EP1080088A1 - Pyridyl-pyrazole derivatives, process for their preparation, and their use as herbicides - Google Patents

Pyridyl-pyrazole derivatives, process for their preparation, and their use as herbicides

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Publication number
EP1080088A1
EP1080088A1 EP99952093A EP99952093A EP1080088A1 EP 1080088 A1 EP1080088 A1 EP 1080088A1 EP 99952093 A EP99952093 A EP 99952093A EP 99952093 A EP99952093 A EP 99952093A EP 1080088 A1 EP1080088 A1 EP 1080088A1
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EP
European Patent Office
Prior art keywords
alkyl
formula
halogenalkyl
halogen
hydrogen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99952093A
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German (de)
French (fr)
Inventor
Kurt Nebel
Alain De Mesmaeker
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Syngenta Participations AG
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Novartis AG
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Publication of EP1080088A1 publication Critical patent/EP1080088A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the invention relates to new, herbicidally active, substituted pyridyl-pyrazole derivatives, a process for the preparation thereof, compositions containing these compounds, as well as their usage in controlling weeds, in particular in crops of useful plants, for example cereals, maize, rice, cotton, soya, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantations and fodder plants, or in inhibiting plant growth.
  • crops of useful plants for example cereals, maize, rice, cotton, soya, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantations and fodder plants, or in inhibiting plant growth.
  • Phenyl-pyrazole compounds having herbicidal activity are known and are described for example in WO 98/12182.
  • substituted pyridyl-pyrazole derivatives have outstanding herbicidal and growth-inhibiting properties.
  • the present invention thus relates to compounds of formula I
  • W is a group (W 2 ),
  • R 8 and R 9 independently of one another, are C ⁇ -C 4 -alkyl; or
  • R 8 and R 9 together form a C 2 -C 5 -alkylene bridge
  • R 2 signifies hydrogen, C C 4 -alkyl, d-C 4 -halogenalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -haiogenalkenyl,
  • R 3 is hydrogen, C C 4 -alkyl, d-d-halogenalkyl, d-d-hydroxyalkyl, C 2 -C 6 -alkenyl, C 2 -C 6 - halogenalkenyl, C 2 -C 6 -alkynyl, halogen, cyano, NH 2 C(S)-, nitro, OHC- or R ⁇ 8 R ⁇ 9 N- ;
  • R 18 and R 19 independently of one another, are hydrogen, C C 4 -alkyl, d-d-halogenalkyl,
  • R 4 signifies hydrogen, d-C 4 -alkyl, C C 4 -halogenalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -halogenalkenyl,
  • R 20 and R 21 are C ⁇ -C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 - C 6 -cycloalkyl, d-C- ⁇ -halogenalkyl, C 3 -C 8 -halogenalkenyl, C ⁇ -C 4 -alkylcarbonyl, C ⁇ -C 4 - halogenalkylcarbonyl, d-C-a-alkylsulphonyl, d-C 8 -halogenalkylsulphonyl, C 2 -C 8 - alkenyisulphonyl, C 2 -C 8 -halogenalkenylsulphonyl, benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, C ⁇ -C 4 -alkyl or C ⁇ -C 4 -halogenalkyl; or R 13
  • R 30 is hydrogen, d-C 8 -alkyl, C C 8 -alkyl-ethylene oxide, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 - cycioalkyl, C r C 8 -halogenalkyl, C 3 -C 8 -halogenalkenyl, C ⁇ -C -alkoxy-C r C 4 -alkyl, C 3 -C 6 - alkenyloxy-d-C 4 -alkyl, C 3 -C 6 -alkynyloxy-C ⁇ -C 4 -alkyl, d-d-alkoxy-d-d-alkoxy-d-d-alkyl, C r C 4 -alkylthio-C ⁇ -C 4 -alkyl, C ⁇ -C 8 -alkoxycarbonyl, C 3 -C 8 -alkenyloxycarbonyl, benz
  • R— N — X t signifies oxygen, sulphur or ⁇ 1 ;
  • X 1 signifies a single bond
  • R 2 is hydrogen, C r C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl or d-C 8 - halogenalkyl; or n 2 is 0, 1 or 2; R 33 is d-C ⁇ -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, d-C 8 -halogenalkyl, C 3 -C 8 - halogenalkenyl, d-d-alkoxy-d-d-alkyl, C3-C6-alkenyioxy-CrC 4 -alkyl, d-d-alkylthio-d- C -alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, C C 4 -al
  • R— — X 2 is oxygen, sulphur or '35 '
  • R34 is hydrogen, d-C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, d-C 8 - halogenalkyl, C 3 -C 8 -halogenalkenyl, C ⁇ -C 4 -alkoxy-d-C 4 -alkyl, C 3 -C 6 -alkenyloxy-d-C 4 -alkyl,
  • R 13 is R 40 C(O)-
  • X 3 is oxygen, sulphur, 51 1 or 52 1 ;
  • R 50 is hydrogen, C ⁇ -C 8 -alkyl, C 3 -C 8 -alkenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, d-C 8 - halogenalkyl, C 3 -C 8 -halogenalkenyl, cyano-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -alkoxy-d-C -alkyl, C 3 -C 6 - alkenyloxy-d-d-alkyl, (oxiranyl)-CH 2 -, oxetanyl-, d-d-alkylthio-d-d-alkyi.
  • R 53 X 4 C(O)-C 1 -C 6 -alkyl, I or
  • R 53 X 4 C(O)-C 3 -C 6 -cycloalkyl
  • X v4 • is oxygen, su .lphur, RS M 'N i — or R ⁇ « 0-N 1 — ;
  • R53 is hydrogen, d-C 8 -alkyl, C 3 -C 8 -aikenyl, C 3 -C 8 -alkynyl, C 3 -C 6 -cycloalkyl, d-C 8 - halogenalkyl, C 3 -C 8 -halogenalkenyl, cyano-d-C 4 -alkyl, C C 4 -alkoxy-C ⁇ -C 4 -alkyl, C 3 -C 6 - alkenyloxy-d-C 4 -alkyl, (oxiranyl)-CH 2 -, oxetanyl-, C ⁇ -C -alkylthio-d-C 4 -alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-C -alkyl or d-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted
  • B 2 is nitro, cyano or R 71 X 6 C(O)-;
  • R 70 is cyano or R 72 X 7 C(O)-;
  • U signifies d- or C 2 -alkylene, -CH 2 -O-, -CH 2 -S-, oxygen or sulphur, as well as agrochemically acceptable salts and stereoisomers of these compounds of formula I.
  • halogen is understood to be iodine, and preferably fluorine, chlorine and bromine.
  • the alkyl, alkenyl and alkynyl groups present in the definitions of the substituents may be straight-chained or branched, and this also applies to the alkyl, alkenyl and alkynyl moiety of the alkylcarbonyl, alkylcarbamoyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkylthio-alkyl, alkylthio-C(O)-, alkenylcarbamoyl, alkenylthio-C(O)-, alkynylthio-C(O)-, alkylsulphonyl, aikylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylalkyl, B alkyl,
  • Alkyl groups are for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert.-butyl as well as the various isomeric pentyl, hexyl, heptyl and octyl radicals. Methyl, ethyl, n-propyl, iso-propyl and n-butyl are preferred.
  • alkenyls which may be mentioned are vinyl, allyl, methallyl, 1 -methylvinyl, but- 2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals with a chain length of 3 to 5 carbon atoms.
  • alkynyls which may be mentioned are 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 or 2- hexynyl, preferably alkynyl radicals with a chain length of 2 to 4 carbon atoms.
  • Halogenalkyl may be alkyl groups that are mono- or multi-substituted, especially mono- to trisubstituted, by halogen, whereby halogen individually signifies iodine and in particular fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
  • alkenyl radicals that are mono-, di- or trisubstituted by halogen, preference is given to those which have a chain length of 3 or 4 carbon atoms.
  • the alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
  • Alkylsulphonyl is for example methyisulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, iso-butylsulphonyl, sec.-butylsulphonyl, tert.- butylsulphonyl; preferably methyisulphonyl and ethylsulphonyl.
  • Halogenalkylsulphonyl is for example fluoromethylsulphonyl, difluoromethyisulphonyl, trifluoromethylsulphonyl, chloromethylsulphonyl, trichloromethylsulphonyl, 2- fluoroethylsulphonyl, 2,2,2-trifluoroethylsulphonyl and 2,2,2-trichloroethylsulphonyl.
  • Alkenylsulphonyl is for example allylsulphonyl, methallylsulphonyl, but-2-en-1 -yl-sulphonyl, pentenylsulphonyl and 2-hexenylsulphonyl.
  • Halogenalkenylsulphonyl is for example 2- and 3-fluoropropenyl-sulphonyl, 2- and 3- chloropropenyl-sulphonyl, 2- and 3-bromopropenyl-suiphonyl, 2,3,3-trifluoropropenyl- sulphonyl, 2,3,3-trichloropropenyl-sulphonyl, 4,4,4-trifluoro-but-2-en-1 -yl-sulphonyl and
  • Cyanoalkyl is for example cyanomethyl, cyanoethyl, cyanoeth-1 -yl and cyanopropyl.
  • Hydroxyalkyl is for example hydroxymethyl, 2-hydroxyethyl and 3-hydroxypropyl.
  • Alkylamino is for example methylamino, ethylamino and the isomeric propyl- and butylamino.
  • Alkenylamino is for example allylamino, methallylamino and but-2-en-1 -yl-amino.
  • Alkynylamino is for example propargylamino and 1 -methylpropargylamino.
  • Halogenalkylamino is for example chloroethylamino, trifluoroethylamino and
  • Di(halogenalkyl)-amino is for example di(2-chloroethyl)-amino.
  • Alkylcarbonyl is in particular acetyl and propionyl.
  • Halogenalkylcarbonyl is in particular trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl and 3,3,3-trichloropropionyl.
  • Alkenylcarbonyl is in particular vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 -yl- carbonyl, pentenylcarbonyl and 2-hexenylcarbonyl.
  • Alkynylcarbonyl is in particular acetylenecarbonyl, propargylcarbonyl, 1 -methylpropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1 -yl-carbonyl and pent-4-yn-1-yl-carbonyl.
  • Alkenyloxy is for example allyloxy, methallyloxy and but-2-en-1-yloxy.
  • Alkoxy-alkyl is for example methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, iso-propoxymethyl and iso-propoxyethyl.
  • Alkynyloxy-alkyl is for example propargyloxy-alkyl and 1 -methylpropargyloxy-alkyl.
  • Alkoxycarbonyl is for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
  • Alkenyloxycarbonyl is for example allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1 -yl- oxycarbonyl, pentenyloxycarbonyl and 2-hexenyloxycarbonyl.
  • Alkynyloxycarbonyl is for example propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1 - yl-oxycarbonyl and 2-methylbutyn-2-yl-oxycarbonyl.
  • Alkoxyalkoxycarbonyl is for example methoxymethoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl and butoxyethoxycarbonyl.
  • Halogenalkoxy is for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2- trichloroethoxy.
  • cycloalkyl radicals considered as substituents are for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • Alkylthioalkyl signifies for example methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.
  • Halogenalkylthio-carbonyl is for example fluoromethylthio-carbonyi, difluoromethylthio- carbonyl, trifluoromethylthio-carbonyl, 2,2,2-trifluoroethylthio-carbonyl, 1 ,1 ,2,2- tetrafluoroethylthio-carbonyl, 2-fluoroethylthio-carbonyl, 2-chloroethylthio-carbonyl and
  • (C 6 H 5 ) substituted d-C 8 -alkylene chain is additionally substituted by phenyl at one of the 8 carbon atoms, whereby the phenyl ring is mono- to trisubstituted by halogen, d-d-alkyl or d-d- halogenalkyl, and the alkylene chain is straight-chained or branched and may be for example methylene, ethylene, methylethylene, propylene, 1 -methyl-propylene and butylene.
  • d-d- or d-Ce-alkyiene chain is additionally substituted by phenyl (C 6 H 5 ) at one of the 4 or 6 carbon atoms, respectively, whereby the phenyl ring is mono- to trisubstituted by halogen, C ⁇ -C 4 -alkyl or C ⁇ -C -halogenalkyl, and the alkylene chain is straight-chained or branched and may be for example methylene, ethylene, methylethylene, propylene, 1 -methyl- propylene and butylene.
  • Notable alkali and alkaline earth metal hydroxides as salt-forming components are e.g. the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium and potassium. Suitable salt-forming components are described for example in WO 97/41112.
  • Examples of amines which are suitable for ammonium salt formation may be both ammonia and primary, secondary and tertiary C ⁇ -C ⁇ 8 -alkylamines d-d-hydroxy- alkylamines and C 2 -C 4 -alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecyiamine, methyl-ethylamine, methyl-iso- propylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl-
  • W 3a (W 3a ) are particularly preferred. Of these compounds, those
  • R T is d-d-alkyl, d-C 4 -halogenalkyl, C 2 - C 4 -alkenyl or C 2 -d-halogenalkenyl;
  • R 3 is chlorine, bromine or methyl;
  • A N-;
  • Rn is hydrogen, fluorine or chlorine;
  • R 5 is halogen, C C -alkyl, d-C 4 -halogenalkyl or cyano; and
  • R ⁇ 2 is halogen.
  • compounds of formula la, wherein W a is the group W a are especially preferred.
  • compounds of formula la, wherein W a is the group W 3 a and R 3 is R ⁇ 8 R ⁇ 9 N- are particularly preferred.
  • R 10 signifies hydrogen or a protecting group, is either a) when R 10 is hydrogen, reacted with a compound of formula III
  • Cleavage of the benzyl protecting group, which is optionally substituted on the phenyl ring, may also take place under reduction conditions, e.g. using sodium in ammonia, analogously to the manner described in Synthetic Communic. 25, 761 (1995); Chem. Ber. 101 , 3265 (1968); or J. Am. Chem. Soc. 71 , 3994 (1949).
  • Cleavage of the benzyl protecting group, which is optionally substituted on the phenyl ring, may also take place by acidic catalysis, e.g. using trifluoroacetic acid optionally in the presence of an inert organic solvent such as toluene, dichloromethane or 1 ,2-dichloro- ethane, analogously to the manner described in Synthetic Communic. 25, 761 (1995).
  • an inert organic solvent such as cyclohexane, toluene, dichloromethane or chloroform
  • Suitable bases are inorganic bases such as carbonates, for example sodium or potassium carbonate, or sodium or potassium bicarbonate; hydroxides such as sodium, potassium or calcium hydroxide; metal oxides such as calcium oxide; hydrides such as sodium hydride; or organic bases such as alkylamines, for example triethylamine, H ⁇ nig's base (di-isopropyl- ethylamine), dimethyl aniline or diazabicycloundecene (DBU).
  • inorganic bases such as carbonates, for example sodium or potassium carbonate, or sodium or potassium bicarbonate
  • hydroxides such as sodium, potassium or calcium hydroxide
  • metal oxides such as calcium oxide
  • hydrides such as sodium hydride
  • organic bases such as alkylamines, for example triethylamine, H ⁇ nig's base (di-isopropyl- ethylamine), dimethyl aniline or diazabicycloundecene (DBU).
  • L in the compound of formula III signifies a leaving group, such as a halide, imidazolyl, triazolyi or R,S(O) 2 -O-.
  • R 3 is hydrogen, whilst taking into consideration the reactivities of the remaining substituents, by means of halogenation e.g. with elementary chlorine, bromine or iodine, sodium hypochlorite (NaOCI) or iodomonochloride (JCI) in an appropriate solvent and optionally in the presence of a base.
  • halogenation e.g. with elementary chlorine, bromine or iodine, sodium hypochlorite (NaOCI) or iodomonochloride (JCI) in an appropriate solvent and optionally in the presence of a base.
  • suitable bases are for example sodium acetate, imidazole or pyridine.
  • reaction temperatures are generally in the range -50°C to boiling point of the solvent employed.
  • the compounds of formula I, wherein R 3 signifies bromine or chlorine may be obtained by reacting the corresponding compounds of formula I, wherein R 3 is hydrogen, with sulphuryl chloride, N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS).
  • NBS N-bromosuccinimide
  • NCS N-chlorosuccinimide
  • the preferred solvent is e.g. carbon tetrachloride.
  • Reactions of this kind are described for example in WO 98/12182 and DE-A-19 638 234.
  • the choice of appropriate preparation method and of corresponding reaction conditions for the functional conversion in the pyridyl moiety is preferably made at an earlier stage of the reaction, taking into consideration the properties (reactivity) of the substituents already present.
  • This functional conversion conveniently takes place in the presence of an appropriate protecting group in the pyrazole increment, e.g. in compounds of formula II, wherein R 10 is for example benzyl.
  • the protecting group e.g. R 10 in the compounds of formula II
  • Such functionalisations in the pyridyl increment are described e.g. in WO 98/21 199.
  • R, 0 signifies a protecting group, such as benzyl, allyl, tert.-butyl, trityl, benzhydryl, alkoxycarbonyl, allyloxycarbonyl, benzyloxycarbonyl, alkylcarbonyl or benzoyl.
  • R 10 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C,-C 4 -alkyl or d-d-alkoxy, are important intermediates.
  • R 3 , R 4 , Rn, R13, n, and n 13 have the significances indicated under formula I, and R,o signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, d-C 4 -alkyl or d-d-alkoxy, are important intermediates.
  • R 3 , R 5 , R,,, R, 3 and n, 3 have the significances indicated under formula I, and R, 0 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C,-C -alkyl or d-d-alkoxy, are important intermediates.
  • the product may be obtained as a mixture of two or more isomers.
  • the isomers may be separated by methods known perse.
  • All application methods that are usual in agriculture may be considered for the usage according to the invention of the compounds of formula I or compositions containing them, such as pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as controlled release of active ingredient.
  • the active ingredient in solution is absorbed onto mineral granulate substrates or polymerised granulates (urea/formaldehyde) and dried.
  • a coating may be additionally given (coated granules), which enables the active ingredient to be dispensed over a certain period of time
  • the compounds may be used in unmodified form, i e. as they are obtained during synthesis, but are preferably processed in conventional manner with the excipients that are customary in formulation techniques, e.g.
  • emulsifiable concentrates directly sprayable or diluable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsuies.
  • Such formulations are described for example in WO 97/34485 on pages 9 to 13.
  • the application process such as spraying, misting, dusting, wetting, scattering or pouring are selected according to the type of agent, the targeted aims and the prevailing conditions.
  • the formulations i.e. the agents, preparations or compositions containing the active ingredient of formula I or at least one active ingredient of formula I and normally one or more solid or liquid formulation excipients, are produced in known manner, e.g. by intimately mixing and/or grinding the active ingredients with the formulation excipients such as solvents or solid carriers.
  • formulation excipients such as solvents or solid carriers
  • surface-active compounds surfactants
  • solvents and solid carriers are given for example in WO 97/34485 on page 6.
  • the surface-active compounds may be non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed for example in WO 97/34485 on pages 7 and 8.
  • the surfactants which are customary in formulation techniques, and are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual” MC Publishing Co ⁇ ., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, M ⁇ nchen/Wien, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81 , are also suitable for the production of the herbicidal compositions according to the invention.
  • the herbicidal formulations normally contain 0.1 to 99 % by weight, especially 0.1 to 95 % by weight, of herbicide, 1 to 99.9 % by weight, especially 5 to 99.8 % by weight, of a solid or liquid formulation excipient and 0 to 25 % by weight, especially 0.1 to 25 % by weight, of a surfactant.
  • compositions may also contain further additives, such as stabilisers, e.g. optionally epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity regulators, binding agents, tackifiers, as well as fertilizers or other active ingredients.
  • stabilisers e.g. optionally epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity regulators, binding agents, tackifiers, as well as fertilizers or other active ingredients.
  • stabilisers e.g. optionally epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil)
  • antifoaming agents e.g. silicone oil, preservatives, viscosity regulators, binding agents, tackifier
  • the active ingredients of formula I may be successfully used either as a mixture comprising the isomers la and lb or as pure isomers la or lb on the plant or the locus thereof at application rates of 0.001 to 4 kg/ha, especially 0.005 to 2 kg/ha.
  • the dosage necessary for the desired effect can be determined by tests. It is dependent on the type of activity, the stage of development of the cultivated plant and of the weed, as well as on the application (locus, time, method) and may vary within a wide range depending on these parameters.
  • the compounds of formula I and normally in particular the isomers of formula la, are notable for their herbicidal and growth-inhibiting properties, which enable them to be used in crops of useful plants, especially cereals, cotton, soya, sugar beet, sugar cane, plantations, rape, maize and rice, as well as for non-selective weed control (Total Vegetation Management, TVM). Crops are also understood to be those which have been made tolerant towards herbicides or classes of herbicide by means of conventional breeding or by genetic engineering.
  • the weeds to be controlled are both monocot and dicot weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Sci ⁇ us, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Sci ⁇ us, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida,
  • Example P6 Preparation of 3-(5-chloro-3-fluoropyridin-2-ylH-chloromethanesulphonyl- 4,5.6.7-tetrahvdro-1.H.-indazole (isomer A) and 3-(5-chloro-3-fluoropyridin-2-yl)-1- chloromethanesulphonyl-4.5.6.7-tetrahvdro-2.H.-indazole (isomer B)
  • the crude product is purified in a flash chromatography column [silica gel; eluant: n-hexane/ethyl acetate 4/1 (v/v)]. 0.16 g of an isomer A with a m.p. of 108-110°C and 0.08 g of an isomer B as a resin are obtained.
  • Table B Physico-chemical data of compounds produced in the above-mentioned tables. The figure before the point indicates the number of the table, e.g. 36.002 means in Table 36 the compound no. 002 of Table A.
  • Test plants Setaria, Solanum.
  • the compounds according to the invention show good herbicidal action in this test.
  • Table B1 shows an example of the good herbicidal activity of the compounds of formula I.
  • Test plant Setaria Solanum dosage [g AS/ha]
  • Monocot and dicot test plants are raised in standard soil in plastic pots in the greenhouse, and sprayed at the 4- to 6-leaf stage with an aqueous suspension or emulsion of the test substances of formula I, prepared from a 25% emulsion concentrate [example F1 , c)] at a rate of 500 I water/ha, corresponding to a dosage of 2000 g active substance/ha.
  • Test plants Setaria, Sinapsis, Solanum, Ipomea.
  • the compounds of formula I show good herbicidal action in this test.
  • Table B2 shows an example of the good herbicidal activity of the compounds of formula I.
  • Test plant Setaria Sinapis Solanum Ipomea dosage [g AS/ha]
  • the active ingredients of formula I according to the invention may also be used in a mixture with known herbicides as co-herbicides for controlling weeds, for example as ready-to-use formulations or as a "tank mix".
  • the following co-herbicides may be considered for example as components for mixing with the active ingredients 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 + Aminotriazol; compound of formula I + Amidosulfuron; compound of formula I + Asulam; compound of formula I + Atrazin; 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

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Abstract

Compounds of formula (I), wherein A is =N- or (a); n13 is 1, 2 or 3; W is a group (W1), (W2), (W3) or (W4); R1 is C1-C4-alkyl, C1-C4-halogenalkyl, C2-C4-alkenyl, C2-C4-halogenalkenyl, C3-C6-cycloalkyl, amino, NHR8 or NR8R9; R8 and R9, independently of one another, are C1-C4alkyl; or R8 and R9 together form a C2-C5-alkylene bridge; R2 signifies hydrogen, C1-C4-alkyl, C1-C4-halogenalkyl, C3-C6-alkenyl, C3-C6-halogenalkenyl, C3-C6-alkynyl, C1-C4-alkylsulphonyl, C1-C4-halogenalkylsulphonyl, C2-C4-alkenylsulphonyl or C2-C4-halogenalkenylsulphonyl; R3 is hydrogen, C1-C4-alkyl, C1-C4-halogenalkyl, C1-C4-hydroxyalkyl, C2-C6-alkenyl, C2-C6-halogenalkenyl, C2-C6-alkynyl, halogen, cyano, NH2C(S)-, nitro, OHC- or R18R19N-; R18 and R19, independently of one another, are hydrogen, C1-C4-alkyl, C1-C4-halogenalkyl, C3-C4-alkenyl, C3-C4-halogenalkenyl, C3-C6-cycloalkyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-halogenalkylcarbonyl, C2-C6alkenylcarbonyl, C2-C6-halogenalkenylcarbonyl, C1-C6-alkylsulphonyl or C1-C6-halogenalkylsulphonyl; n1 is 0, 1 or 2; R4 signifies hydrogen, C1-C4-alkyl, C1-C4-halogenalkyl, C3-C6-alkenyl, C3-C6-halogenalkenyl, C3-C6-alkynyl or C3-C6-cycloalkyl; R5 signifies hydrogen, halogen, C1-C4-alkyl, C1-C4-halogenalkyl, cyano, nitro, amino, NH2C(S)-, C1-C4-alkylcarbonyl, C1-C4-halogenalkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4-halogenalkenylcarbonyl or C2-C4-alkynylcarbonyl; U signifies C1- or C2-alkylene, -CH2-O-, -CH2-S-, oxygen or sulphur; R11 is hydrogen, fluorine, chlorine, bromine or methyl; R13 has the significance indicated in claim 1, as well as agrochemically acceptable salts and stereoisomers of these compounds of formula (I), have good pre- and post-emergent, selective herbicidal properties. The preparation of these compounds and their usage as herbicidal active ingredients are described.

Description

PYRIDYL-PYRAZOLE DERIVATIVES, PROCESS FOR THEIR PREPARAΗON, AND THEIR USE AS HERBICIDES
The invention relates to new, herbicidally active, substituted pyridyl-pyrazole derivatives, a process for the preparation thereof, compositions containing these compounds, as well as their usage in controlling weeds, in particular in crops of useful plants, for example cereals, maize, rice, cotton, soya, rape, sorghum, sugar cane, sugar beet, sunflowers, vegetables, plantations and fodder plants, or in inhibiting plant growth.
Phenyl-pyrazole compounds having herbicidal activity are known and are described for example in WO 98/12182.
It has now surprisingly been found that substituted pyridyl-pyrazole derivatives have outstanding herbicidal and growth-inhibiting properties.
The present invention thus relates to compounds of formula I
wherein
A is =N- or = N-0"
n13 is 1 , 2 or 3;
W is a group (W2),
R, is Cι-C4-alkyl, C C4-halogenalkyl, C2-C4-alkenyl, C2-C4-halogenalkenyl, C3-C6-cycloalkyl, amino, NHR8 or NR8R9;
R8 and R9, independently of one another, are Cι-C4-alkyl; or
R8 and R9 together form a C2-C5-alkylene bridge;
R2 signifies hydrogen, C C4-alkyl, d-C4-halogenalkyl, C3-C6-alkenyl, C3-C6-haiogenalkenyl,
C3-C6-alkynyl, d-d-alkylsulphonyl, d-d-halogenalkylsulphonyl, C2-C4-alkenylsulphonyl or
C2-C -halogenalkenylsulphonyl;
R3 is hydrogen, C C4-alkyl, d-d-halogenalkyl, d-d-hydroxyalkyl, C2-C6-alkenyl, C2-C6- halogenalkenyl, C2-C6-alkynyl, halogen, cyano, NH2C(S)-, nitro, OHC- or Rι8Rι9N- ;
R18 and R19, independently of one another, are hydrogen, C C4-alkyl, d-d-halogenalkyl,
C3-C4-alkenyl, C3-C4-halogenalkenyl, C3-C6-cycloalkyl, C3-C6-alkynyl, d-C6-alkylcarbonyl, d-Ce-halogenalkylcarbonyl, C2-C6alkenylcarbonyl, C2-C6-halogenalkenylcarbonyl, Cι-C6- alkylsulphonyl or d-C-β-halogenalkylsulphonyl;
R4 signifies hydrogen, d-C4-alkyl, C C4-halogenalkyl, C3-C6-alkenyl, C3-C6-halogenalkenyl,
C3-C6-alkynyl or C3-C6-cycloalkyl;
R5 signifies hydrogen, halogen, d-C4-alkyl, d-C4-halogenalkyl, cyano, nitro, amino,
NH2C(S)-, Cι-C4-alkylcarbonyl, C C -halogenalkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4- halogenalkenylcarbonyl or C2-C -alkynylcarbonyl;
Ru signifies hydrogen, fluorine, chlorine, bromine or methyl; R13 is hydrogen, halogen, cyano, CIS(O)2-, CIC(O)-, Nitro, Amino, " \. , HS-,
R20NH- or R20R ιN- ;
R20 and R21, independently of one another, are Cι-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3- C6-cycloalkyl, d-C-β-halogenalkyl, C3-C8-halogenalkenyl, Cι-C4-alkylcarbonyl, Cι-C4- halogenalkylcarbonyl, d-C-a-alkylsulphonyl, d-C8-halogenalkylsulphonyl, C2-C8- alkenyisulphonyl, C2-C8-halogenalkenylsulphonyl, benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, Cι-C4-alkyl or Cι-C4-halogenalkyl; or R13 is R30O-;
R30 is hydrogen, d-C8-alkyl, C C8-alkyl-ethylene oxide, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6- cycioalkyl, CrC8-halogenalkyl, C3-C8-halogenalkenyl, Cι-C -alkoxy-CrC4-alkyl, C3-C6- alkenyloxy-d-C4-alkyl, C3-C6-alkynyloxy-Cι-C4-alkyl, d-d-alkoxy-d-d-alkoxy-d-d-alkyl, CrC4-alkylthio-Cι-C4-alkyl, Cι-C8-alkoxycarbonyl, C3-C8-alkenyloxycarbonyl, benzyloxycarbonyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, whereby these aforementioned aromatic and heteroaromatic rings may be optionally mono- to trisubstituted by halogen, Cι-C -alkyl or Cι-C4-halogenalkyl; or
R31 X, C(O) - [C. -C8-alkylene]- R30 is R3ιXιC(O)-d-C8-alkyl-, | , R31CH(OH)-CrC8-alkyl,
(C6H5)
R— N — Xt signifies oxygen, sulphur or ∞ 1 ; or
X1 signifies a single bond;
R31 signifies hydrogen, Cι-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, Cι-C8- halogenalkyl, C3-C8-halogenalkenyl, d-C4-alkoxy-Cι-C4-alkyl, C3-C6-alkenyloxy-d-C4-alkyl,
Cι-C4-al ylthio-Cι-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, C d-alkyl or Cι-C4-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-C4-alkyl or d-C -halogenalkyl;
R 2 is hydrogen, CrC8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl or d-C8- halogenalkyl; or n2 is 0, 1 or 2; R33 is d-Cβ-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8-halogenalkyl, C3-C8- halogenalkenyl, d-d-alkoxy-d-d-alkyl, C3-C6-alkenyioxy-CrC4-alkyl, d-d-alkylthio-d- C -alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, C C4-alkyl or d-d- halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, Cι-C -alkyl or d-C -halogenalkyl; and where n2 is 0, R33 additionally signifies hydrogen, d-C8-alkylcarbonyl or R34X2C(O)- ;
R— — X2 is oxygen, sulphur or '35 '
R34 is hydrogen, d-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8- halogenalkyl, C3-C8-halogenalkenyl, Cι-C4-alkoxy-d-C4-alkyl, C3-C6-alkenyloxy-d-C4-alkyl,
Cι-C -alkylthio-Cι-C -alkyi, phenyl, phenyl which is mono- to trisubstituted by halogen, Cι- d-alkyl or d-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or Cι-C -halogenalkyl;
R35 signifies hydrogen, d-C8-alkyl or C3-C8-alkenyl; or
R36 is hydrogen, d-C8-alkyl, C2-C8-alkenyl, C3-C8-alkynyl or C3-C6-cycloalkyl;
R37 is hydrogen, C C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, d-C8-halogenalkyl, C C4- alkylcarbonyl, CrC4-halogenalkylcarbonyl, benzoyi or benzoyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or d-d-halogenalkyl; or
R13 is R40C(O)-;
R40 is hydrogen, fluorine, chlorine, C C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6- cycloalkyl, d-C8-halogenalkyi, cyano-d-d-alkyl, C2-C8-haiogenalkenyl, d-d-alkoxy-Ci-d- alkyl, C3-C6-alkenyloxy-d-C4-alkyl, CrC4-alkylthio-d-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-d-alkyl or d-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-C4-alkyl or Ci-d- halogenalkyl; or
X3 is oxygen, sulphur, 51 1 or 52 1 ;
R50 is hydrogen, Cι-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8- halogenalkyl, C3-C8-halogenalkenyl, cyano-Cι-C4-alkyl, Cι-C4-alkoxy-d-C -alkyl, C3-C6- alkenyloxy-d-d-alkyl, (oxiranyl)-CH2-, oxetanyl-, d-d-alkylthio-d-d-alkyi. phenyl, phenyl which is mono- to trisubstituted by halogen, Cι-C -alkyl or d-C -halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or d-C4- halogenalkyl; phenyl-C2-C6-alkyl, C C6-alkyl-CO-C1-C4-alkyl,
C1-C6-alkyl-C(0)-[C1-C4-alkylene]- R53X4C(0)-[C1-C6-all<yiene]-
| , R53X4C(O)-C1-C6-alkyl, I or
(C6Hs) (C6H5)
R53X4C(O)-C3-C6-cycloalkyl;
X v4 • is oxygen, su .lphur, RS M'N i — or R ^« 0-N 1 — ;
R53 is hydrogen, d-C8-alkyl, C3-C8-aikenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8- halogenalkyl, C3-C8-halogenalkenyl, cyano-d-C4-alkyl, C C4-alkoxy-Cι-C4-alkyl, C3-C6- alkenyloxy-d-C4-alkyl, (oxiranyl)-CH2-, oxetanyl-, Cι-C -alkylthio-d-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-C -alkyl or d-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or C1-C4- halogenalkyl; or phenyl-C2-C6-alkyl;
R51, Rs2» R-^and R55 , independently of one another, are hydrogen, Cι-C8-alkyl, C3-C8- alkenyl, C3-C8-alkynyl, d-C8-halogenalkyi or benzyl; or
R13 is B d-Cβ-alkyl, Bι-C2-C8-alkenyl, B C2-C8-alkynyl, B Ci-Ce-halogenalkyl, Bι-C2-C8- halogenalkenyl, B C1-C4-alkoxy-C1-C4-alkylI B1-C1-C4-alkylthio-d-C4-alkyl or BrC3-C6- cycloalkyl;
B1 is hydrogen, cyano, hydroxy, ethylene oxide, C3-C6-cycloalkyl, C C8-alkoxy, C3-C8- alkenyloxy, R60X5C(O)-, d-C4-alkylcarbonyl or d-C4-halogenalkylcarbonyl ;
X5 has the significance of X4;
Rβo has the significance of R53; or
R13 is B2-C(R70)=CH-;
B2 is nitro, cyano or R71X6C(O)-;
R70 is cyano or R72X7C(O)-;
X6 and X have the significance of X^
R71 and R72 have the significance of R53; and
U signifies d- or C2-alkylene, -CH2-O-, -CH2-S-, oxygen or sulphur, as well as agrochemically acceptable salts and stereoisomers of these compounds of formula I.
In the above-mentioned definitions, halogen is understood to be iodine, and preferably fluorine, chlorine and bromine. The alkyl, alkenyl and alkynyl groups present in the definitions of the substituents may be straight-chained or branched, and this also applies to the alkyl, alkenyl and alkynyl moiety of the alkylcarbonyl, alkylcarbamoyl, hydroxyalkyl, cyanoalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, alkylthio, alkylthio-alkyl, alkylthio-C(O)-, alkenylcarbamoyl, alkenylthio-C(O)-, alkynylthio-C(O)-, alkylsulphonyl, aikylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylalkyl, B alkyl, B^alkenyl, Bralkynyl, HOC(O)-alkyl, phenyl-alkyl, Rs3X4C(O)-Cr Cβ-alkyl and R6oXsC(O)-Cι-C8-alkyl groups.
Alkyl groups are for example methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl, tert.-butyl as well as the various isomeric pentyl, hexyl, heptyl and octyl radicals. Methyl, ethyl, n-propyl, iso-propyl and n-butyl are preferred.
Examples of alkenyls which may be mentioned are vinyl, allyl, methallyl, 1 -methylvinyl, but- 2-en-1-yl, pentenyl, 2-hexenyl, 3-heptenyl and 4-octenyl, preferably alkenyl radicals with a chain length of 3 to 5 carbon atoms.
Examples of alkynyls which may be mentioned are 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 or 2- hexynyl, preferably alkynyl radicals with a chain length of 2 to 4 carbon atoms. Halogenalkyl may be alkyl groups that are mono- or multi-substituted, especially mono- to trisubstituted, by halogen, whereby halogen individually signifies iodine and in particular fluorine, chlorine and bromine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2-chloroethyl, 2,2-dichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trichloroethyl.
Halogenalkenyl may be alkenyl groups that are mono- or multi-substituted by halogen, whereby halogen individually signifies bromine, iodine and in particular fluorine and chlorine, for example 2- und 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. Of the alkenyl radicals that are mono-, di- or trisubstituted by halogen, preference is given to those which have a chain length of 3 or 4 carbon atoms. The alkenyl groups may be substituted by halogen at saturated or unsaturated carbon atoms.
Alkylsulphonyl is for example methyisulphonyl, ethylsulphonyl, propylsulphonyl, iso- propylsulphonyl, n-butylsulphonyl, iso-butylsulphonyl, sec.-butylsulphonyl, tert.- butylsulphonyl; preferably methyisulphonyl and ethylsulphonyl. Halogenalkylsulphonyl is for example fluoromethylsulphonyl, difluoromethyisulphonyl, trifluoromethylsulphonyl, chloromethylsulphonyl, trichloromethylsulphonyl, 2- fluoroethylsulphonyl, 2,2,2-trifluoroethylsulphonyl and 2,2,2-trichloroethylsulphonyl. Alkenylsulphonyl is for example allylsulphonyl, methallylsulphonyl, but-2-en-1 -yl-sulphonyl, pentenylsulphonyl and 2-hexenylsulphonyl.
Halogenalkenylsulphonyl is for example 2- and 3-fluoropropenyl-sulphonyl, 2- and 3- chloropropenyl-sulphonyl, 2- and 3-bromopropenyl-suiphonyl, 2,3,3-trifluoropropenyl- sulphonyl, 2,3,3-trichloropropenyl-sulphonyl, 4,4,4-trifluoro-but-2-en-1 -yl-sulphonyl and
4,4,4-trichloro-but-2-en-1 -yl-sulphonyl.
Cyanoalkyl is for example cyanomethyl, cyanoethyl, cyanoeth-1 -yl and cyanopropyl.
Hydroxyalkyl is for example hydroxymethyl, 2-hydroxyethyl and 3-hydroxypropyl.
Alkylamino is for example methylamino, ethylamino and the isomeric propyl- and butylamino.
Dialkylamino is for example dimethylamino, diethyiamino and the isomeric dipropyl- and dibutylamino.
Alkenylamino is for example allylamino, methallylamino and but-2-en-1 -yl-amino.
Alkynylamino is for example propargylamino and 1 -methylpropargylamino.
Halogenalkylamino is for example chloroethylamino, trifluoroethylamino and
3-chloropropylamino.
Di(halogenalkyl)-amino is for example di(2-chloroethyl)-amino.
Alkylcarbonyl is in particular acetyl and propionyl.
Halogenalkylcarbonyl is in particular trifluoroacetyl, trichloroacetyl, 3,3,3-trifluoropropionyl and 3,3,3-trichloropropionyl.
Alkenylcarbonyl is in particular vinylcarbonyl, allylcarbonyl, methallylcarbonyl, but-2-en-1 -yl- carbonyl, pentenylcarbonyl and 2-hexenylcarbonyl.
Alkynylcarbonyl is in particular acetylenecarbonyl, propargylcarbonyl, 1 -methylpropargyl- carbonyl, 3-butynylcarbonyl, but-2-yn-1 -yl-carbonyl and pent-4-yn-1-yl-carbonyl.
Alkenyloxy is for example allyloxy, methallyloxy and but-2-en-1-yloxy.
Alkynyloxy is for example propargyloxy and 1 -methylpropargyloxy.
Alkoxy-alkyl is for example methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl, n- propoxymethyl, n-propoxyethyl, iso-propoxymethyl and iso-propoxyethyl.
Alkenyloxy-alkyl is for example allyloxy-alkyl, methallyloxy-alkyl and but-2-en-1 -yloxy-alkyl.
Alkynyloxy-alkyl is for example propargyloxy-alkyl and 1 -methylpropargyloxy-alkyl.
Alkoxycarbonyl is for example methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, iso- propoxycarbonyl and n-butoxycarbonyl, preferably methoxycarbonyl and ethoxycarbonyl.
Alkenyloxycarbonyl is for example allyloxycarbonyl, methallyloxycarbonyl, but-2-en-1 -yl- oxycarbonyl, pentenyloxycarbonyl and 2-hexenyloxycarbonyl. Alkynyloxycarbonyl is for example propargyloxycarbonyl, 3-butynyloxycarbonyl, but-2-yn-1 - yl-oxycarbonyl and 2-methylbutyn-2-yl-oxycarbonyl.
Alkoxyalkoxycarbonyl is for example methoxymethoxycarbonyl, ethoxymethoxycarbonyl, ethoxyethoxycarbonyl, propoxymethoxycarbonyl, propoxyethoxycarbonyl, propoxypropoxycarbonyl and butoxyethoxycarbonyl.
Halogenalkoxy is for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, 1 ,1 ,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy and 2,2,2- trichloroethoxy.
The cycloalkyl radicals considered as substituents are for example cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The cycioalkoxycarbonyl radicals considered as substituents are for example cyclopropoxycarbonyl, cyclobutoxycarbonyl, cyclopentoxycarbonyl and cyclohexyloxycarbonyl.
Alkylthio signifies for example methylthio, ethylthio, propylthio and butylthio, as well as the branched isomers thereof.
Alkylthioalkyl signifies for example methylthioethyl, ethylthioethyl, methylthiopropyl and ethylthiopropyl.
Halogenalkylthio-carbonyl is for example fluoromethylthio-carbonyi, difluoromethylthio- carbonyl, trifluoromethylthio-carbonyl, 2,2,2-trifluoroethylthio-carbonyl, 1 ,1 ,2,2- tetrafluoroethylthio-carbonyl, 2-fluoroethylthio-carbonyl, 2-chloroethylthio-carbonyl and
2,2,2-trichloroethylthio-carbonyl.
Phenyl, benzyl or benzoyl as part of a substituent such as phenoxy, phenylthio, benzyloxy, benzylthio, phenoxycarbonyl, benzyloxycarbonyl, phenoxycarbonylalkyl, benzyioxy- carbonylalkyl or benzylamino exist in optionally substituted form. The substituents in this case are in ortho-, meta- or para-position. Substituents are e.g. d-d-alkyl, halogen or
Cι-C4-halogenalkyl.
Corresponding significances may also be assigned to the substituents in compound definitions, for example halogenalkenylcarbonyl, alkenyloxy-alkoxy, alkynyloxy-alkoxy, alkoxy-alkoxy-alkoxy, alkylthio-alkylamino, alkylthio-alkylthio, alkoxy-alkylthio, alkenyloxy- alkylthio, alkenyloxy-alkylamino, R30O-, R40C(O)-, R33S(O)n2-, R34X2C(O)-, R5oX3C(O)-, R3ιXιC(O)-alkyl, RssWOJ-cycioalkyl, R36R37NS(O)2-, B^alkyl, Bralkenyl, B alkynyl, B,- halogenalkyl, Brhalogenalkenyl, B alkoxyalkyl, Bralkylthioalkyl, Brcycloalkyl and B2- C(R70)=CH- . R31X1C(0)-[C1-C8-alkylene]- In the definition of R30, the group j , signifies that the R3ιXιC(O)-
(C6H5) substituted d-C8-alkylene chain is additionally substituted by phenyl at one of the 8 carbon atoms, whereby the phenyl ring is mono- to trisubstituted by halogen, d-d-alkyl or d-d- halogenalkyl, and the alkylene chain is straight-chained or branched and may be for example methylene, ethylene, methylethylene, propylene, 1 -methyl-propylene and butylene.
C^Ce-alkyl-C j-JC^C^alkylβne]- ln the definition of R5o, the groups | and
(C6H5)
R53X4C(0) - [C C6-alkylene]-
I , signify that the C C6 alkyl-C(O)- or R53X C(O)-substituted
(C6H5)
d-d- or d-Ce-alkyiene chain is additionally substituted by phenyl (C6H5) at one of the 4 or 6 carbon atoms, respectively, whereby the phenyl ring is mono- to trisubstituted by halogen, Cι-C4-alkyl or Cι-C -halogenalkyl, and the alkylene chain is straight-chained or branched and may be for example methylene, ethylene, methylethylene, propylene, 1 -methyl- propylene and butylene.
In the definitions cyanoalkyl, alkylcarbonyl, alkenylcarbonyl, halogenalkenyl-carbonyl, alkynylcarbonyl, alkoxycarbonyl and halogenalkylcarbonyl, the cyano- or carbonyl-carbon atom is not included in the respectively indicated lower and upper limits of the number of carbon atoms.
In respect of the group W (Wι to W4), the compounds of formula I are generally present as mixtures consisting of the isomers which are substituted in position 3 and 5 of the pyrazole ring by the pyridyl group (pyrid), for example as isomers IW1a and IW1b
for the group Wι. The isomeric ratio may vary depending on the synthesis process. The invention similarly embraces the salts, which the compounds of formula I may form with bases with acidic hydrogen, especially the derivatives with carboxylic acid and sulphonamide groups (e.g. carboxyl-substituted alkyl, alkylene, alkenyl, alkynyl, alkoxyalkyl, alkylthioalkyl and cycloalkyl groups and NH2SO2-, alkylS(O)2NH- and halogenalkylS(O)2NH- substituted pyridyl groups (R13)). The salts in question may be for example alkali metal salts, e.g. sodium and potassium salts; alkaline earth metal salts, such as calcium and magnesium salts; ammonium salts, i.e. unsubstituted ammonium salts and mono- or multi- substituted ammonium salts, e.g. triethylammonium and methylammonium salts; or salts with other organic bases.
Notable alkali and alkaline earth metal hydroxides as salt-forming components are e.g. the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially those of sodium and potassium. Suitable salt-forming components are described for example in WO 97/41112. Examples of amines which are suitable for ammonium salt formation may be both ammonia and primary, secondary and tertiary Cι-Cι8-alkylamines d-d-hydroxy- alkylamines and C2-C4-alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecyiamine, methyl-ethylamine, methyl-iso- propylamine, methyl-hexylamine, methyl-nonylamine, methyl-pentadecylamine, methyl- octadecylamine, ethyl-butylamine, ethyl-heptylamine, ethyl-octylamine, hexyl-heptylamine, hexyl-octylamine, dimethylamine, diethylamine, di-n-propylamine, di-iso-propylamine, di-n- butylamine, di-n-amylamine, di-iso-amylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, iso-propanolamine, n,n-diethanolamine, n-ethyl- propanolamine, n-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, di-butenyl-2-amine, n-hexenyl-2-amine, propylendiamine, trimethylamine, triethylamine, tri-n-propylamine, tri-iso-propylamine, tri-n-butylamine, tri-iso- butylamine, tri-sec.-butylamine, tri-n-amylamine, methoxyethylamin and ethoxyethylamin; heterocyclic amines, such as pyridine, quinoline, iso-quinoline, moφholine, thiomoφholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, such as anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylendiamines, benzidines, naphthylamines and o,m,p-chloranilines; but in particular triethylamines, iso-propylamine and di-iso-propylamine. The salts of the compounds of formula I with basic groups, especially with basic pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl and pyrazolyl rings or the derivatives with amino groups, such as alkylamino and dialkylamino groups in the definition of R3, R5 or R13 are for example salts with inorganic or organic acids, for example hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid or hydriodic acid, as well as sulphuric acid, phosphoric acid, 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, benzenesulphonic acid, p-toluenesulphonic acid and methanesulphonic acid. The possible presence of at least one asymmetrical carbon atom in the compounds of formula I, e.g. in the substituent R13 = OR30, wherein R30 is a branched alkyl, alkenyl, halogenalkyl or alkoxyalkyl group, or R13 = S(O)n2R33, wherein for example n2 = 1 and/or RM is a branched alkyl, alkenyl, halogenalkyl or alkoxyalkyl group, has the consequence that the compounds may appear both in optically active individual isomers and in the form of racemic mixtures. In the present invention, the active ingredients of formula I are understood to include both the pure optical antipodes and the racemates or diastereoisomers.
If an aliphatic C=C-double bond is present, then geometric isomerism may occur. In the present invention, these isomers are also included.
Compounds of formula I, wherein R3 is hydrogen, halogen, d-d-alkyl, d-d-halogenalkyl, C2-C6-alkenyl, C2-C6-haiogenalkenyl, cyano, OHC, amino or nitro, are preferred. Preferred compounds of formula I are characterised in that they correspond to formula la
wherein Wa is a group
Ri. R2, R3. R4, R5> R11, R13, ni and U have the significances given under formula I; and R12 is hydrogen, halogen, d-d-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, d-C4-halogenalkyl, C2-C4- halogenalkenyl, nitro, amino, CHO, d-d-halogenalkoxy, cyano, C3-C6-cycloalkyl, phenoxy, phenoxy which is mono- to trisubstituted by halogen, C C -alkyl or C C -halogenalkyl; benzyloxy or benzyloxy which is mono- to trisubstituted on the phenyl ring by halogen, Cr d-alkyl or Ci-d-halogenalkyl.
Compounds of formula la, wherein Wa is a group W1a, W2a or W a and R3 is halogen, methyl, Ci-d-halogenalkyl, cyano or amino, are especially preferred. Of these, particular preference is given to those compounds in which Wa is the group Wιa. Of these, those in which Ri is d-C4-alkyl, d-d-halogenalkyl, C2-C4-alkenyl or C2-C4-halogenalkenyl; R2 is d- or C2-halogenalkyl; R3 is chlorine, bromine or methyl; A = N-; Rn is hydrogen, fluorine, chlorine or bromine; and R,2 is halogen, are particularly important. Also particularly preferred are compounds of formula la, wherein Wa is the group W2a. Similarly, compounds of formula la, wherein Wa is the group
W3a (W3a) are particularly preferred. Of these compounds, those
that are particularly important are those in which RT is d-d-alkyl, d-C4-halogenalkyl, C2- C4-alkenyl or C2-d-halogenalkenyl; R3 is chlorine, bromine or methyl; A =N-; Rn is hydrogen, fluorine or chlorine; R5 is halogen, C C -alkyl, d-C4-halogenalkyl or cyano; and Rι2 is halogen. Also, compounds of formula la, wherein Wa is the group W a, are especially preferred. Similarly, compounds of formula la, wherein Wa is the group W3a and R3 is Rι8Rι9N-, are particularly preferred.
The process according to the invention for the production of compounds of formula I is carried out analogously to known processes, e.g. that described in WO 98/12182, and is characterised in that in order to produce those compounds of formula I
<R'3>n„ wherein A, Rn, Rι3, nι3 and W have the significances indicated under formula I, for example a compound of formula II
wherein Rn, R13 and nι3 have the significances indicated, and W0 is a group
(Wo,,) ; R2 to R5, n, and U have the significances indicated under formula I,
and R10 signifies hydrogen or a protecting group, is either a) when R10 is hydrogen, reacted with a compound of formula III
R,S(O)2-L (III), wherein R, has the significance indicated under formula I, and L is a leaving group, in an appropriate solvent and in the presence of a base, or b) when R,0 is a protecting group, this is firstly cleaved and subsequently the resulting compound of formula II, wherein R,o signifies hydrogen, is reacted as described under a) with a compound of formula III.
Depending on the properties (reactivity) of the substituents in the groups W0ι to Wo, and in the pyridyl moiety of the compounds of formula II, these will suitably be present either as "free" pyrazole derivatives, in which R10 signifies hydrogen, or as protected pyrazole derivatives, wherein Rι0 is a protecting group.
Appropriate protecting groups are for example benzyl, wherein the phenyl ring may be substituted by halogen, d-d-alkyl, Cι-C6-alkoxy, nitro or cyano; allyl, which may be substituted by d-d-alkyl or halogen; tert.-butyl; trityl; benzhydryl (diphenylmethyl); C,-d- alkoxycarbonyl; allyloxycarbonyl; benzyloxycarbonyl, wherein the phenyl ring may be substituted by halogen, d-d-alkyl or d-d-alkoxy; Cι-C -alkylcarbonyi; or benzoyl, wherein the pheny ring may be substituted by halogen, d-C -alkyl or d-d-alkoxy.
The technology for introducing and cleaving protecting groups is described for example in "Protective Groups in Organic Synthesis", 2nd Edition, Editors Th. W. Greene and P.G.M. Wuts, John Wiley & Sons, Inc., New York, 1991.
Cleavage of the benzyl protecting group, which is optionally substituted on the phenyl ring, in the compounds of formula II (R,0 = benzyl) may take place by oxidation using the Jones reagent, analogously to the manner described in I.I. Grandberg et al., J. Gen. Chem. USSR (Engl. Transl.) 33, 515 (1963), or using a basic solution of hydrogen peroxide in a water/- methanol mixture, analogously to the manner described in Tetrahedron Lett. 24, 1385 (1983).
Cleavage of the benzyl protecting group, which is optionally substituted on the phenyl ring, may also take place under reduction conditions, e.g. using sodium in ammonia, analogously to the manner described in Synthetic Communic. 25, 761 (1995); Chem. Ber. 101 , 3265 (1968); or J. Am. Chem. Soc. 71 , 3994 (1949).
Cleavage of the benzyl protecting group, which is optionally substituted on the phenyl ring, may also take place by acidic catalysis, e.g. using trifluoroacetic acid optionally in the presence of an inert organic solvent such as toluene, dichloromethane or 1 ,2-dichloro- ethane, analogously to the manner described in Synthetic Communic. 25, 761 (1995). The tert.-butyl protecting group in the compounds of formula II (R10 = tert.-butyl) may be cleaved for example with acids, e.g. sulphuric acid solutions, analogously to the manner described in J. Heterocyclic Chem. 30, 389 (1993). The trityl protecting group in the compounds of formula II (R10 = trityl) may be cleaved for example by acidic catalysis with trifluoroacetic acid optionally in the presence of an inert organic solvent such as cyclohexane, toluene, dichloromethane or chloroform, analogously to the manner described in J. Het. Chem. 14, 1171 (1977).
The benzoyl protecting group in the compounds of formula II (R10 = benzoyl) may be cleaved for example using cobalt hexacarbonyl in an inert solvent such as toluene, xylene or acetonitrile, analogously to the manner described in Bull. Chem. Soc. Jpn. 61 , 4473
(1988).
The reaction of the "free", deprotected pyrazole intermediates of formula II, wherein Rio signifies hydrogen, with a compound of formula III, conveniently takes place in an inert solvent such as aliphatic or aromatic hydrocarbons, for example hexanes, petroleum ether, toluene or benzene; halogenated hydrocarbons such as dichloromethane, 1 ,2-dichloro- ethane, chloroform or carbon tetrachloride; ethers such as diethyl ether, tert.-butyl methyl ether; aprotic, polar solvents such as dimethyl sulphoxide (DMSO), dimethyl formamide
(DMF), N-methylpyrrolidone (NMP), dimethyl acetamide or sulpholane.
Suitable bases are inorganic bases such as carbonates, for example sodium or potassium carbonate, or sodium or potassium bicarbonate; hydroxides such as sodium, potassium or calcium hydroxide; metal oxides such as calcium oxide; hydrides such as sodium hydride; or organic bases such as alkylamines, for example triethylamine, Hϋnig's base (di-isopropyl- ethylamine), dimethyl aniline or diazabicycloundecene (DBU).
L in the compound of formula III signifies a leaving group, such as a halide, imidazolyl, triazolyi or R,S(O)2-O-.
The compounds of formula I, wherein in groups W, to W3 the substituent R3 signifies halogen, may be obtained directly from the corresponding compounds of formula I, wherein
R3 is hydrogen, whilst taking into consideration the reactivities of the remaining substituents, by means of halogenation e.g. with elementary chlorine, bromine or iodine, sodium hypochlorite (NaOCI) or iodomonochloride (JCI) in an appropriate solvent and optionally in the presence of a base.
Depending on the selected solvents and processes, suitable bases are for example sodium acetate, imidazole or pyridine.
Suitable solvents are e.g. glacial acetic acid, water, alcohols, for example ethanol, chlorinated hydrocarbons, for example chlorobenzene, carbon tetrachloride, 1 ,2-dichloro- ethane, chloroform or 1 ,1 ,2,2-tetrachloroethane.
Halogenation may also be carried out in the presence of a catalyst, e.g. a Lewis acid such as iron (III) chloride, iron (III) bromide, aluminium chloride or thallium triacetate. The corresponding iodination may also conveniently take place in the presence of an oxidation agent, e.g. nitric acid or sulphur trioxide (SO3).
The reaction temperatures are generally in the range -50°C to boiling point of the solvent employed.
Such halogenation reactions are described e.g. in "Advanced Organic Chemistry", Editor J. March, John Wiley, New York, 1995, page 476 ff.; Chem. Ber. 43, 2106 (1910); J. Het. Chem. 1965, 410; Bull. Soc. Chim. France 1967, 2617; J. Chem. Soc. 1968, 1507; Synthesis 1982, 844; J. Org. Chem. 1984, 4687; and J. Prakt. Chem. 1989, 799. Alternatively, the compounds of formula I, wherein R3 signifies bromine or chlorine, may be obtained by reacting the corresponding compounds of formula I, wherein R3 is hydrogen, with sulphuryl chloride, N-bromosuccinimide (NBS) or N-chlorosuccinimide (NCS). The preferred solvent is e.g. carbon tetrachloride.
Reactions of this kind are described for example in WO 98/12182 and DE-A-19 638 234. The choice of appropriate preparation method and of corresponding reaction conditions for the functional conversion in the pyridyl moiety is preferably made at an earlier stage of the reaction, taking into consideration the properties (reactivity) of the substituents already present. This functional conversion conveniently takes place in the presence of an appropriate protecting group in the pyrazole increment, e.g. in compounds of formula II, wherein R10 is for example benzyl. Then, as indicated above, the protecting group (e.g. R10 in the compounds of formula II) can be cleaved and the R1S(O)2- group introduced into the pyrazole increment. Such functionalisations in the pyridyl increment are described e.g. in WO 98/21 199.
In the following reaction scheme, the possibilities of functional conversion on the pyridyl increment of the compounds of formulae IV, V, VI and VII are listed by way of example, whereby W0 in the compounds of formulae IV to IX is a group W0ι to W04
(W04) , wherein R2 to R5, n, and U possess the significances indicated
under formula I, and R,0 signifies a protecting group, such as benzyl, allyl, tert.-butyl, trityl, benzhydryl, alkoxycarbonyl, allyloxycarbonyl, benzyloxycarbonyl, alkylcarbonyl or benzoyl.
Reaction scheme:
VI VII
CO, EtOH, I^COg, MeJ, PdCI2(PPh3)2, T NMP
VIII IX
To produce the compounds of formula I, wherein W signifies a group W4 (examples P5 to P7), the compounds of formula ll4
wherein A, R,,, R,3, n,3 and U have the significances indicated under formula I, and R,0 signifies hydrogen, benzyl or benzyl which is substituted on the phenyl ring by halogen, C,-C -alkyl or C,-C -alkoxy, are important intermediates. To produce the compounds of formula I, wherein W signifies a group W,, the compounds of formula Hi
wherein A, R2, R3, R,,, R,s and n13 have the significances indicated under formula I, and R10 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C,-C4-alkyl or d-d-alkoxy, are important intermediates.
To produce the compounds of formula I, wherein W signifies a group W2, the compounds of formula ll2
wherein A, R3, R4, Rn, R13, n, and n13 have the significances indicated under formula I, and R,o signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, d-C4-alkyl or d-d-alkoxy, are important intermediates.
To produce the compounds of formula I, wherein W signifies a group W3, the compounds of formula II3
wherein A, R3, R5, R,,, R,3 and n,3 have the significances indicated under formula I, and R,0 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C,-C -alkyl or d-d-alkoxy, are important intermediates.
These intermediates of formulae II, to ll4 are new. The invention thus also relates to these compounds.
A number of known standard processes are available for producing the starting compounds of formula II (construction of the pyrazole rings), the choice of appropriate preparation process depending on the properties (reactivity) of the substituents in the respective intermediates. Such processes are described for example in WO 98/21199 and in the references cited therein.
Details of a few examples are also given by way of example in preparation examples P1 to
P7.
The starting compounds 5-chloro-3-fluoro-2-pyrιdιne-carboxylιc acid chloride and 3,5- dιchloro-2-acetylpyrιdιne used in preparation examples P2 and P4 are either known or may be produced in analogous manner to WO 98/21199.
Where no specific synthesis is carried out in order to isolate pure isomers, the product may be obtained as a mixture of two or more isomers. The isomers may be separated by methods known perse.
In addition, the person skilled in the art is familiar with the order in which certain reactions, e.g. the introduction or cleavage of protecting groups, may be suitably carried out so as to avoid possible secondary reactions.
All application methods that are usual in agriculture may be considered for the usage according to the invention of the compounds of formula I or compositions containing them, such as pre-emergence application, post-emergence application and seed dressing, as well as various methods and techniques such as controlled release of active ingredient. To do this, the active ingredient in solution is absorbed onto mineral granulate substrates or polymerised granulates (urea/formaldehyde) and dried. If desired, a coating may be additionally given (coated granules), which enables the active ingredient to be dispensed over a certain period of time The compounds may be used in unmodified form, i e. as they are obtained during synthesis, but are preferably processed in conventional manner with the excipients that are customary in formulation techniques, e.g. into emulsifiable concentrates, directly sprayable or diluable solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsuies. Such formulations are described for example in WO 97/34485 on pages 9 to 13. The application process, such as spraying, misting, dusting, wetting, scattering or pouring are selected according to the type of agent, the targeted aims and the prevailing conditions.
The formulations, i.e. the agents, preparations or compositions containing the active ingredient of formula I or at least one active ingredient of formula I and normally one or more solid or liquid formulation excipients, are produced in known manner, e.g. by intimately mixing and/or grinding the active ingredients with the formulation excipients such as solvents or solid carriers In addition, surface-active compounds (surfactants) may be used when producing the formulations. Examples of solvents and solid carriers are given for example in WO 97/34485 on page 6.
Depending on the type of active ingredient of formula I to be formulated, the surface-active compounds may be 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 in WO 97/34485 on pages 7 and 8. Furthermore, the surfactants which are customary in formulation techniques, and are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Coφ., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Mϋnchen/Wien, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol Mil, Chemical Publishing Co., New York, 1980-81 , are also suitable for the production of the herbicidal compositions according to the invention.
The herbicidal formulations normally contain 0.1 to 99 % by weight, especially 0.1 to 95 % by weight, of herbicide, 1 to 99.9 % by weight, especially 5 to 99.8 % by weight, of a solid or liquid formulation excipient and 0 to 25 % by weight, especially 0.1 to 25 % by weight, of a surfactant.
Whereas it is preferred to formulate commercial products as concentrates, the end user will normally use dilute formulations
The compositions may also contain further additives, such as stabilisers, e.g. optionally epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil), antifoaming agents, e.g. silicone oil, preservatives, viscosity regulators, binding agents, tackifiers, as well as fertilizers or other active ingredients.
Normally the active ingredients of formula I may be successfully used either as a mixture comprising the isomers la and lb or as pure isomers la or lb on the plant or the locus thereof at application rates of 0.001 to 4 kg/ha, especially 0.005 to 2 kg/ha. The dosage necessary for the desired effect can be determined by tests. It is dependent on the type of activity, the stage of development of the cultivated plant and of the weed, as well as on the application (locus, time, method) and may vary within a wide range depending on these parameters. The compounds of formula I, and normally in particular the isomers of formula la, are notable for their herbicidal and growth-inhibiting properties, which enable them to be used in crops of useful plants, especially cereals, cotton, soya, sugar beet, sugar cane, plantations, rape, maize and rice, as well as for non-selective weed control (Total Vegetation Management, TVM). Crops are also understood to be those which have been made tolerant towards herbicides or classes of herbicide by means of conventional breeding or by genetic engineering. The weeds to be controlled are both monocot and dicot weeds, for example Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Sciφus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following examples illustrate the invention more fully, without restricting it.
Preparation Examples
Example P1 : Preparation of 1 -cvclohex-1 -enyl-pyrrolidine
103.3 ml of cyclohexanone, together with 99.2 ml of pyrrolidine, are introduced into 200 ml of toluene and mixed with 0.3 g of p-toluenesulphonic acid. The mixture is subsequently stirred over night with slight refluxing (oil bath temperature 140°C) on a water separator, and then cooled to room temperature. The toluene phase is washed with water and then with brine, dried over sodium sulphate and concentrated to dryness in a vacuum. Distillation is subsequently carried out in a water jet vacuum. 89 g of the desired title compound are obtained as a slightly yellow oil with a boiling point of 114-117°C/35 torr.
Example P2: Preparation of (5-chloro-3-fluoropyridin-2-yl)-(2-pyrrolidin-1-yl-cvclohex-1- enyl)-methanone
7.5 g of 1 -cyclohex-1 -enyi-pyrrolidine (example P1), together with 5.75 ml of triethylamine, are introduced into 30 ml of absolute acetonitrile. Then, whilst stirring at room temperature, 8.0 g of 5-chloro-3-fluoro-2-pyridine-carboxylic acid chloride in 30 ml of absolute acetonitrile are added dropwise over the course of 30 minutes. Afterwards, stirring is effected over night. The reaction mixture is subsequently diluted with ethyl acetate and washed first of all with diluted hydrochloric acid and then with brine. After drying over sodium sulphate, the organic phase is filtered and concentrated to dryness in a vacuum. 3.93 g of the desired target compound are obtained as a dark oil.
This crude product can be used directly for the next reaction step without further purification.
Example P3: Preparation of 3-(5-chloro-3-fluoropyridin-2-vO-4.5.6.7-tetrahvdro-1.H. indazole
0.74 ml of hydrazine hydrate are slowly added dropwise to 20 ml of glacial acetic acid. Then, 3.93 g of (5-chloro-3-fluoropyridin-2-yl)-(2-pyrrolidin-1-yl-cyclohex-1-enyl)-methanone (example H2) are added. This mixture is stirred over night whilst heating (oil bath temperature 120°C), the dark reaction mixture obtained is subsequently cooled to room temperature and concentrated to dryness in a vacuum. The residue obtained is taken up in ethyl acetate and washed first of all with water and then with brine. After drying over sodium sulphate, the mixture is filtered and concentrated in a vacuum together with 8 g of silica gel. After placing this charged silica gel in a flash chromatography column (silica gel), elution takes place with a 3-component mixture of n-hexane/ethyl acetate/glacial acetic acid 20/10/1 (v/v/v). 1.65 g of the desired title compound are obtained as a yellow, amoφhous solid.
1H-NMR (CDCI3): 9.60-8.90 ppm (broad signal, 1 H); 8.43 ppm (dxd, 1 H); 7.51 ppm (dxd, 1 H); 2.82-2.71 ppm (m, 4 H); 1.89-1.72 ppm (m, 4 H).
Example P4: 3-(3.5-dichloro-2-pyridyl)-5-trif luoromethyl-f1 Hl-pyrazole
15.8 g of 3,5-dichloro-2-acetylpyridine, together with 12.0 ml of trifluoroacetic acid ethyl ester, are introduced into 125 ml of absolute ether. Cooling is effected whilst stirring in an ice bath, and 46.6 ml of a 21% sodium ethylate solution in ethanol are added dropwise. Afterwards, the ice bath is removed and stirring effected over night at 25°C. After cooling the reaction mixture in an ice bath and adding 7.5 ml of glacial acetic acid dropwise, the mixture is concentrated in a vacuum. 39.0 g of the 1 -(3,5-dichloro-2-pyridyl)-3- trifluoromethyl-propane-1 ,3-dione are obtained, which can be used directly for the following cyclisation step.
39.0 g of the 1 -(3,5-dichloro-2-pyridyl)-3-trifluoromethyl-propane-1 ,3-dione
are added to ethanol and 4.85 ml of hydrazine hydrate are slowly added. The reaction mixture is subsequently heated to reflux whilst stirring. After one hour, the mixture is concentrated to dryness in a vacuum, and the residue is partitioned between diluted sodium bicaΦonate solution and ethyl acetate. After shaking and separating the phases, the organic phase is washed with brine, dried over sodium sulphate, filtered and concentrated to dryness. 22.25 g of a yellow oil are obtained, which is purified by means of flash chromatography [silica gel, eluant: n-hexane/ethyl acetate 4/1 (v/v)]. 15.0 g of the desired product are obtained as a yellow solid.
1H-NMR (DMSO-D6): 8.81 ppm (m, 1H); 8.64 ppm (m, 1 H); 8.26 ppm (m, 1 H); 7.45 ppm (broad signal, 1H).
Example P5: Preparation of 3-(5-chloro-3-fluoropyridin-2-ylH-methanesuphonyl-4.5.6.7- tetrahvdro-1.H.-indazole
0.30 g of 3-(5-chloro-3-fluoropyridin-2-yl)-4,5,6,7-tetrahydro-1.H.-indazole (example P3) are introduced into 4 ml of absolute tetrahydrofuran. 0.06 g of a 60% sodium hydride dispersion in hexane are added to this yellow solution. Evolution of gas is ascertained. After stirring for 10 minutes, 0.10 ml of methane sulphochloride are added dropwise and stirred over night at room temperature. The reaction mixture obtained is subsequently diluted with ethyl acetate and washed with 1 molar hydrochloric acid and then with brine. After drying over sodium sulphate, the ethyl acetate phase is filtered and concentrated in a vacuum. Finally, purification takes place in a flash chromatography column [silica gel; eluant: n-hexane/ethyl acetate 2/1 (v/v)]. 0.36 g of the desired title compound are obtained as a white solid with a melting point of 160-162°C.
Example P6: Preparation of 3-(5-chloro-3-fluoropyridin-2-ylH-chloromethanesulphonyl- 4,5.6.7-tetrahvdro-1.H.-indazole (isomer A) and 3-(5-chloro-3-fluoropyridin-2-yl)-1- chloromethanesulphonyl-4.5.6.7-tetrahvdro-2.H.-indazole (isomer B)
0.30 g of 3-(5-chloro-3-f luoropyridin-2-yl)-4,5,6,7-tetrahydro-1.H.-indazole (example P3) are introduced into 4 ml of absolute tetrahydrofuran. 0.06 g of a 60% sodium hydride dispersion in hexane are added to this yellow solution. Stirring is subsequently effected for 10 minutes at room temperature whilst gas is formed. Then, 0.20 g of chloromethane sulphochloride are added dropwise and stirring continued over night. The next day, DC analysis [silica gel 60 F254; eluant: n-hexane/ethyl acetate 2/1 (v/v); UV] of a sample shows that some starting material is still present. Therefore, first of all 0.04 g of a 60% sodium hydride dispersion and - after stirring for 10 minutes - 0.10 g of chloromethane sulphochloride are added again. Stirring then continues for 3 hours, the reaction mixture is diluted with ethyl acetate and is washed first of all with 1 molar hydrochloric acid and then with brine. After drying over sodium sulphate, the mixture is filtered and concentrated in a vacuum. The crude product is purified in a flash chromatography column [silica gel; eluant: n-hexane/ethyl acetate 4/1 (v/v)]. 0.16 g of an isomer A with a m.p. of 108-110°C and 0.08 g of an isomer B as a resin are obtained.
DC [silica gel 60 F254; eluant: n-hexane/ethyl acetate 4/1 (v/v); UV]; Isomer A: Rf-value 0.29; Isomer B: Rf-value 0.13;
1H-NMR (CDCI3) of isomer B: 8.48 ppm (d, 1H); 7.57 ppm (dxd, 1H); 5.03 ppm (s, 2H); 2.81 ppm (t, 2H); 2.47 ppm (t, 2H); 1.88 ppm (m, 2H); 1.78 ppm (m, 2H).
Example P7: Preparation of 3-(5-chloro-3-fluoropyridin-2-yl)-4.5.6,7-tetrahvdro-indazole-1- sulfonic acid dimethylamide
0.24 g of 3-(5-chloro-3-fluoropyridin-2-yl)-4,5,6,7-tetrahydro-1.H.-indazole (example P3) are introduced into 4 ml of absolute tetrahydrofuran. 0.05 g of a 60% sodium hydride dispersion in hexane are slowly added whilst stirring at room temperature. Evolution of gas is ascertained. Stirring continues for 10 minutes, and then 0.15 g of dimethylsulphamoyl chloride are added. This reaction mixture is stirred for a further 3 hours. Afterwards, ethyl acetate is added, and the mixture is washed first of all with water and then with brine. After drying over sodium sulphate, the mixture is filtered and concentrated in a vacuum together with 2 g of silica gel. After placing this charged silica gel in a flash chromatography column, elution takes place with a mixture of n-hexane/ethyl acetate 4/1 (v/v). 0.28 g of the desired title compound are obtained as a white solid with a m.p. of 143-145°C.
The preferred compounds listed in the following tables may also be obtained in analogous manner, and using methods such as those indicated in the references cited.
Table 1 : A preferred group of compounds of formula I corresponds to the general
formula (I,), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula Ii are disclosed. Table 2: A further preferred group of compounds of formula I corresponds to the
general formula (l2), wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula l2 are disclosed.
Table 3: A further preferred group of compounds of formula I corresponds to the
general formula (l3), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l3 are disclosed.
Table 4: A further preferred group of compounds of formula I corresponds to the
general formula (l ), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l4 are disclosed.
Table 5: A further preferred group of compounds of formula I corresponds to the
general formula (l5), wherein the significance of the
corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l5 are disclosed. Table 6: A further preferred group of compounds of formula I corresponds to the
general formula (l6), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l6 are disclosed.
Table 7: A further preferred group of compounds of formula I corresponds to the
general formula (l7), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l7 are disclosed.
Table 8: A further preferred group of compounds of formula I corresponds to the
general formula (l8), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l8 are disclosed.
Table 9: A further preferred group of compounds of formula I corresponds to the
general formula (lg), wherein the significance of the
corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l9 are disclosed. Table 10: A further preferred group of compounds of formula I corresponds to the
general formula (ho), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l10 are disclosed.
Table 11 : A further preferred group of compounds of formula I corresponds to the
general formula ), wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula I,, are disclosed.
Table 12: A further preferred group of compounds of formula I corresponds to the
general formula (I12), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l,2 are disclosed.
Table 13: A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l,3 are disclosed. Table 14: A further preferred group of compounds of formula I corresponds to the
general formula (l,4), wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula lι are disclosed.
Table 15: A further preferred group of compounds of formula I corresponds to the
general formula (Il5), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l,5 are disclosed.
Table 16: A further preferred group of compounds of formula I corresponds to the
general formula (lie), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l16 are disclosed.
Table 17: A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l,7 are disclosed. Table 18: A further preferred group of compounds of formula I corresponds to the
general formula (lie). wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula lι8 are disclosed.
Table 19: A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula lι9 are disclosed.
Table 20: A further preferred group of compounds of formula I corresponds to the
general formula (!»), wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l20 are disclosed.
Table 21 : A further preferred group of compounds of formula I corresponds to the
general formula (I21), wherein the significance
of the corresponding substituents Rn and R13 is indicated in Table A, whereby 699 specific compounds of formula l2, are disclosed. Table 22: A further preferred group of compounds of formula I corresponds to the
general formula (I22), wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l22 are disclosed.
Table 23: A further preferred group of compounds of formula I corresponds to the
general formula (l23), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l23 are disclosed.
Table 24: A further preferred group of compounds of formula I corresponds to the
general formula (l24), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l2 are disclosed.
Table 25: A further preferred group of compounds of formula I corresponds to the
general formula (l25), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l25 are disclosed. Table 26: A further preferred group of compounds of formula I corresponds to the
general formula C26)' wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l26 are disclosed.
Table 27: A further preferred group of compounds of formula I corresponds to the
general formula (l27), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l27 are disclosed.
Table 28: A further preferred group of compounds of formula I corresponds to the
general formula (l28), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l28 are disclosed.
Table 29: A further preferred group of compounds of formula I corresponds to the
general formula (l»), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l29 are disclosed. Table 30: A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula I30 are disclosed.
Table 31 : A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l3ι are disclosed.
Table 32: A further preferred group of compounds of formula I corresponds to the
general formula (I32), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l32 are disclosed.
Table 33: A further preferred group of compounds of formula I corresponds to the
general formula (I33), wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula l33 are disclosed. Table 34: A further preferred group of compounds of formula I corresponds to the
general formula wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula I34 are disclosed.
Table 35: A further preferred group of compounds of formula I corresponds to the
general formula (l35), wherein the significance
of the corresponding substituents R„ and R13 is indicated in Table A, whereby 699 specific compounds of formula l3 are disclosed.
Table 36: A further preferred group of compounds of formula I corresponds to the
general formula (l36), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l36 are disclosed.
Table 37: A further preferred group of compounds of formula I corresponds to the
general formula (I37), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l37 are disclosed. Table 38: A further preferred group of compounds of formula I corresponds to the
general formula (laβ). wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula IM are disclosed.
Table 39: A further preferred group of compounds of formula I corresponds to the
general formula (I39), wherein the significance
of the corresponding substituents R,, and R,3 is indicated in Table A, whereby 699 specific compounds of formula l39 are disclosed.
Table 40: A further preferred group of compounds of formula I corresponds to the
general formula (l40), wherein the significance
of the corresponding substituents R,, and R13 is indicated in Table A, whereby 699 specific compounds of formula l40 are disclosed.
Table 41 : A further preferred group of compounds of formula I corresponds to the
general formula (l ,), wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l , are disclosed.
Table 42: A further preferred group of compounds of formula I corresponds to the
general formula (I 2), wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l42 are disclosed.
Table 43: A further preferred group of compounds of formula I corresponds to the
general formula (I43), wherein the significance
of the corresponding substituents R„ and R,3 is indicated in Table A, whereby 699 specific compounds of formula l43 are disclosed.
Table A
Comp. no. R11 Rl3
.001 H H
.002 F H
.003 Cl H
.004 H F
.005 F F
.006 Cl F
.007 H Cl
.008 F Cl
.009 Cl Cl
.010 H Br
.011 F Br
.012 Cl Br
CO
©
Ov α.
63
H υ α.
Comp. no. Rn Rl3
.174 Cl CH2CHCICOOCH2CH3
.175 H CH2CHCICOOCH(CH3)2
.176 F CH2CHCICOOCH(CH3)2
.177 Cl CH2CHCICOOCH(CH3)2
.178 F CH2CHCICOOC(CH3)3
.179 F CH2CHCICOOCH2(C6H5)
.180 F CH2CHCICOOCH2(p-CI-C6H4)
.181 F CH2CHCICOSCH3
.182 F CH2CHCICOSCH(CH3)2
.183 F CH2CHCICONHCH2CHCH2
.184 F CH2CHCICON(CH2CH3)2
.185 F CH2CHCICONH(CH3)
.186 H CH2CHBrCOOH
.187 F CH2CHBrCOOH
.188 Cl CH2CHBrCOOH
.189 H CH2CHBrCOOCH3
.190 F CH2CHBrCOOCH3
.191 Cl CH2CHBrCOOCH3
.192 H CH2CH(CH3)COOH
.193 F CH2CH(CH3)COOH
.194 F CH2CH(CH3)COOH
.195 H CH2CH(CH3)COOCH2CH3
.196 F CH2CH(CH3)COOCH2CH3
.197 Cl CH2CH(CH3)COOCH2CH3
.198 F CH2SCH3
.199 Cl CH2SCH3
.200 H CH2S(O)CH3
.201 F CH2S(O)CH3
.202 Cl CH2S(O)CH3
.203 H CH2S(O)2CH3
.204 F CH2S(O)2CH3
.205 Cl CH2S(O)2CH3
.206 F CH2SCH2CH3
Comp. no. Rn l3
.267 H CHCHCOOCH2CHCH2
.268 F CHCHCOOCH2CHCH2
.269 Cl CHCHCOOCH2CHCH2
.270 F CHCHCOOCH2CCH
.271 F CHCHCOOCH2C6H5
.272 F CHCHCOOC(CH3)3
.273 H CHC(CI)COOH
.274 F CHC(CI)COOH
.275 Cl CHC(CI)COOH
.276 H CHC(CI)COOCH2CH3
.277 F CHC(CI)COOCH2CH3
.278 Cl CHC(CI)COOCH2CH3
.279 F CHC(CI)COOCH2CHCH2
.280 F CHC(F)COOH
.281 F CHC(Br)COOH
.282 F CHC(CN)COOH
.283 H CCH
.284 F CCH
.285 Cl CCH
.286 H CCCH2OH
.287 F CCCH2OH
.288 Cl CCCH2OH
.289 H CCC(CH3)2OH
.290 F CCC(CH3)2OH
.291 Cl CCC(CH3)2OH
.292 H SH
.293 F SH
.294 Cl SH
.295 H SC(O)CH3
.296 F SC(O)CH3
.297 Cl SC(O)CH3
.298 H SC(O)OCH3
.299 F SC(O)OCH3 Comp. no. R11 Rl3
.333 F SCH2COOCH2CH2CH2CH2CH3
.334 F SCH2COOCH(CH3)2
.335 H SCH(CH3)COOH
.336 F SCH(CH3)COOH
.337 Cl SCH(CH3)COOH
.338 H SCH(CH3)COOCH3
.339 F SCH(CH3)COOCH3
.340 Cl SCH(CH3)COOCH3
.341 H SO2NH2
.342 F SO2NH2
.343 Cl SO2NH2
.344 H SO2NH(CH3)
.345 F SO2NH(CH3)
.346 Cl SO2NH(CH3)
.347 H SO2N(CH3)2
.348 F SO2N(CH3)2
.349 Cl SO2N(CH3)2
.350 H SO2N(CH2CH3)2
.351 F SO2N(CH2CH3)2
.352 Cl SO2N(CH2CH3)2
.353 F SO2N(CH3)(CH2CHCH2)
.354 F SO2N(CH3)(CH2CHCH2)
.355 F S(O)2CH3
.356 F S(O)2CH2CH3
.357 Cl S(O)2CF3
.358 Cl S(O)2CH2CH3
.359 F S(O)2CH(CH3)2
.360 H OH
.361 Cl OH
.362 F OH
.363 H OCH3
.364 Cl OCH3
.365 F OCH3 o ro
©
Ov Ov α. w υ o.
Comp. no. Rn Rl3
.432 Cl OCH2OCH2CH3
.433 H OCH2SCH3
.434 F OCH2SCH3
.435 Cl OCH2SCH3
.436 H OCH2COOH
.437 F OCH2COOH
.438 Cl OCH2COOH
.439 H OCH2COOCH2CH3
.440 F OCH2COOCH2CH3
.441 Cl OCH2COOCH2CH3
.442 H OCH2COOCH2C6H5
.443 F OCH2COOCH2C6H5
.444 Cl OCH2COOCH2C6H5
.445 H OCH2CONHCH2CHCH2
.446 F OCH2CONHCH2CHCH2
.447 Cl OCH2CONHCH2CHCH2
.448 H OCH2CON(CH2CH3)2
.449 F OCH2CON(CH2CH3)2
.450 Cl OCH2CON(CH3)2
.451 H OCH2CN
.452 F OCH2CN
.453 Cl OCH2CN
.454 H CH2COSCH(CH3)2
.455 F CH2COSCH(CH3)2
.456 Cl CH2COSCH(CH3)2
.457 H OCH(CH3)COOH
.458 F OCH(CH3)COOH
.459 Cl OCH(CH3)COOH
.460 H OCH(CH3)COOCH2CH3
.461 F OCH(CH3)COOCH2CH3
.462 Cl OCH(CH3)COOCH2CH3
.463 H OCH(CH3)COOCH2CHCH2
.464 F OCH(CH3)COOCH2CHCH2
Comp. no. R11 Rl3
.523 F COOCH2CHCH2
.524 Cl COOCH2CHCH2
.525 H COOCH(CH3)2
.526 F COOCH(CH3)2
.527 Cl COOCH(CH3)2
.528 F COOCH(CH3)(CH2CH3)
.529 F COOCH2CCH
.530 F COOCH2(2-F-C6H4)
.531 Cl COOCH2(4-CH3-C6H4)
.532 F COOCH2(4-CI-C6H4)
.533 F COOCH(CH3)CHCH2
.534 Cl COOCH(CH3)CHCH2
.535 F COOCH(CH3)CCH
.536 F COOCH(CH3)2CCH
.537 F COOCH2CH2OCH3
.538 Cl COOCH2CH2OCH3
.539 F COOCH2CH2OCH2CHCH2
.540 F COSCH3
.541 Cl COSCH3
.542 F COSCH2CH3
.543 H COSCH(CH3)2
.544 F COSCH(CH3)2
.545 Cl COSCH(CH3)2
.546 F COSCH2CHCH2
.547 H COSCH2C6H5
.548 F COSCH2C6H5
.549 Cl COSCH2C6H5
.550 F CONHCH2CH3
.551 H CON(CH3)2
.552 F CON(CH2CH3)2
.553 Cl CON(CH3)(CH2CCHCH2)
.554 F CON(CH3)(CH2C6H5)
.555 Cl CON(CH3)(CH2C6H5) Comp. no. Rn Rl3
.556 F CON(CH2C6H5)2
.557 H COOCH2COOH
.558 F COOCH2COOH
.559 Cl COOCH2COOH
.560 H COOCH2COOCH3
.561 F COOCH2COOCH3
.562 Cl COOCH2COOCH3
.563 H COOCH2COOCH2CHCH2
.564 F COOCH2COOCH2CHCH2
.565 Cl COOCH2COOCH2CHCH2
.566 H COOCH2CH2COOH
.567 F COOCH2CH2COOH
.568 Cl COOCH2CH2COOH
.569 H COOCH(CH3)COOH
.570 F COOCH(CH3)COOH
.571 Cl COOCH(CH3)COOH
.572 H COOCH(CH3)COOCH2CH3
.573 F COOCH(CH3)COOCH2CH3
.574 Cl COOCH(CH3)COOCH2CH3
.575 H COOCH(CH3)COO(CH2)3CH3
.576 F COOCH(CH3)COO(CH2)4CH3
.577 Cl COOCH(CH3)COO(CH2)5CH3
.578 H COOCH(CH3)COOCH2CHCH2
.579 F COOCH(CH3)COOCH2CHCH2
.580 Cl COOCH(CH3)COOCH2CHCH2
.581 H COOCH(CH3)COOCH2C6H5
.582 F COOCH(CH3)COOCH2C6H5
.583 Cl COOCH(CH3)COOCH2C6H5
.584 H COOCH(CH3)CONHCH2CHCH2
.585 F COOCH(CH3)CONHCH2CHCH2
.586 Cl COOCH(CH3)CONHCH2CHCH2
.587 H COOCH(CH3)CON(CH2CH3)2
.588 F COOCH(CH3)CON(CH2CH3)2 Comp. no. Ri, Rl3
.589 Cl COOCH(CH3)CON(CH2CH3)2
.590 F COOCH(CH3)CONH2
.591 H COOCH(CH3)COSCH3
.592 F COOCH(CH3)COSCH2CH3
.593 Cl COOCH(CH3)COSCH2CH3
.594 H COOCH(CH3)COSCH2CH3
.595 F COOCH(CH3)COSCH(CH3)2
.596 Cl COOCH(CH3)COSCH2CHCH2
.597 H COOCH(C6H5)COOH
.598 F COOCH(C6H5)COOH
.599 Cl COOCH(C6H5)COOH
.600 H COOCH(C6H5)COOCH3
.601 F COOCH(C6H5)COOH2CH3
.602 Cl COOCH(C6H5)COOH(CH3)2
.603 F COOCH(C6H5)COOCH2CHCH2
.604 F COOCH(C6H5)COOCH2CCH
.605 H COOCH(C6H5)COOCH2C6H5
.606 F COOCH(C6H5)COUCH2C6H5
.607 Cl COOCH(C6H5)CONHCH2C6H5
.608 F COOCH(C6Hs)CONHCH2CHCH2
.609 F COOCH(C6H5)CONHCH2CCH
.610 Cl COOCH(C6H5)CONHCH2CCH
.611 F COOCH(C6H5)CONH2
.612 H COOCH(C6H5)CON(CH3)2
.613 F COOCH(C6H5)CON(CH2CH3)2
.614 Cl COOCH(C6H5)CON(CH2CHCH2)2
.615 H COOCH(C6H5)COSCH3
.616 F COOCH(C6H5)COSCH2CH3
.617 Cl COOCH(C6H5)COSCH(CH3)2
.618 H COOC(CH3)2COOH
.619 F COOC(CH3)2COOH
.620 Cl COOC(CH3)2COOH
.621 H COOC(CH3)2COOCH3 Comp. no. Rn Rl3
.622 F COOC(CH3)2COOCH3
.623 Cl COOC(CH3)2COOCH3
.624 H COOC(CH3)2COOCH2CH3
.625 F COOC(CH3)2COOCH2CH2CH3
.626 Cl COOC(CH3)2COOCH(CH3)2
.627 F COOC(CH3)2COOCH2CH2OCH3
.628 F COOC(CH3)2COOCH2CH2OCH2CH3
.629 Cl COOC(CH3)2COOCH2CH2OCH2CH3
.630 H COOC(CH3)2COOCH2CHCH2
.631 F COOC(CH3)2COOCH2CHCH2
.632 Cl COOC(CH3)2COOCH2CHCH2
COOC(CH3)2COOCH(CH3)CHCH2
COOC(CH3)2COOCH2CCH
COOC(CH3)2COOCH(CH3)CCH
COOC(CH3)2COOCH2C6H5
COOC(CH3)2COOCH2C6H5
COOC(CH3)2COOCH2C6H5
COOC(CH3)2COOCH2(2-F-C6H4)
COOC(CH3)2COOCH2(3-CH3-C6H4)
COOC(CH3)2COOCH2(3,5-di-CI-C6H3)
COOC(CH3)2CONHCH2(2-F-C6H4)
COOC(CH3)2CONHCH2(C6H5)
COOC(CH3)2CONHCH2(C6H5)
COOC(CH3)2CONHCH2(C6H5)
COOC(CH3)2CONHCH2CHCH2
COOC(CH3)2CONHCH2CHCH2
COOC(CH3)2CONHCH2CHCH2
COOC(CH3)2CONHCH2CCH
COOC(CH3)2CONHCH2CCH
COOC(CH3)2CONH2
COOC(CH3)2CON(CH2CHCH2)2
COOC(CH3)2CON(CH3)2
COOC(CH3)2CON(CH2CH3)2 Comp. no. R11 H3
.655 F COOC(CH3)2COSCH2(2-F-C6H4)
.656 H COOC(CH3)2COSCH2(C6H5)
.657 F COOC(CH3)2COSCH2(C6H5)
.658 Cl COOC(CH3)2COSCH2(C6Hs)
.659 F COOC(CH3)2COSCH3
.660 F COOC(CH3)2COSCH2CHCH2
.661 F COOC(CH3)2COSCH(CH3)2
.662 Cl COOC(CH3)2COSCH2CH3
.663 H COOCH(CH3)CH2COOH
.664 F COOCH(CH3)CH2COOH
.665 Cl COOCH(CH3)CH2COOH
.666 H COOCH(CH3)CH2COOCH2CH3
.667 F COOCH(CH3)CH2COOCH2CH3
.668 Cl COOCH(CH3)CH2COOCH2CH3
.669 H COOCH(CH3)CH2COOCH2(C6H5)
.670 F COOCH(CH3)CH2COOCH2(C6H5)
.671 Cl COOCH(CH3)CH2COOCH2(C6H5)
.672 F COOCH(CH3)CH2COO(CH2)3CH3
.673 F COOCH(CH3)CH2COO(CH2)4CH3
.674 F COOCH(CH3)CH2COOCH(CH2)2
.675 Cl COOCH(CH3)CH2COOCH(CH2)2
.676 Cl COOCH(CH3)CH2CONHCH(CH2)2
.677 F COOCH(CH3)CH2CONHCH3
.678 H COOCH(CH3)CH2CON(CH3)2
.679 F COOCH(CH3)CH2CON(CH2CH3)2
.680 Cl COOCH(CH3)CH2CON(CH2CH2CH3)2
.681 Cl COOCH(CH3)CH2CONHCH2CHCH2
.682 F COOCH(CH3)CH2CONHCH(CH3)CH2CH2
.683 F COOCH(CH3)CH2CONHCH2CCH
.684 H COOCH(CH3)CH2COSCH3
.685 F COOCH(CH3)CH2COSCH3
.686 Cl COOCH(CH3)CH2COSCH3
.687 H COOCH(CH3)CH2COSCH2CH3 Comp. no. Rn R 13
.688 F COOCH(CH3)CH2COSCH(CH)2
.689 Cl COOCH(CH3)CH2COSCH2C6H5
.690 H COOCH(CH2CH3)CH2COOH
.691 F COOCH(CH2CH3)CH2COOH
.692 Cl COOCH(CH2CH3)CH2COOH
.693 H COOCH(CH2CH3)CH2COOCH2CH3
.694 F COOCH(CH2CH3)CH2COOCH2CH3
.695 Cl COOCH(CH2CH3)CH2COO(CH2)3CH3
.696 F COOCH(CH2CH3)CH2COOCH2CHCH2
.697 H COOCH(CH2CH3)CH2COOCH2C6H5
.698 F COOCH(CH2CH3)CH2COOCH2C6H5
.699 Cl COOCH(CH2CH3)CH2COOCH2C6H5
Table B: Physico-chemical data of compounds produced in the above-mentioned tables. The figure before the point indicates the number of the table, e.g. 36.002 means in Table 36 the compound no. 002 of Table A.
Examples of specific formulations for active ingredients of formula I, such as emulsion concentrates, solutions, wettable powders, coated granules, extruder granules, dusts and suspension concentrates, are described in WO 97/34485 on pages 9-13.
Biological Examples
Example B1 : Pre-emergence herbicidal action of the plants
Monocot and dicot test plants are sown in standard soil in plastic pots. Directly after sowing, the test substances are sprayed on in the form of an aqueous suspension or emulsion, prepared from a 25% emulsion concentrate [example F1 , c)] at a rate of 500 I water/ha, corresponding to a dosage of 2000 g active substance/ha. The test plants are then cultivated in the greenhouse under optimum conditions. After a test period of 3 weeks, the test is evalated on a rating scale of 1-9 (1 = total damage, 9 = no action). Ratings of 1 to 4
(especially 1 to 3) denote good to very good herbicidal action.
Test plants: Setaria, Solanum.
The compounds according to the invention show good herbicidal action in this test.
Table B1 shows an example of the good herbicidal activity of the compounds of formula I.
Table B1 : Pre-emerαence action:
Test plant: Setaria Solanum dosage [g AS/ha]
Comp.no.
3.002 1 2 2000 Equally good results are obtained if the compounds of formula I are formulated according to examples F2 to F8 as described for example in WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocot and dicot test plants are raised in standard soil in plastic pots in the greenhouse, and sprayed at the 4- to 6-leaf stage with an aqueous suspension or emulsion of the test substances of formula I, prepared from a 25% emulsion concentrate [example F1 , c)] at a rate of 500 I water/ha, corresponding to a dosage of 2000 g active substance/ha. The test plants are then further cultivated in the greenhouse under optimum conditions. After a test period of ca. 18 days, the test is evalated on a rating scale of 1-9 (1 = total damage, 9 = no action). Ratings of 1 to 4 (especially 1 to 3) denote good to very good herbicidal action.
Test plants: Setaria, Sinapsis, Solanum, Ipomea.
The compounds of formula I show good herbicidal action in this test.
Table B2 shows an example of the good herbicidal activity of the compounds of formula I.
Tabelle B2: Post-emergence action:
Test plant: Setaria Sinapis Solanum Ipomea dosage [g AS/ha]
Comp.no.
1.002 3 4 3 1 2000
3.002 6 7 5 4 2000
22.002 5 5 4 3 2000
25.002 5 7 5 4 2000
Equally good results are obtained if the compounds of formula I are formulated according to examples F2 to F8 as described for example in WO 97/34485.
The active ingredients of formula I according to the invention may also be used in a mixture with known herbicides as co-herbicides for controlling weeds, for example as ready-to-use formulations or as a "tank mix". The following co-herbicides may be considered for example as components for mixing with the active ingredients 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 + Aminotriazol; compound of formula I + Amidosulfuron; compound of formula I + Asulam; compound of formula I + Atrazin; 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 + Bromophenoxim; 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 + Cyanazin; 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 + Fluazasulfuron; compound of formula I + Fluazifop; compound of formula I + Flumetralin; compound of formula I + Flumetsulam; compound of formula I + Fluometuron; compound of formula I + Flurchloridone; 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 + loxynil; compound of formula I + Isoproturon; compound of formula I + Isoxaben; compound of formula I + Isoxaflutole; compound of formula I + Karbutylate; 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 + Phenoxaprop-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 + Sequestren; compound of formula I + Sethoxydim; compound of formula I + Simetryn; compound of formula I + Simazin; 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 + Terbuthylazin; 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, as well as esters and salts of these components of the mixture with the compound of formula I, which are named for example in The Pesticide Manual, Eleventh Edition, 1997, BCPC.

Claims

What we claim is:
Compounds of formula
wherein
A is =N- or =N-0 ;
n13 is 1 , 2 or 3;
W is a group
R, is C C4-alkyl, d-C^halogenalkyl, C2-C4-alkenyl, C2-C4-halogenalkenyl, C3-C6-cycloalkyl, amino, NHR8or NR8R9;
R8 and R9, independently of one another, are C╬╣-C4-alkyl; or
R8 and R9 together form a C2-C5-alkylene bridge;
R2 signifies hydrogen, C1-C4-alkyl, C^C^halogenalkyl, C3-C6-alkenyl, C3-C6-halogenalkenyl,
CrC╬▓-alkynyl, C╬╣-C4-alkylsulphonyl, CrC4-halogenalkylsulphonyl, C2-C4-alkenylsulphonyl or
C2-C4-halogenalkenylsulphonyl;
R3 is hydrogen, C╬╣-C -alkyl, C C4-halogenalkyl, C C4-hydroxyalkyl, C2-C6-alkenyl, C2-C6- halogenalkenyl, C2-C6-alkynyl, halogen, cyano, NH2C(S)-, nitro, OHC- or R╬╣8R19N- ; R18 and R╬╣9, independently of one another, are hydrogen, C╬╣-C4-alkyl, d-C -haiogenalkyl,
C3-C4-alkenyl, C3-C4-halogenalkenyl, C3-C6-cycloalkyl, C3-C6-alkynyl, d-C6-alkylcarbonyl,
CrCe-halogenalkylcarbonyl, C2-C6alkenylcarbonyl, C2-C6-halogenalkenylcarbonyl, C C6- alkylsulphonyl or Ci-Ce-halogenalkylsulphonyl;
R4 signifies hydrogen, d-C -alkyl, C╬╣-C4-halogenalkyl, C3-C6-alkenyl, C3-C6-halogenalkenyl,
C3-C6-alkynyl or C3-C6-cycloalkyl;
R5 signifies hydrogen, halogen, d-C4-alkyl, d-d-halogenalkyl, cyano, nitro, amino,
NH2C(S)-, d-C4-alkylcarbonyl, d-C4-halogenalkylcarbonyl, C2-C4-alkenylcarbonyl, C2-C4- halogenalkenylcarbonyl or C2-C4-alkynylcarbonyl;
Rn signifies hydrogen, fluorine, chlorine, bromine or methyl;
R13 is hydrogen, halogen, cyano, CIS(O)2-, CIC(O)-, Nitro, Amino, N ji, , HS-,
R20NH- or R20R2╬╣N- ;
R20 and R21, independently of one another, are C C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3- C╬▓-cycloalkyl, d-C8-halogenalkyl, C3-C8-halogenalkenyl, C -C4-alkylcarbonyl, C╬╣-C4- halogenalkylcarbonyl, C╬╣-C8-alkylsulphonyl, C C8-halogenalkylsulphonyl, C2-C8- alkenylsulphonyl, C2-C8-halogenalkenylsulphonyl, benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-C4-alkyl or C C4-halogenalkyl; or
R30 is hydrogen, d-C8-alkyl, C╬╣-C8-alkyl-ethylene oxide, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6- cycloalkyl, C╬╣-C8-halogenalkyl, C3-C8-halogenalkenyl, d-C4-alkoxy-C╬╣-C4-alkyl, C3-C6- alkenyloxy-C,-C4-alkyl, C3-C6-alkynyloxy-C1-C4-alkyl, C╬╣-C4-alkoxy-C╬╣-C4-alkoxy-d-C4-alkyl, C╬╣-C4-alkylthio-d-C4-alkyl, C╬╣-C8-alkoxycarbonyl, C3-C8-alkenyloxycarbonyl, benzyloxycarbonyl, phenyl, benzyl, pyridyl, pyrimidinyl, pyrazinyl or pyridazinyl, whereby these aforementioned aromatic and heteroaromatic rings may be optionally mono- to trisubstituted by halogen, C╬╣-C4-alkyl or d-C4-halogenaikyl; or
R31X, C(O) - [C, -C8-alkylene]- R30 is R3╬╣X╬╣C(O)-d-C8-alkyl-, | , R3iCH(OH)-d-C8-alkyl,
(C6H5)
RaiCH CtOJd-C╬▓-alky -d-Cs-alkyl or RaiCH^C^^rCg-halogenalky -d-C╬▓-alkyl;
RΓÇö N ΓÇö X signifies oxygen, sulphur or ffi 1 ; or Xi signifies a single bond;
R31 signifies hydrogen, d-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, C╬╣-C8- halogenalkyl, C3-C8-halogenalkenyl, d-d-alkoxy-d-d-alkyl, Cs-d-alkenyloxy-d-d-alkyl, C╬╣-C -alkylthio-C╬╣-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d- C4-alkyl or C╬╣-C4-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, C╬╣-C -alkyl or d-d-halogenalkyl;
R32 is hydrogen, d-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl or C╬╣-C8- halogenalkyl; or n2 is 0, 1 or 2;
R33 is C╬╣-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8-halogenalkyl, C3-C8- halogenalkenyl, d-d-alkoxy-d-d-alkyl, C3-C6-alkenyloxy-C╬╣-C4-alkyl, d-C4-alkylthio-d- C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-C4-alkyl or Ci-d- halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or C╬╣-C4-halogenalkyl; and where n2 is 0, R33 additionally signifies hydrogen, d-C8-alkylcarbonyl or R34X2C(O)- ;
RΓÇö N- X2 is oxygen, sulphur or ΓÇó35 '
R34 is hydrogen, C C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, C╬╣-C8- halogenalkyl, C3-C8-halogenalkenyl, d-d-alkoxy-d-d-alkyl, d-d-alkenyloxy-d-d-alkyl, d-C4-alkylthio-C╬╣-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, C1- d-alkyi or C╬╣-C4-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, C╬╣-C -alkyl or d-d-halogenalkyl;
R35 signifies hydrogen, d-C8-alkyl or C3-C8-alkenyl; or
R36 is hydrogen, d-C8-alkyl, C2-C8-alkenyl, C3-C8-alkynyl or C3-C6-cycloalkyl;
R37 is hydrogen, d-C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C C8-halogenalkyl, C╬╣-C4- alkylcarbonyl, C C -halogenalkylcarbonyl, benzoyl or benzoyl which is mono- to trisubstituted on the phenyl ring by halogen, d-C4-alkyl or d-d-halogenalkyl; or
R13 is R 0C(O)-;
R 0 is hydrogen, fluorine, chlorine, d-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C6- cycloalkyl, C╬╣-C8-halogenalkyl, cyano-C╬╣-C -alkyl, C2-C8-halogenalkenyl, C╬╣-C4-alkoxy-d-C4- alkyl, C3-C6-alkenyloxy-d-C4-alkyl, C1-C -alkylthio-C1-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-d-alkyl or d-C -halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, C╬╣-C4-alkyl or Ci-d- halogenalkyl; or R13 is RsoXsCr )-;
X v3 ΓÇó is oxygen, su ilphur, R 5-71 N ╬╣ ΓÇö or R ffi=-o-N ╬╣ ΓÇö ;
Rso is hydrogen, CrC8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, d-C8- halogenalkyl, C3-C8-halogenalkenyl, cyano-d-C4-alkyl, CrC4-alkoxy-C╬╣-C4-alkyl, C3-C6- alkenyloxy-C╬╣-C -alkyl, (oxiranyl)-CH2-, oxetanyl-, Ci-d-alkylthio-d-d-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-C4-alkyl or Ci-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, C╬╣-C4-alkyl or Ci-d- halogenalkyl; phenyl-C2-C6-alkyl, C╬╣-C6-alkyl-CO-C╬╣-C4-alkyl,
C1-C6-alkyl-C(0)-[C1-C4-alkylene]- R53X4C(0)-[C1-C6-alkylene]-
| , RssXtCrC -d-C╬▓-alkyl, I or
(C '6«H"5»)' (C6H5)
R53X4C(O)-C3-C6-cycloalkyl; . . . R.τN — R« 0-N —
X4 is oxygen, sulphur, M ╬╣ or ╬║ ╬╣ ;
Rsa is hydrogen, C C8-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C3-C6-cycloalkyl, C C8- halogenalkyl, C3-C8-halogenalkenyl, cyano-C╬╣-C4-alkyl, C╬╣-C4-alkoxy-C╬╣-C4-alkyl, C3-C6- alkenyloxy-C╬╣-C4-alkyl, (oxiranyl)-CH2-, oxetanyl-, C╬╣-C4-alkylthio-C╬╣-C4-alkyl, phenyl, phenyl which is mono- to trisubstituted by halogen, d-C4-alkyl or Ci-d-halogenalkyl; benzyl or benzyl which is mono- to trisubstituted on the phenyl ring by halogen, d-d-alkyl or Ci-d- halogenalkyl; or phenyl-C2-C6-alkyl;
Rsι, R52. R«and R55 , independently of one another, are hydrogen, Cι-C8-alkyl, C3-C8- alkenyl, C3-C8-alkynyl, Cι-C8-halogenalkyl or benzyl; or
Ri3 is B╬╣-d-C8-alkyl, B╬╣-C2-C8-alkenyl, B C2-C8-alkynyl, B╬╣-C╬╣-C8-halogenalkyl, B╬╣-C2-C8- halogenalkenyl, B╬╣-C╬╣-C4-alkoxy-C╬╣-C4-alkyl, B╬╣-C╬╣-C4-alkylthio-CrC4-alkyl or B╬╣-C3-C6- cycloalkyl;
B, is hydrogen, cyano, hydroxy, ethylene oxide, C3-C6-cycloalkyl, C╬╣-C8-alkoxy, C3-C8- alkenyloxy, R6oXsC(O)-, C╬╣-C -alkylcarbonyl or d-d-halogenalkylcarbonyl ; X5 has the significance of X4; R╬▓o has the significance of R53; or R13 is B2-C(R70)=CH-; B2 is nitro, cyano or R7╬╣X6C(O)-;
R70 is cyano or R72X7C(O)-;
X6 and X7 have the significance of X4;
R71 and R72 have the significance of R^; and
U signifies C1- or C2-alkylene, -CH2-O-, -CH2-S-, oxygen or sulphur, as well as agrochemically acceptable salts and stereoisomers of these compounds of formula I.
2. Compounds of formula I according to claim 1 , whereby they correspond to formula la
wherein
Wa is a group
Ri, R2, R3. R4, R5. R11. R13. ni and U have the significances given in claim 1 ; and R12 is hydrogen, halogen, Ci-d-alkyl, C2-C -alkenyl, C2-C4-alkynyl, Ci-d-halogenalkyl, C2-d- halogenalkenyl, nitro, amino, CHO, d-C4-halogenalkoxy, cyano, C3-C6-cycloalkyl, phenoxy, phenoxy which is mono- to trisubstituted by halogen, C╬╣-C4-alkyl or d-d-halogenalkyl; benzyloxy or benzyloxy which is mono- to trisubstituted on the phenyl ring by halogen, Ci- d-alkyl or Ci-d-halogenalkyl.
3. Process for the preparation of compounds of formula I wherein A, Rn, R13. n╬╣3 and W have the significances indicated in claim 1 , whereby a compound of formula II
wherein Rn, R13 and n╬╣3 have the significances indicated above, and W0 is a group
(Wo,), ( (WWo0e2))., (W03) or
o-t) ; R2 to R5, ni and U have the significances indicated in claim 1 , and
R10 signifies hydrogen or a protecting group, is either a) when Ri0 is hydrogen, reacted with a compound of formula III
R,S(O)2-L (III), wherein Ri has the significance indicated in claim 1 , and L is a leaving group, in an appropriate solvent and in the presence of a base, or b) when R10 is a protecting group, this is firstly cleaved and subsequently the resulting compound of formula II, wherein R10 signifies hydrogen, is reacted as described under a) with a compound of formula III.
4. Compounds of formula ll4
wherein A, Rn, R13, n╬╣3 and U have the significances indicated in claim 1 , and R10 signifies hydrogen, benzyl or benzyl which is substituted on the phenyl ring by halogen, Ci-d-alkyl or C╬╣-C4-alkoxy.
5. Compounds of formula Hi
wherein A, R2, R3, Rn, R╬╣3 and n 3 have the significances indicated in claim 1 , and R10 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C╬╣-C4-alkyl or C╬╣-C -alkoxy.
6. Compounds of formula ll2
wherein A, R3, R4, Rn, R13, ni and n 3 have the significances indicated in claim 1 , and R10 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, Ci-d-alkyl or C╬╣-C4-alkoxy.
Compounds of formula ll3
wherein A, R3, R5. Rn. R13 and n 3 have the significances indicated in claim 1 , and R10 signifies benzyl or benzyl which is substituted on the phenyl ring by halogen, C╬╣-C4-alkyl or d-d-alkoxy.
8. Herbicidal and plant-growth-inhibiting composition, which comprises a herbicidally active content of the compound of formula I and an inert carrier.
9. Herbicidal and plant-growth-inhibiting composition according to claim 8, containing at least one further co-herbicide as an additional component.
10. Process for controlling undesired plant growth, whereby an active ingredient of formula I, or a composition containing this active ingredient, is applied in a herbicidally active quantity to the crops of useful plants or to the locus thereof.
11. Usage of a composition according to claim 8 in the control of undesired plant growth.
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CN1301263A (en) 2001-06-27

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