EP1080088A1 - Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides - Google Patents

Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides

Info

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
Authority
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.)
Withdrawn
Application number
EP99952093A
Other languages
German (de)
English (en)
Inventor
Kurt Nebel
Alain De Mesmaeker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Novartis AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Novartis AG filed Critical Novartis AG
Publication of EP1080088A1 publication Critical patent/EP1080088A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne des composés correspondant à la formule (I) dans laquelle A représente =N- ou (a), n13 vaut 1, 2 ou 3, W représente un groupe (W1), (W2), (W3) ou (W4), R1 représente alkyle C1-C4, halogénalkyle C1-C4, alcényle C2-C4, halogénalcényle C2-C4, cycloalkyle C3-C6, amino, NHR8 ou NR8R9; R8 et R9 représentent indépendamment alkyle C1-C4, ou bien ils forment ensemble un pont alkylène C2-C5; R2 représente hydrogène, alkyle C1-C4, halogénalkyle C1-C4, alcényle C3-C6, halogénalcényle C3-C6, alcynyle C3-C6, alkylsulfonyle C1-C4, halogénalkylsulfonyle C1-C4, alcénylsulfonyle C2-C4 ou halogénalcénylsufonyle C2-C4; R3 représente hydrogène, alkyle C1-C4, halogénalkyle C1-C4, hydroxyalkyle C1-C4, alcényle C2-C6, halogénalkyle C2-C6, alcynyle C2-C6, halogène, cyano, NH2C(S)-, nitro, OHC- ou R18R19N-; R18 et R19 représentent chacun indépendamment hydrogène, alkyle C1-C4, halogénalkyle C1-C4, alcényle C3-C4, halogénalcényle C3-C4, cycloalkyle C3-C6, alcynyle C3-C6, alkylcarbonyle C1-C6, halogénalkylcarbonyle C1-C6, alcénylcarbonyle C2-C6, halogénalcénylcarbonyle C2-C6, alkylsulfonyle C1-C6 ou halogénalkylsulfonyle C1-C6; n vaut 0, 1 ou 2; R4 représente hydrogène, alkyle C1-C4, halogénalkyle C1-C4, alcényle C3-C6, halogénalcényle C3-C6, alcynyle C3-C6 ou cycloalkyle C3-C6; R5 représente hydrogène, halogène, alkyle C1-C4, halogénalkyle C1-C4, cyano, nitro, amino, NH2C(S)-, alkylcarbonyle C1-C4, halogénalkylcarbonyle C1-C4, alcénylcarbonyle C2-C4, halogénalkylcarbonyle C2-C4 ou alcynylcarbonyle C2-C4; U représente alkylène C1 ou C2, -CH2-O-, -CH2-S-, oxygène ou soufre; R11 représente hydrogène, fluor, chlore, brome ou méthyle; R13 possède les notations données dans la revendication 1. L'invention concerne également des sels et stéréo-isomères des composés de la formule (I), acceptables sur le plan agrochimique, lesquels ainsi que les composés possèdent des bonnes propriétés herbicides sélectives, de prélevée et postlevée. L'invention concerne en outre la préparation de ces composés de même que l'utilisation de ceux-ci en tant que principes actifs herbicides.
EP99952093A 1998-05-20 1999-05-18 Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides Withdrawn EP1080088A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH111198 1998-05-20
CH111198 1998-05-20
PCT/EP1999/003404 WO1999059990A1 (fr) 1998-05-20 1999-05-18 Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides

Publications (1)

Publication Number Publication Date
EP1080088A1 true EP1080088A1 (fr) 2001-03-07

Family

ID=4202756

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99952093A Withdrawn EP1080088A1 (fr) 1998-05-20 1999-05-18 Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides

Country Status (5)

Country Link
EP (1) EP1080088A1 (fr)
CN (1) CN1301263A (fr)
AU (1) AU4263799A (fr)
BR (1) BR9910536A (fr)
WO (1) WO1999059990A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6528456B2 (en) 1999-12-08 2003-03-04 Basf Aktiengesellschaft Herbicidal 2-pyrazolyl-6-aryloxypyri(mi)dines
EP1108720A1 (fr) * 1999-12-08 2001-06-20 Basf Aktiengesellschaft 2-Pyrazolyl-6-Aryloxy-Pyri(mi)dine herbicide
WO2003029243A2 (fr) * 2001-09-24 2003-04-10 Basf Aktiengesellschaft 2-aryloxy-6-pyrazolyl-pyridines
BR112021009434A2 (pt) * 2018-12-18 2021-08-17 Indorama Ventures Oxides Llc alcoxilato benzidrilado, método para preparação do alcoxilato benzidrilado, composição, produto embalado, composição de concentrado, formulação química de desempenho, formulação para cuidados pessoais, concentrado emulsificável agroquímico, concentrado de suspensão agroquímica, concentrado líquido solúvel em agroquímico, e, pó molhável agroquímico

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529891A1 (fr) * 1982-07-12 1984-01-13 Nativelle Sa Ets Derives du pyridyl-3 alcoxy-5 pyrazole, procede de preparation et application en therapeutique
DE3623302A1 (de) * 1985-11-09 1987-05-14 Bayer Ag Nicotinsaeurederivate
FR2707295A1 (fr) * 1993-06-07 1995-01-13 Rhone Poulenc Agrochimie Fongicides pyrazoles substitués en position 3 par un hétérocycle.
DE19530606A1 (de) * 1995-08-21 1997-02-27 Basf Ag 1-(Pyridyl)-pyrazole
AU7095496A (en) * 1995-09-26 1997-04-17 Nippon Soda Co., Ltd. Pyrazole compounds, process for preparing the same, and agrohorticultural bactericide
US6063732A (en) * 1996-03-15 2000-05-16 Novartis Crop Protection, Inc. Herbicidal synergistic composition and method of weed control
WO1997041112A1 (fr) * 1996-04-25 1997-11-06 Novartis Ag Sels de sulfonyluree en tant qu'herbicides
CA2266392A1 (fr) * 1996-09-19 1998-03-26 Basf Aktiengesellschaft 1-sulfonyl-3-phenylpyrazoles et leur utilisation comme herbicides et pour le dessechement ou la defoliation de vegetaux
KR20000053201A (ko) * 1996-11-12 2000-08-25 한스 루돌프 하우스, 헨리테 브룬너, 베아트리체 귄터 제초제로서 유용한 피라졸 유도체

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9959990A1 *

Also Published As

Publication number Publication date
BR9910536A (pt) 2001-01-16
WO1999059990A1 (fr) 1999-11-25
AU4263799A (en) 1999-12-06
CN1301263A (zh) 2001-06-27

Similar Documents

Publication Publication Date Title
US6204221B1 (en) Herbicides
WO2004035563A1 (fr) Derives de 3-heterocyclylpyridine utilises comme herbicides
WO2004035564A1 (fr) Derives de pyridine utiles comme herbicides
AU7650300A (en) Novel herbicides
PL200027B1 (pl) Kompozycja herbicydowa
AU738222B2 (en) N-pyridonyl herbicides
WO2005047233A1 (fr) Nouveaux herbicides
AU762586B2 (en) Herbicidal composition
KR20010005578A (ko) 제초제로서의 피라졸 유도체
US6369002B1 (en) N-heteroaryl-substituted pyridine derivatives and their use as herbicides
WO1997041106A1 (fr) Composes pyrazole, leurs procedes de production et herbicides les contenant
KR20080083641A (ko) 벤조일피라졸 화합물 및 그들을 함유하는 제초제
US6380134B1 (en) N-pyridyl herbicide compounds
EP0539676B1 (fr) Dérivés d'oxime des formylpyridylimidazolinones, leur usage herbicide et procédé pour leur préparation
WO2001030782A2 (fr) Nouveaux herbicides
DE3903799A1 (de) N-aryl-stickstoffheterocyclen
EP1080088A1 (fr) Derives pyridil-pyrazole, leur procede de preparation, et leur utilisation en tant qu'herbicides
CA2261125A1 (fr) Derives de pyrazolyle-pyrazol substitues, procede permettant de les preparer et utilisation comme agents a effet herbicide
WO1998006702A1 (fr) 1-(3-pyrazolyl)-pyrazoles substitues a action herbicide et produits intermediaires pour leur fabrication
WO2002024704A1 (fr) Nouveaux herbicides
WO2002024709A2 (fr) Nouveaux herbicides
MXPA98008894A (en) Pirazol compounds, procedures for your production and herbicides that contains them
KR20010042160A (ko) 티에닐알킬아미노-1,3,5-트리아진 및 제초제로서의 그의용도
JPH06340664A (ja) 置換トリアゾロピリジン誘導体、その製造法、その使用方法及びそれを含有する除草剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20001014

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): CH DE FR IT LI

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SYNGENTA PARTICIPATIONS AG

17Q First examination report despatched

Effective date: 20021113

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20030325