WO2005058831A1 - Nouveaux herbicides - Google Patents

Nouveaux herbicides Download PDF

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WO2005058831A1
WO2005058831A1 PCT/EP2004/014123 EP2004014123W WO2005058831A1 WO 2005058831 A1 WO2005058831 A1 WO 2005058831A1 EP 2004014123 W EP2004014123 W EP 2004014123W WO 2005058831 A1 WO2005058831 A1 WO 2005058831A1
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crc
alkoxy
alkyl
hydroxy
halogen
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PCT/EP2004/014123
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Christoph Lüthy
Andrew Edmunds
Renaud Beaudegnies
Sebastian Wendeborn
Jürgen Schaetzer
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Syngenta Participations Ag
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Publication of WO2005058831A1 publication Critical patent/WO2005058831A1/fr

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    • 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
    • C07D405/02—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 two hetero rings
    • C07D405/12—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 two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals

Definitions

  • the present invention relates to novel, herbicidally active picolinoyl derivatives, 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 picolinic acid derivatives, substituted in the 5,6-position, of 1 ,3- bicyclo[3.2.1]octanediones substituted in the 2-position are known from WO 00/15615.
  • the herbicidal activity of the known compounds on weeds and/or grasses is frequently too low, or their selectivity with respect to the cultivated plants is too low. The problem was therefore to seek new and improved herbicidal active substances that do not have those disadvantageous properties.
  • the present invention accordingly relates to compounds of formula I
  • R ⁇ is a C ⁇ -C 6 alkylene, C 2 -C 6 alkenylene or C -C 6 alkynylene group which may be substituted once, twice or three times by halogen, hydroxy, d-Cealkoxy, C 3 -C 6 cycloalkyloxy, C C 6 - alkoxy-CrC ⁇ alkoxy, C Cealkoxy-C Cealkoxy-C C ⁇ alkoxy or by d-Caalkylsulfonyloxy;
  • -ONR ⁇ thio, sulfinyl, sulfonyl, -0S(O) 2 -, -SO 2 NR 12 -, -NR 13 SO 2 -, -N(SO 2 R ⁇ 4o )-, -N(R 14d )C(O)- or -NR 14 -;
  • R 14a is hydroxy, d-C 6 alkoxy, C 3 -C 6 aIkenyloxy, C 3 -C 6 alkynyloxy, benzyloxy, wherein benzyl may in turn be substituted once, twice or three times by d-C 6 alkyl, d-C 6
  • R 1(le is C 1 -C ⁇ al l
  • R 2 is a C C 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C 3 -C 6 cycloalkyl or C 5 -C 6 cycloalkenyl group which is substituted once, twice or three times by chlorine, bromine, iodine, hydroxy, amino, formyl, nitro, cyano, mercapto, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 halo- alkynyl, C 3 -C 6 cycloalkyl, halo-substituted C 3 -C 6 cycloaIkyl, CrC 6 alkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, d-C 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, C
  • Ri 6 a > Rie b and R 16c are hydrogen, d-C 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 d-C 6 alkyl, d-Cehaloalkyl, d-C 6 alkoxy, C ⁇ -C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro;
  • R-i7a, Ri7b, Ri7c, R ⁇ sa, Risb and R 18c are hydrogen, CrC 6 alkyI, C 3 -C 6 alkenyl or C 3 -C 6 alkynyl;
  • X 2 3, 2 4 , X25, 26 and X 27 are oxygen or sulfur;
  • R 1 9 and R 20 are each independently of the others hydrogen, C C 6 alkyl, Ci-Cehaloalkyl, CrC 6 alkoxycarbonyl, CrC 6 alkylcarbonyl, CrC 6 alkoxy-CrC 6 alkyl, or CrC 6 alkoxy-CrC 6 alkyI substituted by d-C 6 alkoxy, or are benzyl or phenyl, wherein phenyl and benzyl may in turn be substituted once, twice or three times by d-C 6 alkyl, d-C 6 halo- alkyl, d-C 6 alkoxy, CrC 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; or R 2 is a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, saturated or partially saturated and which contains from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, wherein the
  • each ring system may contain not more than 2 oxygen atoms and not more than two sulfur atoms, wherein each ring system may not be interrupted by
  • R 5 is CrC 6 alkyl, d-C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 halo- alkynyl, CrC 6 alkoxy, hydroxy, d-C 6 haloaIkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, mercapto, d-C 6 alkylthio, CrC 6 haloalkylthio, C 3 -C 6 alkenylthio, C 3 -C 6 haIoalkenylthio, C 3 -C 6 alkynylthio,
  • R 5a is CrC 6 alkyl, hydroxy, d-C 6 alkoxy, cyano or nitro;
  • R 18 is hydrogen, d-C 6 alkyl, CrC 6 haloalkyl, CrC 6 alkoxycarbonyl, CrC 6 alkylcarbonyl,
  • -SO 2 NR 12 -, -NR 13 SO 2 -, -N(SO 2 R 14c )-, -N(R 14d )C(O)- or -NR 14 -, or R is a C 2 -C 6 alkenylene or C 2 -
  • -ONR ⁇ , -OS(O) 2 -, -SO 2 NR 12 -, -NR 13 SO 2 -, -N(SO 2 R 14C )-, -N(R 14d )C(O)- or -NR 14 -, or R, is a C 2 -
  • R 2 is phenyl or phenyl substituted once or more than once by R 5b ;
  • X is oxygen and at the same time R, is a C 2 -C 6 alkenylene or C 2 -C ⁇ alkynylene group or at the same time R, is a 0,-C 8 alkylene group substituted once, twice or three times by halogen, hydroxy, 0,-C 8 alkoxy, C 3 -C 6 cycloalkyloxy,
  • R 2 is hydrogen
  • R 4 is halogen, d-C 3 haloalkyl, cyano, d-C 3 haloalkoxy, CrC 3 alkylthio, d-C 3 alkylsulfinyl,
  • R 3 is hydroxy or O " M + wherein M + is a metal cation or an ammonium cation; or R 3 is halogen or S(O)qR 80 , wherein
  • R 8 o is CrC 12 alkyl, C 2 -C 12 alkenyl, C 2 -C 12 alkynyl, C 3 -C 12 allenyl, C 3 -C 12 cycloalkyl or C 5 -C 12 cyclo- alkenyl and q is 0, 1 or 2; or R 80 is Ri 2 d-Ci2alkylene or R 122 -C 2 -C 12 alkenylene wherein the alkylene or alkenylene chain may be interrupted by -O-, -S-, -S(O)-, S(O) 2 - or by -C(O)- and/or substituted once or up to five times by R 123 ; or R 8 o is phenyl which may be substituted once, twice, three, four or five times by R 124 ;
  • R 12 ⁇ and R ⁇ 22 are each independently of the other halogen, cyano, rhodano, hydroxy, d-C 6 alkoxy, C 2 -C 6 alkenyloxy, C 2 -C 6 alkynyloxy, CrC 6 alkylthio, d-C 6 alkylsulfinyl, C C 6 alkyl- sulfonyl, C 2 -C 6 alkenylthio, C 2 -C 6 alkynylthio, CrC 6 alkylsulfonyloxy, phenylsulfonyloxy,
  • CrC 6 alkylcarbonyloxy benzoyloxy, CrC 4 alkoxycarbonyloxy, d-C 6 alkylcarbonyl, d-C 4 alkoxycarbonyl, benzoyl, aminocarbonyl, d-C 4 alkylaminocarbonyl, C 3 -C 6 cycloalkyl, phenyl, phenoxy, phenylthio, phenyisulfinyl or phenylsulfonyl, wherein the phenyl-containing groups may in turn be substituted once, twice or three times by halogen, d-C 3 alkyl,
  • R 123 is hydroxy, halogen, d-C 6 alkyl, d-C 6 alkoxy, CrC 6 aIkylthio, d-C 6 alkylsulfinyl, d-C 6 alkylsulfonyl, cyano, carbamoyl, carboxy, d-C alkoxycarbonyl or phenyl, wherein phenyl may be substituted once or more than once by hydrogen, d-C 4 alkyl, d-C 4 ha!oalkyl,
  • R 124 is halogen, d-C 3 alkyl, d-C 3 haloalkyl, hydroxy, C C 3 alkoxy, d-C 3 haloalkoxy, cyano or nitro;
  • Y is an alkylene group Ai or oxygen
  • A is a chemical bond or C(R 24 R 2 5) r ; m is 1 or 2; r is 1 or 2;
  • R2 4 o, R 24 ⁇ , 2 42 , R2 43 , R 244 , R245, R 24 e and R 2 are each independently of the others hydrogen, d-C 3 alkyl, CrC 2 alkylthio, d-C 2 alkylsulfinyl, CrC 2 alkylsulfonyl, d-C 4 alkoxycarbonyl, hydroxy, CrC 2 alkoxy, hydroxy-CrC 2 alkyl, halogen, cyano, d-C 3 haIoalkyl or d-C alkoxy-
  • 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 for example 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
  • alkylsulfonyl is preferably methyl- sulfonyl, ethylsulfonyl, propylsulfonyl or isopropylsulfonyl; preferably methylsulfonyl or ethylsulfonyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine; preferably fluorine, chlorine or bromine.
  • Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms.
  • d-C 4 Haloalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyI, 2-chloroethyl, pentafluoro- ethyl, 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,
  • 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 alkynyl groups substituted once or more than once by halogen are suitable, halogen being either bromine or iodine or also fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3- trifluoropropynyl or 4,4,4-trifluoro-but-2-yn-1-yl.
  • halogen in association with other definitions such as haloalkoxy, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl or halophenyl.
  • R 2 as a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, partially saturated or fully saturated and which contains from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, wherein the ring system is bonded to the substituent X, either directly or via a d-C 4 alkylene, C 2 -C 4 alkenylene, C 2 -C 4 alkynylene, -N(R 18 )-d-C 4 alkyIene, -O-d-C 4 alkylene, -S-d-C 4 alkylene, -S(O)-d-C alkylene 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 wherein the ring system itself may be substituted, is understood to be, for example, C 3 -C 6 oxacycloalkyl, C
  • Heteroaryl for example in the definition of R 2 as a five- or six-membered, monocyclic or fused bicyclic, aromatic ring system, 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-pyrazoI-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 H-pyrrol-2-yl, 1 -methyl-1 H-pyrrol-2-yl, 1 -
  • a heteroaryl group bonded via the nitrogen atom is understood to be, for example, 1 H-pyrrol-1-yl, 1 H-pyrazol-1-yl, 3-methyl-1 H-pyrazol-1 -yl, 3,5-dimethyl-1 H-pyrazol- 1 -yl, 3-trifluoromethyl-1 H-pyrazol-1 -yl, 3-methyl-1 H-1 ,2,4-triazol-1-yl, 5-methyl-1 H-1 ,2,4- triazoI-1 -yl or 4H-1 ,2,4-triazol-4-yl.
  • alkylene chains C 3 -C 6 cycloalkyl groups and alkylene groups interrupted by oxygen or sulfur, and also the three- to six-membered saturated ring systems and heterocyclyl groups in the definition of R 2 , for example oxiranyl, oxetanyl, C 3 -C 5 oxacycloalkyl, C 3 -C 5 thiacycloalkyl, C 3 -C 4 dioxacycIoalkyl, C 3 -C 4 dithiacycloalkyl or C 3 -C 4 oxathiacycloalkyl, may be substituted by one or more d-C 3 alkyl groups, especially by methyl groups.
  • alkylene chains and all alkylene chains and groups interrupted by oxygen or sulfur are unsubstituted.
  • groups containing C 3 -C 6 cycloalkyl, oxiranyl, oxetanyl, C 3 -C 5 oxacycloalkyl, C 3 -C 5 thiacycloalkyl, C 3 -C 4 dioxacycloalkyl, C 3 -C 4 dithiacycloalkyl or C 3 -C 4 oxathiacycloalkyl are also unsubstituted.
  • a chemical group is substituted more than once by substituents listed in a list of substituents, such as for example R in the meaning of a d-C 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene group which is substitued twice or three times by halogen, hydroxy, C C 6 alkoxy, C 3 -C 6 cycloalkyloxy, CrC 6 alkoxy-CrC 6 alkoxy, CrC6alkoxy-CrC 6 alkoxy-Cr C 6 alkoxy or by d-C 2 alkylsulfonyloxy, said chemical group can be substituted by different substituents from said list of substituents.
  • substituents listed in a list of substituents such as for example R in the meaning of a three- to ten-membered ring system, which is substituted more than once by R 5 .
  • substituted more than once for example applying to R 2 having the meaning of phenyl substituted more than once by R 5b , means substituted twice, three, four or five times, preferably substituted twice or three times.
  • the compounds of formula I may occur in various tautomeric forms, as shown by way of example for compounds of formula I wherein R 3 is hydroxy by formulae I', I", I'" and I"", the forms I" and I"" being preferred as isolated forms and formula I"" also representing a rotameric form of I"
  • the compounds of formula I may, when asymmetry exists, be in the ⁇ ' or also in the 'Z' form. If a further asymmetric centre is present, for example an asymmetric carbon atom in the group R 1 -X 1 -R 2 . chiral 'R' and 'S' forms may also occur.
  • 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 d-C ⁇ 8 alkylamines, d-C 4 hydroxyalkylamines and C 2 -C 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-oc
  • Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [ + N(R a R R c R d ) OH] wherein R a , R b , R c and R d are each independently of the others d-C alkyI.
  • Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.
  • Y is an alkylene group Ai; b) m is 1 ; c) A is C(R 244 R 24 5) r wherein r is especially 1 ; d) R 24 o is hydrogen or methyl, especially hydrogen; e) R 24 ⁇ , R2 4 2.
  • R2 43 , R 2 J, 2 4 5, R2 6 and R 2 7 are each independently of the others hydrogen or methyl, and are especially all simultaneously hydrogen; f) R 3 is hydroxy, O " M + , chlorine, d-C 8 alkylthio, C 3 -C 8 alkenylthio, C 3 -C 8 alkynylthio, benzylthio or phenylthio, especially hydroxy or a salt of the form O " M + wherein M + is an agronomically acceptable metal cation or ammonium cation; g) R 4 is chlorine, bromine, cyano, trifluoromethyl, difluoromethyl, difluorochloromethyl, difluoromethoxy, trifluoromethoxy, trifluoroethoxy, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl, especially trifluoromethyl.
  • R ⁇ is d-C 2 alkylene which may be substituted by methyl, ethyl, methoxy or by ethoxy, especially unsubstituted methylene;
  • R 13 is hydrogen, d-C 6 alkyl d-C 4 haloalkyl or CrC 4 alkoxy-CrC 2 alkyl,
  • R 14a is CrC 6 alkoxy, C 3 -C 6 alkenyloxy or C 3 -C 6 alkynyloxy
  • R 14b is hydrogen
  • R 14d is hydrogen and R 14
  • R is a CrC 6 alkylene, C 2 -C 6 alkenylene or C 2 -C 6 alkynylene chain which may be substituted once, twice or three times by halogen, hydroxy, CrC 6 alkoxy, C 3 -C 6 cycIoalkyloxy, d-C 6 alkoxy- CrC 6 alkoxy, CrCealkoxy-d-Cealkoxy-d-Cealkoxy or by CrC 2 aIkylsulfonyloxy; X !
  • R10, R11, Ri2 > R13, ⁇ 4 b, R ⁇ 4 d and R 1 are each independently of the others hydrogen, d-C 6 alkyl, CrCehaloalkyl, d-C 6 alkoxycarbonyl, CrC 6 aIkylcarbonyl, CrC 6 alkoxy-CrC 6 aIkyl, or d-C 6 alkoxy-Cr
  • R 2 is a CrC 8 alkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl or C 3 -C 6 cycloalkyl 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, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 3 -C 6 cycloalkyl, halo-substituted C 3 -C 6 cycIoalkyl, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, d-C 6 haloalkoxy, C 3 -C 6 haloalkenyloxy, cyano-d-C 6 alkoxy, Cr
  • R 15 , R 1 6, Ri7 > R 1 9 and R 20 are each independently of the others hydrogen, CrC 6 alkyl, CrCehaloalkyl, CrC 6 alkoxycarbonyl, CrC 6 alkylcarbonyl, CrC 6 alkoxy-CrCealkyl, or CrC 6 aIkoxy-CrC 6 alkyl 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-C 6 haloalkyl, CrC 6 alkoxy, d-C 6 haloalkoxy, halogen, cyano, hydroxy or by nitro; or R 2 is a three- to ten-membered monocyclic or fused bicyclic ring system which may be aromatic, saturated or partially saturated and which contains from 1 to 4 hetero atoms selected from nitrogen, oxygen and sulfur, wherein the ring system is
  • R 5 is CrC 6 alkyl, CrCehaloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haIoalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 halo- alkynyl, d-C 6 alkoxy, hydroxy, d-Cehaloalkoxy, C 3 -C 6 alkenyloxy, C 3 -C 6 alkynyloxy, mercapto, CrC 6 alkylthio, CrC 6 haloalkyIthio, C 3 -C 6 alkenylthio, C 3 -C 6 haloalkenylthio, C 3 -C 6 alkynylthio, C 2 -C 5 alkoxyalkylthio, C 3 -C 5 acetylalkylthio, C 3 -C 6 alkoxycarbonylalkylthio, C 2 -C 4 cyanoalkylthio,
  • R 5a is CrC 6 alkyl, hydroxy, CrC 6 alkoxy, cyano or nitro;
  • R 3 is hydroxy or O " M + wherein M + is a metal cation or an ammonium cation; or R 3 is halogen or S(O) q R 8 o, wherein R 80 is CrC 12 alkyl, C 2 -C ⁇ 2 alkenyl, C 2 -C ⁇ 2 alkynyl, C 3 -C ⁇ 2 alienyl,
  • Rao is R 121 -CrC 2 alkylene or R 122 -C 2 -C 12 alkenylene wherein the alkylene or alkenylene chain may be interrupted by -O-, -S-, -S(O)-, S(O) 2 - or by -C(O)- and/or substituted once or up to five times by R 123 ; or R 80 is phenyl which may be substituted once, twice, three, four or five times by R 124 ;
  • R 121 and R 122 are each independently of the other halogen, cyano, rhodano, hydroxy,
  • CrC alkoxycarbonyl benzoyl, aminocarbonyl, d-C 4 alkylaminocarbonyl, C 3 -C 6 cycloaIkyl, phenyl, phenoxy, phenylthio, phenyisulfinyl or phenylsulfonyl, wherein the phenyl-containing groups may in turn be substituted once, twice or three times by halogen, d-C 3 alkyl, d-C 3 haloalkyl, hydroxy, d-C 3 alkoxy, d-C 3 haloalkoxy, cyano or by nitro;
  • R 123 is hydroxy, halogen, CrC 6 alkyl, CrC 6 alkoxy, CrC 6 alkylthio, d-C 6 alkylsulfinyl,
  • Ri 2 is halogen, d-C 3 alkyl, CrC 3 haloalkyl, hydroxy, CrC 3 aIkoxy, C C 3 haloalkoxy, cyano or nitro;
  • Y is an alkylene group A t or oxygen
  • A is a chemical bond or C(R 244 R2 4 s) r ; m is 1 or 2; r is 1 or 2;
  • R 24 o, R24i > 2 4 2 > R 24 3, R2-M, R2 4 5, R2 4 ⁇ and R 2 7 are each independently of the others hydrogen,
  • Preferred processes for the preparation of compounds of formula I comprise either a) converting a compound of formula I la
  • Y ⁇ is leaving group such as halogen, cyano or the like, e.g. 1 ,2,4-triazolyl or (1 ,3- dicyclohexyl-isourea-2-yl)oxy, and then converting that compound in the presence of a base, e.g. triethylamine, H ⁇ nig's base, sodium hydrogen carbonate or potassium carbonate, using a dione of formula III
  • a base e.g. triethylamine, H ⁇ nig's base, sodium hydrogen carbonate or potassium carbonate
  • R 240 , R 2 ⁇ , R 242 , R 243 and Y are as defined hereinbefore and R 3 is hydroxy, or in the form of a tautomer thereof of formula Ilia
  • A, R ⁇ R 2 , R 4 , R2 4 o, R 24 ⁇ , R 242 , R 24 3, Xi and Y are as defined hereinbefore, and then treating that compound/those compounds by means 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; or b) converting a compound of formula XI I la
  • a cyanide-containing catalyst e.g. acetone cyanohydrin, trimethylsilyl cyanide, copper cyanide, sodium cyanide or potassium cyanide
  • Xllla Xllla
  • R 1 ; R 2 and R 4 are as defined hereinbefore and Y 4 is halogen or trifluoromethyl- sulfonyloxy
  • a palladium catalyst having suitable ligands, e.g. PdCI 2 (PPh 3 ) 2 , Pd(PPh 3 ) 4 , Pd 2 (dba) 3 , Pd(CH 3 CN) 2 (PPh 3 ) 2 , Pd(OAc) 2 or (racBINAP)PdCI 2
  • an auxiliary catalyst e.g.
  • triphenylphosphine tri(tert-butyl)- phosphine or (Ph 3 ) 2 PCH 2 CH 2 P(Ph 3 ) 2
  • a base e.g. triethylamine
  • further adjuvants e.g. LiCI or Li 2 CO 3
  • R 240 , R 241 , R 242 , R 243 and Y are as defined hereinbefore, to an enol ester compound of formula Xla, to an enol ester compound of formula Xlb or to a mixture of enol ester compounds of formulae Xla and Xlb
  • K 4 is a group capable of further functionalisation, such as, especially, chlorine, bromine, iodine or trifluormethylsulfonyloxy, in a Stille, Suzuki, Sonogashira, Heck or related C-C coupling reaction, in the presence of a metal catalyst, e.g. a palladium, rhodium or nickel catalyst having suitable ligands, e.g.
  • H-CH CH-R 1b -X R 2 (Vf),
  • R ⁇ R 2 and X ! are as defined hereinbefore, R ⁇ , R f and R g are each independently of the others d-C 8 alkyl, and R 1a and R 1b are appropriate sub-groups of the group R ⁇ for example a d-C 4 alkylene group which may be substituted once, twice or three times by d-C 6 alkyl, halogen, hydroxy, d-C 6 alkoxy or by d-C 3 alkoxy-CrC 3 alkoxy; or d) reacting a compound of formula Xb wherein A, R 1 ( R 3 , R 4 , R 240 , R 24 ⁇ , R 242 , R 243 and Y are as defined hereinbefore and K 5 is a group suitable for further functionalisation, e.g.
  • R 2 is a 5- or 6-membered ring system which is interrupted twice by oxygen and/or by sulfur, with a ketalisation agent of formula IX
  • R 6c , R7C, Rsc, Rgc, X3C, X c , Xsc and X 8c according to the particular meanings of R 2 and X 1 ; correspondingly have the subordinate meanings of R 2 and X mentioned above, and Y 3c is a leaving group such as bromine, iodine, mesyloxy, tosyloxy or sulfonyloxy, 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 or, in the case of ketalisation, in the presence of an additional acid, e.g.
  • A, Ri, R 2 , R 3 , R 4 , R 24 o, R2 4 ⁇ , R2 42 , R 24 3, Xi and Y are as defined hereinbefore but a group X-i and/or one or more radicals R 2 , R 3 , R 4 , R 24 o, R2 4 ⁇ , R 242 , R 24 3, R24-1, R2 4 5, R2 4 6 and/or R 247 , each independently of the others, contains a sulfinyl or sulfonyl group, treating a compound of formula la, wherein one or more oxidisable sulfur- or sulfinyl-containing groups are present, with an oxidising agent, e.g. peracetic acid, trifluoroperacetic acid, m-chloroper- benzoic acid, hydrogen peroxide, sodium perbromate, sodium iodate, sodium hypochloride, chlorine or bromine.
  • an oxidising agent e.g. peracetic acid
  • compounds of formula I wherein R 3 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 R 3 is chlorine, which can be obtained from compounds of formula I wherein R 3 is hydroxy, likewise in accordance with known methods, by reaction with a chlorinating agent such as phosgene, thionyl chloride or, preferably, oxalyl chloride.
  • a chlorinating agent such as phosgene, thionyl chloride or, preferably, oxalyl chloride.
  • the mercaptans, thiophenols or heterocyclic thiols substituted in corresponding manner to R 3 and R 80 are reacted in the presence of a base, e.g.
  • compounds of formula I wherein the substituent R 3 is a mercapto group can be oxidised in analogy to known standard methods, for example using peracids , e.g. meta-chloroper- benzoic acid (m-CPBA) or peracetic acid, to form the corresponding sulfoxides and/or sulfones of formula I.
  • peracids e.g. meta-chloroper- benzoic acid (m-CPBA) or peracetic acid
  • m-CPBA meta-chloroper- benzoic acid
  • peracetic acid peracetic acid
  • a suitable coupling reagent e.g. dicyclohexyl- carbodiimide, 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 dione of formula ill with an activated form of the acid, e.g.
  • a suitable coupling reagent e.g. dicyclohexyl- carbodiimide, 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 dione of formula
  • a base e.g. triethylamine, H ⁇ nig's base or potassium carbonate
  • R 1 R 2 , R 4 , R 240 , R 2 ⁇ , R 2 2 , R 24 3, Xi and Y are as defined hereinbefore.
  • These compounds may then either be rearranged directly in situ by adding catalytic amounts of cyanide ions, e.g.
  • the preferred process b) is likewise generally known, e.g. from the published specification WO 02/16305.
  • R 0 a is hydroxy, mercapto, methoxy, CrC 6 alkylthio, CrC 6 alkylsuIfonyl, halogen, trifluoromethyl- sulfonyloxy, CrC 6 hydroxyalkyl, CrC6alkylcarbonyloxy-CrC 6 aIkyl, d-C 6 alkoxycarbonyIoxy- CrC 6 alkyl, benzoyloxy-CrC 6 aIkyl, d-C 6 chloroalkyl, CrC 6 bromoaIkyl or d-C 6 iodoalkyl, which may be used as starting materials for the preparation of compounds of formula I, are in some cases known from the published specification WO 00/15615, or they can be prepared by the processes described therein.
  • R ⁇ R 2 and R 4 are as defined hereinbefore and Y ⁇ is a leaving group such as halogen, cyano or the like, e.g. (1 ,3-dicyclohexyl-isourea-2-yl)oxy or phenoxy, which may be unsubstituted or substituted by an electron-withdrawing group such as halogen, trifluoromethyl, nitro, cyano, d-C 4 alkylcarbonyl, d-C 4 alkoxycarbonyl or d-C alkylsulfonyl, and also compounds of formula lie wherein Y 0 is CrC 4 alkoxy or benzyloxy, which are used as starting materials for the preparation of compounds of formula Ma, may be prepared, for example, by converting, using processes known in principle, for example as described in EP 353 187, a compound of formula XI 11
  • R 4 is as defined hereinbefore and R 0 is especially hydrogen, methyl, methoxy, CrC 6 alkylthio, halogen or a group -R X ⁇ -R 2 which is stable during this process, e.g. -CH 2 OCH 3 , -CH 2 OCH 2 CH 2 OCH 3 , -CH2OCH 2 CH 2 OCH 2 CH 3 , -CH 2 OCH 2 CH 2 CH 2 OCH 3 , -CH 2 OCH 2 CH 2 ⁇ CH 3 CH 2 CH 2 ⁇ CH 3 , -CH 2 CH 2 OCH 3 , -CH 2 CH 2 CH 2 OCH 3 , -CH 2 OCH 2 CH 2 F, -CH 2 OCH 2 -(2-[1 ,3]dioxolanyl), -CH 2 OCH 2 CH 2 SCH 3 , -CH 2 SCH 2 CH 2 OCH 3 , -CH 2 OCH 2 CH 2 NHC(O)CH 3 , -CH 2 OCH 2 CH 2
  • R ob is d-C 4 alkyl or benzyl, into a compound of formula Xlla wherein R 0 , R and Y 0 are as defined hereinbefore, and then converting that compound in known conversion processes, e.g. substitution, reduction and/or C-C coupling reactions, and subsequent hydrolysis or hydrogenolysis (Y 0 having the meaning benzyloxy) of the group Y 0 , into compounds of formula XII and/or compounds of formula II
  • Ri, Xi, R 2 and R are as defined hereinbefore, Y is hydroxy or is as defined for Y ⁇ and Yo, and Ko is a group capable of further functionalisation, using the processes described hereinbefore, to form a group -RrX ⁇ -R 2 wherein R 1 f Xi and R 2 are as defined hereinbefore, and Ko being especially as defined for K 2 , K 3 , l ⁇ or R 0a and K 0 being more especially hydroxy, trifluoromethylsulfonyloxy, methoxy, mercapto, d-C 6 alkylthio, d-C 6 alkylsulfonyl, halogen, CrC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 chloroalkyl, CrC 6 bromoalkyl, d-C 6 - iodoalkyl, C 2 -C 6 chIoroalkenyl, C
  • R 4 and Y 0 are as defined hereinbefore, which is then reacted in the presence of an oxidising agent, e.g. using hydrogen peroxide or using the hydrogen peroxide/urea adduct in the presence of trifiuoroacetic anhydride, to form an N-oxido compound of formula XV
  • R 4 and Y 0 are as defined hereinbefore, which is then converted in the presence of phosphorus oxychloride or trifiuoroacetic anhydride to form a hydroxy compound of formula Xllc
  • R 4 and Y 0 are as defined hereinbefore, which is then transformed using a halogenating agent, e.g. dichlorophenyl phosphate or phosphorus oxybromide, at elevated temperatures to form a compound of formula Xlld
  • a halogenating agent e.g. dichlorophenyl phosphate or phosphorus oxybromide
  • R 4 and Y 0 are as defined hereinbefore and K 3 is chlorine, bromine or iodine, especially chlorine or bromine, which is then converted in a Stille, Suzuki, Sonogashira, Heck or related C-C coupling reaction according to process variant c), e.g. using a boronic acid of formula Vg
  • H-CH CH-K 2b (Vk)
  • K 2 is as defined for RrK 5 or RrX ⁇ -R 2
  • K 2a is as defined for R ⁇ a -K 5 or R 1a -XrR 2
  • K 2b is as defined for R ⁇ b -K 5 or R 1b -X R 2
  • K 5 , R ⁇ , R f , R g , R 1a , R b , R 2 and X are as defined hereinbefore, into a compound of formula Xlle
  • K 5 , R-i, R 2 , R 4 and Y are as defined hereinbefore and K 2 is especially a group suitable for further functionalisation, e.g. methyl, chloromethyl, bromomethyl, iodomethyl, mesyloxymethyl, tosyloxymethyl, dibromomethyl, formyl, methylcarbonyl, n-propylcarbonyl, methylcarbonyloxymethyl, tert-butylcarbonyloxymethyl, benzoyloxymethyl, ethoxycarbonyl- oxymethyl, 1 -ethoxy-vinyl, 1 -butoxy-vinyl, 2-eth ⁇ xy-vinyl, 2-butoxy-vinyl, methylcarbonyl- methyl, ethylcarbonylmethyl, hydroxy-methyl, 3-hydroxy-propyl, 3-chloro-propen-1 -yl, 3- hydroxy-propyn-1 -yl or 3-hydroxy-butyn-1-yl, to form the group
  • Ri is especially an unsubstituted or substituted C 2 -C 6 alkenylene or a C 2 -C 6 - alkynylene group and R 2 , R , Xi and Y 0 are as defined hereinbefore, can advantageously be prepared by reacting a compound of formula XI Ii
  • R 2 and Y 0 are as defined hereinbefore and * is a group capable of further functionalisation, e.g. chlorine, bromine, iodine or trifluoromethylsulfonyloxy, in accordance with process variant c) by means of a -C-C- linking Suzuki, Stille, 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
  • 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 Va
  • H-CH CH-Ri b -XrR 2 (Vf)
  • Ri, R 2 and ⁇ are as defined hereinbefore, R e , R f and R g are each independently of the others CrC 8 alkyl, and R ⁇ a and R ⁇ are corresponding sub-groups of the group R, such as especially a direct bond or a d-C alkylene group which may be substituted once, twice or three times by CrC 6 alkyl, halogen, hydroxy, d-C 6 alkoxy or by CrC 3 alkoxy-d-C 3 alkoxy, and wherein the reagents of formula Vf may in addition result in each case in one or more regio- isomeric products, e.g. those of formula llca, llcb or lice
  • C-C coupling reaction e.g. with (Vg), (Vh), (Vi), (Vj) or (Vk) catalyst: e.g. PdCI 2 (PPh 3 ) 2 Pd(OAc) 2 base: e.g. K 2 C0 3 or NEt 3 (Xllc) auxiliary catalyst: e.g. Cul, P(Ph 3 ) 3 temperature: e.g. 80 - 160°C conversion reaction(s): e.g.
  • Ri, R 2 , R 4 and Xi are as defined for formula I and Y is C ⁇ -C alkoxy, benzyloxy, hydroxy, halogen, cyano or phenoxy, which may be unsubstituted or substituted by an electron-withdrawing group such as halogen, trifluoromethyl, nitro, cyano, CrC 4 alkyl- carbonyl, d-C 4 alkoxycarbonyl or d-C 4 alkylsulfonyl, are novel and the present invention relates also thereto.
  • Y is preferably d-C alkoxy, benzyloxy, hydroxy, halogen or cyano, Y is especially d-C 4 alkoxy, benzyloxy, hydroxy, fluorine, chlorine or cyano, Y is more especially methoxy, ethoxy, hydroxy, chlorine or cyano, and Y is very especially methoxy, ethoxy or hydroxy.
  • R 4 is as defined for formula I and K 0 is hydroxy, trifluoromethylsulfonyloxy, methoxy, mercapto, CrC 6 alkylthio, d-C 6 alkylsulfonyl, halogen, d-C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, CrC 6 chIoroalkyl, CrC 6 bromoalkyl, CrC 6 iodoalkyl, CrC 6 chloroalkenyl, CrC 6 bromoalkenyl, d-Cechloroalkynyl, CrC 6 bromoalkynyl, methoxy-CrC 6 alkyl, CrCealkylcarbonyloxy-d-Ce- alkyl, C ⁇ -C 6 alkoxycarbonyloxy-CrC 6 alkyl, benzoyloxy-CrC 6 alkyl, CrC 6 hydroxyalkyl,
  • K 0 is preferably trifluoromethylsulfonyloxy, methylsulfonyl, halogen, hydroxy, mercapto, methoxy or methylthio
  • K 0 is especially methylsulfonyl, halogen, hydroxy, mercapto, methoxy or methylthio
  • Ko is more especially fluorine, chlorine, bromine or hydroxy
  • Y is preferably CrC 4 alkoxy, benzyloxy, hydroxy, halogen or cyano
  • Y is especially d-C 4 alkoxy, benzyloxy, hydroxy, fluorine, chlorine or cyano
  • Y is more especially methoxy, ethoxy, hydroxy, chlorine or cyano
  • Y is very especially methoxy, ethoxy or hydroxy.
  • the compounds of formula III used as starting materials are generally known from the literature, e.g. from the patent specifications WO 00/15615, EP 1 352 890, or can be prepared in accordance with the processes described therein.
  • the reagents of formulae Va, Vb, Vc, Vd, Ve, Vf, Vg, Vh, Vi, Vj and Vk used according to the known Stille, Suzuki, Sonogashira, Heck or related C-C coupling reactions are also known or can be prepared in accordance with the known processes.
  • All the reactions according to the preparation processes a) to d) 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 or 1 ,5-diazabicyclo[5.4.0]- undec-7-ene.
  • inorganic bases such as hydrides, e.g. dry sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g.
  • 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. n-hexane, benzene, toluene, xylenes, dichloromethane, 1 ,2-dichloroethane or chloro- benzene, at reaction temperatures in the range from -20°C up to the reflux temperature of the reaction mixture, preferably at about 40-10O°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.
  • an inert, organic solvent for example in an aliphatic, halogenated aliphatic, aromatic or halogenated aromatic hydrocarbon, e.g. n-hexane, benzene, toluene, xylenes, dichloromethane, 1 ,2-d
  • 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 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 per se, e.g. chromatography or fractionated 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.
  • 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, dipropylene glycol, dipropylene
  • 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 trimethylammonium 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® (Rhone-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. Those 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 97/34485.
  • 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 C 12 -C 22 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 that 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), CryMA(b), CrylllA, CrylMB(bl) or Cry9c, or vegetative insecticidal proteins (VIP), e.g. VI P1 , VI P2, VI P3 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, Cryl
  • 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, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-transferase, cholesterol oxidases, ecd
  • ⁇ -endotoxins for example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylMB(bl ) or Cry9c, or vegetative insecticidal proteins (VIP), for example VI P1 , VI P2, VI P3 or VIP3A, expressly also hybrid toxins, truncated toxins and modified toxins.
  • 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 CrylMA055, 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-0 374 753, WO 93/07278, WO 95/34656, EP-A-0 427 529, 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-0 367 474, EP-A-0 401 979 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 howardi, southern corn rootworm Melanotus spp., wireworms Cyclocephala borealis, northern masked chafer (white grub) Cyclocephala immaculata, 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 CrylMB(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); Bol
  • 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 86)3 expresses a CrylMB(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-0 392 225).
  • PRPs pathogenesis-related proteins
  • antipathogenic substances examples include antipathogenic substances, transgenic plants capable of synthesising such antipathogenic substances, for example, from EP-A-0 392 225, WO 95/33818 and EP-A-0 353 191.
  • 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-0 392 225); 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 stilbene synthases; bibenzyl synthases; chitinases; glucanases; the so-called
  • 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-trif luoromethyl-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 trifiuoroacetic 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- dichloroethane, dried over sodium sulfate and concentrated by evaporation. Filtration over a short silica gel column (eluant: ethyl acetate / hexane 1 :4) is carried out in order to separate off subsidiary products.
  • 98.4 g of 1 -oxy-5-trif luoromethyl-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-trifluoromethyl-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 P4 Preparation of 6-methyl-5-trifluoromethyl-pyridinecarboxylic acid ethyl ester: 6.9 g (6 mmol) of tetrakis(triphenylphosphine)palladium and 8.3 g (66 mmol) of 2,4,6- trimethyl-cyclotriboroxane are added to a mixture of 15.2 g (60 mmol) of 6-chloro-5- trifluoromethyl-pyridinecarboxylic acid ethyl ester and 33.1 g (0.24 mol) of potassium carbonate in 150 ml of dioxane and the mixture is then heated for 2.5 hours at reflux temperature. The end of the reaction can be determined by thin-layer chromatography.
  • reaction mixture is poured into ice-water and is acidified to pH 5 with concentrated hydrochloric acid.
  • a filtration aid Hyflo®
  • the product is then extracted with ethyl acetate.
  • the organic filtrate dried over sodium sulfate, is then concentrated by evaporation and purified by chromatography on silica gel (eluant: ethyl acetate/hexane 7.5:92.5).
  • aqueous phase which contains the acid, is then acidified to pH 2 with hydrochloric acid and then extracted with ethyl acetate, dried over sodium sulfate and concentrated by evaporation.
  • 6-(2-Methoxy- ethoxymethyl)-5-trifluoromethyl-pyridine-2-carboxylic acid is obtained;
  • Example P9 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 adding 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 chromatographed on silica gel (eluant: ethyl acetate / isohexane 1 :5). 0.9 g of 6-(1 -ethoxy-vinyl)-5-trif luoromethyl-pyridine- 2-carboxylic acid ethyl ester is obtained.
  • the substituents RrX ⁇ -R 2 are generally bonded to the pyridyl ring by way of the free valence at the atom on the left-hand side of the substituent RrX ⁇ -R 2 , as in the case, for example, of compound 1.001.
  • the substituent R X ⁇ -R 2 CH 2 OCH 2 OCH 3 is bonded to the pyridyl ring by way of the free valence of the carbon 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. 1.027.
  • 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.
  • Example B3 Comparison test with compounds from the prior art: Pre-emerqence herbicidal action:
  • compound B from the prior art shows significant damage (40 % phytotoxicity) to wheat and maize, which is unacceptable from an agronomic standpoint.
  • the enhanced action and improvement in selectivity of the compounds according to the invention were not to be expected.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
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Abstract

Ces composés selon la formule (I), dans laquelle les substituants sont tels que définis par la revendication 1, conviennent comme herbicides.
PCT/EP2004/014123 2003-12-12 2004-12-10 Nouveaux herbicides WO2005058831A1 (fr)

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CH21292003 2003-12-12

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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
WO2009015877A1 (fr) 2007-08-01 2009-02-05 Syngenta Limited Nouveaux herbicides
WO2010089993A1 (fr) 2009-02-03 2010-08-12 クミアイ化学工業株式会社 Dérivés de 2-pyridone à cycles condensés et herbicides
CN103408482A (zh) * 2012-07-04 2013-11-27 浙江大学 苯基螺环肟醚烯醇酯类化合物及其用途

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015615A1 (fr) * 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridinecetones utilises comme herbicides
WO2001094339A1 (fr) * 2000-06-09 2001-12-13 Syngenta Participations Ag Herbicides pyridiniques substitues

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000015615A1 (fr) * 1998-09-15 2000-03-23 Syngenta Participations Ag Pyridinecetones utilises comme herbicides
WO2001094339A1 (fr) * 2000-06-09 2001-12-13 Syngenta Participations Ag Herbicides pyridiniques substitues

Cited By (9)

* 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
WO2009015877A1 (fr) 2007-08-01 2009-02-05 Syngenta Limited Nouveaux herbicides
JP2010534696A (ja) * 2007-08-01 2010-11-11 シンジェンタ リミテッド 新規の除草剤
AU2008282081B2 (en) * 2007-08-01 2013-11-28 Syngenta Limited Novel herbicides
US8598365B2 (en) 2007-08-01 2013-12-03 Syngenta Limited Herbicides
EA021065B1 (ru) * 2007-08-01 2015-03-31 Зингента Лимитед Гербицидно активные циклические дионы и их производные, способы их получения, композиции, содержащие эти соединения, и их применение для борьбы с сорняками
WO2010089993A1 (fr) 2009-02-03 2010-08-12 クミアイ化学工業株式会社 Dérivés de 2-pyridone à cycles condensés et herbicides
CN103408482A (zh) * 2012-07-04 2013-11-27 浙江大学 苯基螺环肟醚烯醇酯类化合物及其用途

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