Combination vinylsulfonylacetamido herbicides with antidotes and method of protecting cultivated plants from the side fetotoxicity effects vinylsulfonylacetamido herbicides

 

Describes herbicide-antidote composition containing as a herbicide derivative phenylsulfonylacetate connection formula a or its alkali metal salts, where W is an oxygen atom, a group of the formula CR1R4where R1and R4is a hydrogen atom, Q is an oxygen atom or the group NR6M is 0 or 1, R1- alkyl with a number of carbon atoms from 1 to 6, R2is a hydrogen atom, alkyl with the number of carbon atoms from 1 to 6,3- COR11, OR12, SO2R21, R11is a hydrogen atom, alkyl with the number of carbon atoms from 1 to 6,12- alkyl with a number of carbon atoms from 1 to 6, R5is a hydrogen atom, R6is a hydrogen atom, alkyl with the number of carbon atoms from 1 to 41X2independently from each other - alkoxyl with the number of carbon atoms from 1 to 6, Z is a group CH, as an antidote compound of formula B1, where X1is a halogen atom, Z1- OR7, R7- alkyl with a number of carbon atoms from 1 to 8, n1-1 or 2, W1means W1, W2, R9- alkyl with a number of carbon atoms from 1 to 8, R10- alkyl with a number of carbon atoms from 1 to 8, m1is 0, the weight ratio of compound a to compound B1 from 10:1 to 1: 10. Describes also a method of protecting cultivated plants from the of astani or acreage simultaneously with the herbicide effective amount of a safener of type B1 at a weight ratio of a and B1 from 10:1 to 1:10. The technical result - high herbicide activity in the absence of phytotoxicity. 2 s and 5 C.p. f-crystals, 8 PL.

The invention relates to the technical field of crop protection, specifically to combinations of active substances and antidotes are ideal for use against weeds that compete with crops of useful plants.

Some new herbicide substances show very good properties in this area of engineering. At very low application rates, they can be used against a broad spectrum of grassy and broadleaf weeds.

However, many of the highly effective active substances not very well tolerated such an important cultural plants, such as maize, rice or other grains (i.e. they are not selective), and the scope be narrowed. Therefore, they cannot be used in some cultures or apply at such low application rates, it does not provide the desired broad-spectrum herbicide activity against sorne is face-to-face selectivity in relation to weeds apply in the corn, rice, other grains, and other crops.

As a result of new experimental studies have shown that such plants as corn, rice, wheat, barley and others, can be miraculously protected from caused by these herbicides unwanted damage, if herbicides are used in conjunction with certain compounds which act as antidotes herbicides.

Known composition containing herbicide group of the sulfonylureas and the antidote groups derived pyrazolin-, triazole and pyrazole-carboxylic acids, substituted phenyl, derived benzisoxazole-carboxylic acids and/or derivatives of quinoline-8-axialen-carboxylic acid at a ratio of herbicide and antidote from 1:10 to 10:1 (see European application 0492367 A2, A 01 N 47/36, 01.07.1992).

The objective of the invention is to develop a new herbicide means of active substances on the basis of phenylsulfonylacetate and antidote based on pyrazolin and isoxazolin-carboxylic acids, which have shown an increased synergistic activity.

The problem is solved, we offer herbicide-antidote combinations containing as derived phenylsulfonylacetate with the PU formula CR'R", where R' and R" means a hydrogen atom, Q denotes an oxygen atom, m is 0 or 1, R1means alkyl with the number of carbon atoms of from one to six,
R2means a hydrogen atom, alkyl with the number of carbon atoms of from one to six,
R3means CO-R11, COOR12or SO2R21,
where R11means a hydrogen atom, alkyl with the number of carbon atoms of from one to six,
R12means alkyl with the number of carbon atoms of from one to six,
R21means alkyl with the number of carbon atoms of from one to six,
R5means a hydrogen atom,
R6means a hydrogen atom, alkyl with the number of carbon atoms one to four,
X1X2independently from each other mean alkoxyl with the number of carbon atoms of from one to six and
Z means a group CH,
and the antidote from the group of compounds of the formula (B1)

where X' denotes a halogen atom,
Z' means OR7,
where R7means alkyl with the number of carbon atoms of from one to eight,
n' represents an integer from 1 to 2,
W' means the residue from the group of residues of formula:


where R9means alkyl with a number and the r /> and
m' is 0,
when the weight ratio of compounds (A) to the compound (B1) from 10:1 to 1: 10.

Unless specifically stated otherwise, for residues in the formulas for (A), (B1) and the following formulas are the following definition.

The remains of alkyl, alkoxyl and alkylamino, and also the corresponding unsaturated and/or substituted residues may be the type of carbon skeleton of both linear and branched. Unless otherwise indicated, some of these residues is more preferable structure with a small number of carbon atoms, for example from one to six or respectively from two to six for unsaturated fragments. Alkyl residues involved in the formation of more complex functional groups, such as alkoxygroup and other presents, for example, such groups as methyl, ethyl, n - or isopropyl, n-, ISO - tert - or 2-butyl, Penteli, sexily, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, reptile, such as n-heptyl, 1-etylhexyl and 1,4-dimethylpentyl.

The term "halogen" means, for example, fluorine atom, chlorine, bromine or iodine.

Formula (a) and (B1) encompass all stereoisomers, which show the same topology of connections between atoms, and mixtures thereof. Such compounds contain the ro does not stand out. All possible stereoisomers that differ in the spatial arrangement of atoms, such as enantiomers, diastereomers, Z - and E-isomers, can be obtained by customary methods from mixtures of the stereoisomers or they can be synthesized in stereoselective transformations in conjunction with the use of stereochemical pure starting compounds.

The compounds of formula (A) can form salts in which the hydrogen atom is-SO2-NH-group is replaced domesticity for agricultural use cation. These salts can be represented, for example, salts with metals, especially salts of alkaline or alkaline earth metals, especially sodium salts and potassium, but also salts of ammonia or salts involving organic amines.

Derivative pyrazolin-carboxylic acids of the formula (B1) is known from European patent application 333131, European patent application 269806 (application USA 4891057), European patent application 346620 (patent Australia 89/34951), European patent application 174562 and derivative isoxazolin-carboxylic acid of formula (B1) is known from international application WO 91/08202 (PCT/EP 90/01966 and PCT/EP 90/02020), as well as applications Germany R. 4331448.1 and cited in these sources the literature or they can will eraut interaction with nitrilosides formula (II)
(-)O-N=(+)C-COC(O)Z1(II)
where X' denotes a halogen atom,
n' represents an integer 1 or 2,
Z' means a group OR7where R7means alkyl with the number of carbon atoms of from one to eight.

The reaction of compounds of formulas (I) and (II) is conducted in the medium of organic solvent, preferably a non-polar to malopolyarnoi solvent, such as diethyl ether or tetrahydrofuran (THF).

The initial compounds of formulas (I) and (II) are known (see, for example, J. Org. Chem. 25, 1160 (1960)"; "J. Am. Chem. Soc. 46, 791 (1924)") or can be obtained by ways of peers.

Nitricoxide formula (II) are obtained "in situ" of the derivatives of 2-halogeno-2-hydroxylaminoxymes acid in the presence of a base and subjected to interaction with the compound of the formula (I) contained in the reaction mixture, preferably at temperatures between -15oC and the boiling point of the used solvent, especially at room temperature.

As herbicide active substances in the framework of the invention are suitable such herbicideresistant formula (A), for use as sole active substance is not possible or optimal to cereals and/or maize due to severe damage to cultural raster R. 4335297.9 (PCT/EP 94/03369), R. 4415049.0 and R. 4419259.2, and patent applications U.S. 5449812 or they can be obtained in the following way:
The compound of formula (III)

subjected to interaction with a heterocyclic carbamate of formula (IV)

where R* denotes a substituted or unsubstituted phenyl or alkyl with the number of carbon atoms one to four,
the remaining residues A, m, Q, R1, R2, R3, R5X1X2and Z have the above values.

The reaction of compounds of formulas (III) and (IV) is conducted preferably in the presence of a base as catalyst, in an inert organic solvent, such as, for example, dichloromethane, acetonitrile, dioxane or tetrahydrofuran (THF) at temperatures between 0oC and the boiling point of the used solvent.

As a basis it is possible to use organic bases such as 1,8-diazabicyclo[5.4.0]undec-7-ene, trimethylaluminium or triethylaluminium.

Of special interest relevant to the invention a combination of herbicide and antidote, if antidotes (B1)
W' means

X' denotes a halogen atom,
n' is 1 or 2, and (Xuly OR7,
R7means alkyl with the number of carbon atoms of from one to eight,
R9means alkyl with the number of carbon atoms of from one to eight,
R10means alkyl with the number of carbon atoms of from one to eight.

Especially preferred when the antidotes, in the formula (B1) where W' means

X' denotes a halogen atom,
n' is 1 or 2,
m' is 0,
Z' is the residue of a formula OR7,
R7means alkyl with the number of carbon atoms one to four,
and
R9means alkyl with the number of carbon atoms one to four.

The following groups of compounds are suitable, for example, as antidotes for the above herbicide active substances started formula (A):
a) compounds of the type dichlorobenzimidazole-3-carboxylic acid (i.e. of the formula (B1), in which W'=W1 and (X)n= 2,4-Cl2), preferably compounds such as ethyl ester of 1-(2,4-dichlorophenyl)-5-methyl-5-ethoxy-carbonyl-2-pyrazolin-3-carboxylic acid (B1-1), and similar in structure to the compounds described in the international patent application PCT/EP 90/02020.

b) compounds of the type of 5,5-diphenyl-2-isoxazolin-3-carboy (B1-9) or n-propyl ether (B1-10) or ethyl ester of 5-(4-forfinal)-5-phenyl-2-isoxazolin-3-carboxylic acid (B1-11), described in the patent Germany R. 4331448.1.

b) Active substances of the type derived Phenoxyethanol or propionic acid, or aromatic carboxylic acids, such as, for example,
(Ester) 2,4-dichlorophenoxyacetic acid (2,4-D),
Ether 2-methyl-4-chlorphenoxamine acid (mecoprop, MSRA) or
(Ether 2-methoxy-3,6-dichlorobenzoyl acid (dicamba).

Of special interest relevant to the invention a combination of herbicides and antidotes, if in the compounds of formula (A) or their salts
R1means alkyl with the number of carbon atoms of from one to six,
R2means a hydrogen atom, alkyl with the number of carbon atoms one to four,
R3means CO-R11, CO-OR12,
m is 0 or 1,
R5means a hydrogen atom,
R11means a hydrogen atom, alkyl with the number of carbon atoms of from one to six,
R12means alkyl with the number of carbon atoms of from one to six,
R21means alkyl with the number of carbon atoms one to four,
the remains of X1and X2mean alkoxyl with the number of carbon atoms and from one to two,
Z denotes CH-group.

Preferred relevant to the invention the compounds of formula (a) and their salts and ethyl,
R2means a hydrogen atom, alkyl with the number of carbon atoms one to four, preferably methyl or ethyl,
R3means formyl, acetyl, n-propionyl, Isopropenyl-, 2-methylpropionyl, n-butanol, methoxycarbonyl, etoxycarbonyl, methylsulphonyl,
m is 0 or 1,
R5means a hydrogen atom,
A represents methylene group,
Q denotes an oxygen atom or methylaminopropyl (N3),
X1means a methoxy group, ethoxypropan,
X2means a methoxy group or ethoxypropan,
Z denotes CH-group.

The antidotes of formula (B1) such as antidotes these groups from a) to b) reduce or remove fetotoxicities effects that may occur as the result of herbicide active substances of the formula (A) in crops of useful plants, without significant impact on the effectiveness of these herbicide active substances in relation to weeds. In the result, it is possible to considerably extend the scope of traditional plant protection products and distribute them, for example, for crops such as wheat, barley, corn and other grains, which is still the application of these herbicides was disabled>/p>Herbicide active substance and the above-mentioned antidotes can be used together (in the form of ready preparative forms or in tank mixtures), but they may be applied separately, one after the other in any sequence. The mass ratio of antidote and active substances beginning can vary within wide limits, preferably from 1:100 to 100:1, especially from 1:10 to 10:1. Optimal for each case the number of herbicide active substances and antidote depend on the type of the applied herbicide active substances and used antidote, and on the type of treated vegetation; they can be defined in each specific case on the basis of appropriate preliminary experiments.

Main area of application of antidotes is presented primarily corn and grain crops (wheat, rye, barley, oats), rice, sorghum, and cotton and soybeans, preferably it crops of grain and corn.

Depending on the properties of the antidotes of formula (B1) can be applied for pre-treatment of seed of cultivated plants (seed dressing) or to bring them before sowing in the prepared furrow, or to apply them together with the herbicide before or after the processing of planted areas until germination. Preferably the combined application of the herbicide. This can be used in tank mixes or ready preparative form.

Effective consumption norms antidote can vary within wide limits depending on the evidence and the applied herbicide active substances. They usually lie in the range from 0.001 to 5 kg, preferably 0.005 to 0.5 kg, of active substance per hectare.

The object of the present invention is thus a method of protecting cultivated plants from the side fetotoxicity action of herbicides of formula (A), wherein the plant seed or planting area put an effective amount of the compounds of formula (B1) simultaneously with the herbicide active substance of the formula (A).

Depending on the biological and/or physico-chemical parameters on the basis of the compounds of formulas (B1) and their combinations with one or more of these herbicide active substances can be prepared in a variety of preparative form. There is, for example, such formulation, as wettable powders, concentrates, emulsions, soluble powders, water-soluble concentrates, concentrated emulsion-type emulsions oil-in-water" systems based on oil or water, suspension-emulsion system, the concentrated suspensions, dusty, miscible with oils, solvents, disinfectants, granules in the form of microgranules, granules by spraying, granules deposited on the surface and adsorbed gastusin the beginning, granules for soil and for spraying, water soluble granules, dispersible in water, the granules, the composition of ultra low volume spraying, microcapsules and waxes.

Some types of medications forms are in principle known and are described, for example, in the book Winnacker-Kuechler, "Chemische Technologie", T. 7, Ed. C. Hauser, Munich, 4th edition 1986; Wade van Valkenburg, "Pesticide Formulations", Marcel Dekker, N. Y., 1973; K. Martens, "Spray Drying Handbook", 3rd edition 1979, G. Goodwin LTD., London.

Need to prepare preparative forms of auxiliary tools, such as inert materials, surfactants, solvents and other additives, are also known. They are described, for example, in: Watkins, "Handbook of Insecticide Dust Diluents and Carriers", 2nd edition, Darland Boks, Caldwell N. J., H. v.Olphen, "Introduction to Clay Colloid Chemistry", 2nd edition, J. Willey & Sons, N. Y.; C. Marsden, "Solvents Guide", 2nd edition, Interscience, 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; Schoenfeldt, "Grenzflaechenactive Aethylenoxydadducte", Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Kuechler, "Ch and combination with other substances with pesticidal activity, for example, insecticides, acaricides, herbicides, fungicides, and also with antidotes, fertilizers and/or growth regulators, for example, in the form of ready-to-use formulations or tank mixes.

Wettable powders are evenly distributed in the water drugs, which, together with the active substance and, in addition to a diluent or inert substance, also contain and surfactants of ionic and/or nonionic nature (wetting and dispersing agents), for example polyoxyethylene ALKYLPHENOLS, polyoxyethylene fatty alcohols, polyoxyethylene higher alkylamines followed, sulphates, ethers of fatty alcohols and glycols, alkanesulfonyl, alkylbenzenesulfonate, sodium salt of sulfonated lignin, sodium salt of 2,2'-dynafilter-6,6'-disulfonate, dibutylethanolamine sodium or sodium salt oleoylethanolamide. To obtain a wettable powder herbicide funds finely pulverized, for example, in such a conventional apparatus, as hammer mills, mill-dryer and vozduhonosnye mills, and simultaneously or at the end of the operation they are mixed with other components of the formulation.

Concentrates EMU is Ohe, dimethylformamide, xylene or more high-boiling aromatic compounds or hydrocarbons or mixtures of organic solvents with addition of one or more surfactants of ionic and/or nonionic nature (emulsifiers). As emulsifiers can be used, for example, calcium salt alkylarylsulfonates (dodecylbenzenesulfonate calcium) or nonionic emulsifiers, as polyglycolide esters of fatty acids, alkylsilane ethers of polyglycols, ethers of polyglycols and fatty alcohols, condensation products of propylene oxide and ethylene oxide, simple polyalkylene ethers, esters sorbitan, for example esters sorbitan with fatty acids, or esters based polyoxyethylene sorbitan, for example polyoxyethylene esters sorbitan and fatty acids.

Dusty get when grinding applicable beginning with finely powdered solid substances, for example talc, with such natural clays like kaolin, bentonite and pyrophyllite, or infusorial the earth.

The concentrated suspensions can be water or oil-based. They can be prepared, for example, when wet grinding in conventional ball mills the other types of preparative forms.

Emulsions such as emulsions of the type oil-in-water" can be obtained, for example, by means of stirrers, colloid mills and/or static mixing using aqueous organic solvents and adding, if necessary, surface-active substances are used for example for the manufacture of other types of preparative forms.

The granules can be obtained either by spraying the active substance onto granulated inert material with good absorptive capacity, or the application of concentrates of active substances by means of increasing the adhesion means (adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils, apowersoft such substances vehicles as sand, kaolinites or terrain granulated inert material. The corresponding active substances can also be granulated by the method normally used for the production of granular fertilizers. If desired, thus you can get and their mixtures with fertilizers.

Diverging in the water the granules receive typically, such conventional methods, such as spraying the solution in drying, granulation in a fluidized bed, on a disk granulators, visul for drip drying, disk, conveyor, extrusion granulators see, e.g., "Spray-Drying Handbook", 3rd edition 1979, G. Goodwin Ltd., London; J. E. Browning, "Agglomeration", Chemical and Engineering 1967, pages 147 FF.; "Perry's Chemical Engineer''s Handbook", 5th edition, McGraw-Hill, New York 1973, pp. 8-57.

Other details about the preparation preparative forms of plant protection products can be found, for example, in the book of G. C. Klingman, "Weed Control as a Science", John Wiley and Sons Inc., New York, 1961, pages 81-96 and J. D. Freyer, S. A. Evans "Weed Control Handbook", 5th edition, Blackwell Scientific Publications, Oxford, 1968, pages 101-103.

Agrochemical compositions contain, as a rule, from 0.1 to 99 wt.%, mainly from 0.1 to 95 wt.%, active substances of the formula (B1) or a mixture of active substances herbicide/safener (a) and (B1) and from 1 to 99.9 wt.%, mainly from 5 to 99.8 wt.%, solid or liquid additive and from 0 to 25 wt.%, mainly from 0.1 to 25 wt.%, surface-active substances.

In wettable powders, the active substance is from about 10 to 90 wt.%, and missing up to 100 wt.% consists of the usual components preparative forms. In concentrates of emulsions of the active substance is from about 1 to 80 wt.%. Formulation in the form of powders contain about 1 to 20 wt.% the active substance. In solutions for spraying contains from about 0.2 to 20 MVA partially determined by its state of aggregation, that is, liquid or solid. As a rule, its content in dispersible in water, the granules is in the range from 10 to 90 wt.%.

Along with this, the abovementioned formulations of active substances can contain in some cases, conventional adhesives, wetting, dispersing agents, emulsifiers, which improves the fluidity of the compositions tools, preservatives, means for antifreeze and solvents, fillers, carriers and colorants, defoamers, means for reducing entrainment of dust and tools that affect the pH value and viscosity.

As components relevant to the invention combinations of active substances in mixed formulation or in tank mixes can be applied, for example, known active substances, such as listed in Weed Research 26, 441-445 (1986), or in "The Pesticide Manual", 9th edition, The British Crop Protection Council, 1990/91, Bracknel, UK and cited in these sources the literature. As known from the literature herbicides which can be combined with the compounds of the formula (A) include, for example, the following compounds (note: connections are called or trivial name on the recommendations of the International organization for standardization (ISO) or the chemical name mastermatic)-phenoxy] -2-nitrophenyl] -2-methoxyacridine] -amino]-oxy]-acetic acid and its methyl ester; alachlor; aloxide; ametrine is high; amidosulfuron; amitrole; AMS or sulpham ammonium; anilofos; Azul; atrazine; azimsulfuron (DPX-A8947); isoprotein; Barban; VAZ 516 N or 2-phenyl-5-fluoro-4H-3,1-benzoxazin-4-one; benzoin; benfluralin; beforeit; enculture-methyl; bensulide; bentazon; benzien; bentover; benzoylpropionic; benzthiazole; bialaphos; bifenox; bromacil; bromobutyl; bromophenoxy; bromoxynil; brauron; buminate; butoxide; butachlor; butamifos; buenaflor; booteasy; butalin; butyl; cafestol (SN-900); carbutamide; Capistrano (S-A); CDAA or N,N-di-2-propenyl-2-chloracetamide; CDEC or 2-korallovy ether pttc acid; chlorethoxyfos; chloramben, chlorazepam-butyl; chlormezanone (ICI-A); chlorbromuron; chlorbutol; chlorgenic; gliptoteka-methyl; ozone chloride; chlorimuron-ethyl; chlornitrofen; chlortoluron; chloroxuron; chlorpropham; chlorsulfuron; chlorthal-dimethyl; chlorine; cinmetacin; chinaculture; clethodim; clodinafop and esters based on it (for example, clodinafop-propargyl); clomazone; clomipram; chloroxygen; clopyralid; cumyluron (JC 940); cyanazine; cycloate; cycloaliphatic (AC 104); cycloxydim; cyclotron; cyhalofop and esters based on it (for example, butyl ether, DEH-112); cipro; diclofop and such esters, as diclofop-methyl; diacetyl; Difenoxin; difenzoquat; diflufenican; dimefuron; dimethachlor; deltamethrin; dimethenamid (SAN-582H); deltason, clomazone; dimethipin; demetracopoulos; dinitramine; dinoseb; dinoterb; diphenamid; deprophetis; Diquat; dithiopyr; Diuron; DNOC; Eglinton-ethyl; EL-177 or 1-(1,1-dimethylethyl)-N-methyl-5-cyano-1H-pyrazole-4-carboxamide; endothal; ARTS; asbroker; ethalfluralin; atomiculture-methyl; tidiman; idiosyn; ethofumesate; F5231 or N-[4-fluoro-2-chloro-5-[4-(3-forproper)-4,5-dihydro-5-keto-1H-tetrazol-1-yl] -phenyl] -econsultant; amoxifen and esters based on it (for example, ethyl ester, HN-252); etamesonic (HW 52); fenoprop; phenoxy; fenoxaprop and fenoxaprop-P and their esters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; phenoxide; fenuron; femprep-methyl; flazasulfuron; fluazifop and fluazifop-P and their esters, for example fluazifop-butyl and fluazifop-P-butyl; fluchloralin; flumetsulam; flumeturon; flumiclorac and its esters (for example, pentalogy ether, S-23031); flumioxazin (S-482); flubiprofen; flupoxam (KNW-739); foregiven; foreglimpse-ethyl; flourophenyl (UBIC-4243); fluridone; flurochloridone; fluroxypyr; floramon; fomesafen; fosamine; voreloxin; glofo is false esters; haloxyfop-P (= R-haloxyfop) and its esters; hexazinone; imazamethabenz; imazapyr; imazaquin and its salts, for example ammonium salt; imazethapyr; imazethapyr; imazosulfuron; ioxynil; isosorbid; isopropylene; Isoproturon; Sauron; isoxaben; isocaporate; carbocylic; lactofen; lentil; linuron; MSRA; SRV; mecoprop; mefenacet; mefluidide; metamitron; metazachlor; methabenzthiazuron; methamphetamine; metasol; methoxyphenol; methyldibromo; metaventure; metaventure; metobromuron; metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metalformer; MN; molinet; monolid; monocarbonic debilitat; monolinuron; monuron; MT, 128 -, or 5-methyl-N-phenyl-6-chloro-N-(3-chloro-2-propenyl)-3-pyridazinone; MT 5950 or N-[4-(1-methylethyl)-3-chlorophenyl]-2-methylpentane; nitroanilide; napropamide; naptalam; NC 310 or 5-benzyloxy-4-(2,4-dichlorobenzoyl)-1-methylpyrazole; neburon; nicosulfuron; snipercraft; nicraly; nitrogen; nitrophorin; norflurazon; arrancars; oryzalin; oxadiargyl (RP-020630), oxadiazon; oxycontin; paraquat; Babolat; pendimethalin; PERFLUORO; fenazepam; phenmedipham; picloram; piperophos; peribuccal; pirivena-butyl; pretilachlor; primisulfuron-methyl; procesin; prodiamine; propleuron; progenitin-ethyl; prometon; Promethean; prosulfocarb; prosulfuron (CGA-152005); panahar; pyrazoline; person; pyrazosulfuron-ethyl; paradoxien; peridot; pyrithiobac (KN-2031); pyrexia and its esters, for example propargilovyh ether; hinkler; hinnerk; chinatop and esters based on it; hisamoto and hisamoto-P and esters based on them, such as hisamoto-ethyl; hisamoto-P-tefuryl and-ethyl; renature; rimsulfuron (DPX-E 9636); S 275 or 2-[5-(propenyloxy)-2-fluoro-4-chlorophenyl]-4,5,6,7-tetrahydro-2-indazol; sebumeter; sethoxydim; sibron; Simazine; simetryn; SN 106279, or 2-[[7-[4-(trifluoromethyl)-2-chlorphen-oxy] -2-naphthalenyl] -oxy]-propanoic acid and its methyl ester; sulfentrazone (FMC-97285, F-6285); colfuturo; sulfometuron-methyl; sulfosate (ICI-A0224); TCA; tabulam (GCP-5544); tebuthiuron; terbacil; thermocarb; turbuhaler; terbumeton; terbutylazine; terbutryn; TFH 450 or N, N-di-ethyl-3-(6-methyl-2-ethylphenyl-sulfonyl)-1H-1,2,4-triazole-1-carboxamide; tanishlar (NSK-850); diazafluoren; tenopir (Mos-13200); thidiazuron (SN-124085); thifensulfuron-methyl; thiobencarb; thiocarbonyl; tralkoxydim; triallate; triasulfuron; threatened; tribenuron-methyl; triclopyr; tridiphane; triacetin; trifluralin; triflusulfuron and esters (e.g. methyl ester DPX-66037); timetron; citadep; vernolate; WL RR-600; MVN-001; KIH-9201; ET-751; KIH-6127 and KIH-2023.

For immediate practical application marketed formulation if necessary in the normal way diluted, for example, wettable powders, concentrates, emulsions, dispersible compositions and dispersible in water, the granules diluted with water. Dusty, granules for soil and on its surface, as well as complete solutions for spraying before use, usually not more diluted with other inert substances.

With the change of external conditions, such as temperature, humidity, the type of herbicide and so on, so does the consumption rate corresponding to the invention of compounds of the formula (A). It can vary within wide limits, for example from 0.001 to 10.0 kg or more of active substance per hectare, but preferably this value is in the range of 0.005 to 5 kg/ha

The following examples serve to illustrate the invention:
A. Examples of preparative forms
a) a dust is obtained by mixing and grinding in an impact mill, 10 parts by weight of the compounds of formula (B1) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1) and 90 parts by weight of talc as inert component.

b) Easy desperta the compounds of formula (B1) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1), 64 weight parts containing kaolin quartz as inert component, 10 parts by weight of ligninsulfonate potassium and 1 weight part of sodium salt oleoylethanolamide as wetting agent and dispersant.

C) Easily dispersible in water concentrate dispersion obtained by mixing and grinding in a ball mill until the particle size less than 5 microns 20 parts by weight of the compounds of formula (B1) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1), 6 weight parts polyglycolic ether of alkylphenol (Triton X 207), 3 parts by weight of polyglycolic ether isotridecanol (8 EO) and 71 weight parts of paraffinic mineral oil (boiling range, for example, about 255-277oC).

g) emulsifiable Concentrate is obtained from 15 parts by weight of the compounds of formula (B1) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1), 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated Nonylphenol as emulsifier.

d) Dispersible in water, the granules can be obtained by grinding in a rod mill:
75 parts by weight of the compounds of formula (B1) or a mixture of the active substances from gerbil polivinilovogo alcohol and
7 " kaolin
with subsequent granulation of the obtained powder in the pellet mill fluidized bed by spraying water as a granulating liquid.

e) Dispersible in water granulate receive preliminary grinding and homogenization in a colloid mill:
25 parts by weight of the compounds of formula (B1) or a mixture of the active substances of the herbicide of the formula (a) and a safener of the formula (B1),
5 "2,2'-dynafilter-6,6'-disulfonate sodium
2 " sodium salt oleoylethanolamide,
1 " polyvinyl alcohol,
17 " of calcium carbonate and
50 " of water
followed by grinding in a ball mill and drying the resulting suspension by spraying through a nozzle into the drying tower.

Biological examples
Example 1
Various cultivated plants grown in the greenhouse in plastic pots with a diameter of 9 cm to a given development phase and then treated with herbicide or a mixture of herbicide and antidote. The herbicide of the formula (a) and compounds of formula (B) is applied in the form of aqueous suspensions or emulsions with water flow at the rate of 300 l/ha, four weeks after treatment, conduct a visual assessment for any kind of plant damage caused by herbicides, priniciple from 0 to 100% in comparison with untreated control plants.

The results of the experiments presented in the table. 1-3, show that different corresponding to the invention of the antidotes not adversely affect herbicide activity and can selectively apply herbicides on such crops as wheat, barley and corn.

Example 2
Repeat example 1 of this application with the only difference that determine phytotoxicity in rice crops, in this case, applying means consisting solely of active substances A8, a10 and known from application EP 04922367 active substance X, complex methyl ester 4-iodine-2-[3-(4-methoxy-6-methyl-1,3,5-triazine-2-yl)-aridoculture] -benzoic acid as sodium salt, or products containing these active substances and antidote B1-9. Funds, their doses and the results of the experiment are summarized in Table 4.

Example 3
Plants wheat, barley and Avena fatua (AVFA) grown in the greenhouse (18oDay, 12oWith the night) in plastic pots with a diameter of 9 cm to the stage of 3-4 leaves and then process them known by means of the herbicide, chlorimuron-ethyl, and antidote designated in this application as "B1-1", and the proposed means of herbicide A5 or A6 and antidote B1-1. All funds applied in the form of aqueous preparations with a flow rate of Vonyc plants compared with untreated control plants, and after four weeks carry out a visual assessment of herbicide action against AVFA compared with untreated control plants. Evaluations are conducted in interest on a scale from 0 to 100%. 0% means that the damage was not observed, and 100% complete plant death.

The experiment results represent the average values for the four tests are summarized in table 5.

The results of table 5 indicate the best activity proposed funds in the absence of phytotoxicity.

Example 4
Corn and Sorghum halepense (S) grown (22oDay and 16oWith the night) in the greenhouse in plastic pots with a diameter of 9 cm to stage 4 leaves and then process them known means of herbicide chlorimuron-ethyl and antidote designated in this application as "W1-9', and also offer a means of herbicide A7, A8, A9 or A13 and antidote B1-9. All funds applied in the form of aqueous preparations with water flow at the rate of 300 l/ha, four weeks after treatment, conduct a visual evaluation of the phytotoxicity and weed-killing effect compared with untreated control plants. Is interest on a scale from 0 to 100%. 0% means that the damage was not observed, and , is presented in table 6.

The results of table 6 indicate the best activity proposed funds in the absence of phytotoxicity.

Example 5
Listed in table 7 plants are grown (18oDay and 12oWith the night) in the greenhouse in plastic pots with a diameter of 9 cm to the stage of 3-4 leaves and then process them known means of herbicide chlorimuron-ethyl and antidote specified in this application as "B1-1", and the proposed means of herbicide a10 and antidote -1 B1. All funds applied in the form of aqueous preparations with water flow at the rate of 300 l/ha two weeks after treatment, conduct a visual evaluation of phytotoxicity as compared with untreated control plants, and after 4 weeks on herbicide action in comparison with untreated control plants. Evaluations are conducted in interest on a scale from 0 to 100%. 0% means that the damage was not observed, and 100% complete plant death.

The experiment results represent the average values for the four tests are summarized in table 7.

The results of table 7 indicate the best activity we offer tools with complete or almost complete absence of phytotoxicity.

All stalinschinoy activity.

Example 6
Seed treatment
Corn seeds treated with antidote B 1-9, taken in an amount of 4 g/kg seed, and put in unprotected soil. Per hectare, accounting for 25 kg of seeds. Treatment herbicide A8, taken in an amount of 90 g/ha, carry out post-emergent plants in the stage of 2-4 leaves, while the herbicide is applied in the form of a mixture with 300 l/ha of water. The weight ratio of herbicide to antidote is 1 : 1,11. 6 weeks after treatment plants perform visual assessment of crop damage and development of all above-ground parts of plants compared to control plants. Is interest on a scale from 0 to 100% in comparison with untreated control plants. 0% means that the plants are not damaged, 50% - 50% of plants and green parts of the plants die, and 100% of all the plants died.

The results of the experiments are summarized in table 8.

A comparison of the experiences III the results of the comparative experiments demonstrates the achievement of the proposed method, a synergistic effect.


Claims

1. Herbicide-antidote combination of herbicide - derived phenylsulfonylacetate and antidote, characterized in that as ata/58/580676.gif">
where W denotes an oxygen atom;
A represents a group of formula CR'R", where R' and R" means a hydrogen atom;
Q denotes an oxygen atom or a group NR6;
m is 0 or 1;
R1means alkyl with the number of carbon atoms of from one to six;
R2means a hydrogen atom, alkyl with the number of carbon atoms of from one to six;
R3means CO-R11, COOR12, SO2R21where R11means a hydrogen atom, alkyl with the number of carbon atoms of from one to six, R12means alkyl with the number of carbon atoms of from one to six, R21means alkyl with the number of carbon atoms of from one to six;
R5means a hydrogen atom;
R6means a hydrogen atom, alkyl with the number of carbon atoms one to four;
X1X2independently from each other mean alkoxyl with the number of carbon atoms of from one to six;
Z means a group CH,
and as an antidote compound of formula B1

where X' denotes a halogen atom;
Z' means OR7where R7means alkyl with the number of carbon atoms of from one to eight;
n' represents an integer 1 or 2;
W' means

2. Herbicide-antidote combination under item 1, wherein R1means alkyl with the number of carbon atoms of from one to six, R2means a hydrogen atom, alkyl with the number of carbon atoms one to four, R3means CO-R11, CO-OR12and SO2R21m is 0 or 1, R5means a hydrogen atom, R11means a hydrogen atom, alkyl with the number of carbon atoms of from one to six, R12means alkyl with the number of carbon atoms of from one to six, R21means alkyl with the number of carbon atoms one to four, X1and X2mean alkoxyl with the number of carbon atoms and from one to two, Z denotes CH-group.

3. Herbicide-antidote combination under item 1 or 2, characterized in that it presents in the form of a formulation (herbicide), containing from 0.1 to 99 wt.% the active substances a and B1 and from 1 to 99.9 wt.% the usual components preparative forms.

4. Herbicide-antidote combination according to any one of paragraphs.1-3, characterized in that it contains active substances of type a and B1) in a weight ratio from 1:2 to 2:1.

5. Method of protecting cultivated plants from the side Pitot is whether the area sown simultaneously with the herbicide is applied an effective amount of a safener of type B1, with a combination of herbicide and antidote B1 is defined in one of the paragraphs.1-4 and antidote B1 and herbicide And taken in a weight ratio of from 1:10 to 10:1, preferably from 1:2 to 2:1.

6. The method according to p. 5, wherein the cultivated plants are presented in cereals, plants of rice or maize plant.

7. The method according to p. 5 or 6, characterized in that the herbicide And applied at a rate of from 0.001 to 10 kg/ha

 

Same patents:

The invention relates to agriculture and can be used in plant breeding

The invention relates to agriculture, namely to chemical herbicides used for weed control

The invention relates to chemical means of weed control

The invention relates to a new method of production (its variants) aminophenylalanine formula I, having the properties of plant growth regulators or herbicides, as well as intermediate products for their production

The invention relates to (adjuvant) improving the efficiency of application of herbicides on the basis of the sulfonylureas

The invention relates to novel acylated to aminophenylacetylene General formula I which possess herbicide action and selectivity of action in comparison with the previously known compounds of this series

The invention relates to a means to control weeds, in particular to the herbicide agent containing as an active ingredient (A) nitrile 1-(3-chloro-4,5,6,7-tetrahydropyrazolo-[1,5-a]-pyridine-2-yl)-5-(methylpropylamine)-4-pyrazolecarboxylate acid, and optionally, as an active ingredient (B) a substance selected from the group comprising bentazon, molinet, Diuron, thiobencarb, butachlor, pretilachlor, timepart, fenoxaprop-ethyl, clomipram, cinmetacin, bromobutyl, chinkara, mefenacet, pyrazosulfuron-ethyl, asbroker, chinaculture, tanishlar, cumyluron, MK 243, nitroanilide, anilofos, belforest, bifenox, SN-900, MSRA, nitrofen, oxadiazon, pendimethalin, simetryn, sulcotrione (SA), trifluralin, piperophos, perimutter, ethoxysulfuron, benzylbromide, pyrazolate, paradoxien, benzefoam, cycloaliphatic, cyhalofop, NBA-061 and azimsulfuron

The invention relates to the field of agriculture, particularly to a method of increasing the resistance of sunflower to the toxic effects of the herbicide

The invention relates to the field of agriculture, particularly to a method of increasing the resistance of sunflower to fetotoksicheskoe impact of herbicide

The invention relates to the field of chemistry and agriculture, specifically to the derived SIM-triazine [2-trimethylammoniumchloride-4,6-bis(ethoxycarbonylmethylene)]-1,3,5-triazine (THAT) formula

< / BR>
as compounds that protect against fetotoksicheskoe actions of herbicides in the cultivation of sunflower (antidote)

Pesticide tool // 2159038
The invention relates to agriculture, in particular pesticide means on the basis of the metal phosphide

The invention relates to herbicide drug selective action to combat grasses and weeds in the cultivation of cultivated plants, in particular in the cultivation of corn, herbicide and antagonistic agent (the antidote), and protecting useful plants, not the weeds from fetotoksicheskoe action of the herbicide, and to the use of this drug or a combination of the herbicide/antidote for combating weeds in crops of useful crops

The invention relates to the restoration of fertility of soils contaminated with pesticides and other xenobiotics, and can be used in agriculture and forestry, as well as to solve problems of protection of the lithosphere

The invention relates to a method of protecting agricultural crops from pesticide residues and can also be used when addressing cleanup of the lithosphere

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

Up!