Means of protecting crops from phyto-toxic side effects of herbicides, connection method thereof, a method of controlling undesirable vegetation
(57) Abstract:Describes a means of protecting crops from phyto-toxic side effects of the herbicides containing the biologically active substances (antidote) one or more compounds of the formula (I), where X denotes independently from each other halogen, or (C1-C4-halogenated, n denotes an integer from 1 to 3, R1denotes hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl, R2and R3denote independently from each other hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-quinil, (C3-C6-cycloalkyl, (C1-C6-halogenated, mono - or di (C1-C4-alkoxy)- (C1-C4)-alkyl, [(C1-C6)-alkyl]-carbonyl, di-[(C1-C4)-alkyl)]-aminocarbonyl, cyano, [(C1-C12)-alkyl]-oxycarbonyl, phenyl, unsubstituted by one or more residues selected from halogen and ceanography, in the amount of 0.002-95 wt.%, the rest of the target additives. Describes the connection of the formula (I) where (X)ndenotes 2,4-Cl2, R1denotes hydrogen or (C1-C4)-alkyl, R2denotes hydrogen elastam the compounds of formula (II), where Y denotes chlorine or bromine and (X)nand R1defined as in formula (I), with an olefin of the formula (III),where R2, R3defined as in formula (I), a method of controlling undesirable vegetation in crops by processing plants, seeds of plants or the planting area of herbicides in combination with a safener of the formula (I) with a ratio of herbicide: safener is from 10:1 to 1:10 and the consumption rate of 0.005 to 10 kg/ha in the calculation of the antidote. The technical result - the reduction fetotoksicheskoe of herbicides on crops. 4 C. and 8 C.p. f-crystals, 3 PL.The invention relates to a means for protection against phyto-toxic side effects of herbicides. When applying herbicides may be undesirable, unacceptable damage to cultivated plants, especially in the case of herbicidal after maturation of cultivated plants, so there is a need to avoid the danger of possible phytotoxicity.Such compounds, which have properties to protect cultivated plants from fetotoksicheskoe damage by herbicides, without affecting its own herbicide action of these funds, referred to as "antidotes" or "antidotes".In the German patent application P-3808896.7 proposed derivatives of 1-phenyl - 1-/pyrid-2-yl/-pyrazole as antidotes.The use of alkoxyethanol as antidotes proposed in the German patent application P 3923649.8 (NOAH 89/F 235).The object of the present invention are sasysusie cultivated plants tools, which contain as active substances derived esters of 4,5-pyrazolin-3-carboxylic acid of the formula (I):where:X, independently of one another, denotes halogen or halogenated,n denotes an integer of 1-3,R1denotes hydrogen, alkyl, cycloalkyl, trialkylsilyl, trialkylsilyl or alkyloxyalkyl, R2and R3independently of one another, denote hydrogen, alkyl, C3-C6-cycloalkyl, alkenyl, quinil, halogenated, alkoxyalkyl, oxyalkyl, alkoxycarbonyl, alkylsulphonyl, alkylaminocarbonyl; if necessary substituted phenyl; halogen or cyano, with the remains of R2and R3C-atom position 5 pyrazolinones cycle may form a ring.Formula (I) includes all possible geometric isomers and stereoisomers. In the formula (I) ha is alkenyl denotes a linear or branched alkenyl, moreover, the double bond can be in any place alkenylphenol residue; and quinil denotes a linear or branched quinil, and also here the triple bond can be localized in any way in alchenilla residue; halogenated is a one - or multiply substituted with halogen alkyl; alkoxyalkyl and oxyalkyl mean one - or multi-substituted by alkoxyl or hydroxyl alkyl. The specified values for alkyl are set for alkyl residues contained in the combinations, as alkyloxyalkyl, allyloxycarbonyl and alkylaminocarbonyl.Of particular interest are proposed according to the invention means on the basis of the compounds of formula (I), whereX, independently of one another, denotes halogen or1-C4-halogenated,n denotes an integer of 1-3,R1stands WITH1-C6-alkyl, C3-C6-cycloalkyl, three-(C1-C4-alkyl)-silyl, three-(C1-C4-alkyl)-millimeter or (C1-C6-alkyloxy)-C1-C6-alkyl,R2and R3,independently of one another, denote hydrogen, C1-C6-alkyl, C2-C6alkenyl,4-alkoxy)-C1-C4-alkyl, C1-C6-oxyalkyl, (C1-C6-alkyl)-carbonyl, mono - or di-(C1-C4-alkyl)-aminocarbonyl, cyano, halogen, (C1-C12-alkyl)-oxycarbonyl, phenyl or phenyl which is substituted by one or more residues from the group comprising halogen, C1-C4-alkyl, C1-C4-alkoxy or cyano.Halogenated preferably represents trifluoromethyl, 2-chloroethyl, 1,1,2,2-tetraborate or hexaferrites; the halogen is preferably fluorine, chlorine or bromine.Alkyl preferably denotes one of the residues: methyl, ethyl, n-propyl, isopropyl; butyl, pentalonia and hexyl isomers; cyclopentyl and cyclohexyl.Alkenyl means preferably one of the residues: vinyl, 1-propen-1-yl, 1-propen-2-yl, isomers butenyl, pentenyl and hexenyl.Quinil preferably represents ethinyl, 1-PROPYNYL or 2-PROPYNYL.The preferred proposed according to the invention means on the basis of the compounds of formula (I), whereX, independently of one another, denotes fluorine, chlorine, bromine or trifluoromethyl, preferably, depending on the circumstances, in 2 - or 4-position;
-C4-R2denotes hydrogen, C1-C4-alnil,2-C4alkenyl,R3stands WITH1-C4-alkyl, C3-C4alkenyl,2-C4-quinil,1-C4-halogenated, mono or di(C1-C4-alkoxy)-C1-C4-alkyl; C1-C4-oxyalkyl; mono - or di-(C1-C4-alkyl)-aminocarbonyl; cyano, (C1-C12-alkyloxy)-carbonyl, phenyl or phenyl which one - or multiply substituted with halogen, in particular fluorine or chlorine.Especially preferred proposed according to the invention means compounds of formula (I), where:X, independently of one another, denotes fluorine, chlorine, bromine or trifluoromethyl, preferably 2 - or 4-position in the phenyl ring,n = 2 or 3,R2denotes hydrogen, C1-C4-alkyl, C2-C4alkenyl or2-C4-quinil,R3 stands WITH1-C4-alnil, which is unsubstituted or mono - or multiply substituted with halogen; and (C1-C12-alkyl)-oxycarbonyl or cyano.The compounds of formula (I) are partly known from WO 88/06583 as the original product to nd the formula (I) is unknown.The subject invention also are not previously described compounds of the formula (I) in which:R1denotes cycloalkyl, preferably3-C6-cycloalkyl, trialkylsilyl, trialkylsilyl or alkyloxyalkyl, preferably (C1-C6-alkoxy)-C1-C6-alkyl,or the compounds of formula (I) in which:(X)nrepresents 2 or 3 of the remainder of the phenyl ring, preferably two balance in the 2,3 - or 2,4-position, especially in the 2,4-position of the phenyl ring, from the group comprising halogen and halogenated, as, for example, WITH1-C4-halogenated, preferably residues: 2,4-Cl2; 2,4 F2; 2,4-Br2, 2-Cl-4-F; 2-F4-Cl, 2,4-(CF3)2; 2-CF3-4-Cl; 2-CI-4-CF3; 2-F-4-CF3; 2-CF-4-F; 2-CF3-4-Br; 2-Br-4-CF3in particular 2,4-Cl2.The above compounds of formula (I) can be obtained, for example, the fact that the compound of formula (II):where Y denotes chlorine or bromine and (X)nand R1have the above values, enter into interaction with the olefins of formula (III):where R2and R3have the above values.Components can use the NII 1:1,05+1:20, preferably in a molar ratio of 1:1,1+1:5.The compounds of formula (II) partially known or can be synthesized by ordinary methods. Get them, for example, from the corresponding anilines by diazotization and combinations with the corresponding 2-chloro-acetoacetate esters. The compounds of formula (III) also get the usual ways, for example by Reinsalu by Wittig corresponding ketones or aldehydes of the formula R2R3.The interaction of compounds of formulas (II) and (III) is generally carried out at 0 to 150 C, preferably at 20 to 100C, if necessary in the presence of organic bases, as spatial employed amines, such as triethylamine or pyridine, or inorganic bases, such as potassium carbonate, potassium hydroxide or sodium carbonate, without or in the presence of an organic solvent, as, if necessary, halogenated aliphatic or aromatic hydrocarbon or an ether, for example, a solvent such as toluene, xylene, dichloroethane, dimethoxyethane, di - or triglyme, cyclohexane, petroleum ether or chlorobenzene.Bases and solvents are listed only as examples, not limiting the scope of ototoxic side effects of herbicides for use in crops of useful plants. The compounds of formula (I) is able to eliminate the harmful side effects of herbicides largely or completely, without reducing the effectiveness of these herbicides against harmful plants. The scope of conventional herbicides can significantly extend by adding antidote compounds of formula (I).The object of the present invention is therefore also a way of protecting cultivated plants against fetotoxicity side effects of herbicides, which is characterized by the fact that the plants, plant seeds or the acreage is treated with a compound of formula (I) before, after or simultaneously with the herbicide.Herbicides, fetotoxicities side effects which can be reduced by using compounds of the formula (I) are, for example, carbamates; THIOCARBAMATE; halogenation; substituted derivatives of phenoxy, naphthoxy and phenoxyphenylacetic acids and derivatives heterooligomerization acids as esters of hinomisaki, honokalani, pyridyloxy, benzoxazolinone-, benzothiazolylsulfenamide acids, and further derivatives cyclohexandione. Of these preferred esters of phenoxyphenoxy and heterooligomerization the ri taking into account in particular lower alkyl, alkeneamine and alkyline esters.For example, without limiting the scope of protection of the invention, mention should be made of the following herbicides:A) Herbicides of type complex (C1-C4)-alkyl, (C2-C4)-alkenyl or (C3-C4)-etkinlik esters heterooligomerization acids as methyl ether 2-/4-/2,4-dichlorphenoxy/-phenoxy-propionic acid; methyl ester of 2-/4-/4-bromo-2-chlorophenoxy/-phenoxy/-propionic acid; methyl ester of 2-/4-/4-triptoreline/-phenoxy/-phenoxy/-propionic acid; methyl ester of 2-/4-/2-chloro-4-triftormetilfosfinov/-propionic acid; methyl ester 2-/4-/2,4-dichlorobenzyl/-phenoxy/-propionic acid; 2-isopropylidenedioxy (R)-2-/4-/6-chlorination-2-yl-oxy/-phenoxy/-propionate; ethyl ester of 4-/4-/4-triptoreline/-phenoxy/-Penta-2-ene acid; ethyl ester of 2-/4-/3,5-dichloropyridine-2-oxy/-phenoxy/-propionic acid; propargilovyh ether 2-/4-/3,5-dichloropyridine-2-oxy/-phenoxy/-propionic acid; ethyl ester of 2-/4-/6-chloro-benzoxazol-2-yl-oxy/-phenoxy/-propionic acid; ethyl ester of 2-/4-/6-chlorobenzothiazole-2-yl-oxy/-phenoxy/-propionic acid; methyl ester 2-/4-/3-chloro-5-trifluoromethyl-2-pyridyloxy/-phenoxy/-fir 2-/4-/6-chloro-2-honokalani/-phenoxy/-propionic acid; ethyl ester of 2-/4-/6-fluoro-2-honokalani/-phenoxy/-propionic acid; propargilovyh ether 2-/4-/5-chloro-3-perperidis-2-oxy/-fooxy/-propionic acid; ethyl ester of 2-/4-/6-chloro-2-hinomisaki/-phenoxy/-propionic acid; trimethylsilylmethylamine ether 2-/4-/3,5-dichloropyridine-2-oxy/-phenoxy/-propionic acid; ethyl ester of 2-/4-/3-chloro-5-triptoreline-2-pyridyloxy/-phenoxy/-propionic acid;B) Herbicides based chloroacetanilide as N-methoxymethyl-2,6-diethyl-chloroacetanilide; 2-chloro-N-/2-ethyl-6-were/-N-/2-methoxy-1-methylethyl/-ndimethylacetamide; 2,6-dimethylaniline N-/3-methyl-1,2,4-oxadiazol-5-yl-methyl/-, Chloroacetic acid;C) Derivatives of cyclohexandione as S-ethyl-N-dipropylthiocarbamate or S-ethyl-N,N-Diisobutyl-THIOCARBAMATE.G) Derivative of cyclohexadiene as2-/N-ethoxymethyl/-5-/2-ethylthiophen/-3-hydroxy-2-cyclohexane-1-he,2-/N-ethoxymethyl/-5-/2-phenylthiomethyl/-3-hydroxy-2-cyclohexen-1-one or 2-/1-allyloxymethyl/-4-methoxycarbonyl-5,5-dimethyl-3-oxocyclohexa;2-/N-ethoxypropionate/-5-mesityl-3-hydroxy-2-cyclohexen-1-he [or also referred to as 5-/2,4,6-trimetilfenil-3-hydroxy-2-/1-/amoxiillin/-propyl/-cyclohex-2-EN-1-he];2-/-ethoxymethylene-1-he (BASF 517); ()-2-/E-3-chlorellaceae/-5-/2-ethylthiophen/-3-oxocyclohexa-2 northward.Of herbicides which can be combined according to the invention with compounds of the formula (I), preferably should be specified in paragraph (A) compounds, in particular the ethyl ester of 2-/4-/6-chlorobenzoxazol-2-yl-oxy/-phenoxy/-propionic acid; ethyl ester of 2-/4-/6-chlorobenzothiazole-2-yl-oxy/-phenoxypropionic acid and propargilovyh ether 2-/4-/5-chloro-3-fluoro-pyridyl-2-oxy/-phenoxy/-propionic acid. Specified in paragraph (G) of substances in particular has a value of 2/N-ethoxypropionate/5-mesityl-3-hydroxy-2-cyclohexen-1-it.The weight ratio of safener [connection I]: herbicide may vary within wide limits and is preferably in the region of 1:10+10:1, especially 2:1+1:10.Optimal, depending on the circumstances, the amount of herbicide and antidote depend on the type of herbicide or used antidote, and also on the nature of cultivated plants and plants may be determined from time to time by the relevant experiments.The main areas of use of antidotes are primarily grain crops (wheat, rye, barley, oats), rice, maize, sorghum, however, also hlati for preprocessing of the seed of cultivated plants (seed dressing) or to make before sowing in furrows for planting, and apply to, after or simultaneously with the herbicide before or after emergence of the plants. Predsjedava processing includes processing the planting area before planting and processing planted, but not yet overgrown acreage.However, preferably the simultaneous application of safener to herbicide in the form Tapc mixes or ready-made formulations.The compounds of formula (I) or their combinations with one or more of these herbicides or groups of herbicides can be formulated in different ways, depending on what set of biological and/or chemico-physical parameters. As opportunities formulation consider, for example, the following: emulsifiable concentrates (EC), emulsions (W), suspendiruemye concentrates (SC), capsule suspensions (CS), water-soluble concentrates (SL), water-soluble powders (SP), water-soluble granules (SG), dispersible in water powders wettable powders] (WP); dispersible in water, the granules (WG); miscible with oil solutions (OL); medications for dusting (DP), granules (GR) in the form of microgranules, granules in the form of nozzles, extraction and adsorption; ultrascalable formulations, microcapsules and waxes.Necessary for the formulation AIDS such as inert materials, surfactants, solvents and other additives are also known and described, for example, in: Watkins “Handbook of Jnsecticide Dust Diluente and Carriere”,2nd ed., Darland Books, Caldewell M. I.; H. V. Olphen Jntroduction to Clay Colloid Chemistry”,2nd ed., I. Wiley and sons, n.y., 1950; McCutcheon''s “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood n.y.; Sisley and Wood “Encyclopedia of Surface Active Agents”, Chem. Pybl. Co. Jnc. n.y., 1964; Schonfeldt “Grenzflachenak tive Alhylenoxiaddukte”, Wiss. Verlagsgesellschaft Stuttgart, 1976; Winnacker-Kucrler Chemische Technologie volume 7, C. Hauser Verlag. Munich, 4th ed.1986.Based on these formulirovaniya can also be found in combination with other, pesticide effective substances, fertilizers and/or growth regulators, for example in the form of a finished formulation or as a Tank mixture. Wettable powders are uniformly dispergirujutsja in water drugs that outfit with a biologically active substance, in addition to a diluent or inert substance, also contain a wetting, for example, polyoxyethylene ALKYLPHENOLS, polyoxyethylene fatty alcohols and fatty s is, for example ligninsulfonate sodium 2,2’-dynafilter-6,6’-disulfonate sodium, dibutylaminoethanol sodium or alarmlistener sodium.Emulsifiable concentrates are prepared by dissolving the biologically active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or more high-boiling aromatic hydrocarbons or hydrocarbons, with the addition of one or more emulsifiers. As emulsifiers can be used, for example: alkyl-arylsulfonate calcium, as dodecylbenzenesulfonate calcium; or non-ionic emulsifiers, as a complex polyglycolide esters of fatty acids, simple alkylarylsulphonate esters, simple polyglycolide ethers of fatty alcohols, condensation products of propylene oxide with ethylene oxide, simple alkyl polyethers, esters arbitarily acids, esters polyoxyethylenesorbitan acids or complex polyoxyethylenesorbitan ethers.Preparation for dusting produced by milling biologically active substance with finely powdered solid substances, for example talc, natural clays like kaolin, bentonite and pyrophyllite, or diatomaceous semi to adsorb, granulated inert material or by applying concentrates biologically active substance by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils, to the surface of the media as sand, kaolinites or granulated inert material. Also suitable biologically active substances can be conventional pelletized to obtain pellets of fertilizer method is desirable in the case of a mixture with fertilizers.As a rule, proposed according to the invention the formulation contain 1-95 wt.%, preferably 2-90 wt.%, biologically active substances, i.e., the biologically active substance of the formula (I), or a combination of biologically active substances, i.e., the biologically active substance of the formula (I), or a combination of biologically active substances of the formula (I) with the means of protection of plants (herbicide).In wettable powders, the concentration of the biologically active substance is, for example, about 10-90 wt.%, the remainder to 100 wt.% consists of the usual parts for the formulation. In the case of emulsifiable concentrates, the concentration of biologically active substances can be approximately 1-85 wt.%, preferably 5-80 wt.%. Pyvva; solutions for spraying - about 0.2 to 25 wt.%, preferably 2-20 wt.%, biologically active substances. In the case of granules, the content of biologically active substances depends partly on whether the active compound is liquid or solid and which auxiliary granulating means, fillers, etc. are used.Along with this, these formulations of biologically active substances, if necessary, contain, depending on the circumstances, conventional adhesives, wetting, dispersing agents, emulsifiers, promotes penetration tools, solvents, fillers or carriers.For use in retail form of concentrates, if necessary, in the usual manner is diluted, for example, in the case of wettable powders, emulsifiable concentrates, dispersions and partly also in the case of microgranulates - using water. Powdered and granular compositions, as well as solutions for spraying before use, usually no longer diluted by any other inert substances.The required rate of application of the compounds of formula (I) is changed in accordance with external conditions, such as temperature, humidity, the kind used by the ger is preferably, however, it is 0.01-5 kg/ha.The following examples serve to explain the invention.A. Examples of formulation(a) Preparation for dusting receive that 10 weight.h. the compounds of formula (I) is mixed with 90 weight.h. talc or inert substances and crushed in an impact mill.b) Easy despergiruemaya in water, wettable powder is the fact that 25 weight.h. the compounds of formula (I), 64 weight.h. calentadores quartz as inert substance, 10 weight.h. ligninsulfonate potassium and 1 weight.h. oleoylethanolamide sodium as wetting agent and dispersant are mixed and milled in a rod mill.C) Easy despergiruemaya in water despergiruemaya concentrate get that 20 weight.h. the compounds of formula (I) is mixed with 6 weight.h. simple alkylphenol ether Triton207), 3 weight.h. simple isotridekanolethoxylate ether (8 EO = 8 ethylenoxide links) and 71 weight.h. paraffinic mineral oil (boiling, for example, about 255 to above S) and grind in a ball mill to a fineness of below 5 microns.g) Emulsifiable concentrate is obtained from 15 weight.h. the compounds of formula (I), 75 weight.h. cyclohexanone as solvent and 10 weight.h. ethoxylated Nonylphenol is a new acid and antidote (10:1) is obtained from: 12,00% wt. ethyl ester of 2-/4-/6-chlorobenzoxazol-2-yl-oxy)-phenoxy/-propionic acid1.20 wt.% the compounds of formula (I)69,00 wt.% xylene7,80% wt. dodecylbenzenesulfonate calcium6,00% wt. ethoxylated of Nonylphenol (10 EO) and4.00 wt.% ethoxylated castor oil (40 EO).The preparation is carried out as described in example a).e) Easily emulsifiable in water concentrate of ester peroxycarbonates acid and antidote (1:10) is obtained from:4.0 wt.% ethyl ester 2-/4-6-chlorobenzoxazol-2-yl-oxy/-phenoxy/-propionic acid,40.0 wt.% the compounds of formula (I)30.0 wt.% xylene20.0 wt.% cyclohexanone4.0 wt.% dodecylbenzenesulfonate calcium and2.0 wt% ethoxylated castor oil (40 EO).W) Despergiruemaya in water granulate get that mix 75 weight.h. the compounds of formula (I), 10 weight.h. ligninsulfonate calcium, 5 weight.h. lauryl sodium3 weight.h. polyvinyl alcohol and7 weight.h. kaolin,grind on rod mill and powder granularit in the fluidized bed by spraying spraying water as a fluid granulation.C) Despergiruemaya in water granulate Planeta sodium2 weight.h. oleoylethanolamide sodium1 weight.h. polyvinyl alcohol,17 weight.h. calcium carbonate and50 weight.h. waterhomogenized and pre-ground in a colloid mill, then grind in a ball mill, and the thus obtained suspension is sprayed and dried in a tower to spray drying using a one-component jet.and Prepared in the usual ways granulate, for example, consists of:2-15 weight.h. biologically active substances of the formula (I) and98-85 weight.h. inert granular material, as attapulgite, pumice and quartz sand.B. examples of obtainingExample 1Ethyl ester 1-/2,4-dichlorophenyl/-5-methyl-5-dodecyloxy carbonyliron-3-carboxylic acidof 31.8 g dolezelova ether methylacrylate acid and 37.6 g of triethylamine is heated to 70 ° C. Within half an hour to this mixture was added dropwise 14.8 g of 2,4-dichloropyridazine ethyl ester 2-chloropicolinic acid of formula (II) with X1=X2=Y=CL, R’=C2H5(PA) in 50 ml of toluene. Then stirred for 4 hours at 80C, after cooling, is sucked off from the precipitate and carefully concentrated in vacuo. After Colo is irazola in the form of an oil with a refractive index .Example 2Methyl ether 1-/2,3-dichlorophenyl/-5-cyano-5-methyl-pyrazolin-3-carboxylic acid19,0 g methylacrylamide and 7.6 g of triethylamine is heated to 70 ° C. Within half an hour to this mixture was added dropwise 14.8 g of 2,3-dichloropyridazine ethyl ester 2-chloropicolinic acid, (IB), in 50 ml of dimethoxyethane. Then stirred for 4 hours at 80 ° C, after cooling, is sucked off from the precipitate and carefully concentrated in vacuo. From the mother liquor precipitated colorless residue (9.2 grams) with so pl. 66-670.Example 3Ethyl ester 1-/2,4-dichlorophenyl/-5-methyl-5-etoxycarbonyl-pyrazolin-3-carboxylic acidof 22.8 g of ethyl ether methylacrylate acid and 14.8 g of compound of formula (PA) (see example 1), heated to 50-60C. Within half an hour to this mixture was added dropwise 7.6 g of triethylamine. Then outweigh following 2 hours at 70C, after cooling, is sucked off from the precipitate and carefully concentrated under reduced pressure. Get 18,1 g blignault oil; the refractive index .Example 4Ethyl ester 1-/2,4-dichlorophenyl/-5-methyl-5-phenyl-pyrazolin-3-carboxylic acid23.7 g of 2-methylstyrene and 14.8 g of compound (PA) (see example 1) together with 50 ml of a saturated aqueous solution of carbon concentrated under reduced pressure. After column chromatography (solvent n-heptane/acetic ester 1:1/ through silica gel gain of 6.9 g of the above pyrazoline in the form of a colourless solid with so pl. 87-89S.In the following table 1 shows other compounds of formula (I), which are similar to the methods of examples 1-4.EXAMPLE 1Wheat and barley are grown in the greenhouse in plastic pots up to the stage of 3-4 leaves and then treated with proposed according to the invention is that of compounds and herbicides for post-harvest method. Herbicides and the compounds of formula I thus put in the form of aqueous suspensions, respectively, of emulsions with normal flow in terms of 800 l/ha 3-4 weeks after treatment of the plants is assessed visually for each type of damage due to the applied herbicides, and in particular take into account the size of the prolonged suppression of growth. The degree of damage, respectively, antidote action of the compounds of formula (I) alone or in combination with herbicides is determined in % damage.Results /see table 2/ show that proposed in the invention compounds can effectively reduce severe damage to the sludge, clearly declining appear in the case of cultivated plants heavy damage, and completely liquidated minor injuries. Mixtures of herbicides and proposed according to the invention compounds are therefore well suitable for selective weed control in crops.EXAMPLE 2In a series of experiments similar to example 1, which, however, are made with a large number of repeated tests with the appropriate application, get listed in table 3 results. Partially deviating absolute values in the activities explained climatic influences, which were not exactly the same in both series of experiments.1. Means of protecting crops from phyto-toxic side effects of herbicides containing one or more protective of biologically active substances (antidotes) and special additives, characterized in that the biologically active substances (antidote) it contains one or more compounds of the formula (I)where X denotes independently from each the denotes hydrogen, (C1-C4)-alkyl, (C1-C4)-alkoxy-(C1-C4)-alkyl,R2and R3denotes independently from each other hydrogen, (C1-C6)-alkyl, (C2-C6)-alkenyl, (C2-C6)-quinil, (C3-C6-cycloalkyl, (C1-C6-halogenated, mono - or di-(C1-C4-alkoxy)-(C1-C4)-alkyl, [(C1-C6)-alkyl]-carbonyl, di-[(C1-C4)-alkyl)]-aminocarbonyl, cyano, [(C1-C12)-alkyl]-oxycarbonyl, phenyl, unsubstituted or substituted by one or more residues selected from halogen and ceanography,in the amount of from 0.002 to 95 wt.% in the calculation of the tool, the rest is the usual for plant protection additives target.2. Means under item 1, wherein in the formula (I) R2denotes hydrogen, (C1-C4)-alkyl or (C2-C4)-alkenyl, R3means (C1-C4)-alkyl, (C2-C4)-alkenyl, di-[(C1-C4)-alkoxy]-(C1-C4)-alkyl, [(C1-C4)-alkyl]-carbonyl, cyano, [(C1-C12)-alkyl]-oxycarbonyl or phenyl.3. Means under item 1 or 2, characterized in that in formula (I) X denotes independently of one another F, Cl is kenil; R3means (C1-C4)-alkyl, (C2-C4)-alkenyl, di-[(C1-C4)-alkoxy]-(C1-C4)-alkyl, [(C1-C4)-alkyl]-carbonyl, cyano, [(C1-C12)-alkyl]-oxycarbonyl or phenyl.4. Tool for PP.1-3, characterized in that it further comprises a herbicide.5. Means on p. 4, characterized in that it further comprises a herbicide selected from the group of derivatives phenoxyphenylacetic acids and derivatives heterooligomerization acids, the weight ratio of herbicide to antidote from 1.6:10 to 8:1.6. Means on p. 5, characterized in that as it contains herbicide fenoxaprop-ethyl.7. The compound of formula (I)where (X)ndenotes 2,4-CL2;R1denotes hydrogen or (C1-C4)-alkyl;R2denotes hydrogen or methyl;R3means (C1-C4)alkoxy-carbonyl or carboxyl.8. The compound of formula (I) under item 7, characterized in that theR1represents ethyl;R2denotes methyl;R3means etoxycarbonyl.9. The way poluchenii or bromine;(X)nand R1defined as in formula (I) under item 7 or 8, is subjected to the interaction with the olefin of formula (III)where R2and R3defined as in formula (I) under item 7 or 8,with subsequent isolation of the target product.10. The method of controlling undesirable vegetation in crops, characterized in that the treated plants, plant seeds or planting the area with herbicide in combination with the compound of the formula (I) as the antidote according to any one of paragraphs.1, 2, 3, 7 and 8, when the ratio of herbicide : safener is from 10:1 to 1:10 and the consumption rate of 0.005 to 10 kg/ha in the calculation of the antidote.11. The method according to p. 10, characterized in that the treated plants, plant seeds or planting the area with herbicide selected from the group of derivatives phenoxythiocarbonyl acids and heterooligomerization acids, in combination with the compound of the formula (1) as an antidote if the weight ratio of herbicide to antidote from 1.6:10 to 8:1.12. The method according to p. 11, characterized in that as herbicide use phenoxypropanol.
< / BR>and their salts, where R1means H or F; R2means H, halogen, C1-C4-alkyl; R3means of CH3; connection I use for combating phytopathogenic fungi
FIELD: agriculture, insecticides.
SUBSTANCE: invention relates to insecticide covers for seeds that comprise one or some binding substances taken among the group including polymers and copolymers of polyvinyl acetate, methylcellulose, polyvinyl alcohol, vinylidene chloride, acryl, cellulose, polyvinylpyrrolidone and polysaccharide, and insecticide and a filling agent also. A binding agent forms matrix for insecticide and a filling agent. Also, invention relates to a method for control of insect-pests that involve applying a cover on seeds. Also, invention relates to a method for preparing seeds with cover that involves mixing a binding agent, carrier and insecticide, applying a mixture of seed, drying and applying an additional filming cover. Method for protecting the germinating seedlings involves applying the insecticide cover on seeds. Invention provides reducing the phytotoxic effect of insecticide on seeds.
EFFECT: valuable agricultural properties of insecticide cover.
24 cl, 5 tbl, 5 ex