EA001418B1 - Herbicidal composition - Google Patents

Abstract

1. A selectively herbicidal composition which comprises, besides customary inert formulation auxiliaries, as active ingredient a mixture of a) a herbicidally active amount of a herbicide selected from the group consisting of the compounds of the formula Ia and/or Ib in which R is hydrogen or fluorine and/or Ic or of a salt of the compounds of the formulae Ia and/or Ib and/or Ic and b) a herbicidally antagonistically active amount of a compound of the formula II a in which R010 is -CH(CH3)C5H11-n and X2 is chlorine. 2. A composition according to claim 1, which comprises, as compound of the formula Ia, the compound of the formula Id 3. A composition according to claim 1, which comprises, as herbicide, either the compound of the formula Ia or Id and, as safener, the compound of the formula IIa in which X2 is chlorine and R010 is 1-methylhexyl. 4. A composition according to claim 1, which comprises a herbicidally active amount of a herbicide selected from the group consisting of the compounds of the formulae Ia and/or Ib in which R is hydrogen or fluorine, or of a salt of the compounds of the formulae Ia and/or Ib. 5. A method for the selective control of weeds and grasses in crops of useful plants, which comprises treating the useful plants, their seeds or vegetative propagation material or the area on which they are grown either simultaneously or separately with a herbicidally active amount of a herbicide of the formula Ia and/or Ib and/or Ic and a herbicidally-antagonistically active amount of a safener of the formula IIa. 6. A method according to claim 5, wherein crops of useful plants or areas on which the crops of useful plants are grown are treated with 0.001 to 2 kg/ha of a herbicide of the formula Ia and/or Ib and/or Ic and an amount of 0.001 to 0.5 kg/ha of a safener of the formula IIa. 7. A method according to claim 5, wherein the crops of useful plants are cereals or rice.

Description

The present invention relates to new selective herbicidal compositions for controlling herbaceous plants and weeds in crops of agricultural plants, in particular in crops of grain crops and rice, which contain a herbicide and a protective agent (antidote) that protects agricultural plants, but not weeds, from phytotoxic the action of the herbicide, as well as the use of these compositions for weed control in crops of agricultural plants.

When applying herbicides, agricultural plants can also be seriously damaged, for example, depending on the concentration of the herbicide and the application method, the particularities of the agricultural plant itself, soil composition and climatic factors such as light characteristics, temperature and rainfall.

To solve this and similar problems, it has already been proposed to use various compounds as protective agents that can counteract the harmful effects of the herbicide on an agricultural plant, i.e. protect the agricultural plant from it, while maintaining, without practically reducing the herbicidal effect on the weeds to be destroyed. However, it was found that the proposed protective agents often have a very specific effect not only in relation to agricultural plants, but also in relation to the herbicide, which in some cases also depends on the application method, i.e. a particular protective agent is often only suitable for a particular crop and a particular class of herbicides or a particular herbicide.

It was found that the protective agents described in applications EP-A-492366, W) 91/07874 and W9 94/00987 are suitable for protecting cultivated plants from the phytotoxic effect of herbicides from the classes of sulfonylureas and sulfamoylureas, which are described in applications EPA-679646, EP-A-502740, EP-A-0477808 and I8 patent 5009699.

Thus, the invention relates to a selective herbicidal composition containing, in addition to conventional inert forms, inert additives such as carriers, solvents and wetting agents, a mixture of

a) a herbicidally effective amount of a herbicide selected from the group comprising compounds of formula 1a and / or 1b, where n

main _{3 (1b)>}

K is hydrogen or fluorine, and / or 1c

or a salt of the compounds of formulas 1a and / or 1b and / or 1c and

b) to prevent the phytotoxic effect of the herbicide effective to exert a protective effect of the amount of the compound of formula 11a

where K ₀₁₀ denotes hydrogen, C ₁ -C ₈ alkyl or C ₁ C ₈ alkyl substituted with C ₁ -C ₆ alkoxy or C ₃ C ₆ alkenyloxy group,

X ₂ is hydrogen or chlorine, compounds of formula 11b ₁

where E is nitrogen or methine,

K ₁₁ is —CC1 ₃ or phenyl unsubstituted or substituted by halogen,

K ₁₂ and K _{13 are} each independently hydrogen or halogen, and K ₁₄ is C ₁ -C ₄ alkyl, compounds of formula 11b ₂

where K ₁₂ and K ₁₃ have the above meanings, K ₆₆ , KB ₇ and K each independently of one another are C ₁ -C ₄ alkyl, compounds of formula 11c ^OCH s (1a)

where A2 denotes a group (Hc)

K ₂₅ and K ₂₆ independently of one another are hydrogen, C 1 C ₈ alkyl, C ₃ -C ₈ cycloalkyl, C _{3 to} C ₆ alkenyl, C ₃ -C ₆ alkynyl group of the formula

or C ₁ -C ₄ alkyl substituted with a C ₁ C ₄ alkoxy group, or a group of the formula

- _<3 ^V;

or K ₂₅ and K ₂₆ together form a C ₄ C ₆ alkylene bridge which may be interrupted by oxygen, sulfur, 80, 8Θ ₂ , ΝΗ or ^ (C _g C ₄ alkyl) group;

K ₂₇ is hydrogen or C ₁ -C ₄ alkyl;

K _aa is hydrogen, halogen, cyano, trifluoromethyl, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, -COOC ,, -ΟΘΝΒ ^ Β ^, -COK _n , -8O ^ K _to K _t or -O8O ₂ -C ₁ -C ₄ alkyl;

K _d is hydrogen, halogen, cyano, nitro, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, -COOCr -CONC _to K _t , -COC _p , - 8o ^ K _to K _t, -O8O ₂ -C ₁ -C ₄ alkyl, C ₁ -C ₆ alkoxy C ₁ -C ₆ alkoxy, substituted C ₁ S4alkoksigruppoy or halogen, S3S ₆ alkenyloxy or C ₃ -C ₆ alkenyloxy group, substituted by halogen or a C3-C6 alkynyloxy group;

or K _aa and K _b together form a C ₃ C ₄ alkylene bridge that can be substituted with halogen or C1-C4 alkyl, or form a C ₃ -C ₄ alkylene bridge that can be substituted with halogen or C1-C4 alkyl, or form a C4 alkadienylene bridge, which may be substituted with halogen or C ₁ C ₄ alkyl;

K _b and K _{k are} independently hydrogen, halogen, C ₁ -C ₄ alkyl, trifluoromethyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ alkylthio or -COOC ;;

K is hydrogen, halogen, nitro, C ₁ C ₄ alkyl or methoxy;

Ka is hydrogen, halogen, nitro, C ₁ C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl,

-COOK, or -CONK _to K _t ;

Re is hydrogen, halogen, C ₁ C ₄ alkyl, -SOOKr trifluoromethyl or methoxy, or Ra and R _e together form a C ₃ -C ₄ alkylene bridge;

Cg represents hydrogen, halogen or C ₁ -C 4 alkyl;

K _x and K _{y are} independently hydrogen, halogen, C ₁ -C ₄ alkyl, C ₁ C ₄ alkoxy, C ₁ -C ₄ alkylthio, -COOC ₂₈ , trifluoromethyl, nitro or cyano;

Cr K _to and K _t independently of each other are hydrogen or C ₁ -C ₄ alkyl;

or K _k and K _t together form a C ₄ C ₆ alkylene bridge which may be interrupted by oxygen, ΝΗ or ^ (C _g C ₄ alkyl) group;

K _p is C ₁ -C ₄ alkyl, phenyl or phenyl substituted with halogen, C ₁ -C ₄ alkyl, methoxy, nitro or trifluoromethyl;

K ₂₈ is hydrogen, C ₁ -C ₁₀ alkyl, C ₁ C ₄ alkoxy-C ₁ -C ₄ alkyl, C ₁ -C ₄ alkylthio-C ₁ -C ₄ alkyl, di-C ₁ -C ₄ alkylamino-C ₁ -C ₄ alkyl, halogen C ₁ -C ₈ alkyl, C ₂ -C ₈ alkenyl, halogen-C ₂ -C ₈ alkenyl, C3-C8 alkynyl, C3-C7 cycloalkyl, halogen-C3-C7 cycloalkyl, C ₁ -C ₈ alkylcarbonyl, allylcarbonyl , C3-C7 cycloalkylcarbonyl, benzoyl, which may be unsubstituted or contains up to three identical or different substituents on the phenyl ring selected from the group consisting of halogen, C ₁ -C ₄ alkyl, halogen-C ₁ C ₄ alkyl, halogen-C ₁ - C ₄ alkoxy or C ₁ C ₄ alkoxy; or furoyl, thienyl; or C ₁ -C ₄ alkyl which is substituted by phenyl, galoidfenilom, S1S4alkilfenilom, C1-S4alkoksifenilom, halo-S1S4alkilfenilom, halo-C1-S4alkoksifenilom, C1-S6alkoksikarbonilom, S1S4alkoksi S8alkoksikarbonilom-C1-C3-S8alkeniloksikarbonilom, C ₃ -C ₈ alkynyloxycarbonyl, C1-C8 alkylthiocarbonyl, C3-C8 alkenylthiocarbonyl, C3-C8 alkynylthiocarbonyl, carbamoyl, mono-C ₁ -C ₄ alkylaminocarbonyl, di-C1-C4 alkylaminocarbonyl; or phenylaminocarbonyl, which may be unsubstituted or contains up to three identical or different substituents on the phenyl ring, selected from the group consisting of halogen, C1-C4 alkyl, halogen-C1-C4 alkyl, halogen-C1C4 alkoxy or C1-C4 alkoxy, or contains one substituent selected from cyano or nitro, or dioxolan-2-yl which can be unsubstituted or substituted with one or two C ₁ C ₄ alkyl radicals, or dioxan-2-yl which can be unsubstituted or substituted with one or two C1-C4alkyl radicals, or C1-C4 alkyl which may be substituted iano-, nitro, carboxyl or C1-S1S8alkiltio S8alkoksikarbonilom, compounds of formula 11e

K34 together form a group of the formula

II

ΝΌ — sleep, /

I "(Not) where K ₃₃ and K _{34 are} independently C ₁ -C ₆ alkyl or C ₂ -C ₆ alkenyl, or K ₃₃ and

K ₃₅ and K ₃₆ independently represent hydrogen or C ₁ -C ₆ alkyl, or K ₃₅ and K ₃₆ together form a group of the formula

K ₃₇ and K _{38 are} independently hydrogen or C ₁ -C ₄ alkyl, or K ₃₇ and K ₃₈ together form - (CH ₂ ) ₅ -;

K ₃₉ is hydrogen, C ₁ -C ₄ alkyl or a group

or K ₃₃ and K ₃₄ together form a group of the formula

K40, ^K 41 ^, K42, K43, H44, H45, K46, K47, K4 ₈ , K49, K50, K ₅₁ , K ₅₂ , K ₅₃ , K ₅₄ and K ₅₅ independently represent hydrogen or C ₁ -C ₄ alkyl; compounds of the formula ΙΙΓ

where K ₆₃ denotes hydrogen or chlorine and K ₆₄ denotes cyano or trifluoromethyl, or compounds of the formula ΙΙ§

where K ₆₅ denotes hydrogen or methyl.

The invention also includes agrotechnically acceptable salts which the compounds of formulas 1a, 1b and 1c can form, for example, with amines, alkali metal bases and alkaline earth metal bases or quaternary ammonium bases.

Preferred salt forming substances from alkali metal hydroxides and alkaline earth metal hydroxides include lithium, sodium, potassium, magnesium or calcium hydroxides, but sodium or potassium are particularly preferred.

Examples of amines that are suitable for the formation of the ammonium salt are not only ammonia, but also primary, secondary and tertiary C1-C18 alkylamines, C1-C4 hydroxyalkylamines and C2-C4 alkoxyalkylamines, for example methylamine, ethylamine, n-propylamine, isopropylamine, four butyl isomers namylamine, isoamylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, methylethylamine, methylisopropylamine, methylethylamine, methylnonylamine, methylpentadecylamine, methyloctylamine utylamine, ethylheptylamine, ethylloctylamine, hexylheptylamine, hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, ethanol Ν, Ν-diethanolamine, л ethylpropanolamine, Ν-butylethanolamine, allylamine, n-butenyl-2-amine, n-pentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl- 2-amine, propylene diamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, triisobutylamine, tri- sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines, for example, pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines, for example, anilines, methoxyanilines, ethoxyanilines, ortho-, meta-, paratoluidines, phenylenediamines, benzidines, naphthylamines and ortho-, meta-, parachloranilines; but triethylamine, isopropylamine and diisopropylamine are particularly preferred.

The alkyl groups indicated in the definitions of substituents in the compounds of formulas 11aΙΙ§ may be straight or branched chain and, for example, are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl and pentyl, hexyl, heptyl, octyl, nonyl, decyl and their branched isomers. These alkyl groups can have additional substituents, for example, halogen, in particular fluorine, chlorine or bromine, alkoxy, thioalkyl, cycloalkyl, phenyl, amino, acyl (for example, K ₈ CO—) or oxo (O =). Suitable alkoxy, thioalkyl, haloalkyl and haloalkoxy groups are derivatives of these alkyl groups.

Examples of unsaturated substituent groups are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptinyl, octynyl and isomers that differ in different positions of the unsaturated bond or bonds in the molecule, isomers that contain branching and, in the case of alkenes, cisyl trans isomers.

Examples of alkenyloxy, alkynyloxy, haloalkenyl and haloalkenyloxy groups can be prepared from these alkyl groups.

Cycloalkyl groups include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Suitable cycloalkenes may be mono- or polyunsaturated.

The concept of substituted involves not only monosubstitution, but also polysubstitution, if possible in the group under consideration.

Among the salts of the compounds of formula 1a, the compound of formula 16

is particularly preferred for the composition of the invention.

A particularly preferred composition of the invention comprises either a compound of formula 1a or 16 as a herbicide, and as a protective agent a compound of formula 11a in which X ₂ is chloro and Cosh is 1 methylhexyl.

Preferred compositions of the present invention include, as a protective agent, a compound of formulas 11a, 11b ₁ , b ₂ or 11 _s .

Preferred among these compositions are compositions that include, as a protective agent, a compound of formula 11b ₁ or 11b ₂ .

Another group of preferred compositions includes, as a protective agent, a compound of formula 11a, in particular a compound of formula 11a in which X ₂ is chloro and K ₀₁₀ is —CH (CH ₃ ) C ₅ H ₁₁ -p.

Protective agents, particularly preferred for use in the compositions of the invention, are given in the tables below.

Table 1 Compounds of Formula 11a

o — sn ₂ —c — o— ^ ₁₀ o

Compound No. x ₂ ^K 010 4.01 C1 -CH (CH ₃ ) -C ₅ N _p- n 4.02 C1 -CH (CH ₃ ) -sn ₂ osn ₂ sn = sn ₂ 4.03 C1 n 4.04 C1 C ₄ H ₉ -H

table 2

Compounds of formula 11b ₁

Compound No. ^K 11 ^to 12 *thirteen E 5.01 sun ₃ phenyl 2-C1 n CH 5.02 sun ₃ phenyl 2-C1 4-C1 CH 5.03 sun ₃ phenyl 2-P n CH 5.04 sun ₃ 2-chlorophenyl 2-P n CH 5.05 s ₂ n ₅ CC1 ₃ 2-C1 4-C1 N 5.06 sun ₃ phenyl 2-C1 4-CP ₃ N 5.07 sun ₃ phenyl 2-C1 4-CP ₃ N 5.08 sun ₃ 2-fluorophenyl 2-C1 n CH

Table 3

Compounds of formula 11b ₂

Table 4

Compounds of formula 11c

Compound No. ^A 2 ' ^to 26 7.001 DOS. BUT N 7.002 .BUT SNZ N 7.003 sun ₃ 7.004 main BUT sun ₃

Table 5 Compounds of formula 11e%

Ν — C — CHC1 _g (He)

Compound No. ^K 68 * 67 * 66 *12 ^K 13 6.01 sun ₃ sun ₃ sun ₃ 2-C1 4-C1 6.02 sun ₃ s ₂ n ₅ sun ₃ 2-C1 4-C1 6.03 sun ₃ s ₂ n ₅ s ₂ n ₅ 2-C1 4-C1

Table 6

Compounds of formula III *

Compound No. ^K 63 ^K 64 9.01 N ΟΝ 9.02 C1 SR ₃

Table 7

Compounds of formula 11d

C1

Compound No. * 65 10.01 N 10.02 sun ₃

Protective agents are given in table. 1-7, and their preparation is described, for example, in applications EP-A-492366, \\ 'O 91/07874 and \ CO 94/00987.

The herbicidal compositions of the invention that are most important include one of the following combinations of active ingredients:

1a + 4.01; 1a + 4.02; 1a + 4.03; 1a + 4.04; 1b, where K is hydrogen, + 4.01; 1b, where K is hydrogen, + 4.02; 1b, where K is hydrogen, + 4.03; 1b, where K is hydrogen, + 4.04; 1b, where K is fluoro, + 4.01; 1b, where K is fluoro, + 4.02; 1b, where K is fluoro, + 4.03; 1b, where K is fluoro, + 4.04;

1a + 5.01; 1a + 5.02; 1a + 5.03; 1a + 5.04; 1a + 5.05; 1a + 5.06; 1a + 5.07; 1a + 5.08; 1b, where K is hydrogen, + 5.01; 1b, where K is hydrogen, + 5.02; 1b, where K is hydrogen, + 5.03; 1b, where K is hydrogen, + 5.04; 1b, where K is hydrogen, + 5.05; 1b, where K is hydrogen, + 5.06; 1b, where K is hydrogen, + 5.07; 1b, where K is hydrogen, + 5.08; 1b, where K is fluoro, + 5.01; 1b, where K is fluoro, + 5.02; 1b, where K is fluoro, + 5.03; 1b, where K is fluoro, + 5.04; 1b, where K is fluoro, + 5.05; 1b, where K is fluoro, + 5.06; 1b, where K is fluoro, + 5.07; 1b, where K is fluoro, + 5.08;

1a + 6.03; 1b, where K is hydrogen, + 6.03; 1b, where K is fluoro, + 6.03;

1a + 7.01; 1a + 7.02; 1a + 7.03; 1a + 7.04; 1b, where K is hydrogen, + 7.01; 1b, where K is hydrogen, + 7.02; 1b, where K is hydrogen, + 7.03; 1b, where K is hydrogen, + 7.04; 1b, where K is fluoro, + 7.01; 1b, where K is fluoro, + 7.02; 1b, where K is fluoro, + 7.03; 1b, where K is fluoro, + 7.04.

The invention also relates to a method for selectively controlling weeds in useful plant cultures, which comprises treating useful plants, their seeds or vegetative propagation material or their sown areas, together or separately, with a herbicidally effective amount of a herbicide of formula 1a and / or 1b and an effective to prevent the harmful effects of the herbicide, the amount of the protective agent of the formula ΙΙ.

Agricultural plants that can be protected by a protective agent of formula II from the harmful effects of the above herbicides are preferably, in particular, crops and rice.

In addition, it should be noted that beneficial crops may also include those that have developed resistance to herbicides or to specific classes of herbicides using conventional selection methods or genetic engineering methods.

The weeds to be destroyed can be either monocotyledonous or dicotyledonous weeds, for example, 81e11apa, Schioptea, Adgois, Beepea, Auepa, 8e1apa, 81par18, Eoiuos, 8o1apis, Pseudocisula, Esenopusa, Apocialis , Vgoshiz, A1oresigiz, 8bigish baerepze, Kochyoe, Suregiz, AiShop, 8aa, Hap1yit, Atagapiiz, Sperorois, 1rothoea, Syuzapuyesh, Oa1shsh, Uy1a and Uyogisa.

Sown areas should be understood as areas of soil on which agricultural plants or their seeds have already been planted, as well as areas intended for planting these agricultural plants.

Depending on the ultimate goal, the protective agent of formula II can be used for pre-treatment of seeds of a cultivated plant (seed treatment or processing of material for propagation), or it can be applied to the soil at a pre- or post-emergence stage. In addition, it can be applied alone or with the herbicide when the plants have already sprouted. Therefore, treatment of plants or seeds with a protective agent as a whole can be carried out regardless of the time of treatment with the herbicide. However, the plant can also be treated by simultaneously applying the herbicide and the protective agent (i.e., in the form of a tank mixture prepared in one tank).

The concentration of the protective agent in relation to the herbicide will mainly depend on the method of application. When a field treatment is carried out either using a mixture prepared in one tank, which includes a combination of a protective agent and a herbicide, or by separately adding a protective agent and a herbicide, the ratio of the herbicide to the protective agent is usually in the range from 1: 100 to 1: 1, preferably from 1:50 to 5: 1.

For field cultivation, usually from 0.001 to 5.0 kg / ha, preferably from 0.001 to 0.5 kg / ha of protective agent is used.

The concentration of the herbicide is usually in the range from 0.001 to 2.0 kg / ha, preferably from 0.005 to 1.0. kg / ha.

The compositions of the invention are suitable for all treatment methods commonly used in agriculture, including pre-emergence treatment, post-emergence treatment and seed treatment.

For seed dressing, usually 0.001 to 10 g of a protective agent / kg of seeds is used, preferably 0.05 to 2 g of a protective agent / kg of seeds. If the protective agent is used in liquid form shortly before planting, it is preferable to use solutions of the protective agent containing the active substance in a concentration of from 1 to 10,000 ppm, preferably from 1,00 to 1,000 ppm, for better absorption.

For processing, it is preferable to use the protective agents of formula II or a combination of these protective agents with herbicides of the formula 1a, and / or 1b, and / or 1c together with excipients commonly used in formulations, for example, for the preparation of emulsion concentrates, coating pastes, ready to the use of sprayable or dilute solutions, diluted emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Formulations are prepared in the usual manner, for example, by homogenously mixing and / or grinding the active ingredients with excipients for a liquid or solid composition, for example, with solvents or solid excipients. Surfactants (detergents) can be additionally used to prepare formulations.

Suitable solvents are: aromatic hydrocarbons, preferably fractions having C ₈ Cl ₂ carbon atoms, for example xylene mixtures or substituted naphthalenes, phthalates such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffins, alcohols and glycols or their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, ketones such as cyclohexanone, highly polar solvents such as Y-methyl-2-pyrrolido , Dimethyl sulfoxide or dimethylformamide, and non-epoxidized vegetable oils or epoxidised vegetable oils such as epoxidised coconut oil or soybean oil, or water.

The solid fillers commonly used, for example, for dusts and dispersible powders, are typically natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. To improve the physical properties, it is also possible to add finely divided silicic acid or finely dispersed absorbing polymers. Suitable granular absorption carriers are porous type carriers, for example pumice, broken brick, sepiolite or bentonite, and suitable non-absorbent carriers are materials such as calcite or sand. In addition, a large number of pre-granulated materials of inorganic or organic origin can be used, for example, dolomite or powdered plant residues are particularly preferred.

Depending on the nature of the active substance of the formula I to be included in the formulation, suitable surfactants are nonionic, cationogenic and / or anionic surfactants, as well as mixtures of surfactants that provide good emulsifying, dispersing and wetting properties.

Suitable anionic surfactants can be so-called water-soluble soaps, as well as water-soluble synthetic surfactants.

Soaps to be mentioned are alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and higher fatty acids (C1 ₀ -C ₂₂ ), for example, sodium or potassium salts of oleic or stearic acid, or mixtures of natural fatty acids which can be obtained, in particular, from coconut or tall oil. In addition, methyl taurine salts of fatty acids should be mentioned.

More often, however, so-called synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated derivatives of benzimidazole or alkylaryl sulfonates.

Fatty alcohol sulfonates or fatty alcohol sulfates are usually used in the form of alkali metal salts, alkaline earth metal salts, unsubstituted or substituted ammonium salts, and they contain an alkyl radical with 8-22 carbon atoms, which also includes an alkyl fragment of acyl radicals, for example, in the form of sodium or a calcium salt of lignosulfonic acid, dodecyl sulfate, or a mixture of sulfates of fatty alcohols derived from natural fatty acids. This group also includes salts of sulfated and sulfonated fatty alcohol / ethylene oxide adducts. Sulfonated derivatives of benzimidazole preferably contain 2 sulfonic acid groups and one fatty acid residue containing from about 8 to 22 carbon atoms. Alkylaryl sulfonates, for example, are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or a condensation product of naphthalenesulfonic acid and formaldehyde.

Suitable phosphates are also suitable, for example, salts of phosphoric acid ester and paranonylphenol adduct with 4-14 moles of ethylene oxide units or phospholipids.

Suitable nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkyl phenols, and these derivatives contain 3-30 glycol ether groups and 820 carbon atoms in the (aliphatic) hydrocarbon fragment and 6-18 carbon atoms in alkyl moiety of alkyl phenols.

Other suitable non-ionic surfactants are water-soluble polyadducts of polyethylene oxide and polypropylene glycol, ethylene diamine propylene glycol and alkylpropylene glycol containing 1-10 carbon atoms in the alkyl chain, the polyadducts containing 20-250 groups of ethylene glycol ether and 10-0-100 propylene groups. These compounds typically contain 1-5 fragments of ethylene glycol per propylene glycol fragment.

Examples of nonionic surfactants that should be mentioned are nonylphenol polyethoxylates, polyethoxylated castor oil and polyglycol ethers, polypropylene and polyethylene oxide adducts, tributylphenol polyethoxylate, polyethylene glycol polyethylene and octylphenol.

Fatty acid esters of polyoxyethylene sorbitan are also suitable materials, such as polyoxyethylene sorbitan trioleate.

The cationic surfactants are preferably quaternary ammonium salts, which have as an Ν substituent at least one alkyl radical having from 8 to 22 carbon atoms and also contain unsubstituted or halogenated lower substituents. alkyl, benzyl or hydroxy- lower alkyl. Salts in the form of halides, methyl sulfates or ethyl sulfates are preferred, for example, stearyltrimethylammonium chloride or benzyldi (2chloroethyl) ethylammonium bromide.

Surfactants that are commonly used for the manufacture of formulations and which can also be used in the compositions of the invention are described, in particular, in MS S'Sysseop'S Es1gdei18 apb EtikShega Appia1, MS PnMypd Sogr. Шбдемюоб No. \ ν 1eg5eu. 1981, with N. §! Asye in Teyb-Taksyeyi Sis | 8igGas1ai15 Ussb], Sag1 Napzeg Uegksch, Mii1sy / U1eiaa, 1981, and with M. and 1. AM1 in Jesusbore 1a 8gGas1ap15, t. Νον Wagk, 1980-1981.

Herbicidal compositions usually contain from 0.1 to 99 wt.%, Preferably from 0.1 to 95 wt.% A mixture of active substances in the form of a mixture of a compound of formula 1a and / or 1b and / or 1c and compounds of formula II from 1 to 99.9 wt.% Excipients for the solid or liquid composition and from 0 to 25 wt.%, Preferably from 0.1 to 25 wt.% Of a surfactant.

Although commercially available products are preferably formulated as concentrates, the end user typically uses diluted compositions.

The compositions may also contain other additives, such as stabilizers, for example, epoxidized or non-epoxidized vegetable oils (epoxidized coconut oil, rapeseed oil or soybean oil), antifoam agents, for example silicone oil, preservatives, viscosity regulators, binders, adhesives, as well as fertilizers or other active substances.

Various methods and methods may be suitable for applying the protective agents of formula ΙΙ or compositions containing them to protect agricultural plants from the harmful effects of herbicides of the formula 1a, and / or 1b, and / or 1c. These, for example, include the following methods.

Ι) Seed dressing

a) Dressing the seeds with a wettable powder composition containing the active substance of the formula путем by shaking in a vessel until the protective agent is evenly distributed on the surface of the seeds (dry treatment). Typically, 1 to 500 g of active ingredient of formula II (4-2 g of wettable powder) per 100 kg of seeds is used.

b) Seed treatment with an emulsion concentrate of the active substance of the formula II in accordance with method a) (wet treatment).

c) Dressing by immersing the seeds in a mixture containing 100-1000 ppm of the active substance of the formula II for 1-72 hours, leaving them wet or further drying them (soaking the seeds).

Seed dressing or treatment of sprouted seedlings is obviously the preferred treatment method, since treatment with the active ingredient is fully concentrated on the target crop. Typically, from 1 to 1,000 g of antidote is used, preferably from 5 to 250 g of antidote per 100 kg of seeds, however, depending on the method used, which also allows the use of other active substances or trace elements, deviations from the indicated concentration limits are possible aside increase and decrease (multiplicity of impregnation).

II) Application as a mixture prepared in one tank

Apply a liquid composition of a mixture of antidote and herbicide (mutual ratio from 10: 1 to 1: 100) with a herbicide consumption rate of from 0.005 to 5.0 kg / ha. This mixture prepared in one tank is added before or after sowing.

III) Furrowing

The protective agent in the form of an emulsion concentrate, wettable powder or granulate is introduced into the open furrow into which the seeds were sown. After closing the furrow, the herbicide is applied by the usual method of pre-emergence treatment.

Iv) controlled release of the active substance

A solution of the active substance II is applied to mineral granular substrates or to polymerized granules (urea / formaldehyde) and allowed to dry. If necessary, a coating can be applied (coated granules), which allows for controlled release of the active substance after a certain period of time.

Preferred formulations have, in particular, the following composition: (% means wt.%)

Dusty mixture of active substances - 0.1-10%, preferably 0.1-5% solid carrier - 99.9-90%, preferably 99.9-99%

Suspension concentrates mixture of active substances - 5-75%, preferably 10-50% water - 94-24%, preferably 88-30% surfactant - 1-40%, preferably 2-30%

Wettable powders, a mixture of active ingredients - 0.5-90%, preferably 1-80% surfactant - 0.520%, preferably 1-15% solid carrier - 5-95%, preferably 15-90%

Granules a mixture of active substances - 0.1-30%, preferably 0.1-15% solid carrier - 99.5-70%, preferably 97-85%

Below the invention is illustrated in more detail by examples, not limiting its scope.

Examples of formulations based on mixtures of herbicides of the formula 0. and / or] b, and / or K and a protective agent of the formula II (% means wt.%).

G1. Solutions but) b) in) d) the mixture is acting substances 5% 10% fifty% 90% 1-methoxy-3- (3methoxypropoxy) propane twenty% twenty% polyethylene glycol with mol. wt. 400 twenty% 10% Y-methyl-2pyrrolidone thirty% 10% aromatic hydrocarbon mixture C9-C12 75% 60%

The solutions are suitable for use as microdrops.

D.2. Wettable Powders but) b) in) d) mixture of active substances 5% 25% fifty% 80% lignosulfonate triya 4% 3% sodium lauryl sulfate 2% 3% - 4% diisobutylnaphthylene sulfonate sodium 6% 5% 6% octylphenol polyethoxylate (7-8 moles of ethylene oxide units) one% 2% finely divided silicic acid one% 3% 5% 10% kaolin 88% 62% 35% -

The active ingredients are thoroughly mixed with additives and this mixture is ground in a suitable mill. As a result, wettable powders are obtained, which can be diluted with water to obtain suspensions of any desired concentration.

E3. Coated Granules but) b) in) mixture of active substances 0.1% 5% fifteen% finely divided silicic acid 0.9% 2% 2% inorganic carrier (01.1-1 mm), for example, CaCO ₃ or δίθ ₂ 99.0% 93% 83%

The active substances are dissolved in methylene chloride, the solution is sprayed onto a carrier and then the solvent is removed under vacuum.

E4. Coated Granules but) b) in) mixture of active substances 0.1% 5% fifteen% polyethylene glycol with a pier. wt. 200 1,0% 2% 3% finely divided silicic acid 0.9% one% 2% inorganic carrier (0 0.1-1 mm), for example, CaCO ₃ or δίθ ₂ 98.0% 92% 80%

The finely divided active substances are uniformly fed into the mixer to a carrier moistened with polyethylene glycol. In this way, dust-free coated granules are obtained.

E5. Extruded bath granulate but) b) in) d) mixture of active substances 0.1% 3% 5% fifteen% sodium lignosulfonate 1.5% 2% 3% 4% carboxymethyl cellulose 1.4% 2% 2% 2% kaolin 97.0% 93% 90% 79%

Active ingredients are mixed with additives and the mixture is moistened with water. This mixture is extruded and then dried in a stream of air.

P6. Dusty but) b) in) mixture of active substances 0.1% one% 5% talc 39.9% 49% 35% kaolin 60.0% fifty% 60%

Ready-to-use dusts are obtained by mixing the active ingredients with carriers and grinding the mixture in an appropriate mill.

ethylene glycol 5% 5% 5% 5% nonylphenol polyethoxylate (1 5 moles of ethylene oxide units) one% 2% sodium lignosulfonate 3% 3% 4% 5% carboxymethyl cellulose lulose one% one% one% one% 37% aqueous formaldehyde solution 0.2% 0.2% 0.2% 0.2% silicone oil emulsion 0.8% 0.8% 0.8% 0.8% water 87% 79% 62% 38%

The finely divided active ingredients are uniformly mixed with additives. The result is a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.

It is often more preferable to formulate separate formulations based on the active substance of the formula 1a, and / or 1b, and / or 1c and on the basis of another component of the formula II and mix them in water immediately before loading into the machine for applying pesticides in the required ratio of the components of the mixture in the form tank mixture (mixture prepared in one tank).

The ability of the protective agents of formula II to protect cultivated plants from the phytotoxic effect of herbicides of the formula Y, and / or GO and / or k is illustrated in the following examples.

Biological Examples

Example B1 Post-emergence treatment of crops with mixtures of a herbicide of the formula kg and / or GO and / or k and a protective agent of the formulas Cha-Id:

Wheat is grown in a greenhouse in plastic flower pots to a stage of 2.5 leaves. At this stage, the experimental plants are treated either with herbicides of the formula GO and / or k and / or k only, or with a mixture of herbicides with a protective agent of the formulas Pa-Id. The treatment is carried out with an aqueous suspension of the test compounds (formulation from example 7) at the rate of 500 l of water / ha. 28 days after treatment, an assessment is made using a percentage scale. The results show that wheat damage caused by a herbicide of formula k, and / or k, and / or k, can be significantly reduced by using protective agents of the formulas Ia-Id.

The same results were obtained in the manufacture on the basis of compounds of the formula k, and / or k preparative forms in accordance with examples P1-P6.

E7. Suspension Concentrates but) b) in) d) mixture of active substances 3% 10% 25% fifty%

Claims (7)

CLAIM 1. Herbicidal composition of selective action, containing along with the usual in preparative forms of inert excipients as an active substance a mixture of a) a herbicidally effective amount of a herbicide selected from the group including K is hydrogen or fluorine and / or 1c or a salt of compounds of formulas 1a and / or 1b, and / or 1c and b) to prevent the phytotoxic action of the herbicide effective for the manifestation of the protective action of the amount of the compounds of formula 11a where K ₀₁₀ denotes -CH (CH ₃ ) C ₅ H ₁₁ -n and X ₂ is chlorine. 2. The composition according to claim 1, which contains as a compound of formula 1a a compound of formula 16 3. The composition according to claim 1, which, as a herbicide, contains either a compound of formula 1a, or 16, and as a protective agent, contains a compound of formula 11a, in which X ₂ is chlorine and K ₀₁₀ is 1 methyl hexyl. 4. The composition according to claim 1, which contains a herbicidally effective amount of a herbicide selected from the group consisting of: where K is hydrogen or fluorine, or a salt of compounds of formulas 1a and / or 1b. 5. A method of selectively controlling weeds and herbaceous plants in crops of agricultural plants, which includes the treatment of these agricultural plants, their seeds or their seedlings or their acreage, together or separately, with an effective amount of the herbicide of formula 1a and / or 1b, and / or 1c and in order to prevent the phytotoxic action of the herbicide, an effective amount of the protective agent of the formula II for the manifestation of the protective action. 6. The method according to claim 5, which includes the treatment of crops of agricultural plants or acreage intended for planting agricultural plants, with a herbicide of formula 1a and / or 1b in an amount of 0.001-2 kg / ha, and / or 1c in an amount of 0.001-0, 5 kg / ha protective agent of formula II. 7. The method according to claim 5, where the agricultural plants are cereals or rice.