SK4722003A3 - Agrochemical compositions with quinoline safeners and use thereof - Google Patents

Abstract

Agrochemical composition in the form of a concentrate comprising, in addition to customary formulation auxiliaries, a quinoline safener, wherein the quinoline safener has the formula (I) in which M is hydrogen, a mono-, di-or trivalent metal, ammonium, N(R)4 or HN(R)3, in which the radicals R are identical or different from each other and are C1-C16alkyl or C1-C16hydroxyalkyl, or M is S(R1)3 or P(R1)4, in which the radicals R1 are identical or different from each other and are C1-C20alkyl, C1-C20alkenyl, C1-C20alkynyl, aryl substituted by C1-C20alkyl, C1-C20alkenyl, C1-C20alkynyl or heteroaryl substituted by C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl or heteroaryl substituted by C1-C20alkyl, C2-C20alkenyl, C2-C20alkynyl, or 2 radicals R1 together with the sulphur or phosphorus atom to which they are bonded form a 5- or 6-membered ring.

Description

An agrochemical composition comprising quinoline antidotes and uses thereof

Technical field

The present invention relates to novel agrochemical compositions in the form of concentrates containing a quinoline antidote.

BACKGROUND OF THE INVENTION

Quinolines, their preparation and their action as antidotes are known from a number of patent documents and publications such as DE-A-2 546 845, (JS-A-3 351 525, Chem. Abstr. 79 (1973) 53154r and EP-A-94,349.

SUMMARY OF THE INVENTION

The present invention relates to agrochemical compositions in the form of concentrates containing, in addition to conventional formulation ingredients, a quinoline antidote having the general formula I

Cl (I) o-ch ₂ co where M is hydrogen, mono-, di- or trivalent metal, ammonium, N (R) 4 or HN (R) ₃ , wherein the R groups are the same or different and are (C 1 -C 16) alkyl or (C 1 -C 16) hydroxyalkyl, or M is S (R ¹ ) 3 or P (R ¹ ) 4, wherein the R ¹ groups are the same or different and are an alkyl group C 1 -C 20 alkenyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl substituted with C 2 -C 20 alkenyl, C 2 -C 2 alkynyl up to 20 carbon atoms or a heteroaryl group substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 atoms or R ² together with the sulfur or phosphorus atom to which they are attached form a five or six membered ring.

The metal atoms M which may be present in the quinoline antidote of the general formula I are preferably alkali metals and alkaline earth metals, in particular sodium, potassium, calcium, magnesium and in particular aluminum and iron, which are preferred representatives of the trivalent metal group.

Between alkyl and hydroxyalkyl groups R are also groups containing 12 to 16 carbon atoms and also those containing 1 to 4 carbon atoms. The N (R) ₄ and HN (R) ₃ groups particularly preferably contain a long chain and 2 or 3 short chain alkyl groups such as hexadecyltriethylammonium, tetradecyltriethylammonium, dodecyltriethylammonium, dodecylethyldimethylammonium and tetradodecylammonium. Preferred alkyl groups R ¹ contain 1 to 12, especially 1 to 6, carbon atoms. The alkyl groups R 1 and R ¹ may be further substituted, for example, with a halogen atom, an alkoxy group or a haloalkoxy group, preferably having 1 to 4 carbon atoms. Preferred alkenyl and alkynyl groups R ¹ contain 2 to 12 carbon atoms. They may contain more than one unsaturated bond and may be substituted by a halogen atom, an alkoxy group or a haloalkoxy group, preferably containing in each case 1 to 4 carbon atoms. Suitable examples of R ¹ include phenyl, naphthyl, tetrahydronaphthyl, indanyl and indenyl, wherein the phenyl is preferred. These groups may be substituted by the above-mentioned alkyl groups, alkenyl groups and alkynyl groups. Preferred heteroaryl groups R ¹ are five-membered and six-membered rings containing, in particular, nitrogen and / or oxygen atoms, such as pyridyl, pyrimidinyl, triazinyl, thienyl, thiazolyl, pyrazolyl, imidazolyl, piperidyl, dioxolanyl a morpholinyl group and a tetrahydrofuryl group. These heterocycles may also be further substituted by the above-mentioned alkyl groups, alkenyl groups and alkynyl groups. In either case, the two R ¹ groups together with the sulfur or phosphorus atom to which they are attached may form a ring. This process advantageously results in five-membered and six-membered rings which are saturated. Sulfonium and phosphonium cations which may be used in the present invention are described, for example, in International Patent Application WO 00/44227.

Preferred agrochemical compositions of the present invention comprise a quinoline antidote of formula I wherein M is hydrogen, sodium, potassium or tri (hydroxyethyl) ammonium.

Another group of preferred agrochemical compositions comprises a quinoline antidote of formula (I) wherein M is a calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetrafenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium alkyl portion of the alkyltrimethylammonium moiety; 12 to 16 carbon atoms, tetramethylammonium, trimethylhydroxyethylenammonium, tetradodecylammonium or dodecylethyldimethylammonium.

The compositions of the present invention have the advantage that the salts of the formula I have a very high melting point compared to the corresponding esters, which is very advantageous from the formulation point of view. The salts can be mixed into this type of formulation at higher concentrations than would be possible with the use of esters. Good solubility of the salts in water is also suitable; depending on the choice of cation, it can even be specifically regulated.

Antidotes of formula I may be prepared by conventional methods, for example by reaction of the corresponding methyl or 1-methylhexyl ester, both of which are known from European Patent Application EP-A-94 349, with an equimolar amount of metal hydroxide in an alcoholic solvent at room temperature.

In this way, the salts listed in the following table can be obtained.

Table 1

Compounds of formula I

Compound number M Melting point (° C) 1.1 On the > 250 1.2 The > 265 1.3 ca 1.4 mg 1.5 nh ₄ 227-228 1.6 NH (CH ₂ CH ₂ OH) ₃ 132-152 1.7 N [CH ₃₎ < 1.8 N (C ₁₂ H ₂₅ ) 4 1.9 N (C ₁₂ H ₂₅ ) (C ₂ H ₅ ) (CH ₃ ) 2 1.10 N (C ₁₂ H ₂₅ ) (CH ₃ ) 3 1.11 N (C ₁₂ H ₂₅ ) (C ₂ H ₅ ) ₃ 1.12 N (CH ₃ ) ₃ (CH ₂ CH ₂ OH) 1.13 Al 1.14 fe 1.15 H 232-233 1.16 S (CH _{3) 3} 1.17 S (C ₆ H ₅ ) ₃ 1.18 P (C ₆ H ₅ ) ₄ 1.19 P (C ₆ H ₅ ) ₃ CH ₃ 1.20 P (C ₆ H ₅ ) ₃ CH ₂ C ₆ H 5

Antidotes of Formula II

O-CH3COOM 'wherein M is calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetrafenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium containing from 12 to 16 carbon atoms in the alkyl moiety, alkyltriethylammonium radicals, alkyltriethylammonium dodecylethyldimethylammonium are novel and are also subject to the present invention.

The compositions of the present invention may also comprise a herbicide. This is preferably in the form of a compound selected from the group consisting of sulfonylureas, sulfonamides, imidazolinones, carbazones, aryloxyphenoxypropionates, cyclohexanediones, arylcarboxylic acids and aryloxycarboxylic acids.

Herbicides which are particularly suitable for combination with the antidotes of the formula I are in particular sulfonylureas, preferably triasulfuron, tribenuron, metsulfuron, tifensulfuron, flupyrsulfuron, iodosulfuron, rimsulfuron, nicosulfuron, cinosulfuron, bensulfuron, flenslamosulfuron, trifloxysulfoson, trifloxysulfoson, , chloransulam, florasulam and analogs thereof and imidazolinone, preferably imazetabenz, imazetapyr, imazachine, imazamox and analogs thereof, and also carbazones, preferably flucarbazone, propoxycarbazone, amicarbazone and analogs thereof, further aryloxyphenoxypropionates, fodxlizopopiz, , cyhalofop, haloxyfop and analogs and cyclohexanediones, preferably setoxydim, cletodim, tralkoxydim and analogs thereof, and arylcarboxylic acids, preferably dicamba and clopyralide, oxopyrazoline derivatives such as those described in International Patent Application WO 99/47525ar, and xylic acids, preferably 2,4-D, mecoprop, fluroxypyr and analogs thereof, further amicarbazone, azafenidine, benfluamide, benzfendizone, benzobicyclone, cinidonethyl, diclosulam, fentrazamide, flufenacet, flufenpyr, foramsulfuron, indanofan, mesosulfureno, mesosulfuron, petoxamide, picolinafen, profoxidim, profluazole, propoxycarbazone, pyraflufen, pyrazogyl, sulfosulfuron, tepraloxydim and tritosulfuron.

For application, the antidotes of the formula I, if necessary together with the herbicide, are suitably formulated together with the additives commonly used in the formulation of agrochemical compositions in the form of concentrates, for example emulsion concentrates (EC, EW and SL), suspension concentrates (SC ), suspension capsules (CS), liquids (FW and OF), powders (SP) or granules (WP, WG, SG and DG), with WP, WG, SG and SC concentrates being preferred. The abbreviations used according to the present invention correspond to the international names of unformulated and formulated pesticides listed in the FAO Specifications for Plant Protection Products, First Edition, January 1999, page 144 et seq. The compositions of the present invention are prepared in a known manner, for example by thoroughly mixing and / or grinding the active ingredients together with liquid or solid additives such as solvents or solid carriers. Furthermore, surfactants can also be used in the preparation of the formulations.

Suitable solvents include, for example: aromatic hydrocarbons, preferably fractions containing 8 to 12 carbon atoms, such as mixtures of xylenes or substituted naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols such as is ethanol, 2-ethylhexanol, oleyl alcohol, n-octanol, isotridecanol, cyclohexanol, tetrahydrofuryl alcohol and glycols such as ethylene glycol, dipropylene glycol, hexylene glycol, and also their ethers and esters such as butyl lactate, triethyl citrate, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether or ethylene glycol monomethyl ether; methylbenzoate, ketones such as cyclohexanone, acetophenone, butyrolactone, diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, N-octylpyrrolidone, dimethylsulfoxide or N, N-dimethylformamide and epoxidized and non-oxidized vegetable oils such as different trees, such as Pentadesma Sabine and the like (tallow oil), coconut oil, rapeseed oil or soybean oil; or water. Solvents available under the trade names and may also be suitable include Exxsol D-80®, Edenor ME-SU®, Edenor ME C6-10®, Emery 2231®, Polyglycol P 1200E®, Exxate 700®, Exxate 900®, Exxate 1000®, Atplus®, Solvesso 150®, Solvesse 200®, Benzoflex 9-88®, Genagen 4166®.

Substances which are used as solid carriers, for example for powders and dispersible powders, as a rule natural minerals such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly dispersed silica or highly dispersed absorbent polymers may also be added to improve the physical properties of the formulation. Suitable absorbent particulate carriers for the preparation of granules are porous type materials such as pumice, crushed bricks, sepiolite or bentonite, and suitable non-absorbent carriers are, for example, calcite and sand. Also suitable are solid urea / formaldehyde condensates and melamine / formaldehyde condensates. In addition, many pre-granulated materials of inorganic or organic origin, in particular dolomite or a mixture of plant residues, may also be used.

Suitable surfactants, depending on the nature and type of the active compound to be formulated, are nonionic, cationic and / or anionic surfactants and surfactant mixtures with good emulsifying, dispersing and wetting properties.

Suitable anionic surfactants may include not only those known as water-soluble surfactants, but also water-soluble synthetic surfactants.

Surfactants which may be mentioned include alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (containing 10 to 22 carbon atoms), such as sodium or potassium salts of oleic acid or stearic acid, or mixtures natural fatty acids, which can be obtained, for example, from coconut oil or tallow oil. Examples also include fatty acid methyltaurinates.

More commonly, however, substances known as synthetic surfactants are used, in particular fatty alcohol sulfonates, fatty alcohol sulfates, benzimidazole sulfone derivatives or alkylarylsulfonates.

Typically, fatty alcohol sulfonates or fatty alcohol sulfonates are present as alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and contain alkyl groups containing 8 to 22 carbon atoms, the alkyl group also including an alkyl group of an acyl group, for example sodium or a calcium salt of lignosulfonic acid, a dodecylsulfuric acid ester, or a mixture of fatty alcohol sulfate prepared from natural fatty acids. They also include salts of sulfuric acid esters and sulfonic acid / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfo groups and one fatty acid radical containing 8 to 22 carbon atoms. Alkylarylsulfonates are, for example, sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid / formaldehyde condensate.

Other suitable compounds are the corresponding phosphates, such as the phosphoric acid ester salts of the p-nonylphenol (4-14) ethylene oxide adduct, or phospholipids.

Examples of nonionic surfactants include polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids, and alkylphenols which may contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon chain and 6 to 18 atoms carbon in the alkyl group of alkylphenols. Other suitable nonionic surfactants are the water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol, and an alkylpolypropylene glycol having 1 to 10 carbon atoms in the alkyl chain containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene groups. The above compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Examples of nonionic surfactants include nonylphenolpolyethoxyethanes, castor oil polyglycol ethers, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octyifenoxypolyethoxyethanol.

Other suitable substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.

In particular, the cationic surfactants are quaternary ammonium salts which contain at least one alkyl group containing 8 to 22 carbon atoms as a substituent on a nitrogen atom and which contain a lower halogenated or free alkyl group, a benzyl group or a lower hydroxyalkyl group as further substituents. The salts are preferably in the form of halides, methylsulphates or ethylsulphates, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

Surfactants commonly used in the art are described, for example, in the following publications: Mc Cutcheon ' s Detergents and Emulsifiers Annual MC Publishing Corp. &amp; Ridgewood, New Jersey, 1981, Stache, H., Tensid-Taschenbuch [surfactant guide], Carl Hanser Verlag, Minich / Vienna, 1981, and M. and J. Ash, Encyclopedia of Surfactants, Vol. I-III, Chemical

Publishing Co., New York, 1980-81.

The agrochemical compositions of the present invention generally contain 0.1 to 99% by weight, in particular 0.1 to 95% by weight of an antidote, if appropriate together with a herbicide, 1 to 99% by weight of a solid or liquid formulation additive and 0 to 25% by weight. %, in particular 0.1 to 25% by weight, of a surfactant.

The composition may also contain other additives such as stabilizers, for example, non-oxidized or epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), anti-foaming agents such as silicone oil, preservatives, viscosity control agents, binders, thickeners and fertilizers of another active substance.

The present invention also relates to a method of selectively controlling weeds in crops which comprises treating the crops, their seeds or clippings or the place where they are grown with a herbicidally effective amount of a herbicide and a herbicidally antagonistic effective amount of an antidote of formula I, either simultaneously or separately .

The areas under crops are the areas of land on which the crops of the crops are sown or the seeds of these crops are sown and also the land on which the crops are to be grown.

Suitable crops which can be protected against the damaging effect of the abovementioned herbicides by means of antidotes of the formula I are, in particular, cereals, corn, sorghum and millet, rice, sugar cane, commercial grasses and ornamental grasses and soybeans, cotton, sugar beet and others. broadleaf crops. Crops also include those that have become resistant to herbicides or classes of herbicides in conventional plant growing methods or recombinant methods.

The weeds that can be controlled may be monocotyledonous and dicotyledonous weeds such as Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Poa, Phalaris, Alopecurus , Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Gallium, Viola, Lamium, Veronica and Cynodon.

Depending on the intended use, the antidote of formula (I) may be used to pre-treat the seeds of useful plants (seed dressings or cuttings) or added to the soil before or after sowing. However, it can also be applied after emergence of plants, either alone or together with a herbicide. Thus, the treatment of plants or seeds with an antidote may in principle be performed independently of the time of application of the herbicide. However, plants can also be treated by applying the herbicide and the antidote simultaneously (e.g. in the form of a tank mix). In the present invention, the antidote and herbicide may be present in separate concentrates, but may also be present in a single concentrate.

Prior to use, the concentrates are treated with conventional diluents such as water, oils or liquid fertilizers or mixtures thereof. In addition, adjuvants such as nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with or without surfactants may also be used active substances, vegetable oil derivatives with or without surfactants, alkylated derivatives of vegetable or mineral oils with or without surfactants, fish oils and other animal oils of animal origin and their alkylated derivatives with or without surfactants, natural above fatty acids, preferably those containing 8 to 28 carbon atoms, and alkyl ester derivatives thereof, organic acids containing an aromatic ring system and one or more carboxyl residues, and alkylated derivatives thereof further, suspensions of vinyl acetate polymers or vinyl acetate / acrylic acid copolymers, mixtures of individual adjuvants with each other and in combination with organic solvents may have a further advantageous effect. Examples of nonionic surfactants which are suitable are polyglycol ether derivatives of aliphatic and cycloaliphatic alcohols, saturated and unsaturated fatty acids and alkylphenols, which may preferably contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon group and 6 to 6 carbon atoms. 18 carbon atoms in the alkyl group of alkylphenols. Other suitable nonionic surfactants are polyethylene adducts with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol, preferably having 1 to 10 carbon atoms in the alkyl chain, which are water-soluble and preferably contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene groups. The above compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Other examples of nonionic surfactants are nonylphenolpolyethoxyethanols, castor oil polyethylene glycol ethers, polypropylene / polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. Among the anionic surfactants, particularly preferred are alkyl sulfates, alkyl sulfonates, alkylarylsulfonates, alkylated phosphoric acid derivatives and ethoxylated derivatives thereof. The alkyl groups usually contain 8 to 24 carbon atoms. Preferred nonionic surfactants are known under the trade names: polyoxyethylene-alkylamine (e.g., AMIET® 105 (Kao Co.)), polyoxyethylene-oleylamine (e.g., AMIET® 415 (Kao Co.)), nonylphenolpolyethoxyethanes, polyoxyethylene stearylamine (e.g., AMIET® 320) ), N-polyethoxyethylamines (e.g. GENAMIN® (Hoechst AG)), N, N, N ', N'-tetra (polyetoxypolypropoxyethyl) ethylenediamines (e.g. TERRONIL® and TETRONIC® (BASF Wyandotte Corp.)),

BRIJ ® (Atlas Chemicals), ETHYLAN ® CD and ETHYLAN ® D (Diamond Shamrock), GENAPOL ® C, GENAPOL ® 0, GENAPOL ® S and GENAPOL ® X080 (Hoechst AG), EMULGEN ® 104P, EMULGEN ® 109P and EMULGEN ® 408 (Kao Co.); DISTY (R) 125 (Geronazzo), SOPROPHOR (R) CY 18 (Rhône Poulenc S.A.); NONISOL® (Ciba-Geigy), MRYL® (ICI); TWEEN ® (ICI); EMULSOGEN® (Hoechst AG); AMIDOX ® (Stephan Chemical Co.), ETHOMID ® (Armak Co.); PLURONIC® (BASF Wyandotte Corp.), SOPROPHOR® 461 P (Rhone Poulenc SA), SOPROPHOR® 496 / P (Rhone Poulenc SA), ANTAROX FM-63 (Rhone Poulenc SA), SLYGARD 309 (Dow Corning), SILWET 408, SILWET L-7607N (Osi Specialties). In particular, the cationic surfactants are quaternary ammonium salts which contain at least one alkyl group containing 8 to 22 carbon atoms as a substituent on a nitrogen atom and which contain a lower halogenated or free alkyl group, a benzyl group or a lower hydroxyalkyl group as further substituents. The salts are preferably in the form of halides, methylsulfates or ethylsulfates, for example stearyltrimethylammonium chloride or benzyl-di (2-chloroethyl) ethylammonium bromide. The oils used are either of mineral or natural origin. Natural oils may also be of animal or vegetable origin. In the case of animal oils, beef tallow is particularly preferred, but fish oils (e.g., sardine oil) and derivatives thereof may also be used. In most cases, vegetable oils are seed oils of different origins. Examples of vegetable oils are, in particular, coconut oils, rapeseed oils or sunflower oils and derivatives thereof. Surfactants, oils, in particular vegetable oils, derivatives thereof such as alkylated fatty acids and mixtures thereof, for example preferably with anionic surfactants such as alkylated phosphoric acid derivatives, alkyl sulfates and alkylarylsulfonates and higher fatty acids, which are commonly used in areas of formulations and additives and which are also used in the compositions and spray compositions of the present invention are described, for example, in Mc Cutcheon ' s Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood New Jersey, 1988, Stache,

H., Tensid-Taschenbuch (surfactant guide), Carl Hanser Verlag, Munich / Vienna, 1990, M. and J. Ash, Encyclopedia of Surfactants, Vol. I-IV, Chemical Publishing Co., New York, 1981-89, G. Kapusta, A Compendium of Herbicide Adjuvants, Southern Illinois Univ., 1998, L. Thomson Harvey, A Guide to Agricultural Spray Adjuvants Used in the United States, Thomson Pubns., 1992. Preferred adjuvants are commercially available under the tradenames Merge, Score, Actipron, Amigo, Emery, Edenor, Partna and Hasten.

The amount of antidote applied relative to the herbicide to be administered depends mainly on the type of application. In the case of a pole treatment, which is carried out either using a tank mix comprising a combination of antidote and herbicide or by applying the antidote and herbicide separately, the herbicide to antidote ratio generally ranges from 1: 100 to 1: 1, preferably 1:50 to 5: 1 .

In the case of field treatment, the application rates are generally in the range of 0.001 to 5.0 kg of antidote / ha, preferably in the range of 0.001 to 0.5 kg of antidote / ha.

The amount of herbicide applied is generally in the range of 0.001 to 2 kg / ha, but preferably in the range of 0.005 to 1 kg / ha.

The compositions of the present invention are suitable for all application methods commonly used in agriculture, such as pre-emergence application, post-emergence application and seed dressing.

Various methods and techniques, such as those described below, are suitable for the use of the antidotes of formula (I) or compositions containing them for the protection of crop plants against the harmful effects of herbicides:

(i) Seed dressing

a) Pickling the seeds with an antidote formulated as a wettable powder by shaking the container until the surface of the seeds is homogeneously coated (dry seed treatment).

About 1 to 500 g of antidote (4 g to 2 kg of wettable powder) is used per 100 kg of seed.

b) Pickling the seeds with an antidote emulsion concentrate according to method a) (pickling the seeds in a liquid).

c) Pickling the seeds by dipping the seeds in a liquid containing 100 to 1000 ppm of an antidote, preferably 1 to 72 hours, followed, if necessary, by drying the seeds (seed soaking). If necessary, only a short dip of the seeds is sufficient.

Seed pickling or germinating seedlings treatment are obviously preferred routes of application, since antidote treatment is targeted to a particular crop. As a rule, 1 to 1000 g of antidote, preferably 5 to 250 g of antidote, are used per 100 kg of seed, but it is also possible to deviate from the above-mentioned concentrations in both directions depending on the methodology which also allows to add other active substances or micronutrients seed treatment).

ii) Application as a tank mix

A liquid preparation of an antidote / herbicide mixture (the ratio of the amount being in the range of 10: 1 to 1: 100) is used, the amount of herbicide applied being in the range of 0.005 to 5.0 kg per hectare. This tank mix is applied before or after vacuuming.

iii) Sowing application

The antidote, in the form of an emulsion concentrate, wettable powder or granules, is applied to the uncovered seeds in the seed furrow. After covering the seed furrow, the herbicide is applied pre-emergence in a conventional manner.

(iv) Controlled release of the active substance

The dissolved antidote of formula I is applied to a mineral granular carrier or polymer granules (urea / formaldehyde) and allowed to dry. If appropriate, a coating (coated granules) may be applied to allow slow release of the active agent over time.

In particular, preferred formulations have the following composition: (active ingredient = antidote + herbicide;% = weight percent).

Emulsifiable concentrates:

active ingredient mixture: 1 until 90%, preferably 5 to 20% surfactant: 1 until 30%, preferably 10 to 20% liquid carrier: 5 until 94%, preferably 70 to 85%

powders:

active ingredient mixture:

solid carrier:

0.1 to 10%, preferably 0.1 to 5%

99.9 to 90%, preferably 99.9 to 99%

Suspension concentrates: active ingredient mixture:

Water:

surfactant:

Wettable powders:

active ingredient mixture:

surfactant:

solid carrier:

up to 75%, preferably 10 to 50% 94 to 24%, preferably 88 to 30% to 40%, preferably 2 to 30%

0.5 to 90%, preferably 1 to 80%

0.5 to 20%, preferably 1 to 15% to 95%, preferably 15 to 90%

granules:

active ingredient mixture:

solid carrier:

0.1 to 30%, preferably 0.1 to 15%

99.5 to 70%, preferably 97 to 85%

Dispersible granules:

active ingredient mixture:

surfactant:

solid carrier:

0.5 to 90%, preferably 1 to 80%

0.5 to 20%, preferably 1 to 15% to 95%, preferably 15 to 90% more

The following examples illustrate the present invention in detail in no way limit it.

DETAILED DESCRIPTION OF THE INVENTION

Examples of formulations of mixtures of herbicides and antidotes of formula I (active ingredient mixture = antidote + herbicide;% = weight percent)

Fl Emulsion Concentrates

a) b) c) d) mixture of active substance 5% 10% 25% 50% calcium dodecylbenzenesulfonate 6% 8% 6% 8% polyglycol ether ric. oil (36 mol EO) 4% - 4% 4% octylphenyl polyglycol ether (7-8 mol EO) - 4% - 2% cyclohexanone - - 10% 20% a mixture of aromatic hydrocarbons C9-12 85% 78% 55% 16% Emulsions of any desired concentration the they can prepare

F2 Solutions from these concentrates dilute with water.

a) b) c) d) mixture of active substance 5% 10% 50% 90% l-methoxy-3- (3-methoxypropoxy) propane - 20% 20% - polyethylene glycol MW 400 20% 10% - - N-methyl-2-pyrrolidone - - 30% 10% a mixture of aromatic hydrocarbons C9-12 75% 60% - -

The solutions are suitable for use as microspheres.

F3 Wettable powder a) b) c) d) active mixture substances 5% 25% 50% 80% Lignosulfonate sodium 4% - 3% - lauryl sodium 2% 3% - 4% diisobutylnaphthalenesulfonate sodium - 6% 5% 6% polyglycol ether of octylphenyl (7-8 moles EO) - 1% 2% - highly dispersed silica 1% 3% 5% 10% kaolin 88% 62% 35% - Activated the substances are mixed thoroughly with additives and grind with <

together in a suitable mill. This gives powders which can be diluted with water to give a suspension of any desired concentration.

F4 Coated granules

a) b) c) mixture of active substance 0, 1% 5% 15% highly dispersed silica 0, 9% 2% 2% inorganic carrier (0 0.1-1 mm), 99.0% 93% 83%

for example CaCO ₃ or SiO ₂

The active substance was dissolved in dichloromethane, the carrier was sprayed with the solution, and the solvent was then evaporated in vacuo.

F5 Coated granules

a) b) c) mixture of active substance 0,1% 5% 15% polyethylene glycol MW 200 1,0% 2% 3% highly dispersed silica 0,9% 1% 2% inorganic carrier (0 0.1-1 mm), 98.0% 92% 80% for example CaCO ₃ or SiO ₂ Apply in a mixer finely ground active substance on a carrier, which has been pre-wetted with polyethylene glycol. They are thus obtained dust-free coated granules. F6 Extruded granules a) b) c) d) mixture of active substance 0,1% 3% 5% 15% sodium lignosulfonate 1,5% 2% 3% 4% carboxymethylcellulose 1,4% 2% 2% 2% kaolin 97,0% 93% 90% 80%

The active ingredient is mixed with the ingredients, ground and moistened with water. This mixture is extruded and then dried in a stream of air.

F7 Powders mixture of the active substance talc kaolin

a) b) c) 0,1% 1% 5% 39,9% % 49 35 ° 60,0% 50% 601

Powders ready for use are obtained by mixing the active ingredient with carriers and grinding the mixture in a suitable mill.

Preferred WP formulations of the present invention comprise 5 to 50% by weight of an antidote or antidote + herbicide, 1 to 15% by weight of a dispersant (e.g. lignosulfonates such as Attisol II, Ufoxan 3A), 0 to 30% by weight of a wetting agent (e.g. is Genapol X-080, Morwet EFW, Genapol LRO), 5 to 90% by weight of a carrier (e.g., Pergopak M, sodium sulfate, silica, aluminum silicate, Sopropon TA 72).

F8 Suspension concentrates

a) b) c) d) mixture of active substance 3% 10% 25% 50% ethylene glycol 5% 5% 5% 5% nonylphenyl polyglycol ether (15 mol EO) - 1% 2% - sodium lignosulfonate 3% 3% 4% 5% ' carboxymethylcellulose 1% 1% 1% 1% 37% aqueous formaldehyde solution 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0,8% 0,8% 0, 8% 0,8% Water 87% 79% 62% 38% Suspension concentrates a) to glycol. If appropriate, they may: (d) they also need not contain: further include, for example ethylene 0.2%

xanthan gum.

Particularly suitable SC formulations contain 1 to 700 g / l antidote or herbicide + antidotes, 0 to 100 g / l dispersant (e.g. Soprophor 3D33, Soprophor 4D384, Atlox 4913, Morwet D425), 0 to 30 g / l water (e.g. Genapol X-080, Morwet EFW, Genapol LRO, sodium lauryl sulphate), 0 to 50 g / l of buffer (for example citric acid, lactic acid, sodium phosphates, sodium carbonate and sodium hydroxide), 0 to 100 g / l of antifreeze (for example propylene glycol) , glycerols, sodium sulfate), 0 to g / l thickening agent (Kelzan S, Rheozan, Laponite BD, Thixosil, Aerosil 200, Attagel 50, Bentone 36), 0 to 50 g / l preservative (e.g. Proxel GXL, formalin, orthophenylphenol ), 0 to

400 g / l filler (for example calcium carbonate, kaolin, diatomaceous earth, silica) and 0 to 50 g / l antifoam (for example Rhodosil 426 R, silicone oils, Fluowet 80 B).

F9 Dispersible granules

a) b) c) d) mixture of active substance 5% 25% 50% 80% sodium lignosulfonate 4% - 3% - sodium lauryl sulfate 2% 3% - 4% sodium diisobutylnaphthalenesulfonate - 6% 5% 6% octylphenyl polyglycol ether (7-8 mol EO) - 1% 2% - highly dispersed silica 1% 3% 5% 10% kaolin 88% 62% 35%

The finely divided active substance is thoroughly mixed with the ingredients. A suspension concentrate is obtained from which a suspension of any desired concentration can be prepared by dilution with water.

The water-soluble active agents, for example the salts of the compounds of the formula I according to the invention, can also be formulated preferably as SG formulations. These preferably contain 0 to 50% by weight of an antidote of formula I in salt form, 0 to 20% by weight of a dispersant (e.g. Morwet D425, Borresperse NA, Geropon TA72, Soprophor FL, Soprophor S40), 0 to 20% by weight of a wetting agent (e.g. EFW, Tinovetin B, Genapol LRO), 0 to 5% by weight of an antifoam (e.g., Rhodosil 426, Fluowet 80B) and 0 to 99% by weight of a carrier (e.g., ammonium sulfate, sodium sulfate, kaolin, carbonates, diatomaceous earth).

It is often more advantageous to formulate the active compound of the formula I and the herbicide individually and mix them in water in the application equipment in the desired mixing ratio shortly before application, for example in the form of a tank mix.

The ability of the antidotes of formula I to protect crops from the phytotoxic effect of herbicides is illustrated in the following examples.

The examples that follow illustrate the present invention in more detail.

Example

Corn, barley and wheat seeds are sown in a greenhouse in plastic pots containing 0.5 L of garden soil. Once the plants have emerged and reach the 2-3 leaf stage, the antidote of formula A is applied and, for comparison, the known antidote Cloquintocet-mexyl (The Pesticide Manual, 11th edition (BCPC) 1997, No. 154) together with the herbicide (as an antidote mixture) of formula I and clodinafop; as a tank mix in the case of the herbicides tralkoxydim, mesotrione, thifensulfuron, propoxycarbazone and florasulam). The protective action of the antidote (in% of phytotoxicity) is evaluated 20 days after application. As shown in Tables 2 to 8 below, all antidotes used are as or more active as Cloquintocet-mexyl.

Table 2

The action of the antidote on the herbicide of the general formula A

herbicide 407 + cloquintocet 500 250 125 g / ha herbicide (A) + 1.15 H 500 250 125 g / ha herbicide (A) + 1.01 On the 500 250 125 g / ha herbicide (A) + 1.02 The 500 250 125 g / ha Barley Manitou 20 10 10 5 0. 0 20 10 0 0 0 0

The herbicide of formula A is 8- (2,6-diethyl-4-methylphenyl) -9-oxo-1,2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1,4,5] 2,2-dimethylpropionic acid oxadiaze23 pin-7-yl ester.

The herbicide / antidote mixture was used as WG 24.

Table 3

Effect of antidote on ciodinafop

clodinafop + cloquintocet 240 120 60 g / ha clodinafop + 1.15 240 120 60 g / ha clodinafop + 1.01 240 120 60 g / ha clodinafop + 1.02 240 120 60 g / ha Barley Manitou 20 5 5 0 0 0 0 0 0 25 0 0

The herbicide / antidote mixture was used as WG 36.

Table 4

Effect of antidote on tralkoxydim

tralkoxydim + cloquintocet 500 + 125 250 + 62.5 g / ha tralkoxydim + 1.15 500 + 88.5 250 + 44.25 g / ha tralkoxydim + 1.01 500 + 97 250 + 48.5 g / ha tralkoxydim + 1.02 500 + 102 250 + 51 g / ha Arina wheat 10 0 0 0 10 0 0 0

Tralkoxydim is used as SC 250, atidotum as WP 25.

Table 5

Effect of antidote on mesotrione

mesotrione mesotrione mesotrione mesotrione tCloquintocet + 1.15 + 1.01 + 1.02 500 + 125 500 + 88.5 500 + 97 500 + 102 250 + 62.5 250 + 44.25 250 + 48.5 250 + 51 g / ha g / ha g / ha g / ha Sweet corn 5 5 0 5 Marista 5 0 0 0

Mesotrione is used as SC 100, antidote as WP 25.

Table 6

Effect of antidote on tifensulfuron

thifensulfuron thifensulfuron thifensulfuron thifensulfuron + cloquintocet + 1, 15 + 1.01 + 1.02 100 + 50 100 + 17.5 100 + 19.5 100 + 20.5 25 + 12.5 50 + 8.75 50 + 9.75 50 + 10.25 g / ha g / ha g / ha g / ha Arina wheat 0 0 0 0 0 0 0 0

Tifensulfuron is used as WG 75, antidote as WP 25.

Table 7

Effect of antidote on propoxycarbazone

Propoxycarbonyl. + cloquintocet 100 + 50 100 + 25 g / ha Propoxycarbonyl. + 1.15 200 + 35 100 + 17.5 g / ha Propoxycarbonyl. + 1.01 200 + 39 100 + 19.5 g / ha Propoxycarbonyl. + 1.02 200 + 41 100 + 20.5 g / ha Arina wheat 40 40 30 30 25 30 30 30

Propoxycarbazone is used as WG 70, antidote as WP 25.

Table 8

Effect of antidote on florasulam

florasulam florasulam florasulam florasulam + cloquintocet 4- 1,15 + 1.01 + 1.02 100 + 25 100 + 17.5 100 + 19.5 100 + 20.5 50 + 12.5 50 + 8.75 g / ha g / ha g / ha g / ha Arina wheat 30 30 20 15 25 25

Florasulam is used as SC 50, antidote as WP 25.

For ready-to-use mixtures (Tables 2 and 3), the herbicide of formula A and the antidote are used together in WG 24. This formulation contains 24% by weight of the herbicide of formula A, 6% by weight of the antidote, 10% by weight of Morwet, 5% Tinivetin B as wetting agent, 2% Geropon as dispersant, 1% silicone oil as antifoam, and 12% carrier (10% Pergopak M, 5% anhydrous sodium sulfate, 7% Doatom 236 B). Clodinaflop together with antidotes is used as WG 36. WG 36 has the following composition: 36.2% clodinaflop, 7.8% antidote 1.02 or 6.7% antidote 1.15 or 6.8% antidote 1.05 or 7.3 % by weight antidotes 1.01, 15% by weight (Jfoxane 3A as dispersant, 2% by weight Geropon TA-72 as dispersant, 1% by weight silicone oil as antifoam (Antifoam A TK 50) and 38% by weight carrier (15% by weight Pergopack M , 10% by weight anhydrous sodium sulfate, the remainder to 100% Diatom 236 B).

In general, WG formulations which are particularly suitable for the needs of the present invention are those containing 1 to 45% by weight herbicide + antidotes, 5 to 25% by weight dispersant, 0 to 5% by weight antifoam and 10 to 40% by weight carrier. .

However, the herbicide and antidote can also be used as a formulation according to Examples F1 to F9. Essentially the same results are achieved.

For tank mix application (Tables 4 to 8), the antidotes are used as WP 25 in the following composition: 25% by weight antidotes of formula I or Cloquintocet, 5% by weight lignosulfonate (Attisol II), 1% isotridecanol EO 8 (Genapol X) -080), 5% urea / formaldehyde condensate (Pergopack M), 3% furandione / trimethylpentene polymer (Sopropon TA 72) and 61% aluminum silicate (Kaolin Pulver AG).

When formulated as WG, SC or SG, essentially the same results are obtained. A typical SC formulation for use according to the present invention comprises: 400 g / l antidote 1.01, 1.02, 1.05 or 1.15, 20 g / l dispersant Soprophor 4D384, 20 g / l Genapol X-080, 5 g / l buffer (citric acid) , 60 g / l antifreeze (propylene glycol), 2 g / l thickener (Kelzan S), 0 to 50 g / l preservative (Proxel GXL), 50 g / l filler (kaolin), 5 g / l antifoam ( Rhodosil 426 R). A typical WG formulation of the present invention comprises 1 to 45% by weight of an antidote, 5 to 25% by weight of a dispersant, 0 to 5% by weight of an antifoam, and 10 to 40% by weight of a carrier. those listed for the SC formulation.

For tank mix application, the remaining herbicides may be applied as described above for the herbicide of formula A; however, since this is true with respect to the above experiments, they can also be used in commercially available formulations.

An agrochemical composition in the form of a concentrate, characterized in that it contains, in addition to the conventional formulation auxiliaries, a quinoline antidote of the general formula I

Claims (12)

PATENT CLAIMS Cl (I) o-ch ₂ co where M is hydrogen, mono-, di- or trivalent metal, ammonium, N (R) 4 or HN (R) ₃ , wherein the R groups are the same or different and are (C 1 -C 16) alkyl or (C 1 -C 16) hydroxyalkyl, or M is S (R ¹ ) 3 or P (R ¹ ) 4, wherein the R ¹ groups are the same or different and are an alkyl group C 1 -C 20 alkenyl, C 2 -C 20 alkenyl, C 2 -C 20 alkynyl, C 1 -C 20 alkyl substituted with C 2 -C 20 alkenyl, C 2 -C 2 alkynyl up to 20 carbon atoms or a heteroaryl group substituted with an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms in carbon, or 2 R ¹ groups together with the sulfur atom or the phosphorus atom to which they are attached form a 5- or 6-membered ring. Composition according to claim 1, characterized in that it comprises a quinoline antidote of the general formula I, in which M is a hydrogen atom, a sodium atom, a potassium atom or tri (hydroxyethyl) ammonium. Composition according to claim 1, characterized in that it comprises a quinoline antidote of the general formula I, wherein M is a calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetrafenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium alkyl group, alkyltrimethylammonium alkyl moieties. alkyl, triethylammonium containing from 12 to 16 carbon atoms in the alkyl moiety, tetramethylammonium, trimethylhydroxyethylenammonium, tetradodecylammonium or dodecylethyldimethylammonium. Composition according to claim 1, characterized in that it comprises a herbicide. Composition according to claim 1, characterized in that it contains as a herbicide a substance selected from the group consisting of sulfonylureas, sulfonamides, imidazolinones, carbazones, aryloxyphenoxypropionates, cyclohexanediones, arylcarboxylic acids and aryloxycarboxylic acids. The composition of claim 1, wherein the concentrate is SC, CS, EW, OF, FW, WG, SG, DG, SP, WP, EC, or SL. The composition of claim 1, wherein the concentrate is SC, WG, SG or WP. A method for controlling the growth of unwanted plants, characterized in that after dilution with conventional diluents on the useful plants or their environment, the composition according to claim 1 is applied independently of the time of application of the herbicide. The method of claim 8, wherein the diluents comprise an adjuvant. A method for controlling the growth of unwanted plants, characterized in that a herbicidally effective amount of the composition according to claim 4 is applied to the crop plants or their environment after dilution with conventional diluents. The method of claim 10, wherein the diluent comprises an adjuvant. 12. A compound of formula II Cl (II) o-ch ₂ co where M is calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetrafenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium containing from 12 to 16 carbon atoms in the alkyl portion of 12 to 16 carbon atoms; carbon atoms, tetramethylammonium, trimethylhydroxyethylenammonium, tetradodecylammonium or dodecylethyldimethylammonium.