que définis dans les spécifications de l'invention. L'invention concerne également des compositions contenant les composés représentés par la formule générale (I) ainsi que des procédés permettant de lutter contre les végétaux parasites, et ce, en mettant en contact la végétation ou son environnement avec une quantité suffisante d'un composé représenté par la formule générale (I). L'invention concerne en outre des mélanges et des compositions comprenant, d'une part une quantité herbicide suffisante d'un composé représenté par la formule spécifique (Iz) dans laquelle les J, R1a, R1b, R1c, R2a, R2b, R3, R4, R5, T, U, W, Y et Z sont tels que définis dans les spécifications de l'invention, et d'autre part une quantité suffisante d'un autre herbicide ou d'un phytoprotecteur. L'invention concerne enfin un procédé de lutte sélective contre les végétaux parasites dans une culture, par mise en contact du lieu d'une culture avec une quantité suffisante d'un composé représenté par la formule spécifique (Iz) et d'une quantité suffisante d'un phytoprotecteur.
PCT/US2004/010711 2003-05-27 2004-04-07 Herbicides a base d'azolecarboxamide Ceased WO2004106324A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/096,104 US20060069132A1 (en) 2004-04-07 2005-03-31 Azolecarboxamide herbicides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US47386603P 2003-05-27 2003-05-27
US60/473,866 2003-05-27
USPCT/US03/32965 2003-10-15
PCT/US2003/032965 WO2004035545A2 (fr) 2002-10-18 2003-10-15 Herbicides a base d'azolecarboxamide

Related Child Applications (1)

Application Number Title Priority Date Filing Date
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Publication Number Publication Date
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US7390810B2 (en) 2003-05-01 2008-06-24 Bristol-Myers Squibb Company Pyrazole-amine compounds useful as kinase inhibitors
WO2007109172A3 (fr) * 2006-03-16 2009-04-30 Renovis Inc Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 et leurs utilisations
JP2009519909A (ja) * 2005-12-09 2009-05-21 ザ リージェンツ オブ ザ ユニバーシティ オブ カリフォルニア 小分子によるヒト癌におけるｇｌｉタンパク質ターゲティング
WO2009049180A3 (fr) * 2007-10-11 2009-05-28 Vertex Pharma Amides d'hétéroaryle utilisés comme inhibiteurs de canaux sodiques sensibles à une différence de potentiel
JP2009530304A (ja) * 2006-03-16 2009-08-27 レノビス， インコーポレイテッド Ｐ２ｘ７調節因子としてのビシクロへテロアリール化合物およびその使用
EP2184273A1 (fr) 2008-11-05 2010-05-12 Bayer CropScience AG Composés substitués par l'halogène comme pesticides
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EP2253617A1 (fr) 2009-05-20 2010-11-24 Bayer CropScience AG Composés halogénés comme pesticides
WO2011003796A1 (fr) 2009-07-06 2011-01-13 Basf Se Composés pyridazine destinés à la lutte contre les nuisibles invertébrés
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US8263806B2 (en) 2005-12-01 2012-09-11 Basf Se Method for producing sulfonamides
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US9125414B2 (en) 2009-07-24 2015-09-08 Basf Se Pyridine derivatives compounds for controlling invertebrate pests
WO2016174049A1 (fr) 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Combinaisons anti-parasitaires comprenant des composés à substitution halogène
WO2017043563A1 (fr) * 2015-09-08 2017-03-16 参天製薬株式会社 Procédé de production de pyridine-carboxamide
US9675070B2 (en) 2013-03-04 2017-06-13 Bayer Cropscience Aktiengesellschaft Halogen-substituted compounds
US9920002B2 (en) 2007-10-12 2018-03-20 Basf Se Methods for producing sulfonic acid diamides
US9936699B2 (en) 2014-08-08 2018-04-10 Bayer Cropscience Aktiengesellschaft Halogen-substituted compounds
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KR20200116918A (ko) * 2018-01-26 2020-10-13 엔터프라이즈 테라퓨틱스 리미티드 화합물
CN115572282A (zh) * 2021-07-05 2023-01-06 华东理工大学 含芳杂环结构的吡唑酰胺类化合物及其制备方法和应用

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