WO2005058037A1 - Picolinylpyrazoles utilises comme herbicides - Google Patents

Picolinylpyrazoles utilises comme herbicides Download PDF

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WO2005058037A1
WO2005058037A1 PCT/EP2004/014112 EP2004014112W WO2005058037A1 WO 2005058037 A1 WO2005058037 A1 WO 2005058037A1 EP 2004014112 W EP2004014112 W EP 2004014112W WO 2005058037 A1 WO2005058037 A1 WO 2005058037A1
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crc
halogen
twice
dalkyl
cyano
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PCT/EP2004/014112
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Christoph Lüthy
Andrew Edmunds
Renaud Beaudegnies
Sebastian Wendeborn
Jürgen Schaetzer
William Lutz
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Syngenta Participations Ag
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    • 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
    • C07D401/06—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 carbon chain containing only aliphatic carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—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
    • A01N43/64—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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • 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
    • C07D401/14—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 three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to novel, herbicidally active picolinoylpyrazoles, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Certain herbicidally active derivatives of picolinic acids disubstituted in the 3,5-position are known, such as, for example from EP-A-0316491 , the 3,5-substituted picolinoyl derivatives of 1 ,3-cyclohexanediones substituted in the 2-position and from JP 54009279 the 3,5- substituted picolinoyl derivatives of 2,4-dihydro-3-pyrazolones substituted in the 4-position.
  • EP-A-1 286985 also discloses certain substituted nicotinoylpyrazoles.
  • the present invention accordingly relates to compounds of formula I
  • R ! is -L 10 -R 4> -Ln-XrRs, -NR 6 R 7 , -X 2 -R 8 or
  • L 2> L 4 , L- 6 and L 8 are each independently of the others CrC 4 alkylene which may be substituted once, twice or three times by CrC 4 alkyl, halogen or by C C 4 alkoxy and to which ]-C alkylene group there may additionally be spirocyclically bound a C 2 -C 5 alkylene group, and wherein that C 2 -C 5 alkylene group may in turn be interrupted once or twice by oxygen, sulfur, sulfinyl or by sulfonyl and/or substituted by CrC 4 alkyl or by C ⁇ -C alkoxy;
  • L 3 , L 5) L and L 9 are each independently of the others C C 4 alkylene which may be substituted once, twice or three times by CrC alkyl, halogen or by C C alkoxy;
  • R 2 is halogen, CrC 4 haloalkyl, cyano, C C 3 haloalkoxy, C C 4 alkylthio, C C 4
  • R 4 is halogen, cyano, rhodano, d-Cealkoxycarbonyl, C 3 -C 6 alkenyloxycarbonyl, C 3 -C 6 alkynyl- oxycarbonyl, benzyloxycarbonyl, C(O)NR 2 5aR26a, formyl, d-C 6 alkylcarbonyl, d-C 6 haloalkyl- carbonyl, C ⁇ -C 4 alkoxy-d-C 4 alkylcarbonyl, d-dalkoxy-d-dalkoxy-d-dalkylcarbonyl, N- (CrC alkyl)-d-C 4 alkylsulfonylamino-CrC 4 alkylcarbonyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 - haloalkenyl, C 2 -C 6 alkynyl, C 2 -
  • R 25 a is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C alkyl, C C 4 haloalkyl, C C 3 alkoxy, C ⁇ -C 3 haloalkoxy, C ⁇ -C 3 alkylthio, C C 3 alkylsulfinyl, C C 3 alkylsulfonyl, C C 3 haloalkylthio, cyano, nitro, C ⁇ -C 4 alkoxycarbonyl or by d-C alkylcarbonylamino;
  • R 26a is hydrogen, CrCealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 25a together with R 26a and the respective N atom to which they are bonded form a carbo- cyclic 3- to 6-membered ring
  • Ln is a C ⁇ -C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene group which may be substituted once, twice or three times by halogen, hydroxy, d-C 6 alkoxy, C 3 -C 6 cycloalkyloxy, d-C 6 - alkoxy-d-C 6 alkoxy, CrC 6 alkoxy-CrC 6 alkoxy-CrC 6 alkoxy or by C C 2 alkylsulfonyloxy;
  • Rub, R ⁇ 4 d and R are each independently of the others hydrogen, CrC 6 alkyl, d-C 6 haloalkyl, CrCealkoxycarbonyl, d-C 6 alkylcarbonyl, CrC 6 alkoxy-CrC 6 alkyl, or d-Cealkoxy-CrCealkyl substituted by CrC 6 alkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by CrC 6 alkyl, d-C 6 halo- alkyl, CrC 6 alkoxy, d-Cehaloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 14a is hydroxy, d-C 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy or benzyloxy; is C
  • R 5 is hydrogen or a CrC 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl or C 3 -C 6 cycloalkyl group which may be substituted once, twice or three times by chlorine, bromine, iodine, hydroxy, amino, formyl, nitro, cyano, mercapto, C C 6 alkoxy, 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, halo-substituted C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, cyano-CrC 6 alkoxy, d-C
  • R ⁇ ea, i 6 b and R 18c are hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 cycloalkyl or phenyl, wherein phenyl may be substituted once, twice or three times by CrC 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxy, CrC 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; Ri 7 a, i7b, i7c > Risa, ⁇ sb and R 18c are hydrogen, CrC 8 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; X 23 , X 24 , X25, X26 and X 27 are oxygen or sulfur;
  • R 15 , R 16 . R 17 , R 19 and R 2 o are each independently of the others hydrogen, CrC 6 alkyl, d-Cehaloalkyl, CrCealkoxycarbonyl, d-C 6 alkylcarbonyl, CrCealkoxy-CrCealkyl, or CrC 6 alkoxy-CrC 6 alkyl substituted by d-C 6 alkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by CrC 6 alkyl, CrC 6 haloalkyl, d-C 6 alkoxy, d-Cehaloalkoxy, halogen, cyano, hydroxy or by nitro; or R 5 is a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, saturated or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and wherein
  • R 5a is CrC 6 alkyl, hydroxy, CrC 6 alkoxy, cyano or nitro;
  • R 18 is hydrogen, CrC 6 alkyl, d-C 6 haloalkyl, CrCealkoxycarbonyl, CrC 6 alkylcarbonyl,
  • CrC 6 alkoxy-CrC 6 alkyl or CrC 6 alkoxy-CrC 6 alkyl substituted by CrC 6 alkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by
  • R 6 is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, d-Cehaloalkyl, hydroxy, CrC 6 alkoxy,
  • R ⁇ 9a and R 20a are each independently of the other hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl, benzyl, heteroaryl, CrC 6 alkoxy, C 3 -C 6 alkenyloxy, benzyloxy, CrC 4 alkylthio or a group NR21R22;
  • R 21 and R 22 are each independently of the other hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl,
  • R 21 and R 22 may be substituted once, twice or three times by halogen, d-dalkyl, d-C 4 halo- alkyl, d-C 3 alkoxy, CrC 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl,
  • X 4 is oxygen, -NR 23 -, -S-, -S(O)- or -S(O) 2 -;
  • R 23 is hydrogen, CrC 6 alkoxy, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloaikyl, d-C 3 - alkoxy, C r C 3 haloalkoxy, C C 3 alkylthio, Crdalkylsulfinyl, d-C 3 alkylsulfonyl, C C 3 halo- alkylthio, cyano, nitro, CrC 4 alkoxycarbonyl or by Crdalkylcarb ⁇ nylamino;
  • R 24 is hydrogen or a CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, CrC 6 alkoxy, C r C 3 alkoxy-
  • X 5 is oxygen or sulfur
  • R 25 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C alkyl, d-C 4 haloalkyl, CrC 3 alkoxy, d-C 3 halo- alkoxy, C ⁇ -C 3 alkylthio, C C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro,
  • R 26 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 25 together with R 26 and the respective N atom to which they are bonded form a carbo- cyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-C alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by CrC 4 alkylcarbonylamino; or R 6 is -L 3 -R 27 ;
  • R 27 is formyl, CrC 6 alkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, CrCealkoxycarbonyl, cyano, C(X 6 )NR 28 R 29l phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 halo- alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 aIkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d-
  • X 6 is oxygen or sulfur
  • R 28 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, C C 3 halo- alkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, C C 3 alkylsulfonyl, C C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 29 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 28 together with R 29 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-C alkyl, d-dhaloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, C ⁇ -C 3 alkylthio, C C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by CrC 4 alkylcarbonylamino;
  • R 7 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, d-Cehaloalkyl, C 3 -C 6 cycloalkyl, phenyl, benzyl, heteroaryl, C(X 7 )R 30 or NR 33 R 34 , wherein phenyl, benzyl and heteroaryl may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 - alkoxy, CrC 3 haloalkoxy, d-C 3 alkylthio, CrC 3 alkylsulfinyl, d-C 3 alkylsulfonyl, CrC 3 halo- alkylthio, cyano, nitro, d-C alkoxycarbonyl or by d-dalkylcarbonylamino;
  • X 7 is oxygen or sulfur
  • R 30 is hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, CrC 6 alkoxy, C 3 -C 6 alkenyl- oxy, benzyloxy, d-C 4 alkylthio or a group NR 31 R 32 ;
  • R 3 ⁇ and R 33 are each independently of the other hydrogen, -C ⁇ alkyl, C 3 -C 6 alkenyl or
  • C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkyl- carbonylamino;
  • R 32 and R 34 are each independently of the other hydrogen, CrCealkyl, C 3 -C 6 alkenyl or
  • X 8 is oxygen, -NR 36 -, -S-, -S(O)- or -S(O) 2 -;
  • R 36 is hydrogen, CrC 6 alkoxy, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-C alkyl, d-C 4 haloalkyl, d-C 3 - alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, C C 3 halo- alkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by C C 4 alkylcarbonylamino;
  • R 35 is hydrogen or a d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-C
  • R 37 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C C 3 alkoxy, d-C 3 halo- alkoxy, C ⁇ -C 3 alkylthio, d-C 3 alkylsulfinyl, C C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 38 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 37 together with R 38 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-member
  • R 39 is formyl, CrC 6 alkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, CrC 6 alkoxycarbonyl, cyano, C(X ⁇ 0 )NR 40 R ⁇ , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, C C 4 alkyl, d-C 4 haIoalkyl, C C 3 alkoxy, C C 3 halo- alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d-C 4 alkyl, CrC
  • R 40 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C haloalkyl, d-C 3 alkoxy, d-C 3 halo- alkoxy, d-C 3 alkylthio, CrC 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyI or by d-C 4 alkylcarbonylamino; R 4 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R ⁇ together with R 41 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membere
  • R 42 is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, CrC 6 haloalkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, C(Xn)R 43 or NR 46 R 47 ;
  • Xn is oxygen or sulfur;
  • R ⁇ is hydrogen, d-C 6 alkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, CrC 6 alkoxy, C 3 -C 6 alkenyl- oxy, benzyloxy, C C 4 alkylthio or a group
  • R ⁇ and R 46 are each independently of the other hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, C r C 4 haloalkyl, C C 3 alkoxy, d-C 3 haloalkoxy, C C 3 alkylthio, C C 3 alkylsulfinyl, C r C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-dalkyl- carbonylamino;
  • R ⁇ and R 47 are each independently of the other hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R ⁇ j together with R ⁇ or R ⁇ together with R 47 , in each case with the respective N atom to which they are bonded, form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, CrC 3 alkoxy, C C 3 haloalkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, C C 3 alkyl- sulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkylcarbonyl- amino; or R 42 is wherein
  • X 12 is oxygen, -NR 49 -, -S-, -S(O)- or -S(O) 2 -;
  • R 49 is hydrogen, CrC 6 alkoxy, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 - alkoxy, d-C 3 haloalkoxy, C C 3 alkylthio, C C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, C C 3 halo- alkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by C ⁇ -C alkylcarbonylamino;
  • R ⁇ is a d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, CrC 6 alkoxy, CrC 3 alkoxy-d-C 3 alkoxy,
  • CrC 6 alkyl C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group either via a C atom or via a N atom
  • the phenyl- and heteroaryl-containing groups may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, C ⁇ -C 3 haloalkoxy, C C 3 alkyl- thio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxy- carbonyl or by d-C 4 alkylcarbonylamino;
  • X 13 is oxygen or sulfur
  • R 50 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, C C 3 alkoxy, CrC 3 halo- alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro,
  • R 51 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 50 together with R 51 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy,
  • R 52 is formyl, CrC 6 alkylcarbonyl, C 3 -C 6 cycloalkyIcarbonyl, benzoyl, CrCealkoxycarbonyl, cyano, CCX JNRssR ⁇ , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, C C 4 alkyl, C C 4 haloalkyl, d-C 3 alkoxy, C C 3 halo- alkoxy, CrC 3 alkylthio, C ⁇ -C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by C ⁇ -C alkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, CrC 4 alkyl, d-C 4
  • R 53 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyi, d-C haloalkyl, d-C 3 alkoxy, d-C 3 halo- alkoxy, CrC 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, CrC alkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 54 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 53 together with R ⁇ and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted
  • R 8 is hydrogen or a C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-C 6 alkoxy, d-C 3 alkoxy- C C 3 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 alkylthio, CrC 6 alkylsulfinyl, d-C 6 - alkylsulfonyl, cyano, C(X ⁇ 5 )NR 55 R 56 , C 3 -C 6 cycloalkyl, phenyl, phenoxy or by 5- or 6- membered heteroaryl or heteroaryloxy, and wherein heteroaryl or heteroaryloxy may in turn be interrupted once by oxygen or by sulfur or once, twice or three times by nitrogen and may be bonded to the CrC 6 alkyl, C 3 -C
  • R 56 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 55 together with R 56 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by CrC 4 alkylcarbonylamino; or R 8 is cyano, C(O)-R 76 or C(S)-R 77 ;
  • X 3 is oxygen, -NR 57 -, sulfur, -S(O)- or -S(O) 2 -;
  • R 57 is hydrogen, C ⁇ -C 6 alkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, CrC 6 haloalkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, C(X ⁇ 6 )R 58 or NR 6 ⁇ R 62 ;
  • X 16 is oxygen or sulfur
  • R 58 is hydrogen, CrC 6 alkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, d-C 6 alkoxy, C 3 -C 6 alkenyl- oxy, benzyloxy, d-C 4 alkylthio or a group NR 59 R 6 o;
  • R 59 and R 6 ⁇ are each independently of the other hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or
  • C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-C 4 alkyl, d-C 4 haloalkyl, CrC 3 alkoxy, CrC 3 haloalkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, C C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C alkyl- carbonylamino;
  • R 60 and R 62 are each independently of the other hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or
  • X 17 is oxygen, -NR 6 - ) -S-, -S(O)- or -S(O) 2 -;
  • R ⁇ is hydrogen, d-C 6 alkoxy, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C 3 - alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, C C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, C C 3 haIo- alkylthio, cyano, nitro, d-C alkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 63 is a CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, CrC 6 alkoxy, CrC 3 alkoxy-d-C 3 alkoxy,
  • CrCealkyl C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group either via a C atom or via a N atom, and wherein the phenyl- and heteroaryl-conta ⁇ ning groups may be substituted once, twice or three times by halogen, C C 4 alkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, C C 3 alkyl- thio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxy- carbonyl or by d-C 4 alkylcarbonylamino;
  • X 18 is oxygen or sulfur
  • R 65 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 halo- alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, C C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by CrC 4 alkylcarbonylamino;
  • R 66 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 65 together with R 66 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, C C 4 alkyl, d-C 4 haloalkyl, C C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, C C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkylcarbonylamino; or R 57 is -L 9 -R 67 ;
  • R 6 is formyl, CrC 6 alkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, d-C 6 alkoxycarbonyl, cyano, C(X ⁇ 9 )NR 68 R 69 , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, d-dalkyl, d-C 4 haloalkyl, d-C 3 alkoxy, d-C 3 halo- alkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, C C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C 4 alkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d
  • CrC 4 haloalkyl d-C 3 alkoxy, C C 3 haloalkoxy, C C 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkyl- sulfonyl, CrC 3 haloalkylthio, cyano, nitro or by d-C 4 alkoxycarbonyl; or R 6 is C 3 -C 6 cycloalkyl or C 5 -C 6 cycloalkenyl each of which may in turn be substituted once, twice or three times by d-C alkyl, halogen or by C C 4 alkoxy; X 19 is oxygen or sulfur;
  • R 68 is hydrogen, C C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-C haloalkyl, d-C 3 alkoxy, C C 3 halo- alkoxy, d-C 3 alkylthio, C r C 3 alkylsulfinyl, C C 3 alkylsulfonyl, CrC 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-C alkylcarbonylamino
  • R 69 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 68 together with R 69 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring
  • R 71 is hydrogen or a d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, CrC 6 alkoxy, d-C 3 alkoxy- d-C 3 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, d-C 6 alkylthio, CrC 6 alkylsulfinyl, d-C 6 - alkylsulfonyl, cyano, C(X 2 ⁇ )NR 72 R 3 , C 3 -C 6 cycloalkyl, phenyl, phenoxy or by 5- or 6- membered heteroaryl or heteroaryloxy, wherein heteroaryl or heteroaryloxy may in turn be interrupted once by oxygen or by sulfur or once, twice or three times by nitrogen and may be bonded to the CrC 6 alkyl, C 3
  • R 72 is hydrogen, CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-C 3 alkoxy, C C 3 halo- alkoxy, CrC 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino; R 73 is hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 72 together with R 73 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted
  • X 35 is oxygen or sulfur
  • R 1 25 is hydrogen, Crdalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; 126 is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 125 together with R 126 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-me'mbered
  • R74, R75, R76, R77, R78 and R 79 are each independently of the others hydrogen, C ⁇ -C 6 alkyl,
  • C C alkylthio or NR 127 R 128 wherein phenyl, benzyl or heteroaryl may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, C C 3 alkoxy, d-dhaloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R127 is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, CrC 3 alkylsulfonyl, C C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by CrC 4 alkylcarbonylamino;
  • R 128 is hydrogen,drC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or Ri 27 together with R 128 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-C 3 alkoxy, d-C 3 haloalkoxy, d-C 3 alkylthio, C r C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 80 and R 8 ⁇ are each independently of the other hydrogen, d-dalkyl, cyclopropyl, allyl or propargyl;
  • X 22 is hydroxy, O ' M + wherein M + is an alkali metal cation or ammonium cation, or is halogen, d-C 12 alkylthio, Crd 2 alkylsulfinyl, Crd 2 alkylsulfonyl, CrC 12 haloalkylthio, d-C 12 halo- alkylsulfinyl, CrC 1 haloalkylsulfonyl, CrC 6 alkoxy-CrC 6 alkylthio, CrC 6 alkoxy-CrC 6 alkyl- sulfinyl, CrC 6 alkoxy-CrC 6 alkylsulfonyl, C 3 -C 12 alkenylthio, C 3 -C 12 alkynylthio, d-dalkoxy- carbonyl-d-dalkylthio, CrC alkoxycarbonyl-d-C 4 alkylsulfinyl
  • R 82 is halogen, d-C 3 alkyl, CrC 3 haloalkyl, hydroxy, CrC 3 alkoxy, d-C 3 haloalkoxy, cyano or nitro; and also to agronomically acceptable salts, tautomers, isomers and enantiomers of those compounds.
  • alkyl groups in the substituent definitions may be straight-chained or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl and octyl and branched isomers thereof.
  • Alkoxy, alkylthio, alkenyl and alkynyl radicals are derived from the mentioned alkyl radicals.
  • the alkenyl and alkynyl groups may be mono- or poly-unsaturated, in which case an allenyl group and a mixed alkene-alkynyl group are also included.
  • Alkoxy groups are accordingly methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec- butoxy, isobutoxy, tert-butoxy.
  • Alkylthio groups and oxidised forms thereof preferably have a chain length of from 1 to 3 carbon atoms; preference is given to, for example, methylthio, ethylthio, n-propylthio and isopropylthio; especially methyl- and ethyl-thio.
  • Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl or isopropylsulfinyl, and alkylsulfonyl is preferably methylsulfonyl, ethylsulfonyl, propylsulfonyl or isopropylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine; preferably fluorine, chlorine or bromine.
  • Halo-substituted alkyl groups that is to say haloalkyl groups, preferably have a chain length of from 1 to 6 carbon atoms.
  • Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoro- ethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1 ,1-difluoro-2,2,2-trichloroethyl, 2,2,2- trichloroethyl, 1 ,1 ,2,2-tetrafluoroethyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl or 2,2,3,4,4,4-hexafluorobutyl; preferably fluoromethyl, difluoromethyl, difluorochloromethyl, dichlorofluoromethyl, trifluoromethyl, 2-chloroethyl, 2,2,2-trifluoroethyl, 2,2,3,3-
  • haloalkenyl groups alkenyl groups substituted once or more than once by halogen are suitable, halogen being especially fluorine or chlorine, for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloro- propenyl or 4,4,4-trif luoro-but-2-en-1 -yl.
  • fluorine or chlorine for example 2,2-difluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyl, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloro- propenyl or 4,4,4-trif luoro-but-2-en-1 -yl.
  • haloalkynyl for example alkynyl groups substituted once or more than once by halogen are suitable, halogen being bromine or iodine or also fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trif luoropropynyl or 4,4,4-trif luoro-but-2-yn-1 -yl.
  • halogen in association with other definitions such as haloalkoxy, haloalkylthio, haloalkyl- sulfinyl, haloalkylsulfonyl or halophenyl.
  • R 4 or R 5 as a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and wherein the ring system is bound to the substituent -i either directly or via a d-dalkylene, C 2 -C 4 alkenylene, C 2 -C 4 alkynylene, -N(R 18 )-d-C 4 alkylene, -O-C r C alkylene, -S-d-C 4 alkylene, -S(O)-CrC aIkylene or -SO 2 -d-C 4 alkylene group, and each ring system may contain not more than 2 oxygen atoms and not more than two sulfur atoms, and the ring system may itself be substituted, is to be understood in the context of the present invention as meaning, for example, phenyl, naphthyl, indenyl
  • Heteroaryl such as, for example, in the definition of R 6 , R 7 , R 8 or R 9 or in the case of a five- or six-membered, monocyclic or fused bicyclic, aromatic ring system R 4 or R 5 , is understood to be especially an aromatic 5- or 6-membered heteroaryl group bonded via a carbon atom, which group may be interrupted once by oxygen, once by sulfur and/or once, twice or three times by nitrogen, for example 1 -methyl-1 H-pyrazol-3-yl, 1 -ethyl-1 H-pyrazol-3-yl, 1-propyl- 1 H-pyrazol-3-yl, 1 H-pyrazol-3-yl, 1 ,5-dimethyl-1 H-pyrazol-3-yl, 4-chloro-1 -methyl-1 H-pyrazol- 3-yl, 3-isoxazolyl, 5-methyl-3-isoxazolyl, 3-methyl-5-isoxazolyl, 5-isoxazolyl, 1
  • a heteroaryl group bonded via the N atom is understood to be, for example, 1 H- pyrrol-1-yl, 1H-pyrazol-1-yl, 3-methyl-1H-pyrazol-1-yl, 3,5-dimethyl-1H-pyrazol-1-yl, 3- trif luoromethyl-1 H-pyrazol-1 -yl, 3-methyl-1 H-1 ,2,4-triazol-1 -yl, 5-methyl-1 H-1 ,2,4-triazol-1 -yl or 4H-1 ,2,4-triazol-4-yl.
  • d-C 4 alkylene which may be substituted once, twice or three times by d-dalkyl, halogen or by d-dalkoxy, wherein a carbon atom of the chain forms together with R 9 a C 2 -C 6 alkylene chain which may be interrupted once or twice by oxygen, sulfur, sulfinyl or by sulfonyl and may be substituted by d-dalkyl or by d-dalkoxy, is to be understood in the context of the present invention as being, for example, the following cyclic C 2 -C 6 alkylene groups: C 3 -C 6 oxacycloalkyl, C 2 -C 5 dioxacycloalkyl, C 3 -C 6 oxacycloalkyl- Crdalkyl, C 3 -C 6 dioxacycloalkyl-CrC 2 alkyl or similar oxygen- or sulfur-containing groups, especially a C 3 -C 6 cyclo
  • L 2 , L , L 6 and L 8 as d-C 4 alkylene, to which d-dalkylene group there may be spirocyclically bound a C 2 -C 5 alkylene group, is to be understood as meaning, for example, a d-C 3 alkylene chain that contains a cyclopropyl group or that is substituted by a 1 ,3-dioxolan-2-yl group, such as, for example,
  • the marked 'C atom represents the left-hand side valence of the definitions containing the respective substituent L.
  • the marked 'C atom represents the left-hand side valence of the definitions containing the respective substituent L.
  • the marked 'C atom is linked to the substituent X 3 .
  • such alkylene chains for example d-dalkylene for U and U, can also be substituted by one or more d-C 3 alkyl groups, especially by methyl groups.
  • Such alkylene chains and the alkylene groups interrupted by oxygen or by sulfur are preferably unsubstituted.
  • groups containing C 3 -C 6 cycloalkyl, oxiranyl, oxetanyl, C 3 -C 5 oxa- cycloalkyl, C 3 -C 5 thiacycloalkyl, C 3 -C 4 dioxacycloalkyl, C 3 -C 4 dithiacycloalkyl or C 3 -C 4 oxathia- cycloalkyl are also unsubstituted.
  • the compounds of formula I may occur in various tautomeric forms, as shown by way of example for compounds of formula I wherein X 22 is hydroxy by formulae I', I", I'" and I"", the form I" being preferred as isolated form.
  • the present invention accordingly includes also all those stereoisomeric and tautomeric forms of the compound of formula I.
  • the invention relates also to the salts which the compounds of formula I are able to form preferably with amines, alkali metal and alkaline earth metal cations or quaternary ammonium bases.
  • Suitable salt formers are described, for example, in WO 98/41089.
  • alkali metal and alkaline earth metal hydroxides as salt formers special mention may be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, but especially the hydroxides of sodium and potassium.
  • amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary CrC 18 alkylamines, d-dhydroxyalkylamines and C 2 -C 4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropyl- amine, the four butylamine isomers, n-amylamine, isoamylamine, n-hexylamine, heptyl- amine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecyl- amine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-octadec
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [ + N(R a R b R c R d ) OH] wherein R a , R b , R 0 and R d are each independently of the others d-dalkyl.
  • Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • R 80 is methyl, ethyl, isopropyl or propargyl; b) R 81 is hydrogen or methyl; c) X 22 is hydroxy, a salt of formula O " M + wherein M is an agronomically acceptable metal cation or ammonium cation, or d-dalkylsulfonyloxy, tosyloxy, especially hydroxy; d) R 2 is chlorine, bromine, cyano, trifluoromethyl, difluoromethyl, difluorochloromethyl, difluoromethoxy, trifluoromethoxy, trifluoroethoxy, difluoromethylthio, trifluoromethylthio, trifluoroethylthio, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl, especially trifluoromethyl; or e) Ri is a group NR 6 R 7 ,
  • R 1 is a group -X 3 -L R 9 wherein X 3 is oxygen;
  • l_ ⁇ is a methylene or ethylene chain which may be substituted by methyl, ethyl, methoxy or by ethoxy, special emphasis being given to those compounds wherein R, as -X 3 -L R 9 is the side chain -O-L O-R 70 wherein R 70 is d-C 3 alkyl, allyl, propargyl, d-dalkoxy-Ci-dalkyl or C(O)-R 78 and R 78 is NR 127 R ⁇ 28 ;
  • Ri as -X 3 -LrR ⁇ is the group -O-L X2o-R7o wherein X 20 is especially oxygen and a carbon atom of the chain U together with R 0 forms a C 2 -C 6 alkylene chain which may be interrupted once by oxygen and substituted once or twice by
  • R ! is a group NR 6 R 7 or a group -X 3 -L Rg wherein X 3 is -NR 57 - and wherein is a methylene or ethylene chain which may be substituted by methyl, ethyl, methoxy or by ethoxy, and of that group of compounds of formula I special mention should be made of those wherein NR 6 R 7 is a heterocyclic group selected from morpholin-4-yl, pyrazol-1-yl and
  • R 7 is C(X 7 )R 30 ; and preferably R 6 is methyl or ethyl; X 7 is oxygen; and
  • R 30 is d-dalkyl, C 3 -C 6 cycloalkyl or phenyl.
  • L is preferably an unsubstituted d-C 3 alkylene chain or a dalkylene chain substituted once by methyl.
  • R is a group -L-n-XrRs wherein L-n is d-C 2 alkylene which may be substituted by methyl, ethyl, methoxy or by ethoxy, especially unsubstituted methylene;
  • Ri is a group -Ln-XrRs wherein R 5 is CrC 6 alkylene which may be substituted by methyl, ethy
  • the bidentate linking member -L ⁇ Xr is preferably -CH 2 O-, -CH 2 CH 2 O- or -CH 2 N(SO 2 CH 3 )-.
  • Ri is a group -L 10 -R wherein L 10 is a direct bond or is a d-C 3 alkylene or C 2 -C 3 alkenylene group which may be substituted from one to three times by halogen, methyl, ethyl, methoxy or by ethoxy; especially a direct bond or an unsubstituted d-C 2 alkylene chain;
  • R is a group -L 10 -R wherein R 4 is halogen or cyano, or is a d-dalkyl group which may be substituted by halogen, methoxy or by ethoxy, or is a three- to six-membered monocyclic ring system which may be saturated, partially saturated or unsaturated and may contain 1 or 2 hetero atoms selected from nitrogen, oxygen and sulfur and may itself be substituted by methyl or methoxy or by methoxymethyl; R-i is especially fluorine, chlorine, bromine, cyano, methyl, ethyl, n-propyl, isopropyl, cyclopropyl, methoxymethyl, ethoxymethyl, tetrahydro- furan-2-yl, tetrahydrofuran-3-yl, 1 ,3-dioxolan-2-yl, 1 ,3-dioxolan-4-yl, (2-methyl-[1 ,3]diox
  • Ri is -L11-X1-R5, -NR 6 R 7 , -X 2 -R 8 , -X 3 -L Rg, d-dhaloalkyl, C 2 -C 6 haloalkenyl, C 2 -C 6 halo- alkynyl or halogen;
  • l_ 2 , U, L- 6 and L 8 are each independently of the others d-dalkylene which may be substituted once, twice or three times by d-dalkyl, halogen or by d-dalkoxy and to which d-C 4 alkylene group there may additionally be spirocyclically bound a C 2 -C 5 alkylene group, and wherein that C 2 -C 5 alkylene group may in turn be interrupted once or twice by oxygen, sulfur, sulfinyl or by sulfonyl and/or substituted by d-dalkyl or by
  • R 1 0. R11.
  • R12, R 1 3, Ri4b. and R 14 are each independently of the others hydrogen, d-dalkyl, d-dhaloalkyl, CrCealkoxycarbonyl, d-dalkylcarbonyl, CrC 6 alkoxy-CrC 6 alkyl, or CrCealkoxy-CrCealkyl substituted by d-dalkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by d-dalkyl, CrCehaloalkyl, d-dalkoxy, d-dhaloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 1 a is hydroxy, d-dalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy or benzyloxy;
  • R 14c is CrC 6 alkyl
  • R 5 is hydrogen or d-dalkyl, or is a d-C 8 alkyl, C 3 -C 8 alkenyl or C 3 -C 8 alkynyl or C 3 -C 6 cyclo- alkyl group which is substituted once, twice or three times by halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, d-C 6 alkoxy, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, d-dalkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 -cycloalkyl, halo-substituted C 3 -C 6 cycloalkyl, C 3 -C 6 - alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, cyan
  • R ⁇ e, i7, 19 and R 2 o are each independently of the others hydrogen, d-dalkyl, d-dhaloalkyl, d-dalkoxycarbonyl, d-dalkylcarbonyl, Crdalkoxy-d-dalkyl, or Crdalkoxy-Crdalkyl substituted by d-dalkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by d-dalkyl, d-dhaloalkyl, CrC 6 alkoxy, d-dhaloalkoxy, halogen, cyano, hydroxy or by nitro; or R 5 is a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, saturated or partially saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and wherein the ring system is bound to
  • R 5a is CrC 6 alkyl, hydroxy, d-dalkoxy, cyano or nitro;
  • R 18 is hydrogen, d-dalkyl, d-dhaloalkyl, d-dalkoxycarbonyl, d-dalkylcarbonyl, d-dalkoxy-d-Cealkyl, or CrCealkoxy-CrCealkyl substituted by d-dalkoxy, or benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by CrC 6 alkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R 6 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, d-Cehaloalkyl, hydroxy, d-dalkoxy,
  • R 19a and R 20a are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, d-dalkoxy, C 3 -C 6 alkenyloxy, benzyloxy, d-C 4 alkylthio or a group
  • R 21 and R 22 are each independently of the other hydrogen, d-C 6 alkyl, C 3 -C 6 alkenyl,
  • R 23 is hydrogen, d-dalkoxy, Crdalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, C C 3 alkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhalo- alkylthio, cyano, nitro, CrC 4 alkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 24 is hydrogen or a d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-dalkoxy, d-
  • R 25 is hydrogen, Crdalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, C C 4 haloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 26 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 25 together with R 26 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and
  • R 28 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 29 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 28 together with R 29 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by
  • R 30 is hydrogen, d-dalkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, d-dalkoxy, C 3 -C 6 alkenyl- oxy, benzyloxy, d-dalkylthio or a group NR 31 R 32 ;
  • R 3 ⁇ and R 33 are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, C C 3 alkoxy, C C 3 haloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-C 3 alky!sulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 32 and R 34 are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 alkenyl or d-dalkynyl; or R 3 ⁇ together with R 32 or R 33 together with R 3 , in each case with the respective N atom to which they are bonded, form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, C C 3 alkoxy, d-dhaloalkoxy, d-C 3 alkylthio, d-dalkylsulfinyl, d-C 3 alkyl- sulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; or R 7 is -L 4 -X 8 -R 35
  • R 36 is hydrogen, Crdalkoxy, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, Crdhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-C 3 alkylthio, d-dalkylsulfinyl, d-C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 35 is hydrogen or a d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-dalkoxy, d-
  • R 37 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, C C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; R 38 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 37 together with R 38 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and
  • R 39 is formyl, d-dalkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, CrC 6 alkoxycarbonyl, cyano, C(X 10 )NR 40 R 4 ⁇ , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, d-dalkyl, C C 4 haloalkyl, C C 3 alkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d-dalkyl, d-d
  • R 40 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, Crdalkylsulfinyl, d-dalkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 4 ⁇ is hydrogen, Crdalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R ⁇ together with R 41 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by
  • R ⁇ I and R 46 are each independently of the other hydrogen, CrCealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, C C 3 alkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 45 and R 47 are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -dalkynyl; or R ⁇ i together with R ⁇ or R 6 together with R 47 , in each case with the respective N atom to which they are bonded, form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, C C 3 haloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; or R 42 is -Le-X ⁇ -R ⁇ ; wherein X 12
  • R 49 is hydrogen, d-dalkoxy, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino;
  • R 48 is a CrC 6 alkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-dalkoxy, d-
  • R 52 is formyl, d-dalkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, d-dalkoxycarbonyl, cyano, C(X ⁇ )NR 53 R 54 , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-C 3 alkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d-dalkyl,
  • R 53 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, C C 3 alkylthio, d-dalkylsulfinyl, d-C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R ⁇ is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 53 together with R ⁇ and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by
  • R 8 is hydrogen or a d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-C 6 alkoxy, d-dalkoxy- d-C 3 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 alkylthio, CrC 6 alkylsulfinyl, d-C 6 - alkylsulfonyl, cyano, C(X 15 )NR 55 R 56 , C 3 -C 6 cycloalkyl, phenyl, phenoxy or by 5- or 6- membered heteroaryl or heteroaryloxy, and wherein heteroaryl or heteroaryloxy may in turn be interrupted once by oxygen or by sulfur or once, twice or three times by nitrogen and may be bonded to the d-dalkyl, C 3 -C
  • R 55 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-C 4 haloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, C C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; R 56 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 55 together with R 56 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur
  • R 57 is hydrogen, CrCealkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, d-dhaloalkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, C(X 16 )R5 8 or NR 6 ⁇ R 6 2; X 16 is oxygen or sulfur;
  • R 58 is hydrogen, d-Cealkyl, C 3 -C 6 cycloalkyl, phenyl, heteroaryl, d-dalkoxy, C 3 -C 6 alkenyl- oxy, benzyloxy, d-C 4 alkylthio or a group NR 59 R 60 ;
  • R 59 and R 6 ⁇ are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • Reo and R 62 are each independently of the other hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -dalkynyl; or R 59 together with R 60 or R 6 ⁇ together with R 62 , in each case with the respective N atom to which they are bonded, form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, C C 3 alkoxy, d-dhaloalkoxy, d-dalkylthio, C C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; or R 57 is -L 8 -X 17 -R 63
  • R M is hydrogen, d-dalkoxy, CrCealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or is phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-C 3 alkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; R 63 is a d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-dalkoxy, CrC 3 al
  • R 65 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; R 66 is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 65 together with R 66 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen
  • R 6 7 is formyl, d-dalkylcarbonyl, C 3 -C 6 cycloalkylcarbonyI, benzoyl, C C 6 alkoxycarbonyl, cyano, C(X ⁇ g)NR 68 R 69 , phenyl or heteroaryl, wherein benzoyl and phenyl may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; and wherein heteroaryl may be substituted once, twice or three times by halogen, d-dalkyl, d-
  • R 68 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-C haloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino
  • R 6 g is hydrogen, d-Cealkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 68 together with R 69 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may
  • R 71 is a d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, which groups may be substituted once, twice or three times by halogen, hydroxy, d-dalkoxy, CrC 3 aikoxy-d-C 3 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, CrC 6 alkylthio, d-C 6 alkylsulfinyl, CrC 6 alkylsulfonyl, cyano, C(X 2 ⁇ )NR 72 R 73 , C 3 -C 6 cycloalkyl, phenyl, phenoxy or by 5- or 6-membered heteroaryl or heteroaryloxy, wherein heteroaryl or heteroaryloxy may in turn be interrupted once by oxygen or by sulfur or once, twice or three times by nitrogen and may be bonded to the d-Cealkyl, C 3 -C 6 al
  • R 7 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino; R 73 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 72 together with R 73 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by
  • R 70 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C(O)-R 78 , C(S)-R 79 or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, C C 3 alkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C 4 alkylcarbonylamino; or R 9 is formyl, d-dalkylcarbonyl, C 3 -C 6 cycloalkylcarbonyl, benzoyl, CrCealkoxycarbonyl, cyano, C(X 35 )NR
  • R 1 25 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-C 3 alkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-C 3 haloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-dalkylcarbonylamino;
  • Ri2 ⁇ is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 125 together with R ⁇ 26 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-dalkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-C alkylcarbonylamino;
  • R7 4 , R75, R76, R77, R78 and R 79 are each independently of the others hydrogen, d-dalkyl,
  • R 127 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl or phenyl which may be substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-C 3 alkoxy, d-dhaloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-C 4 alkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 128 is hydrogen, d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl; or R 127 together with R 128 and the respective N atom to which they are bonded form a carbocyclic 3- to 6-membered ring which may be interrupted by oxygen or by sulfur and/or substituted once, twice or three times by halogen, d-dalkyl, d-dhaloalkyl, d-dalkoxy, d-dhaloalkoxy, d-dalkylthio, d-C 3 alkylsulfinyl, d-dalkylsulfonyl, d-dhaloalkylthio, cyano, nitro, d-dalkoxycarbonyl or by d-dalkylcarbonylamino;
  • R 80 and R 8 ⁇ are each independently of the other hydrogen, d-dalkyl, cyclopropyl, allyl or propargyl;
  • X 22 is hydroxy, O " M + wherein M + is an alkali metal cation or ammonium cation, or is halogen,
  • the compounds of formula I can be prepared by means of processes that are known perse and are described, for example, in EP-A-352 543, EP-A-344775, US 6,211 ,403 und EP-A-1 286985.
  • Yi is a leaving group, e.g. halogen, cyano, acyloxy or phenoxy which may be substituted by an electron-withdrawing group, e.g. halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-C 4 alkoxycarbonyl or d-C 4 alkylsulfonyl, or the like, and then reacting that compound in the presence of a base, e.g. triethylamine, H ⁇ nig's base, sodium hydrogen carbonate or potassium carbonate, with a pyrazole of formula III
  • a base e.g. triethylamine, H ⁇ nig's base, sodium hydrogen carbonate or potassium carbonate
  • R 80 and R 81 are as defined hereinbefore and X 22 is hydroxy or O " M + wherein M + is as defined hereinbefore, and then treating the reaction mixture in the presence of the base used, e.g. triethylamine or di(isopropyl)ethylamine, with the aid of a cyanide-containing catalyst, e.g. acetone cyanohydrin, trimethylsilyl cyanide, copper cyanide, sodium cyanide or potassium cyanide, or by means of fluoride ions, e.g. potassium fluoride, or by means of dimethylaminopyridine; or
  • the base used e.g. triethylamine or di(isopropyl)ethylamine
  • a cyanide-containing catalyst e.g. acetone cyanohydrin, trimethylsilyl cyanide, copper cyanide, sodium cyanide or potassium cyanide, or by means of fluoride ions, e.g. potassium flu
  • Ri and R 2 are as defined hereinbefore and Y is halogen or trifluoromethane- sulfonyloxy
  • a palladium catalyst having suitable ligands, e.g. PdCI 2 (PPh 3 )2, Pd(PPh 3 ) 4) Pd (dba) 3 , Pd(CH 3 CN) 2 (PPh 3 ) or Pd(OAc) 2 , and optionally in the presence of a further auxiliary catalyst, e.g.
  • triphenylphosphine tri(tert-butyl)phosphine, (Ph 3 ) 2 PCH 2 CH 2 P(Ph 3 )2 or (Ph 3 ) 2 PCH 2 CH 2 CH 2 P(Ph 3 )2, and in the presence of a base, e.g. triethylamine, and optionally further adjuvants, e.g. LiCI or Li 2 CO 3 , using carbon monoxide and a pyrazole of formula III
  • R ⁇ R 2 , R 80 und R 8 ⁇ are as defined hereinbefore, and then treating that compound with the aid of a cyanide-containing catalyst, e.g. acetone cyanohydrin, trimethylsilyl cyanide, copper cyanide, sodium cyanide or potassium cyanide, in the presence of a trialkylamine base, e.g. triethylamine, to obtain a compound of formula I; or
  • a cyanide-containing catalyst e.g. acetone cyanohydrin, trimethylsilyl cyanide, copper cyanide, sodium cyanide or potassium cyanide
  • R ⁇ R 2 , R 80 , Rs ⁇ and X 22 are as defined hereinbefore and X 2 is oxygen or sulfur, in the presence of a suitable base, e.g. potassium carbonate, anhydrous sodium hydroxide or sodium hydride, with an alkylating agent of formula IVa or IVb
  • R 8 is an unsubstituted or substituted d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, and Rg and l_ ⁇ are as defined hereinbefore, and Y 2 is a leaving group such as chlorine, bromine, iodine, mesyloxy or tosyloxy; or
  • R 8 is an unsubstituted or substituted d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, and R 9 and are as defined hereinbefore; or
  • R ⁇ R , R 8 o, Rs ⁇ and X ⁇ are as defined hereinbefore and K ⁇ is a leaving group, e.g. halogen or alkylsulfonyl, in the presence of a base, e.g. potassium tert-butanolate, sodium amylate, sodium hydride, dry sodium or potassium hydroxide, or an amine, e.g. triethylamine, H ⁇ nig's base or dimethylaminopyridine, with an alcohol or a mercaptan of formula Vc or Vd
  • R 8 is an unsubstituted or substituted d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, and L-i and Rg are as defined hereinbefore, and X 2 or X 3 is oxygen or sulfur, or with an amine of formula Ve or VI
  • R 9 , R 70 and X 2 o are as defined hereinbefore and Y 3 is a leaving group such as bromine, iodine, tosyloxy or d-dalkylsulfonyloxy, and M + is a metal cation of an alkali metal base, such as lithium, sodium or potassium, optionally in the presence of an additional base, e.g. potassium carbonate, or, in the case of ketalisation of a carbonyl function, in the presence of an additional acid, e.g. p-toluenesulfonic acid, trifluoroacetic acid or sulfuric acid; or
  • Ri is -L 10 -R 4 or -L ⁇ -XrRs wherein L 10 or L is especially an unsubstituted or substituted d-dalkenylene or a C 2 -C 6 alkynylene group and R 4 , when L 1 0 is a direct bond, is especially a five- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic or partially saturated and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, reacting a compound of formula Id wherein R ⁇ R 2 , R 80 , R 8 ⁇ and X are as defined hereinbefore and K 3 is a group capable of functionalisation, such as chlorine, bromine, iodine or trifluoromethylsulfonyloxy, by means of a -C-C- linking Suzuki, Stilie, Sonogashira or Heck reaction, in the presence of a noble metal catalyst having suitable ligands, e.g.
  • a base e.g. triethylamine, Hunig's base, sodium tert-butanolate, potassium tert-butanolate, sodium carbonate, potassium carbonate, caesium carbonate, potassium fluoride or caesium fluoride, and optional
  • triphenylphosphine tri(tert-butyl)phosphine, (Ph 3 ) 2 PCH 2 CH 2 P(Ph 3 ) 2 or (Ph 3 ) 2 PCH 2 CH 2 CH 2 P(Ph 3 )2, with a boronic acid, e.g. of formula Xa or Xb
  • L 10 , Ln, R 4 , R 5 and X ⁇ are as defined hereinbefore, R e , R f and R g are each independently of the others d-dalkyl and L 0a , L ⁇ 0b , 11a and L 11b are appropriate subgroups of the groups L 10 and L- ⁇ , such as especially a direct bond or a d-dalkylene group which may be substituted once, twice or three times by CrCealkyl, halogen, hydroxy, d-dalkoxy or by d-dalkoxy-d-dalkoxy; or h) for the preparation of compounds of formula I wherein the substituent definitions include sulfinyl or sulfonyl groups, treating a compound of formula I wherein the corresponding substituent definitions include thio groups with an oxidising agent, e.g. peracetic acid, trifluoroperacetic acid, m-chloro-perbenzoic acid, hydrogen peroxide,
  • compounds of formula I wherein X 22 is other than hydroxy or halogen can be prepared, in accordance with conversion methods generally known from the literature, by nucleophilic substitution reactions of chlorides of formula I wherein X 22 is chlorine, which can be obtained from compounds of formula I wherein X 22 is hydroxy, likewise in accordance with known methods, by reaction with a chlorinating agent, such as phosgene, thionyl chloride or oxalyl chloride. In that process, for example, mercaptans, thiophenols or heterocyclic thiols are reacted in the presence of a base, e.g.
  • compounds of formula I wherein the substituent X 22 is a mercapto group can be oxidised in analogy to known standard methods, for example using peracids, e.g. meta- chloroperbenzoic acid (m-CPBA) or peracetic acid, to form the corresponding sulfoxides and/or suifones of formula I.
  • peracids e.g. meta- chloroperbenzoic acid (m-CPBA) or peracetic acid
  • a suitable coupling reagent e.g. dicyclohexylcarbodiimide, N- ethyl-N'-(3-dimethylamino-propyl)-carbodiimide (EDC), 2-chloro-1 -methyl-pyridinium iodide or N,N-dimethyl-(1-chloro-2-methyl-propen)amine, or as a result of reaction of a pyrazole of formula III with an activated form of the acid, e.g.
  • R ⁇ R 2 , R 8 o, Rs ⁇ and X 22 are as defined hereinbefore, which may then either be rearranged directly in situ by adding catalytic amounts of cyanide ions, e.g. from about 1 % to about 15 % acetone cyanohydrin, to form the compound of formula I, or may first be isolated and purified and then, in a second step, rearranged in the presence of catalytic amounts of a cyanide source, e.g. from about 0.1 % to about 5 % potassium cyanide ions or from about 0.5 % to about 10 % acetone cyanohydrin, and a fresh amount of a trialkylamine base, e.g.
  • R 1 ; R 2 , R 80 , R 8 ⁇ and X 22 are as defined hereinbefore and X 2 is oxygen or sulfur and which are used as starting materials in process variants c) and d), for example, either a compound of formula le
  • Ri, R 2 , R 8 o, R ⁇ i and X 22 are as defined hereinbefore and K 4 is a cleavable group, such as methoxy when X 2 is oxygen, or is a disulfide bridge of a dimeric compound le, is reacted in the presence of an ether-cleaving reagent, e.g. boron trichloride, boron tribromide, aluminium trichloride, sodium methylmercaptide, sodium ethylmercaptide or trimethylsilyl iodide, or a compound of formula le wherein t is benzyloxy or dimeric disulfide is reduced catalytically in the presence of hydrogen.
  • an ether-cleaving reagent e.g. boron trichloride, boron tribromide, aluminium trichloride, sodium methylmercaptide, sodium ethylmercaptide or trimethylsilyl iodide, or
  • Ri, R 2 , R 8 o, Rs ⁇ and X 22 are as defined hereinbefore and Ko is a sub-group of capable of functionalisation, as defined especially in accordance with the meanings of K 1; K 2 , Ks and/or K* above, such as especially fluorine, chlorine, bromine, iodine, hydroxy, methylthio, methylsulfonyl, bromomethyl, hydroxymethyl, formyl, methylcarbonyl, 2- hydroxyethoxy, 2-bromoethoxy, benzyloxy or dimeric disulfide, can likewise be prepared in accordance with process variant a) or in accordance with process variant b) from the corresponding compounds of formula XII or XIII
  • R2 and Y 4 are as defined hereinbefore and Y is d-dalkoxy, benzyloxy, hydroxy, fluorine, chlorine, cyano or phenoxy which may be substituted by an electron-withdrawing group, e.g.
  • halogen trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl, Y being especially C C alkoxy, benzyloxy, hydroxy, chlorine or cyano; and Ko being especially hydroxy (corresponding to formula la wherein X 2 is oxygen), K ⁇ wherein K 1 is, for example, halogen or methylsulfonyl (corresponding to formula lb), K 3 wherein K 3 is, for example, chlorine, bromine or iodine (corresponding to formula Id), Ki wherein l ⁇ is, for example, methylthio, benzyloxy or methoxy (corresponding to formula le), or a disulfide bridge of a dimeric compound XII or XIII (corresponding to formula le wherein X 2 is sulfur), aa) by reacting the compound in question with a pyrazole of formula III
  • R,, R 2 , R 80 , R 81 and X 22 are as defined hereinbefore and X 2 is oxygen or sulfur, in accordance with process variant c) with an appropriate alkylating agent of formula IVc
  • R ⁇ R 2 , Rso, Rsi and X22 are as defined hereinbefore and K 1 is halogen or alkylsulfonyl, with an alcohol or mercaptan of formula Vg or Vh
  • is methoxy or methylthio and X 3 is oxygen or sulfur
  • K 23 , L,, R 6 and Y 2 are as defined hereinbefore.
  • Y 0 is d-dalkoxy, benzyloxy or phenoxy which may be unsubstituted or substituted by an electron-withdrawing group such as halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl, which are used as starting materials in the preparation of compounds of formula lla, can be prepared analogously to known methods, as described e.g. in EP-A-0 353 187, by converting a compound of formula XIII
  • R 2 is as defined hereinbefore, Ko is hydrogen, methoxy, methylthio, methylsulfonyl, halogen or another group R that is stable in this process, and Y 4 is chlorine, bromine or trifluoromethylsulfonyloxy, under carbonylation conditions at elevated pressure and elevated temperatures in the presence of a palladium catalyst having suitable ligands, e.g. PdCI 2 (PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pd(CH 3 CN) 2 (PPh 3 )2, Pd 2 (dba) 3 or Pd(OAc) 2 , and optionally in the presence of an auxiliary catalyst, e.g.
  • a palladium catalyst having suitable ligands, e.g. PdCI 2 (PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pd(CH 3 CN) 2 (PPh 3 )2, Pd 2 (dba) 3 or Pd(OAc) 2
  • triphenylphosphine tri(tert-butyl)phosphine, (Ph 3 ) 2 PCH 2 CH 2 P(Ph 3 ) 2 or (Ph 3 ) 2 PCH 2 CH 2 CH 2 P(Ph 3 ) 2 , and in the presence of a base, e.g. triethylamine, using carbon monoxide and an alcohol of formula IX
  • R 0 is d-dalkyl, benzyl or phenyl which may be unsubstituted or substituted by an electron-withdrawing group such as halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl, into a compound of formula Xlla
  • Ko, Ri and R 2 are as defined hereinbefore and Y is d-dalkoxy, benzyloxy, hydroxy, fluorine, chlorine, bromine, cyano or phenoxy which may be unsubstituted or substituted by an electron-withdrawing group, e.g. halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl.
  • an electron-withdrawing group e.g. halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl.
  • R 2 and Y 0 are as defined hereinbefore, which is then converted in the presence of an oxidising agent, e.g. hydrogen peroxide or the hydrogen peroxide/urea adduct in the presence of trifluoroacetic anhydride, into an N-oxido compound of formula XV
  • an oxidising agent e.g. hydrogen peroxide or the hydrogen peroxide/urea adduct in the presence of trifluoroacetic anhydride
  • R 2 and Y 0 are as defined hereinbefore, which is then either a) reacted in the presence of phosphorus oxychloride or trifluoroacetic anhydride to form a hydroxy compound of formula XI lc
  • R ⁇ R 6 , R 3 o are as defined hereinbefore, converted in the presence of an activating reagent, e.g. oxalyl chloride or trifluoroacetic anhydride, and optionally in the presence of an acid-binding agent, e.g. triethylamine or H ⁇ nig's base, directly into the compounds of formula lid
  • an activating reagent e.g. oxalyl chloride or trifluoroacetic anhydride
  • an acid-binding agent e.g. triethylamine or H ⁇ nig's base
  • R ⁇ R 2 and Y 0 are as defined hereinbefore and R 1 is especially also a group -NR C(O)R 30> which can then be converted in accordance with a) for the isolation of an intermediate of formula XI lc by known and general conversion methods such as halogena- tion, e.g. by means of dichlorophenyl phosphate, further nucleophilic reactions with alcohols, mercaptans or amines of formula
  • R ⁇ is a group -X 2 -R 8 or -X 3 -l_rR 9 , X2 and X 3 are oxygen, and l_ ⁇ , R 2 , R 9 and Y 0 are as defined hereinbefore, and R 8 is an unsubstituted or substituted d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, can also be prepared either by treating a compound of formula XI Id
  • R 2 and Y 0 are as defined hereinbefore, and X 2 is oxygen or sulfur, in accordance with process variant c) in the presence of a suitable base with an alkylating agent of formula
  • R 8 is an unsubstituted or substituted d-dalkyl, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl group, and R 9 and U are as defined hereinbefore, respectively.
  • the reaction described in accordance with process variant d) is generally known as a Mitsunobu reaction and is especially suitable for the preparation of those compounds of formulae I and lid wherein R ⁇ is a group -X -R 8l -Xs-U-Rg or -X LrX2o-R7o and X 2 and X 3 are oxygen and R 8 and l_ ⁇ are a d-dalkylene group branched in the a/pfra-position or substituted in that position by halogen or by alkoxy, or together with R 9 or with R 70 forms, by means of a further d-dalkylene chain, a 3- to 6-membered ring system.
  • Ri is a group -L 10 -R 4 or -L-n-X s and wherein L 10 and Ln are especially an unsubstituted or substituted C -C 6 alkenylene or a C 2 -C 6 alkynylene group and R 4 , when L 10 is a direct bond, is especially a five- to ten-membered, monocyclic or fused bicyclic ring system which may be aromatic or partially saturated, and which may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, and R 2 , Rs, Xi and Y 0 are as defined hereinbefore, can advantageously be prepared by reacting a compound of formula XI le wherein R 2 and Y 0 are as defined hereinbefore, and Ks is group capable of further functionalisation, such as chlorine, bromine, iodine or trifluoromethylsulfonyloxy, in accordance with process variant g) by means of a -C-C- linking Suzuki, Stille,
  • a base e.g. triethylamine, H ⁇ nig's base, sodium tert-butanolate, potassium tert-butanolate, sodium carbonate, potassium carbonate, caesium carbonate, potassium fluoride or caesium fluoride,
  • triphenylphosphine tri(tert-butyl)phosphine, (Ph 3 ) 2 PCH2CH 2 P(Ph 3 )2 or (Ph 3 )2PCH2CH 2 CH 2 P(Ph 3 ) 2 , with a boronic acid, e.g. of formula Xa or Xb
  • L ⁇ 0 , Ln, R 4 , R 5 and Xi are as defined hereinbefore
  • R e , R f and R g are each independently of the others d-dalkyl
  • L 10a , L 10b , L 11a and L are appropriate subgroups of the groups L 10 and L ⁇ , such as especially a direct bond or a d-dalkylene group which may be substituted once, twice or three times by d-Cealkyl, halogen, hydroxy, d-dalkoxy or by d-C 3 alkoxy-C ⁇ -C 3 alkoxy, and wherein the reagents Xg and Xh can in addition each result in one or more regio-isomeric products, for example
  • K 0 , K 2 and R 2 are as defined hereinbefore and Y is accordingly Y 0 , hydroxy or Y ⁇ which are used as starting materials in the preparation of compounds of general formulae If and especially lc, can likewise be prepared in accordance with the generally known methods or in accordance with the preparation processes c) to h) given above for formulae I and lie.
  • R ⁇ and R 2 are as defined hereinbefore and Y is d-C 4 alkoxy, benzyloxy, hydroxy, fluorine, chlorine, bromine, cyano or phenoxy which may be unsubstituted or substituted by an electron-withdrawing group, e.g. halogen, trifluoromethyl, nitro, cyano, d-dalkylcarbonyl, d-dalkoxycarbonyl or d-dalkylsulfonyl, are novel and the present Application relates also to the use thereof in the preparation of compounds of formula I.
  • All the reactions according to the preparation processes a) to h) for forming compounds of formula I and also intermediates of formula II are advantageously carried out in aprotic and inert organic solvents.
  • solvents are hydrocarbons, e.g. benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, e.g. dichloromethane, chloroform, tetrachloro- methane or chlorobenzene, ethers, e.g. diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles, e.g.
  • acetonitrile or propionitrile and amides, e.g. N,N-dimethylformamide, diethylformamide or N-methyl- pyrrolidinone.
  • the temperatures in those reactions are preferably from -20°C to +120°C. When the reactions are exothermic, they can usually be carried out at room temperature. In order to shorten the reaction time or also in order to initiate the reaction, the reaction mixture may, where appropriate, be heated briefly up to its boiling point. Relatively new application techniques such as ultrasound and the use of microwaves are also highly suitable. It is often possible, especially when using microwaves, for the reaction times to be substantially reduced at relatively mild temperatures of from about 100°C to about 150°C.
  • 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 and 1 ,5-diazabicyclo[5.4.0]- undec-7-ene.
  • inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. dry sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. sodium or potassium hydrogen carbonate.
  • reaction a preparation of the compounds of formulae I, If, and II, lib and XII, wherein Yi and Y are chlorine, is carried out using a chlorinating agent, e.g. oxalyl chloride, thionyl chloride, phosgene, (1 -chloro-2-methyl-propenyl)-dimethyl-amine, phosphorus pentachloride, phosphorus oxychloride or dichlorophosphate, preferably using oxalyl chloride.
  • the reaction is preferably carried out in an inert, organic solvent, for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, e.g.
  • reaction temperatures in the range from -20°C up to the reflux temperature of the reaction mixture, preferably at about 40-100°C, and in the presence of a catalytic amount of N,N-dimethylformamide. It can also, where appropriate, be carried out directly in the chlorinating agent used, without additional solvent.
  • the end products of formula I can be isolated in conventional manner by concentrating or evaporating off the solvent and can be separated and purified by recrystallising or by triturating the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons, or by distillation or by means of column chromatography or by means of HPLC techniques using a suitable eluant.
  • the product may be obtained in the form of a mixture of two or more isomers, e.g. chiral centres in the case of alkyl groups or cis/trans isomerism in the case of alkenyl groups or ⁇ ' or 'Z' forms. All those isomers can be separated using methods known perse, e.g. chromatography or fractional crystallisation, or, by specifically controlling the reactions, a desired form can be produced in a relatively high concentration or in pure form.
  • the compounds of formula I according to the invention can be used as herbicides in unmodified form, that is to say as obtained in the synthesis, but they are generally formulated in various ways, using formulation adjuvants such as carriers, solvents and surface-active substances, to form herbicidal compositions.
  • formulation adjuvants such as carriers, solvents and surface-active substances.
  • the formulations can be in various physical forms, e.g.
  • the formulations can be produced, for example, by mixing the active ingredient with the formulation adjuvants to obtain compositions in the form of finely divided solids, granules, spherules, solutions, dispersions or emulsions.
  • the active ingredients can also be formulated with other adjuvants, such as finely divided solids, mineral oils, organic solvents, water, surface-active substances or combinations thereof.
  • the active ingredients can also be contained in very fine microcapsules consisting of a polymer. Microcapsules contain the active ingredients in a porous carrier. This enables active ingredients to be released into the surroundings in controlled amounts. Microcapsules usually have a diameter of from 0.1 to 500 microns.
  • the active ingredients contain active ingredient in an amount of about from 25 to 95 % by weight of the capsule weight.
  • the active ingredients can be present in the form of a monolithic solid, in the form of fine particles in solid or liquid dispersion or in the form of a suitable solution.
  • the encapsulating membranes comprise, for example, natural and synthetic gums, cellulose, styrene-butadiene copolymers, polyacrylonitrile, polyacrylate, polyester, polyamides, polyureas, polyurethane or chemically modified polymers and starch xanthates or other polymers known in this context to the person skilled in the art.
  • the formulation adjuvants that are suitable for producing the compositions according to the invention are known perse.
  • liquid carriers there may be used: water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydrides, acetonitrile, acetophenone, amyl acetate, 2-butanone, chlorobenzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1 ,2-dichloro- propane, diethanolamine, p-diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N,N-dimethylformamide, dimethyl sulfoxide, 1 ,4-dioxane, dipropylene glycol, di
  • Water is generally the carrier of choice for dilution of the concentrates.
  • Suitable solid carriers are, for example, talc, titanium dioxide, pyrophyllite clay, silica, attapulgite clay, kieselguhr, chalk, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husks, wheat flour, soybean flour, pumice, wood flour, ground walnut shells, lignin and similar substances such as are described, for example, in CFR 180.1001. (c) & (d).
  • a large number of surface-active substances can advantageously be used both in solid and in liquid formulations, especially in those which can be diluted with a carrier before application.
  • Surface-active substances can be anionic, cationic, non-ionic or polymeric, and they can be used as emulsifying agents, wetting agents or suspension agents or for other purposes.
  • Typical surface-active substances include, for example, salts of alkyl sulfates, e.g. diethanolammonium lauryl sulfate; salts of alkylarylsulfonates, e.g. calcium dodecylbenzene- sulfonate; addition products of alkylphenols and alkylene oxides, e.g.
  • nonylphenol ethoxylates addition products of alcohols and alkylene oxides, e.g. tridecylalcohol ethoxylates; soaps, e.g. sodium stearate; salts of alkylnaphthalenesulfonates, e.g. sodium dibutylnaphthalenesulfonate; dialkyl esters of sulfosuccinate salts, e.g. sodium di(2-ethyl- hexyl)sulfosuccinate; sorbitol esters, e.g. sorbitol oleate; quaternary amines, e.g.
  • lauryl trimethyiammonium chloride polyethylene glycol esters of fatty acids, e.g. polyethylene glycol stearate; block copolymers of ethylene oxide and propylene oxide; and salts of mono- and di-alkyl phosphate esters; and also further substances described, for example, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981.
  • Further adjuvants which can usually be used in herbicidal formulations include crystallisation inhibitors, viscosity-modifying substances, suspension agents, dyes, antioxidants, foaming agents, light-absorbing agents, mixing adjuvants, anti-foams, complex-formers, neutralising or pH-modifying substances and buffers, corrosion inhibitors, fragrances, wetting agents, take-up enhancers, micro-nutrients, plasticisers, glidants, lubricants, dispersants, thickening agents, antifreeze agents, microbicidal agents, and also liquid and solid fertilisers.
  • the formulations may also comprise additional active substances, e.g. further herbicides, herbicide safeners, plant growth regulators, fungicides or insecticides.
  • compositions according to the invention may additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.
  • the amounts of oil additive used in the composition according to the invention are generally from 0.01 to 10 %, based on the spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rapeseed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® (Rh ⁇ ne-Poulenc Canada Inc.), alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • a preferred additive contains as active components, for example, essentially 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight of customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of C 8 -C 22 fatty acids, the methyl derivatives of C ⁇ 2 -C ⁇ 8 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid, being especially important.
  • esters are known as methyl laurate (CAS- 111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS- 112-62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Cognis GmbH).
  • These and other oil derivatives are also known from the Compendium of Herbicide Adjuvants, 5th Edition, Southern Illinois University, 2000.
  • the application and action of the oil additives can be further improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO g7/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C12-C 2 2 fatty alcohols having a degree of ethoxylation of from 5 to 40.
  • Examples of commercially available surfactants are the Genapol types (Clariant AG).
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltrisiloxanes, which are commercially available, for example, as Silwet L-77®, and also perfluorinated surfactants.
  • concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, CA) and Actipron® (BP Oil UK Limited, GB).
  • the mentioned surface-active substances can also be used alone, that is to say without oil additives, in the formulations.
  • an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action.
  • Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation).
  • the concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • Such oil additives, which are present in admixture with solvents, are described, for example, in US-A-4,834,908.
  • a commercially available oil additive known therefrom is known by the name MERGE® (BASF Corporation).
  • a further oil additive that is preferred according to the invention is SCORE® (Syngenta Crop Protection Canada).
  • alkyl pyrrolidones e.g. Agrimax®
  • formulations of alkyl pyrrolidones such as, for example, polyacrylamide, polyvinyl compounds or poly-1 -p-menthene (e.g. Bond®, Courier® or Emerald®)
  • Bond® polyacrylamide
  • polyvinyl compounds or poly-1 -p-menthene
  • Solutions comprising propionic acid for example Eurogkem Pen-e-trate®, can also be admixed as action-enhancing agents with the spray mixture.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of compound of formula I and from 1 to 99.9 % by weight of a formulation adjuvant which preferably contains from 0 to 25 % by weight of a surface-active substance.
  • a formulation adjuvant which preferably contains from 0 to 25 % by weight of a surface-active substance.
  • commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
  • the rates of application of compounds of formula I may vary within wide limits and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), the crop plant, the weed or grass to be controlled, the prevailing climatic conditions, and other factors governed by the method of application, the time of application and the target crop.
  • the compounds of formula I according to the invention are generally applied at a rate of from 1 to 2000 g/ha.
  • the invention relates also to a method of selectively controlling grasses and weeds in crops of useful plants, which comprises treating the useful plants or the area of cultivation or locus thereof with the compounds of formula I.
  • the weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum, Rottboellia, Cyperus, Abutilon, Sida, Xanthium,
  • Crops are to be understood as including those which have been made tolerant to herbicides or classes of herbicides (e.g. ALS-, GS-, EPSPS- and HPPD-inhibitors) by means of conventional breeding or genetic engineering methods.
  • herbicides or classes of herbicides e.g. ALS-, GS-, EPSPS- and HPPD-inhibitors
  • An example of a crop that has been made tolerant by conventional breeding methods to, for example, imidazolinones such as imazamox is Clearfield® summer rape (canola).
  • crops made tolerant to herbicides by genetic engineering methods are maize varieties resistant to, for example, glyphosate or glufosinate, which are commercially available under the trade names RoundupReady® and LibertyLink®.
  • Useful plants are to be understood as expressly including pest-resistant and/or fungus- resistant transgenic useful plants.
  • pest-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • Toxins that can be expressed by such transgenic plants include, for example, insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus popliae; or insecticidal proteins from Bacillus thuringiensis, such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry ⁇ c, or vegetative insecticidal proteins (VIP), e.g. VIP1 , VIP2, VIP3 or VIP3A; or insecticidal proteins of bacteria-colonising nematodes, for example Photorhabdus spp.
  • insecticidal proteins for example insecticidal proteins from Bacillus cereus or Bacillus popliae
  • Bacillus thuringiensis such as ⁇ -endotoxins, e.g. CrylA(b), CrylA(c), CrylF, CrylF
  • Xenorhabdus spp. such as Photorhabdus luminescens, Xenorhabdus nematophilus
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins
  • toxins produced by fungi such as Streptomycetes toxins
  • plant lectins such as pea lectins, barley lectins or snowdrop lectins
  • agglutinins proteinase inhibitors, such as trypsine inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luff in, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transf erase, cholesterol oxidases, ecdys
  • ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl) or Cry ⁇ c
  • VIP vegetative insecticidal proteins
  • VPP vegetative insecticidal proteins
  • Hybrid toxins are produced recombinantly by a new combination of different domains of those proteins (see, for example, WO 02/15701).
  • a truncated toxin is a truncated CrylA(b), which is expressed in Bt11 maize of Syngenta Seeds SAS, as described hereinbelow.
  • modified toxins one or more amino acids of the naturally occurring toxin is/are replaced.
  • non-naturally present protease recognition sequences are inserted into the toxin, such as, for example, in the case of CrylllA055, a cathepsin-D- recognition sequence is inserted into a CrylllA toxin (see WO 03/018810).
  • Examples of such toxins or transgenic plants capable of synthesising such toxins are disclosed, for example, in EP-A-0374753, WO 93/07278, WO 95/34656, EP-A-0427529, EP-A-451 878 and WO 03/052073.
  • Cryl-type deoxyribonucleic acids and their preparation are known, for example, from WO 95/34656, EP-A-0367474, EP-A-0401 979 and WO 90/13651.
  • the toxin contained in the transgenic plants provides the plants with tolerance to harmful insects.
  • insects can occur in any taxonomic group of insects, but are especially commonly found in beetles (Coleoptera), two-winged insects (Diptera) and butterflies (Lepidoptera).
  • insects from different taxonomic groups are especially common in maize crops: Ostrinia nubilalis, European corn borer Agrotis ipsilon, black cutworm Helicoverpa zea, corn earworm Spodoptera frugiperda, fall armyworm Diatraea grandiosella, soiled corn borer Elasmopalpus lignosellus, lesser cornstalk borer Diatraea saccharalis, sugarcane borer Diabrotica virgifera virgifera, western corn rootworm Diabrotica longicornis barberi, northern corn rootworm Diabrotica undecimpunctata h ⁇ wardi, southern corn rootworm Melanotus spp., wireworms Cyclocephala borealis, northern masked chafer (white grub) Cyclocephala immaculate, southern masked chafer (white grub) Popillia japonica, Japanese beetle Chaetocnema pulicaria, corn flea beet
  • Transgenic plants containing one or more genes that code for an insecticidal resistance and express one or more toxins are known and some of them are commercially available. Examples of such plants are: YieldGard® (maize variety that expresses a CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(bl) toxin); YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(bl) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CrylA(c) toxin);
  • transgenic crops are:
  • MIR604 Maize from Syngenta Seeds SAS, Chemin de I'Hobit 27, F-31 790 St. Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055 modified by insertion of a cathepsin-D-protease recognition sequence. The preparation of such transgenic maize plants is described in WO 03/018810.
  • MON 863 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(bl) toxin and has resistance to certain Coleoptera insects.
  • NK603 MON 810 Maize from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of conventionally bred hybrid maize varieties by crossing the genetically modified varieties NK603 and MON 810.
  • NK603 x MON 810 Maize transgenically expresses the protein CP4 EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, including the European corn borer.
  • fungus-resistant transgenic crop plants are to be understood as being those which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called “pathogenesis-related proteins” (PRPs, see e.g. EP-A-0 392225).
  • PRPs pathogenesis-related proteins
  • antipathogenic substances examples include antipathogenic substances, transgenic plants capable of synthesising such antipathogenic substances, for example, from EP-A-0392225, WO 95/33818 and EP-A-0353 191.
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • Antipathogenic substances which can be expressed by such transgenic plants include, for example, ion channel blockers, such as blockers for sodium and calcium channels, for example the viral KP1 , KP4 or KP6 toxins; stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called "pathogenesis-related proteins" (PRPs; see e.g. EP-A-0392225); antipathogenic substances produced by microorganisms, for example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance genes", as described in WO 03/000906).
  • ion channel blockers such as blockers for sodium and calcium channels
  • the viral KP1 , KP4 or KP6 toxins for example the viral KP1 , KP4 or KP6 toxins
  • stilbene synthases such as the viral KP1
  • pest-resistant and/or fungus-resistant transgenic useful plants include expressly those useful plants which, in addition to pest-resistance and/or fungus-resistance, also possess herbicide tolerance.
  • herbicide- tolerant useful plants preference is given according to the invention to those having tolerance to glyphosate, glufosinate ammonium, ALS (acetolactate synthase) inhibitors, e.g. sulfonylureas, for example primisulfuron, prosulfuron and trifloxysulfuron, or bromoxynil, such as Bt11 maize or Herculex I® maize.
  • Areas of cultivation are areas of land on which the crop plants are already growing and also areas of land on which it is intended to grow those crop plants.
  • Example P1 Preparation of 1 -oxy-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester: 197 g (2.1 mol) of hydrogen peroxide in the form of the urea adduct are stirred into a solution of 132 g (0.6 mol) of 5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester in 1000 ml of 1 ,2- dichloroethane. 346 g (1.65 mol) of trifluoroacetic anhydride are then added over 2.5 hours at a temperature of -10°C, with cooling (CO 2 /acetone bath).
  • reaction mixture is then stirred for a further 2 hours at a temperature of 0°C and then for 12 hours at ambient temperature.
  • the reaction mixture is then poured into ice-water and adjusted to pH 6-7 with 30 % sodium hydroxide solution.
  • the mixture is extracted several times with 1 ,2-dichloro- ethane, dried over sodium sulfate and concentrated to dryness by evaporation.
  • the residue is chromatographed on silica gel (eluant: ethyl acetate / hexane 1 :4). 98.4 g of 1-oxy-5- trifluoromethyl-pyridine-2-carboxylic acid ethyl ester (m.p. 64.5 to 65°C) are obtained.
  • Example P3 Preparation of 6-chloro-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester: 16.5 g (70 mmol) of 6-hydroxy-5-trif luoromethyl-pyridine-2-carboxylic acid ethyl ester in 20 ml of phenyl dichlorophosphate are heated in a small pressure reactor for 30 minutes at a temperature of 170°C. The cooled reaction mixture is taken up in ethyl acetate, washed once with cold sodium chloride solution, dried over sodium sulfate and then concentrated.
  • Example P5 Preparation of 6-(morpholin-4-yl)-5-trifluoromethyl-pyridine-2-carboxylic acid: 7 g (23 mmol) of 6-(morpholin-4-yl)-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester are added to a mixture of 30 ml of dioxane and 25 ml of water in the presence of 1.55 g of potassium hydroxide and the reaction mixture is stirred at ambient temperature for 30 minutes. The reaction mixture is then acidified to pH 3 and extracted with ethyl acetate, dried over sodium sulfate and concentrated slightly. Addition of hexane causes 6-(morpholin- 4-yl)-5-trif luoromethyl-pyridine-2-carboxylic acid to precipitate out: m.p.: 116-117°C; yield 93.2 %.
  • reaction mixture is then extracted with water against dichloromethane, dried over MgSO 4 and then concentrated by evaporation.
  • the resulting residue is purified by column chromatography (eluant: ethyl acetate / hexane 3:7), 6-(acetyl-methyl-amino)-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester being isolated as main component; m.p. 145-145.5°C.
  • reaction mixture After one hour's stirring at ambient temperature, the reaction mixture is concentrated by evaporation and the reaction product that remains behind is purified using a short silica gel column (eluant: ethyl acetate / hexane 1 :4). 2.85 g (93.4 %) of 6-(tetrahydrofuran- 3-yloxy)-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester are obtained (m.p.: 45- 45.5°C).
  • Example P10 6-Methyl-5-trifluoromethyl-pyridinecarboxylic acid ethyl ester: 6.9 g (6 mmol) of tetrakis(triphenylphosphine)paliadium and 8.3 g (66 mmol) of 2,4,6-tri- methyl-cyclotriboroxane are added to a solution of 15.2 g (60 mmol) of 6-chloro-5-trifluoro- methyl-pyridinecarboxylic acid ethyl ester and 33.1 g (0.24 mol) of potassium carbonate in 150 ml of dioxane and the mixture is heated for 2.5 hours at reflux temperature. The end point of the reaction is determined by thin-layer chromatography.
  • reaction mixture is poured into ice-water and is adjusted to pH 5 with concentrated hydrochloric acid.
  • a filtration aid e.g. Hyflo®
  • Hyflo® a filtration aid
  • the organic extract dried over sodium sulfate, is concentrated to dryness by evaporation and purified by chromatography on silica gel (eluant: ethyl acetate / hexane 7.5:92.5).
  • Example P11 6-Bromomethyl-5-trif luoromethyl-pyridine-2-carboxylic acid ethyl ester: 1 g (4.3 mmol) of 6-methyl-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester and 0.92 g of N-bromo-succinimide are dissolved in 20 ml of carbon tetrachloride. A catalytic amount of aza.aza-diisobutyronitrile is added and the mixture is heated at reflux temperature using a light source (200 Watt). The reaction product is filtered off and purified using an HPLC technique (eluant: ethyl acetate/hexane 1 :4).
  • HPLC technique eluant: ethyl acetate/hexane 1 :4
  • Example P12 6-(2-Methoxy-ethoxymethyl)-5-trifluoromethyl-pyridine-2-carboxylic acid: 0.6 g (2 mmol) of 6-bromomethyl-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester, dissolved in 3 ml of tetrahydrofuran, is introduced into a solution of 0.25 g (5.8 mmol) of sodium hydride (55 % dispersion in oil) in 10 ml of dry tetrahydrofuran. The mixture is stirred for 2 hours at ambient temperature. The end point of the reaction is determined by means of thin-layer chromatography. Water is added to the reaction mixture.
  • the organic constituents of the reaction mixture are extracted with diethyl ether and discarded.
  • the aqueous phase is adjusted to pH 2 with hydrochloric acid and extraction with ethyl acetate is carried out; the organic phase is dried over sodium sulfate and then concentrated to dryness by evaporation.
  • Example P13 4-(6-Diethylamino-5-trif luoromethyl-pyridine-2-carbonv0-2-methyl-2,4-dihydro- pyrazol-3-one:
  • the volume of the organic phase is concentrated and chromatographed on silica gel (eluant: ethyl acetate / methanol / triethylamine 85:10:5).
  • the volume of the organic phase is concentrated again.
  • Example P14 5-Trifluoromethyl-6-vinyl-pyridine-2-carboxylic acid ethyl ester: 3 g (11.8 mmol) of chloro-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester are dissolved in degassed dioxane, and 4.13 g (13.02 mmol) of tributylvinyltin are added. After the addition of 273 mg (0.236 mmol) of Pd(Ph 3 P) , the reaction mixture is stirred for 20 hours at 95°C. The reaction mixture is concentrated and is chromatographed on silica gel (eluant: ethyl acetate / isohexane 1 :5).
  • Example P15 6-(1-Ethoxy-vinyl)-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester: 1.6 g (6.31 mmol) of chloro-5-trifluoromethyl-pyridine-2-carboxylic acid ethyl ester are dissolved in 32 ml of degassed dioxane, and 2.5 g (6.92 mmol) of 1-ethoxy-1 -tributylvinyltin are added. After the addition of 146 mg (0.126 mmol) of Pd(Ph 3 P) 4 , the reaction mixture is stirred for 20 hours at 95°C.
  • reaction mixture is concentrated and is chromatographed on silica gel (eluant: ethyl acetate / isohexane 1 :5). 0.9 g of 6-(1-ethoxy-vinyl)-5-trifluoro- methyl-pyridine-2-carboxylic acid ethyl ester are obtained.
  • substituents Ri are bonded to the pyridyl ring by way of the free valence at the atom on the left-hand side of the substituent R ⁇ as in the case, for example, of compound 1.001.
  • substituent R 1 OCH 2 OCH 3 is bonded to the pyridyl ring by way of the free valence of the oxygen atom on the left-hand side of the substituent.
  • the linking atom is, in addition, marked by means of an apostrophe, as in the case, for example, of compound no. 1.142.
  • Monocotyledonous and dicotyledonous test plants are cultivated in a greenhouse in standard soil in plastic pots and, at the 4- to 6-leaf stage, are sprayed with an aqueous suspension of the test compounds of formula I prepared from a 25 % wettable powder (Example F3, b) according to WO 97/34485) or with an emulsion of the test compounds of formula I prepared from a 25 % emulsifiable concentrate (Example F1 , c) according to WO 97/34485), corresponding to concentrations of 125 and 250 g of active ingredient per hectare (500 litres of water per ha). The test plants are then grown on in the greenhouse under optimum conditions.
  • Examples according to Table B3 on selected test plants likewise exhibit good to very good post-emergence action.

Abstract

Cette invention concerne des composés représentés par la formule (I) dans laquelle les substituants sont tels que définis dans la revendication 1, ainsi que des sels acceptables d'un point de vue agronomique/des N-oxydes/isomères/énantiomères de ces composés pouvant être utilisés comme herbicides.
PCT/EP2004/014112 2003-12-12 2004-12-10 Picolinylpyrazoles utilises comme herbicides WO2005058037A1 (fr)

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CH21302003 2003-12-12
CH02130/03 2003-12-12

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WO2005058037A1 true WO2005058037A1 (fr) 2005-06-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1848430A2 (fr) * 2004-12-31 2007-10-31 Reddy US Therapeutics, Inc. Nouveaux dérivés de benzylamine en tant qu'inhibiteurs de cetp
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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS549279A (en) * 1977-06-24 1979-01-24 Ishihara Sangyo Kaisha Ltd Tetrazolypyridylketone and herbicides coatining the same
EP0352543A1 (fr) * 1988-07-15 1990-01-31 Nissan Chemical Industries Ltd. Dérivés de pyrazole et herbicides les contenant
EP0567133A1 (fr) * 1992-04-23 1993-10-27 Kumiai Chemical Industry Co., Ltd. Dérivés de l'acide picolinique et compositions herbicides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS549279A (en) * 1977-06-24 1979-01-24 Ishihara Sangyo Kaisha Ltd Tetrazolypyridylketone and herbicides coatining the same
EP0352543A1 (fr) * 1988-07-15 1990-01-31 Nissan Chemical Industries Ltd. Dérivés de pyrazole et herbicides les contenant
EP0567133A1 (fr) * 1992-04-23 1993-10-27 Kumiai Chemical Industry Co., Ltd. Dérivés de l'acide picolinique et compositions herbicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; NISHIYAMA, RYUZO ET AL: "Pyrazolyl pyridyl ketones", XP002325156, retrieved from STN Database accession no. 1979:186940 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1848430A2 (fr) * 2004-12-31 2007-10-31 Reddy US Therapeutics, Inc. Nouveaux dérivés de benzylamine en tant qu'inhibiteurs de cetp
EP1848430A4 (fr) * 2004-12-31 2011-12-28 Reddys Lab Ltd Dr Nouveaux dérivés de benzylamine en tant qu'inhibiteurs de cetp
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

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