KR840000270B1 - Insect compositions - Google Patents

Abstract

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Description

Herbicide composition

The present invention relates to 1 part by weight of 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenylether (A) and pyrazole derivatives (B) represented by Formula (I). (B) blended at a ratio of 0.3 to 3 parts by weight, showing a significant synergistic effect that cannot be expected for each single commercial use, and can be used to kill many kinds of problem weeds as a low dose capacity. will be.

In the above general formula, X represents a penacyl group or 4-methylphenacyl group.

At present, a number of herbicides have been put into practical use as power herbicides, and are widely used as a single agent and a mixed agent. However, hydrangea weeds come in many varieties and are effective herbicides for yearly weeds, but few herbicides are effective for perennial weeds. As a result, perennial weeds are increasing, and the control is therefore despairing.

Perennial weeds are generally very active, long-lived, and strong seaweeds. Therefore, as a herbicide, the thing of the broad property of the herbicide spectle which can kill many kinds of weeds is desired.

In addition, in recent years, the introduction of mechanization and the early stage of transplantation are spreading rapidly, providing a place suitable for weed generation more than before, and complete weed control cannot be expected for one weeding. There is a tendency. As a result, the same or different herbicides are repeatedly used several times. The repeated use of such herbicides is not only large and requires a lot of effort, but also poses undesirable problems such as water weakness and soil residue resulting from large amounts of use.

The present inventors have continued to search for safe herbicides for the purpose of ameliorating these problems in conventional herbicides, by completely spraying all the weeds in a single spray, and having a high stability against water and having very low toxic toxicity. As a result, by knowing that the outstanding herbicide which improved these problems is obtained by mix | blending two active ingredients, this invention was completed.

That is, the present invention is a mixture of a known 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenylether (A) and a pyrazole compound (I) of general formula (I) as a herbicide for water intake. .

In more detail, this invention (A) which is one of the components of this herbicidal composition has a high effect with respect to wild grass, selectivity with rice bark, and high safety with rice. In addition, broadleaf weeds and perennial weeds such as olme, tadpoles, etc. are also active as early growth treatment, but the effect is weakened as the growth progresses.

On the other hand, the pyrazole-based compound (B) does not adversely affect the water supply in the faucet, and the annual herbaceous weeds, broadleaf weeds, and beetroic acids also have an effect on perennial weeds such as peels. However, if the weeds are treated to some extent when the drug is treated, the effect is lowered, especially the effect on the grass becomes insufficient.

However, the mixture of both was used to examine the herbicidal effects and the like, and as a result, it was surprising that the grass width was extended beyond the range of application obtained as an individual herbicide. Weeds, tadpoles, beetles, and even perennial weeds, such as snares, have been extended, and further, the effect of spreading can be expanded without compromising the safety of the water supply. Moreover, this herbicide can fully exhibit the effect as a mixture of much lower doses than a single unused dose, and can increase the herbicidal efficacy enough as a one-time treatment agent, and its effect lasts for a long time.

The compound (I) of formula (I), which is an active ingredient of one of the herbicides of the present invention, can be easily substituted by alkylating compound (II) as a substituted alkylating agent corresponding to group X, for example, as shown in the following scheme. It can manufacture.

(Wherein X is as defined above)

As the substituted alkylating agent corresponding to the group X, for example, halides such as chlorides, sulfides and oxides are particularly suitably used.

The reaction represented by the above formula is suitably carried out in the presence of a solvent, and the solvent is not particularly limited as long as it is not involved in the present reaction. For example, ethers such as diethyl ether, tetrahydrofuran and dioxane Aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, and trichlorethane, ketones such as acetone and isobutyl methyl ketone, ethyl acetate, and amyl acetate Esters, acetonitrile and the like and mixed solvents thereof, but aromatic hydrocarbons and ethers are suitably used. When using a halide as a substituted alkylating agent, it is preferable to use a deoxidizer, and such deoxidizers include, for example, inorganic bases such as sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, N, N-diethylaniline, and the like. Organic bases.

The reaction temperature is not particularly limited and is performed as a reflux temperature of the room temperature to the solvent. The reaction time depends on the reactant and the reaction temperature and is usually 30 minutes to 24 hours.

After the completion of the reaction, the target product is isolated according to the conventional method and, if necessary, is purified by a method such as column chromatography, recrystallization or the like.

The manufacturing method of the compound of Formula (1) which is an active ingredient of this invention is demonstrated according to the following manufacture.

[Production Example 1]

A mixture of 1.425 g of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-hydroxypyrazole, 15 ml of benzene, 0.505 g of triethylamine, and 0.995 g of phenacylbromide was stirred and heated for 1 hour. Reflux. After cooling, water was added to separate the salts, washed with 5% aqueous sodium bicarbonate solution, followed by water, dried over anhydrous sodium sulfate, and the solvent was organic to yield 1.75 g of an oily substance. This was separated by column chromatography (elution as silica gel: benzene: ethyl acetate: 6: 1) to give 1.2 g (yield: 59.6%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- Phenaciloxypyrazole (Na-1) is obtained. Melting point 109.5-110.5 ° C. (recrystallized from n-hexane).

[Production Example 2]

To 10 g of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-hydroxypyrazole, 70 ml of acetonitrile and 4.85 g of potassium carbonate (anhydrous) were added, stirred at room temperature for 2 hours, and phenacylbromide 7.7 The solution dissolved in 10 ml of acetonitrile was added, it stirred, and it refluxed for 1 hour. The salts are filtered off, the filtrate is concentrated and benzene is added, washed with an aqueous sodium bicarbonate solution followed by water. After drying over anhydrous sodium sulfate and distilling off the solvent, n-hexane was added to crystallize and filtered. 12.88 g (yield: 91.2%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- Phenaciloxypyrazole (Na-1) is obtained. Melting point 109.5-110.5 ° C. (recrystallized from n-hexane).

According to the method of 1-2 for the above preparation, the following compounds are prepared.

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (4-methylphenacyloxy) pyrazole

4- (2,4-dichlorobenzoyl) -5- (3,5-dichloro-4-methylphenacyloxy) -1,3-dimethylpyrazole

Melting point 124-125 ℃

4- (2,4-dichlorobenzoyl) -5- (3,5-dichloro-4-methoxyphenacyloxy) -1,3-dimethylpyrazole

Melting point 135-136 ℃

The mixture shown in the present invention is a novel combination of non-documentation, and of course, no document mentions its specific potency. The synergism according to the present invention is recognized as a wide range of mixing ratios, and a useful herbicide can be prepared by mixing the compound (B) represented by the general formula (I) at a ratio of 0.3-3 parts by weight with respect to 1 part by weight of the compound (A). have. The herbicide of the present invention thus completed has an effect even when treated before and after germination of weeds, and a high effect can also be obtained by soil treatment and foliage spray treatment. It is useful not only for water, but also for various grains, legumes, cotton, vegetables, orchards, grasses, grasslands, tea gardens, fields, woodlands, and non-crop lands.

The mixture of the present invention may be sprayed as it is, but may be mixed with a carrier and other auxiliary agents as necessary to form a formulation commonly used as a herbicide, for example, a powder, a powder, a granule, a granule, a hydrating agent, an emulsion, an aqueous solution, an aqueous solution. Agent, suspending agent and the like are used.

Suitable solid carriers used in the preparation of the herbicides of the present invention include clays, talc, mica, lobite, pumice, burr keyrite, gypsum, calcium carbonate, and the like represented by kaolinite group, montmorillonite group or attabarzite group. Inorganic substances such as dromite, diatomaceous earth, magnesium lime, apatite, zeolite, silicic anhydride, synthetic calcium silicate, soybean flour, edible powder, hoe powder, wheat flour, wood powder, starch, vegetable organic materials such as crystalline cellulose, Kumar Synthetic or natural polymer compounds such as ron resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, kobal gums, terminal gums, waxes such as carnabarab and beeswax, or urine Etc. can be mentioned.

Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil and white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene and methylnaphthalin, carbon tetrachloride, chloroform and tri Chlorinated hydrocarbons such as chlorethylene, monochlorbenzene, and 0-chlortoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetphenone, and isophorone Esters such as ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, methanol, n-hexanol, ethylene glycol, dimethylene glycol, cyclohexanol, benzyl alcohol, etc. Alcohols, ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether LE may be mentioned alcohols, dimethyl formamide, and a polar solvent or water, such as dimethyl sulfoxide.

Surfactants used for the purpose of emulsification, dispersion, wetting, expansion, binding, disintegration control, active ingredient stabilization, fluidity improvement, rust prevention, etc. may be any of nonionic, anionic, cationic and cationic, but are usually used. Silver nonionic and / or anionic ones are used. Suitable nonionic surfactants include, for example, polymerized addition of ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, and polymerization of ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol. Addition, polymerization addition of ethylene oxide to alkalnaphthol, such as butyl naphthol and octylnaphthol, polymerization addition of ethylene oxide to higher fatty acids such as palmyric acid, stearic acid and oleic acid, dilaurylphosphate stearyl phosphate Polymerized addition of ethylene oxide to mono or dialkyl phosphoric acid such as polymerized product. Polymerized and added ethylene oxide to amines such as dodecylamine and stearic acid amide. Higher fatty acid esters of polyhydric alcohols such as sorbitan and ethylene oxide And polymerized addition of ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, alkyl sulphate ester salts such as sodium lauryl sulfate and oleyl alcohol sulfate amine salts, alkyl sulfonates such as sulphate and dioctyl ester sodium and 2-ethylhexene sulfone sodium, and isopropyl naphthalene sulphate. Aryl sulfonates, such as sodium fonate, the methylene naphthalene sulfonate, sodium lignin sulfonate, and dodecylbenzene sulfon sodium, etc. are mentioned.

In addition, the herbicide of the present invention contains casein, gelatin, albumin, glue, sodium arginate, carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose for the purpose of improving the properties of the formulation and enhancing the biological effect. You may use together high molecular compounds, such as polyvinyl alcohol, and another adjuvant.

The above carriers and various auxiliaries are appropriately used alone or in combination according to the purpose in consideration of the formulation of the preparation, the application scene, and the like.

The powder contains, for example, 1 to 25 parts by weight of the active ingredient compound, and the balance is a solid carrier.

The hydrating agent usually contains, for example, 25 to 90 parts by weight of the active ingredient compound, and the balance is added to the protective colloid material, thixotropy agent, antifoaming agent and the like as a solid carrier and a dispersion wetting agent.

The granules usually contain, for example, 1 to 35 parts by weight of the active ingredient compound, and the balance is mostly a solid carrier. The active ingredient compound is uniformly mixed with the solid carrier or uniformly fixed or adsorbed on the surface of the solid carrier, and the grain diameter is about 0.2 to 1.5 mm.

The emulsion contains, for example, 5 to 30 parts by weight of an active ingredient compound, which contains about 5 to 20 parts by weight of an emulsifier, the remainder being a liquid carrier, and a rust inhibitor is added as necessary.

The formulation example of this herbicide is shown below.

Formulation Example 1

20 parts by weight of compound (B-1), 20 parts by weight of compound (A), 2.5 parts by weight of dodecylbenzenesulfonate, 2.5 parts by weight of lignin sulfonate and 55 parts by weight of diatomaceous earth are well ground and mixed to obtain a hydrate.

Formulation Example 2

15 parts by weight of compound (B-2), 5 parts by weight of compound (A), 15 parts by weight of emulsifier sorbol SM 100 (Tohoka Kagaku®) and 65 parts by weight of xylene are mixed well to obtain an emulsion.

Formulation Example 3

5 parts by weight of compound (B-1), 3 parts by weight of compound (A), 3 parts by weight of white carbon, 5 parts by weight of lignin sulfonate, and 84 parts by weight of clay are mixed well, added with water, and then well assembled and dried. Get granules.

Formulation Example 4

40 parts by weight of bentonite, 5 parts by weight of lignin sulfonate and 55 parts by weight of clay are pulverized and mixed, and then granulated and dried after mixing with water, kneading to form granules containing no active ingredient. 7 parts by weight of compound (B-1) and 7 parts by weight of compound (A) are impregnated to 86 parts of the granular material to form a granule.

[Test Example 1]

Put water into 1 / 5000a wagnellpot filled with 3kg of faucet soil and put it into the faucet state. In this port, sowing seeds of broadleaf weeds such as estuary bark, tadpoles, grass of grass, and flowers of knot After planting tubers of Sanyi, transplanted 2.5 seedlings of rice seedlings again, growing plants with pots in a greenhouse at 20-25 ° C, and preparing a certain amount of medicine with a hydrating agent at the time of the first leafing period 7 days after sowing. And diluted in water and then treated with 10 cc per pot. It was then grown in a greenhouse and examined herbicidal effects 25 days after drug treatment. The herbicidal effect was expressed as numbers of 0-10 according to observations of abscess rate, degree of whitening, and the like. The results are shown in the first table.

Billion second rate

[Table 1]

The numbers in Table (1) above are the estimated values (PE) of the weed suppression values of the compounding agents calculated by the following Colby's formula as a synergistic assay.

PE = Pa + Pb (10-Pa) / 10 (Pa: suppression value in ag of herbicides)

(Pb: Inhibitory value in herb bg)

As a result, the measured value (PC) of the inhibitory value of a compounding agent is larger than the expected value (PE), and it demonstrates that the synergistic effect is remarkable.

Claims (1)

(A) To 1 part by weight of 2,4-dichlorophenyl-3'-methoxy-4'-nitrophenylether (A) and pyrazole derivatives represented by the general formula (I) A herbicide composition, characterized in that the composition is mixed in a proportion of 0.3 to 3 parts by weight.

In the above general formula, X represents a penacyl group or 4-methylphenacyl group.