KR960000549B1 - Synergistic composition and method for selective weed control in rice - Google Patents

Abstract

No content.

Description

Synergistic Compositions and Selective Weed Control Methods in Rice

The present invention relates to synergistic compositions containing mixtures of herbicide active ingredients which are extremely suitable for the selective control of weeds in rice crops. The invention also relates to methods of controlling weeds in rice and to the use of the novel compositions.

In the present invention, the most common and important of the weeds of rice are the species of the following genus: Alisma (Amber): Ammania: Cyperus Kind of grass)]: Echinochloa [Echinochloa (pool of barn yard)]: Eleocharis [Eleocharis]: Fimbristylis (peripheral grass)]: Sirpus [Scirpus Genus) and Monochoria.

N- [2- (2-methoxyethoxy) -phenylsulfonyl] -N '-(4,6-dimethoxy-1,3,5-triazin-2-yl) of the following structural formula (I)- Urea has proven to be an excellent selective herbicide for weeds in crops of useful plants:

Such active ingredients, as well as their preparation and use, are described in US Pat. No. 4 479 821.

In addition, general formulas (II), (III), (IV), (V), (VI), (VII), (VII), (VII), (VII), (VII), (VII), and (VIIIII) ), (XIV) and (XV) compounds are also known as selective herbicides. Some of these are already commercially useful.

The following general formula (II) wherein R ¹ represents C ₁ -C ₄ alkoxycarbonyl or C ₁ -C ₄ alkoxy includes the following specific examples:

(IIa): 5- (2,4-dichlorophenoxy) -2-nitrobenzoic acid methyl ester, Pesticide Manual 5th Ed. (1977), 41, known from The British Crop Protection Council, London; And

(IIb): 4- (2,4-dichlorophenoxy) -2-methoxynitrobenzene, pesticide manual (Pesticide Manual) 5th Ed. (1977), 175, known from The British Crop Protection Council, London.

Formula (III), wherein R ² represents chlorine or methyl, includes the individual active ingredients as follows:

(IIIa): 2,4-dichlorophenoxyacetic acid, insecticide manual 5th Ed. (1977), 330, known from The British Crop Protection Council, London; And

(IIIb): 4-chloro-2-methylphenoxyacetic acid, insecticide manual 5th Ed. (1977), 330, known from The British Crop Protection Council, London.

The following general formula (IV), wherein R ³ represents ethyl or 1,2-dimethylpropyl, includes the following specific examples:

(IVa) 2,4-bis-ethylamino-6-methylthio-1,3,5-triazine, insecticide manual 5th Ed. (1977) 472, known from The British Crop Protection Council, London; And

(IVb) 2 [(1,2-dimethylpropyl) amino] -4-ethylamino-6-methylthio-1,3,5-triazine, Insecticide Manual 5th Ed. (1977), 197, known from The British Crop Protection Council, London.

The following general formula (V) wherein R ⁴ represents C ₁ -C ₄ alkoxy or C ₁ -C ₄ alkoxymethyl includes the following specific examples.

(Va): N- (butoxymethyl) -2-chloro-N- (2,6-diethylphenyl) acetamide, insecticide manual 5th Ed. (1977), 60, known from The British Crop Protection Council, London; And

(Vb): N- (propoxyethyl) -2-chloro-N- (2,6-diethylphenyl) acetamide, insecticide manual 7th Ed. (1983), 9970, known from The British Crop Protection Council, London.

R ⁵ represents 2- (2-chloroethoxy) -phenyl, 2-methoxycarbonylbenzyl or 4-ethoxycarbonyl-1-methyl-5-pyrazolyl, and R ⁶ represents methoxy or methyl In addition, the following general formula (VI), in which A represents a nitrogen or methine group, includes in particular the following individual substances:

(VIa): N- [2- (2-chloroethoxy) -phenylsulfonyl] -N '-(4-methoxy-6-methyl-1,3,5-triazin-2-yl) -urea , Known from European Patent EP-A-44807;

(VIb): N- (2-methoxycarbonylbenzylsulfonyl) -N '-(4,6-dimethoxypyrimidin-2-yl) -urea, known from EP-A-51466; And

(VIc): N- (4-ethoxycarbonyl-1-methylpyrazol-5-ylsulfonyl) -N '-(4,6-dimethoxypyrimidin-2-yl) -urea, EP-A Known from -87780.

The following general formula (VII) wherein R ⁷ represents 1-piperidinyl, 1-hexahydroazinyl or diethylamino and R ⁸ represents ethyl, 4-chlorobenzyl or 1,1-dimethylbenzyl is as follows: Specific examples are included.

(Iiia): S-ethyl-N, N-hexamethylene thiocarbamate, insecticide manual 5th Ed. (1977), 369, known from The British Crop Protection Council, London;

(Iiib): S-1,1-dimethylbenzyl-N, N-pentamethylene thiocarbamate, known from JP-PS 51 098 331; And

(Xc): S-4-chlorobenzyl-N, N-diethyl thiocarbamate, insecticide manual 5th Ed. (1977), 106, known as The British Crop Protection Council, London.

The compounds of the formulas (VII), (VII), (VII), (XI), (XI), (XIIII), (XIV) and (XIV) are represented by the following formulas:

3,7-dichloroquinoline-8-carboxylic acid of formula (III) known from DE-OS 3 108 873:

2- (2-naphthyloxy) -propionic acid methyl ester of the structural formula known from DE-OS 2 247 076:

Insecticide Manual 7th Ed. (1983) 9390, N- (1-ethylpropyl) -3,4-dimethyl-2,6-dinitroaniline of the structural formula known from The British Crop Protection Council, London:

Insecticide Manual 5th Ed. (1977), 393, 5-tert butyl-3- (2,4-dichloro-5-isopropoxyphenyl) -1,3,4- of the formula (VII) known from The British Crop Protection Council, London. Oxadiazol-2-one:

Insecticide Manual 5th Ed. (1977) 35, 3-isopropyl-1H-benzo-2,1,3-thiadiazin-4-one-2,2-dioxide of formula (VIIII) known from The British Crop Protection Council, London:

2- (2-benzothiazolyloxy) -N-methylacetanilide of the formula (XIII) known from DE-OS 2 822 155:

Insecticide Manual 5th Ed. (1977), 439, 3,4-dichloropropionanilide of the following structural formula (VII) known from The British Crop Protection Council, London:

Insecticide Manual 5th Ed. (1977), 427, S-2-methylpiperidinocarbonylmethyl-0,0-dipropyldithiophosphate ester of formula (VV) known from The British Crop Protection Council, London:

Surprisingly, the synergistic effect of a mixture of both quantitatively changeable active ingredients, one of which is the active ingredient (I) and the other of the active ingredient (XII), allows the control of most important rice weeds without damaging the rice crop. Was found. For example, the major weeds in rice crops such as Alisma, Ammania, Cyperus, Echinoloa, Eleocharis, Warb Bristilis, Cyrpus and MonoKorea are the pre- and post-germination methods. Can be selectively removed.

Therefore, according to the present invention, one of N- [2- (2-methoxyethoxy) -phenylsulfonyl) -N '-(4,6-dimethoxy-1,3,5 of the following structural formula (I) A novel synergistic composition for the selective control of weeds, which contains both active ingredients in the form of a mixture of -triazin-2-yl) -urea, the other being the active ingredient of the general formula (XII) Is provided:

[Formula 1]

[Formula 12]

A mixture of the active ingredient of general formula (I) and the active ingredient of general formula (XII), as generally expected, further broadens the spectrum of action of weed control agents normally present in relation to rice, as well as both in two respects. It is extremely surprising that a synergistic effect is obtained that broadens the range of action of the formulation.

First, the individual doses of compounds (I) and (XII) can be significantly reduced while maintaining a high level of action, and secondly, even when the effects of the two compounds are completely ineffective when the dose is extremely low. The mixture can still achieve high levels of weed control. As a result, the weed spectrum is significantly expanded and further marginal safety is increased in rice, as necessary and desirable in case of inadvertent overdose of the active ingredient.

The composition according to the invention can be used for both rice crops grown in water (rice fields) and rice crops grown in dry land (highland rice).

The active ingredient mixture according to the present invention contains the active ingredient of general formula (I) and the active ingredient of general formula (XII) in any mixing ratio, and generally contains an excess of any one component compared to the other components. Since the mixing ratio is not very important, both an excess of the components of the formula (I) and an excess of the components of the formula (XII) are allowed. The preferred mixing ratio of the active ingredient (I) to the co-component of formula (XII) is 1: 1 to 1: 2000, in particular 1: 5 to 1: 500. The active ingredient mixtures according to the invention show an excellent action against weeds without the effect of a dozen on rice crops when advantageously used at a dose rate of 0.005 to 3 kg, preferably 0.01 to 1 kg per hectare.

Suitable solvents are: aromatic hydrocarbons, preferably aromatic hydrocarbons containing 8 to 12 carbon atoms, for example xylene mixtures or substituted naphthalenes; Phthalates such as dibutyl phthalate or dioctyl phthalate; Aliphatic hydrocarbons such as cyclohexane or paraffin; Alcohols and glycols such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ethers and esters thereof; Ketones such as cyclohexanone; Strong polar solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide; And also optionally epoxidized vegetable oils such as, for example, epoxidized coconut oil or soy bean oil; Or water.

Solid carriers used in spraying and dispersible powders are usually natural mineral fillers such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acid or highly disperse absorbent polymers can be added to improve physical properties. Suitable particulate adsorptive carriers are, for example, porous forms such as pumice, crushed bricks, sepiolite or bentonite; Suitable non-absorbent carriers are also materials such as calcite or sand. In addition, many inorganic or organic glandular substances, for example dolomite or powdered plant residues (eg cork powder, sawdust) can be used.

Particularly advantageous among the dosing aids which can significantly reduce the dosage rate are also phosphatidylethanolamine, phosphatidylserine, which can be obtained, for example, from animal or plant cells, especially brain, heart, lung, liver, egg yolk or soybeans, Synthetic phospholipids or natural (animal or vegetable) phospholipids from the ceparin and lecithin family such as phosphatidylcholine, spinomielin, phosphatidylinositol, phosphatidylglycerol, lysocithin, plasmagen or cardiolipin. Commercial mixtures that can be used are, for example, phosphatidylcholine mixtures. Synthetic phospholipids are for example dioctanoyl phosphatidylcholine and dipalmitoylphosphatidylcholine. Suitable surfactant compounds may be nonionic, cationic and / or anionic surfactants with good emulsifying, dispersing and wetting properties. The term “surfactant” is also understood to include mixtures of surfactants.

Suitable anionic surfactants can be both so-called water-soluble soaps and water-soluble synthetic surfactant compounds.

Alkali metal salts, alkaline earth metal salts or substitutions of high fatty acids (C ₁₀ -C ₂₂ ), such as sodium salts or potassium salts of, for example, oleic or stearic acid, or natural fatty acid mixtures obtainable from coconut oil or animal oils as soaps. Or unsubstituted ammonium salts may be mentioned. Fatty acid methyltaurine salts may also be mentioned.

However, so-called synthetic surfactants are often used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.

Fatty sulfonic acid salts or fatty sulfates are usually substituted or unsubstituted alkali metal salts, alkaline earth metal salts, such as sodium or calcium salts of fatty alcohol sulfate mixtures obtained from lignosulfonic acid, dodecyl sulfate esters or natural fatty acids. It is in the form of ammonium salts and contains C ₈ -C ₂₂ alkyl radicals (including alkyl sites of acyl radicals). Such compounds also include sulfate ester salts and sulfonic acid salts of fatty alcohol / ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain one fatty acid radical containing 8 to 22 carbon atoms and two sulfonic acid groups. Examples of alkylarylsulfonic acid salts are the sodium, calcium or triethanolamine salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid, or naphthalenesulfonic acid / formaldehyde condensation reaction products. Also suitable are the corresponding phosphates, such as, for example, phosphate ester salts of adducts of 4 to 14 moles of ethylene oxide and p-nonylphenol.

Suitable nonionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which have 3 to 30 glycol ether groups and 8 to 20 carbons in the (aliphatic) hydrocarbon radical. And alkyl radicals of alkylphenols containing 6 to 18 carbons. More suitable nonionic surfactants are water soluble adducts of polyethylene oxide and polypropylene glycol, ethylene diaminopoly propylene glycol and alkylpolypropylene glycols containing from 1 to 10 carbons in the alkyl chain, which adducts range from 20 to 250 It contains ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit.

Representative examples of nonionic surfactants are nonylphenolpolyethoxyethanol, castor oil polyglycol ether, polypropylene / polyethyleneoxide adduct, tributylphenoxypolyethoxyethanol, polyethyleneglycol and octylphenoxypolyethoxyethanol. Fatty acid esters of polyoxyethylene sorbitan such as, for example, polyoxyethylene sorbitan trioleate are also suitable as nonionic surfactants.

Cationic surfactants, in particular, contain at least one C ₈ -C ₂₂ alkyl radical as an N-substituent and, as another substituent, 4 containing an unsubstituted or halogenated lower alkyl, benzyl or hydroxy lower alkyl radical. It is a quaternary ammonium salt. The salt is preferably in the form of a halide, methylsulfate or ethylsulfate, for example stearyltrimethylammonium chloride or benzyldi (2-chloroethyl) ethylammonium bromide.

Surfactants commonly used in the formulation art are described, for example, in the literature:

McCutcheon's Detergents and Emulsifiers Annual ＂, MC Publishing Corp. Ridgewood, New Jersey, 1979; Dr. Helmut Stache, “Tensid Taschenbuch”, 2nd Edition, Carl Hanser Verlag, Munich / Vienna, 1981; M. and J. Ash ＂Encyclopedia of Surfactants＂ vols. I-III, Chemical Publishing Co., New York, 1980-1981.

Pesticide formulations are usually from 0.1 to 95%, in particular from 0.1 to 80% of the active ingredient mixtures of formulas (I) and (XII), from 1 to 99.9% of solid or liquid auxiliaries and from 0 to 25%, especially from 0.1 to 25% It contains surfactant.

Preferred formulations consist especially of the following components (% by weight).

Emulsion concentrate

Active ingredient mixture 1-20% preferably 5-10%

5-30% surfactant, preferably 10-20%

Liquid carrier 50-94% preferably 70-85%

Spray

Active ingredient mixture 0.1-10% preferably 0.1-1%

Solid carrier 99.9-90% preferably 99.9-99%

Suspension concentrate

Active ingredient mixture 5-75% preferably 10-50%

Water 94-25% preferably 88-30%

1-40% surfactant, preferably 2-30%

Wettable Powder

Active ingredient mixture 0.5-90% preferably 1-80%

0.5-20% surfactant, preferably 1-15%

Solid carrier 5.0-95% preferably 15-90%

Granulation

Active ingredient mixture 0.5-30% preferably 3-15%

Solid carrier 99.5% -70% preferably 97-85%

Commercial products are preferably formulated in concentrates, while end consumers typically use dilute formulations. Administration is carried out by diluting at a low concentration of about 0.001% of the active ingredient.

Other bactericidal active ingredients or compositions can be mixed with the above-described compositions according to the invention. For example, insecticides, fungicides, fungicides, fungicides, fungicides and nematicides in addition to compounds of general formula (I) and general formula (XII), in order to broaden the spectrum of action. Can be added to Antagonists (emollients) may also be added to protect cultivated plants from overdose of the herbicide or herbicide mixture due to inadvertent use.

Compositions according to the invention are generally formulated in detail according to the following examples.

Formulation Examples

Example F1

Formulation Examples for Synergistic Active Ingredient Mixtures of Formulas (I) and (XII) (% by Weight)

a) wettable powder

The active ingredient mixture is thoroughly mixed with the adjuvant and ground well in a suitable mill. Dilution with water gives a wettable powder capable of producing a suspension in the required concentration.

b) emulsion concentrate

Dilution with water makes it possible to prepare an emulsion of the required concentration from this concentrate.

c) spray

Mixing of the active ingredient mixture with the carrier and pulverizing the mixture in a suitable mill yields a sparge that can be easily used.

d) Extruder

The active ingredient mixture is mixed with the adjuvant, milled and then wet with water. The mixture is extruded and then dried under air flow.

(e) coating granules

In a mixer, the mixture of the finely divided active ingredient is uniformly administered to kaolin wetted with polyethylene glycol. In this way, a granule coated without dust is obtained.

(f) suspension concentrate

The finely ground active ingredient mixture is closely mixed with the adjuvant. This yields a suspension concentrate which can be prepared in suspension of any concentration required by dilution with water.

There is always a synergistic effect as far as herbicides are concerned when the herbicidal action of the active ingredient mixtures of (I) and (XII) is greater than the sum of the total action of the individually administered active ingredients.

The expected herbicidal E for a mixture of the two herbicides can be calculated as follows (Comparative: COLBY, S.R., Calculating Synergistic and antagonistic response of herbicide combinations, Weeds 15, pages 20-22, 1967).

[Equation 1]

In the above formula, X = percent growth inhibition when the herbicide (I) was treated with a dose of pkg per hectare compared to the untreated control (= 0%).

Y = percent growth inhibition when the herbicide (XII) was administered at a dose of qkg per hectare compared to the untreated control.

E = expected herbicidal action (percent growth inhibition compared to untreated control) after administration of the preparation mixture of (I) and (XII) at a dosage of p + qkg active ingredient per hectare.

If the observed action is actually greater than the expected value E, then a synergy is achieved.

Claims (7)

In addition to the carrier and / or other auxiliaries, the active ingredient is N- [2- (2-methoxyethoxy) -phenylsulfonyl)]-N '-(4,6-dimethoxy- of general formula (I) Synergistic composition for selective weed control in rice, characterized in that 1,3,5-triazin-2-yl) -urea and the other active ingredient is a compound of the general formula (XII); A composition according to claim 1, wherein component (I) is present in the composition in a weight ratio of 1: 1 to 1: 2000 relative to the second component of formula (XII). The composition according to claim 2, wherein the weight ratio of component (I) to component (XII) is from 1: 5 to 1: 500. A method of selective control of weeds in rice, characterized in that the paddy field is treated with an effective amount of the composition according to claim 1 before the plants germinate. 5. An effective amount of rice cultivation land according to claim 1, wherein the presence of weed alisma, ammonia, ciferus, echinoloa, eleocharis, whipbristils, cyprus or monoKorea is expected. Treatment with a composition according to claim 1. 6. The method according to claim 5, wherein the rice crop is treated with the composition at a dosage rate corresponding to 0.005 to 3 kg, preferably 0.01 to 1 kg, of total active ingredient per hectare. Use of an effective amount of the composition according to claim 1 for selective weed control in rice crops.