JPS6340162B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides N-(α,α-dimethylbenzyl)-α
-bromo-tert-butylacetamide and general formula () [In the formula, X represents a chlorine atom, R ₁ represents a hydrogen atom,
It represents a lower alkoxyl group or _-COOR2 ( _R2 represents a lower alkyl group), and n represents an integer of 2 to 3. ] This relates to a mixed herbicide obtained by mixing one or more diphenyl ether compounds represented by the following. As a general rule, herbicides cannot be fully effective unless they kill all of the many types of weeds that occur in fields, paddy fields, orchards, and other areas targeted for weed control. For example, if some weeds survive, they can grow larger and more harmful, reducing the effectiveness of herbicides by half. Due to these characteristics of weed control, herbicides that are particularly effective against a wide variety of weeds and have a broad herbicidal spectrum are desired. If you just want to increase the herbicide effect, you may be able to achieve your goal by increasing the amount of herbicide applied, but this will also increase the chemical damage to the crop, which goes against the original goal of weed control, which is to secure yield. Become. Furthermore, since environmental pollution caused by certain types of pesticides has recently become a problem, there is a desire to develop herbicides that are effective even when applied in small amounts, even if they are pesticides with little persistence. Under the above circumstances, the present inventors are conducting research with the aim of developing an excellent herbicide that meets the above conditions, and among them, N-(α,α-dimethylbenzyl)- α-bromo-tert-butylacetamide (hereinafter abbreviated as compound A) and general formula ()
It was discovered that a mixture of one or more of the compounds shown in A herbicide of the present invention having a herbicidal spectrum was obtained. To explain the present invention in more detail, Compound A, which is one of the components of this herbicide, is
There is a description in the issue as a herbicide, and it can be used to kill field weeds such as crabgrass, whiteweed, blueberry, etc.
It is known that it has a herbicidal effect on paddy field weeds such as Japanese cypress, Japanese cyperus, Japanese cyperus, Japanese cyperus, and other rice field weeds. However, the effect against certain weeds, such as chickweed and Japanese parsley, is weak, and if the application amount is reduced, the herbicidal effect against Japanese millet, Japanese azalea, Japanese cypress, Japanese cucumber, etc. decreases and becomes insufficient. In order to compensate for the drawbacks of this compound, we investigated mixtures with various herbicides, and found that mixtures with diphenyl ether compounds represented by the general formula (), as will be explained in detail later in the examples, The agent exhibits a synergistic effect that could not be predicted from the combined use of individual agents, and is endowed with the extremely useful property of being able to control many weeds with a low dose.
The present invention was completed based on these new findings. Examples of the compound represented by the general formula (), which is one of the bases of the herbicide of the present invention, include: etc., but the present invention is not limited to these exemplified compounds. In the following specification, the above-mentioned compound numbers or symbols will be used for explanation. To compensate for the shortcomings of a single herbicide, it is common to apply a mixture of herbicides.Usually, when herbicides are applied in a mixture, they almost always exhibit an additive effect, and each single herbicide has an additive effect. The application rate cannot be reduced. However, the herbicide of the present invention has a remarkable synergistic effect, and even when mixed at low application rates,
The application of each single herbicide shows an unexpectedly strong herbicidal effect. As a result, the herbicide of the present invention can simultaneously control many types of weeds at low dosages, and is also effective against large, well-grown weeds that are less effective when applied individually. can be,
It has come to have excellent properties as a herbicide. The synergistic effect according to the present invention is observed in a wide range of mixing ratios, and it is preferable to mix 0.01 to 10 parts by weight of the compound represented by the general formula () with respect to 1 part by weight of compound A to obtain a useful herbicide. can be created. The herbicide of the present invention, which has been completed in this way, is effective even when treated before and after the germination of weeds, and can be applied not only to paddy rice but also to highly effective soil treatment and foliar spray treatment. thing,
It is useful for various grains, legumes, cotton, vegetables, orchards, lawns, pastures, tea gardens, mulberry gardens, forest land, non-agricultural land, etc. 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 used after being prepared into granules, wettable powders, emulsions, flowable preparations, 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 attapulgite group, talc, mica, pyrophyllite, pumice, vermiculite, 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, cobal gum, dammar gum, wax such as carnauba wax, beeswax, etc. and urea. 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, and preventing rust 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 alkyl phenols such as isooctylphenol and nonylphenol. products obtained by polymerizing and adding ethylene oxide to alkylnaphthols such as butylnaphthol and octylnaphthol, products obtained by polymerizing ethylene oxide to higher fatty acids such as palmitic acid, stearic acid, and oleic acid, stearyl phosphoric acid, dilauryl phosphoric acid, etc. Polymerized addition of ethylene oxide to mono- or dialkyl phosphoric acid, dodecylamine,
Examples include those obtained by polymerizing and adding ethylene oxide to an amine such as stearic acid amide, those obtained by polymerizing and adding ethylene oxide to a higher fatty acid ester of a polyhydric alcohol such as sorbitan, and those obtained by polymerizing and adding ethylene oxide and propylene oxide. Suitable anionic surfactants include, for example, sodium laliur sulfate, alkyl sulfate salts such as oleyl alcohol sulfate amine salt, alkyl sulfonates such as sodium sulfosuccinate dioctyl ester, and sodium 2-ethylhexene sulfonate; Examples include 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 (A), 20 parts by weight of Compound (1), 2.5 parts by weight of dodecylbenzenesulfonate, 2.5 parts by weight of ligninsulfonate and 55 parts by weight of diatomaceous earth were thoroughly ground and mixed to form a wettable powder. obtain. Formulation Example 2 15 parts by weight of compound (A), 10 parts by weight of compound (2), 15 parts by weight of emulsifier Solpol SM100 (registered trademark of Toho Chemical) and 60 parts by weight of xylene are thoroughly mixed to obtain an emulsion. Formulation Example 3 6 parts by weight of compound (A), 5 parts by weight of compound (2), 3 parts by weight of white carbon, 5 parts by weight of lignin sulfonate, and 81 parts by weight of clay were thoroughly ground and mixed, and water was added and kneaded well. After granulation and drying, granules are obtained. Formulation Example 4 5 parts by weight of compound (A), 1 part by weight of compound (4), 1 part by weight of isopropyl phosphate, 60 parts by weight of clay and 30 parts by weight of talc are thoroughly ground and mixed to obtain a powder. Formulation Example 5 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. Add 6 parts of compound (A) to 93.5 parts by weight of this granule.
Part by weight and 0.5 part by weight of compound (4) are impregnated to obtain granules. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples. Example 1 A 14 cm diameter Wagner pot filled with 1.5 kg of paddy soil each was filled with water to create a paddy field, and the pots were filled with Japanese millet, bulrush, Japanese azalea, and Japanese azalea.
Seeds of broad-leaved weeds such as Kikashigusa were sown, and overwintering stocks of Pinus spp.
I planted the tubers of black bream. Furthermore, the rice seedlings at the 3-leaf stage were transplanted, and the pots were placed in a iron house at 25-30℃ to grow the plants. On the 7th day after sowing, when the barnyard grass was at the 0.7-leaf stage, a prescribed amount of chemical was applied to the water. It was formulated into a Japanese preparation, diluted with water, and treated at 15 c.c. per pot. After that, they were grown in the Firelon House, and after being treated with chemicals, they were grown for 25 days.
The herbicidal effect was investigated on the second day. The herbicidal effect was expressed as a number from 0 to 10 as shown below based on the observation of the weed suppression rate, the degree of death, etc. The results are shown in Table 1. Weed suppression rate 0: 0-9% 1: 10-19 2: 20-29 3: 30-39 4: 40-49 5: 50-59 6: 60-69 7: 70-79 8: 80-89 9: 90-99 10: 100 (completely dead)

[Table] Example 2 A 1/5000 are Wagner pot was filled with paddy soil, wild plants were grown in the paddy field, and the flooded soil was treated with a prescribed amount of each drug formulated into granules during the first leaf stage of the wild plants. The pots were placed in a heat iron house at 25 to 30°C to grow under control, and on the 25th day after the treatment, the fresh weight of the above-ground parts of the remaining wild plants was measured, and the ratio to the untreated plot was calculated. The results are shown in Table 2.

[Table] The results shown in Table 2 (Weed, Vol. 15, pp. 20-22)
Analyze using Colby's method as described in (1967).
Colby's method is as follows: Expected growth rate of mixture (%) = Observed value of single compound [] (
%) x Compound [] Single observed value (%)/100 If the expected value is greater than the observed value, it is determined that there is a synergistic effect. According to this formula, for example, in the case of a mixed application of compound (A) 6g/Aru and compound (4) 4g/Al, Expected value = 38 x 79/100 = 30.0% Observed value = 0%, so Expected value > Observed value. , it can be determined that there is a clear synergistic effect. Furthermore, there is the isoeffect line method as a method for determining synergistic effects (Weed Research Vol. 14, pp. 12-18, 1972, Hideo Chisaka).
The isoeffect line method is a composition consisting of different mixing ratios of herbicide [] and herbicide [], for example, 80
By determining several combinations showing the % growth inhibition rate and plotting them as shown in FIG. 1, synergistic, additive, and antagonistic effects can be easily determined. When a synergistic effect is shown, an actual isoeffect line is shown below the additive effect line as a reference. In Example 2, as shown in Figure 1, the iso-effect line for suppressing 80% of noviidae for the mixture is located below the additive effect line, and even with this analysis method, it is clear that there is a synergistic effect. It was shown that Example 3 After filling a 1/5000a Wagner pot with soil and making it into a paddy field, Japanese millet was sown. 25℃
The plants were grown in a greenhouse and treated with a prescribed amount of the dosage form shown in Formulation Example 2 at the one-leaf stage. The herbicidal effect was investigated 30 days after chemical treatment. The fresh weight of the above-ground parts of Japanese millet was measured, and the growth inhibition rate was calculated. The result is the third
Shown in the table. Based on this table, the data showing the synergistic effect is summarized using Tammes' method [Tammes, PML: Neth J. Plant Path], which is cited in the cited literature of "Weed Research" No. 14, pp. 12-18 (1973). .，70th
Vol. 73-80 (1964)]. The results are shown in Figure 2. As is clear from Figure 2, the 90% iso-effect curve lies inside the additive effect curve, and it can be said that this mixture has a synergistic effect.

[Table] Example 4 A 1/5000a Wagner pot was filled with soil to form a paddy field, and tubers of Urikawa were buried in the soil. Grow in a greenhouse at 25℃ and mix example 2 during germination.
A prescribed amount of the drug was administered using the dosage form shown in . 30 days after drug treatment
The herbicidal effect was adjusted on the following day. The fresh weight of the above-ground parts of Urikawa was measured, and the growth inhibition rate was calculated. The results are shown in Table 4. Based on this table, the data showing the synergistic effect is summarized in "Weed Research" No. 14, No. 12~
Cited in the citations on page 18 (1973).
Tammes' method [Tammes, PML: Neth J
Plant Path., Vol. 70, pp. 73-80 (1964)]. The results are shown in Figure 3. As is clear from Figure 3, the 90% iso-effect curve lies inside the additive effect curve, and it can be said that this mixture has a synergistic effect.

【table】 [Brief explanation of the drawing]

Figure 1 shows 80% of Novie in Example 2.
Iso-effect lines for growth inhibition are shown. The solid line indicates the additive effect line, and the vertical axis is the weight (g) of compound (4) per are.
, the horizontal axis shows the weight (g) per area of compound (A). FIG. 2 shows iso-effectiveness lines for 90% growth inhibition against Japanese millet in Example 3. The horizontal axis is the compound
(A) shows the application amount, and the vertical axis shows the application amount of compound (2). Moreover, FIG. 3 shows the iso-effect line for 90% growth inhibition on the cucumber in Example 4. The horizontal axis shows the application amount of compound (A), and the vertical axis shows the application amount of compound (3).

Claims (1)

[Claims] 1 N-(α,α-dimethylbenzyl)-α-bromo-tert-butylacetamide and general formula [In the formula, X represents a chlorine atom, R ₁ represents a hydrogen atom,
It represents a lower alkoxyl group or _-COOR2 ( _R2 represents a lower alkyl group), and n represents an integer of 2 to 3. ] A herbicide characterized by being mixed with one or more diphenyl ether compounds represented by: 2 N-(α,α-dimethylbenzyl)-α-bromo-tert-butylacetamide and 2,4,6-trichlorophenyl 4′-nitrophenyl ether in a ratio of 1:0.2 to 10 (weight ratio) The herbicide according to claim 1, which is a mixture of: 3 N-(α,α-dimethylbenzyl)-α-bromo-tert-butylacetamide and 2,4-dichlorophenyl 3′-methoxy-4′-nitrophenyl ether at a ratio of 1:0.2 to 5 (weight ratio ) The herbicide according to claim 1, which is obtained by mixing the herbicide in the ratio of: 4 N-(α,α-dimethylbenzyl)-α-bromo-tert-butylacetamide and 2,4-dichlorophenyl 3′-methoxycarbonyl-4′-nitrophenyl ether in a ratio of 1:0.2 to 5 (by weight) 2. The herbicide according to claim 1, which is obtained by mixing the herbicides in a ratio of: 5 Mix N-(α,α-dimethylbenzyl)-α-bromo-tert-butylacetamide and 2,4-dichlorophenyl 4′-nitrophenyl ether at a ratio of 1:0.2 to 10 (weight ratio) The herbicide according to claim 1.