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WO2004082382A1 - Synergistic herbicidal composition comprising a herbicidally active compound in combination with an insecticide - Google Patents

Synergistic herbicidal composition comprising a herbicidally active compound in combination with an insecticide Download PDF

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Publication number
WO2004082382A1
WO2004082382A1 PCT/EP2004/002779 EP2004002779W WO2004082382A1 WO 2004082382 A1 WO2004082382 A1 WO 2004082382A1 EP 2004002779 W EP2004002779 W EP 2004002779W WO 2004082382 A1 WO2004082382 A1 WO 2004082382A1
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Prior art keywords
methyl
demeton
cypermethrin
superseded record
superseded
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PCT/EP2004/002779
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French (fr)
Inventor
Willy T. RÜEGG
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Syngenta Participations Ag
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Publication of WO2004082382A1 publication Critical patent/WO2004082382A1/en

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    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

Definitions

  • the present invention relates to a novel herbicidal composition
  • a novel herbicidal composition comprising a combination of herbicidal active ingredients that is suitable for selective weed control in crops of useful plants, such as, for example, in crops of maize.
  • the invention further relates to a method for the control of weeds in crops of useful plants, and to use of that novel composition for that purpose.
  • R is C.-C 2 alkyl or chlorine, R. is hydrogen or C . -C 4 alkyl and R 2 is C ⁇ -C 4 alkyl, have herbicidal activity.
  • the compounds of formula I and the preparation thereof are described, for example, in WO 98/31681 , and mixtures of those compounds with herbicides and safeners are known from WO 99/65314 and WO 02/98229.
  • variable amounts of active ingredients that is to say, a compound of formula I with one or more of the active ingredients listed below which are known for their insecticidal activity and some of which are also commercially available, exhibits a herbicidally synergistic action that is capable of controlling, both pre-emergence and post-emergence, the majority of weeds occurring especially in crops of useful plants.
  • a novel synergistic composition for selective weed control comprises as active ingredient a mixture of a) a herbicidally effective amount of at least one compound of formula I wherein R is C.-C 2 alkyl or chlorine, ⁇ is hydrogen or C.-C 4 alkyl and R 2 is C.-C alkyl, or an agronomically acceptable salt of such a compound, especially the sodium or ammonium salt, and b) an amount effective for herbicide synergism of one or more compounds or organisms producing such compounds selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (IR-isomer), allyxycarb, alpha- cypermethrin, phosphine (aluminium
  • XMC xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 , which are known only for their insecticidal activity, improves the action of the compound of formula I on its own on the weeds to be controlled without the insecticidal/acaricidal properties of those other active ingredients being adversely affected.
  • the composition according to the invention permits a greater flexibility with regard to subsequent crops.
  • composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica, and against undesired volunteer crops.
  • agronomically important weeds such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorg
  • composition according to the invention is suitable for all the methods of application usual in agriculture, such as pre-emergence application, early post-emergence application, post-emergence application, late post-emergence application and seed dressing.
  • Application of the active ingredients for uptake by the plants both above ground and below ground can be carried out in combinations that are applied simultaneously or in combinations that are separated in time (for example 7 days apart) during the growing season of the crop plant.
  • the composition according to the invention is suitable especially for weed control in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, maize and soybeans, and also for non-selective weed control.
  • Crops are to be understood as also including those which have been rendered tolerant towards herbicides or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) by conventional methods of breeding or genetic engineering.
  • herbicides or classes of herbicides such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors
  • An example of a crop that has been rendered tolerant towards imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • Crops are to be understood as also including those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle).
  • Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds).
  • the Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-0 451 878, EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529.
  • Plant crops or the seed thereof may be tolerant towards herbicides and, at the same time, also resistant to insect feeding (stacked transgenic events).
  • Seed may, for example, have the ability to express a Cry3 protein and, at the same time, be tolerant towards glyphosate.
  • Preferred herbicide-synergistic compositions comprise either a compound of formula la
  • Especially preferred synergistic mixtures according to the invention comprise the following active ingredient combinations:
  • IPSP IPSP Superseded record no. 1175 sazofos Superseded record no. 1177 sobenzan Superseded record no. 1178 sodrin Superseded record no. 1181 sofenphos 460 soprocarb 461 sopropyl O-(methoxyaminothiophos- 462 phoryl)salicylate isothioate Superseded record no. 1189 isoxathion 468 iodofenphos Superseded record no. 1193 name Pesticide Manual 12 th ed., Entry no.:
  • composition according to the invention comprises the compounds of formula I and the active ingredients or organisms abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1R-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athi- dathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyflu
  • the rate of application can vary within a wide range and depends on the nature of the soil, the type of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), on the cultivated plant, the weed to be controlled, the prevailing climatic conditions and on other factors determined by the type of application, the time of application and the target crop.
  • the active ingredient mixture according to the invention may be used at a rate of application of from 1 to 5000 g of active ingredient mixture/ha.
  • mixtures of the compounds of formula I with the compounds or organisms abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (IR-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-
  • emulsifiable concentrates e.g. emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, combinations of suspension and emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules.
  • suspoemulsions emulsifiable concentrates
  • wettable powders e.g. wettable powders, soluble powders, dusts, granules or microcapsules.
  • spraying, atomising, dusting, wetting, scattering or pouring are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the formulations i.e.
  • compositions, preparations or mixtures comprising the compounds (active ingredients) of formula I and abamectin, acephate, acetamiprid, acrinathrin, acrylo- nitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (l/ -isomer), allyxycarb, alpha- cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azo- thoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benz
  • methocrotophos methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phos
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
  • compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.
  • the amounts of oil additive in the composition according to the invention are generally from 0.01 to 2 %, based on the spray mixture.
  • the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
  • Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rape- seed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rh ⁇ ne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow.
  • mineral oils or an oil of vegetable origin for example rape- seed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rh ⁇ ne-Poulenc Canada Inc.
  • alkyl esters of oils of vegetable origin for example the methyl derivatives
  • an oil of animal origin such as fish oil or beef tallow.
  • Special preference is given to an additive that essentially comprises as active components 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight customary emulsifiers and pH modifiers.
  • Especially preferred oil additives comprise alkyl esters of higher fatty acids (C 8 -C__ 2 ), especially the methyl derivatives of C ⁇ 2 -C 18 fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9).
  • a preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE).
  • the application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants.
  • surface-active substances such as non-ionic, anionic or cationic surfactants.
  • suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
  • Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated C ⁇ 2 -C_ 2 fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
  • silicone surfactants especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants.
  • oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) and Actripron® (BP Oil UK Limited, GB).
  • an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action.
  • Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types.
  • the concentration of such solvents can be from 10 to 80 % by weight of the total weight.
  • oil additives which are also described, for example, in US-A-4 834 908, are especially preferred for the composition according to the invention.
  • a most especially preferred oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in US-A-4 834 908 in col. 5, as Example COC-1.
  • a further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada.)
  • alkyl pyrrolidones such as are commercially available e.g. as Agrimax®
  • formulations of synthetic latices such as, for example, polyacrylamide, polyvinyl compounds or poly- 1-p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®
  • propionic acid for example Eurogkem Pen-e-trate®
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture of the compounds of formula I with the compounds abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1/ -isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendio- carb
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxi- dised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxi- dised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • anti-foams for example silicone oil
  • preservatives for example silicone oil
  • viscosity regulators binders
  • tackifiers tackifiers
  • a suitable nitrogen source is NITRO-30® SRN (30-0-0; 10.38 lbs/gal, 3.1 lbs of N/gal), a slow- release nitrogen-containing solution with a content of 85 % nitrogen in the form of methylene urea.
  • NITRO-30® is commercially available and can be obtained, for example, from Monterey Chemical Co. Fresno, CA 93745-5000, USA.
  • Emulsifiable concentrates active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • active ingredient mixture 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Emulsif iable concentrates a) b) c) d) active ingredient mixture 5% 10% 25% 50% calcium dodecylbenzene- sulfonate 6% 8% 6% 8% castor oil polyglycol ether 4% - 4% 4%
  • Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
  • the solutions are suitable for application in the form of microdrops.
  • Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2 %
  • the active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.
  • the active ingredient 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 ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
  • Suspension concentrates a) b) c) d) active ingredient mixture 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
  • the finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • the compounds of formula I and the mixing partner(s) selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (Ift-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendio- carb, benfuracarb, bensultap, benzoximate, beta-cyflu
  • the compound of formula I and the mixing partners listed above can also be applied to the crops at separate times.
  • insecticidally active mixing partner it is possible for the insecticidally active mixing partner to be applied a few days after the compound of formula I without the synergistic herbicidal action of that combination being significantly affected.
  • compositions according to the invention may additionally comprise growth regulators, such as, for example, trinexapac (744), chlormequat chloride (129), clofencet (148), cyclani- lide (170), ethephon (281), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadi- one-calcium (595), uniconazole (746) or thidiazuron (703).
  • growth regulators such as, for example, trinexapac (744), chlormequat chloride (129), clofencet (148), cyclani- lide (170), ethephon (281), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat
  • composition according to the invention may also comprise fungicides, such as, for example, azoxystrobin (43), epoxico- soloole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cypro- conazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311 ), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426),
  • Y % herbicjdal action in the case of treatment with a compound selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1 f.-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, ben ⁇ oximate, beta
  • Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds in aqueous suspension are applied by spraying (500 I of water/ha). The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The test plants are then culti- vated in a greenhouse under optimum conditions. Evaluation of the tests is made after 36 days (% action, 100 % denotes that the plants have died, 0 % denotes no phytotoxic action). The mixtures used in this test give good results.
  • test plants are raised in plastics pots under greenhouse conditions to the 2- to 3-leaf stage.
  • a standard soil is used as the cultivation substrate.
  • the herbicides are applied individually and as mixtures to the test plants.
  • the test compounds are applied in the form of an aqueous suspension in 500 I of water/ha. The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. Evaluation of the tests is made after 33 days (% action, 100 % denotes that the plants have died, 0 % denotes no phytotoxic action). In this test also, the mixtures used give good results.

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

A herbicidal composition which, in addition to comprising customary inert formulation adjuvants, comprises: a) a herbicidally effective amount of at least one compound of formula (I) wherein R is C1-C2alkyl or chlorine, R1 is hydrogen or C1-C4alkyl and R2 is C1-C4alkyl, or an agronomically acceptable salt of such a compound, especially the sodium or ammonium salt, and b) an amount effective for herbicide synergism of an active ingredient known for its insecticidal action.

Description

SYNERGISTIC HERBICIDAL COMPOSITION COMPRISING A HERBICIDALLY ACTIVE COMPOUND IN COMBINATION WITH AN INSECTICIDE
Herbicidal Composition
The present invention relates to a novel herbicidal composition comprising a combination of herbicidal active ingredients that is suitable for selective weed control in crops of useful plants, such as, for example, in crops of maize. The invention further relates to a method for the control of weeds in crops of useful plants, and to use of that novel composition for that purpose.
The compounds of formula I
Figure imgf000002_0001
wherein R is C.-C2alkyl or chlorine, R. is hydrogen or C.-C4alkyl and R2 is Cι-C4alkyl, have herbicidal activity. The compounds of formula I and the preparation thereof are described, for example, in WO 98/31681 , and mixtures of those compounds with herbicides and safeners are known from WO 99/65314 and WO 02/98229.
Surprisingly, it has now been found that a combination of variable amounts of active ingredients, that is to say, a compound of formula I with one or more of the active ingredients listed below which are known for their insecticidal activity and some of which are also commercially available, exhibits a herbicidally synergistic action that is capable of controlling, both pre-emergence and post-emergence, the majority of weeds occurring especially in crops of useful plants.
According to the present invention, therefore, a novel synergistic composition for selective weed control is proposed that, in addition to comprising customary inert formulation adjuvants, comprises as active ingredient a mixture of a) a herbicidally effective amount of at least one compound of formula I
Figure imgf000003_0001
wherein R is C.-C2alkyl or chlorine, ^ is hydrogen or C.-C4alkyl and R2 is C.-C alkyl, or an agronomically acceptable salt of such a compound, especially the sodium or ammonium salt, and b) an amount effective for herbicide synergism of one or more compounds or organisms producing such compounds selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (IR-isomer), allyxycarb, alpha- cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, a∑adirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azo- thoate, Bacillus sphaericus, Bacillus ihuringiensis, Bacillus ihuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta- cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon telrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlor- pyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cyper- methrin, zeta-cypermethrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'- DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton- S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvin- phos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, hep- tenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydβmeton-methyl, oxy- deprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos- ethyl, pirimiphos-melhyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos-methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1 R)- isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thio- fanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron. trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901. It is extremely surprising that the combination of a compound of formula I with one or more active ingredients selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1 f?-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athi- dathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus ihuringiensis, Bacillus ihuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disul- fide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufo- mate, cryolite, cyanofenphos, cyanophos, cyanthoale, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cyper- methrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O- (methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxy- deprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos- ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyra- zophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyri- proxyfen, quinalphos, quinalphos-methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, letrachlorvinphos, tetramethrin, tetramethrin [(1R)- isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thio- fanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion. XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 , which are known only for their insecticidal activity, improves the action of the compound of formula I on its own on the weeds to be controlled without the insecticidal/acaricidal properties of those other active ingredients being adversely affected. The result of this is a considerable broadening of the weed spectrum and an additional increase in selectivity for crops of useful plants, as is necessary and desirable in the case of inadvertent overdosage of the active ingredient. Furthermore, while maintaining outstanding control of weeds in useful plants, the composition according to the invention permits a greater flexibility with regard to subsequent crops.
The composition according to the invention can be used against a large number of agronomically important weeds, such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Phaseolus, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica, and against undesired volunteer crops. The composition according to the invention is suitable for all the methods of application usual in agriculture, such as pre-emergence application, early post-emergence application, post-emergence application, late post-emergence application and seed dressing. Application of the active ingredients for uptake by the plants both above ground and below ground can be carried out in combinations that are applied simultaneously or in combinations that are separated in time (for example 7 days apart) during the growing season of the crop plant. The composition according to the invention is suitable especially for weed control in crops of useful plants, such as cereals, rape, sugar beet, sugar cane, plantation crops, rice, maize and soybeans, and also for non-selective weed control.
Crops are to be understood as also including those which have been rendered tolerant towards herbicides or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors) by conventional methods of breeding or genetic engineering. An example of a crop that has been rendered tolerant towards imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant towards herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady® and LibertyLink®.
Crops are to be understood as also including those which have been rendered resistant to harmful insects by genetic engineering methods, for example Bt maize (resistant to European corn borer), Bt cotton (resistant to cotton boll weevil) and also Bt potatoes (resistant to Colorado beetle). Examples of Bt maize are the Bt 176 maize hybrids of NK® (Syngenta Seeds). The Bt toxin is a protein that is formed naturally by Bacillus thuringiensis soil bacteria. Examples of toxins, or transgenic plants able to synthesise such toxins, are described in EP-A-0 451 878, EP-A-0 374 753, WO 93/07278, WO 95/34656 and EP-A-0 427 529. Plant crops or the seed thereof may be tolerant towards herbicides and, at the same time, also resistant to insect feeding (stacked transgenic events). Seed may, for example, have the ability to express a Cry3 protein and, at the same time, be tolerant towards glyphosate.
Preferred herbicide-synergistic compositions comprise either a compound of formula la
Figure imgf000008_0001
or a compound of formula lb
Figure imgf000008_0002
each in combination with a compound selected from abamec- tin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1/ϋ-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus ihuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfen- vinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, buto- carboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cypheno- thrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobu- carb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyamino- thiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda- cyhalothrin, lirimfos, lufenuron, lythidalhion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isolhiocyanate, metol- carb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocroto- phos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1R)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamido- thion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flu- fenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901.
Especially preferred synergistic mixtures according to the invention comprise the following active ingredient combinations:
compound of formula a or lb + lambda-cyhalothrin compound of formula a or lb + permethrin compound of formula a or lb + tefluthrin compound of formula a or lb + thiamethoxam compound of formula a or lb + lambda-cyhalothri n + permethrin compound of formula a or lb + lambda-cyhalothri ini + tefluthrin compound of formula a or lb + lambda-cyhalothri ini + thiamethoxam compound of formula a or lb + permethrin + tefluthrin compound of formula a or lb + permethrin + thiamethoxam compound of formula a or lb + tefluthrin + thiamethoxam compound of formula a or lb + lambda-cyhalothrin + permethrin + tefluthrin compound of formula la or lb + lambda-cyhalothrin + permethrin + thiamethoxam compound of formula la or lb + tefluthrin + thiamethoxam + lambda- cyhalotrin compound of formula la or lb + lambda-cyhalothrin + permethrin + tefluthrin + thiamethoxam compound of formula la or lb + bifenthrin compound of formula la or lb + carbofuran compound of formula la or lb + chlorpyrifos compound of formula la or lb + cyfluthrin compound of.formula la or lb + cypermethrin compound of formula la or lb + dimethoate compound of formula la or lb + endosulfan compound of formula la or lb + esfenvalerate compound of formula la or lb + indoxacarb compound of formula la or lb + malathion compound of formula la or lb + methomyl compound of formula la or lb + parathion-methyl/-ethyl compound of formula la or lb + propargite compound of formula la or lb + tebupirimfos + cyfluthrin compound of formula la or lb + terbufos compound of formula la or lb + zeta-cypermethrin compound of formula la or lb + Bacillus thuringiensis + toxins thereof
The following compounds used in the composition according to the invention are described in The Pesticide Manual, 12th ed., British Crop Protection Council, 2000:
name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) abamectin 1 acephate 4 acetamiprid 6 acrinathrin 11 acrylonitrile Superseded record no. 814 alanycarb 17 aldicarb 18 aldoxycarb Superseded record no. 815 aldrin Superseded record no. 816 allethrin (1 f?-isomer), 19 allyxycarb Superseded record no. 818 alpha-cypermethrin 197 phosphine (aluminium phosphide) 616 amidithion (822) aminocarb Superseded record no. 825 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) amiton Superseded record no. 827 amitraz 26 anabasine Superseded record no. 829 athidathion Superseded record no. 835 azadirachtin 42 azamethiphos 44 azinphos-ethyl 46 azinphos-methyl 47 azothoate Superseded record no. 840
Bacillus sphaericus 50
Bacillus ihuringiensis 52
Bacillus ihuringiensis delta endotoxin. barium polysulfide Superseded record no. 843 bendiocarb 60 benfuracarb 62 bensultap 68 beta-cyfluthrin 190 beta-cypermeth ri n 198 benzoximate 72 bifenthrin 76 bioallethrin 78 bioallethrin S-cyclopentenyl isomer 79 biopermethrin Superseded record no. 859 bioresmethrin 80 borax 85 bromfenvinfos Superseded record no. 865 bromophos Superseded record no. 871 bromophos-ethyl Superseded record no. 872 bufencarb Superseded record no. 875 buprofezin 97 butacarb Superseded record no. 877 name Pesticide Manual 12 ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) butathiofos Superseded record no. 878 butocarboxim 101 butonate Superseded record no. 883 butoxycarboxim 102 cadusafos 107 hydrogen cyanide 432 calcium polysulfide 109 camphechlor Superseded record no. 892 carbanolate Superseded record no. 894 carbaryl 113 carbofuran 116 carbon disulfide Superseded record no. 896 carbon tetrachloride Superseded record no. 897 carbophenothion Superseded record no. 898 carbosulfan 117 cartap 121 chlorbicyclen Superseded record no. 910 chlordane 128 chlordecone Superseded record no. 912 chlordimeform Superseded record no. 913 chlorethoxyfos 129 chlorfenapyr 130 chlorfenvinphos 131 chlorfluazuron 132 chlormephos 136 chloropicrin 140 chlorphoxim Superseded record no. 939 chlorprazophos Superseded record no. 940 chlorpyrifos 144 chlorpyrif os-methyl 145 chlorthiophos Superseded record no. 943 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) chromafenozide 150 clothianidin 165 coumaphos 173 coumithoate Superseded record no. 955 crotoxyphos Superseded record no. 959 crufomate Superseded record no. 960 cryolite 176 cyanofenphos Superseded record no. 969 cyanophos 182 cyanthoate Superseded record no. 970 cycloprothrin 185 cyfluthrin 189 cyhalothrin 192 cypermethrin 196 alpha-cypermethrin 197 beta-cypermethrin 198 theta-cypermethrin 199 zeta-cypermethrin 200 cyphenothrin 201 cyromazine 204 dazomet 210 bromo-DDT 213
DDT 213 pp'-DDT 213 decarbofuran Superseded record no. 984 deltamethrin 217 demephion Superseded record no. 987 demephion-O Superseded record no. 987 demephion-S Superseded record no. 987 demeton-S-methyl, demeton-methyl, 218 demeton-O-methyl name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) demeton-O, demeton-S, demeton Superseded record no. 988 demeton-S-methylsulphon Superseded record no. 989 diafenthiuron 220 dialifos Superseded record no. 992 diazinon 221 dicapthon Superseded record no. 1000 dichlofenthion Superseded record no. 1001 dichlorvos 230 dicrotophos 237 dicyclanil 238 dieldrin Superseded record no. 1020 diflubenzuron 244 dimefox Superseded record no. 1031 dimethoate 257 dimethrin Superseded record no. 1032 dimethylvinphos 260 dimetilan Superseded record no. 1035 dinex Superseded record no. 1038 dinotefuran ___oo diofenolan Superseded record no. 1048 dioxabenzofos Superseded record no. 1049 dioxacarb Superseded record no. 1050 dioxathion Superseded record no. 1051 disulfoton 273 dithicrofos Superseded record no. 1057
DNOC 277 emamectin 284
EMPC Superseded record no. 1069 empenthrin 285 endosulfan 287 endothion Superseded record no. 1070 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:)
EPN 290 epofenonane Superseded record no. 1075 esfenvalerate 295 ethiofencarb 301 ethion 302 ethoate-methyl Superseded record no. 1084 ethoprophos 305 ethylene dibromide 309 ethylene dichloride Superseded record no. 1086 etofenprox 312 etrimfos Superseded record no. 1092 famphur 316 fenchlorphos Superseded record no. 1098 fenethacarb Superseded record no. 1099 fenfluthrin Superseded record no. 1100 fenitrothion 328 fenobucarb 329 fenoxycarb 332 fenpirilhrin Superseded record no. 1105 fenpropathrin 334 fensulfothion Superseded record no. 1108 fenthion 338 fenvalerate 342 fipronil 347 flucofuron Superseded record no. 1115 flucycloxuron 359 flucythrinate 363 flufenprox Superseded record no. 1118 flumethrin 364 fluvalinate Superseded record no. 1130 fonofos Superseded record no. 1137 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) formetanate 393 formothion Superseded record no. 1139 fosmethilan Superseded record no. 1141 fospirate Superseded record no. 1142 fosthiazate 396 fosthietan Superseded record no. 1143 furathiocarb 400 furethrin Superseded record no. 1147 gamma-HCH 417
GY-81 411 halofenozide 413 heptachlor 419 heptenophos 420 hexaflumuron 427 hydramethylnon 431 hydrogen cyanide 432 hydroprene 433 midacloprid 446 miprothrin 448 ndoxacarb 453
IPSP Superseded record no. 1175 sazofos Superseded record no. 1177 sobenzan Superseded record no. 1178 sodrin Superseded record no. 1181 sofenphos 460 soprocarb 461 sopropyl O-(methoxyaminothiophos- 462 phoryl)salicylate isothioate Superseded record no. 1189 isoxathion 468 iodofenphos Superseded record no. 1193 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) kelevan Superseded record no. 1195 kinoprene 471 lambda-cyhalothrin 193 lirimfos Superseded record no. 1197 lufenuron 477 lythidathion Superseded record no. 1199 phosphine 616 malathion 478 mazidox Superseded record no. 1201 mecarbam 488 mecarphon Superseded record no. 1204 menazon Superseded record no. 1206 mephosfolan Superseded record no. 1207 mercurous chloride 499 mesulfenfos Superseded record no. 1209 metam 504 methacrifos Superseded record no. 1212 methamidophos 511 methidathion 513 methiocarb 514 methocrotophos Superseded record no. 1219 methomyl 515 methoprene 516 methoxychlor 517 methoxyfenozide 518 methyl bromide 520 methyl isothiocyanate 524 metolcarb 531 metoxadiazone Superseded record no. 1233 mevinphos 537 mexacarbate Superseded record no. 1235 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) milbemectin 538 mipafox Superseded record no. 1238 mirex Superseded record no. 1239 monocrotophos 543 morphothion Superseded record no. 1245 naled 549 naphthalene Superseded record no. 1248 nicotine 561 nifluridide Superseded record no. 1253 nitenpyram 562 nithiazine Superseded record no. 1255 nitrilacarb Superseded record no. 1257 novaluron 567 oleic acid 572 omethoate 573 oxamyl 581 oxydemeton-methyl 588 oxydeprofos Superseded record no. 1268 oxydisulfoton Superseded record no. 1269 parathion 593 parathion-methyl 594 pentachlorophenol 600 permethrin 603 petroleum oil 604 phenkapton Superseded record no. 1274 phenothrin 606 phenthoate 607 phorate 612 phosalone 613 phosfolan Superseded record no. 1282 phosmet 614 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) phosnichlor Superseded record no. 1283 phosphamidon 615 phoxim 617 phoxim-methyl Superseded record no. 1284 pirimetaphos Superseded record no. 1287 pirimicarb 627 pirimiphos-ethyl Superseded record no. 1288 pirimiphos-methyl 628 prallethrin 631 primidophos Superseded record no. 1292 profenofos 638 promacyl . Superseded record no. 1297 promecarb Superseded record no. 1298 propaphos 645 propetamphos 649 propoxur 654 prothiofos 658 prothoate Superseded record no. 1304 pymetrozine 660 pyraclofos 661 pyrazophos 664 pyresmethrin Superseded record no. 1309 pyrethrins 667 pyridaphenthion 671 pyrimidifen 675 pyrimitate Superseded record no. 1312 pyriproxyfen 677 quinalphos 680 quinalphos-methyl Superseded record no. 1318 quinothion Superseded record no. 1322 resmethrin 688 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) rotenone 690
RU 15525 691 sabadilla 693 schradan Superseded record no. 1331 silafluofen 696 sodium fluoride Superseded record no. 1341 sodium hexafluorosilicate Superseded record no. 1342 sophamide Superseded record no. 1344 spinosad 702 sulcofuron 709 sulfluramid 712 sulfotep 715 sulfuryl fluoride 718 su I prof os 719 tau-fluvalinate 388 tazimcarb Superseded record no. 1354
TDE Superseded record no. 1356 tebufenozide 725 tebupirimfos 727 teflubenzuron 732 tefluthrin 733 temephos 734
TEPP Superseded record no. 1358 terallethrin Superseded record no. 1359 terbufos 737 tetrachlorvinphos 741 tetramethrin 747 tetramethrin [(f?)-isomer] 748 thiamethoxam 751 thicrofos Superseded record no. 1369 thiocarboxime Superseded record no. 1372 name Pesticide Manual 12th ed., Entry no.:
(The e-Pesticide Manual 12th ed., Version
2.1 Entry no.:) thiodicarb 757 thiofanox 758 thiometon 759 thiosultap-sodium 271 tolfenpyrad 765 tralomethrin 768 transfluthrin 769 transpermethrin Superseded record no. 1382 triazamate 774 triazophos 776 trichlorfon 780 trichloronate Superseded record no. 1394 tridec-4-enyl acetate 785 trifenofos Superseded record no. 1397 triflumuron 790 trimethacarb 795 triprene Superseded record no. 1401 vamidothion 801
XMC 807 xylylcarb 808
ZXI 8901 812
Bistrifluron is described in K. S. Kim et al., Proc. Br. Crop Prot. Conf. - Pests Dis., 2000, 1, 41. Flonicamid (Λ/-(cyanomethyl)-4-(trifIuoromethyl)-3-pyridinecarboxamide) is known from M. Morita et al., Proc. Br. Crop Prot. Conf. - Pests Dis., 2000, 1 , 59 and EP-A-0 580 374. Methothrin (4-(methoxymethyl)benzyl (1 RS)-cis, frans-2,2-dimethyl-3-(2-methylprop-1 - enyl)cyclopropanecarboxylate) is registered under Chemical Abstracts No. CAS RN [34388- 29-9]; [11114-02-6]. Thiacloprid ((Z)-3-(6-chloro-3-pyridylmethyl)-1 ,3-thiazolidin-2-ylidene- cyanamide) is known from A. Elbert er al., Proc. Br. Crop Prot. Conf. - Pests Dis., 2000, 1, 21. Thiocyclam (Λ/,Λ/-dimethyl-1 ,2,3-trithian-5-ylamine hydrogen oxalate) is described in W. Berg & H. J. Knutti, Proc. Br. Insectic. Fungic. Conf. 8th, 1975, 2, 683.
The composition according to the invention comprises the compounds of formula I and the active ingredients or organisms abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1R-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athi- dathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disul- fide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufo- mate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cyper- methrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-
(methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kino- prene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothio- cyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphami- don, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, pro- poxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(I R)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamido- thion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flu- fenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 in any desired mixing ratio, usually with an excess of the one component over the other components. The mixing ratios (ratio by weight) between the compound of formula I and the mixing partners are generally from 1 :2000 to 2000:1 , especially from 200:1 to 1 :200.
The rate of application can vary within a wide range and depends on the nature of the soil, the type of application (pre- or post-emergence; seed dressing; application to the seed furrow; no tillage application etc.), on the cultivated plant, the weed to be controlled, the prevailing climatic conditions and on other factors determined by the type of application, the time of application and the target crop. In general, the active ingredient mixture according to the invention may be used at a rate of application of from 1 to 5000 g of active ingredient mixture/ha.
The mixtures of the compounds of formula I with the compounds or organisms abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (IR-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfen- vinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, buto- carboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chroma- fenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cypheno- thrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, ema- mectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobu- carb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyaminothio- phosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda- cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocroto- phos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufen- ozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetra- chlorvinphos, tetramethrin, tetramethrin [(1R)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermelhrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 can be used in unmodified form, i.e. as obtainable from synthesis. Preferably, however, they are formulated in customary manner with the adjuvants conventionally employed in formulation technology, such as solvents, solid carriers or surfactants, into e.g. emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, combinations of suspension and emulsion (suspoemulsions), wettable powders, soluble powders, dusts, granules or microcapsules. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, i.e. the compositions, preparations or mixtures comprising the compounds (active ingredients) of formula I and abamectin, acephate, acetamiprid, acrinathrin, acrylo- nitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (l/ -isomer), allyxycarb, alpha- cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azo- thoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta- cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bio- resmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlor- pyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, cro- toxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyflu- thrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zela-cypermethrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methyl- sulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimeti- lan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fen- valerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O- (methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb. methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos-methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau- fluvalinaie, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1R)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluaerypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 and, where appropriate, one or more solid or liquid formulation adjuvants, are prepared in a manner known perse, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, e.g. solvents or solid carriers. In addition, surface-active compounds (surfactants) can also be used in the preparation of the formulations.
Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending on the nature of the active ingredient to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants and mixtures of surfactants having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO 97/34485.
The surfactants customarily employed in formulation technology, which are described inter alia in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna, 1981 and M. and J. Ash, "Encyclopedia of Surfactants", Vol l-lll, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The compositions according to the invention can additionally include an additive comprising an oil of vegetable or animal origin, a mineral oil, alkyl esters thereof or mixtures of such oils and oil derivatives.
The amounts of oil additive in the composition according to the invention are generally from 0.01 to 2 %, based on the spray mixture. For example, the oil additive can be added to the spray tank in the desired concentration after the spray mixture has been prepared.
Preferred oil additives comprise mineral oils or an oil of vegetable origin, for example rape- seed oil, olive oil or sunflower oil, emulsified vegetable oil, such as AMIGO® obtainable from Rhδne-Poulenc Canada Inc., alkyl esters of oils of vegetable origin, for example the methyl derivatives, or an oil of animal origin, such as fish oil or beef tallow. Special preference is given to an additive that essentially comprises as active components 80 % by weight alkyl esters of fish oils and 15 % by weight methylated rapeseed oil, and also 5 % by weight customary emulsifiers and pH modifiers.
Especially preferred oil additives comprise alkyl esters of higher fatty acids (C8-C__2), especially the methyl derivatives of Cι2-C18fatty acids, for example the methyl esters of lauric acid, palmitic acid and oleic acid. Those esters are known as methyl laurate (CAS-111-82-0), methyl palmitate (CAS-112-39-0) and methyl oleate (CAS-112-62-9). A preferred fatty acid methyl ester derivative is Emery® 2230 and 2231 (Henkel subsidiary Cognis GMBH, DE).
The application and action of the oil additives can be improved by combining them with surface-active substances, such as non-ionic, anionic or cationic surfactants. Examples of suitable anionic, non-ionic and cationic surfactants are listed on pages 7 and 8 of WO 97/34485.
Preferred surface-active substances are anionic surfactants of the dodecylbenzylsulfonate type, especially the calcium salts thereof, and also non-ionic surfactants of the fatty alcohol ethoxylate type. Special preference is given to ethoxylated Cι2-C_2fatty alcohols having a degree of ethoxylation of from 5 to 40. Examples of commercially available, preferred surfactants are the Genapol types (Clariant AG, Muttenz, Switzerland). The concentration of surface-active substances in relation to the total additive is generally from 1 to 30 % by weight.
Also preferred for use as surface-active substances are silicone surfactants, especially polyalkyl-oxide-modified heptamethyltrisiloxanes, such as are commercially available as e.g. Silwet L-77®, and also perfluorinated surfactants.
Examples of oil additives that consist of mixtures of oils or mineral oils or derivatives thereof with surfactants are Edenor ME SU®, Turbocharge® (Zeneca Agro, Stoney Creek, Ontario, CA) and Actripron® (BP Oil UK Limited, GB).
The addition of an organic solvent to the oil additive/surfactant mixture can also bring about a further enhancement of action. Suitable solvents are, for example, Solvesso® (ESSO) and Aromatic Solvent® (Exxon Corporation) types. The concentration of such solvents can be from 10 to 80 % by weight of the total weight.
Such oil additives, which are also described, for example, in US-A-4 834 908, are especially preferred for the composition according to the invention. A most especially preferred oil additive is known by the name MERGE®, is obtainable from the BASF Corporation and is essentially described, for example, in US-A-4 834 908 in col. 5, as Example COC-1. A further oil additive that is preferred according to the invention is SCORE® (Novartis Crop Protection Canada.)
In addition to the oil additives listed above, in order to enhance the action of the compositions according to the invention it is also possible for formulations of alkyl pyrrolidones, such as are commercially available e.g. as Agrimax®, to be added to the spray mixture. Formulations of synthetic latices, such as, for example, polyacrylamide, polyvinyl compounds or poly- 1-p-menthene, such as are commercially available as e.g. Bond®, Courier® or Emerald®, can also be used to enhance action. Solutions that contain propionic acid, for example Eurogkem Pen-e-trate®, can also be added as action-enhancing agents to the spray mixture.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of active ingredient mixture of the compounds of formula I with the compounds abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1/ -isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendio- carb, benfuracarb, bensultap, benzoximate, beta-cyflulhrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-melhyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cypheno- thrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, ema- mectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobu- carb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(meth- oxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphami- don, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, pro- poxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(IR)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, tri- chloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 , from 1 to 99.9 % by weight of a solid or liquid formulation adjuvant and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxi- dised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients. The compositions according to the invention are preferably used in the presence of a nitrogen source. Such nitrogen sources are described, for example, in EP-A-0 584 227. A suitable nitrogen source is NITRO-30® SRN (30-0-0; 10.38 lbs/gal, 3.1 lbs of N/gal), a slow- release nitrogen-containing solution with a content of 85 % nitrogen in the form of methylene urea. NITRO-30® is commercially available and can be obtained, for example, from Monterey Chemical Co. Fresno, CA 93745-5000, USA.
Preferred formulations have especially the following compositions (% = percent by weight):
Emulsifiable concentrates: active ingredient mixture: 1 to 90 %, preferably 5 to 20 % surfactant: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
active ingredient mixture: 0.1 to 10 %, preferably 0.1 to 5 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient mixture: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surfactant: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient mixture: 0.5 to 90 %, preferably 1 to 80 % surfactant: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient mixture: 0.1 to 30 %, preferably 0.1 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
The following Examples further illustrate, but do not limit, the invention.
F1. Emulsif iable concentrates a) b) c) d) active ingredient mixture 5% 10% 25% 50% calcium dodecylbenzene- sulfonate 6% 8% 6% 8% castor oil polyglycol ether 4% - 4% 4%
(36 mol of ethylene oxide) octylphenol polyglycol ether - 4 % - 2 %
(7-8 mol of ethylene oxide) cyclohexanone - - 10 % 20 % arom. hydrocarbon 85 % 78 % 55 % 16 % - -co mixture C9-C12
Emulsions of any desired concentration can be obtained from such concentrates by dilution with water.
F2. Solutions a) b) c) active ingredient mixture 5 5 %% 1 100 %% 5 500 %% 90 %
1 -methoxy-3-(3-methoxy- propoxy)-propane - 20% 20% polyethylene glycol mol. wt.400 2 200 %% 10% .
N-methyl-2-pyrrolidone - - 30% 10% arom. hydrocarbon 75 % 60 % mixture C9-C12
The solutions are suitable for application in the form of microdrops.
F3. Wettable powders a) b) c) d) active ingredient mixture 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalene- sulfonate - 6% 5% 6% octylphenol polyglycol ether - 1 % 2 %
(7-8 mol of ethylene oxide) highly disperse silicic acid 1 % 3 % 5 % 10 % kaolin 88% 62% 35%
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, yielding wettable powders which can be diluted with water to give suspensions of any desired concentration.
F4. Coated granules a) b) ) active ingredient mixture 0.1 % 5% 15% highly disperse silicic acid 0.9 % 2% 2% inorg. carrier 99.0 % 93% 83%
(diameter 0.1 - 1 mm) e.g. CaCO3 or SiO2
The active ingredient 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 ingredient mixture 0.1 % 5% 15% polyethylene glycol mol. wt.200 1.0% 2% 3% highly disperse silicic acid 0.9 % 1 % 2% inorg. carrier 98.0 % 92% 80%
(diameter 0.1 -1 mm) e.g. CaCO3 or SiO2
The finely ground active ingredient is applied uniformly, in a mixer, to the carrier moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
F6. Extruder granules a) b) C) d) active ingredient mixture 0.1 % 3% 5% 15% sodium lignosulfonate 1.5 % 2% 3% 4% carboxymethylcellulose 1.4 % 2% 2% 2% kaolin 97.0 % 93% 90% 79% The active ingredient is mixed and ground with the adjuvants and the mixture is moistened with water. The resulting mixture is extruded and then dried in a stream of air.
F7. Dusts a) b) c) active ingredient mixture 0.1 % 1 % 5 % talcum 39.9 % 49 % 35 % kaolin 60.0 % 50 % 60 %
Ready-to-use dusts are obtained by mixing the active ingredient with the carriers and grinding the mixture in a suitable mill.
F8. Suspension concentrates a) b) c) d) active ingredient mixture 3 % 10 % 25 % 50 % ethylene glycol 5 % 5 % 5 % 5 % nonylphenol polyglycol ether - 1 % 2 % -
(15 mol of ethylene oxide) sodium lignosulfonate 3 % 3 % 4 % 5 % carboxymethylcellulose 1 % 1 % 1 % 1 %
37% aqueous formaldehyde 0.2 % 0.2 % 0.2 % 0.2 % solution silicone oil emulsion 0.8 % 0.8 % 0.8 /o 0.8 % water 87 % 79 % 62 % 38 %
The finely ground active ingredient is intimately mixed with the adjuvants, yielding a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
It is often more practical for the compounds of formula I and the mixing partner(s) selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (Ift-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendio- carb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cyclop roth rin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, elrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(meth- oxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphami- don, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, pro- poxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(IR)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamido- thion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flu- fenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 to be formulated separately and then to be combined in the applicator in the desired mixing ratio in the form of a "tank mixture" in water shortly before application. The compound of formula I and the mixing partners listed above can also be applied to the crops at separate times. For example, it is possible for the insecticidally active mixing partner to be applied a few days after the compound of formula I without the synergistic herbicidal action of that combination being significantly affected.
The compositions according to the invention may additionally comprise growth regulators, such as, for example, trinexapac (744), chlormequat chloride (129), clofencet (148), cyclani- lide (170), ethephon (281), flurprimidol (355), gibberellic acid (379), inabenfide (421), maleic hydrazide (449), mefluidide (463), mepiquat chloride (465), paclobutrazol (548), prohexadi- one-calcium (595), uniconazole (746) or thidiazuron (703). The composition according to the invention may also comprise fungicides, such as, for example, azoxystrobin (43), epoxico- nazole (48), benomyl (60), bromuconazole (89), bitertanol (77), carbendazim (107), cypro- conazole (189), cyprodinil (190), diclomezine (220), difenoconazole (228), diniconazole (247), epoxiconazole (48), ethirimol (284), etridiazole (294), fenarimol (300), fenbuconazole (302), fenpiclonil (311 ), fenpropidin (313), fenpropimorph (314), ferimzone (321), fludioxonil (334), fluquinconazole (349), flutolanil (360), flutriafol (361), imazalil (410), ipconazole (426), iprodione (428), isoprothiolane (432), kasugamycin (438), kresoxim-methyl (439), spirox- amine (441), mepronil (466), myclobutanil (505), nuarimol (528), pefurazoate (554), pency- curon (556), phthalide (576), probenazole (590), prochloraz (591), propiconazole (607), pyrazophos (619), pyroquilon (633), quinoxyfen (638), quintc__,_ine (639), tebuconazole (678), tetraconazole (695), thiabendazole (701 ), thifluzamide (705), triadimefon (720), triadimenol (721), tricyclazole (734), tridemorph (736), triflumizole (738), triforine (742), triticonazole (745) or vinclozolin (751 ). The number given in brackets after each active ingredient refers to the Entry No. of the respective active ingredients in The Pesticide Manual, 11th ed., British Crop Protection Council, 1997.
Biological Examples:
A synergistic effect exists whenever the action of the active ingredient combination of the compounds of formula I and one or more active ingredients selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (I -isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresrnethrin, bistrifluron, borax, bromfen- vinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chroma- fenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cypheno- thrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, ema- mectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobu- carb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyaminothio- phosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda- cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocroto- phos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufen- ozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1f.)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, tri- chloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 is greater than the sum of the actions of the active ingredients applied individually. The herbicidal action to be expected, We, for a given combination of two active ingredients can be calculated as follows (see COLBY, S.R. "Calculating synergistic and antagonistic response of herbicide combinations", Weeds 15, pages 20-22; 1967):
Figure imgf000041_0001
wherein:
X = % herbicidal action in the case of treatment with the compound of formula I using an application rate of p kg per hectare, in comparison with untreated control (= 0%).
Y = % herbicjdal action in the case of treatment with a compound selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1 f.-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, ben∑oximate, beta-cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfen- vinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chroma- fenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyfluthrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cypheno- thrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton- methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, ema- mectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobu- carb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyaminothio- phosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda- cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocroto- phos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, paralhion, parathion-melhyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos- methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufen- ozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(IR)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, tri- chloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 using an application rate of q kg per hectare, in comparison with untreated control. We = expected herbicidal action (% herbicidal action in comparison with untreated control) after treatment with the compounds of formula I and abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1R-isomer), allyxycarb, alpha-cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos- methyl, azothoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta- cyfluthrin, beta-cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bioresmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos- ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, car- baryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlorpyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, crotoxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyflulhrin, cyhalolhrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methylsulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimetilan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, etho- prophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlor- phos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropa- thrin, fensulfothion, fenthion, fenvalerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O-(methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxydeprofos, oxydisulfoton, parathion, parathion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos-ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pyme- trozine, pyraclofos, pyrazophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyri- midifen, pyrimitate, pyriproxyfen, quinalphos, quinalphos-methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluoro- silicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzu- ron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1/?)-isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin, triazamate, triazofos, trichlorfon, trichloronate, tridec-4-enyl acetate, trifenofos, triflumuron, trimethacarb, triprene, vamidothion, XMC, xylylcarb, spirodiclofen, acetoprole, fluacrypyrim, pyridalyl, noviflumuron, flufenerim, amidoflumet, ethiprole, acequinocyl, etoxazole, bifenazate, spiromesifen and ZXI 8901 at a rate of application of p + q kg of active ingredient per hectare. If the action actually observed is greater than the expected value We, there is a synergistic effect.
The synergistic effect of the combinations of the compound of formula I with the active ingredients mentioned above will be demonstrated in the following Examples.
Test description pre-emergence test:
Monocotyledonous and dicotyledonous test plants are sown in standard soil in plastics pots. Immediately after sowing, the test compounds in aqueous suspension are applied by spraying (500 I of water/ha). The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. The test plants are then culti- vated in a greenhouse under optimum conditions. Evaluation of the tests is made after 36 days (% action, 100 % denotes that the plants have died, 0 % denotes no phytotoxic action). The mixtures used in this test give good results.
Test description post-emergence test:
The test plants are raised in plastics pots under greenhouse conditions to the 2- to 3-leaf stage. A standard soil is used as the cultivation substrate. At the 2- to 3-leaf stage, the herbicides are applied individually and as mixtures to the test plants. The test compounds are applied in the form of an aqueous suspension in 500 I of water/ha. The rates of application depend on the optimum concentrations determined under field conditions and greenhouse conditions. Evaluation of the tests is made after 33 days (% action, 100 % denotes that the plants have died, 0 % denotes no phytotoxic action). In this test also, the mixtures used give good results.

Claims

What is claimed is:
1. A selective herbicidal composition that comprises as active ingredient a mixture of a) a herbicidally effective amount of at least one compound of formula I
Figure imgf000046_0001
wherein R is G.-C2alkyl or chlorine, R. is hydrogen or C.-C4alkyl and R2 is CrC4alkyl, or an agronomically acceptable salt of such a compound, and b) an amount effective for herbicide synergism of one or more compounds or organisms producing such compounds selected from abamectin, acephate, acetamiprid, acrinathrin, acrylonitrile, alanycarb, aldicarb, aldoxycarb, aldrin, allethrin (1f?-isomer), allyxycarb, alpha- cypermethrin, phosphine (aluminium phosphide), amidithion, aminocarb, amiton, amitraz, anabasine, athidathion, azadirachtin, azamethiphos, azinphos-ethyl, azinphos-methyl, azo- thoate, Bacillus sphaericus, Bacillus thuringiensis, Bacillus thuringiensis delta endotoxins, barium polysulfide, bendiocarb, benfuracarb, bensultap, benzoximate, beta-cyfluthrin, beta- cypermethrin, bifenthrin, bioallethrin, bioallethrin S-cyclopentenyl isomer, biopermethrin, bio- resmethrin, bistrifluron, borax, bromfenvinfos, bromophos, bromophos-ethyl, bufencarb, buprofezin, butacarb, butathiofos, butocarboxim, butonate, butoxycarboxim, cadusafos, hydrogen cyanide, calcium polysulfide, camphechlor, carbanolate, carbaryl, carbofuran, carbon disulfide, carbon tetrachloride, carbophenothion, carbosulfan, cartap, chlorbicyclen, chlordane, chlordecone, chlordimeform, chlorethoxyfos, chlorfenapyr, chlorfenvinphos, chlorfluazuron, chlormephos, chloropicrin, chlorphoxim, chlorprazophos, chlorpyrifos, chlor- pyrifos-methyl, chlorthiophos, chromafenozide, clothianidin, coumaphos, coumithoate, cro- toxyphos, crufomate, cryolite, cyanofenphos, cyanophos, cyanthoate, cycloprothrin, cyflu- thrin, cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, dazomet, bromo-DDT, DDT, pp'-DDT, decarbofuran, deltamethrin, demephion, demephion-O, demephion-S, demeton, demeton-O, demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl, demeton-S-methyl- sulphon, diafenthiuron, dialifos, diazinon, dicapthon, dichlofenthion, dichlorvos, dicrotophos, dicyclanil, dieldrin, diflubenzuron, dimefox, dimethoate, dimethrin, dimethylvinphos, dimeti- lan, dinex, dinotefuran, diofenolan, dioxabenzofos, dioxacarb, dioxathion, disulfoton, dithicrofos, DNOC, emamectin, EMPC, empenthrin, endosulfan, endothion, EPN, epofenonane, esfenvalerate, ethiofencarb, ethion, ethoate-methyl, ethoprophos, ethylene dibromide, ethylene dichloride, etofenprox, etrimfos, famphur, fenchlorphos, fenethacarb, fenfluthrin, fenitrothion, fenobucarb, fenoxycarb, fenpirithrin, fenpropathrin, fensulfothion, fenthion, fen- valerate, fipronil, flonicamid, flucofuron, flucycloxuron, flucythrinate, flufenprox, flumethrin, fluvalinate, fonofos, formetanate, formothion, fosmethilan, fospirate, fosthiazate, fosthietan, furathiocarb, furethrin, gamma-HCH, GY-81 , halofenozide, heptachlor, heptenophos, hexaflumuron, hydramethylnon, hydrogen cyanide, hydroprene, imidacloprid, imiprothrin, indoxacarb, IPSP, isazofos, isobenzan, isodrin, isofenphos, isoprocarb, isopropyl O- (methoxyaminothiophosphoryl)salicylate, isothioate, isoxathion, iodofenphos, kelevan, kinoprene, lambda-cyhalothrin, lirimfos, lufenuron, lythidathion, phosphine, malathion, mazidox, mecarbam, mecarphon, menazon, mephosfolan, mercurous chloride, mesulfenfos, metam, methacrifos, methamidophos, methidathion, methiocarb, methocrotophos, methomyl, methoprene, methothrin, methoxychlor, methoxyfenozide, methyl bromide, methyl isothiocyanate, metolcarb, metoxadiazone, mevinphos, mexacarbate, milbemectin, mipafox, mirex, monocrotophos, morphothion, naled, nicotine, nifluridide, nitenpyram, nithiazine, nitrilacarb, novaluron, oleic acid, omethoate, oxamyl, oxydemeton-methyl, oxy- deprofos, oxydisulfoton, parathion, parath ion-methyl, pentachlorophenol, permethrin, petroleum oil, phenkapton, phenothrin, phenthoate, phorate, phosalone, phosfolan, phosmet, phosnichlor, phosphamidon, phoxim, phoxim-methyl, pirimetaphos, pirimicarb, pirimiphos- ethyl, pirimiphos-methyl, prallethrin, primidophos, profenofos, promacyl, promecarb, propaphos, propetamphos, propoxur, prothiofos, prothoate, pymetrozine, pyraclofos, pyra- zophos, pyresmethrin, pyrethrins, pyridaben, pyridaphenthion, pyrimidifen, pyrimitate, pyri- proxyfen, quinalphos, quinalphos-methyl, quinothion, resmethrin, rotenone, RU 15525, sabadilla, schradan, silafluofen, sodium fluoride, sodium hexafluorosilicate, pentachlorophenol, sophamide, spinosad, sulcofuron, sulfluramid, sulfotep, sulfuryl fluoride, sulprofos, tau-fluvalinate, tazimcarb, TDE, tebufenozide, tebupirimfos, teflubenzuron, tefluthrin, temephos, TEPP, terallethrin, terbufos, tetrachlorvinphos, tetramethrin, tetramethrin [(1 R)- isomer], thiacloprid, thiamethoxam, thicrofos, thiocarboxime, thiocyclam, thiodicarb, thiofanox, thiometon, thiosultap-sodium, tolfenpyrad, tralomethrin, transfluthrin, transpermethrin,
PCT/EP2004/002779 2003-03-18 2004-03-17 Synergistic herbicidal composition comprising a herbicidally active compound in combination with an insecticide WO2004082382A1 (en)

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Cited By (9)

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WO2005053407A1 (en) * 2003-12-01 2005-06-16 Syngenta Participations Ag Pesticidally active combinations
WO2007060146A2 (en) * 2005-11-25 2007-05-31 Basf Se Herbicidal mixtures
CN102210319A (en) * 2010-03-31 2011-10-12 莫吉维特制药有限公司 Parasiticide formulation
CN103039497A (en) * 2012-12-28 2013-04-17 广西安泰化工有限责任公司 Insecticide composition containing dinotefuran and azadirachtin
CN104115863A (en) * 2014-08-19 2014-10-29 甘肃省农业科学院植物保护研究所 Weeding composition
CN106135260A (en) * 2015-04-28 2016-11-23 云南省农业科学院农业环境资源研究所 A kind of containing natural pyrethrum and the composition pesticide of Buprofezin and application
CN108142415A (en) * 2017-12-26 2018-06-12 河北农业大学 Method for preparing entomopathogenic nematode capsule
CN110140724A (en) * 2018-02-13 2019-08-20 江苏龙灯化学有限公司 A kind of Pesticidal combination
US11889833B2 (en) 2022-01-14 2024-02-06 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

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WO2002087322A2 (en) * 2001-04-27 2002-11-07 Syngenta Participations Ag Herbicidal composition

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WO1999065314A1 (en) * 1998-06-16 1999-12-23 Basf Aktiengesellschaft Herbicidal mixtures having a synergistic effect
WO2002087322A2 (en) * 2001-04-27 2002-11-07 Syngenta Participations Ag Herbicidal composition

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005053407A1 (en) * 2003-12-01 2005-06-16 Syngenta Participations Ag Pesticidally active combinations
US7973083B2 (en) 2003-12-01 2011-07-05 Syngenta Crop Protection Llc Pesticidally active compounds
WO2007060146A2 (en) * 2005-11-25 2007-05-31 Basf Se Herbicidal mixtures
WO2007060146A3 (en) * 2005-11-25 2007-08-02 Basf Ag Herbicidal mixtures
CN102210319A (en) * 2010-03-31 2011-10-12 莫吉维特制药有限公司 Parasiticide formulation
CN103039497A (en) * 2012-12-28 2013-04-17 广西安泰化工有限责任公司 Insecticide composition containing dinotefuran and azadirachtin
CN104115863A (en) * 2014-08-19 2014-10-29 甘肃省农业科学院植物保护研究所 Weeding composition
CN106135260A (en) * 2015-04-28 2016-11-23 云南省农业科学院农业环境资源研究所 A kind of containing natural pyrethrum and the composition pesticide of Buprofezin and application
CN108142415A (en) * 2017-12-26 2018-06-12 河北农业大学 Method for preparing entomopathogenic nematode capsule
CN108142415B (en) * 2017-12-26 2020-09-04 河北农业大学 Method for preparing entomopathogenic nematode capsule
CN110140724A (en) * 2018-02-13 2019-08-20 江苏龙灯化学有限公司 A kind of Pesticidal combination
US11889833B2 (en) 2022-01-14 2024-02-06 Enko Chem, Inc. Protoporphyrinogen oxidase inhibitors

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