WO2004035545A2 - Herbicides a base d'azolecarboxamide - Google Patents

Herbicides a base d'azolecarboxamide Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
haloalkyl
alkenyl
compound
ethyl
Prior art date
Application number
PCT/US2003/032965
Other languages
English (en)
Other versions
WO2004035545A3 (fr
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
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU2003301443A priority Critical patent/AU2003301443A1/en
Priority to PCT/US2004/010711 priority patent/WO2004106324A1/fr
Publication of WO2004035545A2 publication Critical patent/WO2004035545A2/fr
Publication of WO2004035545A3 publication Critical patent/WO2004035545A3/fr

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

La présente invention concerne des composés de formule (I), ainsi que leurs N-oxydes et des sels appropriés pour l'agriculture, utiles pour lutter contre la végétation adventice. Dans ladite formule, J représente (J-1), (J-2),(J-3), (J-4), (J-5), (J-6), (J-7), (J-8) et R1a, R1b, R1c, R2a, R2b, R3, R4, R5, T, U, W, Y et Z sont tels que définis selon l'invention. L'invention concerne également des compositions contenant lesdits composés de formule (I) et un procédé de lutte contre la végétation adventice qui consiste à mettre en contact la végétation ou son environnement avec une quantité efficace d'un composé de formule (I). L'invention concerne également des mélanges et des compositions comprenant une quantité efficace d'un point de vue herbicide d'un composé de formule (Iz) dans laquelle J, R1a, R1b, R1c, R2a, R2b, R3, R4, R5, T, U, W, Y et Z sont tels que définis selon l'invention ; et une quantité efficace d'un autre herbicide ou d'un phytoprotecteur. L'invention concerne également un procédé de lutte sélective contre la végétation adventice dans une culture qui consiste à mettre en contact le locus d'une plante cultivée avec une quantité efficace d'un composé de formule (Iz) et avec une quantité efficace d'un phytoprotecteur.
PCT/US2003/032965 2002-10-18 2003-10-15 Herbicides a base d'azolecarboxamide WO2004035545A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2003301443A AU2003301443A1 (en) 2002-10-18 2003-10-15 Azolecarboxamide herbicides
PCT/US2004/010711 WO2004106324A1 (fr) 2003-05-27 2004-04-07 Herbicides a base d'azolecarboxamide

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US41969602P 2002-10-18 2002-10-18
US60/419,696 2002-10-18
US47386603P 2003-05-27 2003-05-27
US60/473,866 2003-05-27

Publications (2)

Publication Number Publication Date
WO2004035545A2 true WO2004035545A2 (fr) 2004-04-29
WO2004035545A3 WO2004035545A3 (fr) 2004-08-05

Family

ID=32110262

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/032965 WO2004035545A2 (fr) 2002-10-18 2003-10-15 Herbicides a base d'azolecarboxamide

Country Status (3)

Country Link
AR (1) AR044745A1 (fr)
AU (1) AU2003301443A1 (fr)
WO (1) WO2004035545A2 (fr)

Cited By (73)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007009717A1 (fr) * 2005-07-18 2007-01-25 Syngenta Participations Ag Derives de pyrazole-4- carboxamide utilises comme microbiocides
EP1860942A2 (fr) * 2005-03-24 2007-12-05 Renovis, Inc. Composes bicycloheteroaryle utilises en tant que modulateurs de p2x7 et leurs utilisations
WO2008029084A1 (fr) * 2006-09-06 2008-03-13 Syngenta Limited Composés et compositions herbicides
EP1911751A1 (fr) * 2005-06-21 2008-04-16 Mitsui Chemicals, Inc. Derive d'amide et pesticide contenant un tel compose
US7390810B2 (en) 2003-05-01 2008-06-24 Bristol-Myers Squibb Company Pyrazole-amine compounds useful as kinase inhibitors
EP1968577A2 (fr) * 2005-12-09 2008-09-17 The Regents of the University of California Ciblage de proteines gli dans un cancer humain par de petites molecules
EP1996585A2 (fr) * 2006-03-16 2008-12-03 Renovis, Inc. Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 modulators et leurs utilisations
EP2001474A2 (fr) * 2006-03-16 2008-12-17 Renovis, Inc. Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 et leurs utilisations
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés
EP2184273A1 (fr) 2008-11-05 2010-05-12 Bayer CropScience AG Composés substitués par l'halogène comme pesticides
WO2010099279A1 (fr) * 2009-02-27 2010-09-02 Dow Agrosciences Llc N-alcoxy-amides de 6-(phényle substitué)-4-aminopicolinates et de 2-(phényle substitué)-6-amino-4-pyrimidinecarboxylates et leur utilisation comme herbicides sélectifs pour les cultures
US7816371B2 (en) 2006-03-16 2010-10-19 Renovis, Inc. Bicycloheteroaryl compounds as P2X7 modulators and uses thereof
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
EP2308866A1 (fr) 2009-10-09 2011-04-13 Bayer CropScience AG Phenylpyri(mi)dinylpyrazoles et leur utilisation comme fongicides
WO2011117213A1 (fr) 2010-03-23 2011-09-29 Basf Se Composés de pyridazine pour lutter contre les ravageurs invertébrés
AU2004315003B2 (en) * 2004-01-28 2011-11-17 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US8263806B2 (en) 2005-12-01 2012-09-11 Basf Se Method for producing sulfonamides
WO2012126766A1 (fr) 2011-03-18 2012-09-27 Bayer Cropscience Ag Dérivés de n-(3-carbamoylphényl)-1h-pyrazole-5-carboxamide et leur utilisation pour lutter contre des animaux nuisibles
WO2013039990A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
WO2013040117A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
WO2013040021A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
WO2013092522A1 (fr) 2011-12-20 2013-06-27 Bayer Intellectual Property Gmbh Nouveaux amides aromatiques insecticides
US8642597B2 (en) 2007-08-27 2014-02-04 Basf Se Pyrazole compounds for controlling invertebrate pests
US8710056B2 (en) 2009-07-06 2014-04-29 Basf Se Pyridazine compounds for controlling invertebrate pests
WO2014122083A1 (fr) 2013-02-06 2014-08-14 Bayer Cropscience Ag Dérivés de pyrazole halosubstitués en tant qu'agents phytosanitaires
WO2014151255A1 (fr) 2013-03-15 2014-09-25 Monsanto Technology Llc Méthodes et compositions pour lutter contre les mauvaises herbes
US8853125B2 (en) 2008-09-24 2014-10-07 Basf Se Pyrazole compounds for controlling invertebrate pests
WO2015101622A1 (fr) 2014-01-03 2015-07-09 Bayer Cropscience Ag Nouveaux pyrazolyl-hétéroarylamides utilisables comme pesticides
WO2015108982A2 (fr) 2014-01-15 2015-07-23 Monsanto Technology Llc Procédés et compositions pour la lutte contre les mauvaises herbes utilisant des polynucléotides epsps
CN104829613A (zh) * 2015-04-13 2015-08-12 上海创诺医药集团有限公司 二芳基取代的吡唑并环类衍生物、其制备方法及其在医药领域的应用
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US9125414B2 (en) 2009-07-24 2015-09-08 Basf Se Pyridine derivatives compounds for controlling invertebrate pests
CN105646395A (zh) * 2014-12-02 2016-06-08 沈阳中化农药化工研发有限公司 一种噻唑酰胺类化合物及其应用
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
WO2016174049A1 (fr) 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Combinaisons anti-parasitaires comprenant des composés à substitution halogène
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US9675070B2 (en) 2013-03-04 2017-06-13 Bayer Cropscience Aktiengesellschaft Halogen-substituted compounds
WO2017157885A1 (fr) 2016-03-16 2017-09-21 Bayer Cropscience Aktiengesellschaft Dérivés de n-(cyanobenzyl)-6-(cyclopropylcarbonylamino)-4-(phényl)-pyridine-2-carboxamide et composes apparentés utilisés comme agents phytosanitaires pesticides
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
EP3284739A1 (fr) 2017-07-19 2018-02-21 Bayer CropScience Aktiengesellschaft Composés (hét)aryl substitués comme produit de lutte contre les parasites
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
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
CN108719301A (zh) * 2018-08-29 2018-11-02 浙江工业大学 一种1-甲基-3-三氟甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN108863934A (zh) * 2018-08-29 2018-11-23 浙江工业大学 一种1-甲基-3-二氟甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN108991003A (zh) * 2018-08-29 2018-12-14 浙江工业大学 一种含吡唑环的酰胺衍生物在制备除草剂中的应用
CN109156471A (zh) * 2018-08-29 2019-01-08 浙江工业大学 一种1，3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN109169693A (zh) * 2018-08-29 2019-01-11 浙江工业大学 一种新型含吡唑环的酰胺类化合物在制备除草剂中的应用
CN109293640A (zh) * 2018-10-31 2019-02-01 青岛清原化合物有限公司 一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途
US10239830B2 (en) * 2015-02-11 2019-03-26 Icahn School Of Medicine At Mount Sinai Benzenesulfonamide upregulators of NPC1 for Neimann-Pick disease and other lysosomal storage disorders
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
CN112119063A (zh) * 2018-05-18 2020-12-22 富士胶片株式会社 3-二氟甲基吡唑化合物的制造方法及3-二氟甲基吡唑-4-羧酸化合物的制造方法以及吡唑烷化合物
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0253775A (ja) * 1988-08-18 1990-02-22 Nissan Chem Ind Ltd ピラゾールカルボキサミド誘導体及び除草剤
JPH02129171A (ja) * 1988-11-08 1990-05-17 Nissan Chem Ind Ltd ピラゾールカルボキサニリド誘導体及び有害生物防除剤

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
J.J. PARLOW: "Synthesis of pyrazolecarbonylaminopyridinecarboxamides as herbicides" JOURNAL OF HETEROCYCLIC CHEMISTRY., vol. 35, 1998, pages 1493-1499, XP002273124 HETEROCORPORATION. PROVO., US ISSN: 0022-152X *
PARLOW JOHN J ET AL: "Utility of Complementary Molecular Reactivity and Molecular Recognition (CMR/R) Technology and Polymer -Supported Reagents in the Solution-Phase Synthesis of Heterocyclic Carboxamides" JOURNAL OF ORGANIC CHEMISTRY, AMERICAN CHEMICAL SOCIETY. EASTON, US, vol. 62, 1997, pages 5908-5919, XP002213047 ISSN: 0022-3263 *

Cited By (144)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7390810B2 (en) 2003-05-01 2008-06-24 Bristol-Myers Squibb Company Pyrazole-amine compounds useful as kinase inhibitors
US7414056B2 (en) 2003-05-01 2008-08-19 Bristol-Myers Squibb Company Pyrazole-amide compounds useful as kinase inhibitors
US8563736B2 (en) 2004-01-28 2013-10-22 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US11760742B2 (en) 2004-01-28 2023-09-19 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US10435385B2 (en) 2004-01-28 2019-10-08 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
AU2004315003B2 (en) * 2004-01-28 2011-11-17 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US8710234B2 (en) 2004-01-28 2014-04-29 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US10995081B2 (en) 2004-01-28 2021-05-04 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US9920026B2 (en) 2004-01-28 2018-03-20 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US9185912B2 (en) 2004-01-28 2015-11-17 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
US8168825B2 (en) 2004-01-28 2012-05-01 Mitsui Chemicals, Inc. Amide derivatives, process for preparation thereof and use thereof as insecticide
EP1860942A4 (fr) * 2005-03-24 2010-03-17 Renovis Inc Composes bicycloheteroaryle utilises en tant que modulateurs de p2x7 et leurs utilisations
EP1860942A2 (fr) * 2005-03-24 2007-12-05 Renovis, Inc. Composes bicycloheteroaryle utilises en tant que modulateurs de p2x7 et leurs utilisations
EP1865774A4 (fr) * 2005-03-24 2010-03-24 Renovis Inc Composes bicycloheteroaryle servant de modulateurs de p2x7 et utilisations de ceux-ci
EP1865774A1 (fr) * 2005-03-24 2007-12-19 Renovis, Inc. Composes bicycloheteroaryle servant de modulateurs de p2x7 et utilisations de ceux-ci
AU2006260299B2 (en) * 2005-06-21 2012-06-28 Mitsui Chemicals, Inc. Amide derivative and insecticide containing the same
AU2006260299B8 (en) * 2005-06-21 2012-11-29 Mitsui Chemicals, Inc. Amide derivative and insecticide containing the same
JP5149003B2 (ja) * 2005-06-21 2013-02-20 三井化学アグロ株式会社 アミド誘導体ならびに該化合物を含有する殺虫剤
US8067638B2 (en) 2005-06-21 2011-11-29 Mitsui Chemicals, Inc. Amide derivative and insecticide containing the same
EP1911751A4 (fr) * 2005-06-21 2010-10-20 Mitsui Chemicals Agro Inc Derive d'amide et pesticide contenant un tel compose
EP1911751A1 (fr) * 2005-06-21 2008-04-16 Mitsui Chemicals, Inc. Derive d'amide et pesticide contenant un tel compose
WO2007009717A1 (fr) * 2005-07-18 2007-01-25 Syngenta Participations Ag Derives de pyrazole-4- carboxamide utilises comme microbiocides
US8003626B2 (en) 2005-07-18 2011-08-23 Syngenta Crop Protection, Inc. Pyrazole-4-carboxamide derivatives as microbiocides
US8263806B2 (en) 2005-12-01 2012-09-11 Basf Se Method for producing sulfonamides
EP1968577A2 (fr) * 2005-12-09 2008-09-17 The Regents of the University of California Ciblage de proteines gli dans un cancer humain par de petites molecules
EP1968577A4 (fr) * 2005-12-09 2011-07-20 Univ California Ciblage de proteines gli dans un cancer humain par de petites molecules
EP2001474A2 (fr) * 2006-03-16 2008-12-17 Renovis, Inc. Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 et leurs utilisations
US7816371B2 (en) 2006-03-16 2010-10-19 Renovis, Inc. Bicycloheteroaryl compounds as P2X7 modulators and uses thereof
EP1996585A4 (fr) * 2006-03-16 2010-03-10 Renovis Inc Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 modulators et leurs utilisations
US8546579B2 (en) 2006-03-16 2013-10-01 Evotec (Us) Inc. Bicycloheteroaryl compounds as P2X7 modulators and uses thereof
EP2001474A4 (fr) * 2006-03-16 2010-03-10 Renovis Inc Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 et leurs utilisations
JP2009541206A (ja) * 2006-03-16 2009-11-26 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
EP1996585A2 (fr) * 2006-03-16 2008-12-03 Renovis, Inc. Composés de bicyclohétéroaryle en tant que modulateurs de p2x7 modulators et leurs utilisations
WO2008029084A1 (fr) * 2006-09-06 2008-03-13 Syngenta Limited Composés et compositions herbicides
US9204647B2 (en) 2007-08-27 2015-12-08 Basf Se Pyrazole compounds for controlling invertebrate pests
US8642597B2 (en) 2007-08-27 2014-02-04 Basf Se Pyrazole compounds for controlling invertebrate pests
US9920002B2 (en) 2007-10-12 2018-03-20 Basf Se Methods for producing sulfonic acid diamides
US10888579B2 (en) 2007-11-07 2021-01-12 Beeologics Inc. Compositions for conferring tolerance to viral disease in social insects, and the use thereof
US9375008B2 (en) 2008-09-24 2016-06-28 Basf Se Pyrazole compounds for controlling invertebrate pests
JP2012503622A (ja) * 2008-09-24 2012-02-09 ビーエーエスエフ ソシエタス・ヨーロピア 無脊椎動物系害虫を防除するためのピラゾール化合物
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés
US8853125B2 (en) 2008-09-24 2014-10-07 Basf Se Pyrazole compounds for controlling invertebrate pests
CN102224149B (zh) * 2008-09-24 2014-09-10 巴斯夫欧洲公司 防治无脊椎动物害虫的吡唑化合物
US8729083B2 (en) 2008-09-24 2014-05-20 Basf Se Pyrazole compounds for controlling invertebrate pests
CN102224149A (zh) * 2008-09-24 2011-10-19 巴斯夫欧洲公司 防治无脊椎动物害虫的吡唑化合物
EP2184273A1 (fr) 2008-11-05 2010-05-12 Bayer CropScience AG Composés substitués par l'halogène comme pesticides
JP2012507482A (ja) * 2008-11-05 2012-03-29 バイエル・クロップサイエンス・アーゲー 新規ハロゲン置換化合物
EP2352723B1 (fr) * 2008-11-05 2016-11-23 Bayer Intellectual Property GmbH Composés pesticides de pyrazole carboxamides à substitution n-aryle ou n-hétéroaryle
US20150099766A1 (en) * 2008-11-05 2015-04-09 Bayer Cropscience Ag Novel halogen-substituted compounds
US8946234B2 (en) 2008-11-05 2015-02-03 Bayer Cropscience Ag Halogen-substituted compounds
EP2352723A2 (fr) * 2008-11-05 2011-08-10 Bayer CropScience AG Composés substitués par halogène utilisés comme pesticides
US8889694B2 (en) 2009-02-27 2014-11-18 Dow Agrosciences, Llc. N-alkoxyamides of 6-(substituted phenyl)-4-aminopicolinates and 2-(substituted phenyl)-6-amino-4-pyrimidinecarboxylates and their use as selective herbicides for crops
WO2010099279A1 (fr) * 2009-02-27 2010-09-02 Dow Agrosciences Llc N-alcoxy-amides de 6-(phényle substitué)-4-aminopicolinates et de 2-(phényle substitué)-6-amino-4-pyrimidinecarboxylates et leur utilisation comme herbicides sélectifs pour les cultures
US8536331B2 (en) 2009-02-27 2013-09-17 Dow Agrosciences, Llc. N-alkoxyamides of 6-(trisubstituted phenyl)-4-aminopicolinates and their use as selective herbicides for crops
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
US9029639B2 (en) 2009-07-06 2015-05-12 Basf Se Pyridazine compounds for controlling invertebrate pests
US8710056B2 (en) 2009-07-06 2014-04-29 Basf Se Pyridazine compounds for controlling invertebrate pests
US9125414B2 (en) 2009-07-24 2015-09-08 Basf Se Pyridine derivatives compounds for controlling invertebrate pests
EP2784071A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784070A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784072A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
EP2784073A1 (fr) 2009-10-09 2014-10-01 Bayer CropScience AG 3-phenyl-4-pyri(mi)dinyl-1h-pyrazoles et leur utilisation comme fongicides
WO2011042389A2 (fr) 2009-10-09 2011-04-14 Bayer Cropscience Ag Phenylpyri(mi)dinylazoles
EP2308866A1 (fr) 2009-10-09 2011-04-13 Bayer CropScience AG Phenylpyri(mi)dinylpyrazoles et leur utilisation comme fongicides
US10801028B2 (en) 2009-10-14 2020-10-13 Beeologics Inc. Compositions for controlling Varroa mites in bees
US9121022B2 (en) 2010-03-08 2015-09-01 Monsanto Technology Llc Method for controlling herbicide-resistant plants
US11812738B2 (en) 2010-03-08 2023-11-14 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
US9988634B2 (en) 2010-03-08 2018-06-05 Monsanto Technology Llc Polynucleotide molecules for gene regulation in plants
WO2011117213A1 (fr) 2010-03-23 2011-09-29 Basf Se Composés de pyridazine pour lutter contre les ravageurs invertébrés
WO2011117806A2 (fr) 2010-03-23 2011-09-29 Basf Se Composés pyridazine pour lutter contre les nuisibles invertébrés
US9126945B2 (en) 2011-03-18 2015-09-08 Bayer Intellectual Property Gmbh N-(3-carbamoylphenly)-1H-pyrazole-5-carboxamide derivatives and the use thereof for controlling animal pests
WO2012126766A1 (fr) 2011-03-18 2012-09-27 Bayer Cropscience Ag Dérivés de n-(3-carbamoylphényl)-1h-pyrazole-5-carboxamide et leur utilisation pour lutter contre des animaux nuisibles
US9422557B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
WO2013040117A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
WO2013039990A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
US9422558B2 (en) 2011-09-13 2016-08-23 Monsanto Technology Llc Methods and compositions for weed control
WO2013040021A1 (fr) 2011-09-13 2013-03-21 Monsanto Technology Llc Procédés et compositions de lutte contre les mauvaises herbes
US9416363B2 (en) 2011-09-13 2016-08-16 Monsanto Technology Llc Methods and compositions for weed control
US10829828B2 (en) 2011-09-13 2020-11-10 Monsanto Technology Llc Methods and compositions for weed control
US10760086B2 (en) 2011-09-13 2020-09-01 Monsanto Technology Llc Methods and compositions for weed control
EP3434780A1 (fr) 2011-09-13 2019-01-30 Monsanto Technology LLC Procédés et compositions de lutte contre les mauvaises herbes
EP3434779A1 (fr) 2011-09-13 2019-01-30 Monsanto Technology LLC Procédés et compositions de lutte contre les mauvaises herbes
EP3296402A2 (fr) 2011-09-13 2018-03-21 Monsanto Technology LLC Procédés et compositions pour lutter contre les mauvaises herbes
US10806146B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
US10808249B2 (en) 2011-09-13 2020-10-20 Monsanto Technology Llc Methods and compositions for weed control
EP3382027A2 (fr) 2011-09-13 2018-10-03 Monsanto Technology LLC Procédés et compositions de lutte contre les mauvaises herbes
US9204645B2 (en) 2011-12-20 2015-12-08 Bayer Intellectual Property Gmbh Insecticidal aromatic amides
WO2013092522A1 (fr) 2011-12-20 2013-06-27 Bayer Intellectual Property Gmbh Nouveaux amides aromatiques insecticides
US10240161B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10934555B2 (en) 2012-05-24 2021-03-02 Monsanto Technology Llc Compositions and methods for silencing gene expression
US10240162B2 (en) 2012-05-24 2019-03-26 A.B. Seeds Ltd. Compositions and methods for silencing gene expression
US10041068B2 (en) 2013-01-01 2018-08-07 A. B. Seeds Ltd. Isolated dsRNA molecules and methods of using same for silencing target molecules of interest
US10683505B2 (en) 2013-01-01 2020-06-16 Monsanto Technology Llc Methods of introducing dsRNA to plant seeds for modulating gene expression
WO2014122083A1 (fr) 2013-02-06 2014-08-14 Bayer Cropscience Ag Dérivés de pyrazole halosubstitués en tant qu'agents phytosanitaires
US9487489B2 (en) 2013-02-06 2016-11-08 Bayer Cropscience Aktiengesellschaft Halogen-substituted pyrazole derivatives as pest-control agents
US9675070B2 (en) 2013-03-04 2017-06-13 Bayer Cropscience Aktiengesellschaft Halogen-substituted compounds
US10612019B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10609930B2 (en) 2013-03-13 2020-04-07 Monsanto Technology Llc Methods and compositions for weed control
US10568328B2 (en) 2013-03-15 2020-02-25 Monsanto Technology Llc Methods and compositions for weed control
WO2014151255A1 (fr) 2013-03-15 2014-09-25 Monsanto Technology Llc Méthodes et compositions pour lutter contre les mauvaises herbes
US9856495B2 (en) 2013-07-19 2018-01-02 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9777288B2 (en) 2013-07-19 2017-10-03 Monsanto Technology Llc Compositions and methods for controlling leptinotarsa
US11377667B2 (en) 2013-07-19 2022-07-05 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9850496B2 (en) 2013-07-19 2017-12-26 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10597676B2 (en) 2013-07-19 2020-03-24 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US9540642B2 (en) 2013-11-04 2017-01-10 The United States Of America, As Represented By The Secretary Of Agriculture Compositions and methods for controlling arthropod parasite and pest infestations
US10927374B2 (en) 2013-11-04 2021-02-23 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US10100306B2 (en) 2013-11-04 2018-10-16 Monsanto Technology Llc Compositions and methods for controlling arthropod parasite and pest infestations
US10557138B2 (en) 2013-12-10 2020-02-11 Beeologics, Inc. Compositions and methods for virus control in Varroa mite and bees
WO2015101622A1 (fr) 2014-01-03 2015-07-09 Bayer Cropscience Ag Nouveaux pyrazolyl-hétéroarylamides utilisables comme pesticides
US10273226B2 (en) 2014-01-03 2019-04-30 Bayer Animal Health Gmbh Pyrazolyl-heteroarylamides as pesticides
WO2015108982A2 (fr) 2014-01-15 2015-07-23 Monsanto Technology Llc Procédés et compositions pour la lutte contre les mauvaises herbes utilisant des polynucléotides epsps
US10334848B2 (en) 2014-01-15 2019-07-02 Monsanto Technology Llc Methods and compositions for weed control using EPSPS polynucleotides
US11091770B2 (en) 2014-04-01 2021-08-17 Monsanto Technology Llc Compositions and methods for controlling insect pests
US10988764B2 (en) 2014-06-23 2021-04-27 Monsanto Technology Llc Compositions and methods for regulating gene expression via RNA interference
US11807857B2 (en) 2014-06-25 2023-11-07 Monsanto Technology Llc Methods and compositions for delivering nucleic acids to plant cells and regulating gene expression
US10378012B2 (en) 2014-07-29 2019-08-13 Monsanto Technology Llc Compositions and methods for controlling insect pests
US11124792B2 (en) 2014-07-29 2021-09-21 Monsanto Technology Llc Compositions and methods for controlling insect pests
US9936699B2 (en) 2014-08-08 2018-04-10 Bayer Cropscience Aktiengesellschaft Halogen-substituted compounds
CN105646395A (zh) * 2014-12-02 2016-06-08 沈阳中化农药化工研发有限公司 一种噻唑酰胺类化合物及其应用
US10968449B2 (en) 2015-01-22 2021-04-06 Monsanto Technology Llc Compositions and methods for controlling Leptinotarsa
US10239830B2 (en) * 2015-02-11 2019-03-26 Icahn School Of Medicine At Mount Sinai Benzenesulfonamide upregulators of NPC1 for Neimann-Pick disease and other lysosomal storage disorders
AU2016219231B2 (en) * 2015-02-11 2020-08-20 Icahn School Of Medicine At Mount Sinai Benzenesulfonamide upregulators of NPC1 for neimann-pick disease and other lysosomal storage disorders
CN104829613B (zh) * 2015-04-13 2020-06-09 赤峰蒙广生物科技有限公司 二芳基取代的吡唑并环类衍生物、其制备方法及其在医药领域的应用
CN104829613A (zh) * 2015-04-13 2015-08-12 上海创诺医药集团有限公司 二芳基取代的吡唑并环类衍生物、其制备方法及其在医药领域的应用
WO2016174049A1 (fr) 2015-04-30 2016-11-03 Bayer Animal Health Gmbh Combinaisons anti-parasitaires comprenant des composés à substitution halogène
US10883103B2 (en) 2015-06-02 2021-01-05 Monsanto Technology Llc Compositions and methods for delivery of a polynucleotide into a plant
US10655136B2 (en) 2015-06-03 2020-05-19 Monsanto Technology Llc Methods and compositions for introducing nucleic acids into plants
WO2017157885A1 (fr) 2016-03-16 2017-09-21 Bayer Cropscience Aktiengesellschaft Dérivés de n-(cyanobenzyl)-6-(cyclopropylcarbonylamino)-4-(phényl)-pyridine-2-carboxamide et composes apparentés utilisés comme agents phytosanitaires pesticides
EP3284739A1 (fr) 2017-07-19 2018-02-21 Bayer CropScience Aktiengesellschaft Composés (hét)aryl substitués comme produit de lutte contre les parasites
CN112119063A (zh) * 2018-05-18 2020-12-22 富士胶片株式会社 3-二氟甲基吡唑化合物的制造方法及3-二氟甲基吡唑-4-羧酸化合物的制造方法以及吡唑烷化合物
CN112119063B (zh) * 2018-05-18 2023-10-17 富士胶片株式会社 3-二氟甲基吡唑化合物的制造方法及3-二氟甲基吡唑-4-羧酸化合物的制造方法以及吡唑烷化合物
CN108991003B (zh) * 2018-08-29 2021-02-19 浙江工业大学 一种含吡唑环的酰胺衍生物在制备除草剂中的应用
CN109169693B (zh) * 2018-08-29 2021-03-16 浙江工业大学 一种新型含吡唑环的酰胺类化合物在制备除草剂中的应用
CN108719301A (zh) * 2018-08-29 2018-11-02 浙江工业大学 一种1-甲基-3-三氟甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN109156471B (zh) * 2018-08-29 2020-12-15 浙江工业大学 一种1,3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN108863934A (zh) * 2018-08-29 2018-11-23 浙江工业大学 一种1-甲基-3-二氟甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN108991003A (zh) * 2018-08-29 2018-12-14 浙江工业大学 一种含吡唑环的酰胺衍生物在制备除草剂中的应用
CN109156471A (zh) * 2018-08-29 2019-01-08 浙江工业大学 一种1，3-二甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN109169693A (zh) * 2018-08-29 2019-01-11 浙江工业大学 一种新型含吡唑环的酰胺类化合物在制备除草剂中的应用
CN108863934B (zh) * 2018-08-29 2020-09-08 浙江工业大学 一种1-甲基-3-二氟甲基-1h-吡唑-4-酰胺衍生物在制备除草剂中的应用
CN109293640A (zh) * 2018-10-31 2019-02-01 青岛清原化合物有限公司 一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途
CN109293640B (zh) * 2018-10-31 2020-05-19 青岛清原化合物有限公司 一种取代的含氮杂芳环甲酰胺衍生物及其除草组合物和用途

Also Published As

Publication number Publication date
AU2003301443A8 (en) 2004-05-04
WO2004035545A3 (fr) 2004-08-05
AR044745A1 (es) 2005-10-05
AU2003301443A1 (en) 2004-05-04

Similar Documents

Publication Publication Date Title
WO2004035545A2 (fr) Herbicides a base d'azolecarboxamide
WO2004106324A1 (fr) Herbicides a base d'azolecarboxamide
US20060069132A1 (en) Azolecarboxamide herbicides
AU725548B2 (en) Heteroaryl azole herbicides
AU2004309325B2 (en) Herbicidal pyrimidines
EP2225211B1 (fr) Dérivés herbicides de pyridazinone
US20100298141A1 (en) Substituted pyridine n-oxide herbicides
US5985799A (en) Tricyclic herbicidal heterocycles
US6060432A (en) Herbicidal sulfonamides
WO2005070889A1 (fr) Amides herbicides
EP0922032A1 (fr) Pyridinylcetones et pyrazolylphenylcetones herbicides
US20060229205A1 (en) Herbicidal heterocycles
CA2309260C (fr) Pyrimidines substituees en position 2 et 4 et leur utilisation dans des compositions herbicides
WO1998056789A1 (fr) Herbicides de type pyrimidinylazole
AU2002225656A1 (en) Herbicidal heterocycles
WO2014014904A1 (fr) Cycloalkyl 1,2,4-triazine-3,5-diones substituées en tant qu'herbicides
WO1996031517A1 (fr) Anilides herbicides heteroaryl-substitues
US5739326A (en) Heterobicyclic herbicides
WO1998035954A1 (fr) Herbicides comprenant des hydrazones bicycliques
AU7252698A (en) Herbicidal sulfonamides
US20040033896A1 (en) Substituted pyrimidine and pyridine herbicides

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: JP

WWW Wipo information: withdrawn in national office

Ref document number: JP

DPE2 Request for preliminary examination filed before expiration of 19th month from priority date (pct application filed from 20040101)