KR840000265B1 - Insect compositions - Google Patents

Abstract

A compn. contg. pyrazoles (I; X=phenacyl, 4-methoxyphenacyl) and 2-chloro-2', 6'-diethyl-N-(propoxyethyl)acetoanilide is a synergistic herbicide. Thus, a compn. contg. 4-(2, 4-dichlorobenzoyl) -1, 3-dimethyl -5- hydroxypyrazole and 2-chloro-2' ,6'-diethyl-N-(propoxyethyl)acetoanilide (3+0.5 g/are) controlled Echinochroacrus-galli, Scirpus jincoides, Sagittaria pygmaea, Cyperus serotinus, and broad-leaf weeds in rice. Other combinations are listed. Preparative data is given.

Description

Herbicide composition

The present invention relates to 2-chloro-2 ', 6'-diethyl-N- (propoxyethyl) acet anilide (A) and pyrazole derivatives represented by the following general formula (I): (A) 1 (B) Mixing 1 to 10 parts by weight, which brings about a remarkable synergistic effect that can not be expected in each short-term application, and can be used to kill many kinds of weeds with low usage A herbicide composition characterized by the above-mentioned.

In the formula, X represents a penacyl group or 4-methoxyphenacyl group.

At present, a number of herbicides have been put to practical use as a herbicide for power receiving, and are widely used as a single agent and a mixture. However, there are many types of hydrangea weeds and herbicides effective for annual weeds are numerous, but few herbicides are effective for perennial weeds. As a result, perennial weeds are increasing, and control is urgently desired.

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

In addition, in recent years, the introduction of mechanization and the early stage of transplantation have been widened rapidly, giving a suitable place for weed generation more than the conventional one, and a single herbicide application cannot expect complete weed control. It's flowing. As a result, the same or different herbicides are repeatedly used several times, and the repeated use of such herbicides requires not only a lot of effort, but also poses undesirable problems such as weakness of the water due to a large amount of application and residue in the soil. have.

As a result of improving the problems of the conventional herbicides, the present inventors have completely controlled all the weeds in one spray, and further continued to search for safe herbicides having high safety against water and very low toxin toxicity. The present invention was completed by knowing that an excellent herbicide which solved these problems was obtained by blending two active ingredients.

That is, the present invention relates to 2-chloro-2 ', 6'-diethyl-N- (propoxyethyl) acetanilide (A) and pyrazole compound (B) as described in Japanese Patent Application No. 53-23379. Composition.

When explaining the present invention in more detail, (a), one of the components of the herbicide is a wild perennial weed, which is a perennial weed, which has become a problem of wild grass, broadleaf weeds, and recent growth Although it is effective as an initial treatment and it is a herbicide which does not have weakness as a normal usage amount even for rice, the effect becomes weak when weed growth progresses.

On the other hand, pyrazole-based compounds (B) do not cause weakening in faucets in faucets, and have annual effects on perennial weeds such as rice weeds, broadleaf weeds, and bead-proof acids. However, when the weeds are grown to some extent, the drug is lowered, and the effect on the grass is insufficient. However, the mixed application of both, the herbicidal effect, the weakness and the like, as a result of the study, the weed width is extended beyond the range of application as a single agent to the surprising, the weed width is the rice family, The general broadleaf weeds, tadpoles, beetles, and even perennial weeds, such as snares, have been found to extend their spraying potential without compromising safety of the water supply. Moreover, this herbicide can fully exhibit the effect as a mixture of much lower doses than the monobolic application amount, and can increase the herbicidal effect enough enough as a single treatment agent, and its effect lasts for a long time.

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

(Wherein, X is the same as the foregoing.)

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

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

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

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

The manufacturing method of the compound (b) of Formula (I) which is an active ingredient of this invention is demonstrated by the following preparation examples.

[Production Example 1]

A mixture of 1.425 g of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-hydroxy pyrazole, 15 ml of benzene, 0.505 g of triethylamine, and 0.995 g of etasilbromide was stirred and heated for 1 hour. Reflux. After cooling, water is added to separate the salt, washed with 5% aqueous sodium bicarbonate solution, followed by water, dried over anhydrous sodium sulfate, and the solvent is distilled off to give 1.75 g of an oily substance. This was separated by column chromatography (eluted as silica gel: benzene: ethyl acetate = 6: 1) and 1.2 g (yield 59.6%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-phenacyl Oxypyrazole (Compound No. 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 as a room temperature for 2 hours, and phenacyl A solution of 7.7 g of bromide dissolved in 10 ml of acetonitrile was added, and the mixture was stirred and refluxed for 1 hour. The salts are filtered off and the filtrate is concentrated, benzene is added and washed with aqueous sodium bicarbonate solution followed by water. It was dried as anhydrous sodium sulfate, crystallized by adding n-hexane to the residue obtained by distilling off the solvent, and it was filtered. 12.88 g (yield 91.2%) of 4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5-phena Siloxypyrazole (Compound No. 1) is obtained. Melting point 109.5-110.5 ° C. (recrystallized from n-hexane).

The following compounds are prepared according to the methods of Preparation Examples 1 to 2 described above.

4- (2,4-dichlorobenzoyl) -1,3-dimethyl-5- (4-methylphenacyloxy) pyrazole (Compound No. 2)

The admixture shown in the present invention is a novel combination of non-documentation and, of course, no document mentions its specific effect enhancement. The synergy according to the present invention is recognized as a mixing ratio in a wide range, 0.1 to 10 parts by weight, preferably 2 to 6 parts by weight of the compound (B) represented by the general formula (I) to 1 part by weight of the compound (A). By mixing in proportions, useful herbicides can be made. The herbicide of the present invention thus completed has an effect even if it is treated before and after germination of the weeds, and a high effect is obtained even in soil treatment and transverse spraying treatment. It is useful not only for water, but also for various grains, cotton, vegetables, orchards, grasses, grasslands, tea gardens, mulberry fields, woodlands, and non-farmlands.

In the present invention, the admixture may be sprayed with the original itself, or 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 particulate, a granule, a hydrate, an emulsion, It is prepared by using an aqueous solution, a water soluble agent, an oil suspending agent and the like.

Suitable solid carriers used in the preparation of the herbicide of the present invention include clays, talc, mica, sidestones, pumice, vermucurite, gypsum, carbonic acid, and the like represented by kaolinite group, montmorillonite group, or attabarite group. Inorganic materials such as calcium, dromide, diatomaceous earth, magnesium lime, apatite, zeolite, silicic anhydride, synthetic calcium silicate, soybean flour, tobacco powder, walnut flour, wheat flour, wood flour, starch, vegetable organic materials such as crystalline cellulose, Synthetic or natural polymer compounds such as coumarone resins, petroleum resins, alkyd resins, polyvinyl chloride, polyalkylene glycols, ketone resins, ester gums, kobal gums, and damalum gums, waxes such as carnauba wax and beeswax; Or urine.

Suitable liquid carriers include aromatic hydrocarbons such as ketosine, mineral oil, toluene, xylene, ethylbenzene, cumene, methylnaphthalin, carbon tetrachloride, chloroform, trichloroethylene, monochlorobenzene, o-chlorotoluene and the like Ethers such as hydrocarbons, dioxane and tetrahydrofuran, acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexane, acetphenone, ketones such as isophorone, ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate Esters such as dibutyl maleate and diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol and benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether and diethylene Polar solvents such as ether alcohols such as glycol ethyl ether and diethylene glycol butyl ether, dimethylformamide and dimethyl sulfoxide or Water and the like.

Surfactants used for the purpose of emulsification, dispersion, wetting, expansion, bonding, disintegration control, stabilization of active ingredients, improvement of fluidity, rust prevention, etc. can be used with any of nonionic, anionic, cationic and zwitterionic compounds. Usually, nonionic and / or anionic ones are used. Examples of suitable nonionic surfactants include those in which ethylene oxide is polymerized with higher alcohols such as lauryl alcohol, stearyl alcohol, oleyl alcohol, and alkylnaphthols such as butylnaphthol and octylnaphthol. Polymerization addition of ethylene oxide to higher fatty acids such as polymerization addition, palmitic acid, stearic acid and oleic acid, polymerization addition of ethylene oxide to mono or dialkyl phosphoric acid such as stearic acid and dilauryl phosphoric acid, Ethylene oxide may be polymerized with amines such as dodecylamine and stearic acid amide, higher fatty acid esters of polyhydric alcohols such as sorbitan, and polymerized addition of ethylene oxide and propylene oxide thereto. . As a suitable anionic surfactant, For example, Alkyl sulfate ester salts, such as sodium lauryl sulfate oleyl alcohol sulfate esteramine salt, Alkyl sulfonic acid salts, such as sodium sulfosuccinate dioctyl ester sodium and sodium 2-ethylhexene sulfonate, and isopropyl, for example. Aryl sulfonates, such as sodium naphthalene sulfonate, sodium methylene naphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzene sulfonate, etc. are mentioned.

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

The above-mentioned carrier and various auxiliary agents are suitably 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 is, for example, usually contains 1 to 25 parts by weight of the active ingredient compound, the remainder is a solid carrier.

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

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

Emulsions usually contain, for example, 5 to 30 parts by weight of an active ingredient compound, 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 (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 (1), 5 parts by weight of compound (A), 15 parts by weight of emulsifier Sotball SM-100 (Tohoka Chemical Co., Ltd.) and 65 parts by weight of xylene are mixed well to obtain an emulsion.

Formulation Example 3

5 parts by weight of compound (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 were mixed well, kneaded well with water, and then granulated and dried to granulate. Get

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, granulated and dried after mixing with water, and kneaded to form granules containing no active ingredient. The granules are obtained by coating 8 parts by weight of compound (1) and 1.5 parts by weight of compound (a) in 90.5 parts by weight of the granular material.

Next, test examples will be described to further illustrate the usefulness of the present invention.

[Test Example 1]

A faucet soil was filled in a polyethylene pot having an inner diameter of 8 cm, and the tadpole was grown in the faucet state, and each predetermined amount of freshwater soil was prepared with a hydrating agent in one side of the tadpole. Pots were kept in a greenhouse at 25 to 30 ° C, nurtured, and the ground by-product weight of the tadpoles remaining at 30 days after the treatment was measured, and the aerobic treatment ratio was calculated.

As a test compound, the combination of compound (1) and compound (a) is used, and the result is shown in a 1st table | surface.

[Table 1]

In the above table, the number in () is the estimated value of the compounding agent, and (a) the expected value of a / 2g ⁺ (b) b / 2g is (a) ag and (b) bg respectively. Is calculated as 1/2). As a result, the synergistic effect is demonstrated from the fact that the measured value of the blending agent is significantly smaller than expected.

[Test Example 2]

Water is put into a 1 / 5000a wagnell pot filled with 3 kg of faucet soil and placed in a faucet state, and sowing seeds of broad-leaf weeds such as scabbard, tadpole, water squirrel, field beetle and node flower. Olme, you planted tubers of the garden. 2.5 seedlings were transplanted again, plants were grown at room temperature of 20-25 ° C. in pots, and a certain amount of medicine was prepared with a hydrating agent at the time when the blood was 1 sided on the 7th day after sowing, and diluted with water. 10 μs per pot was processed. It was then grown in a greenhouse and examined herbicidal effects 25 days after drug treatment. In addition, the herbicidal effect was expressed as a number of 0-10 according to the observation of the absorptivity, the degree of whitening, etc. as follows. The results are shown in the second table.

Retardation rate

0: 0 ~ 9% 6: 60 ~ 69%

1: 10 ~ 19% 7: 70 ~ 79%

2: 20 ~ 29% 8: 80 ~ 89%

3: 30 ~ 39% 9: 90 ~ 99%

4: 40 ~ 49% 10: 100% (Full Test)

5: 50 ~ 59%

[Table 2]

In the table above, the numbers are the expected values (PE) of weed suppression of the formulations calculated according to the following Colby's formula as a general test for synergy.

PE = Pa + Pb (10-Pa) / 10 (Pa: inhibition value in ag of herbicide (A))

(Pb: inhibition value in bg of herbicide (b))

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 synergistic effect is remarkable.

Claims (1)

2-chloro-2 ', 6'-diethyl-N- (propoxyethyl) acetanilide (A) and pyrazole derivatives (B) represented by the following general formula (I) (B) A herbicide composition, characterized in that the composition in the ratio of 1 to 10 parts by weight.

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