LT3258B - Selective herbicidic preparation and method for using thereof - Google Patents

Abstract

The selective herbicide preparation for killing grass and weeds in useful plant crops consists of:a) efficient amount of herbicidal sulfonyl carbamide according to the (I) formulawhere R1 and R2, independent of each other, mean methyl and methoxyl;R3 means hydrogen, halogen, methyl or methoxyl; andb) amount of protective substance herbicidal antagonist chinolin derivative according to the (II) formulawhere R is hydrogen or C1-C8-alkyl and X is hydrogen or chlorine.

Description

The present invention relates to a selective herbicide for controlling herbicides and weeds in useful crop crops, particularly cereal crops, comprising a herbicide and an anticancer agent (a safener, an antidote) that protects useful plants (but not weeds) from the phytotoxic action of the herbicide. Also described is the use (method) of this preparation or herbicide / antidote combination in combating weeds in useful crops.

Depending on factors such as herbicide dose and application / treatment type, crop species, soil characteristics and climatic conditions, such as light season, temperature and reduced atmospheric pressure, the use of herbicides can severely damage crops. Particularly serious damage occurs when crops which are resistant to the action of the herbicide are replaced by other crops which do not have or have very low herbicide resistance instead of crop rotation.

Various materials have already been proposed to overcome this problem, which are suitable for eliminating the harmful specific effects of the herbicide on crop plants, meaning they can protect crop plants without significantly affecting the weed effect of the herbicide. In addition, it is demonstrated that the proposed antidotes are often crop specific, crop specific and herbicidal and, depending on the application, often act specifically, meaning that a particular antidote is often only applicable to a particular crop and one particular class of herbicide. . From European patent no. A-0 094349 describes known quinoline derivatives which protect crop plants against the phytotoxic action of a certain class of herbicide such as phenoxypropionic acid ethers, urea, carbamate aba diphenyl ether.

It has been observed that special, European patent no. The known quinoline derivatives described in A-0 094349 are suitable for protecting crop plants against the phytotoxic action of a particular class of sulfonylurea herbicide.

Thus, the present invention provides a selective herbicide formulation which comprises, in addition to inactive additives as carrier substances, an effective component comprising:

(a) an effective amount of a herbicidal sulfonylurea of formula (I)

(I) in which

R _x and R ₂ independently of one another are methyl and methoxyl,

R ₃ represents hydrogen, halogen, methyl or methoxyl;

(b) a safener, a quinoline derivative of the formula (II) in an amount of a herbicide antagonist

O-CH 1 -C-O-ϋ

II

in which

R is hydrogen or C _x -C ₈ alkyl and

X is hydrogen or chlorine.

As alkyl groups, straight or branched alkyl groups, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, secondary butyl or tertiary butyl, are attracted, as are various isomeric pentyls, hexyls, heptyls and octyls.

Halogen may be fluorine, chlorine, bromine or iodine, but most commonly fluorine.

The compounds of formula (I) may form salts in which the hydrogen of the SO ₂ -NH- group is replaced by a foliar cation. These salts are, for example, metal salts, in particular alkaline or alkaline earth metal salts, or also ammonium salts or salts with organic amines.

Cationic ammonium compounds suitable amine may be exemplified and ammonia as well as primary, secondary and tertiary ^C 1 ^C 18 -alkylamino, C _x -C ₄ -hidroksialkilaminai and C ₂ -C ₄ -alkoksialkilaminai such as methylamine, ethylamine, n-propylamine , isopropylamine, the four butylamine isomers, n-Amylamines, izoamilaminas, hexylamino, heptilaminas, octylamino, nonilaminas, decilaminas, pentadecylamino, Hexadecylamino, heptadecilaminas, oktadecilaminas, methylethylamino, methylisopropylamino, methylhexylamino, metilnonilaminas, metilpentadecilaminas, methyloctadecylamine, etilbutilaminas, etilheptilaminas, etiloktilaminas, heksilheptilaminas , hexyloctylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, di-n-amylamine, diisoamylamine, dihexylamine, diheptylamine, dioctylamine, ethanolamine, n-propanolamine, N-propanolamine, N -ethylpropanolamine, N-butylethanolamine, alkylamine, n-butenyl-2-amine n, npentenyl-2-amine, 2,3-dimethylbutenyl-2-amine, dibutenyl-2-amine, n-hexenyl-2-amine, propylenediamine, trimethylamine, triethylamine, tri-n-propylamine, triisopropylamine, tri-n- butylamine, triisobutylamine, tri-sec-butylamine, tri-n-amylamine, methoxyethylamine and ethoxyethylamine; heterocyclic amines such as pyridine, quinoline, isoquinoline, morpholine, piperidine, pyrrolidine, indoline, quinuclidine and azepine; primary arylamines such as: aniline, methoxyamylin, ethoxyaniline, o, m, ptoluidine, phenylenediamine, benzidine, naphthylamine and o, m, p-chloroaniline; but especially triethylamine, isopropylamine and diisopropylamine.

In the preparation of the present invention, the compounds of formula (I) or salts thereof are preferred, wherein R ₃ is hydrogen or 4-fluoro.

provided for compounds of formula (I), methoxyl. These compounds are particularly antidotes of formula (II) wherein X is chlorine and R is C ₄ -C ₈ alkyl, with methyl hexyl being particularly preferred.

Further, the preference for which R _x is suitable are those

Particular preference is given to the preparation of the present invention with a herbicidally active sulfoLT 3258 B nylurea of formula (I) wherein R 1 is methyl and R ₂ is methoxyl. A particularly suitable antidote for the preparation of the present invention of formula (II) is that wherein X is chlorine and R is C ₄ -C ₈ alkyl, and in particular 1-methylhexyl.

Particular preference is given to the preparation according to the invention having a herbicidally effective amount of a sulfonylurea according to formula (Ia).

OCI- To $

C (Ia) and as quinoline derivatives antagonizing the herbicide by the formula (Ha)

Cl

0- C K ^ -C · il-L'H (C Hj Xc Ha), C Ha i s l!

(Ha)

The sulfonylurea herbicide of the formula (I) and its production are known from European patent no. A-496701 Description.

The quinoline derivatives of the formula (II) and their preparation are equally known and described in European patent no.

A-0094349.

The present invention also provides a method of selective control of weeds in useful crop plants, wherein the useful plants, their seeds or growing areas are simultaneously or independently treated with an effective amount of a herbicidal sulfonylurea of formula (I) and herbicide antagonist quinoline. of the compounds of formula (II).

Of the crops which are protected by the quinoline derivatives against the harmful effects of the herbicides mentioned above, particular attention shall be paid to those which are important in the food industry, in the textile industry such as sugar cane and in particular millet, maize, rice and other cereal crops such as wheat, rye, barley and oats, with particular reference to wheat, barley, rye and oats, wheat and barley being particularly preferred.

To control weeds, it can handle both single weeds and many weeds. Of the cultivated areas, those already planted with crops, as well as cultivated soils for the cultivation of crops, are of greater interest.

The antidote according to formula (II) can be used to improve the seeding quality of the crop (seed treatment) by placing it in the soil before or after sowing. But it can also be used alone or in combination with a herbicide before or after emergence. The time of treatment of plants or seeds with antidotes is, in principle, independent of the time of application of phytotoxic chemicals. However, simultaneous treatment of plants with phytotoxic agents and an antidote is also possible. Pre-sowing includes both pre-sowing and cultivation of sown areas that have not yet germinated.

The ratio of the application rate of the antidote to the amount of herbicide depends on the type of application. When treating the fields, be it a combination of an antidote and an herbicide (mixture), or a separate use of an antidote and an herbicide, the ratio of an antidote to an herbicide is, as a rule, 1: 100 to 10: 1, preferably 1:20 to 10: 1.

As a rule, between 0.001 and 5 kg of antidote per hectare is applied for field treatment, and preferably 0.005 to 0.5 kg of antidote / ha.

The rate of application of the herbicide is, as a rule, between 0.001 and 2 kg per hectare, but the most suitable dose is between 0.001 and 0.5 kg / ha,

For seed treatment, the antidote is 0.001 to 10 g / kg of seed, preferably 0.05 to 2 g / kg of seed. If the antidote is used in liquid form, the seed solutions immediately prior to sowing are the concentration of the substance by dipping, those containing 1 to about 10000 ppm of active ingredient, preferably 100 to 1000 ppm.

in the form of.

compilation, watering,

The compounds of formula (II), or combinations thereof with application of antagonizing herbicides, are simply formulated in formulations and formulated in the form of emulsion concentrates, coloring pastes, spray, dilute solutions, dilute emulsions, spray powders, spray powders, as well as the types of capsules packaged, for example, in polymeric materials, the methods of application such as spraying, fogging, spraying, spreading, as well as the types of agents used and the material ratios are appropriately selected according to the purpose pursued.

Molded Materials, Vol. y. preparations consisting of a substance of the formula (II) or of a substance of the formula (I) in combination with an anticoagulant herbicide of the formula (II) and, where appropriate, a solid or liquid adjuvant, in a known preparation or composition, e.g. and / or by grinding with additives such as diluents, solid carriers and, where appropriate, surfactants (tensides).

Solvents may be: aromatic hydrocarbons, especially C ₈ -C ₁₂ fractions such as xylene mixtures or naphthalenes, phthalic acid esters such as dibutyl or dioctyl phthalate, aliphatic hydrocarbons such as cyclohexane or paraffin, alcohols or glycols as their ethers. and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl or ethyl ether, ketone as cyclohexanone, highly polarized solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as epoxidized vegetable oils as epoxidized coconut nut oil or soya oil; or water.

As solid carriers, for example, in the form of dustable powders, spreadable powders, natural crushed rocks such as calcite, talc, kaolin, montmorillonite or atapulgite are used. High dispersion silicic acid or high dispersion absorbent polymers may be added to maintain physical properties. Porous types such as pumice stone, brick scrap, sepionite or concrete are used as granular absorbent granules, such as calcite or sand as non-absorbent granule carriers, and many times crushed inorganic or natural organic materials can be used, as especially dolomite or crushed plant remains.

O

As surfactants, nonionic, cationic and / or anionic surfactants with good emulsifying, spreading and wetting properties, depending on the material to be formulated according to formula (I) and the herbicide antagonizing antidote according to formula (II), may be present. By the term tensides are meant mixtures of tensides.

Suitable anionic surfactants include both so-called soluble soaps and soluble synthetic surfactants.

As soaps may be listed alkaline earth or ammonium, in each case substituted aukštes20 Niujie fatty acids (C ₁₀ -C ₂₂₎ salts as an example.

mixtures of oleic or stearic acids or natural fatty acids such as coconut oil or tallow Na or K salt. The salts of the fatty acid methyltaurine may also be mentioned below.

However, so-called synthetic tensides are commonly used, especially sulfonated fats, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Sulfonated fats are, as a rule, alkaline or earth alkaline or, as appropriate, substituted ammonium salts having an alkyl radical of 8 to 22 carbon atoms to which a carboxyl group is attached, for example: lignin sulfonic acid, dodecyl sulfuric acid ester or natural fatty acids acid Na- or Cadrus salts. Also included here are the sulfate salts and the fatty-acid alcohol-ethylene oxide adduct salts of sulfonic acids. The sulfonated benzimidazole derivatives usually have 2 sulfonic acid groups and one fatty acid radical with 8-22 atoms. Alkylarylsulfonates are, for example: Na-, Ca- or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or naphthalenesulfonic acid-formaldehyde condensation products.

Corresponding phosphates may also be mentioned below, such as the salts of the pnonylphenol- (4-14) -ethylene oxide esters of phosphoric acid esters or phospholipids.

Nonionic tensides include, in particular, aliphatic or cycloaliphatic alcohols, polyglycolether derivatives, saturated or unsaturated fatty acids and alkylphenols, which may have 3-30 glycol ether groups and 8-20 carbon atoms in the hydrocarbon radical and 6-18 carbon atoms in the alkylphenol alkyl radical.

Further suitable nonionic surfactants are soluble polyethylene oxide products having 20-250 ethylene glycol ether groups and 10-100 propylene glycol ether groups, as well as polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1-10 carbon atoms in the alkyl chain.

The listed compounds generally have a propylene glycol unit, 1-5 ethylene glycol units.

Examples of nonionic surfactants include nonylphenolpolyethoxyethanol, castor oil polyglycolether, polypropylene-polyethylene oxide, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.

Next. fatty acid esters of polyoxyethylene sorbitan are also considered, such as polyoxyethylene sorbitantrioleate.

Of the cationic tensides, the most preferred are the quaternary ammonium salts having at least one alkyl radical of 8-22 C atoms as N-substituents, and the lower, optionally halogenated alkylbenzyl or lower hydroxyalkyl radicals being provided as further substituents. The salts are usually halides, methylsulphates or ethylsulphates, such as stearyltrimethylammonium chloride or benzyl di- (2chloroethyl) -ethylammonium bromide.

Tensides used in forming techniques are described in the following publications:

Mc Cutcheon's Detergents and Emulsifiers Annual MC Publishing Corp., Ridgewood New Jersey, 1981. Stache, H., Tensid-Taschenbuch, Carl Hanser Verlag, Munich / Wien, 1981.

The agrochemical mixtures will, as a rule, contain from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight of the substance according to formula II or from 1 to 99.9% by weight of the compound ANTIDOT / herbicide, in particular from 5 to 99.8, of a solid or liquid additive and from 0 to 25% by weight, in particular 0.1 to 25% by weight, of tenside.

Then, when the manufactured product is most suitable concentrated, as a rule, dusting powder is used.

The formulation may also contain the following impurities: stabilizers, foam absorbers, viscosity regulators, coupling agents, binders, as well as fertilizers or other materials required to achieve a special effect.

The use of compounds of formula (II) or preparations containing them for the control of crop plants against the harmful herbicide of formula (I) involves consideration of various methods and means, such as:

(i) seed treatment

(a) Seed dressing of the seed material of formula (II) by shaking (shaking) in a container to uniform distribution of the powder on the seed surface (dry dressing), using about 1 to 500 g of material of formula (II) (4 g to 2 g) kg of powder) 100 kg of seeds.

b) Seed treatment of the emulsion with concentrate of formula (II) according to method a) (wet staining).

(c) seed treatment by immersion of the seeds in a solution of 100 to 1000 ppm of the compound of formula (II) for a period of 1 to 72 hours, followed by drying (seed treatment by immersion).

As a rule, from 1 to 1000 g of an antidote, preferably from 5 to 250 g, per 100 kg of seed are used, but deviations from the upper or lower concentration limits are possible when using a technique that allows the use of additives of other substances.

(ii) Mixture application

Liquid treatment with a mixture of an antidote and a herbicide (in a ratio of between 10: 1 and 1: 100) at a rate of 0.001 to 2 kg per hectare.

This mixture is applied before or after sowing.

(iii) Seed application in furrows

Antidote in the form of an emulsion concentrate, spray powder or granules is placed in a seeded seed furrow, then the furrow is covered. This way the herbicide is applied before emergence.

(iv) Controlled Release

The material of formula (II) is added to a mineral granule-carrier solution or a polymerized granulate (urea / formaldehyde) and left to dry. In this case, a sheath (sheath granulate) is formed which allows the material to be delivered in a dosage at a predetermined time.

Preparation of Mixtures of Substances of Formula (I) with Antidote of Formula (II) (% -Wt%)

F1. Solutions a) b) c) d) Mixture of materials 5% 10% 50% 90% Dipropylene glycol-methyl ether - 20% 20% - Polyethylene glycol MG400 20% 10% - - N-methyl-2-pyrrolidone - - 30% 10% Aromatic hydrocarbons mixture C ₉ -C ₁₂ 75% 60% - - The solutions are ready for use small droplets. F2. Spray powder a) b) c) d) Mixture of materials 5% 25% 50% 80% Na ligandsulfonate 4% - 3% - Na-lauryl sulfate 2% 3% - 4% Na-diisobutylnaphthalenesulfonate - 6% 5% 6% Octylphenol-polyglycol ether (7-8 Mol EO)) - 1% 2% -

High Dispersion Silicic Acid

88% 62% 35%

The material is well mixed with additives and well ground in a mill. This gives a powder that can be diluted

water to the desired concentration suspensions. F3. Sheathed grannies a) b) c) Mixture of material 0.1% 5% 15% High Dispersion Silicic Acid 0.9% 2% 2% Inorganic carriers (0.1-1 mm) as e.g. CaCO ₃ or SiO ₂ 99% 93% 83%

The substance is dissolved in methylene chloride, sprayed on vehicle, followed by solvent is evaporated in a vacuum. F4. Coated granules a) b) c) Mixture of material 0, 1% 5% 15% Polyethylene glycol MG200 1.0% 2% 3% High Dispersion Silicic Acid 0, 9% 1% 2% Inorganic carriers (0.1-1 mm) as e.g. CaCO ₃ or SiO ₂ 98.0% 92% 80%

Finely ground materials are evenly applied to the moistened carrier in the mixer. In this way, we obtain shell granules (without dust).

F5. Extruded Granules a) b) c) d) Mixture of materials 0.1% 3% 5% 15% Na-lignin sulfonate 1.5% 2% 3% 4% Carboxymethylcellulose 1.4% 2% 2% 2% Kaolin 97% 93% 90% 79%

The material is mixed with additives, rinsed and moistened with water. This mixture is extruded and finally air-dried.

F6. Preparation in the form of dust a) b) c) Mixture of materials 0.1% 1% 5% Talk 39.9% 49% 35% Kaolin 60% 50% 60%

A suitable dustable powder is obtained, where the material is mixed with carrier materials and ground in a mill.

F7. Suspensions-concentrates a) b) c) d) Mixture of material 3% 10% 25% 50% Ethylene glycol 5% 5% 5% 5% Nonylphenol-polyglycol ether (15 Mol EO) - 1% 2% - Na-lignin sulfonate 3% 3% 4% 5% Carboxymethylcellulose 1% 1% 1% 1% 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%

Finely ground materials are thoroughly mixed with additives. This gives a suspension concentrate which can be diluted with water to make a suspension of the desired concentration.

Biological examples

The ability of the compounds of formula (II) to protect crops against the phytotoxic effects of potent herbicides can be seen in the following examples.

BI Example: Phytotoxic effect of herbicide of formula (I) and herbicidal mixture of formula (II) on wheat and barley after germination

Wheat and barley were grown in plastic cups up to the 4-leaf stage under house-growing conditions. At this stage, the test plants were treated exclusively with the herbicide according to Table I and also separately with the mixture of herbicide and antidote according to Table 2. The treatment was carried out with an aqueous suspension according to Example F7, spraying with 500 l of water / ha. 28 days after treatment, results were evaluated on a percentage scale. 100% means test plants killed, 0% means no phytotoxic effects. The results obtained are shown in Table BI. The results show that the antidote according to Table 2 clearly reduces the damage to the wheat and barley herbicide according to Table I.

Table 1: Compounds of Formula I

Jung. No. ^R 1 r ₂ r ₃ Phys. parameters 1.01 ch ₃ ch ₃ H 1.02 and ₃ ch ₃ H 1.03 and ₃ and ₃ H 1.04 ch ₃ and ₃ 4-F > 140 ° C

Table 2: Compounds of Formula II

X

O Clli-C.-0-ft

I!

O

Jung. No. X R 2.01 Cl I-Methylhexyl 2.02 Cl hydrogen 2.03 Cl n-octyl 2.04 Cl I-Methylpropyl

Table BI:

The application rate of the antidote in the table is 125 g / ha

Herbicide Jung. No. Herbicide amount of use Antidoto Compound No. Phytotoxic effect,% Wheat Barley 1.01 60 g / ha - - 80 1.01 30 g / ha - - 65 1.01 60 g / ha 2.01 - 40 1.01 30 g / ha 2.01 - 20th 1.02 15 g / ha - 85 - 1.02 15 g / ha 2.01 15th - 1.02 15 g / ha 2.02 15th - 1.02 15 g / ha 2.03 25th - 1.02 15 g / ha 2.04 15th - 1.03 15 g / ha - - 70 1.03 8 g / ha - - 40 1.03 15 g / ha 2.01 - 30th 1.03 8 g / ha 2.01 - 10th 1.04 60 g / ha - 15th 40 1.04 60 g / ha 2.01 0 20th

The same results are obtained from the compounds of formula (I) according to Examples F1 to F6.

some preparation and (II) formulas

Claims (9)

1. A herbicidal selective herbicide for crop useful crops, characterized in that the mixture, together with carriers and additives, comprises: (a) an effective amount of a herbicidal sulfonylurea of formula (I) K, wherein R _x and R ₂ , independently of one another, represent methyl or methoxyl; R ₃ represents hydrogen, halogen, methyl or methoxyl; and (b) a quinoline derivative of the herbicide antagonist quinoline of formula (II) v II wherein R is hydrogen or C _x -C ₈ alkyl and X is hydrogen or chloro. A horn preparation according to claim 1, wherein R _x is methoxyl, X is chlorine and R is 1-ylhexyl. 3. A preparation according to claim 1, wherein R _x is methyl and R ₂ is methoxyl. 4. A formulation according to claim 3, wherein X is chlorine and R is C ₄ -C ₈ alkyl. 5. A formulation according to claim 4 wherein R is 1-methylhexyl. 6. A preparation according to claim 1, characterized in that it contains a herbicidally effective amount of a sulfonylurea of formula (Ia) and an amount of a protective herbicide antagonist quinoline derivative of formula (Ha). (Ha) 7. The selective control of the herbicide according to the formula (I) of claim 1 and the herbicide antagonist 1,5-diphenylpyrazole, together with the herbicide according to formula (I) and the herbicide antagonist. In an amount of a 3-carboxylic acid derivative according to formula 1 (II). 8. The method of claim 7, wherein the crop plants or their growing areas are treated with (0.001-2) kg / ha of the compound of formula (I) of claim 1 and (0.001-5) kg / ha of the compound. 10 according to formula (II) in claim 1. Use of the method of claim 7 for selective control of weeds and grasses in cereals. Use of the method according to claim 9 in cereals, characterized in that the cereals are wheat and barley.