WO2000031066A1 - (thio)amides de l'acide n-pyrazolyl-phenoxynicotinique substitues, utilisables comme herbicides - Google Patents

(thio)amides de l'acide n-pyrazolyl-phenoxynicotinique substitues, utilisables comme herbicides Download PDF

Info

Publication number
WO2000031066A1
WO2000031066A1 PCT/EP1999/008659 EP9908659W WO0031066A1 WO 2000031066 A1 WO2000031066 A1 WO 2000031066A1 EP 9908659 W EP9908659 W EP 9908659W WO 0031066 A1 WO0031066 A1 WO 0031066A1
Authority
WO
WIPO (PCT)
Prior art keywords
cyano
fluorine
halogen
substituted
methyl
Prior art date
Application number
PCT/EP1999/008659
Other languages
German (de)
English (en)
Inventor
Karl-Heinz Linker
Klaus-Helmut Müller
Mark Wilhelm Drewes
Dieter Feucht
Rolf Pontzen
Ingo Wetcholowsky
Original Assignee
Bayer Aktiengesellschaft
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 Bayer Aktiengesellschaft filed Critical Bayer Aktiengesellschaft
Priority to AU13824/00A priority Critical patent/AU1382400A/en
Publication of WO2000031066A1 publication Critical patent/WO2000031066A1/fr

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
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—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 substituted N-pyrazolylphenoxynicotinklare- (thio) - amides. Process for their preparation and their use as herbicides.
  • N-phenylphenoxynicotamides e.g. the compound N- (2,4-difluorophenyl) -2- (3-trifluoromethylphenoxy) -3-pyridine-carboxamide (diflufenican) are already known as herbicidally active substances (cf. EP-A-53011; Pestic. Sci. 18 (1987), 15-28).
  • Substituted N-pyrazolyl-phenoxynicotinklare- (thio) amides are not yet known from the literature.
  • n stands for the numbers 0, 1 or 2
  • Q represents O (oxygen) or S (sulfur),
  • R 1 represents hydrogen or represents optionally substituted alkyl, alkenyl or alkynyl
  • R 2 represents hydrogen or optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl or phenyl
  • R 3 for hydroxyl, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, or for optionally substituted alkyl, alkoxy,
  • R 4 represents hydrogen, cyano, halogen, or optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl,
  • R 5 for cyano, halogen, SF 5 , or for optionally optionally substituted alkyl
  • R 6 represents hydrogen, cyano, halogen, or in each case optionally substituted alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, and
  • R 7 represents hydrogen, halogen or optionally substituted alkyl
  • hydrocarbon chains such as alkyl
  • the hydrocarbon chains are also straight-chain or branched, in each case in conjunction with heteroatoms, such as in alkoxy.
  • R 1 preferably represents hydrogen, alkyl with 1 to 6 carbon atoms optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy, or alkenyl or alkynyl each optionally substituted by cyano or halogen, each having 2 to 6 carbon atoms.
  • R 2 preferably represents hydrogen, alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy, each represents alkenyl or alkynyl which has 2 to 6 carbon atoms and is optionally substituted by cyano or halogen, and each optionally through cyano.
  • R 3 preferably stands for hydroxy, amino, nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, halogen, for alkyl, alkoxy, alkoxycarbonyl, alkylthio, which are each optionally substituted by cyano, halogen or C r C 4 alkoxy,
  • R 4 preferably represents hydrogen, cyano, halogen, or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms each optionally substituted by cyano, halogen or C 1 -C 4 -alkoxy.
  • R 3 preferably represents cyano, halogen, SF 5 , or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 4 carbon atoms each optionally substituted by cyano, halogen or C r C 4 alkoxy.
  • R 6 preferably represents hydrogen, cyano, halogen, or alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl, each having 1 to 4 carbon atoms, optionally substituted by cyano, halogen or C, -C 4 -alkoxy.
  • R 7 preferably represents hydrogen, halogen or optionally by cyano
  • R 1 particularly preferably represents hydrogen, in each case methyl, ethyl, n- or i-propyl, n- or i-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or in each case optionally by cyano, Fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl.
  • R 2 particularly preferably represents hydrogen, in each case methyl, ethyl, n- or i-propyl, n-, i- or s-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, each in each case optionally by cyano, fluorine , Chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl, each optionally substituted by cyano, fluorine, chlorine. Bromine, methyl, ethyl, n- or i-propyl substituted cyclopropyl, cyclobutyl. Cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutyimethyl, cyclopentylmethyl or
  • Cyclohexylmethyl or for optionally by nitro, cyano. Fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methoxy carbonyl, Ethoxycarbonyl, n- or i-propoxy-carbonyl substituted phenyl.
  • R 3 particularly preferably represents hydroxy, amino, nitro. Cyano, carboxy, carbamoyl, thiocarbamoyl, fluorine. Chlorine, bromine, for each methyl, ethyl, n- or i-propyl, n-, i- substituted by cyano, fluorine, chlorine, methoxy or ethoxy. s- or t-butyl, methoxy, ethoxy. n- or i-
  • R 4 particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy -
  • Methylthio Ethylthio, n- or i-propylthio.
  • R ⁇ particularly preferably represents cyano, fluorine. Chlorine, bromine, SF 5 , or for methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i-propoxy,, methylthio, ethylthio, each optionally substituted by cyano, fluorine, chlorine, bromine, methoxy or ethoxy , n- or i-Propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl.
  • R 6 particularly preferably represents hydrogen, cyano, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, methoxy, ethoxy, n- or i, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy - Propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfmyl, ethylsulfinyl, n- or i-propylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl.
  • R 7 particularly preferably represents hydrogen, fluorine, chlorine, bromine or optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy
  • R 1 very particularly preferably represents hydrogen.
  • R 2 very particularly preferably represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyanomethyl, cyanoethyl, cyanopropyl,
  • R 3 very particularly preferably represents nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyanomethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy , Methoxy carbonyl, ethoxycarbonyl or
  • R 4 very particularly preferably represents hydrogen or fluorine.
  • R 5 very particularly preferably represents cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl, difluoromethoxy or trifluoromethoxy.
  • R 6 very particularly preferably represents hydrogen or fluorine.
  • R 7 very particularly preferably represents hydrogen or methyl.
  • n the numbers 0, 1 or 2
  • R 1 represents hydrogen
  • R 2 represents hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl,
  • R 3 for nitro, cyano, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, cyanomethyl, trifluoromethyl, methoxy, ethoxy, difluoromethoxy, methoxycarbonyl, ethoxycarbonyl or cyclopropyl,
  • R 4 represents hydrogen or fluorine
  • R 5 for cyano, fluorine, chlorine, bromine, methyl, trifluoromethyl, difluoromethoxy or
  • R 6 represents hydrogen or fluorine
  • R 7 represents hydrogen or methyl.
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in the following table:
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • R 1 , R 4 , R ⁇ R 6 and R 7 have, for example, the meanings listed in Group 1.
  • R 1 , R 4 , R ', R 6 and R 7 have, for example, the meanings listed in Group 1.
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 8
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 10
  • R 1 . R 4 , R ⁇ R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 12
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 14
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 16
  • R 1 . R 4 , R ⁇ R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 18
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 20
  • R 1 , R ⁇ R ⁇ R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 22
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 24
  • R 1 , R 4 , R ⁇ R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 26
  • R 1 , R 4 , R ⁇ R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 28
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 30
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 32
  • R 1 , R 4 . R 3 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 . R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 34
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 36
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 38
  • R 1 , R 4 , R 3 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 42
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 48
  • R 1 , R 4 , R s , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 50
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 52
  • R 1 , R 4 , R 3 . R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 3 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 54
  • R 1 , R 4 , R 3 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 56
  • R 1 , R 4 , R 3 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 58
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, the meanings listed in Group 1.
  • Group 60
  • R 1 , R 4 , R 3 , R 6 and R 7 have, for example, those listed in Group 1
  • R 1 , R 4 , R 5 , R 6 and R 7 have, for example, those listed in Group 1
  • Residual definitions can be combined with one another, i.e. also between the specified preferred ranges.
  • the new substituted N-pyrazolylphenoxynicotinic acid (thio) amides of the general formula (I) have interesting biological properties. They are particularly characterized by their strong herbicidal activity.
  • R 1 , R 2 and R 3 have the meaning given above,
  • Y represents halogen, imidazolyl, alkoxy, aryloxy or aralkoxy
  • R 1 , R 2 , R 3 and R 7 have the meaning given above, and
  • R 4 , R 5 and R 6 have the meaning given above,
  • Formula (II) provides a general definition of the aminopyrazoles to be used as starting materials in process (a) according to the invention for the preparation of compounds of the general formula (I).
  • n, R 1 , R 2 and R 3 preferably have those meanings which are preferred, particularly preferred or very particularly preferred for n in connection with the description of the compounds of the general formula (I) according to the invention , R 1 , R 2 and R 3 have been specified.
  • the starting materials of the general formula (II) are known and / or can be prepared by processes known per se (cf. WO-A-94/08999, WO-A-9806702, J. Am. Chem. Soc. 81 (1959) , 2456-2464).
  • Formula (III) provides a general definition of the carboxylic acid derivatives to be used further as starting materials in process (a) according to the invention.
  • Q, R 4 , R 5 , R 6 and R 7 preferably have those meanings which are preferred, particularly preferred or very particular in connection with the description of the compounds of the general formula (I) according to the invention have preferably been given for Q, R 4 , R 5 , R 6 and R 7 ;
  • Y preferably represents fluorine, chlorine, bromine, imidazolyl, methoxy, ethoxy, phenoxy or benzyloxy, in particular chlorine.
  • the starting materials of the general formula (III) are known and / or can be prepared by processes known per se (cf. EP-A-53011, J. Med. Chem. 18
  • Formula (IV) provides a general definition of the N-pyrazolyl nicotinic acid amides to be used as starting materials in process (b) according to the invention for the preparation of compounds of the general formula (I).
  • process (b) according to the invention for the preparation of compounds of the general formula (I).
  • Formula (IV) n, R 1 , R 2 , R 3 and R 7 preferably have those meanings which have already been mentioned above in connection with the description of the compounds of the general formula (I) according to the invention as preferred, particularly preferred or very particularly preferred for n , R 1 , R 2 , R 3 and R 7 have been given;
  • X preferably represents fluorine, chlorine or bromine, in particular fluorine or chlorine.
  • aminopyrazoles of the general formula (II) - above - optionally in the presence of a reaction auxiliary, such as e.g. Triethylamine or potassium carbonate, optionally in the presence of a diluent, e.g. Acetone, acetonitrile or toluene, at temperatures between 0 ° C and 150 ° C.
  • a reaction auxiliary such as e.g. Triethylamine or potassium carbonate
  • a diluent e.g. Acetone, acetonitrile or toluene
  • Formula (V) provides a general definition of the phenols to be used as starting materials in process (b) according to the invention.
  • R 4 , R 5 and R 6 preferably have those meanings which are preferred, particularly preferred or very particularly preferred for R already in connection with the description of the compounds of the general formula (I) according to the invention 4 , R 5 and R 6 have been specified.
  • the starting materials of the general formula (V) are known synthetic chemicals.
  • Suitable diluents for carrying out processes (a) and (b) according to the invention are, in addition to water, above all inert organic solvents. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as, for example
  • Propanol ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, their mixtures with water or pure water.
  • Suitable reaction auxiliaries for processes (a) and (b) according to the invention are generally the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate,
  • DBU Diazabicyclo [5,4,0] -undec-7-ene
  • Phase transfer catalysts are also suitable as further reaction aids for processes (a) and (b) according to the invention.
  • Examples of such catalysts are: Tetrabutylammonium bromide. Tetrabutylammonium chloride, tetraoctylammonium chloride, tetrabutylammonium hydrogen sulfate, methyl trioctylammonium chloride, hexadecyl trimethylammonium chloride, hexadecyl trimethylammonium bromide, benzyl trimethylammonium chloride, benzyl triethylammonium benzyl triethylammonium Benzyl triethylammonium hydroxide, benzyl tributyl ammonium chloride, benzyl tributylammonium bromide, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tributyl hex
  • reaction temperatures can be varied within a substantial range when carrying out processes (a) and (b) according to the invention. In general, temperatures between 0 ° C and 150 ° C, preferably between 10 ° C and 120 ° C.
  • the processes according to the invention are generally carried out under normal pressure. However, it is also possible to carry out the processes according to the invention under elevated or reduced pressure - generally between 0.1 bar and 10 bar.
  • the starting materials are generally used in approximately equimolar amounts. However, it is also possible to use one of the components in a larger excess.
  • the reaction is generally carried out in a suitable diluent in the presence of a reaction auxiliary and the reaction mixture is generally stirred for several hours at the required temperature. Working up is carried out according to customary methods (cf. the production examples).
  • the active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are all plants that grow in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
  • the active compounds according to the invention can e.g. can be used in the following plants:
  • Pisum Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
  • Sorghum Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria. Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera, Aegilops, Phalaris.
  • the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants, in particular also to transgenic plants.
  • the active compounds according to the invention are suitable for combating total weeds, for example on industrial and rail tracks and on paths and squares with and without tree growth.
  • the active compounds according to the invention for combating weeds in permanent crops for example forest, ornamental wood, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm,
  • the compounds of formula (I) according to the invention show strong herbicidal activity and a broad spectrum of activity when used on the soil and on above-ground parts of plants. To a certain extent, they are also suitable for the selective control of monocotyledon and dicotyledon weeds in monocotyledon and dicotyledon crops, both in the pre-emergence and in the post-emergence process.
  • the active compounds can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active substance-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.
  • formulations are prepared in a known manner, e.g. B. by mixing the active ingredients with extenders, ie liquid solvents and / or solid carriers, optionally using surface-active agents, ie emulsifiers and / or dispersants and / or foam-generating agents.
  • water is used as an extender, e.g. also organic
  • Solvents are used as auxiliary solvents.
  • the following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons such as cyclohexane or paraffins, for example petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.
  • aromatics such as xylene, toluene, or alkylnaphthalenes
  • chlorinated aromatics and chlorinated aliphatic hydrocarbons such as Chlorobenzene
  • Possible solid carriers are: e.g. Ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam-generating agents are possible: e.g.
  • non-ionic and anionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates;
  • Possible dispersants are: e.g. Lignin sulfite liquor and methyl cellulose.
  • Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations.
  • Other additives can be mineral and vegetable oils.
  • Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.
  • the formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.
  • the active compounds according to the invention can also be used for combating weeds, in a mixture with known herbicides, finished formulations or tank mixes being possible.
  • Acetochlor Acifluorfen (-sodium), Aclonifen. Alachlor, Alloxydim (-sodium),
  • Chloridazon Chlorimuron (-ethyl), Chloronitrofen, Chlorsulfuron, Chlortoluron, Cinidon (-ethyl), Cinmethylin, Cinosulfuron, Clethodim, Clodinafop (-propargyl), Clomazone, Clomeprop, Clopyralid, Clopyrasulfuron (-mulam) ), Cumyluron, Cyanazines, Cybutryne, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP. Desmedipham, Diallate, Dicamba,
  • Diclofop (-methyl), Diclosulam, Diethatyl (-ethyl), Difenzoquat, Diflufenican, Difluefenzopyr, Dimefuron, Dimepiperate, Dimethachlor, Dimethametryn, Dimethenamid, Dimexyflam, Dinitramine, Diphenamid, Diquat, Epithonium, Dithiopyran EPTC, Esprocarb, Ethalfluralin, Ethametsulfuron (-methyl), Ethofumesate, Ethoxyfen, Ethoxysulfuron, Etobenzanid, Fenoxaprop (-P-ethyl), Flamprop (-isopropyl), Flamprop (-isopropyl-L), Flamprop (-methyl), Flazasulfuron, Fluazifop (-P-butyl), Fluazolate, Flucarbazone, Flufenacet, Flumetsulam, Flumiclorac (-
  • Metazachlor Metschizthiazuron, Metobenzuron, Metobromuron, (alpha-) Metolechlor, Metosulam, Metoxuron, Metribuzin, Metsulft ⁇ ron (-methyl), Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Orben- carburon, Norflurazon Oxadiargyl, oxadiazon, oxasulfuron, oxaziclomefone. Oxyfluorfen, paraquat, pelargonic acid, pendimethalin, pentoxazone, phenmedipham. Piperophos,
  • Pretilachlor Primisulfuron (-methyl), Prometryn, Propachlor, Propanil. Propaquizafop, Propisochlor, Propyzamide, Prosulfocarb, Prosulfuron, Pyraflufen (-ethyl), Pyrazolate, Pyrazosulfuron (-ethyl), Pyrazoxyfen, Pyribenzoxim, Pyributicarb, Pyridate, Pyriminobac (-methyl), Pyrithiobac (-sac), Quith Quinoclamine, Quizalofop (-P-ethyl), Quizalofop (-P-tefuryl), Rimsulfuron, Sethoxydim, Simazine, Simetryn, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Sulfosulfuron, Tebutam, Tebuthoxylazine, Teprutoxyl Terbutryn,
  • a mixture with other known active compounds such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.
  • the active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. They are used in the customary manner, for example by watering, spraying, spraying or scattering.
  • the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.
  • the amount of active ingredient used can vary over a wide range. It essentially depends on the type of effect desired. In general, the application rates are between 1 g and 10 kg of active ingredient per hectare of soil, preferably between 5 g and 5 kg per ha.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Seeds of the test plants are sown in normal soil. After about 24 hours, the soil is sprayed with the active ingredient preparation in such a way that the desired amount of active ingredient is applied per unit area.
  • the concentration of the spray liquor is chosen so that the desired amount of active ingredient is applied in 1000 liters of water per hectare.
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.
  • Test plants with a height of 5 - 15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area.
  • the concentration of the spray liquor is chosen so that in
  • the degree of damage to the plants is rated in% damage compared to the development of the untreated control.
  • the compounds according to Preparation Examples 1 and 17 show good tolerance to crop plants, such as Wheat, effective against weeds.

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 de nouveaux (thio)amides de l'acide N-pyrazolyl-phénoxynicotinique substitués, de formule générale (I), dans laquelle n représente 0, 1 ou 2; Q représente O (oxygène) ou S (soufre); R1 représente hydrogène ou alkyle, alcényle ou alkynyle éventuellement substitué; R2 représente hydrogène ou alkyle, alcényle, alkynyle, cycloalkyle, cycloalkylalkyle ou phényle éventuellement substitué; R3 représente hydroxy, amino, nitro, cyano, carboxy, carbamyle, thiocarbamyle, halogène, ou bien alkyle, alcoxy, alkoxycarbonyle, alkylthio, alkylsulfinyle, alkylsulfonyle, alkylamino, dialkylamino, alcényle, alkynyle, cycloalkyle, cycloalkylalkyle, aryle, arylalkyle, hétérocyclyle ou hétérocyclylalkyle éventuellement substitué, ou bien, dans le cas où n est 2 et que deux résidus R3 sont liés à deux atomes cycliques adjacents, représente avec un second résidu R3 alcanediyle (alkylène); R4 représente hydrogène, cyano, halogène, ou bien alkyle, alcoxy, alkylthio, alkylsulfinyle ou alkylsulfonyle éventuellement substitué; R5 représente cyano, halogène, SF¿5?, ou bien alkyle, alcoxy, alkylthio, alkylsulfinyle ou alkylsulfonyle éventuellement substitué; R?6¿ représente hydrogène, cyano, halogène, ou bien alkyle, alcoxy, alkylthio, alkylsulfinyle ou alkylsulfonyle éventuellement substitué; et R7 représente hydrogène, halogène ou alkyle éventuellement substitué. L'invention concerne également leur procédé de fabrication et leur utilisation comme herbicides.
PCT/EP1999/008659 1998-11-24 1999-11-11 (thio)amides de l'acide n-pyrazolyl-phenoxynicotinique substitues, utilisables comme herbicides WO2000031066A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU13824/00A AU1382400A (en) 1998-11-24 1999-11-11 Substituted n-pyrazolyl-phenoxynicotinic acid-(thio)amides that can be used as herbicides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19854081.7 1998-11-24
DE1998154081 DE19854081A1 (de) 1998-11-24 1998-11-24 Substituierte N-Pyrazolyl-phenoxynicotinsäure-(thio)amide

Publications (1)

Publication Number Publication Date
WO2000031066A1 true WO2000031066A1 (fr) 2000-06-02

Family

ID=7888774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/008659 WO2000031066A1 (fr) 1998-11-24 1999-11-11 (thio)amides de l'acide n-pyrazolyl-phenoxynicotinique substitues, utilisables comme herbicides

Country Status (3)

Country Link
AU (1) AU1382400A (fr)
DE (1) DE19854081A1 (fr)
WO (1) WO2000031066A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6335357B1 (en) 1997-04-07 2002-01-01 Mitsubishi Chemical Corporation Pyrazole derivatives, process for preparing the same, intermediates, and pest control agent containing the same as active ingredient
JP2004269515A (ja) * 2003-02-18 2004-09-30 Nippon Nohyaku Co Ltd 置換複素環アミド誘導体、その中間体及び農園芸用薬剤並びにその使用方法
WO2004098589A1 (fr) * 2003-05-02 2004-11-18 Elan Pharmaceuticals, Inc. Derives amides de l'acide carboxylique de 4- bromo - 5 - (2- chloro - benzoylamino) - 1h - pyrazole 3 et composes associes en tant qu'antagonistes de recepteur de b1 de la bradykinine pour le traitement de maladies inflammatoires
WO2013087577A1 (fr) 2011-12-13 2013-06-20 Bayer Intellectual Property Gmbh Amides d'acide arylcarboxylique n-(1,2,5-oxadiazol-3-yl)-, n-(1,3,4-oxadiazol-2-yl)-, n-(tetrazol-5-yl)- et n-(triazol-5-yl) et leur utilisation comme herbicides
WO2013124245A1 (fr) * 2012-02-21 2013-08-29 Bayer Intellectual Property Gmbh Amides d'acide n-(tétrazol-5-yl)arylcarboxylique, n-(triazol-5-yl)arylcarboxylique et n-(1,3,4-oxadiazol-2-yl)arylcarboxylique à substitution nitro en position 4 présentant une action herbicide
US20140066301A1 (en) * 2011-03-15 2014-03-06 Bayer Intellectual Property Gmbh N-(1,2,5-oxadiazol-3-yl)pyridinecarboxamides and use thereof as herbicides
JP2017512808A (ja) * 2014-04-02 2017-05-25 バイエル・クロップサイエンス・アクチェンゲゼルシャフト 置換されているピラゾリル−ニコチン（チオ）アミド誘導体及び殺菌剤としてのそれらの使用
RU2629952C2 (ru) * 2011-11-03 2017-09-05 Байер Интеллектуэль Проперти Гмбх 5-фенилзамещенные n-(тетразол-5-ил)- и n-(триазол-5-ил)-амиды арилкарбоновых кислот, а также их применение в качестве гербицидов

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB0317472D0 (en) * 2003-07-25 2003-08-27 Pfizer Ltd Nicotinamide derivatives useful as PDE4 inhibitors

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2198488A5 (en) * 1972-09-01 1974-03-29 Dynachim Sarl Amide derivs of phenyl-1-pyrazolones - by reaction of an acid halide on an aminopyrazolone
US4072680A (en) * 1977-04-28 1978-02-07 E. R. Squibb & Sons, Inc. Derivatives of pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine
EP0053011A1 (fr) * 1980-11-21 1982-06-02 May & Baker Limited Dérivés herbicides de nicotinamide
WO1993025535A1 (fr) * 1992-06-11 1993-12-23 Rhone Poulenc Agriculture Ltd. Pyrazole-(thio)-carboxamides herbicides

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2198488A5 (en) * 1972-09-01 1974-03-29 Dynachim Sarl Amide derivs of phenyl-1-pyrazolones - by reaction of an acid halide on an aminopyrazolone
US4072680A (en) * 1977-04-28 1978-02-07 E. R. Squibb & Sons, Inc. Derivatives of pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine
EP0053011A1 (fr) * 1980-11-21 1982-06-02 May & Baker Limited Dérivés herbicides de nicotinamide
WO1993025535A1 (fr) * 1992-06-11 1993-12-23 Rhone Poulenc Agriculture Ltd. Pyrazole-(thio)-carboxamides herbicides

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CECCHI, LUCIA ET AL: "Synthesis of 1,5-diaryl-3-methyl-1H-pyrazolo[4,5-c]isoquinolines and studies of binding to specific peripheral benzodiazepine binding sites", JOURNAL OF PHARMACEUTICAL SCIENCES, vol. 78, no. 6, 1989, Washington D.C.; ISSN 0022-3549, pages 437 - 442, XP000867420 *
CHEMICAL ABSTRACTS, vol. 64, no. 7, 1966, Columbus, Ohio, US; abstract no. 9706d, column 9706; XP002128784 *
J. KLOSA: "Synthesis of carboxylic acid amides from carboxylic acids and amines by means of polyphosphoric acid", JOURNAL FÜR FRAKTISCHE CHEMIE, vol. 31, no. 1-2, 1966, Leipzig; ISSN 0021-8383, pages 41 - 48 *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6335357B1 (en) 1997-04-07 2002-01-01 Mitsubishi Chemical Corporation Pyrazole derivatives, process for preparing the same, intermediates, and pest control agent containing the same as active ingredient
JP2004269515A (ja) * 2003-02-18 2004-09-30 Nippon Nohyaku Co Ltd 置換複素環アミド誘導体、その中間体及び農園芸用薬剤並びにその使用方法
WO2004098589A1 (fr) * 2003-05-02 2004-11-18 Elan Pharmaceuticals, Inc. Derives amides de l'acide carboxylique de 4- bromo - 5 - (2- chloro - benzoylamino) - 1h - pyrazole 3 et composes associes en tant qu'antagonistes de recepteur de b1 de la bradykinine pour le traitement de maladies inflammatoires
JP2006526015A (ja) * 2003-05-02 2006-11-16 エラン ファーマシューティカルズ，インコーポレイテッド 炎症疾患治療のためのブラジキニンｂ１受容体アンタゴニストとしての４−ブロモ−５−（２−クロロ−ベンゾイルアミノ）−１ｈ−ピラゾール−３−カルボン酸アミド誘導体および関連化合物
US7417152B2 (en) 2003-05-02 2008-08-26 Elan Pharmaceuticals, Inc. 4-bromo-5-(2-chloro-benzoylamino)-1H-pyrazole-3-carboxylic acid amide derivatives and related compounds as bradykinin B1 receptor antagonists for the treatment of inflammatory diseases
US7432379B2 (en) 2003-05-02 2008-10-07 Elan Pharmaceuticals, Inc. Substituted pyrazole derivatives and related compounds as bradykinin B1 receptor antagonists
US20140066301A1 (en) * 2011-03-15 2014-03-06 Bayer Intellectual Property Gmbh N-(1,2,5-oxadiazol-3-yl)pyridinecarboxamides and use thereof as herbicides
US9035064B2 (en) * 2011-03-15 2015-05-19 Bayer Intellectual Property Gmbh N-(1,2,5-oxadiazol-3-yl)pyridinecarboxamides and use thereof as herbicides
RU2629952C2 (ru) * 2011-11-03 2017-09-05 Байер Интеллектуэль Проперти Гмбх 5-фенилзамещенные n-(тетразол-5-ил)- и n-(триазол-5-ил)-амиды арилкарбоновых кислот, а также их применение в качестве гербицидов
WO2013087577A1 (fr) 2011-12-13 2013-06-20 Bayer Intellectual Property Gmbh Amides d'acide arylcarboxylique n-(1,2,5-oxadiazol-3-yl)-, n-(1,3,4-oxadiazol-2-yl)-, n-(tetrazol-5-yl)- et n-(triazol-5-yl) et leur utilisation comme herbicides
CN103987701A (zh) * 2011-12-13 2014-08-13 拜耳知识产权有限责任公司 N-(1,2,5-噁二唑-3-基)-、n-(1,3,4-噁二唑-2-基)-、n-(四唑-5-基)-和n-(三唑-5-基)-芳基甲酰胺及其作为除草剂的用途
JP2015505849A (ja) * 2011-12-13 2015-02-26 バイエル・インテレクチユアル・プロパテイー・ゲー・エム・ベー・ハー Ｎ−（１，２，５−オキサジアゾール−３−イル）−、ｎ−（１，３，４−オキサジアゾール−２−イル）−、ｎ−（テトラゾール−５−イル）−、およびｎ−（トリアゾール−５−イル）アリールカルボン酸アミド類ならびにそれらの除草剤としての使用
US9204650B2 (en) 2011-12-13 2015-12-08 Bayer Intellectual Property Gmbh N-(1,2,5-oxadiazol-3-yl)-, N-(1,3,4-oxadiazol-2-yl)-, N-(tetrazol-5-yl)-, and N-(triazol-5-yl) aryl carboxylic acid amides and use thereof as herbicides
RU2619102C1 (ru) * 2011-12-13 2017-05-12 Байер Интеллектуэль Проперти Гмбх Амиды n-(1,2,5-оксадиазол-3-ил)-, n-(1,3,4-оксадиазол-2-ил)-, n-(тетразол-5-ил)- и n-(триазол-5-ил)-арилкарбоновых кислот и их применение в качестве гербицидов
WO2013124245A1 (fr) * 2012-02-21 2013-08-29 Bayer Intellectual Property Gmbh Amides d'acide n-(tétrazol-5-yl)arylcarboxylique, n-(triazol-5-yl)arylcarboxylique et n-(1,3,4-oxadiazol-2-yl)arylcarboxylique à substitution nitro en position 4 présentant une action herbicide
CN104125948A (zh) * 2012-02-21 2014-10-29 拜耳知识产权有限责任公司 具有除草活性的4-硝基-取代的n-(四唑-5-基)芳基羧酸酰胺、n-(三唑-5-基)芳基羧酸酰胺以及n-(1,3,4-噁二唑-2-基)芳基羧酸酰胺
US9169219B2 (en) 2012-02-21 2015-10-27 Bayer Intellectual Property Gmbh Herbicidally active 4-nitro-substituted N-(tetrazol-5-yl)-, N-(triazol-5-yl)-, and N-(1,3,4-0XADIAZOL-2-yl)aryl carboxylic acid amides
JP2017512808A (ja) * 2014-04-02 2017-05-25 バイエル・クロップサイエンス・アクチェンゲゼルシャフト 置換されているピラゾリル−ニコチン（チオ）アミド誘導体及び殺菌剤としてのそれらの使用

Also Published As

Publication number Publication date
DE19854081A1 (de) 2000-05-25
AU1382400A (en) 2000-06-13

Similar Documents

Publication Publication Date Title
DE19918725A1 (de) Substituierte N-Cyano-sulfonsäureanilide
EP1095027B1 (fr) Phenyluracile substitue
WO2000031066A1 (fr) (thio)amides de l'acide n-pyrazolyl-phenoxynicotinique substitues, utilisables comme herbicides
EP0946544B1 (fr) Heterocyclyluraciles
WO2000012480A2 (fr) 3-aryle-pyrazoles substitues
EP1095028B1 (fr) Uraciles d'acylaminophenyle substituees
WO2000043375A2 (fr) Composes heterocycliques d'aryle substitues
EP1178985A1 (fr) Thienocycloalk(en)ylamino-1,3,5-triazines substituees
WO1999065869A1 (fr) N-aryl-o-alkyl-carbamates substitues
DE19946852A1 (de) Substituierte N-Phenyl-phenoxynicotinsäure-(thio)amide
EP0946543A1 (fr) Heterocyclyluraciles
EP0984945A1 (fr) Iminoalcoxy-phenyluraciles substitues, leur fabrication et leur utilisation comme herbicides
WO2001010853A1 (fr) 2-imino-thiazolines substituees
EP1204651B1 (fr) 5-chlorodifluoromethyl-1,3-4-thiadiazol-2yl-oxyacetanilides herbicides
EP1066267B1 (fr) Phenyluraciles substituees
WO2000034257A1 (fr) 2-imino-thiazolines substituees et leur utilisation comme herbicides
EP1178956A1 (fr) N-cyano-amidines substituees
WO1999007698A1 (fr) (hetero)aryloxypyrazoles utilises comme herbicides
WO1998032746A1 (fr) Phenyltriazoline(thi)ones substitues et leur utilisation comme herbicides
DE19746267A1 (de) Substituierte N-Aryl-O-aryloxyalkyl-carbamate
WO2000047579A1 (fr) Benzo-thiazolyl-alkylamino-1,3,5-triazines substituees utilisees comme herbicides
WO2000010971A1 (fr) N-aryl-o-alkylcarbamates substitues
WO2000015606A1 (fr) Ferbames n-aryl-o-alkyle substitue
EP1080077A1 (fr) 1,3-diaza-2-(thi)oxo-cycloalcanes substitues
WO2000042032A1 (fr) 2-imino-thiazolines substituees

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref country code: AU

Ref document number: 2000 13824

Kind code of ref document: A

Format of ref document f/p: F

AK Designated states

Kind code of ref document: A1

Designated state(s): AE AL AM AT AU AZ BA BB BG BR BY CA CH CN CR CU CZ DE DK DM EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SL SZ TZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

NENP Non-entry into the national phase

Ref country code: CA

122 Ep: pct application non-entry in european phase