Mixture from herbicides and antidotes and method for protection of cultural plants against phytotoxic side effect of herbicidically active substance

FIELD: organic chemistry, agriculture.

SUBSTANCE: claimed mixture from herbicides and antidotes contains (A) herbicidically active substance based on phenylsulfonylureas of formula I and salts thereof (in formula R1 is hydrogen or C1-C6-alkyl; R2 is C1-C3-alkyl; R3 is C1-C3-alkoxy; R4 is hydrogen or C1-C4-alkyl; Hal is fluorine, chlorine, bromine, or iodine); and (B) antidote of formulae II or III , wherein X is hydrogen, halogen, C1-C4-alkyl; C1-C4-alkoxy, nitro or C1-C4-haloalkyl; Z is hydroxyl, C1-C8-alkoxy, C3-C6-cycloalkoxy, C2-C8-alkenyloxy, C2-C8-alkynyloxy; R5 is C1-C2-alkandiyl chain optionally substituted with one or two C1-C4 alkyl residues or (C1-C3-alcoxy)carbonyl; W is bivalent heterocyclic residue; n = 1-5; in weight ratio herbicide/antidote of 100:1-1:100. Also disclosed is method for protection of cultural plants against phytotoxic side effect of herbicidically active substance of formula I. Claimed method includes antidote application of formulae II or III on plant, plant parts, plant seeds or seeding areas before or together with herbicidically active substance in amount of 0.005-0.5 kg/hectare in weight ratio of 100:1-1:100.

EFFECT: mixture for effective selective weed controlling in cultural plant, particularly in maize and grain cultures.

8 cl, 2 ex, 7 tbl

 

Description

This invention relates to the field of plant protection, more specifically it relates to a mixture of herbicides and antidotes, and way of protecting cultivated plants from phyto-toxic side effects herbicide-active substances.

Some modern herbicide active substances exhibit very good properties, useful in their application, and can be used with very low consumption rates against a broad spectrum of grassy and broadleaf weeds.

However, many of the highly active substances are poorly tolerated (selectively) in some important cultivated plants, such as corn, rice or cereal, so their use is very limited. Therefore, in some cultures, or is not to be used, or can only be used with very small consumption norms, which do not provide the necessary wide herbicide action against harmful plants. In particular, many herbicides, corresponding to the following formula (a), cannot be applied selectively fully against harmful plants in maize, rice, cereal and other crops.

Carried out by the authors of the present invention, the new experimental developments unexpectedly showed that cultivated plants, such as corn, rice, wheat, rye and others, you can protect against unwanted damage caused by the aforementioned herbicides, when used together with certain compounds which act as antidotes or safener.

The closest analogue of the invention is a mixture of herbicides and antidotes containing herbicide-active substance from the group of substituted phenylsulfonylacetate formula (X)

have

R' denotes methyl or ethyl,

R denotes methoxy or deformedarse,

R"' represents chlorine or deformedarse,

and the antidote from the group replaced xenolinux group of carboxylic acids and their derivatives, and substituted nitrogen-containing heterocycle carboxylic acids and their derivatives (see patent application EP 0 492 367 A2, A 01 N 47/36, 01.07.1992).

The objective of the invention is to develop a mixture of herbicides on the basis of phenylsulfonylacetate and antidotes from the group of substituted hinolinovogo carboxylic acids and their derivatives, and substituted nitrogen-containing heterocycle carboxylic acids and their derivatives, with less toxicity.

The problem is solved, we offer a mixture of herbicides and antidotes, containing:

A) herbicide-active substance from the group of substituted phenylsulfonylacetate formula (A)

where

R1is hydrogen, alkyl with 1-6 the volumes of carbon

R2- alkyl with 1-3 carbon atoms,

R3- alkoxy with 1-3 carbon atoms,

R4is hydrogen or alkyl with 1-4 carbon atoms,

Hal is fluorine, chlorine, bromine or iodine,

and their salts

and

B) the antidote from the group of compounds of formulas (B1) and (B2),

in which

X is hydrogen, halogen, alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, nitro group or haloalkyl with 1-4 carbon atoms,

Z is hydroxyl, alkoxy with 1-8 carbon atoms, cycloalkane with 3-6 carbon atoms, alkenylacyl with 2-8 carbon atoms or alkyloxy with 2-8 carbon atoms,

R5- alcantarilla chain with 1-2 carbon atoms which may be substituted by one or two alkyl residues with 1-4 carbon atoms or alkoxycarbonyl with 1-3 carbon atoms in the CNS part,

W is a divalent heterocyclic residue, corresponding to the formula (W1) and (W2)

where

R6is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, cikalkis with 3-12 carbon atoms or phenyl,

R7is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the alkyl and CNS side, respectively, hydroxyalkyl with 1-6 carbon atoms or cycloalkyl with 3-12 carbon atoms,

n is an integer of 1-5,

when the weight ratio of herbicide : safener of 100:1-1:100.

In a preferred embodiment, a mixture of herbicides and antidotes contains herbicide-active substance of the formula (A) or its salt,

where R1is methyl, R2is methyl, R3- methoxy, R4is hydrogen, Hal is chlorine or iodine.

In another preferred embodiment, a mixture of herbicides and antidotes contains a safener of the formula (B1) or (B2), where

Z is hydroxyl, alkoxy with 1-8 carbon atoms or cycloalkene with 3-7 carbon atoms,

R6- alkyl with 1-8 carbon atoms, haloalkyl with 1-4 carbon atoms,

R7is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the CNS part and 1 to 4 carbon atoms in the alkyl part,

X is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, haloalkyl with 1-2 carbon atoms.

Particularly preferred mixture of herbicides and antidotes containing complex ethyl ester 1-(2,4-dichlorophenyl)-5-(etoxycarbonyl)-5-methyl-2-pyrazolin-3-carboxylic acid as an antidote.

Further preferred mixtures of herbicides and antidotes, representing a compound (herbicide tool) and containing from 0.1 to 99 wt.% active substances of the formulae (a) and (B1) or (B2) and 1-99,9 wt.% conventional auxiliary additives.

Most before Occitania mixture of herbicides and antidotes, containing the active substances of the formulae (a) and (B1) or (B2) in a weight ratio of from 1:10 to 10:1.

The object of the invention is also a method of protecting cultivated plants from phyto-toxic side effects herbicide-active substances of the formula (a) and their salts, in which the safener of the formula (B1) or (B2) are applied to plants, plant parts, plant seeds or the area sown before, after or simultaneously with herbicide-active substance. The amount of antidote (B1) or (B2) is at this from 0.005 to 0.5 kg/ha, and a weight ratio to herbicide-active substance (a) is 1:100-100:1.

Under cultivated plants, preferably understand cereals or maize.

The compounds of formula (A) can form salts in which the hydrogen groups substituted useful for agriculture cation. These salts can be, for example, metal salts, in particular alkali metal salts (e.g. sodium or potassium), or salts of alkaline earth metals, and ammonium salts or salts of organic amines. The formation of salts may also occur by attaching a strong acid to the heterocyclic part of the compounds of formula (A). Appropriate salts are, for example, salts of such acids as hydrochloric, nitric, trichloroacetic, acetic acid or palmitic.

In the following text under "herbicide is m (A)" refers to compounds of formula (a) and their salts.

Some compounds of formula (A), (B1) or (B2) may contain one or more asymmetric carbon atoms or double bonds, which in the General formula is not expressly stated. The possible stereoisomers defined by their specific spatial form, such as enantiomers, diastereomers, Z - and E-isomers, are covered by these formulas can be obtained by customary methods from mixtures of the stereoisomers or by stereoselective reactions in combination with the use of stereochemical pure starting materials. Thus, these stereoisomers in pure form and mixtures thereof can be used according to the invention.

The compounds of formula (A) are known, for example, from the application EP-A-007687, applications EP-A-0291851, application DE-A-7900472, application US-A-4566898 and International application WO 92/13845.

The compounds of formula (B1) is known from the application EP-A-333131, applications EP-A-269806, applications EP-A-346620 and International applications PCT/EP 90/01966 (WO-91/08202) and PCT/EP 90/02020 (WO-91/07874) and cited literature there. The compounds of formula (B2) is known from the application EP-A-94349, applications EP-A-191736 and applications EP-A-0492366 and cited literature there. In addition, some compounds described in the application DE-A-4225493.

As antidotes for the above herbicides are preferably used:

a) derived dichlorobenzimidazole-3-carboxylic acid (i.e. of the formula (B1), where =W1 and (X) n=2,4-CL2), as, for example, ethyl ester 1-(2,4-dichlorophenyl)-5-(etoxycarbonyl)-5-methyl-2-pyrazolin-3-carboxylic acid, and used compounds such as described in International application WO 91/07874;

b) compounds of the type triazole-carboxylic acid (i.e. of the formula (B1), where W=W2 (X)n=2,4-Cl2), as for example, ethyl ester 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid, and used compounds such as described in applications EP-A-174562 and EP-A-346620;

in) connection type 8-quinoline-exucuse acid (i.e. of the formula (B2), where (X)n=5-CL2hydrogen, Z=OH, R5=CH2), like this:

1-methyl-Gex-1 silt ester (5-chloro-8-xenolinux)-acetic acid,

1,3-dimethyl-but-1-silt ester (5-chloro-8-xenolinux)-acetic acid,

4-allyl-oxy-butyl ester (5-chloro-8-xenolinux)-acetic acid,

1 allyloxy-prop-2-silt ester (5-chloro-8-xenolinux)-acetic acid,

ethyl ester (5-chloro-8-xenolinux)-acetic acid,

methyl ester (5-chloro-8-xenolinux)-acetic acid,

allyl ester (5-chloro-8-xenolinux)-acetic acid,

2-(2-propylidene-aminoxy)-1-ethyl ester (5-chloro-8-xenolinux)-acetic acid,

2-oxo-prop-1-silt ester (5-chloro-8-xenolinux)-acetic acid,

and note the badge of the connection, such as described in applications EP-A-86750, EP-A-94349, and EP-A-191736, or EP-A-0492366;

g) compounds of the type (5-chloro-8-xenolinux)-malonic acid (i.e. of the formula (B2), where (X)n=5-Cl2Z=OH, R5=-CH(COO-alkyl)-), as for example, diethyl ester (5-chloro-8-xenolinux)-malonic acid, methyl-ethyl ester (5-chloro-8-xenolinux)-malonic acid, and used compounds such as described in the application DE-A-4225493.0.

The antidotes of formula (B1) and (B2) reduce or inhibit fetotoxicities effects that can occur when using herbicide-active substances of the formula (A) in cultivated plants, without reducing the effectiveness of herbicide action of herbicides against weeds.

Herbicide existing active substances and these antidotes can be used together (as finished products or as a pre-mixed) or they can be used sequentially one after the other. The weight ratio of safener:herbicide can be varied in a wide range of values, preferably in the range from 1:10 to 10:1. In each case, the optimal number of herbicide and antidote depend on the type of herbicide or used antidote, as well as the type of cultivated plants, they can each time to determine the appropriate preliminary experiments.

The antidotes of formula (B1) and (B2) can be used, which depending on their properties, for pre-treatment of seed of cultivated plants (seed treatment), or before sowing seeds in the sowing furrow, or together with the herbicide before emergence of the plants or after germination. Predsjedava processing includes processing the planting area before planting and processing of cropped area to germination. Preferably the combined use of herbicides. You can use pre-mix or ready-made compositions. The required norms of consumption used antidotes can vary in a large range. They greatly depend on what kind of effect I want to get and what kind of herbicide used.

The above composition of the proposed mixture containing from 0.1 to 95 wt.% active substances of the formulae (a) and (B1) or (B2) and 1-99,9 wt.% conventional auxiliary additives, can be a sprayable powders, emulsifiable concentrates, water-soluble powder, water soluble concentrates, emulsion concentrates, such as emulsion, oil-in-water and water-in-oil"spray solutions or emulsions, wettable powders, suspensions, capsules, dispersions based on oil or water, suspension-emulsion concentrates, suspension concentrates, powdered drugs, mixed with oil solutions, disinfectants, granulates, in fo the IU micro, spray, suspendiruemye and adsorption granules, granules for application to soil, water soluble granules, water dispersible granules, ultramontanism drugs, microcapsules and waxes.

These types of drugs, in principle, known and described, for example, in the sources Winnacker-Kü'hler "Chemische Technologie", Band 7, C.Hauser Verlag, Munich, 4. Aufl. 1986; Wade van Valkenburg, "Pesticide Formulations", 3rd Ed. 1979, G.Goodwin Ltd. London.

Necessary in the formulation of drugs auxiliary tools, such as inert materials, surfactants, solvents and other additives target is also known and described, for example, in the following sources: Watkins, "Handbook of insecticide dust diluents and carriers", 2nd Ed., Darland Books, Caldwell N.J.; H.v.Olphen "Intruduction to clay colloid chemistry", 2nd Ed., J.Wiley & Sons, N.Y., Marsden "Solvents Guide, 2nd Ed., In-terciece, N.Y. 1963; McCutcheon''s "Detergents and emulsifiers annual", MC Publ.Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of surface active agents", Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, "Grenzflåchenaktive Äthylenoxidaddukte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler "Chemische Technologie", Band 7, C. Hauser Verlag Munich, 4th. Aufl. 1986.

On the basis of these preparations can also be found in combination with other pesticide active substances, fertilizers and/or plant growth regulators, for example, in the form of a finished formulation or pre-prepared mix.

The sprayed powder is uniformly dispersible in water with the drug, which is output along with active early and addition of diluents and inert substances contains more surfactants of ionic and/or nonionic type (wetting, dispersants), for example, polyoxyethylene ALKYLPHENOLS, polyoxyethylene fatty alcohols and fatty amines, sulfates, ethers of fatty alcohols and polyglycols, alkanesulfonyl, alkylarylsulfonate, sodium salt of ligninsulfonate, sodium salt of 2,2'-dynafilter-6,6'-disulfonate, sodium salt of dibutylaminoethanol or sodium salt railneteurope acid.

Emulsifiable concentrates are obtained by dissolving the active substance or active substances in an organic solvent, such as butanol, cyclohexanone, dimethylformamide, xylene or high-boiling aromatic or aliphatic hydrocarbons with the addition of one or more surfactants of ionic and/or nonionic type (emulsifiers). As emulsifiers can be used, for example: calcium salt of alkylarylsulfonate, such as dodecylbenzenesulfonate calcium, or nonionic emulsifiers, such as esters of polyglycols and fatty acids, ethers of alkylarylsulphonate, ethers of polyglycols and fatty alcohols, condensation products of propylene oxide-ethylene oxide (for example, blakolmer), alkylpyridine, esters of sorbitol and fatty acids, esters of polyoxyethylenesorbitan and fatty acids or other esters of polyoxyethylenesorbitan.

Sprayed cf is DSTV obtained by grinding the active substance or active substance with finely dispergirovannykh solids, for example talc, natural clays such as kaolin, bentonite or pyrophyllite, or diatomaceous earths.

The granules can be obtained by spraying the active substance or active substances on the adsorption-capable of granulated inert material or by applying concentrates of active substances by means of adhesives, such as polyvinyl alcohol, sodium polyacrylate or mineral oils, to the surface of carriers such as sand, kaolinites or granulated inert material. Dispersible in water granulate receive, as a rule, conventional methods such as spray drying, granulation in the fluidized bed, disk granulation, mixing with high speed mixer and extrusion without solid inert material. You can also be pelletized suitable active substance customary for obtaining fertilizer manner - preferably in a mixture with fertilizers.

In sprayable powders the concentration of the active substance is, for example, from about 10 to 90 wt.%, the rest up to 100 wt.% are the usual components of such drugs. In emulsifiable concentrates, the active substance is contained in an amount of from approx.1 up to 80 wt.%. Dust-like formulations contain from about 1 to 20 wt.% the active substance, spray solutions containing from about 0.2 to 20 wt.% the active substance. In the case of granules, such as water dispersible granules, the content of the active substance depends partly on whether the active substance is solid or liquid. Typically, the content dispersible in water granules is from 10 to 90 wt.%.

In addition, these formulations of active substances may contain conventional adjuvants, such as wetting, dispersing agents, emulsifiers, means to increase penetration, solvents, fillers or carriers.

For the application of commercially available formulations can as usual be diluted, for example, in the case of sprayed powders, emulsifiable concentrates, dispersions and water-dispersible granules diluted with water. Powdered drugs and granules and sprayable solutions are usually before the application is not diluted with other inert substances. Especially good efficiency means according to the invention can be achieved, if added to the composition in addition to the existing surface-active substances other wetting in a concentration of from 0.1 to 0.5 wt.% as a pre-obtained mixture, for example, non-ionic wetting or wetting type sulfates simple PoE-oil fatty alcohols (see, for example, the application DE 4029304.1). The required amount of antidote varies depending on environmental conditions such as temperature, humidity, the type of herbicides, etc.

On the basis of these drugs possible combinations with other influencing plant substances, such as pesticides, such as insecticides, acaricides, fungicides and herbicides and/or fertilizers and/or plant growth regulators, you can get them as ready-made business forms or as a pre-prepared mixture.

As components for combination with the active substances according to the invention in the finished work forms or pre-prepared mixtures applicable, for example, known active substances as described, for example, in Weed Research 26, 441-445 (1986), or "The pesticide manual", 9th Edition, The british crop protection council, 1990/91, Bracknel, England, and cited in the literature. As known from the literature herbicides which can be combined with compounds of formula (I)include, for example, the following substances (note: the compounds are named or "normal names" according to the International Organization for Standardization (ISO), or their chemical names, sometimes along with their usual code numbers):

Acetochlor, Acifluorfen, Klonipin, [[[1-[5-[2-chloro-4-(trifter-methyl)-phenoxy]-2-nitrophenyl]-2-methoxyacridine]-amino]-oxy]-acetic acid or methyl ester [[[1-[5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrophenyl]-2-methoxyacridine]-amino]-oxy]-acetic acid (DCA 7088), Alachlor, al oxides, Ametrine is high, Amidosulfuron, Amitrole, sulpham ammonium, i.e. AMC, Anilofos, Azul, Atrazine, Isoprotein, Barban, 5-fluoro-2-phenyl-4H-3,1-Benz-oxazin-4-one, i.e. BASS 516 N., Benazolin, Benfluralin, Beforethat, Busulphan-methyl, Bensulide, Bentazone, Benzefoam, Bentover, Benzoylperoxy-ethyl, Benzthiazole, Bialaphos, Bifenox, Bromacil, Bromobutyl, Bromophenoxy, Bromoxynil, Brauron, Buminate, Butoxide, Butachlor, Butamifos, Buenaflor, Booteasy, Bifenthrin, Papenbrock, Butyl, Carbetamide, 2-chloro-N,N-di-2-propylacetamide (NDAA), complex korallovy ether pttc acid (HEDC), 2-[4-[(5-chloro-3-fluoro-2-pyridinyl)-oxy]-phenoxy]-propionic acid and its complex 2-propenyloxy ether, Chlorethoxyfos, Chloramben, Houseforsale, Chlorbromuron, Chlorbutol, Chlorgenic, Chlorofluro-methyl, ozone chloride, Chloroaromatic, Chlornitrofen, Chlorotoluron, Chloroxuron, Chlorpropham, Chlorsulfuron, Chlortalidone, Chlorine Cinmetacin, Cynosurion, Clethodim, Clomazone, Clomipram, Chloroxygen, Clopyralid, Cyanazine, Cycloate, Cyclotron, Cyberswat, Seperatin, Supersol, 2,4-dichloro-proximally acid, dalapon, Desmedipham, Desmetryn, Diallate, Dicamba, Dichlobenil, Dichlorprop, Diclofop-methyl, Diacetyl, Difenoxin, Difenzoquat, Diflufenican, Dimefuron, Dimethachlor, Deltamethrin, Deltason, Dimethipin, Timeresolution, Initram is h, Dinoseb, Dinoterb, Diphenamid, DIPROPYLENE, Diquat, Dithiopyr, Diuron, dinitrocresol, Eglinton-ethyl, 5-cyano-1-(1,1-dimethylethyl)-N-methyl-3H-pyrazole-4-carboxamide, Endothal, Eptam, Aspro-carb, Ethalfluralin, Ethanesulfonic-methyl, Tidiman, Idiosyn, Ethofumesate, N-[2-chloro-4-fluoro-5-[4-(3-fluoro-propyl)-4,5-dihydro-5-oxo-1 H-tetrazol-1-yl]-phenyl]-econsultant (R),1-[5-(N-methylsulphonyl)-amino-2,4-dichlorophenyl]-3-methyl-4-deformity-triazole-5-he (F6285), Fenoprop, Phenoxy, Fenoxaprop-ethyl, Fenuron, Planrep-methyl, Flazasulfuron, Fluazifop and its ester derivatives, Fluchloralin, Flumetsulam, N-[2,6-differenl]-5-methyl-(1,2,4)-triazole[1,5A]-pyrimidine-2-sulfonamide, Flumeturon, Flubiprofen, Fluorodifen, Fluoroglycofen-ethyl, Floridon, Fluorochloridone, Fluroxypyr, Flurtamone, Fomesafen, Fosamine, Voreloxin, Glufosinate, Glyphosate, Galasoft, Haloxyfop and difficult-ether derivatives, Hexazinone, N-[2,3-dichlorophenyl]-4-(ethoxyethoxy)-benzamide (Hw 52), Imazamethabenz, Imazapyr, Imazighen, Imazethapyr, Imazethapyr, Imazosulfuron, Ioxynil, Isoprocarb, Isopropylene, Isoproturon, Ioron, Isoxaben, Isocaporate, Carbuterol, Lactofen, Lenacil, Linuron, 2-methyl-4-chlorophenoxyacetate acid, 2-methyl-4-chlorphenoxamine acid, Mecoprop, Mefenacet, Mefluidide, Metamitron, Metazachlor, Methabenzthiazuron, METAM, Metasol, Metaxylene is, Methyldibromo, Metobromuron, Metolachlor, Metoxuron, Metribuzin, Metalforever, hydrazide maleic acid, Molinet, Monolid, mono-urea of dihydrofolate, Monolinuron, Monuron, 6-chloro-N-(3-chloro-6-propenyl)-5-methyl-N-phenyl-3-pyridazinone (MT-128), N-[3-chloro-4-(methylethyl)-phenyl]-2-methyl-pentane (MT-5950), Nitroanilide, Napropamide, Naptalam, 4-(2-,4-dichlorobenzoyl)-1-methyl-5-benzyloxyphenol, Neburon, Nicosulfuron, Snipercraft, Nicraly, Nitrofen, Nitrofluorene, Norflurazon, Arrancars, Oryzalin, Oxadiazon, Oxyfluorfen, Paraquat, Pebulate, Pendimethalin, Perfsuite, Phenmedipham, Fenazepam, Picloram, Piperophos, Perimutter, Pirivena-butyl, Pretilachlor, Primisulfuron-methyl, Prolatin, Prodiamine, Propleuron, Propinsi-ethyl, Prometon, Prometryn, Propachlor, Propanil, Proposats and its ester derivatives, Propazine, Propham, Propyzamide, Prosulfuron, Prosulfocarb, Panahar, Pyrazoline, Person, Pyrazosulfuron, Paradoxien, Peridot, Jinjarak, Hinnerk, Chinatop and difficult-ether derivatives, Hisamoto and difficult-ether derivatives, Hisamoto-ethyl, Heslopharrison, Renature, Damron, 2-[4-chloro-2-fluoro-5-(2-propenyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazol (S 275), 2-[7-fluoro-3,4-dihydro-3-oxo-4-(2-PROPYNYL)-2H-1,4-benzo-oxazin-6-yl]-4,5,6,7-tetrahydro-1H-isoindole-1,3(2H)-dione (S 482), Sebumeter, Sethoxydim, Sibron Simazine, Simetryn, 2-[[7-[2-chloro-(4-trifluoromethyl)-phenoxy]-naphthalenyl]-oxy]-propionic acid and its methyl ester, Sulfometuron, Salvadoran, Flazasulfuron, Tetrachlorodibenzo, Tabulam, Tebuthiuron, Terbacil, Thermocarb, Turbuhaler, Terbumeton, TERBUTHYLAZINE, Terbutryn, N,N-di-ethyl-3-[(2-ethyl-6-were-sulfonyl]-1 H-1,2,4-triazole-1-carboxamide (TFH), Diazafluoren, Thifensulfuron is methyl, Thiobencarb, Thiocarbonyl, Tralkoxydim, Triallate, Triasulfuron, Threatened, Tribenuron-methyl, Triclopyr, Tridiphane, Triacetin, Trifluralin, Treemature, Vernolate, 5-phenoxy-1-[3-(trifluoromethyl)-phenyl]-1 H-tetrazol (WL 110547).

The following examples illustrate the possible formulations of the mixture:

a) Pulverized composition was obtained by mixing 10 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2) and 90 weight. parts of talc as inert substance, followed by grinding the mixture in an impact mill.

b) Easily dispersible in water, a wettable powder was obtained by mixing 25 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2), 64 weight. parts kalisoderjasimi quartz as inert substance, 10 weight. parts ligninsulfonate potassium and 1 weight. part alarmlistener sodium in quality is TBE wetting and dispersing funds, followed by grinding the mixture in a pin mill.

C) Easily dispersible in water dispersion concentrate was obtained by mixing 20 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2), 6 weight. parts of alkylphenol ether (trade mark Triton X 207), 3 weight. parts isotridekanolethoxylate ether (8 EO) and 71 weight. parts of a paraffin mineral oil (boiling range, for example, from about 255 to above 277° (C) followed by grinding the mixture until the particle size below 5 microns in a ball mill for dispersion.

g) Emulsifiable concentrate was obtained by mixing 15 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2), 75 weight. parts of cyclohexanone as solvent and 10 weight. parts atsetilirovanie of Nonylphenol as emulsifier.

d) Dispersible in water granulate was obtained by mixing 75 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2), 10 weight. parts ligninsulfonate calcium, 5 weight. parts alarmlistener sodium, 3 weight. parts of polyvinyl alcohol and 7 weight. parts of kaolin, followed by grinding the mixture in a pin mill and granulating the powder in the fluidized bed when spraying water as granules of the tank liquid.

e) Dispersible in water granulate was obtained from 25 weight. parts of the compounds of formula (B1) or (B2) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) or (B2), 5 weight. parts of 2,2'-dynafilter-6,6'-disulfonate sodium, 2 weight. parts alarmlistener sodium, 1 weight. part of polyvinyl alcohol, 17 weight. parts of calcium carbonate and 50 weight. parts water gomogenizirovannom and grinding in a colloidal mill, followed by grinding in a ball mill, spraying the resulting suspension in a spray column of nozzles and drying.

The invention is illustrated by the following examples:

Example 1

Wheat and barley (as cultivated plants) and meticu ordinary (as a weed) were grown in a greenhouse in plastic pots to the stage of the third sheet, then was treated with a mixture of herbicide and antidote according to the method of post-harvest processing. The herbicide of the formula (a) and the antidotes of formula (B) was applied in the form of aqueous suspensions or emulsions with a consumption rate per water 300 liters per 1 hectare, four weeks after treatment was evaluated plants visually in relation to the extent of the damage caused by the herbicide, and took into account, in particular the degree of inhibition of growth. The evaluation results are given in percent in comparison with untreated control plants (see Table 1).

Even observed what s in cultivated plants with a large overdose of heavy herbicide damage is markedly reduced, and minor damage completely disappear. For herbicide action of compounds G1 and G2 Supplement antidotes according to the invention are not affected, as shown in the example meliza ordinary. The mixture according to the invention of herbicides (a) and antidotes (B) is very suitable for selective weed control in cereal crops.

Table 1:

The effect in post-harvest processing (%%)
the herbicide/ safenerthe consumption rate g act. in-VA/hawheat*barley*meliza ordinary* (Apera spica vent.)
G150

25

12
75

60

40
80

65

50
-

100

98
G1+A150+25

25+12

12+6
20

10

0
45

25

15
-

100

98
G1+A250+25

25+12

12+6
15

5

0
50

15

5
-

100

99
G1+A350+25

25+12

12+6
30

15

5
50

25

10
-

100

98
G1+A450+25

25+12

12+6
25

10

5
-
/br> -

-
-

100

99
G4+A550+25

25+12

12+6
15

10

0
40

20

0
-

100

98
the herbicide/ safenerthe consumption rate g act. in-VA/hawheat*barley*meliza ordinary* (Apera spica vent.)
G250

25

12
90

65

60
90

65

55
-

100

100
G2+A150+25

25+12

12+6
20

0

0
35

20

10
-

100

98
G2+A350+25

25+12

12+6
30

10

5
30

10

10
-

98

98
G2+A450+25

25+12

12+6
25

10

10
40

10

0
-

98

98
G2+A550+25

25+12

12+6
10

10

0
15

10

0
-

99

99

Abbreviations in Table 1:

* = wheat, barley and meliza in stage three leaves,

G1=N-[(4-methoxy--6-methyl-1,3,5-triazine-2-yl)-aminocarbonyl]-5-iodine-2-methoxycarbonyl-benzosulfimide,

G2=N-[(4-methoxy--6-methyl-1,3,5-triazine-2-yl)-AMI is carbonyl]-5-chloro-2-isopropoxy-carbonyl-benzosulfimide,

A1 = diethyl ester (5-chloro-8-xenolinux)-malonic acid,

A2=2-methyl-hexyl ester (5-chloro-8-xenolinux)-acetic acid,

A3 = complex ethyl ester 1-(2,4-dichlorophenyl)- 5-(etoxycarbonyl)-5-methyl-2-pyrazolin-3-carboxylic acid,

A4 = complex ethyl ester 1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylic acid,

A5 = 1-methyl-ethyl ester (5-chloro-8-xenolinux)-malonic acid.

Example 2

Maize varieties Felix and DEA were grown in a greenhouse in plastic pots to fourth leaf stage and then treated with a mixture of a herbicide of formula (a) and a safener of the formula (B) according to the method of post-harvest processing. The herbicide and the antidote was applied in the form of aqueous suspensions or emulsions with a consumption rate per water 300 liters per 1 hectare, four weeks after treatment was evaluated plants visually in relation to the extent of the damage caused by the herbicide, and took into account, in particular, the degree of inhibition of growth. The evaluation results are given in percent in comparison with untreated control plants (see Table 2).

The results showed that the compounds of the formula (B) can effectively reduce caused by herbicide in plants corn damage. Even observed in cultivated plants with a large overdose of heavy herbicide damage noticeably red eye reduction which are, and minor damage completely disappear. The mixture according to the invention of herbicides (a) and antidotes (B) is very suitable for selective weed control in corn.

Table 2:

The effect in post-harvest processing (%%)
the herbicide/safenerthe consumption rate g actu-VA/hacorn (Felix)corn (Dea)
G1503020
252010
12100
G1+A550+5000
25+2500
12+1200

Abbreviations in Table 2:

* = in stage three or four leaves,

G1 = see Table 1,

A1 = see Table 1.

In the studies of the properties of mixtures of herbicide G1 and summarized in tables 3-5 antidotes of formula (B1) and (B2)in which the radicals X, W, Z, and R5have a value other than values antidotes A1-A5, it turned out that those other mixture properties are not inferior to the compounds of tables 1, 2. At this rate of application of herbicide was 0.005 and 5 kg/ha, and the Orme flow antidote was 0.005 to 0.5 kg/ha, the weight ratio of herbicide and antidote ranged from 1:10 to 10:1.

td align="center"> phenyl
Table 3

Connection # (X)nR6R7Z
I2,4-Cl2CH3NOH
II2,4-Cl2NNOH
III2,4-Cl2CH3CH3OS6H11
IV2,4-Cl2With2H5ISO-C3H7OS6H5
V3,4-(CF3)2NCF3Och3
VI2,4-Br2CH3N-C4-N9OS2H5
VIINCF3With6H11OH
VIII2,4-F2With6H11CH2HEOch3
IX2-CF3, 4-C1(CH2)2Och3OH
X3,4-(CF3)2With3H5CF3OH

tr>
Table 4

Connection # (X)nR6Z
I3-ClCHCl2OS2H5
II4-NO2CHC12Och3
III2-CH3, 4-ClCH3Och3
IV2,4-Cl2HHE
V3-CF3CCl3OS2H5
VI4-FWith3H5Och3
VII3-Cl, 4-FCCl3OS6H11
VIII2,4-Cl2,

5-och3
CCl3OS3H7-N.
IXHISO-C3H7Och2CH=CH2
XHCF3Och2With SN

Table 5

Connection#. (X)nR5Z
IHCH2OH
IIHCH2OS3H7-N.
III5-ClCH2Och2CH=CH2
IV5-NO2CH2Och3
V5-ClCH2Och2-SN
VI5-Cl, 2-CH3CH2CH2OS6H11
VIIHCH2OS6H11
VIII5-C2H5CH2OS2H5

Table 5 (continued)
Connection#. (X)nR5Z
IX5,7-Cl Och3
II4-NO2Och3
XICH2CH2Och3
XII5-ClOS2H5
XIIIHOC2H5
XIV5-ClOch(CH3)2
XV5-och3OS2H5

Comparative experience

Corn and weed plants grown in the greenhouse in plastic pots to the stage of 3-4 leaves and then treated with a mixture specified in Table 6 of the herbicide or a mixture of antidote A3 in amounts shown in table 7. When this treatment is carried out by applying active substances in the form of aqueous suspensions or emulsions with a consumption rate per water 300 liters per 1 hectare Through 24 days after treatment estimate the percentage impact of the active substances on plants compared with untreated control plants is. 0% means that the plants are not damaged, and 100% of the plants are damaged completely.

Table 6

Connection # RR1R2R3Y
G1ICH3Och3CH3N
And1)NC2H5Och3CISN
B2)NCH3OCHF2OCHF2SN

1)trading product chlorimuron-ethyl specified in item 8 of the claims, the closest analogue

2)trading product primisulfuron specified in item 8 of the claims, the closest analogue

The active substance, their rate of consumption, plants and the results of the experiment are summarized in Table 7.

Table 7
Active substance No.The dose of the act. substance g/haHerbicide activity in %
SETVIDIGSAAVEFASORHA
G125

12

6
40

20

5
98

90

80
85

70

60
95

70

75
98

95

85
And50

25

12
45

40

25
75

60

60
65

50

40
95

80

65
-

-

-
B80

40

20
35

20

10
95

80

60
40

30

20
90

70

65
98

90

60
G1+A3 (according to the invention)25+50

12+25

6+12
10

0

0
99

95

80
85

80

80
95

90

70
100

98

90
A+A3 (according closest analogue)50+100

25+50

12+25
35

20

5
60

40

20
60

30

10
90

60

30
-

-

-
B+A3 (according closest analogue)80+160

40+80

20+40
20

0

0
80

40

25
20

0

0
65
40

20
85

60

15

Used in table 7 abbreviations have the following meanings:

ZEAMA = Zea mays

SETVI = Setaria viridis

DIGSA = Digitaria sanguinalis

AVEFA = Avena fatua

SORHA = Sorghum halepense

The comparison of the data of table 7 shows that when coupled with the use of derivatives phenylsulfonylacetate formula (A), in which the phenyl group tizamidine group COOR1and halogen, the antidote of the formula (B1) or (B2) shows antagonistic activity against herbicide activity, which, however, occurs when the joint use of these antidotes and derivatives phenylsulfoximine formula (A), in which the phenyl group is only monogamist group COOR1.

1. A mixture of herbicides and antidotes, containing A) herbicide-active substance from the group of substituted phenyl-sulfonylureas of the formula (A)

where R1is hydrogen, alkyl with 1-6 carbon atoms,

R2- alkyl with 1-3 carbon atoms,

R3- alkoxy with 1-3 carbon atoms,

R4is hydrogen or alkyl with 1-4 carbon atoms,

Hal is fluorine, chlorine, bromine or iodine,

and their salts

and

B) the antidote from the group of compounds of formulas (B1) and (B2),

in which X is hydrogen, Gal is gene alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, the nitro-group or haloalkyl with 1-4 carbon atoms,

Z is hydroxyl, alkoxy with 1-8 carbon atoms, cycloalkane with 3-6 carbon atoms, alkenylacyl with 2-8 carbon atoms or alkyloxy with 2-8 carbon atoms,

R5- alcantarilla chain with 1-2 carbon atoms which may be substituted by one or two alkyl residues with 1-4 carbon atoms or alkoxycarbonyl with 1-3 carbon atoms in the CNS part,

W is a divalent heterocyclic residue, corresponding to the formula (W1) and (W2)

where R6is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, cycloalkyl with 3-12 carbon atoms or phenyl,

R7is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the alkyl and CNS side, respectively, hydroxyalkyl with 1-6 carbon atoms or cycloalkyl with 3-12 carbon atoms,

n is an integer of 1-5,

when the weight ratio of herbicide: safener of 100:1-1:100.

2. A mixture of herbicides and antidotes according to claim 1, characterized in that it contains herbicide active substance of the formula (A), where R1is methyl, R2is methyl, R3- methoxy, R4is hydrogen, Hal is chlorine or iodine, or with the .

3. A mixture of herbicide and antidote according to claim 1, characterized in that it contains a safener of the formula (B1) or (B2), where Z is hydroxyl, alkoxy with 1-8 carbon atoms or cycloalkene with 3-7 carbon atoms, R6- alkyl with 1-8 carbon atoms, haloalkyl with 1-4 carbon atoms, R7is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, alkoxyalkyl with 1-4 carbon atoms in the CNS part and 1 to 4 carbon atoms in the alkyl part, X is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, haloalkyl with 1-2 carbon atoms.

4. A mixture of herbicides and antidotes according to claim 1, characterized in that it contains a complex ethyl ester 1-(2,4-dichlorophenyl)-5-(etoxycarbonyl)-5-methyl-2-pyrazolin-3-carboxylic acid as an antidote.

5. A mixture of herbicides and antidotes according to claim 1, characterized in that it is a composition of (weed-killing tool) and contains from 0.1 to 99 wt.% active substances of the formulae (a) and (B1) or (B2) and 1-99,9 wt.% conventional auxiliary additives.

6. A mixture of herbicides and antidotes according to claim 1, characterized in that it contains active substances of the formulae (a) and (B1) or (B2) in a weight ratio of from 1:10 to 10:1.

7. Method of protecting cultivated plants from phyto-toxic side effects herbicide-active substances of the formula (A)

where R1is hydrogen, alkyl with 1-6 atoms of plastics technology : turning & is Yes,

R2- alkyl with 1-3 carbon atoms,

R3- alkoxy with 1-3 carbon atoms,

R4is hydrogen or alkyl with 1-4 carbon atoms,

Hal is fluorine, chlorine, bromine or iodine,

and their salts, characterized in that the antidote of the formula (B1) or (B2)

in which X is hydrogen, halogen, alkyl with 1-4 carbon atoms, alkoxy with 1-4 carbon atoms, the nitro-group or haloalkyl with 1-4 carbon atoms,

Z is hydroxyl, alkoxy with 1-8 carbon atoms, cycloalkane with 3-6 carbon atoms, alkenylacyl with 2-8 carbon atoms or alkyloxy with 2-8 carbon atoms,

R5- alcantarilla chain with 1-2 carbon atoms which may be substituted by one or two alkyl residues with 1-4 carbon atoms or alkoxycarbonyl with 1-3 carbon atoms in the CNS part,

W is a divalent heterocyclic residue, corresponding to the formula (W1) and (W2)

where R6is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, cycloalkyl with 3-12 carbon atoms or phenyl,

R7is hydrogen, alkyl with 1-8 carbon atoms, haloalkyl with 1-8 carbon atoms, alkoxy-alkyl with 1-4 carbon atoms in the alkyl and CNS side, respectively, hydroxyalkyl with 1-6 carbon atoms or C is cloaker with 3-12 carbon atoms,

n is an integer of 1-5,

applied to plants, plant parts, plant seeds or the area sown before, after or simultaneously with herbicide-active substance, and the antidote (B1) or (B2) described in claims 1 to 6 mix used in amounts of from 0.005 to 0.5 kg/ha at a weight ratio of from herbicide-active substance (s)of 1:100-100:1.

8. The method according to claim 7, wherein the cultivated plants are cereals or maize.



 

Same patents:

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes a synergistic composition of herbicides comprising components (A) and (B) wherein (A) represents herbicide taken among the group of the formula (I):

wherein R1 means (C1-C4)-alkyl; R2 means (C1-C4)-alkyl; R3 means hydrogen atom; X and Y mean (C1-C4)-alkoxy-group; (B) represents one or two herbicides taken among the group of compounds or their acceptable forms: alachlor, metolachlor, acetochlor, dimetenamide, atrazine, cyanasin, metribusin, fluthiamide, nicosulfuron, rimsulfuron, primisulfuron, pendimetalin, sulcotrion, dicamba, mesotrion, isoxachlortol, metosulam, anilofos, fenoxaprop-ethyl, setoxydim, diclofop-methyl, MCPA, bromoxynil, pyridat, clopyralid, iodosulfuron-methyl, ethoxysulfuron, amidosulfuron, gluphosinat-amminium, isopropylammonium-glyphosate, imasetapir wherein components (A) and (B) are taken in the effective doses. Also, invention describes a method for control of weeds by using above indicated herbicide composition. Invention provides the development of the synergistic herbicide composition eliciting high activity.

EFFECT: improved method for control, valuable properties of composition.

6 cl, 26 tbl, 3 ex

The invention relates to the field of plant protection products that can be used against weeds in tolerant or resistant crops sugar beet and which as a herbicide biologically active substances contain a combination of two or more herbicides

The invention relates to chemical means of protection of grain crops from weeds, and in particular to compositions comprising chlorsulfuron and dicamba

The invention relates to an improved process for the preparation of compounds of formula (I), where each of the residues X and Y independently of one another denotes hydrogen, halogen, (C1-C4)-alkyl, (C1-C4)-alkoxygroup or (C1-C4)-allylthiourea, each of the last three residues is unsubstituted or substituted by one or more residues from the group comprising halogen, (C1-C4)-alkoxygroup or (C1-C4)-allylthiourea, means or di[(C1-C4)alkyl]-amino, (C3-C6-cycloalkyl, (C3-C5)-alkenyl, (C3-C5)-quinil, (C3-C5)-alkenylacyl or (C3-C5)-alkyloxy, in which the compound of formula (II) or salts thereof, where X and Y are specified in the formula (I) values are subjected to interaction with 1-6 moles of phosgene per 1 mol of the compounds of formula (II) in the presence of 2-3,5 molar equivalents of an organic aminoaniline per mole of the compounds of formula (II) and in the presence of an aprotic organic solvent at the reaction temperature in the range from -30 to +60oWith

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention describes substituted benzoylcyclohexanediones of the general formula (I):

wherein m = 0 or 1; n = 0 or 1; A means a single bond or alkanediyl (alkylene) with 1-4 carbon atoms; R1 means hydrogen atom or unsubstituted alkyl with from 1 to 6 carbon atoms; R2 means methyl; R3 means hydrogen atom, nitro-, cyano-group, halogen atom, alkyl with from 1 to 4 carbon atoms substituted with halogen atom, alkoxy-group with from 1 to 4 carbon atoms or alkyl sulfonyl with from 1 to 4 carbon atoms; R4 means nitro-group, halogen atom, unsubstituted alkyl with from 1 to 4 carbon atoms of that substituted with halogen atom; Z means heterocycle, and herbicide agent based on thereof. Also, invention describes substituted derivatives of benzoic acid of the general formula (III):

wherein values n, A, R3, R4 and Z are given above. These compounds represent the parent substances used for preparing compound of the formula (I). Compounds of the formula (I) elicit high and selective herbicide activity.

EFFECT: valuable properties of compounds.

7 cl, 8 tbl, 7 ex

FIELD: organic synthesis.

SUBSTANCE: invention provides substituted 1-pyridyl-2-azolyl-1-(2-phenylethenyl)ethan-1-ols having general formula I:

where Py denotes 2-, 3-, or 4-pyridyl, Z nitrogen atom or CH group, and R1 and R2, independently from each other, are hydrogen or halogen atom, or trifluoromethyl group. Claimed compounds are applied as agricultural, industrial, medical, or veterinarian fungicides for controlling harmful fungi.

EFFECT: enhanced fungi control efficiency.

2 cl, 3 tbl

FIELD: organic chemistry, herbicides, agriculture.

SUBSTANCE: invention relates to new substituted benzoylketones of the general formula (I): , all possible tautomeric forms and possible salts that can represent active substance as a component of herbicide agent. In the formula (I) A means (C1-C4)-alkyl; R1 means cyclo-(C3-C6)-alkyl; R2 means hydrogen atom (H), cyano-group (CN); R3 means hydrogen atom (H), halogen atom, CF3, (C1-C4)-alkylsulfonyl; R4 means halogen atom; X means groups: or wherein R5 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, (C1-C4)-alkylthio-group, di-(C1-C6-alkyl)-amino-group; R6 means (C1-C4)-alkyl, (C1-C4)-alkoxy-group, cyclo-(C3-C6)-alkyl; n = 0 or 1 including all possible tautomeric forms and possible salts. Compounds of the formula (I) elicit herbicide activity and can be used in herbicide composition.

EFFECT: valuable properties of compounds.

3 cl, 1 sch, 3 tbl, 13 ex

Wood // 2240690

The invention relates to the chemistry of heterocyclic compounds, namely to substituted 1-(pyridinyl-3)-2-azolylmethyl General formula I

where R means a hydrogen atom, an unbranched or branched alkyl with a number of carbon atoms of from one to eight, cycloalkyl with the number of carbon atoms from three to eight, cycloalkenyl with the total number of atoms from four to ten, alkylsilanes with the total number of atoms from four to ten, X denotes a nitrogen atom or CH group, which possess fungicidal activity and can be used as agricultural, industrial, medical or veterinary fungicides

The invention relates to plant protection, namely the preparation, fungicidal, where the active component is used tebuconazole
Up!