MXPA03003467A - Agrochemical compositions with quinoline safeners. - Google Patents

Abstract

The present invention relates to an agrochemical composition in the form of a concentrate comprising, in addition to the usual formulation aids, a quinoline protective agent, wherein the quinoline protective agent has the following formula (I), (see formula) wherein M is hydrogen, a mono-, di-astrivalent, ammonium, N (R) 4 or HN (R) 3 metal, in which the radicals R are identical or different from each other and are C1-C16 alkyl or hydroxyalkyl C1 -C16, or M is S (R1) 3OP (R1) 4, in which the radicals R1 are identical or different from each other and are C1-C20 alkyl or C2-C20 alkenyl, C2-C20 alkynyl, aryl substituted by C1-C20 alkyl , C2-C20 alkenyl, C2-C20 alkynyl or heteroaryl substituted by C1-C20 alkyl or C2-C20alkynyl C2-C20 alkynyl, or, two radicals R1 together with the phosphorus or sulfur atom to which they are bonded to form a 5-6 ring element

Description

AGROCHEMICAL COMPOSITIONS WITH QUINOLINE PROTECTIVE AGENTS DESCRIPTION OF THE INVENTION The present invention relates to novel agrochemical compositions in the form of concentrates comprising a quinoline protection agent. The quinolines, their preparation and their action as protective agents have been disclosed in a number of publications such as DE-A-2 546 845, US-A-3 351 525, Chem. Abstr. 79 (1973) 53154r and EP-A-94 349. The present invention relates to agrochemical compositions in the form of concentrates comprising, in addition to the usual formulation adjuvants, a quinoline protective agent, in which the quinoline protective agent has the following formula wherein M is hydrogen, a mono-, di- or trivalent, ammonium, N (R) 4 or HN (R) 3 metal, in which the radicals R are identical or different from each other and are Ci-Ci 6 alkyl or hydroxyalkyl d-Cje, or M is S (Ri) 3 or P (Ri) 4, in which the radicals Ri are identical or different from each other and are alkyl Ref. : 145694 Ci-C2c or C2-C2Q alkenyl, C2-C2 alkynyl, aryl substituted by Ci-C20 alkyl, C2-C20 alkenyl, C2-20 alkynyl or heteroaryl substituted by C1-C20 alkyl or C2-C20 alkenyl or C2- alkynyl C20, or, two radicals RL together with the phosphorus or sulfur atom to which they are bound to form a ring of 5 or 6 elements. The metallic M atoms which may be present in the quinoline protecting agents of Formula I are preferably those of the alkali metals and alkaline earth metals, in particular sodium, potassium, calcium, magnesium and, in particular, aluminum and iron as Preferred representatives of trivalent metals. Preferred radicals between the alkyl R and hydroxyalkyl radicals are those having from 12 to 16 carbon atoms and also those having from 1 to 4 carbon atoms. The radicals N (R), and HN (R) 3 especially preferably comprise long chain alkyl radicals and 2 or 3 short chain alkyl radicals, such as, for example, hexadecyltriethyl ammonium, tetradecyltriethylammonium, dodecyltriethylammonium, dodecylethyl dimethylammonium and further tetracycloamylammonium. Preferred alkyl Ri radicals comprise from 1 to 12, in particular from 1 to 6, carbon atoms. The alkyl radicals R and Ri can also be substituted, for example, by halogen, alkoxy or haloalkoxy, preferably having from 1 to 4 carbon atoms in each case. Preferred Ri alkenyl and alkynyl radicals comprise from 2 to 12 carbon atoms. They may comprise more than one unsaturated bond and may be substituted by halogen, alkoxy or haloalkoxy, and preferably have in each case from 1 to 4 carbon atoms. Suitable examples of aryl radicals include phenyl, naphthyl, tetrahydro naphthyl, indanyl and indenyl, with phenyl being most preferred. These radicals can be substituted by the abovementioned alkyl, alkenyl and alkynyl radicals. The heteroaryl radicals Ri which should preferably be mentioned are the rings of 5 and 6 elements, which comprise in particular nitrogen and / or oxygen atoms, such as, for example, pyridyl, pyrimidinyl, triazinyl, trienyl, thiazolyl, pyrazolyl, imidazolyl, piperidinyl, dioxolanyl, morpholinyl and tetrahydrofuryl. These heterocycles can also be substituted by the aforementioned alkyl, alkenyl and alkynyl radicals. In each case, two Rx radicals together with the sulfur or phosphorus atom to which they are bound can form a ring. It is preferable that in this process rings of 5 or 6 saturated elements are formed. The sulfonium and phosphonium cations which can be used in accordance with the present invention have been described, for example, in WO 00/44227. Preferred agrochemical compositions of the present invention comprise a quinoline protective agent of Formula I in which M is hydrogen, sodium, potassium or tri (hydroxyethyl) ammonium. Another group of preferred agrochemical compositions is one comprising a quinoline protecting agent of Formula I in which M is calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium CiZ-Ci6, alkyltriethylammonium Ci2_Ci6 , tetramethylammonium, trimethylhydroxyethylammonium, tetradodecylammonium or dodecylethyldimethylammonium. The compositions according to the present invention have the advantage that the salts of Formula I have very high melting points in comparison with the corresponding esters, which is very valuable in terms of formulation. The salts can be incorporated in this type of formulation with a higher concentration than would have been possible with the esters. The good solubility of salts in water is also useful; depending on the choice of cation, said solubility can even be specifically controlled. The protection agents of Formula I can be prepared by the usual methods, for example, by reacting the corresponding methyl ester or 1-methylhexyl ester, which have been disclosed in EP-A-94 349, with an amount equimolar of a metal hydroxide in an alcoholic solution at room temperature. In this way it is possible to obtain the salts listed in the following table.

Table 1: Compounds of Formula I The protection agents of Formula II CHjCOOM "" wherein M "is calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulphonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium Ci2-Ci6, alkyltriethylammonium Ci2-] 6, tetraethylammonium or dodecylethyldimethylammonium, are novel and are also subject of the present invention invention. The compositions according to the invention may additionally comprise a herbicide. It is preferable that the latter take the form of a representative selected from the group consisting of the sulfonylureas, sulfonamides, imidazolinones, carbazones, aryloxyphenoxypropionates, cyclohexanediones, arylcarboxylic acids and aryloxycarboxylic acids. The herbicides which are particularly suitable in combination with the protective agents of Formula I are, in particular, the sulfonylureas, preferably triasulfuron, tribenuron, metsulfuron, thifenylsulfuron, flupirsulfuron, iodosulfuron, rimsulfuron, nicosulfuron, cinosulfuron, bensulfuron, trifloxysulfuron and the like, in addition the sulfonamides, preferably the flumetsulam, metosulam, cloransulam, florasulam and the like, and the imidazolinones, preferably imazetabenz, imazetapiro, imazaquino, imazamox and the like, and also the carbazones, preferably flurcarbazone, propoxycarbazone, amicarbazone and the like, in addition the aryloxyphenoxypropionates, preferably clodinafop, fenoxaprop, diclofop, propaquizafop, quizalofop, fluazifop, cialofop, haloxifop and the like, and the cyclohexanediones, preferably sethoxydim, clethodim, tralcoxydim and the like, and arylcarboxylic acids, preferably dicamba and clopyralid, oxopyrazoline derivatives such As are known from WO 99/47525, and aryloxycarboxylic acids, preferably 2,4-D, mecoprop, fluroxypyro and the like, in addition, amicarbazon, azafendin, benfluamid, benzfendizon, benzoibiclon, cinidon-ethyl, diclosulam, fentrazamid, flufenacet, flufenpir, fluramsulfuron, indanofan, mesosulfuron, mesotrione, oxaciclomefona, penoxsulam, petoxamide, picolinafen, profoxidim, profluazol, propoxycarbazone, pyraflufen, pyrazogil, sulfosulfuron, tepraloxolidim and tritosul furon. For their application, the protection agents of the Formula I are processed, if appropriate, together with a herbicide, conveniently together with the adjuvants conventionally used in the art of the formulation with which agrochemical compositions are obtained in form of concentrates, for example concentrated emulsions (EC, EW and SL), concentrated suspensions (SC), suspensions for capsules (CS), squeezables (F and OF), powders (SP) or granules (WP, WG, SG and DG ), concentrates of types WP, WG, SG and SC being preferable. The abbreviations used herein correspond to the international names of formulated and non-formulated pesticides that are given in the FAO Manual of Development and Use of Specifications for Plant Protection Products (Manual for the Development and Use of Specifications for Products for the Protection of Plants), Fifth Edition, January, 1999, pages 144 et seq. The compositions according to the present invention are prepared in the known manner, for example by intimately mixing and / or grinding the active substances together with liquid or solid formulation aids, such as, for example, solvents or solid carriers. In addition, it is possible to additionally use the active surface compounds (surfactants) when the formulations are prepared. The following may be suitable as solvents: aromatic hydrocarbons, preferably C8 to C12 fractions, such as, for example, mixtures of substituted xylenes or naphthalenes, aliphatic esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols such as ethanol, 2-ethylhexanol, oleyl alcohol, n-octanol, isotridecanol, cyclohexanol, tetrahydrofurfuryl alcohol and glycols such as dipropylene glycol, hexylene glycol, and also their ethers and ethers such as butyl lactate, triethyl citrate, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, isobornyl, amyl acetate, benzyl acetate, methyl benzoate, acetones such as cyclohexanone, acetophenone, butyrolactone, diacetone alcohol, strongly polar solvents such as N-methyl-2-pyrrolidone, N-octylpyrrolidone, dimethylsulfoxide N , N-dimethyl formamide and epoxidized or non-epoxied vegetable oils such as bait oil, coconut oil, rape seed oil or soy; or the water The solvents that are available under the trade names 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® are also suitable. The materials that are used as solid vehicles, for example for dispersible powders and powders, are usually ground natural minerals such as calcite, talcum, kaolin, montmorillonite or attapulgite. To improve the physical properties of the formulation, highly dispersed silica or highly dispersed absorbent polymers can be added. Suitable particulate absorbent carriers are porous type such as, for example, pumice, crushed bricks, sepiolite or bentonite, and materials to be used as suitable non-absorbent carriers include for example calcite or sand. The urea / formaldehyde condensates and the melamine / formaldehyde condensates are also solid vehicles tested. In addition, a wide range of pregranulated materials of organic and inorganic origin can also be used, such as in particular; the dolomite or the. waste of shredded plants. Suitable active surface compounds are, depending on the type of active substance of the formula I to be formulated, non-ionic, cationic and / or anionic surfactants and mixtures of surfactants with good emulsion dispersion and wetting properties. Suitable anionic surfactants can be not only those which are known as water soluble soaps, but can also be water soluble synthetic surface active compounds. The soaps which may be mentioned are the alkali metal salts, the iron alkaline metal salts or the unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22) such as, for example, the sodium or potassium salts of oleic acid or Stearic or natural mixtures of fatty acids that can be obtained from, for example, coconut oil or bait oil. Fatty acid methyl taurinates can also be mentioned. however, those which are known as synthetic surfactants, in particular fatty acid sulphonates, fatty alcohol sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates, are used more frequently. As a rule, fatty alcohol sulfonates or fatty alcohol sulfates are present as alkali metal salts, iron alkaline metal salts or unsubstituted or substituted ammonium salts and have an alkyl radical of 8 to 22 carbon atoms, including alkyl also the alkyl part of the acyl radicals, for example, the sodium or calcium salt of lignosulfonic acid, of the dodecylsulfonic ester or of a mixture of fatty alcohol sulphate prepared from natural fatty acids. They also include the salts of the sulfuric esters and sulfonic acids of alcohol oxide / fatty ethylene adducts. The sulfonated benzimidazole derivatives preferably comprise 2 sulfo groups and a fatty acid residue of 8 to 22 carbon atoms. Alkylaryl sulfonates are, for example, the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulphonic acid or a condensate of naphthalenesulfonic acid / formaldehyde. Among the other suitable compounds are the corresponding phosphates, such as, for example, the salts of the phosphoric ester of a p-nonylphenol (4-1) -ethylene oxide adduct, or the phospholipids. Examples of nonionic surfactants which may be mentioned include the polyglyclic ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols which may comprise from 3 to 30 glycol ether groups and from 8 to 20 carbon atoms in the radical (aliphatic) hydrocarbon and from 6 to 18 carbon atoms in the alkyl radical of alkylphenols. Other suitable nonionic surfactants include water-soluble polyethylene oxide adducts with polypropylene glycol, ethylene glycol propylene glycol and polypropylene glycol alkyl having 1 to 10 carbon atoms in the alkyl chain comprising from 20 to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups. The compounds mentioned above typically comprise from 1 to 5 ethylene glycol units per propylene glycol unit. Examples of nonionic surfactants that may be mentioned include nonylphenol polyethoxyethanols, polyglycols castor oil ethers, polypropylene oxide / polyethylene adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other substances that are suitable include polyoxyethylene sorbitan fatty acid esters, such as trioleate. of polyoxyethylene sorbitan. The cationic surfactants are mainly quaternary ammonium salts comprising at least one alkyl radical having from 8 to 22 carbon atoms by way of N-substituents and having a halogenated or free lower alkyl, lower benzyl or hydroxyalkyl radicals as other substituents . The salts are preferably in the form of halides, methylsulphates or ethylsulfates, for example stearyltrimethylammonium chloride or benzidyl (2-chloroethyl) ethylammonium bromide. The surfactants conventionally used in the art of formulation have been described, inter alia, in the following publications: ¾Mc Cutcheon's Detergents and Emulsifiers Annual "Me Publishing Corp., Ridgewood New Jersey, 1981, Stache, H., * Tensid-Taschenbuch [Manual of Surfactants], Carl Hansen Verlag, Munich / Vienna, 1981, and M and J. Ash, 'Encyclopedia of Surfactants', Vol. I-III, Chemical Publishing Co., New York, 1980-81. As a rule, the agrochemical preparations according to the present invention comprise from 0.1 to 99% by weight, in particular from 0.1% to 95% by weight, of protective agent, if appropriate together with the herbicide, from 1 to 99.9% by weight of adjuvant, solid or liquid, for the formulation, and from 0 to 25% by weight, in particular from 0.1 to 25% by weight, of a surfactant. The compositions may also comprise other additives such as stabilizers, such as for example epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), anti-foam agents, for example silicone oil, preservatives, regulators of viscosity, binders, adhesives and fertilizers and other active substances. The present invention also relates to a method for the selective control of weeds in crops of useful plants, which comprises treating the useful plants, their seeds or cuttings or the area in which they are grown with an effective amount from the point of herbicidal view, of the herbicide and an herbicide antagonist effective amount, of the protecting agent of Formula I, either simultaneously or separately. It is understood that the areas on which they grow mean the extension of land that supports the growth of the crop plants or on which the seeds of these crop plants have been planted, and also the soils on which the crop is grown. intention to grow these crop plants. Suitable crop plants that can be protected by the protection agents of Formula I against the damaging effect of the aforementioned herbicides, include, in particular, cereals, maize, sorghum, and millet species, rice, and also sugarcane, useful grasses and ornamental lawns, and grains of soy, cotton, sugar beet and other broadleaf crops. Crops must also include those that have been made tolerant to herbicides or to certain classes of herbicides by conventional plant crossing methods or by recombinant methods. The herbs that must be controlled can be monocotyledonous or dicotyledonous herbs, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Oats, Setaria, Sinapis, Lolium, Solanum, Echinocloa, Scirpus, Monochoria, Sagittaria, Bromus, Poa, Phalaris, Alopecurus, Sorghum halepense, Rottboelia, Cyperus, Abutilon, Aids, Xanthium , Amaranthus, Chenopodium, Ipomoea, Chrisantemum, Gallium, Viola, Lamium, Veronica and Cynodon. Depending on the intended use, a protection agent of Formula I may be used to provide pretreatment to the seeds of the crop plant (coating of the seeds or cuttings), or it may be incorporated into the soil before or after the planted. However, it can also be applied after the emergence of the plants, either alone or together with the herbicide. The treatment of the plants or seeds with the protective agent can therefore take place, in principle, independently of the time of application of the herbicide. However, the plants can also be treated by simultaneously applying the herbicide and the protective agent (for example in the form of a tank mixture). In accordance with the present invention, the protection agent and the herbicide may be present in separate concentrates, but also in a single concentrate. Before being used, the concentrates are treated with customary diluents, such as, for example, water, oils or liquid fertilizers or mixtures thereof. In addition, adjuvants can also be used, such as, for example, nonionic surfactants, mixtures of nonionic surfactants, mixtures of anionic surfactants with nonionic surfactants, cationic surfactants, organosilicon surfactants, mineral oil derivatives with or without surfactants, vegetable oil derivatives. with or without the addition of surfactants, alkylated derivatives of oils of vegetable or mineral origin with or without surfactants, fish oils and other animal oils of animal origin and their alkyl derivatives with or without surfactants, natural major fatty acids, preferably those having from 8 to 28 carbon atoms, and their alkyl ester derivatives, organic acids comprising an aromatic ring system and one or more carboxyl residues, and their alkyl derivatives, in addition, suspensions of acetate vinyl polymers or acetate / acrylic ester copolymers; mixtures of individual adjuvants with one another and in combination with organic solvents can produce an increase in effect. Examples of suitable nonionic surfactants include derivatives of polyglyclic ethers of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which may preferably comprise from 3 to 30 ether glycol groups and from 8 to 20 carbon atoms. in the hydrocarbon (aliphatic) radical, and from 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Among the other suitable nonionic surfactants are the adducts of polyethylene oxide with polypropylene glycol, ethylene diaminopolypropylene glycol or the polypropylene glycol alkyl with preferably 1 to 10 carbon atoms in the alkyl chain, which are soluble in water and preferably comprise 20% by weight. to 250 ethylene glycol ether groups and from 10 to 100 propylene glycol ether groups. The compounds mentioned above typically comprise from 1 to 5 ethylene glycol units per propylene glycol unit. In addition, examples of nonionic surfactants which may also be mentioned include nonylphenol polyethoxyethanols, polyethylene glycol esters of castor oil, adducts of polypropylene / polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Also suitable are the polyoxyethylene sorbitan fatty acid esters, such as the polyoxyethylene sorbitan trioleate. Among the anionic surfactants, alkyl sulfate, alkylsulfonates, alkylarylsulfonates, alkylated phosphoric acids, and their ethoxylated derivatives are preferred. Alkyl radicals usually comprise from 8 to 24 carbon atoms. Preferred nonionic surfactants are known under the following trade names: polyoxyethylene cocoalkylamine (e.g., AMIET® 105 (Kao Co.)), Polyoxyethylene oleylamine (e.g., AMIET® 415 (KaO Co.)), nonylphenol polyethoxyethanols, polyoxyethylene stearylamine (for example, AMIET® 320 (KaO Co.)), N-polyethoxyethylamines (for example GENAMIN® (Hoechst AG)), N,, ', N', -tetra ( polyethoxypolipropoxyethyl) ethylenediamines (for example TERRONIL® and TETRONIC® (BASF Wyandotte Corp.)), BRIJ® (Atlas Chemicals), ETHYLAN® CD and ETHILA® D (Diamond Shamrock), GENAPOL® C, GENAPOL (R) O, GENAPOL®? and GENAPOL® X080 (Hoechst AG), EMULGEN® 104P, EMULGEN® 109P and EMULGEN® 408 (Kao Co.); DISTY® 125 (Geronazzo), SOPROPHOR® CY 18 (Rhone Poulenc SA.); Nonisol® (CibaGeicy), MRYL® (ICI); TWEEN® (ICI); EMULSOGEN® (Hoec st AG); AMIDOX® (Stephan Chemical Co.), ETHOMID® (Armak Co.); PLURONIC® (BASF ynadotte Corp.), SOPROPHOR® 461P (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). The cationic surfactants are primarily quaternary ammonium salts comprising at least one alkyl radical having from 8 to 22 carbon atoms in the form of N-substituents and having a lower or free halogenated alkyl, the benzylhydroxyalkyl or lower radicals as other substituents . The salts are preferably in the form of halides, methylsulphs or ethylsulfates, for example stearyltrimethylammonium chloride or benzyldyl (2-chloroethyl) ethylammonium bromide. The oils used are of mineral or natural origin. Natural oils can also be of animal or vegetable origin. In the case of animal oils, the materials that are preferred are mainly tallow derivatives of beef, but fish oils (eg, sardine oil) and their derivatives are also used. Vegetable oils are in most cases seed oils of various origins. Examples that can be mentioned of vegetable oils that are used are in particular coconut oils, rape seed oils or sunflower oils and their derivatives. Surfactants, oils, and in particular vegetable oils, their derivatives such as alkylated fatty acids and mixtures thereof are described, inter alia, with, for example, anionic surfactants such as alkylated phosphoric acids, alkyl sulfates and alkylaryl sulphonates and acids. Higher fatty acids which are conventionally used in the art of formulation, and adjuvants and which may also be used in the spray compositions and mixtures according to the invention, in the document wMc Cutcheon's Detergents and Emulsifiers Annual Me Cutcheon on Detergents and Emulsifiers) "MC Publishing Corp., New Jersey Ridge, 1988, Stache, H., * Tensid-Taschenbuch" [Surfactants Guide], Carl Hansen 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, "Guide to Agricultural Spray Adjuvants Used in the United States (A Guide to Agricultural Spraying Adjuvants Used in the United States), "Thompson Pubns. , 1992. Preferred adjuvants are available commercially under the trade names Merge, Score, Actipron, Amigo, Emery, Edenor Partna and Hasten. The coefficient or rate of application of the herbicide protection agent to be applied depends to a large extent on the type of application. In the case of a soil treatment that is carried out using a tank mix with a combination of a protection agent and herbicide, or by applying the protection agent and the herbicide separately, the ratio between the herbicide and the protective agent is , as a rule, from 1: 100 to 1: 1, preferably from 1:50 to 5: 1. In the case of a soil treatment, the proportions that are applied are, as a rule, from 0.001 to 5.0 kg of protection agent / hectare, preferably from 0.001 to 0.5 kg of protection agent per hectare. The proportions of application of herbicides are, as a rule, between 0.001 and 2 kg / hectare, but it is preferable that they are between 0.005 and 1 kg / hectare. The compositions according to the present invention are suitable for all application methods that are conventionally used in agriculture, such as, for example, pre-emergence application, post-emergence application, and seed coating. There are a variety of methods and techniques such as, for example, those given below, which are suitable for the use of the protection agents of the formula I or compositions comprising them, to protect the crop plants from the damaging effects of herbicides. i) Coating the seeds a) Coating the seeds with a protection agent formulated as a wettable powder, by agitation in a container until the surface of the seed is covered in a uniform manner (dry treatment of the seed). Approximately 1 to 500 g of protective agent (from 4 g to 2 kg of wettable powder) are used per 100 kg of seed. b) Cover the seeds with an emulsion concentrate of the protection agent following method a) (liquid coating of the seed). c) Coating the seeds by immersing the seeds in a bath comprising 100-1000 ppm of protection agent, preferably for 1 to 72 hours, which, if desired, is followed by a drying of the seeds (soaking of the seeds). the seeds) . Sometimes, it will be enough just to briefly dip the seeds. The coating of the seeds or the treatment of the germinated seedlings are naturally the preferred methods of application since the treatment with the protective agent is directed completely to the desired culture. As a rule, from 1 to 1000 g of protective agent, preferably from 5 to 250 g of protective agent per 100 kg of seed, are used, but it is also possible to deviate from the limit concentrations established in both directions, depending on the methodology, which also makes possible the addition of other active substances or micronutrient (repeated treatment of the seeds). ii) Application as tank mix A liquid preparation of a mixture of protection agent and a herbicide (mutual quantitative ratio between 10: 1 and 1: 100) is used, with the coefficient of application of the herbicide, from 0.005 to 5.0 kg per hectare. Said tank mixtures are applied before or after sowing. iii) Application in the furrow of the seeds The protective agent, in the form of an emulsion concentrate, wettable powder or granules, is introduced into the furrow of the sown seeds, without covering. After the furrow of the seeds has been covered, the herbicide is applied before the emergence of the plant, in a customary way. iv) Controlled release of the active substance The dissolved protection agent of Formula I is applied to mineral granules or polymerized granules (urea / formaldehyde) and allowed to dry. If desired, a coating (coated granules) allowing the slow release of the active substance over a specific period can be applied. In particular, the preferred formulations have the following formulation: (mixture of active substance = protective agent + herbicide;% = percentage by weight) Emulsifiable concentrates: Mixture of active substances: from 1 to 90%, preferably from 5 to 20% Surfactant: from 1 to 30%, preferably from 10 to 20% Liquid vehicle: from 5 to 94%, preferably from 70 to 85% Powders: Mixture of active substances: from 0.1 to 10%, preferably 0.1 to 5% Solid vehicle: from 99.9% to 90%, preferably from 99.9 to 99% Concentrated suspensions Mixture of active substances: from 5 to 75%, preferably from 10 to 50% Water: from 94 to 24%, preferably from 88 to 30% Surfactant: from 1 to 40%, preferably from 2 to 30% Wettable powders: Mixture of active substances: from 0.5 to 90%, preferably from 1 to 80% Surfactant: from 0.5 to 20%, preferably from 1 to 15% Solid vehicle: from 5 to 95%, preferably from 15 to 90% Granules: Mixture of active substances: from 0.1 to 30%, preferably 0.1 to 15% Solid vehicle: from 99.5 to 70%, preferably from 97 to 85% Dispersible granules: Mixture of active substances: from 0.5 to 90%, preferably from 1 to 80% Surfactant: from 0.5 to 20%, preferably from 1 to 15% Solid vehicle: from 5 to 95%, preferably from 15 to 90% The examples that follow illustrate the invention in more detail without imposing any limitations.

Examples of formulation of mixtures of herbicides and protection agent of Formula I (mixture of active substances = protective agent + herbicide;% = percentage by weight) Fl. Concentrated emulsions a) b) c) d) Mixture of active substances 5% 10% 25% 50% Calcium dodecylbenzenesulfonate 6 8% 6% 8% Beaver oil polyglycol ether 4% - 4% 4% (36 mol of EO) Octylphenyl polyglycol ether (7-8 - 4% - 2 mol% of EO) Cyclohexanone - - 10% 20% Aromatic hydrocarbon mixture 85% 78% 55% 16% from 9 to 12 carbon atoms Emulsions of any desired concentration can be prepared from said concentrates, by means of a dilution with water.

F2 Solutions a) b) c) Mixture of active substances 5% 10% 50% l-methoxy-3- (3-20% 20% methoxypropoxy) propane F2. Solutions cont | a) b) c) d) Polyethylene glycol MW 400 20% 10% N-methyl-2-pyrrolidone - - 30% Blend of aromatic hydrocarbon 75% 60% of 9 to 12 carbon atoms The solutions are suitable to be used in the form of microdroplets.

F3 Wettable powder a) b) c) d) Mixture of active substances 5% 25% 50% 80% Sodium lignosulfonate 4% - 3% Sodium lauryl sulfate 2% 3% - 4% DÜ5obutilnaphthalenesulfonate of - 6% 5% 6% sodium Octylphenyl polyglycol ether (7-8 - 1% 2% mol of EO) Highly dispersing silica 1% 3% 5% 10% Kaolin 88% 62% 35% The active substance is completely mixed with the additives and is completely ground in a suitable mill. This results in wettable powders that can be dissolved in water so that suspensions of any desired concentration are obtained F4 Coated granules a) b) c) Mixture of active substances 0.1% 5% 15% Silica highly dispersing 0.9% 2% 2% Inorganic vehicle (0 0.1-1 mm), by 99.0% 93% 83% example CaCC or Si02 The active substance is dissolved in methylene chloride, the vehicle is sprayed with the solution, and the solvent is subsequently evaporated in vacuo.

F5 Coated granules a) b) c) Mixture of active substances 0.1% 5% 15% Polyethylene glycol M 200 1.0% 2% 3% Highly dispersible silica 0.9% 1 2% Inorganic vehicle (0 0.1-1 M), by 98.0 92% 80% example CaC03 or Si02 The finely ground active substance is applied uniformly in a mixer to the vehicle which has been wetted with polyethylene glycol. This results in powder-free coated granules.

F6 Extruder granules a) b) c) d) Mixture of active substances 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 substance is mixed with the additives, milled and moistened with water. This mixture is processed in an extruder and subsequently dried in an air stream.

F7 Powders a) b) c) Mixture of active substances 0.1% 1% 5% Talcum 39.9% 49% 35% Kaolin 60% 50¾ 60% Ready-to-use powders are obtained by mixing the active substance with the vehicles and grinding the mixture in a suitable mill. Preferred WP formulations according to the invention comprise between 5 and 50% by weight of protective agent or protective agent + herbicide, from 1 to 15% by weight of dispersant (for example lignosulfonates such as Attisol II, Ufoxan 3A) , from 0 to 30% by weight of wetting agent (for example an isotridecanol E08 such as Genapol X-8Q, Morwet EFW, Genapol LRO), between 5 and 90% by weight of a vehicle (for example the Pergopak M , sodium sulfate, diatomaceous earth, aluminum silicate, Sopropon TA 72).

F8 Concentrated emulsions a) b) c) d) Mixture of active substances 3% 10% 25¾ 50% Ethylene glycol 5% 5% 5% 5% Polyglycol nonylphenyl ether (15 1% 2% mmol EO) Sodium lignosulfonate 3% 3% 4% 5% carboxymethylcellulose 1% 1% 1% 1% Aqueous formaldehyde solution 0.2% 0.2 %% 0.2% 0.2% to 37% Silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38% The concentrated suspensions a) to d) may also be free of ethylene glycol. If appropriate, they may also comprise, for example, 0.2% xanthan rubber. Especially suitable SC formulations comprise from 1 to 700 g / l of protection or herbicide agent + protective agent, from 0 to 100 g / liter of dispersant (for example Soprophor 3D33, Soprophor 4D384, Atlox 4913, Morwet D425), from 0 to 30 g / 1 of wetting agent (for example Genapol X-080, Morwet EFW, Genapol LRO, sodium lauryl sulphate), from 0 to 50% g / liter of buffering agent (for example citric acid, lactic acid, sodium phosphates, sodium carbonate and sodium hydroxide), between 0 and 100 g / liter of antifreeze (for example, propylene glycol, glycerol, sodium sulphate), from 0 to 50 g / liter - of a thickening agent (Kelzan S, Rheozan, Laponite BD, Thixosil, Aeronsil 200, Attagel 50, Bentone 36) , from 0 to 50 g / liter of preservative (for example Proxel GXL, formalin, orthophenylphenol), from 0 to 400 g / liter of fillers (calcium carbonate, kaolin, diatomaceous earth silicon dioxide) and from 0 to 50g / l antifoam agent (for example Rhodosil 426 R; silicone oils, Fluwett 80 B).

F9 Dispersible granules a) b) c) d) Mixture of active substances 5% 25% 50% 80% Sodium lignosulfonate 4% 3% Sodium lauryl sulfate 2% 3% 4% 6% Diisobutylnaphthalenesulfonate 5% 6% sodium Octylphenyl polyglycol ether (7-8 1% 2% mol EO) Highly dispersed silica 3% 5% 10% Kaolin 62¾ 35% The finely ground active substance is intimately mixed with the additives. This results in a concentrated emulsion from which suspensions of any desired concentration can be prepared by dilution with water. Water-soluble active substances, such as, for example, those of Formula I according to the invention can also be advantageously formulated in the form of SG formulations. It is preferable that they comprise between 0 and 50% by weight of the protection agent of Formula I in salt form, from 0 to 20% by weight of dispersant (for example Morwet D425, Borrespense NA, Geropon TA72, Soprophor FL, Soprophor S40), from 0 to 20% by weight of wetting agent (for example Morwet EFW, Trinovetin B, Genapol LRO), from 0 to 5% by weight of antifoaming agent (for example Rhodosil 426, Fluowet 80B) and from 0 to 99 % by weight of a vehicle (for example ammonium sulfate, sodium sulfate, kaolin, carbonate, diatomaceous earth). It is often more convenient to formulate the active substance of Formula I and the herbicide separately, and combine them in water in the applicator in the desired mixing ratio, shortly before application, for example in the form of a "tank" mixture. "The ability of the protection agents of Formula I to protect crop plants against the phytotoxic effect of the herbicides, has been illustrated in the examples that follow. The following examples illustrate the invention in greater detail.

Example Some seeds of corn, barley and wheat are planted in plastic pots containing 0.5 liter of garden soil. After the emergence of the plants until the stage of two to three leaves, we proceed to apply a protection agent of Formula A, and for comparison purposes the known protection agent Cloquintocet-mexilo (The Pesticide Manual, Llava. (BCPC) 1997, No. 154), together with a herbicide (in the form of a prepared mixture, in the case of the herbicide of Formula I and Clodinafop in the form of a tank mixture, in the case of the herbicide Tralcoxidim, Mesotrione, Tifensulfurona, Propoxycarbazone and Florasulam). After 20 days after the application, the protective effect of the protective agent (expressed as a percentage of phytotoxicity) is determined. As shown in the following Tables 2 to 8, all protection agents possess, in comparison with Cloquintocet-mexyl, an equivalent or superior effect.

Table 2; Action of the Protection Agent on the herbicide of formula A The herbicide of the formula A is the ester 8- (2,6-diethyl-4-methylphenyl) -9-oxo-l, 2,4,5-tetrahydro-9H-pyrazolo [1,2-d] [1, 4,5] oxadiazepin-7-yl of 2,2-dimethylpropionic acid. The protection agent / herbicide mixture was used as WG 24.

Table 3: Action of the Protection Agent in clodinafop The protection agent / herbicide mixture was used as WG 36.

Table: Effect of the Protection Agent on Tralcoxidim The Tralcoxidim was applied with the designation SC 250, and the protection agent with the designation WP 25. Table 5: Effect of the Protection Agent on Mesotrione Mesotrione was applied with the designation 100, and the protection agent with the designation WP 25. Table 6: Effect of the Protection Agent on Tifensulfuron The Tifenilsulforona was applied with the designation WC 75, and the protection agent with the designation WP 25.

Table 7: Effect of the Protection Agent on Propoxycarbazone Propoxycarbazone was applied with the designation WG 70, and the protection agent with the designation WP 25.

Table 8: Effect of the Protection Agent on the Florasulam Florasulam was applied with the SC designation 50, and the protection agent with the designation WP 25. In the applications with mixture prepared in advance (Tables 2 and 3), the herbicide of the Formula A and the protection agent were applied together in a WG 24. Said formulation contained 24% by weight of herbicide of Formula A, 6% by weight of protective agent, 10% by weight of Morwet, 5% by weight of Tinivetim B wetting agent, 2% by weight of Geropon as dispersant, 1% by weight weight of silicone oil as anti-foam agent and 12% by weight of vehicle (10% by weight of Pergopack M, 5% by weight of anhydrous sodium sulfate, 7% by weight of Diatomaceous 236 B). Clodinaflop together with the protecting agents were used as WG 36. WG 36 is composed as follows: 36.2 wt% clodinafop, 7.8 wt% protective agent 1.02, or 6.7 wt% protective agent 1.15, or 6.8% by weight of the protective agent 1.05, or 7.3% by weight of the protective agent 1.01, 15% by weight of Ufoxano 3A as a dispersant, 2% by weight of Geropon TA-72 as a dispersant, 1% by weight of oil of silicone as anti-foam agent (Antifoam A TK 50), and 38% by weight of vehicle (15% by weight of Pergopack M, 10% by weight of anhydrous sodium sulfate, remaining at 100% Diatomaceous 236 B). In general, WG formulations, which are particularly suitable for the purposes of the present invention, are those which comprise 1-45% by weight of the herbicide + protective agent, 5-25% by weight of dispersant, 0-5 % by weight of anti-foam agent and 10-40% by weight of vehicle.

However, the herbicide and the protection agent can also be used as a formulation according to Examples Fl to F9. Essentially, the same results are obtained. For application as a tank mix, (Tables 4 to 8), the protective agents were used as WP25 in the following composition: 25% by weight of the protection agent of formula I or Cloquintocet, 5% of lignosulfonate (Attisol II), 1% of isotridecanol EO 8 (Genapol X-080), 5% urea / formaldehyde condensate (Pergopack M), 3% furandione / trimethylpentene polymer (Sopropon TA 72) and 61% aluminum silicate (AG Kn Powder). Formulated as WG, SC or SG, the same results are obtained. A typical SC formulation for the purposes of the present invention comprises: 400 g / 1, of protection agent 1.01, 1.02, 1.05 or 1.15; 20 g / 1 of dispersant Soprophor 4D384, 20 g / 1 of Genapol X-080, 5 g / 1 of buffer (citric acid), 60 g / 1 of frost protection agent (propylene glycol), 2 g / 1 of thickening agents (Kelzan?), from 0 to 50 g / 1 preservative (Proxel GXL), 50 g / 1 filler or inert filler (kn), 5 g / 1 antifoam agent (Rhodorsil 426 R). A typical WG formulation according to the invention contains from 1 to 45% of protection agent, from 5 to 25% of dispersant, from 0 to 5% by weight of antifoam agents and from 10 to 40% by weight of vehicle, the The dispersant, the anti-foaming agent and the vehicle will be the same as those used in the aforementioned SC formulation. The other herbicides can be used for the tank mix application in the same manner as that described for the herbicide of Formula A, but as far as the newly described tests are concerned, they can also be used in the form of their usual formulations in trade .

It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (12)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. An agrochemical composition in the form of concentrates comprising, in addition to the usual formulation adjuvants, a quinoline protective agent, characterized in that the quinoline protective agent has the following formula wherein M is hydrogen, a mono-, di- or trivalent, ammonium, N (R) 4 or HN (R) 3 metal, in which the radicals R are identical or different from each other and are C1-C16 alkyl or hydroxyalkyl Ci-Ci6, or M is S (Ri) 3 or P (Ri) 4, in which the radicals] are identical or different from each other and are C1-C20 alkyl or C2-C20 alkenyl, C2-C20 alkynyl, aryl substituted by C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 2 -C 2 alkynyl or heteroaryl substituted by C 1 -C 20 alkyl or C 2 -C 2 alkenyl or C 2 -C 2 alkynyl, or, two Ri radicals together with the phosphorus or sulfur atom which are linked to form a ring of 5 or 6 elements.

2. A composition according to claim 1, characterized in that it comprises a quinoline protection agent of the Formula I, in which M is hydrogen, sodium, potassium or tri (hydroxyethyl) monium.

3. A composition according to claim 1, characterized in that it comprises a quinoline protection agent of the formula I in which M is calcium, magnesium, aluminum, iron, trimethylsulfonium, triphenylsulfonium, tetraphenylphosphonium, triphenylmethylphosphonium, triphenylbenzylphosphonium, alkyltrimethylammonium Ciz_Ci6 alkytriethylammonium Ci2-CiS, tetramethylammonium, trimethylhydroxyethylammonium, tetradodecylammonium or dodecylethyldimethylammonium.

4. A composition according to claim 1, characterized in that it comprises a herbicide.

5. A composition according to claim 1, characterized in that it comprises as a herbicide, a representative selected from the group consisting of the sulfonylureas, sulfonamides, imidazolinones, carbazones, aryloxyphenoxypropionates, cyclohexandiones, arylcarboxylic acids and aryloxycarboxylic acids.

6. A composition according to claim 1, characterized in that the concentrate is a SC, CS, EW, OF, FW, G, SG, DG, SP, WP, CE or SL.

7. A composition according to claim 6, characterized in that the concentrate is a SC, WG, SG or WP.

8. A method for controlling the growth of unwanted plants, characterized in that it comprises the application of a composition according to claim 1, after having been diluted with the usual diluents, to the crop plants or to their surroundings, independently of the moment of the application of a herbicide.

9. Mejude according to claim 8, characterized in that the diluents comprise adjuvants.

10. Method for controlling the growth of unwanted plants, characterized in that it comprises applying an herbicidally effective amount of a composition according to claim 4, after having been diluted with the usual diluents, to the crop plants or their environment.

11. Method according to claim 10, characterized in that the diluents comprise adjuvants.

12. Compound of the following Formula: wherein M "is calcium, magnesium, aluminum iron, trimethylsulfonium, triphenylsulfonium tetraphenylphosphonium, triphenylmethyl phosphonium triphenylbenzylphosphonium, alkyltrimethylammonium C12-C16 alkyltriethylammonium Ci2-Ci6, tetramethylammonium trimethylhydroxyethylammonium, tetraethylammonium dodecylethyldimethylammonium.