EP0804077A1 - Herbicidal composition - Google Patents

Herbicidal composition

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Publication number
EP0804077A1
EP0804077A1 EP96900566A EP96900566A EP0804077A1 EP 0804077 A1 EP0804077 A1 EP 0804077A1 EP 96900566 A EP96900566 A EP 96900566A EP 96900566 A EP96900566 A EP 96900566A EP 0804077 A1 EP0804077 A1 EP 0804077A1
Authority
EP
European Patent Office
Prior art keywords
alkyl
halogen
substituted
hydrogen
alkoxy
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Withdrawn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
EP96900566A
Other languages
German (de)
French (fr)
Inventor
Jutta Glock
Elmar Kerber
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.)
Novartis AG
Original Assignee
Ciba Geigy AG
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 Ciba Geigy AG, Novartis AG filed Critical Ciba Geigy AG
Publication of EP0804077A1 publication Critical patent/EP0804077A1/en
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines

Definitions

  • the present invention relates to a selective-herbicidal composition for controlling grasses and broad-leaved weeds in crops of useful plants, in particular in crops of maize and cereals such as rye, barley, oats and, in particular, wheat, which composition comprises a herbicide and a safener (counteracting agent, antidote) and which safeguards the useful plants, but not the weeds, against the phytotoxic effect of the herbicide, and to the use of this composition for weed control in crops of useful plants.
  • a herbicide and a safener counteracting agent, antidote
  • safeners which are capable of antagonizing the damaging effect of the herbicide on the crop plant, i.e. of protecting the crop plant from this effect while causing virtually no impairment of the herbicidal effect on the weeds to be controlled.
  • the safeners proposed often have a very specific action both with regard to the crop plants and with regard to the herbicide and in some cases, in addition, depending on the mode of application; in other words, a particular safener is often suitable only for a specific crop plant and a specific class of herbicidal substance, or a specific herbicide.
  • a selective-herbicidal composition which comprises, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, an active substance comprising a mixture of
  • Z is C r C 10 alkyl, C r C 10 alkyl substituted by halogen, C 3 -C 8 cycloalkyl, R 7 O-, R 7 S(O) n -,
  • R 7 R 8 N-, R 8 CO-, R 9 ON CR 8 -, (CH 3 ) 3 Si-, -CN or oxiranyl, CV alkenyl, C 2 -C 8 alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, C r C 6 alkyl,
  • R 8 CO- or R 9 ON CR 8 -, C 3 -C 8 cycloalkenyl, C 3 -C 8 cycloalkenyl substituted by halogen, C C j ⁇ alkyl, phenyl, phenyl substituted by halogen, C r C 6 alkyl, C r C 6 haloalkyl,
  • R 7 is hydrogen, C r Cj 0 alkyl, C 2 -C 8 alkenyl, C -C 8 alkynyl, phenyl or phenyl substituted by halogen, Cj-Cgalkyl, C r C 6 haloalkyl, C r C 6 alkoxy, C r C 6 haloalkoxy or C r C 6 -alkoxy- carbonyl, n is 0, 1 or 2,
  • R 8 is as defined for R 7 or is C C 6 alkoxy, C 3 -C 8 alkenyloxy or C 3 -C 8 alkynyloxy,
  • K is C C ⁇ alkyl, C 2 -C 8 alkenyl or C 2 -C 8 alkynyl
  • R 10 is C r C ⁇ 0 alkyl, C r C 10 alkyl substituted by halogen, R 7 O-, R 7 S(O) n -, -NR 7 R 8 or -CN,
  • R 5 is C r C 10 alkyl, C r C 10 alkyl substituted by halogen, C 3 -C 8 cycloalkyl, R 7 O-, R 7 S(O) n -,
  • R 7 R 8 N-, R 8 CO-, R 9 ON CR 8 -, (CH 3 ) 3 Si-, -CN or oxiranyl, C 2 -C 8 alkenyl, C 2 -C 8 alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, C r C 6 alkyl,
  • R 6 is as defined for R 5 or is hydrogen or together with R 5 forms a C -C 7 alkylene radical, or
  • R 50 is hydrogen, halogen, -NO 2 , -CN, C ⁇ -C 4 alkyl substituted by halogen,
  • Rgo is hydrogen, halogen, -CN, -NO 2 , C C 4 alkyl, C]-C 4 alkyl substituted by halogen,
  • R 70 independently at each occurrence is hydrogen, C ] -C 4 alkyl
  • R 80 is hydrogen, C r C 4 alkyl, C ] -C 4 haloalkyl, halogen, -CO 2 R ⁇ 30 , -SO 2 NR 140 R 150 , -OSO 2 R 170 , -S(O) b R, 80 , -CN or -NO 2 , and
  • R-JO is hydrogen, C r C 4 alkyl, C r C 4 alkyl substituted by halogen or phenyl, C 2 -C 4 alkenyl, phenyl or phenyl substituted by halogen, C r C 4 alkyl, -NO , -CN or C r C 4 alkoxy, where
  • R 100 is hydrogen, C r C 4 alkyl, C r C 4 alkyl substituted by halogen or -OCH 3 ,
  • R 110 and R 12 o independently of one another are C r C 4 alkyl or R 1]0 and R 12 o together are
  • R 130 is hydrogen, C r C 4 alkyl, C r C 4 alkyl substituted by halogen, -CN, -CO 2 R 100 ,
  • R 1 0 is hydrogen or C r C 4 alkyl
  • R 1 0 is hydrogen, C r C 4 alkyl, C r C 4 alkoxy or C 2 -C 4 alkenyl, or R 140 and R 150 together are
  • R 160 is C r C 4 alkyl or C r C 4 haloalkyl
  • R 170 is Cj-C 4 alkyl or -NR- ⁇ oR- ⁇ o- in which R 140 and R 150 are as defined,
  • R 180 is C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkoxyalkyl, C 2 -C 4 alkenyl, C 3 -C 4 alkynyl, phenyl or phenyl substituted by halogen, C]-C 3 alkyl, C r C 3 alkoxy or C C 3 haloalkyl,
  • R 190 is C r C 4 alkyl or C r C 4 alkyl substituted by -F, -Cl or -OR 160 , q is 0 or 1,
  • G is a radical of the formula
  • R 260 is hydrogen or C--C 3 alkyl and R 270 is hydrogen, C r C 3 alkyl or C 2 -C 4 alkenyl,
  • R 2 is hydrogen, C r C 10 alkyl, - oalkyl substituted by C r C 6 alkoxy or Ci-Cgalkoxycarbonyl, C 3 -C 8 alkenyl or benzyl,
  • R 3 or R 4 together with R, form a radical -OCH 2 CH 2 (CH 2 ) m - or -(CH 2 ) m CH 2 CH 2 O-, in which m is 0 or 1 ,
  • R a is hydrogen, C C 8 alkyl, C C 8 alkyl substituted by hydroxy, C r C 8 alkoxy, phenoxy, Cj-Cgalkylthio, phenylthio, (CH 3 ) 3 Si- 1 C 3 -C 8 cycloalkyl, phenyl or di-Cj-Cgalkylamino, C 2 -C alkenyl, C 2 -C 6 alkenyl substituted by halogen, or R a is C 2 -C 6 alkynyl, C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl substituted by C C 3 alkyl, or R a is C 3 -C 6 cycloalkenyl, phenyl, phenyl substituted by C ⁇ -C 8 alkyl, halogen, nitro, -CN, Cj- alkoxy, Cj-Cghaloalkoxy, phenoxy, -NR 7 R 8 or R
  • R a and R b together with the carbon atom to which they are attached, form a radical of the formula -CO-, and m is O or 1; and also salts and stereoisomers of the compounds of the formula I and
  • Ro j o is hydrogen, C r C 8 alkyl or C r C 8 alkyl which is substituted by C r C 6 alkoxy or
  • X 2 is hydrogen or chlorine, of a compound of the formula Ilbj
  • E is nitrogen or methine
  • Rn is -CC1 3 or unsubstituted or halogen-substituted phenyl
  • R 12 and R 13 independently of one another are hydrogen or halogen
  • R 14 is C r C 4 alkyl, of a compound of the formula IIb
  • R 12 and R 13 are as defined above, and
  • R 66 , R ⁇ -; and R 68 independently of one another are C r C 4 alkyl, of a compound of the formula He
  • R* 25 and R 26 independenriy of one another are hydrogen, Cj-Cgalkyl, C 3 -C 8 cycloalkyl,
  • R 1 and R 2 together form a C -Cgalkylene bridge which can be interrupted by oxygen, sulfur, SO, SO 2 , NH or -N ⁇ - alkyl)-,
  • R 27 is hydrogen or - alkyl
  • R ⁇ is hydrogen, halogen, cyano, trifluoromethyl, nitro, C ⁇ -C alkyl, C ⁇ -C 4 alkoxy,
  • R g is hydrogen, halogen, cyano, nitro, C r C alkyl, C r C 4 haloalkyl, C r C alkylthio,
  • R bb and R h independently of one another are hydrogen, halogen, C C 4 alkyl, trifluoromethyl, C r C 6 alkoxy, C r C 6 alkylthio or -COORJ;
  • R c is hydrogen, halogen, nitro, C--C alkyl or methoxy;
  • R d is hydrogen, halogen, nitro,
  • R e is hydrogen, halogen, C r C 4 alkyl, -COOR j , trifluoromethyl or methoxy, or R d and R e together form a C 3 -C 4 alkylene bridge;
  • R f is hydrogen, halogen or C r C 4 alkyl
  • R x and R y independently of one another are hydrogen, halogen, Cj-C 4 alkyl, C r C 4 alkoxy,
  • R j , R k and R m independently of one another are hydrogen or or
  • R k and R m together form a C 4 -C 6 alkylene bridge, which can be interrupted by oxygen, NH or -N(C r C 4 alkyl)-;
  • R_ is Cj-C 4 alkyl, phenyl, or phenyl which is substituted by halogen, C r C alkyl, methoxy, nitro or trifluoromethyl;
  • R 28 is hydrogen, C r C 10 alkyl, C 1 -C 4 alkoxy-C 1 -C 4 alkyl, C r C 4 alkylthio-C r C 4 alkyl, di-
  • C 3 -C 7 cycloalkylcarbonyl benzoyl which is unsubstituted or is substituted on the phenyl ring by up to three identical or different substituents consisting of halogen, C r C 4 alkyl, halo-C r C alkyl, halo-C r C 4 alkoxy or C r C alkoxy; or furoyl, thienyl; or C r C 4 alkyl substituted by phenyl, halophenyl, C r C alkylphenyl, C r C alkoxyphenyl, halo-C r C 4 - alkylphenyl, halo-C r C 4 alkoxyphenyl, C ] -C 6 alkoxycarbonyl, C r C alkoxy-C 1 -C 8 - alkoxycarbonyl, C 3 -C 8 alkenyloxycarbonyl, C 3 -C 8 alkynyloxycarbon
  • R 33 and R 34 independently of one another are C r C 6 alkyl or C 2 -C 6 alkenyl; or R 33 and R-
  • R 35 and R 36 independently of one another are hydrogen or C r C 6 alkyl
  • R 39 ⁇ or R 33 and R ⁇ together are °
  • R 37 and R 38 independently of one another are C C 4 alkyl, or R 37 and R 38 together are -(CH 2 ) 5 - ;
  • R 39 is hydrogen, C r C 4 alkyl or (T il
  • R-40 R4I' R42' R 3' R44' R45' R46' R 7' R48' R49' ⁇ 5 ⁇ »
  • R5I' R52' R53' R54 and R55 independently of one another are hydrogen or C C 4 alkyl; of a compound of the formula Ilf
  • R 63 is hydrogen or chlorine and R 4 is cyano or trifluoromethyl, or of a compound of the formula Ilg
  • R 65 is hydrogen or methyl.
  • the invention also relates to a process for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, their seeds or seedlings or their cultivation area, simultaneously or separately, with a herbicidally effective quantity of a herbicide of the formula I and a herbicide-antagonistically effective quantity of a safener of one of the formulae Ha to Ilg.
  • crops which can be protected by the safeners of the formulae Ila to Ilg against the damaging effect of the abovementioned herbicides
  • maize and cereals such as rye, barley, oats and, in particular, wheat are particularly suitable.
  • crops should also be understood as referring to those which have been made tolerant to herbicides or classes of herbicide by means of conventional breeding or genetic manipulation methods.
  • the weeds to be controlled may be both monocotyledon and dicotyledon weeds.
  • the areas regarded as cultivation areas are the soil areas on which the crop plants are already growing, or soil areas sown with the seed of these crop plants, and also the areas intended for cultivation with these crop plants.
  • alkyl groups mentioned in the definitions of substituents of the compounds of the formulae I and Ha to Ilg can be straight-chain or branched and are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and also pentyl, hexyl, heptyl, octyl, nonyl, decyl and branched isomers thereof.
  • Suitable alkoxy, thioalkyl, haloalkyl and haloalkoxy groups are derived from the alkyl groups mentioned.
  • Examples of unsaturated substituent groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl and isomers, which differ in the different position of the unsaturated bond or bonds in the molecule, isomers which include branching points, and cis and trans isomers in the case of the alkenes.
  • chlorine-substituted propenyl can exist in the two forms
  • substituted compounds of the formula I also constitute isomers which can be obtained and/or employed in pure form or as a mixture.
  • alkenyloxy, alkynyloxy, haloalkenyl and haloalkenyloxy groups can be derived from the alkyl groups mentioned.
  • Cycloalkyl groups comprise, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • Corresponding cycloalkenes can be mono- or polyunsaturated.
  • substituted refers, where possible in the corresponding group, not only to monosubstitution but also to polysubstitution.
  • the invention likewise embraces agriculturally compatible salts which the compounds of the formula I can form, for example, with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases.
  • alkali metal and alkaline earth metal hydroxides as salt formers, particular emphasis should be placed on the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially on those of sodium or potassium.
  • amines suitable for forming ammonium salts are not only ammonia but also primary, secondary and tertiary C--C 18 alkylamines, C r C 4 hydroxyalkylamines and C 2 -C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, eth
  • compositions according to the present invention comprise as herbicide a compound of the formula I in which R 3 and R are methoxy.
  • compositions comprise as herbicide a compound of the formula I in which R 3 and R 4 are methoxy and Z is Cj-Cjoalkyl, C 2 -C 8 alkenyl or C 2 -C 8 haloalkenyl.
  • compositions comprise as safener as compound of the formula Ha, Hb j , ⁇ b 2 or He.
  • Safeners which arc particularly suitable for use in the compositions according to the invention arc listed in the following tables.
  • a safener of the formulae Ila to Ilg can be used for pretreating the seed of the crop plant (dressing of the seed or of the seedlings), or placed in the soil before or after sowing. It can, however, also be applied, on its own or together with the herbicide, following the emergence of the plants.
  • the treatment of the plants or of the seed with the safener can therefore, in principle, take place independenriy of the point in time of the application of the herbicide.
  • the plant treatment can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix).
  • the application rate of safener to herbicide to be applied depends largely on the method of application.
  • the ratio of herbicide to safener is in general from 1: 100 to 1:1 , preferably from 1 :50 to 1:5.
  • the application rates of herbicide are generally between 0.001 and 2 kg/ha, but preferably between 0.005 and 1 kg/ha.
  • compositions according to the invention are suitable for all application methods which are customary in agriculture, for example preemergence application, postemergence application and seed dressing.
  • safener/kg of seed In general, in seed dressing, from 0.001 to 10 kg of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form shortly before sowing, accompanied by seed swelling, then it is expedient to use safener solutions which comprise the active substance in a concentration of from 1 to 10000 ppm, preferably from 100 to 1000 ppm.
  • the safeners of the formula II are advantageously processed together with the auxiliaries which are customary in the art of formulation to give particular formulations, for example emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • the formulations are produced in a known manner, for example by intimate mixing and/or grinding of the active substances with liquid or solid formulation auxiliaries such as, for example, solvents or solid carriers.
  • surface-active compounds surfactants
  • Suitable solvents can be aromatic hydrocarbons, preferably Cg to C J2 fractions, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and ethers and esters thereof, such as ethanol, diethylene glycol, 2-methoxyethanol or 2-ethoxyethanol, ketones, such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and unmodified or epoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.
  • aromatic hydrocarbons preferably Cg to C J2 fractions, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, alipha
  • solid carriers for example for dusts and dispersible powders, use is generally made of ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • ground natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite.
  • highly disperse silica or highly disperse absorbent polymers In order to improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorbent polymers.
  • Suitable granulated, adsorptive granule carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, while suitable nonsorbent carrier materials are, for example, calcite or sand.
  • Suitable surface-active compounds are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. References to surfactants also include surfactant mixtures.
  • Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Soaps which may be mentioned are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (CI Q -C 2 ), for example the sodium or potassium salts or oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tallow oil.
  • Other salts which can be mentioned are the fatty acid methyltaurine salts.
  • so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or fatty sulfates are generally present as alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, examples being the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. Also included here arc the salts of sulfuric esters and sulfonic acids with fatty alcohol-ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.
  • phosphates for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids.
  • Suitable nonionic surfactants are primarily 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.
  • nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide and polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain.
  • the compounds mentioned customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • nonionic surfactants which can be mentioned are nonylphenolpolyethoxy- ethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxy- ethanol.
  • fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylenesorbitan trioleate .
  • the cationic surfactants are primarily quaternary ammonium salts which have, as N-substituent, at least one alkyl radical having 8 to 22 carbon atoms and, as further substituents, lower, unmodified or halogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts arc preferably in the form of halides, methyl sulfates or ethyl sulfates, for example the stearyltrimethylammonium chloride or the benzyldi(2-chloroethyl)ethyl- ammonium bromide.
  • the agrochemical formulations generally contain from 0.1 to 99 per cent by weight, in particular from 0.1 to 95 % by weight, of safener or safener/herbicide active-substance mixture, from 1 to 99.9 % by weight, in particular from 5 to 99.8 % by weight, of a solid or liquid formulation auxiliary, and from 0 to 25 % by weight, in particular from 0.1 to 25 % by weight, of a surfactant.
  • While the preferred commercial product usually comprises concentrated compositions, the end user generally employs dilute compositions.
  • compositions can also comprise further additives, such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active substances.
  • Seed dressing a) The seeds are dressed by shaking them, in a vessel, together with an active substance of the formulae Ha to Ilg formulated as a wettable powder, until the active ingredient is distributed uniformly on the seed surface (dry seed dressing). In this case from about 1 to 500 g of active substance of the formulae Ha to Ilg (4 g to 2 kg of wettable powder) are used per 100 kg of seed.
  • the seeds are dressed by immersing them into a liquor containing 100-1000 ppm of active substance of the formulae Ha to Ilg for from 1 to 72 hours and then, if desired, by drying the seeds (seed soaking).
  • the dressing of the seed and the treatment of the seedling which has begun to germinate are of course the preferred methods of application, since the treatment with the active substance is directed entirely towards the target crop.
  • a liquid preparation of a mixture of antidote and herbicide (mutual quantitative ratio between 10:1 and 1:100) is used, the application rate of herbicide being from 0.005 to 5.0 kg per hectare.
  • Such tank mixes are applied before or after sowing.
  • the safener is introduced into the open seed drill, containing seed, as an emulsion concentrate, wettable powder or in the form of granules. After the seed drill has been covered over, the herbicide is applied preemergence in a customary manner.
  • the active substance of the formulae Ila to Ilg is applied in solution to mineral granule carriers or polymerized granules (urea/formaldehyde), which are then dried. If desired, a coating can be applied (coated granules), which enables the release of the active substance in regulated amounts over a defined period.
  • Active substance mixture 5 % 10 % 25 % 50 %
  • Active substance mixture 5 % 10 % 50 % 90 % l-Methoxy-3-(3-methoxypropoxy)- propane 20 % 20 %
  • Aromatic hydrocarbon mixture 75 % 60 %
  • the active substance is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
  • Active substance mixture 0.1 % 5 % 15
  • the active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
  • the finely ground active substance is applied uniformly in a mixer to the carrier material which has been wetted with polyethylene glycol. Dust-frce coated granules are obtained in this way.
  • Active substance mixture 0.1 % 3 % 5 % 15 %
  • the active substance is mixed with the additives, and the mixture is ground and wetted with water. This mixture is extruded and subsequently dried in a stream of air.
  • Kaolin Ready-to-use dusts are obtained by mixing the active substance with the carriers and grinding the mixture in a suitable mill.
  • the finely ground active substance is intimately mixed with the additives.
  • a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be produced.
  • Example B 1 Postemergence applications of mixtures of a herbicide of the formula I with a safener of the formulae Ila to Ilg to cereals
  • Example B2 Postemergence applications of mixtures of a herbicide of the formula I with a safener of the formulae Ila to Ilg to maize
  • Table B5 Herbicidal action of the compounds of the formula I and a mixture thereof with the safeners of the formula 11 in maize S .
  • Example B3 Postemergence applications of mixtures of a herbicide of the formula I with a safener of t e formulae Ila to Ilg to rice
  • test plants Under greenhouse conditions, the test plants are sown or planted in plastic troughs in standard soil. Water is then introduced up to the surface of the soil. After 3 days, the water level is elevated by 2 cm and the herbicide is applied as an aqueous suspension (Example F7) on its own and in a tank mix with the safeners.
  • the application rates for the herbicide can be seen from Table B6.
  • the application rate for the safener is 125 g/ha. Cultivation of the test plants is then continued in the greenhouse under optimum conditions. 13 days after application, the test is evaluated using a percentage scale. 100 % denotes that the test plant has died, while 0 % denotes no phytotoxic effect. The results obtained show that, with the safeners of the formulae Ha to Ug, the damage caused to rice by the herbicide of the formula I can be substantially reduced.
  • Table B6 Herbicidal action of the compounds of the formula I and a mixture thereof with the safeners of the formula II in rice

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  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
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  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Selective-herbicidal composition which comprises, in addition to customary inert formulation auxiliaries, an active substance comprising a mixture of a) a herbicidally effective quantity of a herbicide of formula (I), and b) a herbicide-antagonistically effective quantity of a compound of formulae (IIa), (IIb1), (IIb2), (IIc), (IIe), (IIf), or (IIg), in which the substituents are as defined in claim 1.

Description

Herbicidal composition
The present invention relates to a selective-herbicidal composition for controlling grasses and broad-leaved weeds in crops of useful plants, in particular in crops of maize and cereals such as rye, barley, oats and, in particular, wheat, which composition comprises a herbicide and a safener (counteracting agent, antidote) and which safeguards the useful plants, but not the weeds, against the phytotoxic effect of the herbicide, and to the use of this composition for weed control in crops of useful plants.
When herbicides are used it is possible, depending for example on the rate and mode of application of the herbicide, on the crop plant, on the nature of the soil and on the climatic conditions, such as period of exposure to light, temperature and amounts of precipitation, for the crop plants too to be damaged to a considerable extent.
In order to counter this and similar problems, a variety of substances have already been proposed as safeners, which are capable of antagonizing the damaging effect of the herbicide on the crop plant, i.e. of protecting the crop plant from this effect while causing virtually no impairment of the herbicidal effect on the weeds to be controlled. In this context it has been found that the safeners proposed often have a very specific action both with regard to the crop plants and with regard to the herbicide and in some cases, in addition, depending on the mode of application; in other words, a particular safener is often suitable only for a specific crop plant and a specific class of herbicidal substance, or a specific herbicide.
It has now been found that safeners known from EP-A-492366, WO 91/7874 and WO 94/987 are suitable for protecting crop plants against the phytotoxic effect of a certain class of N-acylsulfonamide herbicides. Such herbicides are known, for example, from EP-A-592680, EP-A-514551, EP-A-353 640, WO 94/5644, WO 92/16511, EP-A-444 286 and WO 92/1677.
In accordance with the invention, therefore, a selective-herbicidal composition is proposed which comprises, in addition to customary inert formulation auxiliaries such as carriers, solvents and wetting agents, an active substance comprising a mixture of
a) a herbicidally effective quantity of a herbicide of the formula I
in which
Z is CrC10alkyl, CrC10alkyl substituted by halogen, C3-C8cycloalkyl, R7O-, R7S(O)n-,
R7R8N-, R8CO-, R9ON=CR8-, (CH3)3Si-, -CN or oxiranyl, CV alkenyl, C2-C8alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, CrC6alkyl,
Cj-Cghaloalkyl, CrC6alkoxy, C]-C6haloalkoxy or Cj- alkoxycarbonyl,
C3-C8cycloalkyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, R8CO- or R9ON=CR8-,
C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen, CrC10alkyl, phenyl, phenyl substituted by halogen, Cj- alkyl, CrC6haloalkyl, C C6alkoxy,
CrC6haloalkoxy or CrC6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, oxo,
=NOR7, R8CO- or R9ON=CR8-, C3-C8cycloalkenyl, C3-C8cycloalkenyl substituted by halogen, C Cjøalkyl, phenyl, phenyl substituted by halogen, CrC6alkyl, CrC6haloalkyl,
CrC6alkoxy, CrC6haloalkoxy or CrC6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-,
(CH3)3Si-, -CN, oxo, =NOR7, R8CO- or R9ON=CR8-, -NR5R6, R10CON(R6)- or
R10SO2N(R6)-, where
R7 is hydrogen, CrCj0alkyl, C2-C8alkenyl, C -C8alkynyl, phenyl or phenyl substituted by halogen, Cj-Cgalkyl, CrC6haloalkyl, CrC6alkoxy, CrC6haloalkoxy or CrC6-alkoxy- carbonyl, n is 0, 1 or 2,
R8 is as defined for R7 or is C C6alkoxy, C3-C8alkenyloxy or C3-C8alkynyloxy,
K is C C^alkyl, C2-C8alkenyl or C2-C8alkynyl,
R10 is CrCι0alkyl, CrC10alkyl substituted by halogen, R7O-, R7S(O)n-, -NR7R8 or -CN,
C2-C8alkenyl, C2-C8alkenyl substituted by halogen, R7O-, R7S(O)n-, -NR7R8 or -CN, phenyl or phenyl substituted by halogen, C alkyl, CrC6haloalkyl, CrC6alkoxy,
C!-C6haloalkoxy or C C6alkoxycarbonyl, in which R7, n and R8 are as defined,
R5 is CrC10alkyl, CrC10alkyl substituted by halogen, C3-C8cycloalkyl, R7O-, R7S(O)n-,
R7R8N-, R8CO-, R9ON=CR8-, (CH3)3Si-, -CN or oxiranyl, C2-C8alkenyl, C2-C8alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, CrC6alkyl,
Cι-C6haloalkyl, Cj-Cgalkoxy, C^Cghaloalkoxy or Cj-C6alkoxycarbonyl,
C3-C8cycloalkyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, R8CO- or R9ON=CR8-,
C2-Cgalkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen, Cι-C10alkyl, phenyl, phenyl substituted by halogen, CrC6alkyl, CrC6haloalkyl, CrC6alkoxy,
CrC6haloalkoxy or CrC6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, oxo, =NOR7, RgCO- or R9ON=CR8-, C3-C8cycloalkenyl, C3-C8cycloalkenyl substituted by halogen, -Cioalk l, phenyl, phenyl substituted by halogen, C alkyl, Cι-C6haloalkyl,
CrC6alkoxy, CrC6haloalkoxy or CrC6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-,
(CH3)3Si-, -CN, oxo, =NOR7, RgCO- or R9ON=CR8-, or is R7O- in which R7 is as defined, and
R6 is as defined for R5 or is hydrogen or together with R5 forms a C -C7alkylene radical, or
in which
R50 is hydrogen, halogen, -NO2, -CN, Cι-C4alkyl substituted by halogen,
-CN, -OCH3 or -SCH3, C2-C4alkenyl, C2-C4alkenyl substituted by halogen or OCH3,
C2-C4alkynyl, C2-C4alkynyl substituted by halogen, -OCH3 or -Si(CH3)3,
C3-C6cycloalkyl, C3-C6cycloalkyl substituted by -F, -Cl or -CH3, -C(O)R100,
-OCH2CH2OR,oo, -OH, -C(R10o)(ORπo)(OR12o). -CO2R130, -C(O)NR,40R15(), -N3,
-SO2NR140R150, -SO3R160, -OSO2Ri7o. phenyl, phenyl substituted by halogen, -CH3 or
-OCH3, -O-Rjgo, -S(O)bR! o or -(CH2)SG, in which b and s independendy of one another are 0 or 1,
Rgo is hydrogen, halogen, -CN, -NO2, C C4alkyl, C]-C4alkyl substituted by halogen,
-CO2R130, -SO2NRι40R150, -NRi40 i50. Cr or ^alkoxy, -OR190, -S(O)bR190, Cr or
C2haloalkoxy, Cr or C2alkylthio, Cr or C2haloalkylthio, -CN, -OH or -SH, -CO2Rι30,
-SO2NR140R150, -NRj40R15o, -S(O)bR190 or -OR190,
R70 independently at each occurrence is hydrogen, C]-C4alkyl,
C2-C4alkenyl, phenyl, phenyl substituted by halogen, -S(O)bRi9o or -OR190, -S(O)bRi9o»
-ORi90 or halogen,
R80 is hydrogen, CrC4alkyl, C]-C4haloalkyl, halogen, -CO2Rι30, -SO2NR140R150, -OSO2R170, -S(O)bR,80, -CN or -NO2, and
R-JO is hydrogen, CrC4alkyl, CrC4alkyl substituted by halogen or phenyl, C2-C4alkenyl, phenyl or phenyl substituted by halogen, CrC4alkyl, -NO , -CN or CrC4alkoxy, where
R100 is hydrogen, CrC4alkyl, CrC4alkyl substituted by halogen or -OCH3,
C3-C6cycloalkyl, C3-C6cycloalkyl substituted by halogen or -CH3, C2-C4alkenyl or
C2-C4alkynyl,
R110 and R12o independently of one another are CrC4alkyl or R1]0 and R12o together are
-CH2CH2-, -CH2OCH2- or -CH2C(CH3)2CH2-,
R130 is hydrogen, CrC4alkyl, CrC4alkyl substituted by halogen, -CN, -CO2R100,
-NR140R150, -ORJOO or -Si(CH3)3, C3-C4alkynyl, C3-C4alkynyl substituted by -CH3 or
-Si(CH3)3, C3-C6cycloalkyl, C3-C6cycloalkyl-CrC4alkyl, CrC4alkoxy or -Si(CH3)3,
R1 0 is hydrogen or CrC4alkyl,
R1 0 is hydrogen, CrC4alkyl, CrC4alkoxy or C2-C4alkenyl, or R140 and R150 together are
-(CH2)2(CH2)a-(CH2)2- or -(CH2)2O(CH2)2-, in which a is 0 or 1,
R160 is CrC4alkyl or CrC4haloalkyl,
R170 is Cj-C4alkyl or -NR-^oR-^o- in which R140 and R150 are as defined,
R180 is CrC4alkyl, CrC4haloalkyl, C2-C4alkoxyalkyl, C2-C4alkenyl, C3-C4alkynyl, phenyl or phenyl substituted by halogen, C]-C3alkyl, CrC3alkoxy or C C3haloalkyl,
R190 is CrC4alkyl or CrC4alkyl substituted by -F, -Cl or -OR160, q is 0 or 1,
G is a radical of the formula
in which R260 is hydrogen or C--C3alkyl and R270 is hydrogen, CrC3alkyl or C2-C4alkenyl,
R2 is hydrogen, CrC10alkyl, - oalkyl substituted by CrC6alkoxy or Ci-Cgalkoxycarbonyl, C3-C8alkenyl or benzyl,
X and Y independently of one another are =N-, =CH- or =CR-, where either X or Y must be =N-, and in which R is halogen, Cj-C^alkyl, Cj-C^alkyl substituted by halogen, CrC6alkoxy or CrC6haloalkoxy, Cj -C6alkoxy or Cι-C6haloalkoxy, R3 and R4 independently of one another are hydrogen, halogen, Cj-C10alkyl, R7O-, R7S(O)n-, R7R8N-, CrC10haloalkyl, CrC10haloalkoxy, CrC6alkoxy-CrC6alkyl or phenylthio, where R7, n and R8 are as defined, or
R3 or R4, together with R, form a radical -OCH2CH2(CH2)m- or -(CH2)mCH2CH2O-, in which m is 0 or 1 ,
Ra is hydrogen, C C8alkyl, C C8alkyl substituted by hydroxy, CrC8alkoxy, phenoxy, Cj-Cgalkylthio, phenylthio, (CH3)3Si-1 C3-C8cycloalkyl, phenyl or di-Cj-Cgalkylamino, C2-C alkenyl, C2-C6alkenyl substituted by halogen, or Ra is C2-C6alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by C C3alkyl, or Ra is C3-C6cycloalkenyl, phenyl, phenyl substituted by Cι-C8alkyl, halogen, nitro, -CN, Cj- alkoxy, Cj-Cghaloalkoxy, phenoxy, -NR7R8 or R8CO-, in which R7 and R8 arc as defined, or Ra is hydroxyl, halogen, tetrahydrothienyl, tetrahydrofuryl, furyl, pyridyl or thienyl, Rb is hydrogen, CrC8alkyl or phenyl, or
Ra and Rb, together with the carbon atom to which they are attached, form a radical of the formula -CO-, and m is O or 1; and also salts and stereoisomers of the compounds of the formula I and
b) a herbicide-antagonistically effective quantity of a compound of the foπnula Ila
in which
Rojo is hydrogen, CrC8alkyl or CrC8alkyl which is substituted by CrC6alkoxy or
C3-C6alkenyloxy, and
X2 is hydrogen or chlorine, of a compound of the formula Ilbj
in which
E is nitrogen or methine,
Rn is -CC13 or unsubstituted or halogen-substituted phenyl,
R12 and R13 independently of one another are hydrogen or halogen, and
R14 is CrC4alkyl, of a compound of the formula IIb
in which
R12 and R13 are as defined above, and
R66, R^-; and R68 independently of one another are CrC4alkyl, of a compound of the formula He
in which A2 is a group
R*25 and R26 independenriy of one another are hydrogen, Cj-Cgalkyl, C3-C8cycloalkyl,
, or CrC4alkyl which is substituted by
; or R1 and R 2 together form a C -Cgalkylene bridge which can be interrupted by oxygen, sulfur, SO, SO2, NH or -Nζ - alkyl)-,
R27 is hydrogen or - alkyl;
Rω is hydrogen, halogen, cyano, trifluoromethyl, nitro, Cι-C alkyl, Cι-C4alkoxy,
CrC4alkylthio, CrC4alkylsulfιnyl, CrC4alkylsulfonyl, -COORj, -CONRkRm, -COR,.,
-SO2NRkRm or -OSO2-CrC4alkyl;
Rg is hydrogen, halogen, cyano, nitro, CrC alkyl, CrC4haloalkyl, CrC alkylthio,
CrC4alkylsulfinyl, CrC4alkylsulfonyl, -COORj, -CONR,^, -CORn, -SOi^R,,,,
-OSO2-CrC4alkyl, CrC6alkoxy, or CrC6alkoxy substituted by CrC4alkoxy or halogen, C3-C6alkenyloxy, or C3-C6alkenyloxy substituted by halogen, or C3-C6alkynyloxy, or Ra and Rb together form a C3-C4alkylene bridge which can be substituted by halogen or
CrC4alkyl, or form a C3-C4alkenylene bridge which can be substituted by halogen or
Cj-C4alkyl, or form a C4alkadienylene bridge which can be substituted by halogen or
CrC4alkyl;
Rbb and Rh independently of one another are hydrogen, halogen, C C4alkyl, trifluoromethyl, CrC6alkoxy, CrC6alkylthio or -COORJ;
Rc is hydrogen, halogen, nitro, C--C alkyl or methoxy; Rd is hydrogen, halogen, nitro,
Cj-C alkyl, CrC4alkoxy, CrC4alkylthio, CrC4alkylsulfinyl, CrC4alkylsulfonyl,
-COORj or CONRkRm;
Re is hydrogen, halogen, CrC4alkyl, -COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge;
Rf is hydrogen, halogen or CrC4alkyl;
Rx and Ry independently of one another are hydrogen, halogen, Cj-C4alkyl, CrC4alkoxy,
CrC4alkylthio, -COOR28, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm independently of one another are hydrogen or or
Rk and Rm together form a C4-C6alkylene bridge, which can be interrupted by oxygen, NH or -N(CrC4alkyl)-;
R_ is Cj-C4alkyl, phenyl, or phenyl which is substituted by halogen, CrC alkyl, methoxy, nitro or trifluoromethyl;
R28 is hydrogen, CrC10alkyl, C1-C4alkoxy-C1-C4alkyl, CrC4alkylthio-CrC4alkyl, di-
C1-C4alkylamino-C1-C4alkyl, halogen-CrC8alkyl, C2-C8alkenyl, halo-C2-C8alkenyl,
C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl. CrC8alkylcarbonyl, allylcarbonyl,
C3-C7cycloalkylcarbonyl, benzoyl which is unsubstituted or is substituted on the phenyl ring by up to three identical or different substituents consisting of halogen, CrC4alkyl, halo-CrC alkyl, halo-CrC4alkoxy or CrC alkoxy; or furoyl, thienyl; or CrC4alkyl substituted by phenyl, halophenyl, CrC alkylphenyl, CrC alkoxyphenyl, halo-CrC4- alkylphenyl, halo-CrC4alkoxyphenyl, C]-C6alkoxycarbonyl, CrC alkoxy-C1-C8- alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, CrC8alkylthio- carbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, mono-Cj-C4- alkylaminocarbonyl, di-C1-C alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or is substituted on the phenyl by up to three identical or different substituents consisting of halogen, C C4alkyl, halo-CrC4 alkyl, halo-CrC alkoxy or
Cj-C4alkoxy or by a single cyano or nitro substituent, or dioxolan-2-yl which is unsubstituted or is substituted by one or two Cj-C4alkyl radicals, or dioxan-2-yl which is unsubstituted or is substituted by one or two CrC alkyl radicals, or CrC4alkyl which is substituted by cyano, nitro, carboxyl or C--C8alkylthio-CrC8alkoxycarbonyl, of a compound of the formula He
R33 O
\ I I
NC — CHC12 (He)
/
*34
in which
R33 and R34 independently of one another are CrC6alkyl or C2-C6alkenyl; or R33 and R-
together are υ
R35 and R36 independently of one another are hydrogen or CrC6alkyl;
R39 \ or R33 and R^ together are °
R37 R38
R37 and R38 independently of one another are C C4alkyl, or R37 and R38 together are -(CH2)5- ;
R39 is hydrogen, CrC4alkyl or (T il
A)'
or R33 and R3 together are
R-40» R4I' R42' R 3' R44' R45' R46' R 7' R48' R49' θ5θ» R5I' R52' R53' R54 and R55 independently of one another are hydrogen or C C4alkyl; of a compound of the formula Ilf
in which
R63 is hydrogen or chlorine and R 4 is cyano or trifluoromethyl, or of a compound of the formula Ilg
in which
R65 is hydrogen or methyl.
The invention also relates to a process for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, their seeds or seedlings or their cultivation area, simultaneously or separately, with a herbicidally effective quantity of a herbicide of the formula I and a herbicide-antagonistically effective quantity of a safener of one of the formulae Ha to Ilg.
Among crop plants which can be protected by the safeners of the formulae Ila to Ilg against the damaging effect of the abovementioned herbicides, maize and cereals such as rye, barley, oats and, in particular, wheat are particularly suitable. The term crops should also be understood as referring to those which have been made tolerant to herbicides or classes of herbicide by means of conventional breeding or genetic manipulation methods.
The weeds to be controlled may be both monocotyledon and dicotyledon weeds.
The areas regarded as cultivation areas are the soil areas on which the crop plants are already growing, or soil areas sown with the seed of these crop plants, and also the areas intended for cultivation with these crop plants.
The alkyl groups mentioned in the definitions of substituents of the compounds of the formulae I and Ha to Ilg can be straight-chain or branched and are for example methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and also pentyl, hexyl, heptyl, octyl, nonyl, decyl and branched isomers thereof. These alkyl groups can carry further substituents, for example halogen, especially fluorine, chlorine or bromine, alkoxy, thioalkyl, cycloalkyl, phenyl, amino, acyl (e.g. RgCO-) or oxo (O=). Suitable alkoxy, thioalkyl, haloalkyl and haloalkoxy groups are derived from the alkyl groups mentioned.
Examples of unsaturated substituent groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl and isomers, which differ in the different position of the unsaturated bond or bonds in the molecule, isomers which include branching points, and cis and trans isomers in the case of the alkenes. For example, chlorine-substituted propenyl can exist in the two forms
Thus substituted compounds of the formula I also constitute isomers which can be obtained and/or employed in pure form or as a mixture.
Examples of alkenyloxy, alkynyloxy, haloalkenyl and haloalkenyloxy groups can be derived from the alkyl groups mentioned.
Cycloalkyl groups comprise, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Corresponding cycloalkenes can be mono- or polyunsaturated.
The expression "substituted" refers, where possible in the corresponding group, not only to monosubstitution but also to polysubstitution.
The invention likewise embraces agriculturally compatible salts which the compounds of the formula I can form, for example, with amines, alkali metal and alkaline earth metal bases or quaternary ammonium bases. Among the alkali metal and alkaline earth metal hydroxides, as salt formers, particular emphasis should be placed on the hydroxides of lithium, sodium, potassium, magnesium or calcium, but especially on those of sodium or potassium.
Examples of amines suitable for forming ammonium salts are not only ammonia but also primary, secondary and tertiary C--C18alkylamines, CrC4hydroxyalkylamines and C2-C alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, the four isomeric butylamines, n-amylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylhexylamine, methylnonylamine, methylpentadecylamine, methyloctadecylamine, ethylbutylamine, ethylheptylamine, ethyloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, isopropanolamine, N,N-diethanolamine, N-ethylpropanolamine, N-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as, for example, pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as, for example, anilines, methoxy anilines, ethoxyanilines, o-, m- and p-toluidines, phenylenediamines, benzidines, naphthylamines and o-, m- and p-chloroanilines; but especially triethylamine, isopropylamine and diisopropylamine.
Preferred compositions according to the present invention comprise as herbicide a compound of the formula I in which R3 and R are methoxy.
Another group of preferred compositions comprise as herbicide a compound of the formula I in which R3 and R4 are methoxy and Z is Cj-Cjoalkyl, C2-C8alkenyl or C2-C8haloalkenyl.
Among these compounds, particular preference is given to those which comprise as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3)=CH2 or -CH2-CH=CHCl. Particular importance is attached to those compositions which comprise as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3)=CH2 or -CH2-CH=CHC1 and m is 0.
Preferred compositions comprise as safener as compound of the formula Ha, Hbj, πb2 or He.
Among these, particular preference is given to those with the safeners of the formulae lib! and llb and also to those with the safeners of the formula Ila.
Particular value is possessed by compositions which comprise as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3)*=CH2 or -CH2-CH=CHC1 and m is 0, and as safener a compound of the formula Ila, in particular of the formula Haj
Preferred compounds of the formula I are listed in the following tables.
Table 1 : Compounds of the formula la
Compd. No.
1.01 -CH2-CH=CHC1 (Z) 1.02 -CH2-CH=CHC1 (E)
1.03 -CH2-CC1=CH2
1.04 -CH2-CC1=CHC1
1.05 -CH2-C(CH3)=CHC1 1.06 -CH2-CBr=CH2 1.07 -CH2-CC1=CHCH3 1.08 -CH2-CH=CHBr
1.09 -CH2-CHC1-CH2C1 n O
1J0 -CH,
1.11 -CH2-C(CH3)3
1J2 -CH 2" A
1J3 -CH2-CH2CN
1J4 -CH2-CH=CC1CH3
1.15 -CH2-CH=C(CH3)2
1J6 -CH2-CH2-C(CH)3-=CH2
1J7 -CH2-CH=CC12
1J8 -CH=CH-CH2CH3
1J9 -NH2
1.20 -CH2-CH=CHC1
1.21 -CH2-C(CH)3=CH2
The Compounds Nos. 1.01 to 1.21 and their preparation arc described in EP-A-592 680. The compounds 1.03 to 1.21 are mixtures of (Z) and (E) isomers. Table 2: Compounds of the formula lb
Z-S02-NH-CO-CRaRb- -N
N
OCH,
Compd. No. R, R, R-,
The Compounds Nos. 2.01 to 2J0 and their preparation are described in EP-A-514551, those of Nos. 2J 1 to 2J3 in WO 92/1677, those of No. 14 in WO 94/5644 and those of No. 15 in WO 92/16511. Table 3a: Compounds of the foimula lc
Compd. No. R„ Rv CRaRb R. R,
The Compounds Nos. 3.01 to 3.16 and their preparation arc described in EP-A-353 640. Table 3b: Compound of the formula Id
Compd. No. Rx CRaRb R
3J7 -SO2N(CH3)2 -OCH3
Compound No. 3J7 and its preparation is described in EP-A-444286.
Safeners which arc particularly suitable for use in the compositions according to the invention arc listed in the following tables.
Table 4: Compounds of the formula Ha:
Compd. No. X2 Ro10
4.01 Cl -CH(CH3)-C5Hπ-n
4.02 Cl -CH(CH3)-CH2OCH2CH=CH2
4.03 Cl H
4.04 Cl C4H9-n Table 5: Compounds of the formula lib]
Compd. No. Rj4 R π R 12 R 13
(Ub2)
Compd. No. 68 Λ67 R 66 ^12 ••13
6.01 CH3 CH3
6.02 CH3 C2H5 6.03 CH3 C2H5
Table 7: Compounds of the formula lie
Compd. No. R 26
Table 8: Compounds of the formula lie
\33
N — C — CHCI, (He)
Λ34
Compd. No. R33 R 34 R33+R34
8.001 CH2=CHCH2 CH2=CHCH2
Table 9: Compounds of the foπnula Hf
Compd. No. R63 R^
9.01 H CN
9.02 Cl CF3
Table 10: Compounds of the formula Ilg
Compd. No. R65
10.01 H
10.02 CH3
The safeners listed in Tables 4 to 10 and their preparation are known, for example, from EP-A-492366, WO 91 7874 and WO 94/987.
Depending on the intended use, a safener of the formulae Ila to Ilg can be used for pretreating the seed of the crop plant (dressing of the seed or of the seedlings), or placed in the soil before or after sowing. It can, however, also be applied, on its own or together with the herbicide, following the emergence of the plants. The treatment of the plants or of the seed with the safener can therefore, in principle, take place independenriy of the point in time of the application of the herbicide. The plant treatment, however, can also be carried out by simultaneous application of herbicide and safener (for example as a tank mix).
The application rate of safener to herbicide to be applied depends largely on the method of application. In a field treatment carried out either using a tank mix comprising a combination of safener and herbicide or by separate application of safener and herbicide, the ratio of herbicide to safener is in general from 1: 100 to 1:1 , preferably from 1 :50 to 1:5.
In general, in field treatment, from 0.001 to 5.0 kg of safener/ha, preferably from 0.001 to 0.5 kg of safener/ha, are applied.
The application rates of herbicide are generally between 0.001 and 2 kg/ha, but preferably between 0.005 and 1 kg/ha.
The compositions according to the invention are suitable for all application methods which are customary in agriculture, for example preemergence application, postemergence application and seed dressing.
In general, in seed dressing, from 0.001 to 10 kg of safener/kg of seed, preferably from 0.05 to 2 g of safener/kg of seed, are applied. If the safener is applied in liquid form shortly before sowing, accompanied by seed swelling, then it is expedient to use safener solutions which comprise the active substance in a concentration of from 1 to 10000 ppm, preferably from 100 to 1000 ppm.
For application, the safeners of the formula II, or combinations of these safeners with the herbicides of the formula I, are advantageously processed together with the auxiliaries which are customary in the art of formulation to give particular formulations, for example emulsion concentrates, brushable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. The formulations are produced in a known manner, for example by intimate mixing and/or grinding of the active substances with liquid or solid formulation auxiliaries such as, for example, solvents or solid carriers. Furthermore, it is possible in addition to use surface-active compounds (surfactants) for producing the formulations.
Suitable solvents can be aromatic hydrocarbons, preferably Cg to CJ2 fractions, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols, and ethers and esters thereof, such as ethanol, diethylene glycol, 2-methoxyethanol or 2-ethoxyethanol, ketones, such as cyclohexanone, strongly polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, and unmodified or epoxidized vegetable oils, such as epoxidized coconut oil or soya oil; or water.
As solid carriers, for example for dusts and dispersible powders, use is generally made of ground natural minerals, such as calcite, talc, kaolin, montmorillonite or attapulgite. In order to improve the physical properties of the formulation, it is also possible to add highly disperse silica or highly disperse absorbent polymers. Suitable granulated, adsorptive granule carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, while suitable nonsorbent carrier materials are, for example, calcite or sand. In addition, it is possible to use a large number of pregranulated materials of inorganic or organic nature, such as, in particular, dolomite or comminuted plant residues.
Suitable surface-active compounds, depending on the safener and, if appropriate, on the herbicide as well, are nonionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. References to surfactants also include surfactant mixtures.
Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
Soaps which may be mentioned are the alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts of higher fatty acids (CIQ-C 2), for example the sodium or potassium salts or oleic or stearic acid, or of natural fatty acid mixtures which can be obtained, for example, from coconut oil or tallow oil. Other salts which can be mentioned are the fatty acid methyltaurine salts.
More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
The fatty sulfonates or fatty sulfates are generally present as alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, alkyl also including the alkyl moiety of acyl radicals, examples being the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric ester or of a fatty alcohol sulfate mixture prepared from natural fatty acids. Also included here arc the salts of sulfuric esters and sulfonic acids with fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having 8 to 22 carbon atoms. Examples of alkylarylsulfonates are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.
Also suitable are appropriate phosphates, for example salts of the phosphoric ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids.
Suitable nonionic surfactants are primarily 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.
Further suitable nonionic surfactants are the water-soluble adducts, containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, of polyethylene oxide and polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned customarily contain 1 to 5 ethylene glycol units per propylene glycol unit.
Examples of nonionic surfactants which can be mentioned are nonylphenolpolyethoxy- ethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxy- ethanol.
Also suitable are fatty acid esters of polyoxyethylenesorbitan, such as polyoxyethylenesorbitan trioleate .
The cationic surfactants are primarily quaternary ammonium salts which have, as N-substituent, at least one alkyl radical having 8 to 22 carbon atoms and, as further substituents, lower, unmodified or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts arc preferably in the form of halides, methyl sulfates or ethyl sulfates, for example the stearyltrimethylammonium chloride or the benzyldi(2-chloroethyl)ethyl- ammonium bromide.
The surfactants customary in the an of formulation, which can also be used in the compositions according to the invention, are described inter alia in "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., "Tensid-Taschenbuch" | Pocketbook of Surfactants], Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol I-III, Chemical Publishing Co., New York, 1980-81.
The agrochemical formulations generally contain from 0.1 to 99 per cent by weight, in particular from 0.1 to 95 % by weight, of safener or safener/herbicide active-substance mixture, from 1 to 99.9 % by weight, in particular from 5 to 99.8 % by weight, of a solid or liquid formulation auxiliary, and from 0 to 25 % by weight, in particular from 0.1 to 25 % by weight, of a surfactant.
While the preferred commercial product usually comprises concentrated compositions, the end user generally employs dilute compositions.
The compositions can also comprise further additives, such as stabilizers, defoamers, viscosity regulators, binders, adhesives and fertilizers or other active substances.
For the use of safeners of the formulae Ila to Ilg or of compositions comprising them for protecting crop plants against the damaging effects of herbicides of the formula I, a variety of methods and techniques are suitable, examples being the following:
i) Seed dressing a) The seeds are dressed by shaking them, in a vessel, together with an active substance of the formulae Ha to Ilg formulated as a wettable powder, until the active ingredient is distributed uniformly on the seed surface (dry seed dressing). In this case from about 1 to 500 g of active substance of the formulae Ha to Ilg (4 g to 2 kg of wettable powder) are used per 100 kg of seed.
b) The seeds arc dressed with an emulsion concentrate of the active substance of the formulae Ila to Ilg in accordance with method a) (wet seed dressing).
c) The seeds are dressed by immersing them into a liquor containing 100-1000 ppm of active substance of the formulae Ha to Ilg for from 1 to 72 hours and then, if desired, by drying the seeds (seed soaking).
The dressing of the seed and the treatment of the seedling which has begun to germinate are of course the preferred methods of application, since the treatment with the active substance is directed entirely towards the target crop. As a rule, from 1 to 1000 g of antidote, preferably from 5 to 150 g of antidote, are used per 100 kg of seed, it being possible to deviate from these limit concentrations up or down (repeat dressing), depending on the method, which also makes possible the addition of other active substances or micronutrients.
ii) Application as a tank mix
A liquid preparation of a mixture of antidote and herbicide (mutual quantitative ratio between 10:1 and 1:100) is used, the application rate of herbicide being from 0.005 to 5.0 kg per hectare. Such tank mixes are applied before or after sowing.
iii) Application in the seed drill
The safener is introduced into the open seed drill, containing seed, as an emulsion concentrate, wettable powder or in the form of granules. After the seed drill has been covered over, the herbicide is applied preemergence in a customary manner.
iv) Controlled release of active substance
The active substance of the formulae Ila to Ilg is applied in solution to mineral granule carriers or polymerized granules (urea/formaldehyde), which are then dried. If desired, a coating can be applied (coated granules), which enables the release of the active substance in regulated amounts over a defined period.
The examples which follow illustrate the invention in more detail without limiting it.
Formulation examples for mixtures of herbicides of the formula I and safeners of the formulae Ha to Ilg ( = per cent by weight)
FI. Emulsion concentrates a) b) c) d)
Active substance mixture 5 % 10 % 25 % 50 %
Calcium dodecylbenzenesulfonate 6 % 8 % 6 % 8 %
Castor oil polyglycol ether 4 % 4 % 4 %
(36 mol EO)
Octylphenol polyglycol ether 4 % 2 %
(7-8 mol EO)
Cyclohexanone 10 % 20 % Aromatic hydrocarbon mixture 85 % 78 % 55 % 16 % C9-C12
From such concentrates, by dilution with water, it is possible to produce emulsions of any desired concentration.
F2. Solutions a) b) c) d)
Active substance mixture 5 % 10 % 50 % 90 % l-Methoxy-3-(3-methoxypropoxy)- propane 20 % 20 %
Polyethylene glycol MW 400 20 % 10 %
N-Methyl-2-pyrrolidone 30 % 10 %
Aromatic hydrocarbon mixture 75 % 60 %
C9-C12
The solutions arc suitable for use in the form of very fine drops.
F3. Wettable powders a) b) c) d)
Active substance mixture
Sodium ligninsulfonate
Sodium lauryl sulfate
Sodium diisobutylnaphthalene- sulfonate 6 %
Octylphenol polyglycol ether
(7-8 mol EO)
Highly disperse silica 10 %
Kaolin
The active substance is mixed thoroughly with the additives and the mixture is ground thoroughly in a suitable mill. Wettable powders are obtained which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) c)
Active substance mixture 0.1 % 5 % 15
The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.
F5. Coated granules a) b) c)
Active substance mixture
Polyethylene glycol MW 200
Highly disperse silica
Inorganic carrier material 98.0 % 92 % 80 %
() 0J - 1 mm) such as, for example, CaCO3 or Siθ2
The finely ground active substance is applied uniformly in a mixer to the carrier material which has been wetted with polyethylene glycol. Dust-frce coated granules are obtained in this way.
F6. Extruded granules a) b) c) d)
Active substance mixture 0.1 % 3 % 5 % 15 %
Sodium ligninsulfonate 1.5 % 2 % 3 % 4 %
Carboxymethylcellulose 1.4 % 2 % 2 % 2 %
Kaolin 97.0 % 93 % 90 % 79 %
The active substance is mixed with the additives, and the mixture is ground and wetted with water. This mixture is extruded and subsequently dried in a stream of air.
F7. Dusts a) b) c)
Active substance mixture
Talc
Kaolin Ready-to-use dusts are obtained by mixing the active substance with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d)
Active substance mixture
Ethylene glycol
Nonylphenol polyglycol ether
(15 mol EO)
Sodium ligninsulfonate
Carboxymethylcellulose
37% aqueous formaldehyde solution
Silicone oil emulsion
Water
The finely ground active substance is intimately mixed with the additives. In this way a suspension concentrate is obtained from which, by dilution with water, suspensions of any desired concentration can be produced.
The ability of the safeners of the formulae Ha to Ilg to protect crop plants against the phytotoxic effect of herbicides of the formula I is illustrated in the following examples.
Biological examples
Example B 1 : Postemergence applications of mixtures of a herbicide of the formula I with a safener of the formulae Ila to Ilg to cereals
Under greenhouse conditions, wheat is grown in plastic pots to the 2.5 leaf stage. At this stage, both the herbicides of the formula I alone and also the mixture of the herbicides with a safener of the formulae Ila to Ilg are applied to the test plants. Application takes place in the form of an aqueous suspension of the test substances (Formulation Example F7) with 500 1 of water/ha. The application rates for herbicide and safener can be seen in Tables Bl, B2, B3 and B4. 28 days after application, the test is evaluated using a percentage scale. 100 % denotes that the test plant has died, while 0 % denotes no phytotoxic effect. The results obtained (cf. Table B 1 below) show that, with the safeners of the formulae Ila to Ilg, the damage caused to wheat by the herbicide of the formula I can be substantially reduced.
Table Bl: Herbicidal action of the compounds of the formula I without safener:
30 g/ha 15 g/ha 8 g/ha 4 g/ha
65% 65% 65% 65% 65% 65% 65% 30% 20% 10% 5%
Table B2: Herbicidal action of the compounds of the formula I with safener:
Herbicide
No. 1.01 125 g/ha 60 g/ha 30 g/ha
Safener 125 g/ha 60 g/ha 30 g/ha
No.
4.04 5.01 4.01 5.08 5.05 4.02 6.02 Table B3: Herbicidal action of the compounds of the formula I with safener:
Herbicide
No. 1.21 60 g/ha 30 g/ha 15 g/ha 8 g/ha 4 g/ha
Safener 30 g/ha 30 g/ha 30 g/ha 30 g/ha 30 g/ha
No.
4.01 20% 10% 5% 0% 0%
Table B4: Herbicidal action of the compounds of the formula I with safener:
Herbicide
No. 1.01 60 g/ha 30 g/ha 15 g/ha 8 g/ha 4 g/ha
Safener 30 g/ha 30 g/ha 30 g/ha 30 g/ha 30 g ha
No.
4.01 35% 30% 10% 5% 0%
Example B2: Postemergence applications of mixtures of a herbicide of the formula I with a safener of the formulae Ila to Ilg to maize
Under greenhouse conditions, maize is grown in plastic pots to the 2.5 leaf stage. At this stage, both the herbicides of the formula I alone and also the mixture of the herbicides with a safener of the formulae Ila to Ilg are applied to the test plants. Application takes place in the form of an aqueous suspension of the test substances (Formulation Example F7) with 5001 of water/ha. The application rates for herbicide and safener can be seen from Table B5. 19 days after application, the test is evaluated using a percentage scale. 100 % denotes that the test plant has died, while 0 % denotes no phytotoxic effect. The results obtained show that, with the safeners of the formulae Ila to Ilg, the damage caused to maize by the herbicide of the formula I can be substantially reduced.
Table B5: Herbicidal action of the compounds of the formula I and a mixture thereof with the safeners of the formula 11 in maize S .
Herbicide
No. 1.01 8 g/ha 4 g/ha
Safener 125 g/ha 125 g/ha
No.
no safener 70% 45%
8.007 45% 25%
7.003 60% 30% 8.005 60% 20%
7.004 50% 35%
Example B3: Postemergence applications of mixtures of a herbicide of the formula I with a safener of t e formulae Ila to Ilg to rice
Under greenhouse conditions, the test plants are sown or planted in plastic troughs in standard soil. Water is then introduced up to the surface of the soil. After 3 days, the water level is elevated by 2 cm and the herbicide is applied as an aqueous suspension (Example F7) on its own and in a tank mix with the safeners. The application rates for the herbicide can be seen from Table B6. The application rate for the safener is 125 g/ha. Cultivation of the test plants is then continued in the greenhouse under optimum conditions. 13 days after application, the test is evaluated using a percentage scale. 100 % denotes that the test plant has died, while 0 % denotes no phytotoxic effect. The results obtained show that, with the safeners of the formulae Ha to Ug, the damage caused to rice by the herbicide of the formula I can be substantially reduced.
Table B6: Herbicidal action of the compounds of the formula I and a mixture thereof with the safeners of the formula II in rice
"Yamabiko" rice "S-201" rice, water-type
Herbicide
No. 1.01 8 g/ha 4 g/ha 8 g/ha 4 g/ha
Safener No.
no safener 75% 65% 70 60
7.001 35% 30% 20 0

Claims

WHAT IS CLAIMED IS:
1. A selective-herbicidal composition, which comprises, in addition to customary inert formulation auxiliaries, an active substance comprising a mixture of
a) a herbicidally effective quantity of a herbicide of the formula I
in which
Z is C1-C10alkyl, C1-C10alkyl substituted by halogen, C3-C8cycloalkyl, R7O-, R7S(O)n-,
R7R8N-, R8CO-, R9ON=CR8-, (CH3)3Si-, -CN or oxiranyl, C2-C8alkenyl, C2-C8alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, C1-C6alkyl,
C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl,
C3-C8cycloalkyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, R8CO- or R9ON=CR8-,
C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen, C1-C10alkyl, phenyl, phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy,
C1-C6haloalkoxy or C1-C6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, oxo,
=NOR7, R8CO- or R9ON=CR8-, C3-C8cycloalkenyl, C3-C8cycloalkenyl substituted by halogen, C1-Cioalkyl, phenyl, phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl,
C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-,
(CH3)3Si-, -CN, oxo, =NOR7, R8CO- or R9ON=CR8-, -NR5R6, R10CON(R6)- or
R10SO2N(R6)-, where
R7 is hydrogen, C1-C10alkyl, C2-C8alkenyl, C2-C8alkynyl, phenyl or phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6-alkoxy-carbonyl,
n is 0, 1 or 2,
R8 is as defined for R7 or is C1-C6alkoxy, C3-C8alkenyloxy or C3-C8alkynyloxy,
R9 is C1-C10alkyl, C2-C8alkenyl or C2-C8alkynyl,
R10 is C1-C10alkyl, C1-C10alkyl substituted by halogen, R7O-, R7S(O)n-, -NR7R8 or -CN,
C2-C8alkenyl, C2-C8alkenyl substituted by halogen, R7O-, R7S(O)n-, -NR7R8 or -CN, phenyl or phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl, in which R7, n and R8 are as defined, R5 is C1-C10alkyl, C1-C10alkyl substituted by halogen, C3-C8cycloalkyl, R7O-, R7S(O)n-, R7R8N-, R8CO-, R9ON=CR8-, (CH3)3Si-, -CN or oxiranyl, C2-C8alkenyl, C2-C8alkenyl substituted by halogen, phenyl, phenyl substituted by halogen, C1-C6alkyl,
C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl,
C3-C8cycloalkyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, R8CO- or R9ON=CR8-, C2-C8alkynyl, C3-C8cycloalkyl, C3-C8cycloalkyl substituted by halogen, C1-C10alkyl, phenyl, phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, oxo, =NOR7, R8CO- or R9ON=CR8-, C3-C8cycloalkenyl, C3-C8cycloalkenyl substituted by halogen, C1-C10alkyl, phenyl, phenyl substituted by halogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy or C1-C6alkoxycarbonyl, R7O-, R7S(O)n-, R7R8N-, (CH3)3Si-, -CN, oxo, =NOR7, R8CO- or R9ON=CR8-, or is R7O- in which R7 is as defined, and
R6 is as defined for R5 or is hydrogen or together with R5 forms a C4-C7alkylene radical, or
Z is a radical of the formula
in which
R50 is hydrogen, halogen, -NO2, -CN, C1-C4alkyl, C1-C4alkyl substituted by halogen, -CN, -OCH3 or -SCH3, C2-C4alkenyl, C2-C4alkenyl substituted by halogen or OCH3, C2-C4alkynyl, C2-C4alkynyl substituted by halogen, -OCH3 or -Si(CH3)3,
C3-C6cycloalkyl, C3-C6cycloalkyl substituted by -F, -Cl or -CH3, -C(O)R100,
-OCH2CH2OR100, -OH, -C(R100)(OR110)(OR120), -CO2R130, -C(O)NR140R150- -N3, -SO2NR140R150, -SO3R160, -OSO2R170, phenyl, phenyl substituted by halogen, -CH3 or -OCH3, -O-R180, -S(O)bR180 or -(CH2)sG, in which b and s independently of one another are 0 or 1, R60 is hydrogen, halogen, -CN, -NO2, C1-C4alkyl, C1-C4alkyl substituted by halogen,
-CO2R130, -SO2NR140R150, -NR140R150, C1- or C2alkoxy, -OR190, -S(O)bR190, C1- or C2haloalkoxy, C1- or C2alkylthio, C1- or C2haloalkylthio, -CN, -OH or -SH, -CO2R130,
-SO2NR140R150, -NR140R150, -S(O)bR190 or -OR190,
R70 independently at each occurrence is hydrogen, C1-C4alkyl, C1-C4haloalkyl,
C2-C4alkenyl, phenyl, phenyl substituted by halogen, -S(O)bR190 or -OR190, -S(O)bR190,
-OR190 or halogen,
R80 is hydrogen, C1-C4alkyl, C1-C4haloalkyl, halogen, -CO2R130, -SO2NR140R150,
-OSO2R170, -S(O)bR180, -CN or -NO2, and
R90 is hydrogen, C1-C4alkyl, C1-C4alkyl substituted by halogen or phenyl, C2-C4alkenyl, phenyl or phenyl substituted by halogen, C1-C4alkyl, -NO2, -CN or C1-C4alkoxy, where
R100 is hydrogen, C1-C4alkyl, C1-C4alkyl substituted by halogen or -OCH3,
C3-C6cycloalkyl, C3-C6cycloalkyl substituted by halogen or -CH3, C2-C4alkenyl or
C2-C4alkynyl,
R110 and R120 independently of one another are C1-C4alkyl or R110 and R120 together are
-CH2CH2-, -CH2OCH2- or -CH2C(CH3)2CH2-,
R130 is hydrogen, C1-C4alkyl, C1-C4alkyl substituted by halogen, -CN, -CO2R100-
-NR140R150, -OR100 or -Si(CH3)3, C3-C4alkynyl, C3-C4alkynyl substituted by -CH3 or
-Si(CH3)3, C3-C6cycloalkyl, C3-C6cycloalkyl-C1-C4alkyl, C1-C4alkoxy or -Si(CH3)3,
R140 is hydrogen or C1-C4alkyl,
R150 is hydrogen, C1-C4alkyl, C1-C4alkoxy or C2-C4alkenyl, or R140 and R150 together are
-(CH2)2(CH2)a-(CH2)2- or -(CH2)2O(CH2)2-, in which a is 0 or 1,
R160 is C1-C4alkyl or C1-C4haloalkyl,
R170 is C1-C4alkyl or -NR140R150, in which R140 and R150 are as defined,
R 180 is C1-C4alkyl, C1-C4hal oalkyl, C2-C4alkoxyalkyl, C2-C4alkenyl, C3-C4alkynyl, phenyl or phenyl substituted by halogen, C1-C3alkyl, C1-C3alkoxy or C1-C3haloalkyl,
R190 is C1-C4alkyl or C1-C4alkyl substituted by -F, -Cl or -OR160,
q is 0 or 1,
G is a radical of the formula
0
in which R260 is hydrogen or C1-C3alkyl and
R27o is hydrogen, C1-C3alkyl or C2-C4alkenyl,
R2 is hydrogen, C1-C10alkyl, C1-C10alkyl substituted by C1-C6alkoxy or
C1-C6alkoxycarbonyl, C3-C8alkenyl or benzyl,
X and Y independently of one another are =N-, =CH- or =CR-, where either X or Y must be =N-, and in which R is halogen, C1-C6alkyl, C1-C6alkyl substituted by halogen, C1-C6alkoxy or C1-C6haloalkoxy, C1-C6 alkoxy or C1-C6haloalkoxy,
R3 and R4 independently of one another are hydrogen, halogen, C1-C10alkyl, R7O-,
R7S(O)n-, R7R8N-, C1-C10haloalkyl, C1-C10haloalkoxy, C1-C6alkoxy-C1-C6alkyl or phenylthio, where R7, n and R8 are as defined, or
R3 or R4, together with R, form a radical -OCH2CH2(CH2)m- or -(CH2)mCH2CH2O-, in which m is 0 or 1 ,
Ra is hydrogen, C1-C8alkyl, C1-C8alkyl substituted by hydroxy, C1-C8alkoxy, phenoxy, C1-C8alkylthio, phenylthio, (CH3)3Si-, C3-C8cycloalkyl, phenyl or di-C1-C8alkylamino,
C2-C6alkenyl, C2-C6alkenyl substituted by halogen, or Ra is C2-C6alkynyl,
C3-C8cycloalkyl, C3-C8cycloalkyl substituted by C1-C3alkyl, or Ra is C3-C6cycloalkenyl, phenyl, phenyl substituted by C1-C8alkyl, halogen, nitro, -CN, C1-C6alkoxy,
C1-C6haloalkoxy, phenoxy, -NR7R8 or R8CO-, in which R7 and R8 are as defined, or Ra is hydroxyl, halogen, tetrahydrothienyl, tetrahydrofuryl, furyl, pyridyl or thienyl,
Rb is hydrogen, C1-C8alkyl or phenyl, or Ra and Rb, together with the carbon atom to which they are attached, form a radical of the formula -CO-, and
m is 0 or 1 ;
and also salts and stereoisomers of the compounds of the formula I
and b) a herbicide-antagonistically effective quantity of a compound of the formula IIa
in which
R010 is hydrogen, C1-C8alkyl or C1-C8alkyl which is substituted by C1-C6alkoxy or C3-C6alkenyloxy, and
X2 is hydrogen or chlorine,
of a compound of the formula Ilb1
in which
E is nitrogen or methine,
R11 is -CCl3 or unsubstituted or halogen-substituted phenyl,
R12 and R13 independently of one another are hydrogen or halogen, and
R14 is C1-C4alkyl,
of a compound of the formula IIb2 in which
R12 and R13 are as defined above, and
R66, R67 and R68 independently of one another are C1-C4alkyl, of a compound of the formula IIc
in which
A2 is a group
R25 and R26 independenriy of one another are hydrogen, C1-C8alkyl, C3-C8cycloalkyl,
C3-C6alkenyl, C3-C6alkynyl, , or C1-C4alkyl which is substituted by C1-C4alkoxy or ; or R1 and R2 together form a C4-C6alkylene bridge
which can be interrupted by oxygen, sulfur, SO, SO2, NH or -N(C1-C4alkyl)-,
R27 is hydrogen or C1-C4alkyl;
Raa is hydrogen, halogen, cyano, trifluoromethyl, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn,
-SO2NRkRm or -OSO2-C1-C4alkyl;
Rg is hydrogen, halogen, cyano, nitro, C1-C4alkyl, C1-C4haloalkyl, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl, -COORj, -CONRkRm, -CORn, -SO2NRkRm,
-OSO2-C1-C4alkyl, C1-C6alkoxy, or C1-C6alkoxy substituted by C1-C4alkoxy or halogen,
C3-C6alkenyloxy, or C3-C6alkenyloxy substituted by halogen, or C3-C6alkynyloxy, or Ra and Rb together form a C3-C4alkylene bridge which can be substituted by halogen or C1-C4alkyl, or form a C3-C4alkenylene bridge which can be substituted by halogen or C1-C4alkyl, or form a C4alkadienylene bridge which can be substituted by halogen or C1-C4alkyl;
Rbb and Rh independently of one another are hydrogen, halogen, C1-C4alkyl,
trifluoromethyl, C1-C6alkoxy, C1-C6alkylthio or -COORj;
Rc is hydrogen, halogen, nitro, C1-C4alkyl or methoxy; Rd is hydrogen, halogen, nitro, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylsulfinyl, C1-C4alkylsulfonyl,
-COORj or CONRkRm;
Re is hydrogen, halogen, C1-C4alkyl, -COORj, trifluoromethyl or methoxy, or Rd and Re together form a C3-C4alkylene bridge;
Rf is hydrogen, halogen or C1-C4alkyl;
Rx and Ry independently of one another are hydrogen, halogen, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, -COOR28, trifluoromethyl, nitro or cyano;
Rj, Rk and Rm independently of one another are hydrogen or C1-C4alkyl; or
Rk and Rm together form a C4-C6alkylene bridge, which can be interrupted by oxygen, NH or -N(C1-C4alkyl)-;
Rn is C1-C4alkyl, phenyl, or phenyl which is substituted by halogen, C1-C4alkyl, methoxy, nitro or trifluoromethyl;
R28 is hydrogen, C1-Cl0alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkylthio-C1-C4alkyl, di- C1-C4alkylamino-C1-C4alkyl, halogen- C1-C8alkyl, C2-C8alkenyl, halo-C2-C8alkenyl,
C3-C8alkynyl, C3-C7cycloalkyl, halo-C3-C7cycloalkyl, C1-C8alkylcarbonyl, allylcarbonyl,
C3-C7cycloalkylcarbonyl, benzoyl which is unsubstituted or is substituted on the phenyl ring by up to three identical or different substituents consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy or C1-C4alkoxy; or furoyl, thienyl; or C1-C4alkyl substituted by phenyl, halophenyl, C1-C4alkylphenyl, C1-C4alkoxyphenyl, halo-C1-C4-alkylphenyl, halo- C1-C4alkoxyphenyl, C1-C6alkoxycarbonyl, C1-C4alkoxy-C1-C8- alkoxycarbonyl, C3-C8alkenyloxycarbonyl, C3-C8alkynyloxycarbonyl, C1-C8alkylthio- carbonyl, C3-C8alkenylthiocarbonyl, C3-C8alkynylthiocarbonyl, carbamoyl, mono-C1-C4-alkylaminocarbonyl, di-C1-C4alkylaminocarbonyl; or phenylaminocarbonyl which is unsubstituted or is substituted on the phenyl by up to three identical or different substituents consisting of halogen, C1-C4alkyl, halo-C1-C4alkyl, halo-C1-C4alkoxy or C1-C4alkoxy or by a single cyano or nitro substituent, or dioxolan-2-yl which is unsubstituted or is substituted by one or two C1-C4alkyl radicals, or dioxan-2-yl which is unsubstituted or is substituted by one or two C1-C4alkyl radicals, or C1-C4alkyl which is substituted by cyano, nitro, carboxyl or C1-Csalkylthio- C1-C8alkoxycarbonyl, of a compound of the formula IIe
in which
R33 and R34 independently of one another are C1-C6alkyl or C2-C6alkenyl; or R33 and R34
together are ;
R35 and R36 independently of one another are hydrogen or C1-C6alkyl;
or R33 and R34 together are ;
R37 and R38 independently of one another are C1-C4alkyl, or R37 and R38 together are -(CH2)5- ;
R39 is hydrogen, C1-C4alkyl or
; or R33 and R34 together are or ;
R40, R41, R42, R43, R44, R45, R46, R47, R48, R49, R050, R51, R52, R53, R54 and R55 independently of one another are hydrogen or C1-C4alkyl;
of a compound of the formula IIf
in which
R63 is hydrogen or chlorine and
R64 is cyano or trifluoromethyl,
or of a compound of the formula Ilg
in which
R65 is hydrogen or methyl.
2. A composition according to claim 1, which comprises as herbicide a compound of the formula I in which R3 and R4 are methoxy.
3. A composition according to claim 1, which comprises as herbicide a compound of the formula I in which R3 and R4 are methoxy and Z is C1-C10alkyl, C2-C8alkenyl or C2-C8haloalkenyl.
4. A composition according to claim 3, which comprises as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3 )=CH2 or -CH2-CH=CHCl.
5. A composition according to claim 1, which comprises as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3)=CH2 or -CH2-CH=CHCl and m is 0.
6. A composition according to claim 1, which comprises as safener a compound of the formula Ila, Ilb1, IIb2 or IIe.
7. A composition according to claim 6, which comprises as safener a compound of the formula IIb1 or IIb2.
8. A composition according to claim 6, which comprises as safener a compound of the formula IIa.
9. A composition according to claim 1, which comprises as herbicide a compound of the formula I in which Z is -CH2-CH(CH3)2, -CH2-C(CH3)=CH2 or -CH2-CH=CHCl and m is 0, and as safener a compound of the formula IIa.
10. A composition according to claim 9, which comprises as safener a compound of the formula IIa1
11. A process for the selective control of broad-leaved weeds and grasses in crops of useful plants, which comprises treating the useful plants, their seeds or seedlings or their cultivation area, simultaneously or separately, with a herbicidally effective quantity of a herbicide of the formula I and a herbicide-antagonistically effective quantity of a safener of the formulae Ila to Ilg.
12. A process according to claim 1 1, wherein crops of useful plants or cultivation areas for the crops of useful plants are trcated with from 0.001 to 2 kg/ha of a herbicide of the formula I and with a quantity of from 0.001 to 0.5 kg/ha of a safener of the formulae IIa to IIg.
13. A process according to claim 1 1, wherein the crops of useful plants are those of maize or cereals, especially rye, barley, oats or wheat.
EP96900566A 1995-01-19 1996-01-05 Herbicidal composition Withdrawn EP0804077A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH14595 1995-01-19
CH145/95 1995-01-19
PCT/EP1996/000032 WO1996022022A1 (en) 1995-01-19 1996-01-05 Herbicidal composition

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BR (1) BR9607487A (en)
CA (1) CA2209902A1 (en)
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PL (1) PL321244A1 (en)
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WO1998031226A1 (en) * 1997-01-15 1998-07-23 Novartis Ag Herbicidal agent
NZ768373A (en) 2014-10-06 2024-03-22 Vertex Pharma Modulators of cystic fibrosis transmembrane conductance regulator
AU2017240685B2 (en) 2016-03-31 2021-08-12 Vertex Pharmaceuticals Incorporated Modulators of cystic fibrosis transmembrane conductance regulator
HUE056716T2 (en) 2016-09-30 2022-03-28 Vertex Pharma Modulator of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator
LT3551622T (en) 2016-12-09 2021-02-25 Vertex Pharmaceuticals Incorporated Modulator of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator
WO2018227049A1 (en) 2017-06-08 2018-12-13 Vertex Pharmaceuticals Incorporated Methods of treatment for cystic fibrosis
WO2019018395A1 (en) 2017-07-17 2019-01-24 Vertex Pharmaceuticals Incorporated Methods of treatment for cystic fibrosis
TWI799435B (en) 2017-08-02 2023-04-21 美商維泰克斯製藥公司 Processes for preparing compounds
EP3697774B1 (en) 2017-10-19 2025-09-24 Vertex Pharmaceuticals Incorporated Crystalline forms and compositions of cftr modulators
CN111757874B (en) 2017-12-08 2024-03-08 弗特克斯药品有限公司 Methods for preparing modulators of cystic fibrosis transmembrane conductance regulator
TWI810243B (en) 2018-02-05 2023-08-01 美商維泰克斯製藥公司 Pharmaceutical compositions for treating cystic fibrosis
EP3774825A1 (en) 2018-04-13 2021-02-17 Vertex Pharmaceuticals Incorporated Modulators of cystic fibrosis transmembrane conductance regulator, pharmaceutical compositions, methods of treatment, and process for making the modulator

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RU2117662C1 (en) * 1992-03-03 1998-08-20 Кумиай Кемикал Индастри Ко., Лтд. Derivatives of n-sulfonylcarboxylic acid amide including n-containing 6-membered aromatic ring, fungicide and herbicide composition and methods of struggle against weeds and pathogenic fungi
EP0671880A1 (en) * 1992-07-08 1995-09-20 Ciba-Geigy Ag Selective herbicidal composition

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AR000734A1 (en) 1997-08-06
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ZA96400B (en) 1996-08-14
JPH10512272A (en) 1998-11-24
WO1996022022A1 (en) 1996-07-25
PL321244A1 (en) 1997-11-24
BR9607487A (en) 1997-12-23
AU4437296A (en) 1996-08-07

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