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WO1999052893A1 - Nouveaux herbicides au n-pyridonyle - Google Patents

Nouveaux herbicides au n-pyridonyle Download PDF

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Publication number
WO1999052893A1
WO1999052893A1 PCT/EP1999/002313 EP9902313W WO9952893A1 WO 1999052893 A1 WO1999052893 A1 WO 1999052893A1 EP 9902313 W EP9902313 W EP 9902313W WO 9952893 A1 WO9952893 A1 WO 9952893A1
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Prior art keywords
formula
alkyl
compounds
compound
haloalkyl
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PCT/EP1999/002313
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English (en)
Inventor
Kurt Nebel
Walter Kunz
Jean Wenger
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Novartis Ag
Novartis-Erfindungen Verwaltungsgesellschaft Mbh
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Application filed by Novartis Ag, Novartis-Erfindungen Verwaltungsgesellschaft Mbh filed Critical Novartis Ag
Priority to JP2000543452A priority Critical patent/JP2002511461A/ja
Priority to AU37056/99A priority patent/AU738222B2/en
Priority to KR1020007011155A priority patent/KR20010042521A/ko
Priority to BR9909487-8A priority patent/BR9909487A/pt
Priority to EP99919194A priority patent/EP1076655A1/fr
Publication of WO1999052893A1 publication Critical patent/WO1999052893A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • the present invention relates to novel, herbicidally active substituted N-pyridonyl nitrogen heterocycles, to processes for the preparation thereof, to compositions comprising those compounds, and to the use thereof in the control of weeds, especially in crops of useful plants, for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds.
  • crops of useful plants for example cereals, maize, rice, cotton, soybeans, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantation crops and fodder plants, or in the inhibition of plant growth, and also in the non-selective control of weeds.
  • N-Pyridyl-pyrazoles and N-pyridyl-tetramethylenetriazolidine-dione compounds having herbicidal activity are described, for example, in DE-A-3 917 469, DE-A-19 518 054, DE-A-19 530 606 and US-A-5 306 694.
  • N-(2-Pyridyl)-pyridazinone compounds having herbicidal activity are described, for example, in JP-A-58-213 776.
  • the present invention therefore relates to compounds of formula I
  • R-i is hydrogen, fluorine, chlorine, bromine or methyl
  • R 2 is C ⁇ -C alkyl, C ⁇ -C haloalkyl, halogen, nitro, amino, cyano or R 3 O- ;
  • R 43 is hydrogen, d-C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, CrC 8 haloalkyl, cyano-CrC 8 alkyl, C 3 -C 8 haloalkenyl, hydroxy-CrC alkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkyl, C 3 -C 6 - alkenyloxy-C 1 -C 4 alkyl, C 3 -C 6 alkynyloxy-CrC 4 alkyl, C ⁇ -C 4 alkoxy-C ⁇ -C 4 alkoxy-C ⁇ -C 4 -alkyl, C C 4 alkylthio-C ⁇ -C alkyl, C ⁇ -C 8 alkylcarbonyl, CrC 8 alkoxycarbonyl, C 3 -C 8 alkenyl- oxycarbonyl, benzyloxy-Ci- or
  • heteroaromatic rings being unsubstituted or mono- to tri-substituted by halogen, d-dalkyl or by d-C haloalkyl; or
  • R 44 X 16 C(0)-[C 1 -C 8 alkylene]- R 43 is R ⁇ Xie CCOJ-d-Cealkyl- or ;
  • _ ⁇ N — X 16 is oxygen, sulfur or 45 ⁇ ;
  • R 44 is hydrogen, CrC 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, C ⁇ -C 8 haloalkyl, C 3 -C 8 haloalkenyl, d-dalkoxy-d-dalkyl, d-Cealkenyloxy-d-dalkyl, d-C 4 alkylthio-C ⁇ - C 4 alkyl, phenyl, phenyl mono- to tri-substituted by halogen, C ⁇ -C alkyl or by C C -halo- alkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, d-C alkyl or by C ⁇ -C 4 haloalkyl;
  • R 45 is hydrogen, C ⁇ -C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl, d-C 8 haloalkyl or benzyl;
  • R 3 is hydroxy, C C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 all ynyloxy, CrC 6 haloalkoxy, C 3 -C 6 - haloalkenyloxy, C ⁇ -C 6 alkoxy-d-C 6 alkyl, C 3 -C 6 alkenyloxy-CrC 6 alkyl, C 3 -C 6 alkynyloxy- C C 6 alkyl, d-Cealkoxy-d-Cealkoxy-d-Cealkyl, B -Cealkoxy, R 4 (R 5 )N-, C C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 - halocycioalkyl
  • B-i is cyano, OHC-, HOC(O)-, C C ⁇ alkylcarbonyl, d-C 6 haloalkylcarbonyl, C C 6 alkoxy- carbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyloxycarbonyl, benzyloxy, benzyloxy- carbonyl, benzyloxycarbonyl mono- to tri-substituted on the phenyl
  • R 4 and R 5 are each independently of the other hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 - alkynyl, C C 6 haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, d-C 6 alkoxy-C ⁇ -C 6 alkyl, OHC-, d-C 6 alkylcarbonyl, C C 6 haloalkylcarbonyl, C r C 6 alkyl-S(O) 2 - or C C 6 haloalkyl- S(O) 2 -;
  • R 6 and R 7 are each independently of the other hydrogen, C C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 - alkynyl, C C 6 haloalkyl, C 3 -C 6 haloalkenyl, phenyl, phenyl mono- to tri-substituted by halogen, C C alkyl or by d-C 4 haloalkyl, benzyl or benzyl mono- to tri-substituted on the phenyl ring by halogen, C C alkyl or by C r C 4 haloalkyl;
  • Xi is oxygen or sulfur
  • W is a group T ? " ( ⁇ )> T jj " (W2)l rl (Wa) '
  • R 8 is CrC 3 alkyl, C C 3 haloalkyl or amino
  • R 9 is d-C 3 haloalkyl, d-C 3 alkyl-S(O) n1 , CrC 3 haloalkyl-S(O) n1 or cyano; or
  • R 8 and Rg together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge, each of which may be substituted by halogen, C C 3 haloalkyl or by cyano; n-i is O, 1 or 2; R-io is hydrogen, d-C 3 alkyl, halogen, d-C 3 haloalkyl or cyano; or R 10 and R 9 together form a C 3 - or C -alkylene bridge or C 3 - or C 4 -alkenylene bridge, each of which may be substituted by halogen, C C 3 haloalkyl or by cyano; Rn is hydrogen, C C 3 alkyl, halogen or cyano; R- I2 is d-C 3 haloalkyl;
  • R 12 and Rn together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge;
  • R 13 is hydrogen, C C 3 alkyl or halogen;
  • R 13 and R 12 together form a C 3 - or C 4 -alkylene bridge or C 3 - or C 4 -alkenylene bridge;
  • R M is hydrogen, C 1 -C 3 alkyl, halogen, C C 3 haloalkyl, R 33 O-, R 3 S(O) n2 , R 35 (R 36 )N,
  • R 3 ⁇ (R 39 )N-C(R 37 ) N-, hydroxy, nitro or N ⁇ C-S- ;
  • R 33 is C C 3 alkyl, d-C 3 haioalkyl, C 2 -C 4 alkenyl, C 3 - or C -alkynyl or C r C 5 alkoxycarbonyl- C C 4 alkyl;
  • R 34 is C C alkyl or C C 4 haloalkyl; n 2 is 0, 1 or 2;
  • R 35 is hydrogen, C C 4 alkyl, C C 4 haloalkyl, C 3 -C 6 cycloalkyl, OHC- or C C 4 alkylcarbonyl;
  • R 38 is C C 4 alkyl
  • R 15 is hydrogen, C C 4 alkyl, halogen, Crdhaloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 haloalkenyl, C 3 - or C 4 -alkynyl, C C 4 alkoxy, CrC 4 alkylcarbonyl, C C 4 haloaIkylcarbonyl, C 2 -C 4 alkenyl- carbonyl, C 2 -C 4 haioalkenylcarbonyl, C 2 -C alkynyicarbonyl, C -C 4 haloalkynylcarbonyl, d-C 4 alkoxycarbonyl, C C 4 alkylcarbamoyl, C r C 4 alkylS(O) n3 , C 3 - or C -alkynylS(O) n3 ,
  • n 3 is 0, 1 or 2;
  • R ⁇ 6 and R ⁇ 7 are each independently of the other hydrogen, C C 4 alkyl, halogen, C C 4 halo- alkyl or cyano;
  • R 20 and R 2 ⁇ are each independently of the other hydrogen, C C 4 alkyl or C C haloalkyl;
  • R 22 and R 23 are each independently of the other hydrogen, C C 3 alkyl, halogen or hydroxy;
  • R 24 and R 25 are each independently of the other hydrogen or C C 4 alkyl; or
  • R 40 and R 41 are each independently of the other d-C 4 alkyl; or - 5 -
  • R 40 and R together form a C 4 - or C 5 -alkylene bridge
  • R 26 is hydrogen or C C 3 alkyl ;
  • R 29 and R 30 are each independently of the others hydrogen, C C 3 alkyl, C 3 - or C 4 - alkenyl or C 3 -C 5 alkynyl; or R 2 and R 28 together and/or R 2 g and R 30 together in each case form a C 2 -C 5 alkylene bridge or C 3 -C 5 alkenylene bridge, each of which may be interrupted by oxygen, sulfur or -
  • R 31 is hydrogen, d-C 4 alkyl, C C haloalkyl, C 3 - or C 4 -alkenyl, C 3 - or d-haloalkenyl or C 3 - or C -alkynyl;
  • R 32 is hydrogen, d-C 4 alkyl, C C 3 alkoxy-C ⁇ - or -C 2 -alkyl, C C 4 haloalkyl, C 3 - or C 4 -alkenyl,
  • halogen is to be understood as being iodine or, preferably, fluorine, chlorine or bromine.
  • Alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyi and the various isomeric pentyl and hexyl radicals. Methyl, ethyl, n-propyl, isopropyl and n-butyl are preferred.
  • alkenyl radicals examples include vinyl, allyl, methallyl, 1 -methylvinyl, but-2-en-1-yl, pentenyl and 2-hexenyl, with preference being given to alkenyl radicals - 6 -
  • alkynyl radicals examples include ethynyl, propargyl, 1 -methyl- propargyl, 3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent-4-yn-
  • alkynyl radicals having a chain length of from 2 to 4 carbon atoms.
  • Suitable haloalkyl radicals are alkyl groups that are mono- or poly-substituted, especially mono- to tri-substituted, by halogen, halogen being in particular iodine or especially fluorine, chlorine or bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloro- ethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl.
  • Suitable haioalkenyl radicals are alkenyl groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyl, 2- or 3-chloropropenyl, 2- or 3-bromopropenyl, 2,3,3-trifluoropropenyl,
  • alkenyl radicals mono-, di- or tri-substituted by halogen, preference is given to those having a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
  • Suitable haloalkynyl radicals are, for example, alkynyl groups mono- or poly-substituted by halogen, halogen being bromine, iodine or especially fluorine or chlorine, for example 3- fluoropropynyl, 3-chioropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4- trif luoro-but-2-yn-1 -yl.
  • Alkylthio is, for example, methylthio, ethylthio, propylthio or butylthio or a branched isomer thereof.
  • Alkyisulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl or an isomer of pentyl- sulfonyl or hexylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Haloalkylsulfonyl is, for example, fluoromethylsulfonyl, difluoromethylsulfonyl, trifluoro- methylsulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-tri- fluoroethylsulfonyl or 2,2,2-trichloroethylsulfonyl.
  • Cyanoalkyl is, for example, cyanomethyl, cyanoethyl, cyanoeth-1 -yl or cyanopropyl.
  • Hydroxyalkyl is, for example, hydroxymethyl, 2-hydroxyethyi or 3-hydroxypropyl.
  • Alkylamino is, for example, methylamino, ethylamino or an isomer of propylamino or butyl- amino. - 7 -
  • Dialkylamino is, for example, dimethylamino, diethylamino or an isomer of dipropylamino or dibutylamino.
  • Alkenylamino is, for example, allylamino, methallylamino or but-2-en-1-ylamino.
  • Alkynylamino is, for example, propargylamino or 1-methylpropargylamino.
  • Haloalkylamino is, for example, chloroethylamino, trifluoroethylamino or 3-chloropropyl- amino.
  • Di(haloalkyl)amino is, for example, di(2-chloroethyl)amino.
  • Alkylcarbonyl is especially acetyl or propionyl.
  • Haloalkylcarbonyl is especially trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl or
  • Alkenylcarbonyl is especially vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 - ylcarbonyl, pentenylcarbonyl or 2-hexenylcarbonyl.
  • Alkynylcarbonyl is especially acetylenecarbonyl, propargylcarbonyl, 1 -methyipropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1 -ylcarbonyl or pent-4-yn-1-ylcarbonyl.
  • Alkoxy is, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec- butoxy, tert-butoxy or an isomer of pentyloxy or hexyloxy.
  • Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1 -yloxy.
  • Alkynyloxy is, for example, propargyloxy or 1 -methylpropargyloxy.
  • Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl.
  • Alkenyloxyalkyl is, for example, allyloxyalkyl, methallyloxyalkyl or but-2-en-1-yloxyalkyl.
  • Alkynyloxyalkyl is, for example, propargyloxyalkyl or 1-methylpropargyloxyalkyl.
  • Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.
  • Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1- yloxycarbonyl, pentenyloxycarbonyl or 2-hexenyloxycarbonyl.
  • Alkynyloxycarbonyl is, for example, propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1- yloxycarbonyl or 2-methylbutyn-2-yioxycarbonyl.
  • Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoro- ethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy or 2,2,2-trichloroethoxy.
  • Suitable haloalkenyloxy radicals are alkenyloxy groups mono- or poly-substituted by halogen, halogen being in particular bromine, iodine or especially fluorine or chlorine, for example 2- or 3-fluoropropenyloxy, 2- or 3-chloropropenyloxy, 2- or 3-bromopropenyloxy,
  • cycloalkyl radicals suitable as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • halocycloalkyl radicals suitable as substituents are, for example, mono-, di- or up to per-halogenated cycloalkyl radicals, for example fluorocyclopropyl, chlorocyclopropyl, bromocyclopropyl, 2,2-dichlorocyclopropyl, 2,2-difluorocyclopropyl, 2,2-dibromocyclopropyl,
  • substituents in combined definitions such as, for example, alkylcarbonyloxy, alkoxyalkoxyalkyl, alkoxycarbonylalkyl, haloalkoxy- carbonyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, alkylthio-C(O)-, alkenylthio, alkynylthio, alkyl-S(O)-, alkylsulfonyloxy, R 33 O-, R 4 (R 5 )N-, R 35 (R 36 )N-,
  • L in the reagents of formulae VI, XI, XIX, XXVIII, XXXIa, XXXIb and XXXXII denotes a leaving group, such as, for example, halogen, preferably chlorine, bromine or iodine,
  • L T in the reagent of formula XX denotes a leaving group, such as, for example, HOS(O) 2 O-,
  • L 2 in the reagents of formulae XXXIIa and XXXIIc denotes a leaving group, such as, for example, hydroxy, d-C 4 alkoxy or halogen, preferably chlorine, bromine or iodine.
  • a leaving group such as, for example, hydroxy, d-C 4 alkoxy or halogen, preferably chlorine, bromine or iodine.
  • L 3 in the reagent of formula XXXVIII denotes a leaving group, such as, for example, chlorine
  • cyanoalkyl alkylcarbonyl, alkylcarbonyloxy, alkenylcarbonyl, haloalkenyicarbonyl, alkynylcarbonyl, alkoxycarbonyl, alkylthiocarbonyl and haloalkylcarbonyl
  • the upper and lower limits of the number of carbon atoms given in each case do not include the cyano or carbonyl carbon atom, as the case may be.
  • the invention relates also to the salts that the compounds of formula I having azide hydrogen, especially the derivatives with carboxylic acid and sulfonamide groups (e.g.
  • carboxyl-substituted alkyl and alkoxy groups and alkyl-S(O) 2 NH and haloalkyl-S(O) 2 NH groups) are able to form with bases.
  • Those salts are, for example, alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, e.g. calcium and magnesium salts; ammonium salts, that is to say unsubstituted ammonium salts and mono- or poly-substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, attention is drawn, for example, to the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially to the hydroxides of sodium and potassium.
  • Suitable salt formers are described, for example, in WO 97/41112.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary C ⁇ -C ⁇ 8 alkylamines, d-C hydroxyalkylamines and C 2 -C 4 - alkoxyalkylamines, for example methyiamine, ethylamine, n-propylamine, isopropylamine, the four isomers of butylamine, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonyl- amine, methylpentadecylamine, methyloctadecylamine
  • heterocyciic amines for example pyridine, quinoiine, isoquinoline, morpholine, thiomorpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
  • the salts of compounds of formula I having basic groups, especially having basic pyrazolyl rings (W 3 , W 4 ), or the derivatives with amino groups, for example alkylamino and dialkyl- amino groups, in the definition of R 3 , R 8 or R ⁇ are, for example, salts with inorganic or organic acids, for example hydrohalic acids, such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and also sulfuric acid, phosphoric acid and nitric acid, and organic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.
  • hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or
  • Ri is hydrogen, fluorine, chlorine, bromine or methyl; R is methyl, halogen, hydroxy, nitro, amino or cyano; and R 3 , Xi and W are as defined for formula I. - 11 -
  • X10 and X15 are as defined for formula I.
  • Preferred compounds of formula I are those wherein W is a group
  • X 8 , Xn and X 12 are as defined for formula I.
  • Ri is hydrogen, fluorine or chlorine
  • R is chlorine, bromine, cyano or CF 3
  • Xi is oxygen
  • R-i is fluorine or chlorine
  • R 2 is chlorine, bromine or cyano
  • Ri is fluorine
  • R is chlorine
  • R 1 f R 2 and W are as defined for formula I;
  • Xi is O or S;
  • R 3 is d-Cealkoxy-Ci-Ce- alkyl, C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkoxy-C ⁇ -C 6 alkyl, d-C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 2 -C 6 - haloalkyl, C 3 -C 6 haloalkenyl, C 3 -C 6 cycloalkyl, C 3 -C 6 halocycloalkyl, BrC ⁇ -C 6 alkyl,
  • R ⁇ R 2 and W are as defined for formula I and R 03 is a lower alkoxy group, e.g. d- or C -alkoxy, benzyloxy or halogen, e.g. chlorine or bromine, by first reacting a compound of formula IVa with an alkylating agent of formula VI
  • MnO 2 manganese dioxide
  • K 3 Fe(CN) 6 potassium hexacyanoferrate
  • Ri, R 2 and W are as defined for formula I;
  • Xi is S;
  • R 3 is hydroxy, C ⁇ -C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, C ⁇ -C 6 haloalkoxy, C 3 -C 6 haloalkenyioxy, B ⁇ -CrC 6 alkoxy, d-C 6 alkyicarbonyloxy, C 3 -C 8 trialkylsilyloxy, (hydroxy-d-C 5 alkyl)-O- or (B ⁇ -C ⁇ -C 5 hydroxy- alkyl)-O-; and B 1 is as defined for formula I is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises first oxidising a compound of formula III
  • X 1 R 3 wherein R ⁇ R 2 , R 3 and W are as defined for formula I and Xi is S is carried out analogously to known procedures, for example as described in WO 98/42698 and references given therein, and comprises treating a compound of formula I - 17 -
  • R 1 ? R 2 , R 3 and W are as defined and X ⁇ is O in an inert solvent with a sulfur reagent, for example phosphorus pentasulfide or Lawesson reagent.
  • a sulfur reagent for example phosphorus pentasulfide or Lawesson reagent.
  • W is a group Wi — R 9 (W T ) and
  • R10, X 2 and X 3 are as defined for formula I (corresponding to the compound of formula Ilia in Reaction Scheme 2), comprises, for example, converting a compound of formula XII
  • Ri and R 2 are as defined and Hal is fluorine, chlorine or bromine, in the presence of an inert solvent and ammonia, if appropriate in an autoclave at temperatures of from -10 to 180°C, into a compound of formula XIII
  • R 1 R 2 , R 9 , Rio, X 2 and X 3 are as defined, and reacting that compound further in the presence of an inert solvent and a base c) with a compound of formula XIX
  • Ri, and R 11 , R 12 , R ⁇ 3 and X 4 are as defined for formula I (corresponding to the compound of formula lllb in Reaction Scheme 3), comprises, for example, either a) converting a compound of formula XII
  • R T and R 2 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent, into a compound of formula XXI - 20 -
  • R ⁇ 3 is as defined and X is oxygen.
  • X, ⁇ , R25, R 2 6, X9 and X10 are as defined for formula I (corresponding to the compound of formula lllg in Reaction Scheme 4), comprises, for example, reacting either a) a compound of formula XVa
  • R 26 -L (XXVIII), wherein R 26 is d-C 3 aIkyl and L is a leaving group.
  • W is a group W ⁇ — N i, (W 8 ) and
  • R27, 2 8, X11 and X ⁇ 2 are as defined for formula I (corresponding to the compound of formula lllh in Reaction Scheme 5), comprises, for example, reacting a) a compound of formula XVb
  • R ⁇ 4 , R 15 and R 16 are as defined for formula I (corresponding to the compound of formula lllc in Reaction Scheme 6), comprises, for example, condensing a compound of formula XXI
  • R 15 wherein R ⁇ is hydrogen, d-C 3 alkyl or d-C 3 haloalkyl; R i5 is hydrogen, d-C 4 alkyl, d-C 4 haloalkyl, C 2 -C 4 alkenyl, C 3 -C 5 haloalkenyl or C 3 - or C 4 -alkynyl and R ⁇ 6 is hydrogen, C ⁇ -C 4 alkyl or d-C 4 haloalkyl, if appropriate in the presence of an acidic, basic or bifunctional catalyst, e.g. p-toluenesulfonic acid, or b) with a compound of formula XXXIIa
  • R ⁇ 8 and R ⁇ 9 are as defined and R ⁇ 7 is hydrogen, d-C 4 alkyl or C ⁇ -C haioalkyl, if appropriate in the presence of a catalyst, or b) with a compound of formula XXXIIc
  • a halogenating agent e.g. a phosphorus oxyhalide or thionyl halide
  • R 1 ( R 2 , R ⁇ 8 and R ⁇ 9 are as defined and R ⁇ 7 is halogen, and optionally reacting that compound with a cyanide of formula XXXIV
  • W is a group W 5 — N
  • formula I (corresponding to the compounds of formulae llle and lllf, respectively, in Reaction Scheme 8), comprises, for example, reacting a) a compound of formula XXXV
  • Ri, R 2 and R 20 to R 23 are as defined and X 5 to X 8 are oxygen, with the aid of a suitable sulfur reagent, into the corresponding thiono compound of formula Hie or lllf wherein X 5 and/or X 6 and X 7 and/or X 8 are sulfur respectively (Reaction Scheme 8).
  • R29, R30, X13 and X ⁇ 4 are as defined for formula I (corresponding to the compound of formula llli in Reaction Scheme 9), comprises, for example, reacting a) a compound of formula XVc - 29 -
  • W is a group W ⁇ 0 N A ⁇ / '31 wh N N (W ⁇ 0 )
  • H 32 and R 31 , R 32 and X ⁇ 5 are as defined for formula I (corresponding to the compound of formula lllk in Reaction Scheme 10), comprises, for example, a) reacting a compound of formula XXI
  • R 3 ⁇ is C ⁇ -C 4 alkyl, C ⁇ -Chaloalkyl, C 3 - or C 4 -alkenyl, C 3 - or C 4 -haloalkenyl or C 3 - or C 4 -alkynyl and L is a leaving group.
  • Reaction Scheme 2 R, a) CIC(X 2 )0-C 1 -C 4 alkyl or
  • thionation reagent e.g. Lawesson reagent solvent
  • Reaction Scheme 2 shows a selection of suitable preparation procedures, the choice of the reaction routes and the reagents being governed by the reactivities of the substituents in the intermediates.
  • the carbamate and the iso(thio)cyanate of formulae XV and XVI may be cyclised in the presence of an enamine derivative of formula XVII in an inert solvent to form a uracil derivative of formula XVIII, the reaction of the iso(thio)cyanate of formula XVI advantageously being carried out in the presence of from 0.1 to 1.5 equivalents of a base, e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide.
  • a base e.g. sodium hydride, potassium tert-butanolate or an alkaline earth metal oxide or hydroxide, e.g. barium hydroxide.
  • the compounds of formula lllb may be prepared in accordance with known methods, for example in accordance with Reaction Scheme 3 (variant a)), by reacting a 2-halopyrid ⁇ ne - 36 -
  • the hydrazone derivative of formula XXIV may also be obtained from the 2-aminopyridine derivative of formula XIII via diazotisation, preferably with exclusion of water, and subsequent coupling to the ketonic acid of formula XXIII (Japp-
  • the compounds of formula lllg may be prepared analogously to known methods, for example as described in EP-A-0 272 594, EP-A-0 493 323, DE-A-3 643 748, WO 95/23509,
  • a carbamate derivative of formula XVa may be cyclised in the presence of a solvent and a base, or - 38 -
  • an iso(thio)cyanate of formula XVIa may be cyclised, if appropriate in a suitable solvent, with an amino acid derivative of formula XXVI via a compound of formula XXVII in the presence of a base and a suitable solvent to form a compound of formula lllg.
  • R 26 is hydrogen and X 9 and/or X ⁇ 0 are oxygen
  • alkylation e.g. ⁇ -L, R 28 -L, or
  • the compounds of formula lllh may be prepared analogously to known procedures, for example as described in EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955.
  • EP-A-0 210 137, DE-OS-2 526 358, EP-A-0 075 267 or EP-A-0 370 955 for example, in accordance with Reaction Scheme 5 either - 40 -
  • a carbamate derivative of formula XVb may be cyclised in the presence of a solvent and a base, or b) an iso(thio)cyanate of formula XVIb may be cyclised, if appropriate in a suitable solvent, with a carbazate of formula XXIX via a compound of formula XXX in the presence of a base and a suitable solvent to form a compound of formula lllh.
  • halogenation reagent e.g. N * '16
  • the pyrazole compounds of formula lllc may be prepared, for example, either from the hydrazinopyridine derivatives of formula XXI by means of condensation with a 1 ,3-dicarbonyl derivative of formula XXXII (variant a)), or by means of condensation with a ⁇ -carbonylcarboxylic acid derivative of formula XXXIIa wherein L 2 is a leaving group, for example d-C 4 alkoxy, hydroxy or halogen, e.g.
  • R ⁇ 5 is hydrogen
  • an electrophilic reagent e.g. a halogenating agent, such as elemental halogen or sulfuryl - 42 -
  • Ri to R 3 , R ⁇ to R ⁇ 6 and Xi are as defined for formula I, may be obtained, as described above, from compounds of formula lllc by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula Ic may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
  • R 1 R 2 and R 3 are as defined and Hal is fluorine, chlorine or bromine, with hydrazine, preferably in a protic solvent.
  • the compounds of formula Ic may also be obtained in manner analogous to that described in J. Het. Chem. 15, 1221 (1978) and in Reaction Scheme 11 , by substitution of a pyridonyl derivative of formula Xlla that is provided with a leaving group U, 43
  • a halide e.g. a halide, a d-C alkyl- or phenyl-sulfonyl group or an unsubstituted or substituted d- dalkyl- or phenyl-sulfonyloxy group, (variant c) in Reaction Scheme 11), or by substitution of a pyridine derivative of formula XII that is provided with a leaving group U, e.g.
  • a halide a d-dalkyl- or phenyl-sulfonyl group or an unsubstituted or substituted C ⁇ -C 4 alkyl- or phenyl-sulfonyloxy group, (variant d) in Reaction Scheme 11 ), with a pyrazole of formula W 03 or an alkali metal salt thereof, and in the case of variant d) by subsequent functionalisation (oxidation) of the pyridyl moiety of the compound of formula lllc.
  • the substitution reactions according to variants c) and d) may optionally be carried out in the presence of a suitable solvent and a base.
  • the tetrahydroindazole compounds of formula llld may be obtained according to known procedures from the hydrazinopyridine derivatives of formula XXI, for example either by condensation with a cyclohexanone derivative of formula XXXIIb that is acylated in the 2-position, wherein R ⁇ 7 is as defined for formula I with the exception of R i7 as halogen or cyano, (variant a)), or by condensation with a cyclohexanone derivative of formula XXXIIc wherein L 2 is a leaving group, for example C ⁇ -C 4 alkoxy, hydroxy or halogen, e.g.
  • the pyrrolinedione derivatives of formula Hie and the tetrahydroisoindolinedione derivatives of formula lllf may be obtained analogously to known procedures, for example by reaction of an anhydride of formula XXXV (variant a)) or XXXVa (variant b)) with an aminopyridine of formula XIII in an inert solvent, for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid, at temperatures of from 20 to 200°C.
  • an inert solvent for example an ether, e.g. dioxane, or a lower alkylcarboxylic acid, e.g. propionic acid
  • the pyridono derivatives of formulae le and If may also be obtained directly from the corresponding aminopyridone derivatives of formula Xllla
  • the compounds of formula llli may be prepared according to known procedures, for example by first reacting a carbamate of formula XVc (variant a)) or an isothiocyanate of formula XVIc (variant b)) with a hydrazine derivative of formula XXXVI to form a semicarbazide derivative of formula XXXVII and then reacting the latter in the presence of a carbonylating or thiocarbonylating reagent of formula XXXVIII. Both reaction steps are advantageously carried out in a suitable solvent and in the presence of a base.
  • As (thio)carbonylating reagent of formula XXXVIII there come into consideration e.g. phosgene, diphosgene, thiophosgene and carbonyldiimidazole.
  • L 3 in formula XXXVIII is therefore a leaving group, for example halogen, e.g. chlorine or bromine,
  • Ri to R 3 , R 29 , R 30 , Xi, X 13 and X ⁇ are as defined for formula I, may be obtained from the compounds of formula llli in the manner described above, by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula li may also be obtained directly from the corresponding pyridone carbamates of formula XVd
  • the triazolone derivatives of formula lllk may be prepared analogously to known procedures, for example by using as starting material a hydrazinopyridine derivative of formula XXI which, in accordance with variant a), is reacted with a keto acid of formula XXXIX, advantageously in the presence of an acid catalyst, e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulfonic acid, to form a hydrazone derivative of formula XXXX.
  • an acid catalyst e.g. a lower alkylcarboxylic acid, e.g. propionic acid, a mineral acid, e.g. sulfuric acid or hydrochloric acid, or a sulfonic acid, e.g. p-toluenesulf
  • a hydrazinopyridine derivative of formula XXI may be cyclised with an imino ether of formula XXXXIII to form a triazolone derivative of formula lllk wherein X 15 is oxygen and R 31 is hydrogen and then optionally alkylated or thionated as described under variant a).
  • a hydrazinopyridine derivative of formula XXI may be converted first with an aldehyde of formula XXXXIV, then in the presence of a lower alkylcarboxylic acid, e.g. acetic acid, with an alkali metal cyanate to form a compound of formula XXXXV, which may or may not be isolated, and finally cyclised - 50 -
  • a lower alkylcarboxylic acid e.g. acetic acid
  • Ri to R 3 , R 31 , R 32 , Xi and X ⁇ 5 are as defined for formula I, may be obtained from the compounds of formula lllk as described above, by means of oxidation of the pyridyl moiety.
  • the pyridono derivatives of formula Ik may also be obtained directly from the corresponding pyridonylhydrazines of formula XXIa
  • the 2-aminopyridines of formula XIII may also be prepared by degradation reactions according to Curtius, Hofmann or Lossen from corresponding pyridine derivatives with carboxylic acid, carboxylic acid chloride, carboxylic acid azide, carboxylic acid ester or carboxylic acid amide functions in the 2-position.
  • reagents of formulae XIV, XVa, XVb, XVIa, XVIb, XVII, XIX, XX, XXII, XXIIa, XXIII, XXV, XXVI, XXVIII, XXIX, XXXIa, XXXIb, XXXII, XXXIIa, XXXIIb, XXXIIc, XXXIV, XXXV, XXXVa, XXXVI, XXVIII, XXXIX, XXXXI, XXXII, XXXIII and XXXXIV used in Reaction Schemes 2 to 10 are either known or may be prepared in analogy to known methods.
  • the reactions to form compounds of formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xyiene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, such as acetonitrile or propionitrile, amides, such as N,N-dimethylformamide, N,N-diethylformamide or N-methylpyrroiidinone.
  • the reaction temperatures are preferably from -20°C to +120°C.
  • the reactions are generally slightly exothermic and may usually be carried out at room temperature.
  • the reaction mixture may be heated to its boiling point for a short time.
  • the reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethylamine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non-5-ene or 1 ,5- diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate. - 52 -
  • the compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by means of column chromatography and a suitable eluant.
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of - 53 -
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rape oil or soybean oil), anti- foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques.
  • the weeds to be controlled may be either monocotyl- edonous or dicotyledonous weeds, such as, for example, Steliaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica. - 54 -
  • a further 5 g of hydrogen peroxide/urea adduct and 3 ml of trifluoroacetic acid anhydride are then added in two portions in the course of 3 hours and after the exothermic reaction has subsided the reaction mixture is heated at 25-35°C until the reaction is complete.
  • the reaction mixture is then cooled and at -5°C adjusted to pH 7.5 first with 2N sodium hydroxide solution and then with saturated sodium hydrogen carbonate solution and partitioned between dichloromethane and ice-water; the organic phase is separated off, dried over sodium sulfate, filtered and concentrated by evaporation.
  • the solid residue that remains is recrystallised from ethyl acetate/n-hexane, yielding the desired product having a melting point of 142- 143°C.
  • Example P6 Preparation of 1-(2-propar ⁇ yloxy-3-chloro-5-fluoro-Pyridin-6-yl)-3-methyl-4- trifluoromethyl-pyrimidine-2.6-dione. 1 -(2-chloro-3-propar ⁇ yloxy-5-fluoro-pyridin-6-yl)-3- methyl-4-trifluoromethyl-pyrimidine-2.6-dione and 1 -(1 -propar ⁇ yloxy-3-chloro-5-fluoro-2- pyridon-6-yl)-3-methyl-4-trifluoromethyl-pyrimidine-2.6-dione
  • Example P9 Preparation of 2-(5-chloro-3-fluoro-6-hvdroxy-pyridin-2-yl)-4.5.6.7-tetrahvdro- isoindolo-1 ,3-dione and 2-(5-hvdroxy-6-chloro-3-fluoro-pyridin-2-yl)-4.5,6,7-tetrahydro- isoindolo-1 ,3-dione
  • N N ⁇ x R 3 corresponding substituents R 1 t Xi and R 3 are indicated in Table A, so that 423 specific compounds of formula l 2 are disclosed.

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Abstract

L'invention concerne des composés de formule (I), dans laquelle R1 représente hydrogène, fluorure, chlorure, bromure ou méthyle ; R2 représente alkyle C1-C4, haloalkyle C1-C4, halogène, nitro, amino, cyano ou R43O-; R3 est tel que décrit dans la revendication 1; X1 représente oxygène ou soufre; W représente un groupe (W1), (W2), (W3), (W4), (W5), (W6), (W7), (W8), (W9) ou (W10); et R8 à R32, R43 et X2 à X15 sont définis dans la revendication (1). L'invention porte aussi sur des sels et des stéréoisomères desdits composés de formule I, acceptables au plan agrochimique. Lesdits composés, sels et stéroisomères peuvent être utilisés en tant qu'herbicides.
PCT/EP1999/002313 1998-04-08 1999-04-06 Nouveaux herbicides au n-pyridonyle WO1999052893A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
JP2000543452A JP2002511461A (ja) 1998-04-08 1999-04-06 Ｎ−ピリドニル除草剤
AU37056/99A AU738222B2 (en) 1998-04-08 1999-04-06 N-pyridonyl herbicides
KR1020007011155A KR20010042521A (ko) 1998-04-08 1999-04-06 Ｎ-피리도닐 제초제
BR9909487-8A BR9909487A (pt) 1998-04-08 1999-04-06 Herbicidas de n-piridonila
EP99919194A EP1076655A1 (fr) 1998-04-08 1999-04-06 Nouveaux herbicides au n-pyridonyle

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CH840/98 1998-04-08
CH84098 1998-04-08

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BR (1) BR9909487A (fr)
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US9271967B2 (en) 2010-11-08 2016-03-01 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors
US9708315B2 (en) 2013-09-06 2017-07-18 Janssen Pharmaceutica Nv 1,2,4-triazolo[4,3-a]pyridine compounds and their use as positive allosteric modulators of MGLUR2 receptors
US10106542B2 (en) 2013-06-04 2018-10-23 Janssen Pharmaceutica Nv Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors
US10537573B2 (en) 2014-01-21 2020-01-21 Janssen Pharmaceutica Nv Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use
US11369606B2 (en) 2014-01-21 2022-06-28 Janssen Pharmaceutica Nv Combinations comprising positive allosteric modulators or orthosteric agonists of metabotropic glutamatergic receptor subtype 2 and their use

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US9085577B2 (en) 2009-05-12 2015-07-21 Janssen Pharmaceuticals, Inc. 7-aryl-1,2,4-triazolo[4,3-A]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors
US9737533B2 (en) 2009-05-12 2017-08-22 Janssen Pharmaceuticals. Inc. 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders
US8937060B2 (en) 2009-05-12 2015-01-20 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders
US9226930B2 (en) 2009-05-12 2016-01-05 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo [4,3-a] pyridine derivatives and their use for the treatment of prevention of neurological and psychiatric disorders
US8946205B2 (en) 2009-05-12 2015-02-03 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors
US10071095B2 (en) 2009-05-12 2018-09-11 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo [4,3-A] pyridine derivatives and their use for the treatment of neurological and psychiatric disorders
US9012448B2 (en) 2010-11-08 2015-04-21 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of MGLUR2 receptors
US9271967B2 (en) 2010-11-08 2016-03-01 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo[4,3-a]pyridine derivatives and their use as positive allosteric modulators of mGluR2 receptors
US8993591B2 (en) 2010-11-08 2015-03-31 Janssen Pharmaceuticals, Inc. 1,2,4-triazolo[4,3-a] pyridine derivatives and their use as positive allosteric modulators of MGLUR2 receptors
US10106542B2 (en) 2013-06-04 2018-10-23 Janssen Pharmaceutica Nv Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors
US10584129B2 (en) 2013-06-04 2020-03-10 Janssen Pharmaceuticals Nv Substituted 6,7-dihydropyrazolo[1,5-a]pyrazines as negative allosteric modulators of mGluR2 receptors
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CN1295570A (zh) 2001-05-16
KR20010042521A (ko) 2001-05-25
BR9909487A (pt) 2000-12-12
ID27165A (id) 2001-03-08
AU738222B2 (en) 2001-09-13
JP2002511461A (ja) 2002-04-16
AU3705699A (en) 1999-11-01

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