WO1993017016A1 - Sulfonylurees utilisees comme herbicides - Google Patents

Sulfonylurees utilisees comme herbicides Download PDF

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Publication number
WO1993017016A1
WO1993017016A1 PCT/EP1993/000316 EP9300316W WO9317016A1 WO 1993017016 A1 WO1993017016 A1 WO 1993017016A1 EP 9300316 W EP9300316 W EP 9300316W WO 9317016 A1 WO9317016 A1 WO 9317016A1
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WIPO (PCT)
Prior art keywords
formula
hydrogen
alkyl
active ingredient
herbicide
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PCT/EP1993/000316
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English (en)
Inventor
Beat Jau
Rainer KÜHLMEYER
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Ciba-Geigy Ag
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Publication date
Application filed by Ciba-Geigy Ag filed Critical Ciba-Geigy Ag
Priority to BR9305922A priority Critical patent/BR9305922A/pt
Priority to EP93903941A priority patent/EP0626958A1/fr
Priority to JP5514493A priority patent/JPH07504173A/ja
Publication of WO1993017016A1 publication Critical patent/WO1993017016A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D521/00—Heterocyclic compounds containing unspecified hetero rings
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/36—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< directly attached to at least one heterocyclic ring; Thio analogues thereof

Definitions

  • the present invention relates to novel herbicidally active and plant-growth-regulating N-phenylsulfonyl-N'-pyrimidinyl- and N'-triazinylureas, to processes for their preparation, to compositions containing them as active ingredients, and to the use of these compositions for controlling weeds, especially selectively in crops of useful plants, or for regulating and inhibiting the growth of plants.
  • Urea compounds, triazine compounds and pyrimidine compounds which have herbicidal activity are generally known. Such compounds are described, for example, in European Patent Applications Nos. 0007 687, 0030 138, 0073 562 and 0 126711.
  • N-phenylsulfonyl-N'-pyrimidinyl- and N'-triazinylureas are those of the formula I , in which
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen, fluorine, chlorine, bromine, iodine, (W) n -R 8 , -NO 2 , -N(R 9 )R 10 ,
  • R 3 , R 4 , R 5 , R 6 and R 7 independently of one another are hydrogen or C 1 -C 4 alkyl;
  • R 8 is C 1 -C 4 alkyl, C 1 -C 4 alkyl which is substituted by 1, 2, 3 or 4 halogen atoms,
  • R 9 is hydrogen, methoxy, ethoxy or C 1 -C 4 alkyl
  • R 10 is hydrogen or C 1 -C 4 alkyl
  • R 11 is hydrogen, methyl or ethyl
  • R 12 is hydrogen or methyl
  • X is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, C 1 -C 4 haloalkyl, C 1 -C 4 haloalkylthio, C 1 -C 4 alkylthio, halogen, C 2 -C 5 alkoxyalkyl, C 2 -C 5 alkoxyalkoxy, amino, C 1 -C 3 alkylamino or di-( C 1 -C 3 alkyl)amino;
  • Y is C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy, Ci-Qhaloalkylthio, C 1 -C 4 alkylthio,
  • W is oxygen, sulfur, SO or SO 2 ;
  • n is the number 0 or 1;
  • Suitable for X as halogen are: fluorine, chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.
  • Suitable for R 3 , R 4 , R 5 , Rg, R 7 , R 8 , R 9 , R 10 , X and Y as C 1 -C 4 alkyl are: methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, iso-butyl or tert-butyl.
  • the alkyl groups preferably have 1-3 carbon atoms.
  • Suitable for R 8 as C 1 -C 4 alkyl which is substituted by one to four halogen atoms is, in particular, alkyl which is substituted by fluorine, chlorine, bromine or iodine.
  • Preferred amongst these halogen-substituted C 1 -C 4 alkyl groups are alkyl groups which are mono- to trisubstituted by halogen, in particular fluorine or chlorine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl,
  • Suitable for R 8 as C 1 -C 4 alkyl which is substituted by C 1 -C 3 alkylthio are, for example: methylthioethyl, ethylthioethyl, propylthioethyl, isopropylthiomethyl, preferably methylthiomethyl and ethylthioethyl.
  • Suitable for X as C 1 -C 4 haloalkyl is, in particular, alkyl which is substituted by fluorine, chlorine, bromine or iodine. Preferred amongst these radicals are alkyl groups which are mono- to trisubstituted by halogen, in particular fluorine or chlorine, for example fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl,
  • Suitable for X and Y as C 1 -C 4 alkoxy are, for example, methoxy, ethoxy, propyloxy, i-propyloxy, n-butyloxy, iso-butyloxy, sec-butyloxy and tert-butyloxy; preferably methoxy and ethoxy.
  • Suitable for X and Y as C 1 -C 4 haloalkoxy are, for example, difluoromethoxy,
  • Suitable for X and Y as C 2 -C 5 alkoxyalkyl and for R 8 as C 1 -C 3 alkoxy-C 1 -C 4 alkyl are, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl or propyloxymethyl.
  • Suitable for R 8 as C 2 -C 4 alkenyl is straight-chain or branched alkenyl, for example vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl; alkenyl radicals having a chain length of 2 to 3 carbon atoms are preferably suitable.
  • Suitable for R 8 as C 2 -C 4 alkenyl which is substituted by one to four halogen atoms is, for example: 3,3-difluorobut-2-en-1-yl.
  • Suitable for X and Y as C 1 -C 4 alkylthio are, for example: methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, iso-butylthio, sec-butylthio or tert-butylthio, preferably methylthio and ethylthio.
  • Suitable for X and Y as C 1 -C 4 haloalkylthio is, in particular, alkylthio which is substituted by fluorine, chlorine, bromine or iodine. Preferred amongst these are alkylthio groups which are mono- to trisubstituted by halogen, in particular fluorine or chlorine, for example fluoromethylthio, difluoromethylthio, trifluoromethylthio, chloromethylthio, dichloromethylthio or trichloromethylthio.
  • Suitable for Y as C 2 -C 5 alkylthioalkyl are, for example: methylthioethyl, ethylthioethyl, propylthioethyl or isopropylthiomethyl, preferably methylthiomethyl and ethylthioethyl.
  • Suitable forX and Y as C 2 -C 5 alkoxyalkoxy are, for example: methoxymethoxy, methoxyethoxy, methoxypropyloxy, ethoxymethoxy, ethoxyethoxy and
  • Suitable forX as C 1 -C 3 alkylamino are, for example, methylamino, ethylamino, n-propylamino or iso-propylamino.
  • Di(C 1 -C 3 al-kyl)amino as radical X is, for example, dimethylamino, methylethylamino, diethylamino or n-propylmethylamino.
  • the invention also embraces the salts which the compounds of the formula I can form with amines, alkali metal bases or alkaline earth metal bases or quaternary ammonium bases.
  • Preferred alkali metal hydroxides and alkaline earth metal hydroxides as salt-forming substances are lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide or calcium hydroxide, but in particular sodium hydroxide or potassium hydroxide.
  • amines which are suitable for salt formation are primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, n-propylamine, iso-propylamine, the four isomeric butylamine radicals, n-amylamine, iso-amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine,
  • primary, secondary and tertiary aliphatic and aromatic amines such as methylamine, ethylamine, n-propylamine, iso-propylamine, the four isomeric butylamine radicals, n-amylamine, iso-amylamine, hexylamine, hepty
  • methylisopropylamine methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine,
  • hexylheptylamine hexyloctylamine, 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-diethylethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine,
  • heterocyclic amines for example pyridine, quinoline, iso-quinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example anilines, methoxyanilines, ethoxyanilines, o,m,p-toluidines, phenylenediamines, benzidines, naphthylamines and o,m,p-chloroanilines; but in particular ethyl-, propyl-, diethyl- or triethylamine, but especially iso-propylamine and diethanolamine.
  • examples of quaternary ammonium bases are the cations of haloammonium salts, for example the tetramethylammonium cation, the trimethylbenzylammonium cation, the triethylbenzylammonium cation, the tetraethylammonium cation, the trimethylethylammonium cation, but also the ammonium cation.
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X and Y are as defined in formula I.
  • Other preferred compounds are those of the formula in
  • Particularly preferred compounds of the formulae I, II and III are those in which R 2 is hydrogen.
  • Particular preferred compounds of the formulae I, II and III are those in which R 3 is hydrogen.
  • Especially preferred compounds of the formulae I, II and III are those in which R 3 , R 4 , R 5 and R 6 are hydrogen.
  • Particularly important compounds of the formulae I, II and m are those in which R x is hydrogen, in particular those in which Ri and R 2 , R 1 and R 3 , R 1 , R 2 and R 3 or R 1 , R 2 , R 3 , R 4 , R 5 and R 6 are hydrogen.
  • R 1 and R 2 are hydrogen
  • R 3 , R 4 , R 5 , R 6 and R 7 independently of one another are hydrogen or methyl
  • X is methyl, methoxy, methylamino, dimethylamino, difluoromethoxy or chlorine
  • Y is methyl, methoxy, difluoromethoxy, ethoxy or cyclopropyl, with the proviso that a) at least one of the radicals R 3 , R 4 , R 5 , R 6 and R 7 is methyl,
  • the compounds of the formula I can be prepared either by
  • R 2 , R 3 , R 4 , R 5, R 6 and R 7 are as defined in formula I, with a pyrimidinyl carbamate or triazinyl carbamate of the formula V
  • R 1 , E, X and Y are as defined in formula I and R 13 is phenyl or phenyl which is substituted by C 1 -C 4 alkyl or halogen, in the presence of a base, or b) reacting a sulfonylcarbamate of the formula VI ,
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 arc as defined in formula I and R 13 is as defined in formula V, with an amine of the formula VII
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in formula I, with a pyrimidinyl isocyanate or triazinyl isocyanate of the formula VIII
  • R 2 , R 3 , R 4 , R 5 , R 6 and R 7 are as defined in formula I with a compound of the formula VII in the presence of an ammonium, phosphonium, sulfonium or alkali metal cyanate salt of the formula X
  • reaction which give compounds of the formula I are advantageously carried out in aprotic, inert organic solvents.
  • solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane,
  • reaction temperatures are preferably between -20° and +120°C.
  • the reactions are slightly exothermic and can be carried out at room temperature.
  • it is expedient to heat the reaction mixture briefly up to its boiling point The reaction times can also be shortened by adding a few drops of base as reaction catalyst Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine,
  • inorganic bases such as hydrides, such as sodium hydride or calcium hydride, hydroxides such as sodium hydroxide and potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate or hydrogen carbonates such as potassium hydrogen carbonate or sodium hydrogen carbonate, can also be used as bases.
  • the end products of the formula I can be isolated by concentration and/or evaporation of the solvent and purified by recrystallisation or trituration of the solid residue in solvents in which they are not freely soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • R 13 is preferably phenyl which can be substituted by C 1 -C 4 alkyl or halogen, especially preferably phenyl.
  • the phenylsulfonamides of the formula IV are novel compounds which were developed and prepared specifically for the preparation of the active ingredients of the formula I.
  • R 3 , R 4 , R 5 , R 6 and R 7 which have been mentioned above in the case of compounds of the formula I apply to the compounds of the formula IN. They can be prepared from the corresponding phenylsulfonyl chlorides of the formula IX
  • R 2 , R 3 , R 4 , R 5 , R 5 and R 7 are as defined in formula I, by reaction with ammonia. Such reactions are known and familiar to a person skilled in the art.
  • the phenylsulfonyl chlorides of the formula IX are novel compounds which were developed and prepared specifically for the preparation of the active ingredients of the formula I. They are therefore also part of the present invention.
  • the same preferred ranges for R 2 , R 3 , R 4 , R 5 , R 6 and R 7 which have been mentioned above in the case of the compounds of the formula I apply to the intermediates of the formula IX.
  • phenylsulfonyl chlorides of the formula IX are prepared by reacting the suitably substituted 2-chl ⁇ rosulfonylbenzoyl chlorides (see, for example, D.Davis, Soc. 2042, 2044 (1932)) with a compound of the formula XI
  • Phenylsulfonyl chlorides of the formula IX can also be prepared by reacting
  • the sulfonylcarbamates of the formula NI are novel and part of the present invention.
  • the preferred ranges for R 2 , R 3 , R 4 , R 5 , R 6 and R 7 which have been mentioned above in the case of the compounds of the formula I apply to the intermediates of the formula VI. They can be obtained, for example, by reacting the sulfonamides of the formula IV with diphenyl carbamate in the presence of a base. Such reactions are known and familiar to a person skilled in the art
  • the active ingredients of the formula I are applied successfully at application rates of 0.001 to 2 kg/ha, in particular 0.005 to 1 kg/ha.
  • the dosage rate required for the desired action can be determined by experiments. It depends on the type of action, the development stage of the crop plant and of the weed and on the application (location, time, method) and, due to these parameters, can vary within wide ranges.
  • the compounds of the formula I are distinguished by growth-inhibiting and herbicidal properties which make them outstandingly suitable for use in crops of useful plants, in particular in cereals, cotton, soya beans, oilseed rape, maize and rice, their use in soya bean crops and cereals being especially preferred. Weeds in soya bean crops are preferably controlled postemergence.
  • the compounds of the formula I are particularly distinguished by their good degradability. Surprisingly, it has emerged that the compounds of the formula I and further compounds of the formula I, wherein R 3 , R 4 , R 5 , R 6 and R 7 simultaneously are hydrogen, respond well to specific classes of safeners.
  • These safeners or antidotes are capable of protecting the crop plants against damage caused by the herbicide (for example in the case of an unintentional overdose). These antidotes are furthermore capable of preventing damage to crop plants when, in connection with crop rotation, herbicide-resistant crop plants are followed by other crop plants which have no, or only insufficient, resistance to the herbicides.
  • the present invention therefore also relates to a selective herbicidal
  • composition for controlling grasses and weeds in crops of useful plants which is composed of a herbicide of the formula I or a herbicide of the formula I, wherein R 3 , R 4 , R 5 , R 6 and R 7 simultaneously are hydrogen, and a safener (antagonist, antidote) which protects the crop plants, but not the weeds, against the phytotoxic action of the herbicide, and to the use of this composition, or of the combination of herbicide and safener, for weed control in crops of useful plants.
  • a herbicide of the formula I or a herbicide of the formula I, wherein R 3 , R 4 , R 5 , R 6 and R 7 simultaneously are hydrogen
  • a safener antagonist, antidote
  • the safeners used in the composition according to the invention belong to the classes of the quinolin-8-oxyacetic acid derivatives as they are disclosed, for example, in EP-A-0492366 and EP-A 0094 349, the diphenylcarboxylic acid derivatives as they are disclosed, for example, in EP-A-0268 554, and the sulfamoylphenylurea derivatives as they are disclosed, for example, in EP-A-0365 484.
  • the safeners of the formulae S1 to S5 are particularly preferred for use in the composition according to the invention:
  • compositions which comprise a safener of the formulae S1, S2, S3, S4 and S5 are those in which the herbicide of the formula I used is the compound of the formula 2.011 .
  • a safener or antidote can be used for pretreating the seed of the crop plant (seed dressing or treatment of the cuttings) or introduced into the soil before or after sowing.
  • it can be applied as pure active ingredient or together with the herbicide before or after emergence of the plants.
  • the plant or the seed can therefore be treated with the safener essentially independently of the point in time of application of the phytotoxic chemical.
  • the plant can be treated by simultaneous application of phytotoxic chemical and safener (tank mix).
  • Preemergence treatment includes treatment of the area under cultivation before sowing and treatment of the areas under cultivation where seed has been sown but the plants are yet to emerge.
  • the application rate of safener to be applied relative to the herbicide depends largely on the method of application.
  • field treatment which is effected either using a tank mix of a combination of safener and herbicide or by separate application of safener and herbicide, requires a ratio of safener to herbicide of 1:100 to 1:1, preferably 1:20 to 1: 1, in particular 1:1.
  • seed dressing requires much smaller amounts of safener relative to the application rate of herbicide per hectare of area under cultivation.
  • the application rates of herbicide are, as a rule, between 0.001 and 2 kg/ha, but preferably between 0.001 and 0.5 kg/ha.
  • safener/kg of seed 0.001 to 10 g of safener/kg of seed, preferably 0.05 to 2 g of safener/kg of seed, are applied in the case of seed dressing. If the safener is applied in liquid form for seed soaking briefly before sowing, it is expedient to use safener solutions which comprise the active ingredient at a concentration of from 1 to 10000, preferably from 100 to 1000, ppm.
  • the safeners, or combination of safeners, used according to the invention together with the herbicides to be antagonised are expediently employed together with the auxiliaries conventionally used in the art of formulation, which have already been mentioned above in connection with application of the compounds of the formula I.
  • the invention also relates to herbicidal and plant-growth-regulating compositions which comprise a novel active ingredient of the formula I, and to methods for inhibiting the growth of plants.
  • Plant growth regulators are substances which cause agronomically desirable biochemical and physiological and/or morphological modifications in/on the plant
  • the active ingredients comprised in the compositions according to the invention affect plant growth in many ways, depending on the point in time of application, the dosage rate, the type of application and the prevailing environment
  • plant growth regulators of the formula I can inhibit the vegetative growth of plants. This type of action is of interest on lawns, in the production of ornamentals, in fruit plantations, on verges, on sportsgrounds and industrial terrain, but also in the targeted inhibition of secondary shoots, such as in tobacco.
  • inhibition of the vegetative growth in cereals by strengthening the stems results in reduced lodging, and similar agronomic effects are achieved in oilseed rape, sunflowers, maize and other crop plants.
  • inhibition of the vegetative growth means that the number of plants per area can be increased.
  • Another field in which growth inhibitors can be applied is the selective control of ground-cover plants in plantations or crops with plenty of space between the rows, by powerful growth inhibition without destroying these cover crops, so that competition with the main crop is eliminated, but the agronomically positive effects such as prevention of erosion, nitrogen fixation and loosening of the soil, are retained.
  • a method for inhibiting plant growth is understood as meaning controlling the natural development of the plant without altering the life cycle of the plant which is determined by its genetic make-up, in the sense of a mutation.
  • the method of growth regulation is applied at a particular point in time of the development of the plant which is to be determined in the particular case.
  • the active ingredients of the formula I can be applied before or after emergence of the plants, for example already to the seeds or seedlings, to roots, tubers, stalks, leaves, flowers or other parts of the plant. This can be effected, for example, by applying the active ingredient, as pure active ingredient or in the form of a composition, to the plants and/or by treating the nutrient substrate of the plant (soil).
  • the dissolved active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and allowed to dry. If desired, a coating can be applied
  • the compounds of the formula I are employed in unaltered form, as obtained from synthesis, or, preferably, together with the auxiliaries conventionally used in the art of formulation, and they are therefore processed in a known manner to give, for example, emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules and also encapsulations, for example in polymeric substances.
  • the application methods such as spraying, atomising, dusting, wetting, scattering or pouring, as well as the type of the compositions are selected to suit the intended aims and the prevailing circumstances.
  • compositions, preparations or combinations comprising the active ingredient of the formula I and, if desired, one or more solid or liquid additives, are prepared in a known manner, for example by intimately mixing and/or grinding the active ingredients with extenders, for example solvents, solid carriers and, if desired,
  • surfactants are surface-active compounds (surfactants).
  • solvents aromatic hydrocarbons, in particular the fractions C 8 to C 12 , such as mixtures of alkylbenzenes, for example xylene mixtures or alkylated naphthalenes; aliphatic and cycloaliphatic hydrocarbons such as paraffins, cyclohexane or tetrahydronaphthalene; alcohols such as ethanol, propanol or butanol; glycols as well as their ethers and esters, such as propylene glycol or dipropylene glycol ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strongly polar, solvents such as N-methyl-2-pyr ⁇ olidone, dimethyl sulfoxide or water; vegetable oils and esters thereof, such as rapeseed oil, castor oil or soya oil; silicone oils may also be suitable.
  • aromatic hydrocarbons in particular the fractions C 8 to C 12 , such as mixtures of alkylbenzenes,
  • Solid carriers which are used, for example for dusts and dispersible powders are, as a rule, natural ground minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • natural ground minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly-disperse silica or highly-disperse absorptive polymers Possible particulate, adsorptive carriers for granules are either porous types, for example pumice, brick grit sepiolite or bentonite, or non-sorptive carrier materials, such as calcite or sand.
  • a large number of pregranulated materials of inorganic or organic nature can be used such as, in particular, dolomite or comminuted plant residues.
  • Suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties, depending on the nature of the active ingredient of the formula I to be formulated.
  • Surfactants are also to be understood as meaning mixtures of surfactants.
  • Anionic surfactants which are suitable can be either so-called water-soluble soaps or water-soluble synthetic surface-active compounds.
  • Suitable soaps which may be mentioned are the alkali metal salts, alkaline earth metal salts or substituted or unsubstituted ammomum salts of higher fatty acids (C 10 -C 22 ), such as, for example, the sodium salts or potassium salts of oleic or stearic acid, or of natural mixtures of fatty acids which can be obtained, for example, from coconut oil or tallow oil. Mention must also be made of the fatty acid methyltaurinates.
  • the fatty alcohol sulfonates or fatty alcohol sulfates are, as a rule, in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammomum salts, and have an alkyl radical having 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, for example the sodium salt or calcium salt of ligninsulfonic acid, of the dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids.
  • This group also includes the salts of the sulfuric esters and sulfonic acids of fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonyl groups and one fatty acid radical having 8-22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of
  • dodecylbenzenesulfonic acid of dibutylnaphthalenesulfonic acid, or of a
  • Suitable compounds are the corresponding phosphates, such as the salts of the phosphoric ester of p-nonylphenol/(4-14)-ethylene oxide adduct, or phospholipids.
  • Suitable non-ionic surfactants are mainly polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic)
  • hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols are hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
  • non-ionic surfactants which are suitable are the water-soluble polyethylene oxide adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and
  • alkylpolypropylene glycol which have 1 to 10 carbon atoms in the alkyl chain and which contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups.
  • the abovementioned compounds customarily contain 1 to 5 ethylene glycol units per propylene glycol unit
  • non-ionic surfactants examples include butyl-ionic surfactants
  • nonylphenolpolyethoxyethanols castor oilpolyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and
  • Suitable substances are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate.
  • the cationic surfactants are mainly quaternary ammonium salts which contain at least one alkyl radical having 8 to 22 carbon atoms as N substituents and which have lower halogenated or free alkyl, benzyl or lower hydroxyalkyl radicals as further substituents.
  • the salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldi(2-chloroethyl)ethylammonium bromide.
  • the preparations comprise 0.1 to 99 %, in particular 0.1 to 95 %, of active ingredient of the formula 1, 1 to 99 % of the solid or liquid additive and 0 to 25 %, in particular 0.1 to 25 %, of a surfactant
  • compositions are more preferred as commercial goods, the end user, as a rule, uses dilute compositions.
  • compositions can also comprise further additions such as stabilisers, for example epoxidised or unepoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for achieving specific effects.
  • stabilisers for example epoxidised or unepoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soya oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers as well as fertilisers or other active ingredients for achieving specific effects.
  • Emulsifiable concentrates are:
  • Active ingredient 1 to 20 %, preferably 5 to 10 %
  • Surface-active agent 5 to 30 %, preferably 10 to 20 %
  • Liquid carrier 15 to 94 %, preferably 70 to 85 %
  • Active ingredient 0.1 to 10 %, preferably 0.1 to 1 %
  • Solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • Active ingredient 5 to 75 %, preferably 10 to 50 %
  • Active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • Surface-active agent 0.5 to 20 %, preferably .1 to 15 %
  • Solid carrier 5 to 95 %, preferably 15 to 90 %
  • Active ingredient 0.5 to 30 %, preferably 3 to 15 %
  • Solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • Example H3 1.5 g of ammonia are passed for 1 hour at a temperature from 0 to 5°C into a methylene solution obtained as in Example H1. The mixture is filtered and then treated with ice-water, and the organic phase is separated off, washed with water and dried over MgSO 4 . After concentration in vacuo, 2.1 g of the crystalline title compound with a melting point of 113-115°C remain.
  • Example H3
  • the active ingredient is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. This gives wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • Kaolin _ 75.5 % Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • the active ingredient is mixed with the additives, and the mixmre is ground and moistened with water. This mixture is extruded and subsequently dried in a stream of air.
  • the kaolin which has been moistened with polyethylene glycol is coated uniformly with the finely-ground active ingredient Dust-free coated granules are obtained in this manner.
  • the finely ground active ingredient is mixed intimately with the additives. This gives a suspension concentrate from which suspensions of any desired concentration can be prepared by dilution rdth water.
  • Example B1 Herbicidal action before emergence of the plants
  • Plastic pots are filled with expanded vermiculite (density: 0.135 g/cm 3 , water adsorption capacity: 0.565 1/1).
  • the non-adsorptive vermiculite is saturated with an aqueous active ingredient emulsion in deionised water which comprises the active ingredients at a concentration of 70 ppm, and seeds of the following plants are then sown onto the surface: Nasturtium officinalis, Agrostis tenuis, Stellaria media and Digitaria sanguinalis.
  • the test containers are then kept in a controlled-environment cabinet at a temperature of 20°C, an illumination of approx. 20 kLux and a relative atmospheric humidity of 70 %.
  • the pots are covered with translucent material to increase the local atmospheric humidity and watered with deionised water. After day 5, 0.5 % of a commercially available liquid fertiliser is added to the irrigation water. 12 days after sowing, the test is evaluated and the effect on the test plants is assessed using the following key:
  • a number of monocotyledon and dicotyledon weeds were sprayed after emergence (in the 4- to 6-Ieaf stage) with an aqueous dispersion of active ingredient according to Example F6 at a dosage rate of 8-500 g of active ingredient per hectare, and the plants were kept at 24°-26°C and a relative atmospheric humidity of 45-60 %. The test is evaluated 15 days after the treatment.
  • Example B3 Post-emergence phytotoxic effects of herbicide No. 2.011 and of the mixtures herbicide with safeners of the formula S1 and S2 in cereals
  • Example B4 Post-emergence phytotoxic effects of herbicide No. 2.011 and of the mixtures herbicide with safeners of the formula S3 in maize
  • Maize is grown in plastic pots under greenhouse conditions up to the 2.5-leaf stage. At this stage, a herbicide of the formula I as pure active ingredient as well as a mixture of the herbicide with the safener of the formula S3 are applied to the test plants. Application is effected in the form of an aqueous suspension of the test substances using 5001 of water/ha. The application rates of the herbicide are 30/15/8 g/ha, the application rates of the safener 60 g/ha. 12 days after application, the test is evaluated using a percentage key. 100 % means that the test plant has died, 0 % means no phytotoxic effect The results demonstrate that the safener employed is capable of noticeably reducing the herbicide damage in maize. Examples of the good protective action of the safener are listed in Table B4.
  • Maize seed is dressed with the safener of the formula S4 at an equivalent of a dosage rate of 1 g/kg of seed.
  • the maize is subsequently grown in plastic pots under greenhouse conditions until it has reached the 2.5-leaf stage.
  • Untreated maize is grown parallel with treated maize up to the same stage.
  • the herbicide of the formula I is applied to treated and untreated test plants.
  • Application is effected in the form of an aqueous suspension of the herbicide at 5001 of water/ha.
  • the application rate of the herbicide is 30 or 15 g/ha
  • the application rate of the seed-dressing safener of the formula S4 is 1 g/kg of seed. 14 days after application, the test is evaluated using a percentage key. 100 % means that the test plant has died, 0 % means no phytotoxic effect.
  • the results are obtained by the test plant has died, 0 % means no phytotoxic effect.

Abstract

L'invention concerne des composés de la formule (I) dans laquelle E représente -CH= ou -N-, à condition que a) au moins un des radicaux R3, R4, R5, R6, et R7 soit un radical alkyle en C1-C4, b) E représente -CH= lorsque X est un halogène et c) E représente -CH= lorsque X et Y représentent -OCHF2 ou -SCHF2. La signification des autres substituants est donnée dans la description. L'invention concerne également l'utilisation de ces composés comme herbicides et pour contrôler ou inhiber la croissance des plantes.
PCT/EP1993/000316 1992-02-21 1993-02-09 Sulfonylurees utilisees comme herbicides WO1993017016A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
BR9305922A BR9305922A (pt) 1992-02-21 1993-02-09 Sulfoniluréias usadas como herbicidas
EP93903941A EP0626958A1 (fr) 1992-02-21 1993-02-09 Sulfonylurees utilisees comme herbicides
JP5514493A JPH07504173A (ja) 1992-02-21 1993-02-09 除草剤としてのスルホニル尿素

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH539/92-2 1992-02-21
CH53992 1992-02-21

Publications (1)

Publication Number Publication Date
WO1993017016A1 true WO1993017016A1 (fr) 1993-09-02

Family

ID=4189336

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000316 WO1993017016A1 (fr) 1992-02-21 1993-02-09 Sulfonylurees utilisees comme herbicides

Country Status (11)

Country Link
EP (1) EP0626958A1 (fr)
JP (1) JPH07504173A (fr)
AU (1) AU3496493A (fr)
BR (1) BR9305922A (fr)
CA (1) CA2128325A1 (fr)
IL (1) IL104799A0 (fr)
LT (1) LT3236B (fr)
LV (1) LV10440B (fr)
MX (1) MX9300892A (fr)
WO (1) WO1993017016A1 (fr)
ZA (1) ZA931176B (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0597807A1 (fr) * 1992-11-12 1994-05-18 Ciba-Geigy Ag Agent selectivement herbicide
EP0600836A2 (fr) * 1992-12-02 1994-06-08 Ciba-Geigy Ag Agent selectivement herbicide
WO1995008919A1 (fr) * 1993-09-30 1995-04-06 Hoechst Schering Agrevo Gmbh Nouveaux melanges d'herbicides et d'antidotes
EP0657100A2 (fr) * 1993-12-08 1995-06-14 Ciba-Geigy Ag Agent sélectivement herbicide
WO2000017194A1 (fr) * 1998-05-22 2000-03-30 Dow Agrosciences Llc Composes a base de 1-alkyl-4-[(3-oxetanyl-)benzoyl]-5-hydroxypyrazole et leur utilisation comme herbicides

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10218704B4 (de) * 2002-04-26 2006-11-30 Bayer Cropscience Gmbh Halosulfonylbenzoesäurehalogenide, Verfahren zu deren Herstellung und deren Verwendung zur Herstellung von substituierten Phenylsulfonylharnstoffen

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007687A1 (fr) * 1978-05-30 1980-02-06 E.I. Du Pont De Nemours And Company Sulfonamides, procédés pour leur préparation, compositions contenant ces sulfonamides et un procédé pour la régulation de la croissance des plantes
US4892946A (en) * 1979-11-30 1990-01-09 E. I. Du Pont De Nemours And Company Agricultural sulfonamides
EP0496701A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Sulfonylurées comme herbicides

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ZA806970B (en) 1979-11-30 1982-06-30 Du Pont Agricultural sulfonamides
AU550945B2 (en) 1981-07-10 1986-04-10 E.I. Du Pont De Nemours And Company Triazolyl-(imidazolyl)-sulphonyl-ureas
US4523944A (en) 1981-07-16 1985-06-18 Ciba-Geigy Corporation N-Phenylsulfonyl-N'-pyrimidinylureas
US4618363A (en) 1982-01-25 1986-10-21 Ciba-Geigy Corporation N-phenylsulfonyl-N'-triazinylureas
US4537618A (en) 1982-05-26 1985-08-27 Ciba Geigy Corporation N-phenylsulfonyl-N'-pyrimidinylureas
US4780125A (en) 1982-09-01 1988-10-25 Ciba-Geigy Corporation N-phenylsulfonyl-N'-triazinylureas
US4579583A (en) 1982-09-08 1986-04-01 Ciba-Geigy Corporation Novel sulfonylureas
ATE35888T1 (de) 1983-03-28 1988-08-15 Ciba Geigy Ag N-phenylsulfonyl-n'-pyrimidinyl- und triazinylharnstoffe.
EP0126711B1 (fr) 1983-05-16 1989-08-02 Ciba-Geigy Ag Dérivés de pyrimidine actifs comme herbicides et régulateurs de croissance des plantes, leur préparation et leur usage
US4678498A (en) 1985-06-12 1987-07-07 E. I. Du Pont De Nemours And Company Herbicidal sulfonamides
EP0540697B1 (fr) 1991-03-25 1998-06-03 Novartis AG Sulfonylurees

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0007687A1 (fr) * 1978-05-30 1980-02-06 E.I. Du Pont De Nemours And Company Sulfonamides, procédés pour leur préparation, compositions contenant ces sulfonamides et un procédé pour la régulation de la croissance des plantes
US4892946A (en) * 1979-11-30 1990-01-09 E. I. Du Pont De Nemours And Company Agricultural sulfonamides
EP0496701A1 (fr) * 1991-01-25 1992-07-29 Ciba-Geigy Ag Sulfonylurées comme herbicides

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5529974A (en) * 1992-11-12 1996-06-25 Ciba-Geigy Corporation Selective safened herbicidal composition
EP0597807A1 (fr) * 1992-11-12 1994-05-18 Ciba-Geigy Ag Agent selectivement herbicide
EP0600836A2 (fr) * 1992-12-02 1994-06-08 Ciba-Geigy Ag Agent selectivement herbicide
EP0600836A3 (en) * 1992-12-02 1994-07-13 Ciba Geigy Ag Selective herbicidal agent.
US5532203A (en) * 1992-12-02 1996-07-02 Ciba-Geigy Corporation Selective safened herbicidal composition
WO1995008919A1 (fr) * 1993-09-30 1995-04-06 Hoechst Schering Agrevo Gmbh Nouveaux melanges d'herbicides et d'antidotes
US5571772A (en) * 1993-09-30 1996-11-05 Hoechst Schering Agrevo Gmbh Mixtures of triazine sulfonylurea herbicides and pyrazoline safeners
EP0657100A3 (fr) * 1993-12-08 1995-11-02 Ciba Geigy Ag Agent sélectivement herbicide.
EP0657100A2 (fr) * 1993-12-08 1995-06-14 Ciba-Geigy Ag Agent sélectivement herbicide
AP537A (en) * 1993-12-08 1996-09-16 Ciba Geigy Ag Selective herbicidal composition.
US5618774A (en) * 1993-12-08 1997-04-08 Ciba-Geigy Corporation Selective safened herbicidal composition
WO2000017194A1 (fr) * 1998-05-22 2000-03-30 Dow Agrosciences Llc Composes a base de 1-alkyl-4-[(3-oxetanyl-)benzoyl]-5-hydroxypyrazole et leur utilisation comme herbicides
US6140271A (en) * 1998-05-22 2000-10-31 Dow Agrosciences Llc 1-alkyl-4-benzoyl-5-hydroxypyrazole compounds and their use as herbicides

Also Published As

Publication number Publication date
MX9300892A (es) 1993-09-01
LT3236B (en) 1995-04-25
LV10440A (lv) 1995-02-20
EP0626958A1 (fr) 1994-12-07
LV10440B (en) 1996-02-20
IL104799A0 (en) 1993-06-10
CA2128325A1 (fr) 1993-09-02
LTIP348A (en) 1994-09-25
AU3496493A (en) 1993-09-13
JPH07504173A (ja) 1995-05-11
ZA931176B (en) 1993-08-19
BR9305922A (pt) 1997-08-26

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