WO2004035564A1 - Pyridine derivatives useful as herbicides - Google Patents

Pyridine derivatives useful as herbicides Download PDF

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WO2004035564A1
WO2004035564A1 PCT/EP2003/011497 EP0311497W WO2004035564A1 WO 2004035564 A1 WO2004035564 A1 WO 2004035564A1 EP 0311497 W EP0311497 W EP 0311497W WO 2004035564 A1 WO2004035564 A1 WO 2004035564A1
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compound
alkyl
hydrogen
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Kurt Nebel
Jean Wenger
Christoph Lüthy
Roger Graham Hall
Juraj Tuleja
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Syngenta Participations Ag
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic 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
    • C07D401/02Heterocyclic 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
    • C07D401/04Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D401/00Heterocyclic 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
    • C07D401/14Heterocyclic 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
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D471/00Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04Ortho-condensed systems

Abstract

Compounds of formula (I) wherien W is a group W1 (W1), W2 (W2), W3 (W3), W4 (W4), W5 (W5), W6 (W6), W7 (W7), W8 (W8), W9 (W9), W10 (W10), W11 (W11), W12 (W12), and R50, R51, R52, R60, R61, R101, R102, R110, R112, R113, R114, Y110, X110 and X111 are as defined in claim 1, and also the agronomically acceptable salts and stereoisomers of such compounds of formula (I), are suitable for use as herbicides.

Description

PYRIDINE DERIVATIVES USEFUL AS HERBICIDES

Novel herbicides

The present invention relates to novel, herbicidaily active substituted 3-heterocyclyIpyridine 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.

Substituted pyridylpyrazoles having herbicidal action are described, for example, in WO 98/52938.

Novel substituted 2-oxy-3-heterocyclylpyridine derivatives that have herbicidal and growth- inhibiting properties have now been found.

The present invention accordingly relates to compounds of formula I

Figure imgf000003_0001
wherein

R1 is hydrogen, amino, R50CH=N-, R5ι(R52)N-, C C8alkyl, C C8haloalkyl, C3-C8cycloalkyl, C3-C8halocycloalkyl, C3-C8cycloalkyl-C C8alkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8cyclo- alkenyl, C3-C8halocycloalkenyl, C3-C8alkynyl, HC(O)-, d-Cj-alkylcarbonyl, C C8haloalkyl- carbonyl, C3-C8cycloalkylcarbonyI, C3-C8halocycloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haioalkenylcarbonyl, C2-C8alkynylcarbonyl, phenylcarbonyl, phenoxycarbonyl or phenylthiocarbonyl, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by hydroxy, amino, nitro, halogen, Cι-C4alkyl, CrC4haloalkyl, R60 and/or by R6o-C C4alkyleneoxy; or

RT is CrCgalkylsulfonyi, C C8haloalkyIsulfonyl, C2-C8alkenylsulfonyl, C2-C8haloalkenyl- sulfonyl or phenylsulfonyl, it being possible for the phenyl radical in the phenylsulfonyl group to be substituted from one to three times by halogen, Cι-C4alkyl, CrC4haloalkyl, CrC4alkoxy and/or by Cι-C4haloalkoxy; or R! is CrC8alkoxycarbonyl, C3-C8cycloalkoxycarbonyl, C C8haloalkoxycarbonyl, C3-C8- halocycloalkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8haloalkenyloxycarbonyl, C3-C8- alkynyloxycarbonyl, C1-C8alkylthio-C(O)-, C C8haloaikylthio-C(O)-, C3-C8alkenylthio-C(O)-, C3-C8alkynylthio-C(O)-, d-C8alkylthio-C(S)-, d-C8haloalkylthio-C(S)-, C3-C8alkenyl- thio-C(S)-, C3-C8alkynylthio-C(S)-, H2NC(O)-, R5ι(R52)NC(O)-, H2NC(S)-, R5ι(R52)NC(S)-, phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl or pyrazinyl, it being possible for the mentioned aromatic and heteroaromatic rings to be substituted from one to three times by hydroxy, amino, nitro, halogen, d-C4alkyl, CrC4haloalkyl, R60 and/or by R60- C C4alkyleneoxy; or

R is R61-CrC8alkylene-, R61-C3-C8cycloalkylene-, R61-C2-C8alkenylene- or R6ι-C2-C8- alkynylene-;

R50 is CrC8alkyl, d-C8haloalkyl, C3-C8cycloalkyl, C2-C8alkenyl, C2-C8alkynyl or phenyl, it being possible for the phenyl radical to be unsubstituted or substituted one or more times by halogen, d-C alkyl, CrC4haloalkyl, C C4alkoxy, d-C haloalkoxy, B1 and/or by B1-d-C4alkyleneoxy;

B1 is HOC(O)-, d-C4alkoxycarbonyl, C C4haIoalkoxycarbonyl, C3- or C4- alkenyloxycarbonyl, C3- or C -haloalkenyloxycarbonyl or C3- or C4-alkynyloxycarbonyl;

R51 and R52 are each independently of the other hydrogen, Cι-C8aikyl, C3-C8cycloalkyl, d-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8alkynyl, d-C4alkoxy-C C alkyl, d-C^lkylthio-d-C^lkyl, d-C^lkylsulfinyl-C C^lkyl, C C4alkylsulfonyl-d-C4alkyl, d-C8alkylcarbonyl, C3-C8cycloalkylcarbonyl, d-C8haloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C2-C8alkynyIcarbonyI, d-C8alkoxycarbonyl, C C8haloalkoxy- carbonyl, C2-C8alkenyloxycarbonyl, C2-C8haloalkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C C8alkylsulfinyI, C3-C8cycloalkylsulfinyl, d-C8haloalkylsulfinyl, C2-C8alkenylsulfinyl, C2-C8haloalkenylsulfinyl, d-C8alkylsulfonyl, C3-C8cycIoalkylsulfonyl, d-C8haloalkylsulfonyl, C2-C8alkenylsulfonyl or C2-C8haloalkenylsulfonyl; or

R51 and R52, together with the nitrogen atom to which they are bonded, form a three- to eight-membered heterocyclic ring which may contain, as a further hetero atom, sulfur or oxygen; R6o is HC(O)-, cyano, HOC(O)-, d-C4alkoxycarbonyl, C C4haloalkoxycarbonyl, C3-C8cyclo- alkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, C3- or C4-alkenyloxycarbonyl, C3- or C4- haloalkenyloxycarbonyl, C3- or C4-alkynyloxycarbonyl, C C4alkylthio-C(O)-, C3-C8alkenylthio- C(O)-, R62(R6s)NC(O)-, R62(R63)NC(S)-, hydroxy, mercapto, d-C4alkoxy, C C4haloalkoxy, C3-C6cycloalkoxy, C3- or C4-alkenyioxy, C3- or C4-haloalkenyloxy, C3- or C4-alkynyloxy, C C alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl or d-C4alkoxy-d-C4alkoxy;

R6ι is hydroxy, mercapto, cyano, HC(O)-, d-C8alkoxy, Cτ-C8haloalkoxy, C3-C8cycloalkoxy, C3-C8halocycloalkoxy, C3-C8alkenyloxy, C3-C8haloalkenyloxy, C3-C8alkynyloxy, d- C8alkylthio, d-C8haloalkylthio, C3-C8cycloalkylthio, C3-C8alkenylthio, C3-C8haloalkenylthio, C3-C8alkynylthio, HOC(O)-, C C8alkoxycarbonyl, d-Cβhaloalkoxycarbonyl, C3- C8cycloalkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3- C8haloalkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, d-C8alkylcarbonyl, C C8haloalkylcarbonyl, C3-C8cycloalkylcarbonyl, C3-C8halocycloalkylcarbonyl, C2- C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C2-C8alkynylcarbonyi, C1-C8alkylthio-C(O)-, C C8haloalkylthio-C(O)-, C3-C8cycloalkylthio-C(O)-, C3-C8halocycloalkylthio-C(O)-, C3- C8alkenylthio-C(O)-, C3-C8haloalkenylthio-C(O)-, benzyloxy-C(O)-, R62(R63)NC(O)- or

Figure imgf000005_0001

R6ι is phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, phenoxy, naphthyloxy, pyridyloxy, pyrimidyloxy, pyridazinyloxy, pyrazinyloxy or phenylcarbonyl, it being possible for the mentioned aromatic and heteroaromatic rings to be substituted from one to three times by halogen, d-C4alkyl, d-C4haloalkyl, d-C alkoxy, d-C4haloalkoxy, R6o and/or by R6o-CrC alkyleneoxy; or

R61 is phenoxy, phenylthio or phenylamino, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by halogen, hydroxy, amino, C C4alkyl, d-C4haloalkyl, Cι-C alkoxy, Cι-C4haloaIkoxy, R60 and/or by R6o-CrC4alkyleneoxy;

R62 and R63 are each independently of the other hydrogen, d-C8alkyl, d-C8haloalkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8cycloalkyl, C3-C8halocycloalkyl, C3-C8alkynyl, HC(O)-, C C8alkylcarbonyl, C C8haloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C3-C8cycloalkyicarbonyl, C3-C8halocycloalkylcarbonyl, d-C8alkoxycarbonyl, C C8haloalkoxy- carbonyl, C3-C8alkenyloxycarbonyl, C3-C8haloalkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C3-C8cycloalkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, C C8alkylsulfonyI, d-C8haloalkyl- sulfonyi, phenyl, phenylcarbonyl or phenoxycarbonyl, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by halogen, Cι-C4alkyl and/or by d-C4haloalkyl;

R2 is hydrogen, halogen, cyano, nitro, amino, H2NHN-, HOCH2-, HC(O)-, HON=CH-, H2NC(0)-, H2NC(S)-, HOC(O)-, C C4alkoxycarbonyl, C C4alkyIcarbonyl, C C4alkyl, C C4- hydroxyalkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3- or C4-hydroxyalkynyl, mercapto, d-C alkylthio, d-C4haloalkylthio, Cι-C4alkylsulfinyl, C C4haloalkylsulfinyl, C C4alkylsulfonyl or C C4haloalkylsuIfonyl; or

R2 is a group -OR1;

R3 and R4 are each independently of the other hydrogen, halogen, d-C4aIkyl, HOCH2-, HC(O)-, HON=CH-, HOC(O)-, C C4alkoxycarbonyl, H2NC(O)-, H2NC(S)-, C C4haloalkyl, hydroxy, H2NO-, d-C alkoxy, d-C4haloalkoxy, C3-C6alkenyloxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, nitro, amino, H2NHN-, cyano, mercapto, d-C4alkylthio, Cι-C4haloalkylthio, CrC alkylsulfinyl, d-C4haloalkylsulfinyl, C C4alkylsulfonyl or C C4haloalkylsulfonyl;

W is a group W1 (W1),

Figure imgf000006_0001
wherein

R100 is hydrogen, d-C4alkyl, d-C4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or

C4-alkynyl, amino, hydroxy, C3-C6cycloalkyl, C3-C6halocycloalkyl, HC(O)- or acetyl;

R10ι is hydrogen, C C4alkyl, HOCH2-, CrC haIoalkyl, C2-C4alkenyl, C2-C4haloalkenyi, hydroxy, Cι-C4alkoxy, Cι-C4haloalkoxy, HOC(O)-, d-C4alkoxycarbonyl, cyano, H2NC(S)-, H2NC(O)-, nitro, amino, HC(O)NH-, CH3C(0)NH-, HC(O)-, HON=CH-, C C4alkylcarbonyl, mercapto, d-C4alkylthio, C C4haloalkylthio, C C4alkylsulfinyl, d-C haloalkylsulfinyl, d-C4alkyIsulfonyl, d-C4haloalkylsulfonyl, C3- or C -alkenylthio, C3- or C4-haloalkenylthio, C3- or C4-alkenylsulfinyl, C3- or C4-haloalkenylsulfinyl, C3- or C4-alkenylsulfonyl, C3- or C4- haloalkenylsulfonyl, -CH(O-d-C4alkyl)2 or -CH(O-C2-C4alkylene-O); or

R100 and R10ι together form a bridge -(CH2)m-, -(CH2)n-CH=CH-(CH2)o- or -(CH2)n-X-(CH2)o-, it being possible for those bridges to be substituted from one to four times by halogen; m is 3, 4, 5 or 6; n is O, 1 or 2; o is 0, 1 , 2, 3, 4 or 5, with the proviso that the sum of n + o is 1 , 2, 3 or 4 and accordingly a

5-, 6-, 7- or 8-membered ring fused to the pyrazole ring is formed;

X is O, S, SO, SO2 or -NR103;

R103 is hydrogen, C C alkyl, d-C4haloalkyl, C3- or C4-alkenyl, d-C4alkylcarbonyl,

C C4alkylsulfonyl or C C4haloalkylsulfonyl;

R102 is hydrogen, halogen, C C4alkyl, C C4haloalkyl, cyano, H2NC(S)-, H2NC(O)-, HC(O)-, HON=CH-, HOC(O)-, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, nitro, cyano, hydroxy or amino; or

W is a group W2 (W2), W3 (W3),

Figure imgf000007_0002
Figure imgf000007_0001

Figure imgf000007_0003
Figure imgf000008_0001
wherein

X110 is O or S;

Y110 is hydrogen, halogen, cyano, C1-C4alkyl, C2-C4alkenyl or C2-C4alkynyl;

R110 is hydrogen, HC(O)-, HOC(O)-, H2NC(0)-, H2NC(S)-, cyano, halogen, amino, nitro,

C1-C4alkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl or C2-C4alkynyl;

Rt11 is hydrogen, HC(O)-, HOC(O)-, H2NC(O)-, H2NC(S)-, cyano, halogen, amino, nitro, CrC4alkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl or C2-C4alkynyl;

R112 is hydrogen, HC(O)-, HON=CH-, HOC(O)-, H2NC(0)-, H2NC(S)-, cyano, isonitrile, amino, nitro, HOHN-, hydroxy, mercapto, CrC4alkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, CrC4alkoxy, C1-C4haloalkoxy, CrC4alkylthio, CrC4haloalkyIthio, C1-C4al ylsulfinyl, C1-C4haloalkylsulfinyl, CrC4alkylsulfonyl or CrC4haloalkylsulfonyl; and

R113 and R114 are each independently of the other hydrogen, C C4alkyl, CrC4haloalkyl, C3- or C4-alkenyl or C3- or C4-alkynyl, and to the agrochemically acceptable salts and stereoisomers of those compounds of formula I.

The alkyl groups appearing 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 and the various isomeric pentyl, hexyl, heptyl and octyl radicals. Methyl, ethyl, n- propyl, isopropyl and n-butyl are preferred. Alkenyl and alkynyl groups may likewise be straight-chained or branched, this applying also to the alkyl, alkenyl, alkynyl and alkylene and alkenylene moieties of alkylcarbonyl, alkenyl- carbonyl, alkynylcarbonyl, alkoxy-alkyl, alkylthio-alkyl, alkenyloxycarbonyl, alkynyloxy- carbonyl, alkynylthio-C(O)-, alkylthio-C(S)-, alkenylthio-C(S)-, alkynylthio-C(S)-, alkylthio-C(O)-, alkenylthio-C(O)-, alkylsulfonyl, alkenylsulfonyl, alkylsulfinyl-alkyl, alkylsulfonyl-alkyl, cycloalkyl-alkyl, R61-alkylene-, R61-alkenylene-, R60-alkyleneoxy- and B1- alkyleneoxy- groups.

As examples of alkenyl groups there may be mentioned vinyl, allyl, methallyl, 1-methylvinyl, but-2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals having a chain length of from 2 to 5 carbon atoms.

As examples of alkynyl groups there may be mentioned ethynyl, propargyl, 1- methylpropargyl, 3-butynyl, but-2-yn-1-yl, 2-methylbutyn-2-yl, but-3-yn-2-yl, 1-pentynyl, pent- 4-yn-1-yl, 2-hexynyl, 3-heptyn-1-yl and 4-octyn-1-yl, preferably alkynyl radicals having a chain length of 3 or 4 carbon atoms.

In the afore-mentioned definitions, halogen is iodine, preferably fluorine, chlorine or bromine.

Alkoxy radicals preferably have a chain length of from 1 to 8 carbon atoms. Alkoxy is, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert- butoxy, or the pentyloxy, hexyloxy, heptyloxy and octyloxy isomers, preferably methoxy and ethoxy.

Hydroxyalkyl is, for example, 2-hydroxyethyl, 3-hydroxypropyl or 2,3-dihydroxypropyl.

Alkenyloxy is, for example, allyloxy, methallyloxy or but-2-en-1-yloxy.

Alkynyloxy is, for example, propargyloxy or 1-methyIpropargyloxy.

As haloalkyl there come into consideration alkyl groups substituted one or more times, especially from one to three times, by halogen, halogen being, in particular, iodine and, especially, fluorine, chlorine or bromine, e.g. fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl. As haloalkenyl there come into consideration alkenyl groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 2- and 3-fluoropropenyl, 2- and 3-chloropropenyl, 2- and 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl, 4,4,4-trifluoro-but-2-en-1-yl and 4,4,4- trichloro-but-2-en-1-yl. Among the alkenyl radicals substituted once, twice or three times by halogen, preference is given to those that have a chain length of 3 or 4 carbon atoms. The alkenyl groups may be halo-substituted at saturated or unsaturated carbon atoms.

As haloalkynyl there come into consideration alkynyl groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl and 4,4,4-trifluoro-but-2-yn-1-yl. Among the alkynyl groups substituted one or more times by halogen, preference is given to those that have a chain length of 3 or 4 carbon atoms.

Haloalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chIoroethoxy or 2,2,2- trichloroethoxy.

As haloalkenyloxy there come into consideratione alkenyloxy groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 2- and 3-fluoropropenyloxy, 2- and 3-chloropropenyloxy, 2- and 3-bromo- propenyloxy, 2,3,3-trifluoropropenyloxy, 2,3,3-trichloropropenyloxy, 4,4,4-trifluoro-but-2-en-1- yloxy and 4,4,4-trichloro-but-2-en-1-yloxy. Alkylthio is, for example, methylthio, ethylthio, propylthio or isopropylthio.

Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n- butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl or tert-butylsulfinyl, preferably methylsulfinyl or ethylsulfinyl.

Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl or tert-butylsulfonyl, preferably methylsulfonyl or ethylsulfonyl.

Haloalkylsulfonyl is, for example, fluoromethyisulfonyl, difluoromethylsulfonyl, trifluoromethyl- sulfonyl, chloromethylsulfonyl, trichloromethylsulfonyl, 2-fluoroethylsulfonyl, 2,2,2-trifluoro- ethylsulfonyl or 2,2,2-trichloroethylsulfonyl. Alkylcarbonyl is, especially, acetyl or propionyl.

Haloalkylcarbonyl is, especially, trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl or 3,3,3-trichloropropionyl.

Alkoxy-alkoxy is, for example, methoxymethoxy, methoxyethoxy, ethoxymethoxy, ethoxy- ethoxy, n-propoxymethoxy, n-propoxyethoxy, isopropoxymethoxy or isopropoxyethoxy.

Alkenylthio is, for example, allylthio, methallylthio or but-2-en-1-ylthio.

Alkynylthio is, for example, propargylthio or 1-methylpropargylthio.

Haloalkylthio is, for example, fluoromethylthio, difluoromethylthio, trifluoromethylthio, 2,2,2- trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2-fluoroethylthio, 2-chloroethylthio or 2,2,2- trichloroethylthio.

As haloalkenylthio there come into consideration alkenylthio groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 2- and 3-fluoropropenylthio, 2- and 3-chloropropenylthio, 2- and 3-bromo- propenylthio, 2,3,3-trifiuoropropenylthio, 2,3,3-trichloropropenylthio, 4,4,4-trifluoro-but-2-en- 1-ylthio and 4,4,4-trichloro-but-2-en-1-ylthio.

Haloalkylsulfinyl is, for example, fluoromethylsulfinyl, difluoromethylsulfinyl, trifluoromethyl- sulfinyl, 2,2,2-trifluoroethylsulfinyl, 1,1,2,2-tetrafluoroethylsulfinyl, 2-fluoroethylsulfinyl, 2- chloroethylsulfinyl or 2,2,2-trichloroethylsulfιnyl.

Alkenylsulfonyl is, for example, allylsulfonyl, methallylsulfonyl or but-2-en-1-ylsulfonyl.

As haloalkenylsulfinyl there come into consideration alkenylsulfinyl groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 2- and 3-fluoropropenyIsulfinyl, 2- and 3-chloropropenylsulfinyl, 2- and 3-bromopropenylsulfinyl, 2,3,3-trifluoropropenylsulfinyl, 2,3,3-trichloropropenylsulfϊnyl, 4,4,4-trifluoro-but-2-en-1 -ylsulfinyl and 4,4,4-trichloro-but-2-en-1 -ylsulfinyl. As haloalkenylsulfonyl there come into consideration alkenylsulfonyl groups substituted one or more times by halogen, halogen being, in particular, bromine or iodine and, especially, fluorine or chlorine, e.g. 2- and 3-fluoropropenylsulfonyl, 2- and 3-chloropropenylsulfonyl, 2- and 3-bromopropenylsulfonyl, 2,3,3-trifluoropropenylsulfonyl, 2,3,3-trichloropropenylsulfonyl, 4,4,4-trifluoro-but-2-en-1 -ylsulfonyl and 4,4,4-trichloro-but-2-en-1 -ylsulfonyl.

Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl or n-butoxycarbonyl, preferably methoxycarbonyl or ethoxycarbonyl.

Hydroxyalkynyl is, for example, 1-hydroxy-propyn-1-yl, 3-hydroxy-propyn-1-yl, 1- or 2- hydroxy-but-3-yn-1-yl or 1-hydroxy-but-2-yn-1-yl.

Alkenyloxycarbonyl is, for example, allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1-yI- oxycarbonyl, pentenyloxycarbonyl or 2-hexenyloxycarbonyl.

The cycloalkyl radicals that come into consideration as substituents are, for example, cyclo- propyl, cyclobutyl, cyclopentyl and cyclohexyl.

The cycloalkyl groups may be unsubstituted or substituted one or more times by halogen, especially substituted from one to four times by fluorine, chlorine and/or by bromine, e.g. difluorocyclopropyl, dichlorocyclopropyl, dibromocyclopropyl, 2,2,3,3-tetrafluorocyclobutyl and 2,2-difiuoro-3,3-dichlorocyclobutyl.

The cycloalkylcarbonyl radicals that come into consideration as substituents are, for example, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl and cyclohexyl- carbonyl.

Cycloalkoxy is, for example, cyclopropoxy, cyclobutoxy, cyclopentyloxy or cyclohexyloxy.

Cycloalkenyl is, for example, cyciopropenyl, cyclobutenyl, cyclopentenyl or cyclohexenyl. The cycloalkenyl groups may be unsubstituted or substituted one or more times by halogen, especially substituted from one to four times by fluorine, chlorine and/or by bromine, e.g. difluorocyclopropenyl, dichlorocyclopropenyl, dibromocyclopropenyl, 2,3-difluorocyclobutenyl and 2-fluoro-3-chlorocyclobutenyI.

The alkyleneoxy groups, for example in the definition of R- as phenyl, pyridyl, pyrimidyl, pyridazinyl or pyrazinyl wherein the mentioned aromatic and heteroaromatic rings may be substituted from one to three times by R60-C1-C4alkyleneoxy, are CrC4alkoxy radicals substituted by R60, e.g. 2-cyanopropoxy or 2-hydroxyethoxy.

The alkenylene groups, for example in the definition of R, as R61-C2-C8alkenylene-, are C2-C8alkenyl radicals substituted by R61, e.g. 4-methoxybut-2-en-1-yl or 3-cyanoallyl.

The cycloalkylene groups, for example in the definition of R^ as R61-C3-C8cycloalkylene-, are C3-C8cycloalkyl radicals substituted by R61, e.g. 2-hydroxycyclopropyl or 3-cyanocyclobutyl.

Phenyl 'per se' or phenyl as part of a substituent such as, for example, phenoxy, phenyl- amino, phenylcarbonyl, phenoxycarbonyl, phenylthiocarbonyl or phenylsulfonyl, may be in unsubstituted form or in substituted form, in which case the substituents may be in the ortho-, meta- and/or para-position(s). Substituents are, for example, halogen, CrC4alkyl or CrC4haloaIkyl.

When R51 and R52 which, together with the nitrogen atom to which they are bonded, form a three- to eight-membered saturated or unsaturated heterocyclic ring which may contain O or S as further hetero atoms, they denote, for example, the following heterocycles:

Figure imgf000013_0001

R100 and R101 together form a bridge -(CH2)m-, -(CH2)n-CH=CH-(CH2)0- or -(CH2)n-X-(CH2)0- provided that the sum of n + o = 1, 2, 3 or 4, with the result that R100 and R101, together with the nitrogen and carbon atoms of the pyrazole ring to which those substituents R100 and R101 are bonded, form a saturated or unsaturated, 5-, 6-, 7- or 8-membered ring which is fused to the pyrazole ring and which may contain as further hetero atoms O, N or S. Typical ring systems are illustrated, for example, by the following heterocycles:

Figure imgf000014_0001
it being possible for those fused-on rings to be additionally substituted from one to four times by halogen.

Corresponding meanings may also be given to the substituents in combined definitions, for example alkoxy-alkyl, alkylthio-alkyl, alkylsulfinyl-alkyl, alkylsulfonyl-alkyl, haloalkylcarbonyl, alkenylcarbonyl, alkenyloxy carbonyl, alkynylcarbonyl, alkynyloxycarbonyl, haloalkenyl- carbonyl, haloalkoxycarbonyl, haloalkenyloxy, haloalkenyloxycarbonyl, alkylthio-C(O)-, alkylthio-C(S)-, alkenylthio-C(O)-, alkenylthio-C(S)-, haloalkylthio-C(O)-, haloalkenylthio- C(O)-, haloalkylthio-C(S)-, alkynylthio-C(O)-, alkynylthio-C(S)-, cycloalkylthio, cycloalkylthio- C(O)-, cycloalkylsulfinyl, cycloalkyl-alkyl, cycloalkyl-carbonyl, cycloalkoxy-carbonyl, cycloalkyl-sulfonyl, halocycloalkoxy, halocycloalkyl-carbonyl, halocycloalkoxy-carbonyl, halocycloalkylthio-C(O)-, R50CH=N, R51(R52)N-, R51(R52)NC(0)-, R62(R63)NC(0)-, R62(R63)NC(S)- and R^-.

In the definitions of alkylcarbonyl, alkoxycarbonyl, haloalkylcarbonyl, haloalkoxycarbonyl, alkenylcarbonyl, haloalkenylcarbonyl, alkynylcarbonyl, alkenyloxycarbonyl, haloalkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkylcarbonyl, cycloalkoxycarbonyl, halocycloalkyl- carbonyl and halocycloalkoxycarbonyl, the upper and lower limits of the number of carbon atoms given in each case do not include the carbonyl carbon atom.

The invention relates also to the salts which the compounds of formula I are able to form especially with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Suitable salt formers are described, for example, in WO 99/52892 and WO 97/41112.

Among the alkali metal and alkaline earth metal hydroxides as salt formers, special mention should be made of the hydroxides of lithium, sodium, potassium, magnesium and calcium, especially the hydroxides of sodium and potassium. Examples of amines suitable for ammonium salt formation include ammonia as well as primary, secondary and tertiary CrCisalkylamines, d-C4hydroxyalkylamines and C2-C4alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropyl- amine, the four butylamine isomers, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methyl-ethylamine, methyl-isopropylamine, methyl-hexylamine, methyl- nonylamine, methyl-pentadecylamine, methyl-octadecylamine, ethyl-butylamine, ethyl- heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl- 2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n- propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n- amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p- chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.

Preferred quaternary ammonium bases suitable for salt formation correspond, for example, to the formula [N(RaRbRcRd)]OH wherein Ra, Rb, Rc and Rd are each independently of the others C C4alkyl. Other suitable tetraalkylammonium bases with other anions can be obtained, for example, by anion exchange reactions.

In addition to the formation of salts of compounds of formula I having acid hydrogen, especially of the derivatives having carboxylic acid groups (e.g. carboxyl-substituted alkylene, cycloalkylene, alkenylene and alkyleneoxy groups { ^ = R61-C C8alkylene-, R61-C3-C8cycloalkylene- or R6ι-C2-C8alkenylene- wherein R6-, is HOC(O)-, or R = aromatic or heteroaromatic, R6o-CrC4alkyleneoxy-substituted rings wherein R60 is HOC(O)-), or HOC(O)-, HON=CH- or mercapto-substituted pyridyl (R3, R4) and pyrazolyl (R-0ι, R102) groups) and heterocyclic groups W2 to W10 (R-no, Rm, R112), salts of the compounds of formula I having basic groups are also possible, especially having basic pyridyl, pyrimidyl, pyrazinyl and pyridazinyl rings (R1) or having amino or hydrazino groups as in, for example, the definition of R2> R3, R4, R100, R10ι, R102, R110. Rm- R112 and X. Such salts are, for example, salts with inorganic and organic acids such as, for example, hydrohalic acids, e.g. hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, and sulfuric acid, phosphoric acid and nitric acid, and organic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid, propionic acid, glycolic acid, thiocyanic acid, citric acid, benzoic acid, oxalic acid, formic acid, benzenesulfonic acid, p-toluenesulfonic acid and methanesulfonic acid.

The presence of an asymmetric carbon atom or of a sulfinyl group in the compounds of formula I, for example in the substituent R or R2 wherein R50> R51 or R52 is a branched alkyl, alkenyl or haloalkyl group or R5 or R52 is alkylsulfinyl-alkyl or haloalkylsulfinyl, means that the compounds may occur either in the form of optically active single isomers or in the form of racemic mixtures. In the present invention, the compounds of formula I are understood to include both the pure optical antipodes and the racemates and diastereoisomers.

When an aliphatic C=C double bond or a HON=CH group is present, geometric isomerism may occur. Such isomers are also included in the present invention.

Preference is given to compounds of formula I wherein W is the group W1

(W1 ). Amongst those compounds, special preference is given to those

Figure imgf000016_0001
wherein R10o is hydrogen or d-C alkyl; and R10ι is hydrogen, d-C4alkoxy, Cι-C haloalkoxy, C C4haloalkyl, C C4alkylthio, d-C4alkylsulfinyl, d-C4alkylsulfonyl, cyano, H2NC(O)- or H2NC(S)-; or R 00 and R*0ι together form a -(CH2)m- bridge; and R102 is hydrogen, halogen or C C4alkyl.

Preference is likewise given to compounds of formula I wherein R-i is hydrogen, Cι-C8alkyl, C2-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8alkynyl, unsubstituted or substituted phenyl, d-C8alkylcarbonyl, phenylcarbonyl, C C8alkoxycarbonyl, C3-C8alkenyloxycarbonyI, C3-C8alkynyloxycarbonyl or R61-C C8alkylene-. Amongst those compounds, special importance is given to those wherein R* is hydrogen, d-C alkyl, C2-C4haloalkyl, C2-C4- alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, phenyl, phenyl substituted by hydroxy, methoxy, C or C2-alkyl, methoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl and/or methylcarbonyl; R6ι is Cι-C4alkoxy, C C4alkoxycarbonyl, HOC(O)-, allyloxycarbonyl, phenyl or phenyl substituted by C or C2-alkyl, methoxy, hydroxy and/or by R6o-CrC4alkyleneoxy; and R60 is d- or C2-alkoxycarbonyl.

Preference is given also to compounds of formula I wherein R2 is hydrogen, halogen, cyano, -OR1 ; C C4alkyIthio, d-C alkylsulfinyl or d-C4alkylsulfonyl. Amongst those compounds, special preference is given to those wherein R2 is methylthio, methylsulfinyl or methylsulfonyl; and Ri is hydrogen, methyl, allyl, propargyl, methoxycarbonyl or allyloxycarbonyl.

Preference is furthermore given to compounds of formula I wherein R3 and R4 are each independently of the other hydrogen or halogen; amongst those compounds, special preference is given especially to those wherein R3 and R4 are each independently of the other hydrogen, fluorine or chlorine.

The compounds of formula I can be prepared by methods that are known perse and described, for example, in US-A-5 698 708, US-A-5 883 263, WO 97/15570, Synthesis 1986(5), 409-411 and Tetrahedron Lett. 37(7), 1003 (1996), for example for preparing those compounds of formula I

wherein W is a group W1 1); Rι, R2, R3 and R4 are as defined

Figure imgf000017_0001
for formula I; R10o is hydrogen, d-C alkyl, C C4haloalkyl, C3- or C4-alkenyl, C3- or C4-halo- alkenyl, C3- or C4-alkynyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; Rioi is hydrogen, d-C4alkyl, d-C4haloalkyI, hydroxy, C C4aIkoxy, d-C4haloalkoxy, HOC(O)-, C C4alkoxy- carbonyl, H2NC(O)-, d-C4alkylcarbonyl, -CH(O-C C4alkyl)2 or -CH(O-C2-C4alkylene-O); and R102 is hydrogen, halogen, C C4aIkyl, C C4haloalkyl, cyano or HOC(O)-, for example, by cyclising a compound of formula II
Figure imgf000018_0001
wherein R R2, R3, R4, R101 and Rι02 are as defined, in a suitable solvent such as, for example, glacial acetic acid, with the compound of formula XI

H2NNH-R100 (XI), wherein Rι00 is as defined, to form the compound of formula IW1

Figure imgf000018_0002
wherein R1( R2, R3, R4, Rioo, R101 and R102 are as defined, and then, according to the meanings of Rioo, R10i and R102, optionally carrying out further functionalisation according to standard methods, especially, for example, alkylation, freonisation (R101 = alkoxy, haloalkoxy), or subjecting the pyrazole ring (Rι02 = hydrogen) to halogenation (R102 = halogen) (Reaction Schemes 1 and 2).

The process according to the invention for the preparation of compounds of formula I is performed in analogy to known processes such as that described, for example, in WO 98/21199 and comprises, for the preparation of those compounds of formula I

Figure imgf000018_0003

wherein W is a group W1 (W1); R,, R2, R3 and R4 are as

Figure imgf000018_0004
defined for formula I; Rioo is hydrogen, CrC4alkyl, CrC4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; Rι01 is CrC4halo- alkoxy; and Rι02 is hydrogen, halogen, nitro or HC(O)-, for example, cyclising a compound of formula III

Figure imgf000019_0001
in a suitable solvent such as, for example, glacial acetic acid at room temperature or with gentle heating, for example up to 80°C, with the compound of formula XI

H2NNH-R100 (XI) to form the compound of formula IW1 a

Figure imgf000019_0002
the radicals R,, R2, R3, R4 and R100 in compounds of formulae III, XI and IW1a being as defined, and then subjecting the compound of formula IW1a to further functionalisation according to standard methods, for example to a freonisation reaction using Freon 22 (= chlorodifluoromethane) in the presence of an inert solvent such as, for example, dry N,N- dimethylformamide (DMF) at a temperature from 20° to 100°C to obtain the compound of formula IW1b

Figure imgf000019_0003
wherein R101 is haloalkoxy, e.g. OCHF2, and, according to the meaning of R102 above, subjecting the pyrazole ring to an electrophilic aromatic substitution reaction such as, for example, halogenation, nitration or formylation to obtain the compound of formula IW1
Figure imgf000020_0001
wherein R.,, R2, R3, R4, Rι00 and R101 are as defined and R,02 is halogen, especially chlorine, bromine or iodine, NO2 or HC(O)- (Reaction Scheme 2).

For preparation of compounds of formula IW1 substituted at the pyrazole ring (group W1) a large number of described standard methods are available, the selection of suitable preparation methods being dependent upon the properties (reactivities) of the substituents in the relevant intermediates. Such standard methods are described, for example, in WO 98/21199, Synthesis 1999(3), 453-458, J. Chem. Soc, Perkin Trans. 1(5), 925-930 (1989) and J. Chem. Soc, Perkin Trans. 1(7), 1267-1271 (1986). Further illustrative examples are shown in Reaction Schemes 3 and 3a.

Reaction Scheme 3

Figure imgf000020_0002

IW1f lW1g

diazotisation and

Sandmeyer reaction or phenolic boiling

Figure imgf000020_0003

IW1 (R = halogen, OH, cyano) Reaction Scheme 3a

Figure imgf000021_0001

IW1f„ IW1ga

diazotisation and

Sandmeyer reaction or phenolic boiling

Figure imgf000021_0002

IW1 (R = halogen, OH, SH, cyano)

In accordance with Reaction Scheme 3, the 4-nitro-pyrazole derivative of formula IW1f can be reduced according to standard methods, for example using Pd/H2 or Raney nickel/H2, to form the corresponding amino compound of formula IW1g, which can in turn be converted according to standard methods such as, for example, Sandmeyer reaction of the previously formed diazonium salt to form the compound of formula IW1 wherein Rι02 is, for example, halogen or cyano, (e.g. J. Heterocycl. Chem. 24(1), 267-270 (1987) and ibid. 25(3), 955-958 (1988)) or phenolic boiling of the diazonium salt to form the compound of formula IW1 wherein R102 is, for example, OH.

In accordance with Reaction Scheme 3a, the 5-nitro-pyrazole derivative of formula IW1fa can be reduced according to standard methods, for example using Pd/H2 or Raney nickel/H2, to form the corresponding amino compound of formula IW1ga, which can in turn be converted according to standard methods such as, for example, Sandmeyer reaction or phenolic boiling of the previously formed diazonium salt to form the compound of formula IW1 wherein Ri0ι is, for example, halogen, OH, SH or cyano. Those groups may, optionally, be further functionalised, for example the OH or SH groups may be further functionalised to the corresponding alkoxy, alkylthio, haloalkoxy or haloalkylthio groups by means of alkylation or freonisation, or the alkylcarbonyl group may be further functionalised to the corresponding haloalkyl groups using diethylaminosulfur trifluoride (DAST) or sulfur tetrafluoride (SF4). The process according to the invention for the preparation of compounds of formula I

Figure imgf000022_0001

wherein W is a group W1 (W1); R.,, R2, R3 and R4 are as defined

Figure imgf000022_0002
for formula I; R100 is hydrogen, C,-C4alkyl, d-d-haloalkyl, C3- or C4-alkenyl, C3- or C4-halo- alkenyl, C3- or C4-alkynyl, C3-C6cydoalkyl, C3-C6halocycloalkyl or HC(O)-; R101 is mercapto, CrC4alkylthio, CrC4haloalkyIthio, CrC4alkylsulfinyl, CrC4haloalkyIsulfinyl, CrC4alkylsulfonyl or C1-C4haloalkylsulfonyl; and R102 is hydrogen, halogen, CrC4alkyl, d-C4haloalkyl, cyano, H2NC(S)-, H2NC(O)-, HC(O)-, HON=CH-, HOC(O)-, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl or nitro is carried out in analogy to known processes, such as that described, for example, in Angew. Chem., Int. Ed., 39(1), 233-237 (2000), WO 97/00246 and WO 97/15570, and comprises, for example, first treating a compound of formula IV

Figure imgf000022_0003
wherein R,, R2, R3, R4 and R102 are as defined, in the presence of a base such as, for example, an alkali metal hydride or alcoholate, e.g. sodium hydride or potassium tert- butanolate, and an aprotic solvent such as, for example, an ether, e.g. tetrahydrofuran (THF), with carbon disulfide at a temperature from 0° to 80°C and then carrying out alkylation with a compound of formula XII ,-R,o,. (XII), wherein R101a is C1-C4alkyl or C1-C4haloalkyl, and L is a leaving group such as, for example, halogen, especially iodine, bromine or chlorine, or R101a is OS(0)2O- to obtain the compound of formula V
Figure imgf000023_0001
which is subsequently cyclised by reacting, optionally in the presence of a suitable solvent such as, for example, an alcohol with the hydrazine derivative of formula XI

NH2NH-Rιoo (XI), wherein R100 is as defined, to form the compound of formula IW1c

Figure imgf000023_0002
the radicals R-, R2l R3, R , R100, Rioia and R102 in the compounds of formulae V, XI and IW1c being as defined, and, optionally, subsequently oxidising that compound to form the corresponding sulfinyl or sulfonyl derivatives. The oxidation can be performed, for example, using peracids, e.g. m-chloroperbenzoic acid (MCPBA) or hydrogen peroxide, in the presence of a suitable solvent such as, for example, a halogenated hydrocarbon, e.g. dichloromethane, chloroform or carbon tetrachloride at a temperature from -40°C to the reflux temperature of the solvent in question, preferably from 0° to 35°C, it being possible to control the degree of oxidation at the sulfur atom by means of the amount of oxidising agent (compounds of formula IW1e in Reaction Scheme 4 wherein n is 1 or 2).

The preparation of the pyrazole rings in the compounds of formula IW1

Figure imgf000023_0003
wherein Ri, R2, R3, R4, R100, R101 and R 02 are as defined for formula I, is described in greater detail in the following Reaction Schemes 1 , 2 and 4. Reaction Scheme 1

Figure imgf000024_0001

IW1

Reaction Scheme 2

Figure imgf000024_0002

IW1a

freonisation, e.g. electrophilic aromatic substitution

Freon 22, solvent r, e.g. halogenation, nitration or

2#-100 ό formylation

Figure imgf000024_0003

IW1b (R101 e.g. -OCHF2)

Figure imgf000024_0004

IW1 (R102 = halogen, N02 or HC(O)-) Reaction Scheme 4

Figure imgf000025_0001
oxidation, e.g. MCPBA, solvent, e.g. CH2CI2, -40°C to reflux

Figure imgf000025_0002
IW1c

Figure imgf000025_0003

IWIe ^ s l^)

The process according to the invention for the preparation of compounds of formula I is carried out in analogy to known processes such as, for example, that described in WO 99/52892 and comprises, for the preparation of those compounds of formula I

Figure imgf000025_0004
wherein R,, R2, R3, R4 and W are as defined for formula I, for example, first oxidising a compound of formula VI
Figure imgf000026_0001
wherein R2, R3, R4 and W are as defined, in a suitable solvent such as, for example, water, an organic acid, e.g. acetic acid or trifluoroacetic acid, a halogenated hydrocarbon, e.g. dichloromethane or 1 ,2-dichloroethane, or an ester, e.g. ethyl acetate, to form the compound of formula VII

Figure imgf000026_0002
for example using an organic peracid, e.g. m-chloroperbenzoic acid (MCPBA) or peracetic acid, or aqueous hydrogen peroxide solution or a hydrogen peroxide-urea addition product together with a carboxylic acid and/or a carboxylic anhydride, or an inorganic peracid, e.g. pertungstic acid (Caro's acid), at a reaction temperature in the range from -20° to 100°C depending on the solvent or solvent mixture used, and subsequently rearranging the compound of formula VII, optionally in a solvent such as, for example, a halogenated hydrocarbon or an amide in the presence of an anhydride, for example acetic anhydride or trifluoroacetic anhydride (e.g. analogously to J. Org. Chem. 63(3), 950-953 (1999), J. Chem. Res., Synop. (11), 378-379 (1987) and J. Am. Chem. Soc. 109(18), 5523-5524 (1987)) or antimony pentachloride (Katada reaction) and, after aqueous working-up, obtaining the compound of formula lh

Figure imgf000026_0003
and reacting that compound, in the presence of an inert solvent such as, for example, a halogenated hydrocarbon, a ketone or an amide and a base such as, for example, a carbonate, e.g. potassium carbonate, with an alkylating agent of formula XIII

RrL2 (XIII), wherein R, is as defined for formula I with the exception of R1 being hydrogen, amino, R50CH=N-, R5ι(R52)N-, phenyl, pyridyl, pyrimidyl, pyridazinyl or pyrazinyl, and L2 is a leaving group such as, for example, halogen, especially chlorine, bromine or iodine, or a sulfonate,

especially CH3S(O)2O- or H3C — — S(O)2O- (e.g. analogously to Angew.

Chem., Int. Ed. 39(10), 1775-1777 (2000) and Pharmazie 54(3), 178-183 (1999)). This reaction sequence is described in greater detail in Reaction Scheme 5.

Reaction Scheme 5

Figure imgf000027_0001

VI VII

1 ) anhydride, e.g. Ac20, optionally solvent, e g DMF

Figure imgf000027_0002

The process according to the invention for the preparation of compounds of formula I is carried out in analogy to known processes such as, for example, that described in WO 99/52892 and comprises, for the preparation of those compounds of formula I

Figure imgf000027_0003
wherein R,, R2, R3, R4 and W are as defined for formula I, for example, a) first oxidising a compound of formula VIII
Figure imgf000028_0001
wherein R2, R3, R4 and W are as defined and L3 is a leaving group such as, for example, halogen, e.g. chlorine, bromine or iodine, or a Crdalkylsulfonyl or phenylsulfonyl group, to form the corresponding pyridine-N-oxide derivative of formula IX

Figure imgf000028_0002
for example using an organic peracid, e.g. MCPBA or aqueous hydrogen peroxide solution together with a carboxylic acid and/or a carboxylic anhydride, and then subjecting that N- oxide derivative, optionally in an inert solvent such as, for example, an ether, e.g. THF, in the presence of a base such as, for example, an alkali metal hydride or hydroxide to a nucleophilic substitution reaction with a compound of formula XIV

R OH (XIV), wherein Ri is as defined for formula I, (for example, analogously to J. Chem. Soc, Perkin Trans. 1(6), 1637-1643 (1990) and Tetrahedron 43(11), 2557-2564 (1987)) to obtain the compound of formula X

Figure imgf000028_0003
and finally deoxygenating the pyridine-N-oxide function in analogy to known processes such as that described, for example, in J. Am. Chem. Soc. 122(21), 5017-5024 (2000), Heterocycles 51(10), 2385-2397 (1999) and J. Org. Chem. 64(7), 2211-2218 (1999), for example in an alcohol by means of palladium-on-carbon in the presence of hydrogen (Pd/C/H2), or b) first oxidising a compound of formula Villa (Vllla),

Figure imgf000029_0001
wherein R3, R and W are as defined and L3 is a leaving group such as, for example, halogen or a C C4alkylsulfonyl or phenylsulfonyl group, to form the corresponding pyridine- N-oxide derivative of formula IXa

Figure imgf000029_0002
as described above under a), for example using an organic peracid or aqueous hydrogen peroxide solution, then subjecting that derivative, optionally in an inert solvent in the presence of a base, to a nucleophilic substitution reaction with a compound of formula XIV

RrOH (XIV), wherein R- is as defined for formula I, to obtain the compound of formula Xa

Figure imgf000029_0003
and, by means of halogenation in a manner analogous to that described in WO 97/09312 and Tetrahedron Lett. 36(42), 7575-7578 (1995), cyanation in a manner analogous to that described in Synlett 1999(8), 1203-1206, Inorg. Chim. Acta 306(2), 223-226 (2000) and J. Med. Chem. 42(1), 95-108 (1999), Grignard reaction in a manner analogous to that described in J. Med. Chem. 33(8), 2231-2239 (1990), by treatment with Tebbe reagent (titanocene-methylidene complex) in a manner analogous to that described in Angew. Chem., Int. Ed. 39(14), 2529-2533 (2000), or by treatment with Meerwein salt and ammonium persulfate in a manner analogous to that described in Synth. Communic. 19(1-2), 317-325 (1989), introducing the radical R2 into the position ortho to the pyridine-N-oxide group, with simultaneous deoxygenation thereof, and, in accordance with the meaning of R2, further functionalising the resulting compound of formula I; for example, the CH3 group introduced by means of a Grignard reagent or Tebbe reagent (Reaction Scheme 7, R2 = CH3) can be further converted, according to standard methods such as that described, for example, in J. Org. Chem. 64(23), 8576-8581 (1999), WO 00/00474 and Heterocycles 45(8), 1519-1528 (1997), to -CH2OH, -CH2OAc or -CH2CI. Reaction Schemes 6 and 7 illustrate the two synthesis routes indicated under a) and b).

Reaction Scheme 6

Figure imgf000030_0001

VIII IX

Figure imgf000030_0002

Reaction Scheme 7

Figure imgf000031_0001

Villa IXa

introduction of R2: halogenation, e.g. POCIg, PCI5; cyanidation, e.g. (CH3)3SiCN; or

(CH3)3O . BF4 + (NH4)2S208

Figure imgf000031_0002
Figure imgf000031_0003

Xa I (R2 = CI, CN, CH2OH)

Grignard reagent, e.g. CH3MgBr, or Tebbe reagent

1. oxidation, e.g. MCPBA

Figure imgf000031_0004

All further compounds falling within the scope of formula I can be prepared by simple means, giving due consideration to the respective chemical reactivities of the pyridyl moiety and the pyridyl-(heterocyclyl)-W moiety (groups W1 to W12), analogously to standard methods such as those described, for example, in "Methoden der Organischen Chemie" (Houben-Weyl), Volume E 8b, Georg Thieme Verlag Stuttgart, 1994, page 399 ff.; ibid, Volume E 7B, Georg Thieme Verlag Stuttgart, 1992, page 286 ff.; in "Pyrazoles, Pyrazolines, Pyrazolidines, Indazoles and Condensed Rings", Editor R. H. Wiley, Interscience Publishers, John Wiley & Sons, New York, 1967, page 1 ff.; or in "Comprehensive Heterocyclic Chemistry", Editors A. R. Katritzky and C. W. Rees, Pergamon Press, Oxford, 1987, or by derivatisation according to known standard methods such as those described, for example, in "Advanced Organic Chemistry, Third Edition, Editor J. March, John Wiley & Sons, New York, 1985; in "Comprehensive Organic Transformations", Editor R. C. Larock, VCH Publishers, Inc., New York, 1989; or in "Comprehensive Organic Functional Group Transformations", Editors A.R. Katritzky, O. Meth-Cohn, CW. Rees, Pergamon Press, Oxford, 1995, or as described in the following Patent specifications: EP-A-0 361 114, US-A-5 032 165, WO 92/02509, WO 92/06962, WO 95/33728 and WO 96/01254.

A number of illustrative examples are described in Preparation Examples P1 to P29; for example, preparation of compounds of formula I substituted at the pyridyl moiety is described in Preparation Examples P1 to P7, P11 to P19 and P23 to P29.

The compounds of formula I wherein W is a group W2 to W12 can be prepared analogously to the synthesis strategies indicated above for pyrazoles of the group W1 or as described, for example, in "Comprehensive Heterocyclic Chemistry", Editor A.R. Katritzky, Pergamon Press, Oxford 1984, Vol. 3/Part 2B: "Six-membered Rings with Oxygen, Sulfur or two or more Nitrogen Atoms", Editors AJ. Boulton, A.M. McKillop; "Comprehensive Heterocyclic Chemistry II", Editors A.R. Katritzky, Ch.W. Rees, E.F.V. Scriven, Pergamon Elsevier, Oxford, 1996, Vol. 6: "Six-membered Rings with two or more Heteroatoms and fused Carbocyclic Derivatives", Editor AJ. Boulton; and "Methoden der Organischen Chemie" (Houben-Weyl), Volume E 9b/Part 1 'Hetarenes IV, Editor E. Schaumann, Georg Thieme Verlag Stuttgart, 1998.

The end products of formula I can be isolated in conventional manner by concentrating or evaporating off the solvent and can be 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, by distillation or by means of column chromatography and a suitable eluant.

The person skilled in the art will also be familiar with the order in which certain reactions should advantageously be performed in order possibly to avoid subsidiary reactions.

Unless synthesis is specifically aimed at the isolation of pure isomers, the product may be obtained in the form of a mixture of two or more isomers. The isomers can be separated according to methods known per se.

The pyridyl-diketones and pyridyl-keto esters of formulae II and III (Reaction Schemes 1 and 2) can be prepared according to known methods such as are described, for example, in "March's Advanced Organic Chemistry", Editors M.B. Smith, J. March, Wiley Interscience, New York, 2001, page 1665; and in "Comprehensive Organic Transformations", Editor R.C. Larock, VHC Publishers, Inc., New York, 1989, advantageously by a) acylation at the carbon atom with active hydrogen, b) acylation of carboxylic acid esters by other carboxylic acid esters (Claisen condensation, Dieckmann reaction), c) acylation of ketones by carboxylic acid esters, d) acylation of carboxylic acid salts, e) acylation of enamines with subsequent hydrolysis, f) reaction of a pyridyl-nitrile with zinc and an α-halo ester (Blaise reaction), g) rearrangement of epoxy ketones, h) reaction of a pyridylcarboxylic acid chloride with malonic acid monoester and subsequent decarboxylation.

The pyridyl-ketone derivatives of formula IV (Reaction Scheme 4) can be prepared according to known methods such as are described, for example, in "March's Advanced Organic Chemistry", Editors M.B. Smith, J. March, Wiley Interscience, New York, 2001, page 1678; and "Comprehensive Organic Transformations", Editor R.C. Larock, VHC Publishers, Inc., New York, 1989, advantageously by a) hydrolysis of corresponding pyridyl-substituted enol ethers or enamines, b) hydrolysis of geminal dihaloalkyl-pyridine derivatives, c) alkylation of pyridyl-ketones, d) acylation with activated pyridinecarboxylic acid derivatives at the active carbon atom and subsequent cleavage, e) rearrangement of pyridyl-hydroxyalkenes, f) carbonylation of e.g. halo- or triflate-substituted pyridine derivatives in the presence of organometallic compounds, g) hydrolysis of corresponding pyridyl-oximes, -oxime ethers or -imines, h) addition of Grignard compounds to pyridyl-nitriles and subsequent hydrolysis of the addition product, i) reaction of pyridyl-Weinreb amides with Grignard compounds, j) reaction of pyridyl-carboxylic acid halides with dimethyl malonate and subsequent ester cleavage and decarboxylation, k) addition of Grignard compounds to pyridyl aldehydes and subsequent oxidation of the secondary alcohol, or I) ring synthesis of pyridines having a keto function in the 1 -position.

The substituted heterocyclyl-pyridine derivatives of formula VI (Reaction Scheme 5) can be prepared in analogous manner to that indicated, for example, for pyrazoies of the group W1 or in accordance with a synthesis strategy as indicated above for the groups W2 to W12 (compounds of formulae II and III).

The pyridine derivatives of formulae VIII and Villa (Reaction Schemes 6 and 7) can be prepared according to known methods such as, for example, by converting the hydroxypyridines of formula lh, with the aid of chlorination reagents such as, for example, phosphorus oxychloride, phosphorus pentachloride, phosgene or thionyl chloride in the presence of a catalytic amount of N,N-dimethylformamide (DMF), into the corresponding chlorine derivatives of formula VIII or Villa, wherein L3 is chlorine. Such halogenation reactions are described, for example, in WO 02/30901; WO 01/98303; Organic Process Research & Development 5(5), 531-534 (2001); J. Med. Chem. 43(22), 4288-4312 (2000); J. fur Prakt. Chemie (Weinheim, Germany) 342(1), 33-39 (2000); Organic Preparations and Procedures International 30(3), 356-359 (1998); and Pesticide Sci. 42(4), 253-263 (1994).

The pyridine derivatives of formulae VIII and Villa (Reaction Schemes 6 and 7) can also be prepared from the corresponding pyridine-N-oxides of formula VII by reaction with phosphorus oxychloride, phosphorus pentachloride, phosgene, carboxylic acid chlorides, thionyl chloride or sulfonic acid chlorides such as, for example, phenylsulfonic acid chloride, in analogous manner to that described, for example, in Synthetic Communications 31 (16), 2507-11 (2001); Organic Process Research & Development 5(5), 531-534 (2001); Tetrahedron Lett. 42(4), 735-737 (2001); J. Org. Chem. 65(8), 2444-2457 (2000); or US-A-5 502 194.

The pyridine derivatives of formulae VIII and Villa wherein L3 is an alkyl- or phenyl-sulfonyl group can be obtained by metallation in the 2-position of the corresponding pyridine derivative and reaction with a dialkyl disulfide such as, for example, dimethyl disulfide (CH3SSCH3) and subsequent oxidation. Such reactions are described, for example, in European Journal of Organic Chemistry 3, 603-606 (2001); US-A-20020016470; Tetrahedron Lett. 41(22), 4335-38 (2000); Chem. Communic. 11 , 951-952 (2000).

The pyridine derivatives of formulae VIII and Villa wherein L3 is an alkyl- or phenyl-sulfonyl group can be prepared from the corresponding chlorine derivatives of formula VIII or Villa wherein L3 is chlorine by reaction with a thiolate and subsequent oxidation, as described, for example, in WO 00/69825; Tetrahedron Lett. 40(30), 5565-68 (1999); J. Chem. Soc, Perkin Trans II (Physical Organic Chemistry) 11, 2415-22 (1997).

The pyridine derivatives of formulae VIII and Villa wherein L3 is an alkylsulfonyl group can also be obtained by alkylation of the corresponding pyridinethiols (L3 = -SH) and subsequent oxidation, as described, for example, in Pharmazie 55(12), 896-899 (2000); J. Het. Chem. 37(2), 379-382 (2000); Chemistry of Heterocyclic Compounds (New York, Translation of Khimiya Geterotsiklicheskikh Soedinenii) 35(3), 290-292 (1999); Austr. J. Chem. 42(9), 1493-1518 (1989).

The pyridinethiols employed are themselves obtainable a) from the corresponding hydroxypyridine compounds of formula VIII or Villa wherein L3 is -OH (= compounds of formula lh) by reaction with a thionating reagent such as, for example, phosphorus pentasulfide or Lawesson's reagent in analogous manner to that described, for example, in J. of Fluorine Chemistry 93(2), 153-157 (1999), or b) from the corresponding compounds of formula VIII or Villa wherein L3 is chlorine by means of a nucleophilic substitution reaction in the presence of thiourea or sodium thiosulfate and subsequent hydrolysis, using sodium hydrogen sulfide (NaSH) or sodium or potassium sulfide (Na2Saq or K2Saq). Such reactions are known, for example, from Tetrahedron Lett. 38(4), 539-542 (1997); J. Med. Chem. 33(2), 781-789 (1990); Tetrahedron Lett. 34(6), 939-942 (1993); Pharmazie 44(12), 809-813 (1989); Tetrahedron 44(4), 1187-94 (1988); or J. Heterocycl. Chem. 22(5), 1353-56 (1985).

The oxidation of the alkyl- or phenyl-sulfides (L3 -= alkyl-S- or phenyl-S-) to form the corresponding alkyl- or phenyl-sulfonyl compounds of formula VIII or Villa wherein L3 is alkyl-S(0)2- or phenyl-S(0)2- is carried out preferably using oxidising agents such as, for example, sodium hypochlorite, sodium hypobromite, m-chloroperbenzoic acid, hydrogen peroxide, hydrogen peroxide in the presence of a carboxylic acid such as, for example, acetic acid or trifluoroacetic acid, osmium tetroxide (Os04) with (CH3)3NO, or potassium permanganate. Such oxidation reactions are described, for example, in WO 00/69825; WO 98/54139; Chemistry - A European Journal 5(2), 430-441 (1999); Austr. J. Chem. 48(2), 407-425 (1995); J. Chem. Technol. Biotechnol. 47(3), 209-218 (1990); J. Chem. Soc, Perkin Trans 1, 12, 3133-40 (1988); J. Chem. Soc, Chem. Communic 23, 1790-92 (1987); J. Org. Chem. 52(8), 1642-44 (1987); Tetrahedron 41 (7), 1373-84 (1985); and Chem. Lett. 12, 2125-28 (1984).

The reagents of formulae XI, XII, XIII and XIV used in Reaction Schemes 1 , 2 and 4 to 7 either are known or can be prepared in analogy to known methods.

The intermediates of formulae VII, IX, IXa, X and Xa wherein Ri, R2, R3, R4 and W are as defined for formula I and L3 is a leaving group such as, for example, halogen or a C C4alkyl- sulfonyl or phenylsulfonyl group are novel and the invention accordingly relates also to those compounds.

The reactions forming the compounds of formula I are advantageously performed in aprotic, inert, organic solvents. Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetra- chloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, or amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidone. The reaction temperatures are preferably from -20°C to +120°C. The reactions are generally slightly exothermic and 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 briefly heated to a temperature not exceeding its boiling point. The reaction times may likewise be shortened by adding a few drops of a base as reaction catalyst. Suitable bases are, especially, tertiary amines such as trimethyl- amine, 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. However, it is also possible to use inorganic bases such as hydrides, e.g. sodium or calcium hydride, hydroxides, e.g. sodium or potassium hydroxide, carbonates, e.g. sodium or potassium carbonate, or hydrogen carbonates, e.g. potassium or sodium hydrogen carbonate.

The compounds of formula I can be isolated in conventional manner by concentrating and/or evaporating off the solvent and can be 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.

For use, according to the invention, of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is also possible in addition to apply a coating (coated granules) that allows the active ingredient to be released in metered amounts over a specific period of time.

The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.

Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.

Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981, and M. and J. Ash, "Encyclopedia of Surfactants", Vol. Mil, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.

The herbicidal formulations usually contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products are usually formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.

The compounds of formula I are generally applied to the plant or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters. The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic engineering techniques. 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 halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.

The compounds of formula I according to the invention can also be used in admixture with known herbicides as co-herbicides for weed control, for example in the form of a ready- prepared formulation or of a 'tank mix'. By way of example, the following co-herbicides are suitable as mixing partners for the compounds of formula I: compound of formula I + acetochlor; compound of formula I + acifluorfen; compound of formula I + aclonifen; compound of formula I + alachlor; compound of formula I + ametryn; compound of formula I + aminotriazole; compound of formula I + amidosulfuron; compound of formula I + asulam; compound of formula I + atrazine; compound of formula I + BAY FOE 5043; compound of formula I + benazolin; compound of formula I + bensulfuron; compound of formula I + bentazone; compound of formula I + bifenox; compound of formula I + bispyribac-sodium; compound of formula I + bialaphos; compound of formula I + bromacil; compound of formula I + bromoxynil; compound of formula I + bromofenoxim; compound of formula I + butachlor; compound of formula I + butylate; compound of formula I + cafenstrole; compound of formula I + carbetamide; compound of formula I + chloridazone; compound of formula I + chlorimuron-ethyl; compound of formula I + chlorbromuron; compound of formula I + chlorsulfuron; compound of formula I + chlortoluron; compound of formula I + cinosulfuron; compound of formula I + clethodim; compound of formula I + clodinafop; compound of formula I + clomazone; compound of formula I + clopyralid; compound of formula I + cloransulam; compound of formula I + cyanazine; compound of formula I + cyhalofop; compound of formula I + dalapon; compound of formula I + 2,4-D; compound of formula I + 2,4-DB; compound of formula I + desmetryn; compound of formula I + desmedipham; compound of formula I + dicamba; compound of formula I + diclofop; compound of formula I + difenzoquat metilsulfate; compound of formula I + diflufenican; compound of formula I + dimefuron; compound of formula I + dimepiperate; compound of formula I + dimethachlor; compound of formula I + dimethametryn; compound of formula I + dimethenamid; compound of formula I + S-dimethenamid; compound of formula I + dinitramine; compound of formula I + dinoterb; compound of formula I + dipropetryn; compound of formula I + diuron; compound of formula I + diquat; compound of formula I + DSMA; compound of formula I + EPTC; compound of formula I + esprocarb; compound of formula I + ethalfluralin; compound of formula I + ethametsulfuron; compound of formula I + ethephon; compound of formula I + ethofumesate; compound of formula I + ethoxysulfuron; compound of formula I + fenclorim; compound of formula I + flamprop; compound of formula I + flazasulfuron; compound of formula I + fluazifop; compound of formula I + flumetralin; compound of formula I + flumetsulam; compound of formula I + fluometuron; compound of formula I + flurochloridone; compound of formula I + fluoxaprop; compound of formula I + fluroxypyr; compound of formula I + fluthiacet-methyl; compound of formula I + fluxofenim; compound of formula I + fomesafen; compound of formula I + glufosinate; compound of formula I + glyphosate; compound of formula I + halosulfuron; compound of formula I + haloxyfop; compound of formula I + hexazinone; compound of formula I + imazamethabenz; compound of formula I + imazapyr; compound of formula I + imazaquin; compound of formula I + imazethapyr; compound of formula I + imazosulfuron; compound of formula I + ioxynil; compound of formula I + isoproturon; compound of formula I + isoxaben; compound of formula I + isoxaflutole; compound of formula I + karbutilate; compound of formula I + lactofen; compound of formula I + lenacil; compound of formula I + linuron; compound of formula I + MCPP; compound of formula I + metamitron; compound of formula I + metazachlor; compound of formula I + methabenzthiazuron; compound of formula I + methazole; compound of formula I + metobromuron; compound of formula I + metolachlor; compound of formula I + S-metolachlor; compound of formula I + metosulam; compound of formula I + metribuzin; compound of formula I + metsulfuron- methyl; compound of formula I + molinate; compound of formula I + MCPA; compound of formula I + MSMA; compound of formula I + napropamide; compound of formula I + NDA- 402989; compound of formula I + nefenacet; compound of formula I + nicosulfuron; compound of formula I + norflurazon; compound of formula I + oryzalin; compound of formula I + oxadiazon; compound of formula I + oxasulfuron; compound of formula I + oxyfluorfen; compound of formula I + paraquat; compound of formula I + pendimethalin; compound of formula I + phenmedipham; compound of formula I + fenoxaprop-P-ethyl (R); compound of formula I + picloram; compound of formula I + pretilachlor; compound of formula I + primisulfuron; compound of formula I + prometon; compound of formula I + prometryn; compound of formula I + propachlor; compound of formula I + propanil; compound of formula I + propazine; compound of formula I + propaquizafop; compound of formula I + propyzamide; compound of formula I + prosulfuron; compound of formula I + pyrazolynate; compound of formula I + pyrazosulfuron-ethyl; compound of formula I + pyrazoxyphen; compound of formula I + pyridate; compound of formula I + pyriminobac- methyl; compound of formula I + pyrithiobac-sodium; compound of formula I + quinclorac; compound of formula I + quizalofop; compound of formula I + rimsulfuron; compound of formula I + Sequestrene; compound of formula I + sethoxydim; compound of formula I + simetryn; compound of formula I + simazine; compound of formula I + sulcotrione; compound of formula I + sulfosate; compound of formula I + sulfosulfuron-methyl; compound of formula I + tebutam; compound of formula I + tebuthiuron; compound of formula I + terbacil; compound of formula I + terbumeton; compound of formula I + terbuthylazine; compound of formula I + terbutryn; compound of formula I + thiazafluron; compound of formula I + thiazopyr; compound of formula I + thifensulfuron-methyl; compound of formula I + thiobencarb; compound of formula I + tralkoxydim; compound of formula I + triallate; compound of formula I + triasulfuron; compound of formula I + trifluralin; compound of formula I + tribenuron-methyl; compound of formula I + triclopyr; compound of formula I + triflusulfuron; compound of formula I + trinexapac-ethyl, and also esters and salts of those mixing partners of the compound of formula I which are mentioned, for example, in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

The following Examples illustrate the invention further, but do not limit the invention.

Preparation Examples:

Example P1 : Preparation of the compounds 3-(4-chloro-6-methoxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1-methyl-π Hl-pyrazole and 3-(6-chloro-4-methoxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1 -methyl-H Hl-pyrazole

Figure imgf000041_0001

742 mg (2.26 mmol) of the compound 3-(4,6-dichloro-3-pyridyl)-4-chloro-5-difluoromethoxy- 1-methyl-[1H]-pyrazole are introduced into a solution of 183 mg (3.39 mmol) of sodium methanolate in 30 ml of methanol. Stirring is then carried out at 50°C overnight; then an additional 129 mg (2.38 mmol) of sodium methanolate are added and stirring is carried out at 50°C for a further 24 hours. After cooling to 20°C, the solvent is removed in vacuo and partitioning between dilute hydrochloric acid and methylene chloride is carried out. The organic phase separated off is washed with water, dried over sodium sulfate and concentrated completely. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 4/1) yields 180 mg (24.6 % yield) of the compound 3-(4-chloro-6-methoxy-3-pyridyl)-4-chloro-5-difiuoromethoxy-1-methyl-[1 Hl- pyrazole, having a melting point of 81-82°C, and 314 mg (42.9 % yield) of the compound 3-(6-chloro-4-methoxy-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole, having a melting point of 90-91 °C.

Example P2: Preparation of the compounds 3-(4-chloro-6-methoxy-3-pyridyl)-5- difluoromethoxy-1-methyl-ri Hl-pyrazole and 3-(6-chloro-4-methoχy-3-pyridyl)-5- difluoromethoxy-1 -methyl-H Hl-pyrazole

Figure imgf000041_0002

1132 mg (3.85 mmol) of the compound 3-(4,6-dichloro-3-pyridyi)-5-difluoromethoxy-1- methyl-[1 H]-pyrazole are introduced into a solution of 312 mg (5.77 mmol) of sodium methanolate in 30 ml of methanol. Stirring is then carried out at 50°C overnight; then an additional 300 mg (5.50 mmol) of sodium methanolate are added and stirring is carried out at 50°C for a further 24 hours. After cooling to 20°C, the solvent is removed in vacuo and partitioning between dilute hydrochloric acid and methylene chloride is carried out. The organic phase separated off is washed with water, dried over sodium sulfate and concentrated completely. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 2/1) yields 78 mg (7.0 % yield) of the compound 3-(4-chloro-6-methoxy-3-pyridyl)-5-difluoromethoxy-1-methyi-[1 H]-pyrazole, having a melting point of 89-90°C, and 668 mg (59.9 % yield) of the compound 3-(6-chloro- 4-methoxy-3-pyridyl)-5-difIuoromethoxy-1-methyl-[1H]-pyrazole, having a melting point of 124-125°C.

Example P3: Preparation of the compound 3-(6-methoxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1 -methyl-fl Hl-pyrazole

Figure imgf000042_0001

563 mg (1.91 mmol) of the compound 3-(6-chloro-3-pyridyl)-4-chloro-5-difluoromethoxy-1- methyl-[1 H]-pyrazole are added to a solution of 310 mg (5.74 mmol) of sodium methanolate in 20 ml of methanol and the resulting mixture is stirred overnight whilst boiling under reflux; a further 310 mg of sodium methanolate are then added and stirring is carried out for a further 48 hours. The cooled reaction mixture is concentrated in vacuo and the residue is partitioned between dilute hydrochloric acid and methylene chloride. The organic phase separated off is washed with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. The crude product obtained is chromatographed over silica gel (eluant: hexane/ethyl acetate 2/1) and yields 248 mg (44.7 % yield) of the desired target compound having a melting point of 63-64°C.

Example P4: Preparation of the compound 3-(4-chloro-6-hvdroxy-3-pyridyl)-4-chloro-5- difluoromethoχy-1 -methyl-H Hl-pyrazole

Figure imgf000042_0002

9.5 g (47.2 mmol) of trimethylsilyl iodide (l-Si(CH3)3) are added to a solution of 1530 mg (4.72 mmol) of the compound 3-(4-chloro-6-methoxy-3-pyridyl)-4-chloro-5-difluoromethoxy- 1-methyl-[1H]-pyrazole (Example P1) in 90 ml of chloroform. The resulting mixture is heated to 50°C and stirred at that temperature for 1.5 hours. Then, at that temperature, 90 ml of methanol are added and stirring is carried out for a further 15 minutes. After cooling the reaction mixture to 20°C, washing is carried out with aqueous sodium metabisulfite solution (Na2S205 solution) and then with brine. The organic phase is dried over sodium sulfate, filtered and completely concentrated by evaporation in vacuo. The crude product obtained is digested in ether and, after being filtered off and washed with ether, is dried. 1230 mg (84.2 % yield) of the desired target compound having a melting point of 205-206°C are obtained.

Example P5: Preparation of the compound 3-(4,6-dichloro-3-pyridyl-N-oxide)-4-chloro-5- difluoromethoxy-1 -methyl-|"1 Hl-pyrazole

Figure imgf000043_0001

O

564 mg of hydrogen peroxide-urea addition product are added to a solution of 1470 mg (5.0 mmol) of the compound 3-(4,6-dichloro-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl- [1 H]-pyrazole in 17 ml of 1 ,2-dichloroethane. Using a syringe, 1.1 g (0.73 ml, 5.25 mmol) of trifluoroacetic anhydride are added dropwise over 30 minutes and stirring is then carried out at 20°C overnight. A further 282 mg of hydrogen peroxide-urea addition product and 0.50 ml of trifluoroacetic anhydride are then added and stirring is carried out for a further 1 hour. The reaction mixture is then poured into water and extracted with methylene chloride; the organic phase is washed in succession with 1M sodium hydroxide solution, water and brine, dried over sodium sulfate, filtered and completely concentrated in vacuo. The crude product obtained is digested in ether, filtered off and washed with ether. After drying, 1.24 g (80 % yield) of the desired target compound having a melting point of 150-151°C are obtained.

Example P6: Preparation of the compound 3-(6-hydroxy-3-pyridyl)-4-chloro-5-difluoro- methoxy-1 -methyl-f 1 Hl-pyrazole

Figure imgf000043_0002

9.5 ml (70 mmol) of trimethylsilyl iodide (l-Si(CH3)3) are added to a solution of 2030 mg (7.1 mmol) of the compound 3-(6-methoxy-3-pyridyl)-4-chloro-5-dif1uoromethoxy-1-methyl- [1 H]-pyrazole (Example P3) in 136 ml of chloroform. The resulting mixture is heated to 50°C and stirred at that temperature for 1.5 hours. Then, at that temperature, 136 ml of methanol are added and stirring is carried out for a further 15 minutes. After cooling the reaction mixture to 20°C, washing is carried out with aqueous sodium metabisulfite solution (Na2S2O5 solution) and then with brine. The organic phase is dried over sodium sulfate, filtered and completely concentrated by evaporation in vacuo. The crude product obtained is digested in ether and, after being filtered off and washed with ether, is dried. 1060 mg (54.9 % yield) of the desired target compound having a melting point of 225-227°C are obtained.

Example P7: Preparation of the compound IW1 R.0Q7

Figure imgf000044_0001

IW11B.007

853 mg (2.9 mmol) of the compound 3-(2,6-dichloro-3-pyridyl)-5-difluoromethoxy-1-methyl- [1 H]-pyrazole are added to a solution of 70 mg (3.04 mmol) of sodium in 5 ml of methanol. Stirring is then carried out overnight whilst boiling under reflux. After cooling to 20°C, the solvent is evaporated off in vacuo and the residue is partitioned between dilute hydrochloric acid and methylene chloride. The organic phase separated off is washed with water, dried over sodium sulfate and completely concentrated in vacuo. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 9/1) yields 176 mg (29.0 % yield) of the desired compound IW118.007, having a melting point of 77-78°C, and 348 mg (57.3 % yield) of the compound 3-(2-chloro-6-methoxy-3-pyridyl)-5- difluoromethoxy-1-methyl-[1H]-pyrazole, having a melting point of 56-57°C.

Example P8: Preparation of the compound IW1 014

Figure imgf000044_0002

IW118.007 IWV014

97 mg (0.72 mmol) of sulfuryl chloride are added to a solution of 174 mg (0.60 mmol) of the compound IW118.007 (Example P7) in 5 ml of methylene chloride and stirring is carried out at 20°C overnight. The mixture is then washed first with aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 2/1) yields 115 mg (62.8 % yield) of the desired target compound having a melting point of 87-88°C.

Example P9: Preparation of the compound 3-(2-chloro-6-rnethoxy-3-pyridvD-4-chloro-5- difluoromethoxy-1 -methyl-M Hl-pyrazole

Figure imgf000045_0001

232 mg (1.72 mmol) of sulfuryl chloride are added to a solution of 415 mg (1.43 mmol) of the compound 3-(2-chloro-6-methoxy-3-pyridyl)-5-difluoromethoxy-1 -methyl-[1 H]-pyrazole (Example P7) in 10 ml of methylene chloride and stirring is carried out at 20°C overnight. The mixture is then washed first with aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 2/1) yields 400 mg (86.4 % yield) of the title compound in the form of an oil. 1H NMR (CDCI3, TMS): 7.61 ppm (d, 1H); 6.74 ppm (d, 1H); 6.71 ppm (t, 1H); 3.99 ppm (s, 3H); 3.83 ppm (s, 3H).

Example P10: Preparation of the compounds 3-(5-chloro-6-methoxy-3-pyridy0-4-chloro-5- methoxy-1-methyl-π Hl-pyrazole and 3-(5-chloro-6-methoxy-3-pyridyl)-4-chloro-5- difluoromethoχy-1-methyl-riH1-pyrazole

Figure imgf000045_0002

59 mg (0.44 mmol) of sulfuryl chloride are added to a solution of 106 mg (0.366 mmol) of the compound 3-(5-chloro-6-methoxy-3-pyridyl)-5-difluoromethoxy-1-methyl-[1 H]-pyrazole in 5 ml of methylene chloride and stirring is carried out at 20°C overnight. The mixture is then washed first with aqueous sodium hydrogen carbonate solution and then with water, dried over sodium sulfate, filtered and completely concentrated. Purification of the resulting residue by means of column chromatography on silica gel (eluant: hexane/ethyl acetate 9/1) yields 25 mg (21.2 % yield) of the compound 3-(5-chloro-6-methoxy-3-pyridyl)-4-chloro-5- methoxy-1-methyl-[1H]-pyrazole, having a melting point of 86-90°C, and 23 mg (19.5 % yield) of the compound 3-(5-chloro-6-methoxy-3-pyridyI)-4-chloro-5-difluoromethoxy-1* methyl-[1 H]-pyrazole, having a melting point of 119-120°C.

Example P11: Preparation of the compound IW1-..013

Figure imgf000046_0001

IW1 013

1470 mg (1.91 mmol) of the compound 3-(2-chloro-3-pyridyl)-4-chloro-5-difluoromethoxy-1- methyl-[1 H]-pyrazole are added to a solution of 810 mg (15 mmol) of sodium methanolate in 50 ml of methanol and the resulting mixture is stirred at 90°C for 3 days in a pressure vessel. The mixture is then cooled, the solvent is evaporated off in vacuo and partitioning between dilute hydrochloric acid and methylene chloride is carried out. The organic phase separated off is washed with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. The crude product obtained is chromatographed over silica gel (eluant: hexane/ethyl acetate 2/1) and yields 108 mg of the desired compound ^1,-013, having a melting point of 56-57°C, and 101 mg of the compound 3-(2-methoxy-3-pyridyl)-4-chloro-5-methoxy-1- methyl-[1 H]-pyrazole, having a melting point of 81-82°C. In addition, 1074 mg of the starting compound are also recovered.

Example P12: Preparation of the compound 3-(2-chloro-3-pyridyl-N-oxide)-4-chloro-5- difluoromethoxy-1 -methyl-fl Hl-pyrazole

Figure imgf000046_0002

1.55 g of hydrogen peroxide-urea addition product are added to a solution of 4.04 g (13.7 mmol) of the compound 3-(2-chloro-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl- [1H]-pyrazole in 40 ml of 1 ,2-dichloroethane. Using a syringe, 3.02 g (2.03 ml, 14.4 mmol) of trifluoroacetic anhydride are added dropwise over 1 hour and stirring is then carried out at 20°C overnight. A further 380 mg of hydrogen peroxide-urea addition product and 0.50 ml of trifluoroacetic anhydride are then added and stirring is carried out for a further 1 hour. The reaction mixture is then poured into water and extracted with methylene chloride. The organic phase separated off is washed in succession with aqueous sodium hydrogen carbonate solution, water and brine, dried over sodium sulfate, filtered and completely concentrated in vacuo. The crude product obtained is digested in ether, filtered off and washed with ether. After drying, 3.59 g (84.5 % yield) of the desired target compound having a melting point of 156-158°C are obtained.

Example,P13: Preparation of the compound IW1ι.Q64

Figure imgf000047_0001

IWV064 68 mg (1.2 mmol) of propargyl alcohol are added to a suspension of 29 mg (1.2 mmol) of sodium hydride in 5 ml of absolute DMF. Then 328 mg (1.0 mmol) of the compound 3-(2,6- dichloro-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1H]-pyrazole in 1 ml of absolute DMF are added dropwise. Stirring is carried out first at 20°C for 1 hour and then at 90°C for a further hour. After cooling to 20°C, the reaction mixture is poured into water and extracted with methylene chloride. The organic phase separated off is washed with dilute hydrochloric acid, dried over sodium sulfate, filtered and completely concentrated in vacuo. The residue obtained is chromatographed over silica gel (eluant: hexane/ethyl acetate 9/1). 272 mg (78 % yield) of a mixture of the isomeric propargyl ethers IW1 064 and 3-(2-chloro-6- propargyloxy-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-[1 H]-pyrazole are obtained.

Example P14: Preparation of the compound 3-(2-chloro-6-ethoxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1 -methyl-H Hl-pyrazole

Figure imgf000047_0002

328 mg (1.0 mmol) of the compound 3-(2,6-dichloro-3-pyridyI)-4-chloro-5-difluoromethoxy-1- methyl-[1 H]-pyrazole are added to a solution of 23 mg (1.0 mmol) of sodium in 5 ml of absolute ethyl alcohol under nitrogen. The reaction mixture is stirred for 3 hours whilst boiling under reflux. After cooling to 20°C, the solvent is evaporated off in vacuo. The residue obtained is partitioned between dilute hydrochloric acid and methylene chloride. The organic phase separated off is washed with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. After purification over a silica gel column (eluant: hexane/ethyl acetate 9/1) 198 mg (58.6 % yield) of the title compound are obtained in the form of an oil. 1H NMR (CDCI3, TMS): 7.60 ppm (d, 1H); 6.71 ppm (d, 1H); 6.70 ppm (t, 1 H); 4.41 ppm (q, 2H); 3.82 ppm (s, 3H); 1.40 ppm (t, 3H).

Example P15: Preparation of the compound 3-(2-chloro-6-hvdroxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1 -methyl-|"1 HT-pyrazole

Figure imgf000048_0001

2.46 g (1.67 ml, 12.3 mmol) of trimethylsilyl iodide (l-Si(CH3)3) are added to a solution of 400 mg (1.23 mmol) of the compound 3-(2-chloro-6-methoxy-3-pyridyl)-4-chloro-5- difIuoromethoxy-1-methyl-[1H]-pyrazole in 24 ml of chloroform. The mixture is heated to 50°C and stirred at that temperature for 1.5 hours. Then, at that temperature, 24 ml of methanol are added and stirring is carried out for a further 15 minutes. After cooling to 20°C, washing is carried out with aqueous sodium metabisulfite solution (Na2S205 solution) and then with brine. The organic phase is dried over sodium sulfate, filtered and completely concentrated by evaporation in vacuo. The crude product obtained is digested in ether and, after being filtered off and washed with ether, is dried. 334 mg (83.3 % yield) of the title compound having a melting point of 135-136°C are obtained.

Example P16: Preparation of the compound IWI^.002

Figure imgf000048_0002

IW^.014 IWV002

900 mg (4.5 mmol) of trimethylsilyl iodide (l-Si(CH3)3) are added to a solution of 146 mg (0.45 mmol) of the compound IW^.014 (Example P8) in 9 ml of chloroform. The resulting mixture is heated to 50°C and stirred at that temperature for 1.5 hours. Then, at that temperature, 9 ml of methanol are added and stirring is carried out for a further 15 minutes. After cooling to 20°C, washing is carried out with aqueous sodium metabisulfite solution (Na2S205 solution) and then with brine. The organic phase is dried over sodium sulfate, filtered and completely concentrated by evaporation in vacuo. The crude product obtained is digested in ether and, after being filtered off and washed with ether, is dried. 119 mg (85.3 % yield) of the desired target compound having a melting point of 142-143°C are obtained.

Example P17: Preparation of the compound r6-chloro-5-(4-chloro-5-difluoromethoxy-1- methyl-H H1-pyrazol-3-yl)-pyridin-2-yloxyl-acetic acid methyl ester

Figure imgf000049_0001

310 mg (1.0 mmol) of the compound 3-(2-chIoro-6-hydroxy-3-pyridyl)-4-chloro-5- difluoromethoxy-1-methyl-[1H]-pyrazole (Example P15) and 168 mg (0.10 ml, 1.1 mmol) of bromoacetic acid methyl ester are added dropwise, using a syringe, to a suspension of 207 mg (1.5 mmol) of potassium carbonate in 10 ml of acetone. The reaction mixture is stirred for 1 hour whilst boiling under reflux. After cooling to 20°C, filtration is carried out and the filtrate is completely concentrated in vacuo. The residue is partitioned between water and methylene chloride; the organic phase separated off is washed with dilute hydrochloric acid and then with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. After purification of the resulting residue over a silica gel column (eluant: hexane/ethyl acetate 2/1), 305 mg (80 % yield) of the title compound are obtained in the form of an oil. 1H NMR (CDCI3, TMS): 7.67 ppm (d, 1H); 6.88 ppm (d, 1H); 6.71 ppm (t, 1H); 4.96 ppm (s, 2H); 3.82 ppm (s, 3H); 3.80 ppm (s, 3H).

Example P18: Preparation of the compound 3-(2-chloro-6-methoxycarbonyloxy-3-pyridvD-4- chloro-5-difluoromethoxy-1 -methyl-H Hl-pyrazole

Figure imgf000049_0002

50 mg (1.25 mmol) of sodium hydroxide are added to a solution of 300 mg (0.968 mmol) of the compound 3-(2-chloro-6-hydroxy-3-pyridyI)-4-chloro-5-difluoromethoxy-1-methyI-[1 Hl- pyrazole (Example P15) and 119 mg (0.10 ml, 1.26 mmol) of chloroformic acid methyl ester in 5 ml of THF. The resulting mixture is stirred at 20°C for 2 days. After evaporating off the solvent in vacuo, partitioning between water and methylene chloride is carried out; the organic phase separated off is washed with dilute hydrochloric acid and water, dried over sodium sulfate, filtered and completely concentrated in vacuo. The residue obtained is purified over a silica gel column (eluant: hexane/ethyl acetate 2/1). 31 mg (8.7 % yield) of the title compound are obtained in the form of an oil with 1H NMR (CDCI3, TMS): 7.62 ppm (d, 1H); 6.74 ppm (d, 1H); 6.71 ppm (t, 1H); 3.98 ppm (s, 3H); 3.85 ppm (s, 3H), and 290 mg (81.5 % yield) of the subsidiary product 6-chloro-5-(4-chloro-5-difluoromethoxy-1-methyl- [1H]-pyrazol-3-yl)-1-methoxycarbonyl-[1 H]-pyridin-2-one, having a melting point of 79-80°C, are obtained.

Example P19: Preparation of the compound IW1 211

Figure imgf000050_0001

IW1 r211

163 mg (0.50 mmol) of the compound IW^.002 (Example P16) and 128 mg (0.50 mmol) of the compound 2-[(2-chloromethyl-5-ethyl)-phenoxy]-propionic acid methyl ester are added to a suspension of 138 mg (1.0 mmol) of potassium carbonate in 3 ml of N-methylpyrrolidone (NMP). The resulting reaction mixture is stirred first at 20°C for 1 hour and then at 80°C for 3 hours. After cooling to 20°C, the mixture is poured into water and extracted with methylene chloride; the organic phase separated off is washed with dilute hydrochloric acid and then with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. After purification of the residue obtained, over a silica gel column (eluant: hexane/ethyl acetate 2/1), 30 mg (11.3 % yield) of the desired target compound are obtained.

Example P20: Preparation of the compound 3-(2-chloro-3-pyridyl)-4-chloro-5-difluoro- methoxy-1 -methyl-H Hl-pyrazole

Figure imgf000050_0002
5.97 g (23 mmol) of the compound 3-(2-chloro-3-pyridyl)-5-difluoromethoxy-1-methyl-[1H]- pyrazole (Example P21), together with 4.72 g (57.5 mmol) of sodium acetate, are suspended in 35 ml of glacial acetic acid and stirred at 45°C At that temperature, a saturated solution of chlorine gas in glacial acetic acid is slowly added dropwise until TLC analysis shows that reaction is complete (TLC: silica gel 60 F254; mobile phase: toluene/ethyl acetate 4/1). Cooling is then carried out to 20°C and the solvent is evaporated off using a rotary evaporator. The residue is taken up in ethyl acetate and adjusted to pH 7 with dilute sodium hydroxide solution. The organic phase separated off is washed with brine, dried over magnesium sulfate and, after being filtered, completely concentrated by evaporation in vacuo. The crude product obtained is recrystallised from diisopropyl ether/petroleum ether (low-boiling) 3/7. 5.89 g (87 % yield) of the desired target compound having a melting point of 49-51 °C are obtained.

Example P21: Preparation of the compound 3-(2-chloro-3-pyridyl)-5-difluoromethoxy-1- methyl-H Hl-pyrazole

Figure imgf000051_0001

9.61 g (45.8 mmol) of the compound 3-(2-chloro-3-pyridyl)-5-hydroxy-1-methyl-[1H]-pyrazole (Example P22) are introduced into 70 ml of dioxane and then 64 ml of 20 % sodium hydroxide solution are added. Whilst stirring vigorously, heating to 65°C is carried out and Freon 22 (CICHF2) is introduced. After TLC analysis shows that starting material is no longer present (silica gel 60 F254; mobile phase: hexane/AcOEt/AcOH 20/20/1), the mixture is cooled to 20°C and extracted with diethyl ether; the organic phase is washed with brine, dried over sodium sulfate, filtered and completely concentrated in vacuo. After purification over a silica gel column (eluant: hexane/ethyl acetate 3/2), 6.33 g (53 % yield) of the desired target compound are obtained.

13C NMR (CDCI3, TMS) 148.7 ppm (2 C); 145.4 ppm; 145.0 ppm; 138.4 ppm; 128.9 ppm; 122.6 ppm; 115.1 ppm (t); 93.2 ppm; 34.7 ppm. Example P22: Preparation of the compound 3-(2-chloro-3-pyridyl)-5-hvdroxy-1-methyl-ri Hl- pyrazole

Figure imgf000052_0001

110 g (704 mmol) of malonic acid monomethyl ester potassium salt are introduced into 700 ml of dry acetonitrile and, whilst stirring, 108 ml (775 mmol) of triethylamine and then, slowly, 84 g (880 mmol) of anhydrous magnesium chloride are added. An exothermic reaction is observed. Whilst stirring, the temperature is adjusted to 15-20°C using a cooling bath, before 62 g (352 mmol) of the acid chloride of 2-chloro-nicotinic acid in 100 ml of dry acetonitrile are added dropwise, the temperature being maintained in the range mentioned. Stirring is then continued at 20°C for 2 hours; the reaction mixture is then poured into a mixture of 1 litre of ice-water and 300 ml of concentrated hydrochloric acid and is extracted with ethyl acetate. The combined organic phases are washed with brine, dried over sodium sulfate, filtered and completely concentrated in vacuo. There are obtained 102 g of a yellow oil which is directly further reacted.

18.8 ml (357 mmol) of methyl hydrazine are slowly added dropwise to 100 ml of glacial acetic acid (exothermic reaction). Whilst stirring, 72.5 g (340 mmol) of the intermediate in 50 ml of glacial acetic acid are added dropwise; heating is then carried out slowly to 100°C and stirring is continued for 3 hours at that temperature. After cooling to 20°C, the major portion of the solvent is evaporated off in vacuo and the residue is taken up in ethyl acetate and neutralised with dilute sodium hydroxide solution. After extraction and separating off the phases, the organic phase is washed with brine, dried over sodium sulfate, filtered and concentrated. 40.7 g of a residue A are obtained. After saturating the aqueous phase with sodium chloride, extraction with THF is carried out again and the combined THF phases are dried over sodium sulfate, filtered and concentrated by evaporation in vacuo. 16.5 g of a residue B are obtained. The combined residues A and B are chromatographed over a silica gel column (eluant: hexane/ethyl acetate/glacial acetic acid 10/40/1). 20.4 g (29 % yield) of the desired target compound are obtained in the form of a yellowish solid. 1H NMR (DMSO-D6, TMS): 11.35 ppm (broad signal, 1H); 8.35 ppm (m, 1H); 8.20 ppm (m, 1H); 7.45 ppm (m, 1 H); 5.96 ppm (s, 1H); 3.60 ppm (s, 3H). Example P23: Preparation of the compound XW1.001

Figure imgf000053_0001

XW1.001

620 mg (2.0 mmol) of the compound 3-(2-chloro-3-pyridyl-N-oxide)-4-chloro-5-difluoro- methoxy-1-methyl-[1H]-pyrazole (Example P12) are introduced into 5 ml of absolute methanol at 0°C. Whilst stirring, a previously prepared solution of 84.8 mg (2.05 mmol) of sodium hydride in 20 ml of absolute methanol is added dropwise. After continuing to stir at 0°C for 30 minutes, the mixture is warmed up to 20°C and stirred overnight. After evaporating off the solvent in vacuo, partitioning between water and chloroform is carried out. The organic phase is washed with brine, dried over magnesium sulfate, filtered and completely concentrated in vacuo. 247 mg (40 % crude yield) of the desired target compound are obtained. Recrystallisation from diisopropyl ether yields the desired product in pure form, having a melting point of 94-96°C.

Example P24: Preparation of the compound IW1...226

Figure imgf000053_0002

IW1 013 IW1 226

579 mg (2.0 mmol) of the compound IW1 013 (Example P11) are dissolved in 15 ml of 1 ,2- dichloroethane and, whilst stirring at -5°C, 308 mg (2.2 mmol) of nitronium tetrafluoroborate (BF4N02) are added in portions. Whilst stirring, the mixture is warmed up to 20°C and stirring is continued overnight. The organic phase is then washed with ice-water, 10 % aqueous sodium hydrogen carbonate solution and brine, in that order. After drying over magnesium sulfate, the mixture is filtered and completely concentrated by evaporation in vacuo. The residue is purified over a silica gel column (eluant: hexane/ethyl acetate 3/2). 129 mg of the desired target compound, having a melting point of 121-123°C, and 329 mg of the starting compound are obtained. Example P25: Preparation of the compound IW1...014

Figure imgf000054_0001

XW1.001 IW^.014

61.9 μl (0.66 mmol) of phosphorus oxychloride are introduced into 5 ml of 1 ,2-dichloroethane. Whilst stirring, the mixture is heated to 55°C and, at that temperature, a solution of 135 mg (0.44 mmol) of the compound XW1.001 (Example P23) in 3 ml of 1 ,2-dichloroethane is added dropwise. Stirring is continued at that temperature for 1 hour. After cooling to 20°C, ice-water is added, extraction is carried out, and the organic phase separated off is washed with brine, dried over magnesium sulfate, filtered and completely concentrated in vacuo. The residue is purified over a silica gel column using hexane/ethyl acetate 3/2. 14 mg (10 % yield) of the desired target compound are obtained.

1H NMR (CDCI3, TMS): 7.66 ppm (d, 1H); 6.99 ppm (d, 1H); 6.71 ppm (t, 1H); 4.00 ppm (s, 3H); 3.82 ppm (s, 3H).

Example P26: Preparation of the compound 3-(4-chloro-6-(2-r2-methylpropionyloxy1-4-ethyl- benzyloxy)-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-ri Hl-pyrazole

Figure imgf000054_0002

310 mg (1.0 mmol) of the compound 3-(4-chloro-6-hydroxy-3-pyridyl)-4-chloro-5-difluoro- methoxy-1-methyI-[1H]-pyrazole (Example P4) are added to a suspension of 29 mg (1.2 mmol) of sodium hydride in 5 ml of dimethyl sulfoxide. After subsequently stirring for 30 minutes, 256 mg (1.0 mmol) of the compound 2-[(2-chloromethyl-5-ethyl)-phenoxy]- propionic acid methyl ester are added and stirring is carried out at 80°C for 2 hours. After cooling, the mixture is poured into water and extracted with methylene chloride. The organic phase is washed with dilute hydrochloric acid, dried over sodium sulfate, filtered and completely concentrated in vacuo. Purification over silica gel (eluant: hexane/ethyl acetate 1/2) yields 326 mg (63.4 % yield) of the title compound having a melting point of 145-146°C. Example P27: Preparation of the compound 3-(2-chloro-6-(2-r2-methylpropionyloxy1-4-ethyl- benzyloxy)-3-pyridyl)-4-chloro-5-difluoromethoxy-1-methyl-ri Hl-pyrazole

Figure imgf000055_0001

163 mg (0.50 mmol) of the compound 3-(2-chloro-6-hydroxy-3-pyridyl)-4-chloro-5-difluoro- methoxy-1-methyl-[1H]-pyrazole (Example P15) and 128 mg (0.50 mmol) of the compound 2-[(2-chloromethyl-5-ethyl)-phenoxy]-propionic acid methyl ester are added to a suspension of 207 mg (1.5 mmol) of potassium carbonate in 3 ml of N-methylpyrrolidone (NMP). The reaction mixture is stirred first at 20°C for 1 hour and then at 80°C for 3 hours. After cooling to 20°C, the mixture is poured into water and extracted with methylene chloride. The combined organic phases are washed with dilute hydrochloric acid and then with water, dried over sodium sulfate, filtered and completely concentrated in vacuo. After purification of the resulting residue over a silica gel column (eluant: hexane/ethyl acetate 2/1), 128 mg (48.3 % yield) of the title compound are obtained. 1H NMR (CDCI3, TMS): 7.61 ppm (d, 1H); 7.57 ppm (d, 1H); 6.94 ppm (d, 1H); 6.77 ppm (d,1H); 6.71 ppm (t, 1H); 6.60 ppm (s, 1H); 5.49 ppm (m, 2H); 4.80 ppm (q, 1H); 3.83 ppm (s, 3H); 3.75 ppm (s, 3H); 2.61 ppm (q, 2H); 1.57 ppm (d, 3H); 1.23 ppm (t, 3H).

Example P28: Preparation of the compound 3-(2-phenoxy-3-pyridyl-N-oxide)-4-chloro-5- difluoromethoxy-1 -methyl-H Hl-pyrazole

Figure imgf000055_0002

149.6 mg of a 58 % sodium hydride (NaH) dispersion (3.58 mmol) are introduced into 5.0 ml of dry tetrahydrofuran (THF). Whilst stirring, 379.7 mg (3.99 mmol) of phenol in 3.0 ml of dry THF are slowly metered in, using a syringe. After continuing to stir at 20°C for 15 minutes, 620.2 mg (2.0 mmol) of 3-(2-chloro-3-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl- [1 H]-pyrazole in 4.0 ml of dry THF are metered in, using the syringe. The resulting suspension is diluted with 4.0 ml of dry THF and stirring at 20°C is continued overnight. On the next day, the mixture is filtered over Hyflo. After washing with THF, the filtrate is concentrated by evaporation to dryness in vacuo and purification is carried out over a silica gel column (eluant: chloroform/isopropanol 10/1). 0.60 g of the target compound (82 % of theory) is obtained. MS (ES): 368 [M + H]+, 735 [2M + H]+.

Example P29: Preparation of the compound 3-(2-(2-methoxy-5-methvD-phenoxy-6-chloro-3- pyridyl)-4-chloro-5-difluoromethoxy-1 -methyl-M Hl-pyrazole

Figure imgf000056_0001

46.8 ml (0.501 mmol) of phosphorus oxychloride (POCI3) are introduced into 5.0 ml of 1 ,2- dichlorethane at 20°C. Then, at that temperature, 137.8 mg (0.334 mmol) of 3-(2-(2- methoxy-5-methyl)-phenoxy-3-pyridyl-N-oxide)-4-chloro-5-difluoromethoxy-1-methyl-[1H]- pyrazole in 5.0 ml of 1 ,2-dichlorethane are added dropwise. After stirring at 20°C for 3 hours, stirring is carried out first at 40°C for one hour and then at 55°C for 2 hours. After cooling to 20°C, washing is carried out first with dilute sodium hydroxide solution and then with brine; the organic phase is dried over magnesium sulfate, filtered and concentrated by evaporation to dryness in vacuo. The crude product is purified over a silica gel column (eluant: hexane/ethyl acetate 3/1). 63 mg (44 % of theory) of the desired target compound are obtained. MS (ES): 429.9 [M + H]+.

In analogous manner, and using methods as illustrated in the general Reaction Schemes 1 to 7 and in the indicated references, it is also possible to obtain the preferred compounds listed in the following Tables 1 to 17, wherein the substituents R^ R2, R3 and R4 are defined in accordance with Table A, and in Tables 18 to 34, wherein the substituents R.,, R2, R3 and R4 are defined in accordance with Table B, and in Tables 50 and 51 (intermediates having variable substituents R,, R2, R3, R4, and R100, R10ι and R102 in accordance with Tables C and D). Table 1 : A preferred group of compounds of formula I corresponds to the general formula

(IW1 , wherein the meanings of the respective

Figure imgf000057_0001
substituents R, to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW1 , are disclosed.

Table 2: A preferred group of compounds of formula I corresponds to the general formula

(IW12), wherein the meanings of the respective

Figure imgf000057_0002
substituents R^ to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW12 are disclosed.

Table 3: A preferred group of compounds of formula I corresponds to the general formula

(IW13), wherein the meanings of the respective

Figure imgf000057_0003
substituents R, to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW13 are disclosed.

Table 4: A preferred group of compounds of formula I corresponds to the general formula

(IW14), wherein the meanings of the respective

Figure imgf000057_0004
substituents R, to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW14 are disclosed. Table 5: A preferred group of compounds of formula I corresponds to the general formula

(I W15), wherein the meanings of the respective

Figure imgf000058_0001
substituents R^ to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW15 are disclosed.

Table 6: A preferred group of compounds of formula I corresponds to the general formula

(IW16), wherein the meanings of the respective

Figure imgf000058_0002
substituents R, to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW16 are disclosed.

Table 7: A preferred group of compounds of formula I corresponds to the general formula

(IW17), wherein the meanings of the respective

Figure imgf000058_0003
substituents Rt to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW17 are disclosed.

Table 8: A preferred group of compounds of formula I corresponds to the general formula

(IW18), wherein the meanings of the respective

Figure imgf000058_0004
substituents R1 to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW18 are disclosed. Table 9: A preferred group of compounds of formula I corresponds to the general formula

(IW19), wherein the meanings of the respective substituents

Figure imgf000059_0001

R1 to R4 are indicated in Table A, as a result of which 249 specific compounds of formula

IWIg are disclosed.

Table 10: A preferred group of compounds of formula I corresponds to the general formula

(IW110), wherein the meanings of the respective

Figure imgf000059_0002
substituents R^ to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW110 are disclosed.

Table 11 : A preferred group of compounds of formula I corresponds to the general formula

(IW1n), wherein the meanings of the respective

Figure imgf000059_0003
substituents R to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW1^ are disclosed.

Table 12: A preferred group of compounds of formula I corresponds to the general formula

(IW112), wherein the meanings of the respective

Figure imgf000059_0004
substituents R^ to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW112 are disclosed. Table 13: A preferred group of compounds of formula I corresponds to the general formula

(I W113), wherein the meanings of the respective

Figure imgf000060_0001
substituents R^ to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW113 are disclosed.

Table 14: A preferred group of compounds of formula I corresponds to the general formula

(IW114), wherein the meanings of the respective

Figure imgf000060_0002
substituents R1 to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW114 are disclosed.

Table 15: A preferred group of compounds of formula I corresponds to the general formula

(IW115), wherein the meanings of the respective

Figure imgf000060_0003
substituents R to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW115 are disclosed.

Table 16: A preferred group of compounds of formula I corresponds to the general formula

i6 ** t wherein the meanings of the respective

Figure imgf000060_0004
substituents R to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW116 are disclosed. Table 17: A preferred group of compounds of formula I corresponds to the general formula

(IW117), wherein the meanings of the respective

Figure imgf000061_0001
substituents R, to R4 are indicated in Table A, as a result of which 249 specific compounds of formula IW117 are disclosed.

Table A:

Figure imgf000061_0002
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001

Figure imgf000068_0001

Figure imgf000069_0001

Figure imgf000070_0003

Table 18: A preferred group of compounds of formula I corresponds to the general formula

(IW118), wherein the meanings of the respective

Figure imgf000070_0001
substituents R^ to R are indicated in Table B, as a result of which 42 specific compounds of formula IW118 are disclosed.

Table 19: A preferred group of compounds of formula I corresponds to the general formula

(IW119), wherein the meanings of the respective

Figure imgf000070_0002
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW119 are disclosed. Table 20: A preferred group of compounds of formula I corresponds to the general formula

(IW120), wherein the meanings of the respective

Figure imgf000071_0001
substituents R to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW120 are disclosed.

Table 21: A preferred group of compounds of formula I corresponds to the general formula

(IW121), wherein the meanings of the respective

Figure imgf000071_0002
substituents R to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW121 are disclosed.

Table 22: A preferred group of compounds of formula I corresponds to the general formula

(IW122), wherein the meanings of the respective

Figure imgf000071_0003
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW122 are disclosed.

Table 23: A preferred group of compounds of formula I corresponds to the general formula

(IW123), wherein the meanings of the respective

Figure imgf000071_0004
substituents R to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW123 are disclosed. Table 24: A preferred group of compounds of formula I corresponds to the general formula

(IW124), wherein the meanings of the respective

Figure imgf000072_0001
substituents R^ to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW124 are disclosed.

Table 25: A preferred group of compounds of formula I corresponds to the general formula

(IW125), wherein the meanings of the respective

Figure imgf000072_0002
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW125 are disclosed.

Table 26: A preferred group of compounds of formula I corresponds to the general formula

(IW126), wherein the meanings of the respective

Figure imgf000072_0003
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW126 are disclosed.

Table 27: A preferred group of compounds of formula I corresponds to the general formula

(IW127), wherein the meanings of the respective

Figure imgf000072_0004
substituents R to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW127 are disclosed. Table 28: A preferred group of compounds of formula I corresponds to the general formula

(IW128), wherein the meanings of the respective

Figure imgf000073_0001
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW128 are disclosed.

Table 29: A preferred group of compounds of formula I corresponds to the general formula

(IW129), wherein the meanings of the respective

Figure imgf000073_0002
substituents R1 to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW129 are disclosed.

Table 30: A preferred group of compounds of formula I corresponds to the general formula

(IW130), wherein the meanings of the respective

Figure imgf000073_0003
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW130 are disclosed.

Table 31 : A preferred group of compounds of formula I corresponds to the general formula

(IW131), wherein the meanings of the respective

Figure imgf000073_0004
substituents R< to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW131 are disclosed. Table 32: A preferred group of compounds of formula I corresponds to the general formula

(IW132), wherein the meanings of the respective

Figure imgf000074_0001
substituents R^ to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW132 are disclosed.

Table 33: A preferred group of compounds of formula I corresponds to the general formula

(IW133), wherein the meanings of the respective

Figure imgf000074_0002
substituents R^ to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IW133 are disclosed.

Table 34: A preferred group of compounds of formula I corresponds to the general formula

(IWIJM), wherein the meanings of the respective

Figure imgf000074_0003
substituents R, to R4 are indicated in Table B, as a result of which 42 specific compounds of formula IWI^ are disclosed.

Table B:

Figure imgf000074_0004
Figure imgf000075_0001
Figure imgf000076_0002

Table 50: A preferred group of compounds of formula X corresponds to the general formula

(XW1), wherein the meanings of the respective substituents

Figure imgf000076_0001

R, to R4 and Rι00 to R102 are indicated in Table C, as a result of which 70 specific compounds of formula XW1 are disclosed.

Table C:

Figure imgf000076_0003
Figure imgf000077_0001

Figure imgf000078_0002

Table 51 : A preferred group of compounds of formula X corresponds to the general formula

(XW1 , wherein the meanings of the respective

Figure imgf000078_0001
substituents R, to R4 and R102 are indicated in Table D, as a result of which 12 specific compounds of formula XW1, are disclosed. Table D:

Figure imgf000079_0001

Table E: Prepared compounds from the preceding Tables 1-17, A, 18-34, B, 50, C, 51 and D

Figure imgf000080_0001
Biological Examples

Example B1: Herbicidal action prior to emergence of the plants (pre-emergence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown in a greenhouse under optimum conditions. After a test duration of 4 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

Test plants: Kochia, Polygonum (Polygo), Chenopodium (Chenop), Amaranthus (Amara), Sida, Digitaria (Digita), Panicum.

Table B1: Pre-emer ence action

Figure imgf000081_0001

The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples of WO 97/34485.

Example B2: Post-emergence herbicidal action

Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1, c) according to WO 97/34485), are applied by spraying, in an optimum concentration (500 litres of water per ha). The test plants are then grown on in a greenhouse under optimum conditions.

After a test duration of from 2 to 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.

Test plants: Kochia, Polygonum (Polygo), Chenopodium (Chenop), Amaranthus (Amara), Abutilon, Digitaria (Digita), Panicum.

Figure imgf000082_0001

In Tables B1 and B2 above, "-" means that no data are available for the case in question.

The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples of WO 97/34485.

Claims

What is claimed is:
1. A compound of formula I
Figure imgf000083_0001
herein
Ri is hydrogen, amino, R50CH=N-, R5ι( s2)N-, d-C8alkyl, C C8haloalkyl, C3-C8cycloalkyl, C3-C8halocycloalkyl, C3-C8cycloaIkyl-Cι-C8alkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8cyclo- alkenyl, C3-C8halocycloalkenyl, C3-C8alkynyl, HC(O)-, d-C8alkylcarbonyl, d-C8haloalkyl- carbonyl, C3-C8cycloalkylcarbonyl, C3-C8halocycloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C2-C8alkynylcarbonyl, phenylcarbonyl, phenoxycarbonyl or phenylthiocarbonyl, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by hydroxy, amino, nitro, halogen, Cι-C4alkyl, C C4haloalkyl, R6o and/or by R60-C1-C4alkyleneoxy; or
R' is Cι-C8alkylsulfonyl, d-C8haloalkylsulfonyl, C2-C8alkenylsulfonyl, C2-C8haloalkenyl- sulfonyl or phenylsulfonyl, it being possible for the phenyl radical in the phenylsulfonyl group to be substituted from one to three times by halogen, C C4alkyl, d-C haloaIkyl, C C4alkoxy and/or by d-C4haloalkoxy; or
R is d-C8alkoxycarbonyl, C3-C8cycloalkoxycarbonyl, Cι-C8haloalkoxycarbonyl, C3-C8- halocycloalkoxycarbonyl, C3-C8alkenyIoxycarbonyl, C3-C8haloalkenyloxycarbonyl, C3-C8- alkynyloxycarbonyl, CrC8alkylthio-C(0)-, C C8haloalkylthio-C(0)-, C3-C8alkenylthio-C(O)-, C3-C8alkynyithio-C(O)-, CrC8alkylthio-C(S)-, C1-C8haloalkylthio-C(S)-, C3-C8alkenyl- thio-C(S)-, C3-C8alkynylthio-C(S)-, H2NC(O)-, R5ι(R52)NC(O)-, H2NC(S)-, R5ι(R52)NC(S)-, phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl or pyrazinyl, it being possible for the mentioned aromatic and heteroaromatic rings to be substituted from one to three times by hydroxy, amino, nitro, halogen, d-C4alkyl, d-C4haloaikyl, R60 and/or by R60- d-C alkyleneoxy; or
R is R6rCι-C8aIkylene-, R6rC3-C8cycloaIkylene-, R6ι-C2-C8alkenylene- or R6ι- C2-C8alkynylene-; R50 is C C8alkyl, d-C8haloalkyl, C3-C8cycloalkyl, C2-C8alkenyl, C2-C8alkynyl or phenyl, it being possible for the phenyl radical to be unsubstituted or substituted one or more times by halogen, Cι-C4alkyl, C C4haloalkyl, C C4alkoxy, CrC haloalkoxy, B1 and/or by B1 -Cι-C4alkyleneoxy;
B1 is HOC(O)-, Cι-C4alkoxycarbonyl, d-C4haloalkoxycarbonyl, C3- or C4- alkenyloxycarbonyl, C3- or C4-haloalkenyloxycarbonyl or C3- or C -alkynyloxycarbonyl;
R51 and R52 are each independently of the other hydrogen, Cι-C8alkyl, C3-C8cycloalkyl, C -C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8alkynyl, Cι-C4alkoxy-CrC4alkyl, Ci-C alkylthio-C C4alkyl, Cι-C4alkylsuifinyl-C C4alkyl, C C4alkylsulfonyl-Cι-C4alkyl, CrC8alkylcarbonyl, C3-C8cycloalkylcarbonyl, Cι-C8haloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C2-C8alkynylcarbonyl, d-C8alkoxycarbonyl, d-C8haloalkoxy- carbonyl, C2-C8alkenyloxycarbonyl, C2-C8haloalkenyloxycarbonyl, C3-C8alkynyIoxycarbonyl, Cι-C8alkylsulfinyl, C3-C8cycioalkylsulfinyl, Cι-C8haloalkylsulfinyl, C -C8alkenylsulfinyl, C2-C8haIoalkenylsulfinyl, C C8alkylsulfonyi, C3-C8cycloalkylsulfonyl, C C8haloalkylsulfonyl, C2-C8alkenylsulfonyl or C2-C8haloalkenylsulfonyl; or
R5 and R52, together with the nitrogen atom to which they are bonded, form a three- to eight-membered heterocyclic ring which may contain, as a further hetero atom, sulfur or oxygen;
R60 is HC(O)-, cyano, HOC(O)-, Cι-C4alkoxycarbonyl, d-C haloalkoxycarbonyl, C3-C8cyclo- alkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, C3- or C4-alkenyloxycarbonyl, C3- or C4- haloalkenyloxycarbonyl, C3- or C4-alkynyloxycarbonyl, C C4alkylthio-C(O)-, C3-C8alkenylthio- C(O)-, R62(R63)NC(0)-, R62(R63)NC(S)-, hydroxy, mercapto, d-C4alkoxy, C C4haloalkoxy, C3-C6cycloalkoxy, C3- or C4-aikenyloxy, C3- or C4-haloalkenyloxy, C3- or C4-alkynyloxy, Cι-C4alkyithio, C C4alkylsulfinyl, Cι-C4alkylsulfonyl or CrC4alkoxy-C C4alkoxy;
R6ι is hydroxy, mercapto, cyano, HC(O)-, C C8alkoxy, d-C8haIoalkoxy, C3-C8cycloalkoxy, C3-C8halocycioalkoxy, C3-C8alkenyloxy, C3-C8haloalkenyloxy, C3-C8alkynyloxy, C1- C8alkylthio, C -C8haloalkylthio, C3-C8cycloalkylthio, C3-C8alkenylthio, C3-C8haloalkenylthio, C3-C8alkynylthio, HOC(O)-, d-C8alkoxycarbonyl, C C8haloalkoxycarbonyl, C3- C8cycloalkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3- C8haloalkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C C8alkylcarbonyl, d- C8haloalkylcarbonyl, C3-C8cycloalkylcarbonyl, C3-C8halocycloalkylcarbonyl, C2- C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C2-C8alkynylcarbonyl, C C8alkylthio-C(0)-, C C8haloalkylthio-C(O)-, C3-C8cycloalkylthio-C(O)-, C3-C8halocycloalkylthio-C(0)-, C3- C8alkenylthio-C(O)-, C3-C8haloalkenylthio-C(O)-, benzyloxy-C(O)-, R62(R63)NC(0)- or R62(R63)NC(S)-; or
R6i is phenyl, naphthyl, pyridyl, pyrimidyl, pyridazinyl, pyrazinyl, phenoxy, naphthyloxy, pyridyloxy, pyrimidyloxy, pyridazinyloxy, pyrazinyloxy or phenylcarbonyl, it being possible for the mentioned aromatic and heteroaromatic rings to be substituted from one to three times by halogen, C1-C4alkyl, C C4haloalkyl, C C4alkoxy, d-C4haloalkoxy, R60 and/or by R60- C C alkyleneoxy; or
R6ι is phenoxy, phenylthio or phenylamino, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by halogen, hydroxy, amino, C C4alkyl, C C4haloalkyl, C C4alkoxy, CrC4haloalkoxy, R6o and/or by R60-C C4alkyleneoxy;
R62 and R^ are each independently of the other hydrogen, C C8alkyl, d-C8haloalkyl, C3-C8alkenyl, C3-C8haloalkenyl, C3-C8cycloalkyl, C3-C8halocycloalkyl, C3-C8aikynyl, HC(O)-, d-C8alkylcarbonyl, C -C8haloalkylcarbonyl, C2-C8alkenylcarbonyl, C2-C8haloalkenylcarbonyl, C3-C8cycloalkylcarbonyl, C3-C8halocycloalkylcarbonyl, Cι-C8alkoxycarbonyl, Cι-C8haloalkoxy- carbonyl, C3-C8alkenyloxycarbonyl, C3-C8haloalkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C3-C8cycloalkoxycarbonyl, C3-C8halocycloalkoxycarbonyl, d-C8alkylsulfonyI, d-C8haloaikyl- sulfonyl, phenyl, phenylcarbonyl or phenoxycarbonyl, it being possible for the 3 mentioned phenyl radicals to be substituted from one to three times by halogen, Cι-C alkyl and/or by d-C4haloalkyl;
R2 is hydrogen, halogen, cyano, nitro, amino, H2NHN-, HOCH2-, HC(O)-, HON=CH-, H2NC(0)-, H2NC(S)-, HOC(O)-, C C4alkoxycarbonyl, CrC4alkylcarbonyl, C C4alkyl, C C4- hydroxyalkyl, Cι-C4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl, C2-C4alkynyl, C2-C4haloalkynyl, C3- or C4-hydroxyalkynyl, mercapto, C C4alkylthio, C C4haloalkylthio, d-C4alkylsulfinyl, Cι-C4haloalkylsulfinyi, C C4alkyIsulfonyl or C C4haloalkylsulfonyl; or
R2 is a group -OR^
R3 and R4 are each independently of the other hydrogen, halogen, C C4alkyl, HOCH2-, HC(O)-, HON=CH-, HOC(O)-, C C4alkoxycarbonyl, H2NC(0)-, H2NC(S)-, C C4haloalkyl, hydroxy, H NO-, Cι-C4alkoxy, C C haloalkoxy, C3-C6alkenyioxy, C3-C6haloalkenyloxy, C3-C6alkynyloxy, nitro, amino, H2NHN-, cyano, mercapto, Cι-C alkylthio, C C4haloalkylthio, CrC4alkylsulfinyl, C C4haloalkylsulfinyl, C C4alkylsulfonyl or Cι-C4haloalkylsulfonyl;
W is a group WI (W1),
Figure imgf000086_0001
wherein
R10o is hydrogen, C C4alkyl, C C4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or
C4-alkynyl, amino, hydroxy, C3-C6cycloalkyl, C3-C6halocycloalkyl, HC(O)- or acetyl;
R101 is hydrogen, C C4alkyl, HOCH2-, C C4haloalkyl, C2-C4alkenyl, C2-C4haioalkenyl, hydroxy, CrC alkoxy, d-C4haloalkoxy, HOC(O)-, d-C alkoxycarbonyl, cyano, H2NC(S)-, H2NC(0)-, nitro, amino, HC(0)NH-, CH3C(0)NH-, HC(O)-, HON=CH-, C C4alkylcarbonyl, mercapto, Cι-C4alkylthio, Cι-C4haloalkylthio, Cι-C4alkylsulfinyl, C -C4haloalkylsulfinyl, d-C4alkylsulfonyl, Cι-C haloalkylsulfonyl, C3- or C4-alkenylthio, C3- or C4-haloalkenylthio, C3- or C4-alkenylsulfinyl, C3- or C4-haloalkenylsulfinyl, C3- or C4-alkenylsulfonyl, C3- or C4- haloalkenylsulfonyl, -CH(0-d-C4alkyl)2 or -CH(0-C2-C4alkyIene-0); or
R100 and R101 together form a bridge -(CH2)m-, -(CH2)n-CH=CH-(CH2)o- or -(CH2)n-X-(CH2)o-, it being possible for those bridges to be substituted from one to four times by halogen; m is 3, 4, 5 or 6; n is 0, 1 or 2; o is 0, 1 , 2, 3, 4 or 5, with the proviso that the sum of n + o is 1 , 2, 3 or 4 and accordingly a
5-, 6-, 7- or 8-membered ring fused to the pyrazole ring is formed;
X is O, S, SO, S02 or -NRι03;
Rιo3 is hydrogen, C C4alkyl, Cι-C4haloalkyI, C3- or C4-alkenyl, Cι-C4alkylcarbonyl, d-C4alkylsulfonyl or Cι-C4haloalkylsulfonyl;
R102 is hydrogen, halogen, C C4aIkyl, C C4haloalkyl, cyano, H2NC(S)-, H2NC(0)-, HC(O)-, HON=CH-, HOC(O)-, C2-C4alkenyl, C2-C4haloalkenyl, C2-C alkynyl, nitro, cyano, hydroxy or amino; or W is a group W2 (W2), W3 (W3),
Figure imgf000087_0002
Figure imgf000087_0001
Figure imgf000087_0003
wherein
X110 is O or S;
Y110 is hydrogen, halogen, cyano, CrC4aIkyl, C2-C4alkenyl or C2-C4alkynyl; Rno is hydrogen, HC(O)-, HOC(O)-, H2NC(0)-, H2NC(S)-, cyano, halogen, amino, nitro, d-C4alkyl, C C4haIoalkyl, C2-C4alkenyl, C2-C4haloalkenyl or C2-C4alkynyl;
Rm is hydrogen, HC(O)-, HOC(O)-, H2NC(0)-, H2NC(S)-, cyano, halogen, amino, nitro, d-dalkyl, CrC4haloalkyl, C2-C4alkenyl, C2-C4haloalkenyl or C2-C4alkynyl;
R112 is hydrogen, HC(O)-, HON=CH-, HOC(O)-, H2NC(0)-, H2NC(S)-, cyano, isonitrile, amino, nitro, HOHN-, hydroxy, mercapto, C C4aIkyl, C C haloalkyl, C2-C alkenyl, C2-C4haloalkenyl, Cι-C4alkoxy, d-C4haloalkoxy, Cι-C alkylthio, Cι-C4haIoalkylthio, C C4alkylsulfinyl, C1-C4haloalkylsulfinyl, CrC4alkylsulfonyl or d-C4haloalkylsulfonyl; and
R 13 and Rn4 are each independently of the other hydrogen, CrC4alkyl, CrC haloalkyl, C3- or C4-alkenyI or C3- or C4-alkynyl, or an agrochemically acceptable salt or stereoisomer of such a compound of formula I.
2. A compound of formula I according to claim 1 , wherein W is the group W1
Figure imgf000088_0001
3. A compound according to claim 2, wherein R100 is hydrogen or Cι-C alkyl; and R10ι is hydrogen, Cι-C4alkoxy, Cι-C4haloalkoxy, Cι-C4haloalkyl, C C4alkylthio, d-C4alkylsulfinyl, C C4alkylsulfonyl, cyano, H2NC(O)- or H2NC(S)-; or R100 and R10ι together form a bridge -(CH2)m-; and R102 is hydrogen, halogen or Cι-C4alkyl.
4. A compound of formula I according to claim 1 , wherein Ri is hydrogen, CrC8alkyl, C2-C8haloalkyl, C2-C8alkenyl, C2-C8haloalkenyl, C3-C8alkynyl, unsubstituted or substituted phenyl, Cι-C8alkyIcarbonyl, phenylcarbonyl, Cι-C8alkoxycarbonyl, C3-C8aIkenyloxycarbonyl, C3-C8alkynyloxycarbonyl or R61-C C8alkylene-.
5. A compound according to claim 4, wherein Ri is hydrogen, C C4alkyl, C2-C4haloalkyl, C2-C4alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, phenyl, phenyl substituted by hydroxy, methoxy, d- or C2-alkyl, methoxycarbonyl, allyloxycarbonyl, propargyloxycarbonyl and/or methylcarbonyl; R6ι is Cι-C4alkoxy, Cι-C4alkoxycarbonyl, HOC(O)-, allyloxycarbonyl, phenyl or phenyl substituted by C or C2-alkyl, methoxy, hydroxy and/or by R6o-C C4alkyleneoxy; and R60 is C or C2-alkoxycarbonyl.
6. A compound of formula I according to claim 1 , wherein R2 is hydrogen, halogen, cyano, -ORι, d-C4alkylthio, Cι-C4alkylsulfinyl or CrC4alkylsulfonyl.
7. A compound according to claim 6, wherein R2 is methylthio, methylsulfinyl or methylsulfonyl; and Ri is hydrogen, methyl, allyl, propargyl, methoxycarbonyl or allyloxycarbonyl.
8. A compound of formula I according to claim 1 , wherein R3 and R4 are each independently of the other hydrogen or halogen.
9. A compound according to claim 8, wherein R3 and R4 are each independently of the other hydrogen, fluorine or chlorine.
10. A process for the preparation of a compound of formula I according to claim 1
Figure imgf000089_0001
wherein W is a group W1 (W1); Ri, R2, R3 and R4 are as defined in
Figure imgf000089_0002
claim 1 ; R100 is hydrogen, CrC4alkyl, Cι-C4haloalkyl, C3- or C4-alkenyl, C3- or C4-haloalkenyl, C3- or C4-alkynyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; Rioi is hydrogen, C C4alkyl, C C haloalkyl, hydroxy, Cι-C4alkoxy, d-C4haloalkoxy, HOC(O)-, C C4alkoxycarbonyl, H2NC(0)-, d-C alkylcarbonyl, -CH(0-C C4alkyl)2 or -CH(0-C2-C4alkylene-0); and Rι02 is hydrogen, halogen, d-C4alkyl, Cι-C4haloalkyl, cyano or HOC(O)-, which process comprises cyclising a compound of formula II
Figure imgf000090_0001
wherein R^ R2, R3, R4, Ri0ι and Rι02 are as defined, in a suitable solvent with a compound of formula XI
H2NNH-R100 (XI), wherein Rioo is as defined, to form the compound of formula IW1
Figure imgf000090_0002
wherein R,, R2, R3, R4, Rioo, R101 and R102 are as defined, and then optionally carrying out functionalisation according to the meanings of Rioo, «ι and R102.
11. A process for the preparation of a compound of formula I according to claim 1
wherein W is a group W1 R2, R3 and R4 are as
Figure imgf000090_0003
defined in claim 1 ; Rioo is hydrogen, C C4alkyl, Cι-C4haloalkyl, C3- or C4-alkenyl, C3- or C4- haloalkenyl, C3- or C4-aIkynyl, C3-C6cycloalkyl or C3-C6halocycloalkyl; R10i is CrC4haIoalkoxy; and R102 is hydrogen, halogen, nitro or HC(O)-, which process comprises cyclising a compound of formula III
Figure imgf000091_0001
in a solvent at room temperature or with gentle heating, with a compound of formula XI
H2NNH-R100 (XI) to form the compound of formula IW1a
Figure imgf000091_0002
the radicals R1( R2, R3, R4 and R1o0 in the compounds of formulae III, XI and IW1a being as defined, and then subjecting the compound of formula IW1a to a freonisation reaction to obtain the compound of formula IW1b
Figure imgf000091_0003
wherein R101 is haloalkoxy, and, according to the meaning of Rι02 above, subjecting the pyrazole ring to an electrophilic aromatic substitution reaction.
12. A process for the preparation of a compound of formula I according to claim 1
Figure imgf000091_0004
wherein W is a group W1 (W1); R1( R2, R3 and R4 are as defined
Figure imgf000092_0001
in claim 1; R100 is hydrogen, Cι-C4alkyl, C1-C4haloalkyl, C3- or C4-alkenyl, C3- or C4- haloalkenyl, C3- or C4-alkynyl, C3-C6cycloalkyl, C3-C6halocycloalkyl or HC(O)-; R101 is mercapto, Cι-C4alkylthio, Cι-C4haloalkylthio, Cι-C4alkylsulfinyl, CrC4haloalkylsulfinyl, CrC4alkylsulfonyl or CrC4haloalkylsulfonyI; and Rι02 is hydrogen, halogen, Cι-C4alkyl, CrC4haloalkyl, cyano, H2NC(S)-, H2NC(0)-, HC(O)-, HON=CH-, HOC(O)-, C2-C4alkenyl, C2-C4haloaIkenyl, C2-C4alkynyl or nitro, which process comprises first treating a compound of formula IV
Figure imgf000092_0002
wherein R1f R2, R3, R and Ri02 are as defined, in the presence of a base and an aprotic solvent, with carbon disulfide and then carrying out alkylation with a compound of formula XII
Figure imgf000092_0003
wherein Ri0ιa is Cι-C4alkyl or Cι-C4haloalkyl and L, is a leaving group, to obtain the compound of formula V
Figure imgf000092_0004
which is subsequently cyclised by reacting, optionally in the presence of a suitable solvent, with the hydrazine derivative of formula XI
NH2NH-Rιoo (XI), wherein R10o is as defined, to form the compound of formula IW1c
Figure imgf000093_0001
the radicals R1t R2l R3, R4, R100, ioia and Ri02 in the compounds of formulae V, XI and IW1c being as defined, and, optionally, subsequently oxidising that compound.
13. A process for the preparation of a compound of formula I according to claim 1
Figure imgf000093_0002
wherein R^ R2, R3, R4 and W are as defined in claim 1, which process comprises first oxidising a compound of formula VI
Figure imgf000093_0003
wherein R2, R3, R4 and W are as defined, in a suitable solvent to form the compound of formula VII
Figure imgf000093_0004
subsequently rearranging that compound, optionally in a solvent in the presence of an anhydride or antimony pentachloride, to obtain the compound of formula lh
Figure imgf000094_0001
and reacting that compound in the presence of an inert solvent and a base with a compound of formula XIII
Figure imgf000094_0002
wherein Ri is as defined in claim 1 with the exception of Ri being hydrogen, amino, R50CH=N-, R5ι(R52)N-, phenyl, pyridyl, pyrimidyl, pyridazinyl or pyrazinyl, and L2 is a leaving group.
14. A process for the preparation of a compound of formula I according to claim 1
Figure imgf000094_0003
wherein R,, R2, R3, R4 and W are as defined in claim 1 , which process comprises a) first oxidising a compound of formula VIII
Figure imgf000094_0004
wherein R2, R3, R and W are as defined and L3 is a leaving group, to form the corresponding pyridine-N-oxide derivative of formula IX
Figure imgf000094_0005
and then subjecting that N-oxide derivative, optionally in an inert solvent in the presence of a base, to a nucleophilic substitution reaction with a compound of formula XIV
R1-OH (XIV), wherein Ri is as defined in claim 1 , to obtain a compound of formula X
Figure imgf000095_0001
and finally deoxygenating the pyridine-N-oxide function, or b) first oxidising a compound of formula Villa
(Villa),
Figure imgf000095_0002
wherein R3, R4 and W are as defined and L3 is a leaving group, to form the corresponding pyridine-N-oxide derivative of formula IXa
Figure imgf000095_0003
then subjecting that derivative, optionally in an inert solvent in the presence of a base, to a nucleophilic substitution reaction with a compound of formula XIV
RrOH (XIV), wherein Ri is as defined in claim 1 , to obtain the compound of formula Xa
Figure imgf000095_0004
and, by means of halogenation, cyanation, Grignard reaction or by treatment with Tebbe reagent or Meerwein salt and ammonium persulfate, introducing the radical R2 into the position ortho to the pyridine-N-oxide group, with simultaneous deoxygenation thereof, and, in accordance with the meaning of R2, further functionalising the resulting compound of formula I.
15. A herbicidal and plant-growth-inhibiting composition which comprises, on an inert carrier, a herbicidaily effective amount of a compound of formula I.
16. A method of controlling undesired plant growth, which comprises applying a herbicidaily effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
17. A method of inhibiting plant growth, which comprises applying a herbicidaily effective amount of a compound of formula I or of a composition comprising such a compound to the plants or to the locus thereof.
18. A composition according to claim 15, which comprises a further herbicide.
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