JPS6116247B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides 1-(α,α-dimethylbenzyl)-
3-(p-tolyl)urea (A) and the general formula

[Formula] Pyrazole derivative represented by [wherein X represents a phenacyl group or 4-methylphenacyl group]
This relates to a mixed paddy field herbicide that is characterized by being blended with (B) to produce a synergistic effect far beyond what could be expected from the single application of each, and to be able to kill many types of problem weeds with a low application rate. . Currently, many herbicides have been put into practical use as herbicides for paddy fields, and are widely used as single agents or mixtures. However, there are many types of paddy weeds, and although there are many herbicides that are effective against annual weeds, there are few herbicides that are effective against perennial weeds. As a result, the number of perennial weeds has increased, and there is a strong need for their control. Perennial weeds generally grow vigorously, have a long emergence period, and are a type of harmful grass. Therefore, herbicides are desired to have properties with a broad herbicidal spectrum that can kill many types of weeds. In addition, the introduction of mechanization and earlier transplantation of rice cultivation in recent years has rapidly spread, providing a more suitable place for weeds to grow than ever before, and it is expected that a single application of herbicide will provide complete weed control. tend not to be able to do so. For this reason, the same or different herbicides are used several times, but such repeated use not only requires a great deal of labor, but also causes undesirable problems such as chemical damage to paddy rice and soil residue due to large amounts of application. It raises the issue of In order to improve these problems of conventional herbicides, the present inventors have developed a herbicide that can completely control all weeds with a single application and is highly safe for paddy rice.
As a result of continuing the search for a safe herbicide with extremely low human toxicity, it was discovered that an excellent herbicide that solved these problems could be obtained by combining two types of active ingredients, and the present invention was developed. completed. That is, the present invention uses 1-(α,α-dimethylbenzyl)-3-(p-
Tolyl) urea (A) and new pyrazole compounds
It is a mixture with (B). To explain the present invention in more detail, (A), which is one of the components of the herbicidal composition, is effective against annual Cyperaceae weeds and perennial Cyperaceae weeds such as Cyperaceae and Cyperaceae in the early stage of growth. It is expensive, but the effect becomes weaker as growth progresses. In addition, the effect against wildflowers and broad-leaved weeds is insufficient. On the other hand, the pyrazole compound (B) does not cause any phytotoxicity to paddy rice in paddy fields, and is also effective against annual grass weeds, broad-leaved weeds, and perennial weeds such as Cyperus japonica, Omodaka, and Urikawa.
However, if the weeds are treated with chemicals when they have grown to a certain extent, the effect will be reduced, and the effect on wild grasses will be insufficient. However, by applying both in combination, the herbicidal effect
As a result of examining drug damage, the range of herbicides was surprisingly expanded beyond the scope of application obtained with each single agent. It extends to general perennial weeds such as Japanese cypress and Japanese cypress,
Furthermore, it has been found that the application period can be expanded without compromising the safety of paddy rice. In addition, this herbicide is fully effective when mixed at a much lower dose than when used alone.
The herbicidal efficacy is sufficiently increased as a one-time treatment agent, and its efficacy lasts for a long period of time. The compound (B) of the formula (), which is one of the active ingredients of the herbicide of the present invention, can be prepared by converting the compound () to a substituted alkyl group with a substituted alkylating agent corresponding to the group X, as shown in the following reaction formula, for example. It can be easily manufactured by (In the above formula, X is the same as defined above.) As the substituted alkylating agent corresponding to the group X, for example, halides such as chlorides, bromides or iodides are particularly preferably used. The reaction represented by the above formula is preferably carried out in the presence of a solvent, and such a solvent is not particularly limited as long as it does not participate in this 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 trichloroethane, acetone, isobutyl methyl ketone, etc. ketones, ethyl acetate,
Examples include esters such as methyl acetate, acetonitrile, and mixed solvents thereof.
Aromatic hydrocarbons and ethers are preferably used. When using a halide as a substituted alkylating agent, it is preferable to use a deoxidizing agent;
Such deoxidizers include, for example, inorganic bases such as sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, N,N
-Organic bases such as diethylaniline. The reaction temperature is not particularly limited, and the reaction is carried out at room temperature to the reflux temperature of the solvent. The reaction time varies depending on the reactant and reaction temperature, and is usually 30 minutes to 24 hours. After the reaction is completed, the target product is isolated according to a conventional method,
If necessary, it is purified by methods such as column chromatography and recrystallization. The method for producing compound (B) of formula (), which is the active ingredient of the present invention, will be explained using the following production example. Production example 1 4-(2,4-dichlorobenzoyl)-1,3-
1.425 g of dimethyl-5-hydroxypyrazole,
A mixture of 15 ml of benzene, 0.505 g of triethylamine, and 0.995 g of phenacyl bromide is heated under reflux for 1 hour while stirring. After cooling, the salts are separated by adding water, washed with a 5% aqueous sodium bicarbonate solution and then with water, dried over anhydrous sodium sulfate and evaporated to give 1.75 g of an oil. This was separated by column chromatography (silica gel; eluted with benzene:ethyl acetate = 6:1) and 1.2
g (yield: 59.6%) of 4-(2,4-dichlorobenzoyl)-1,3-dimethyl-5-phenacyloxypyrazole (compound B-1) is obtained.
mp 109.5-110.5°C (recrystallized from n-hexane). Production example 2 4-(2,4-dichlorobenzoyl)-1,3-
10 g of dimethyl-5-hydroxypyrazole, 70 ml of acetonitrile, 4.85 g of potassium carbonate (anhydrous)
The mixture was stirred at room temperature for 2 hours, and a solution of 7.7 g of phenacyl bromide dissolved in 10 ml of acetonitrile was added, and the mixture was refluxed for 1 hour while stirring. The salts are removed, the solution is concentrated and benzene is added, washing with dilute aqueous sodium bicarbonate and then water. After drying over anhydrous sodium sulfate and distilling off the solvent, the resulting residue was crystallized by adding n-hexane, and when taken, 12.88 g (yield: 91.2%) of 4-(2,4-dichlorobenzoyl) was obtained. )-1,3-dimethyl-5-phenacyloxypyrazole (compound B-1) is obtained. mp 109.5-110.5°C (recrystallized from n-hexane). The following compounds are produced according to the methods of Production Examples 1 and 2 above. 4-(2,4-dichlorobenzoyl)-1,3-
Dimethyl-5-(4-methylphenacyloxy)
Pyrazole (compound B-2) n ³⁰ _D 1.5945 The mixture shown in the present invention is a novel combination that has not been described in any literature, and of course there is no literature that mentions its unique potency enhancement. The synergistic effect related to the present invention is observed in a wide range of mixing ratios, and the compound (B) represented by the general formula () is mixed in a range of 0.1 to 1 part by weight with respect to 1 part by weight of the compound (A).
5 parts by weight can be mixed to form a useful herbicide. The rice paddy herbicide of the present invention thus completed can be highly effective in soil treatment before and after weed germination. The mixture of the present invention may be sprayed as a raw material itself, or may be mixed with a carrier and other auxiliary agents as necessary to form a formulation commonly used as a herbicide, such as powder, coarse powder, fine granule, etc. It is prepared and used as granules, wettable powders, emulsions, aqueous solutions, aqueous solutions, oil suspensions, etc. Suitable solid carriers for use in preparing the herbicide of the present invention include clays represented by the kaolinite group, montmorillonite group, or attabulgite group, talc, mica, pyrophyllite, pumice, vermiyukilite, and gypsum. , calcium carbonate, dolomite, diatomaceous earth, magnesium lime, apatite, zeolite, anhydrous silicic acid, synthetic calcium silicate and other inorganic substances, soybean flour, tobacco flour, walnut flour, wheat flour, wood flour, starch, crystalline cellulose. vegetable organic substances such as coumaron resin, petroleum resin, alkyd resin, polyvinyl chloride, polyalkylene glycol, ketone resin, synthetic or natural polymer compounds such as ester gum, copal gum, dammar gum, wax such as carnauba wax, beeswax, etc. kind,
Alternatively, urea etc. can be mentioned. Suitable liquid carriers include paraffinic or naphthenic hydrocarbons such as kerosene, mineral oil, spindle oil, white oil, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene, methylnaphthalene, carbon tetrachloride, chloroform, etc. , chlorinated hydrocarbons such as trichloroethylene, monochlorobenzene, O-chlorotoluene, ethers such as dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone, ethyl acetate, amyl acetate, Esters such as ethylene glycol acetate, diethylene glycol acetate, dibutyl maleate, diethyl succinate, alcohols such as methanol, n-hexanol, ethylene glycol, diethylene glycol, cyclohexanol, benzyl alcohol, ethylene glycol ethyl ether, ethylene glycol phenyl ether , ether alcohols such as diethylene glycol ethyl ether and diethylene glycol butyl ether, dimethylformamide,
Examples include polar solvents such as dimethyl sulfoxide, water, and the like. Emulsification, dispersion, wetting, spreading, binding, disintegration control,
Surfactants used for the purpose of stabilizing active ingredients, improving fluidity, preventing rust, etc. can be nonionic, anionic, cationic, or amphoteric, but usually used are nonionic and/or anionic. Suitable nonionic surfactants include, for example, those obtained by polymerizing and adding ethylene oxide to higher alcohols such as lauryl alcohol, stearyl alcohol, and oleyl alcohol, and those obtained by polymerizing and adding ethylene oxide to alkylphenols such as isooctylphenol and nonylphenol. what made me,
Products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, products obtained by polymerizing and adding ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid, monomers such as stearyl phosphoric acid, dilauryl phosphoric acid, etc. Those obtained by polymerizing and adding ethylene oxide to dialkyl phosphoric acid, those obtained by polymerizing and adding ethylene oxide to amines such as dodecylamine and stearic acid amide, and those obtained by polymerizing and adding ethylene oxide to higher fatty acid esters of polyhydric alcohols such as sorbitan, Examples include those obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, sodium lauryl sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salts, alkyl sulfonates such as sodium sulfosuccinate dioctyl ester, and sodium 2-ethylhexene sulfonate. , aryl sulfonates such as sodium isopropylnaphthalene sulfonate, sodium methylene bisnaphthalene sulfonate, sodium lignin sulfonate, and sodium dodecylbenzenesulfonate. Furthermore, the herbicide of the present invention includes casein, gelatin, albumin, glue, sodium alginate, carboxymethyl cellulose, methyl cellulose,
High molecular compounds such as hydroxyethyl cellulose and polyvinyl alcohol and other auxiliary agents can also be used in combination. The above-mentioned carriers and various auxiliary agents are used in the dosage form of the preparation,
They are used individually or in combination as appropriate depending on the purpose, taking into consideration the application situation. Powders, for example, usually contain 1 to 25 parts by weight of the active ingredient compound, with the remainder being a solid carrier. Wettable powders usually contain, for example, 25 to 90 parts by weight of the active ingredient compound, with the remainder being a solid carrier, a dispersing wetting agent, and optionally a protective colloid agent, a thixotropic agent, an antifoaming agent, and the like. Granules, for example, usually contain 1 to 35 parts by weight of the active ingredient compound, with the remainder being mostly 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 particle size is about 0.2 to
It is about 1.5mm. Emulsions, for example, usually contain 5 to 30 parts by weight of the active ingredient compound, this includes about 5 to 20 parts by weight of emulsifier, and the remainder is a liquid carrier;
Rust inhibitors are added if necessary. Examples of formulations of this herbicide are 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
The weight parts are thoroughly ground and mixed to obtain a wettable powder. Formulation Example 2 5 parts by weight of compound (B-2), 5 parts by weight of compound (A), 3 parts by weight of white carbon, 5 parts by weight of lignin sulfonate and 82 parts by weight of clay were thoroughly ground and mixed, and water was added. After kneading, the mixture is granulated and dried to obtain granules. Formulation Example 3 40 parts by weight of bentonite, 5 parts by weight of lignin sulfonate and 55 parts by weight of clay are pulverized and mixed, water is added, kneaded and granulated and dried to produce granules containing no active ingredient. A compound (B-
Granules are obtained by impregnating 8 parts by weight of 1) with 2 parts by weight of compound (A). Next, in order to more specifically demonstrate the usefulness of the present invention, test examples will be given and explained. Test Example 1 A polyethylene pot with an inner diameter of 8 cm was filled with paddy soil, firefly was grown in the paddy field, and at the first leaf stage of firefly, the flooded soil was treated with a predetermined amount of each drug formulated into a wettable powder. The pots were placed in a greenhouse at 25 to 30°C for controlled growth, and 30 days after treatment, the fresh weight of the above-ground parts of the remaining firefly was measured, and the weight of the untreated vs. untreated plots was calculated. The results are shown in Table 1.

[Table] As a result, the actual measured value (Qc) of the ratio of residual grass amount to no treatment of the combination agent was smaller than the expected value (Q _E ), proving that there is a synergistic effect. Test Example 2 A 1/5000a Wagner pot filled with 3 kg of paddy soil was filled with water to create a paddy field, and in this pot, seeds of broad-leaved weeds such as Japanese millet, bulrush, and broad-leaved weeds such as Japanese azalea, azalea, and staghornweed were sown, and tubers of Urikawa and Japanese cypress were sown. was planted. moreover
2. Transplant the rice seedlings at the 5-leaf stage, place the pots in a greenhouse at 20-25℃ and grow the plants. On the 7th day after sowing, when the barnyard grass is at the 1-leaf stage, apply the prescribed amount of the chemical as a hydrating powder. Formulated, diluted in water and treated at 10 c.c. per pot. The plants were then grown in a greenhouse, and the herbicidal effect was investigated 25 days after the chemical treatment. The herbicidal effect was expressed as a number from 0 to 10 as shown below based on the observation of the weed suppression rate, degree of whitening, etc. The results are shown in Table 2. Weed control 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 (completely dead) 5:50-59

[Table] As a result, the actual measured value (Pc) of the weed suppression value of the combination drug was greater than the expected value (P _E ), proving that there is a synergistic effect.

Claims (1)

[Claims] 1 1-(α,α-dimethylbenzyl)-3-(p
-Tolyl) urea and a pyrazole derivative represented by the general formula [Formula] (wherein, X represents a phenacyl group or a 4-methylphenacyl group).