JPH0153642B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention is based on the general formula [] (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group having 1 to 3 carbon atoms, R ₂ represents a hydrogen atom or a hydroxyl group, X represents a halogen atom or a lower alkyl group having 1 to 2 carbon atoms, and n represents (represents an integer from 0 to 2, Z represents a hydrogen atom or a halogen atom) and one or more compounds represented by the general formula [] (In the formula, R ₃ represents a halogen atom, a methoxy group, or a methylthio group, and R ₄ and R ₅ represent a mono- or dialkylamino group, which may be the same or different.) The present invention relates to a herbicidal composition containing a mixture of as an active ingredient, and is intended to control various weeds before or after germination, and provides a herbicide with a wide range of application and high practical value. The isonicotinic acid anilide compound represented by the above general formula [] is used to inhibit the growth of plants, such as preventing elongation of rice plants, preventing aging,
It can be widely used to prevent lodging in paddy fields after planting. This product is effective against all types of grass and exhibits a sufficient growth-inhibiting effect. Effective grass species include crabgrass, cyperus, foxtail grass, wild grass, Japanese cyperus, pigweed, and dogweed, all of which have the effect of suppressing the growth of weeds and dwarfing them for a long period of time. All of the compounds represented by the general formula [] have a strong herbicidal effect on weeds in fields or paddy fields before or after germination. Its action is characterized by its reaction with the isonicotinic acid anilide compound represented by the general formula [], and it exhibits a strong herbicidal effect, especially against broad-leaved weeds, but it also has a strong herbicidal effect on weeds of the Poaceae family, such as grasshopper, grasshopper, and foxtail grass. Or, weeds that have grown to a certain extent have quite inferior drawbacks. In other words, although it is insufficiently effective against grass weeds and growing weeds, it has a strong herbicidal effect against broad-leaved weeds before or immediately after germination, making it a promising herbicide. Single use has the disadvantage that the application period and applicable weeds are narrow. Typical examples of compounds represented by the general formula [] include 2-chloro-4,6-bis(ethylamino)S-triazine ("simazine"), 2-
Chlor-4-ethylamino-6-isopropylamino S-triazine ("atrazine"), 2-methylthio-4,6-bis(ethylamino)S-triazine ("simetrine"), 2-chloro-4-diethylamino- 6-ethylamino S-triazine (“trietadine”), 2-chloro-4,6-bis(isopropylamino)S-triazine (“propazine”), 2-methylthio-4-(1,2-dimethylpropylamino) -6-ethylamino S-triazine (“dimetamethrine”), 2-methylthio-
4-ethylamino-6-isopropylamino S-
Triazine (“Ametrine”), 2-methylthio-
4,6-bis(isopropylamino)S-triazine (“promethrin”), 2-chloro-4,6-
Bis(diethylamino)S-triazine (“chlorazine”), 2-methoxy-4-ethylamino-6
-isopropylamino S-triazine ("Atraton"), 2-methylthio-4-isopropylamino-6-methylamino S-triazine ("Desmetrin"), 2-methoxy-4,6-bis(ethylamino)S-triazine (``simeton''), etc. As a result of research on species with the aim of supplementing the above-mentioned drawbacks, the present inventors discovered that an isonicotinic acid anilide compound represented by the general formula [ ] and a triazine compound represented by the general formula The present invention was completed based on the discovery that a mixed treatment during the pre-emergence or post-emergence growth period provides excellent herbicidal effects without causing any harm to crops. The composition of the present invention exhibits a strong herbicidal effect on both grass weeds and broad-leaved weeds due to additive effects,
In addition to expanding the types of weeds that can be weeded, unexpected synergistic effects were observed. In other words, it is interpreted that the compound represented by the general formula [] strongly suppresses the growth of weeds, and the compound represented by the general formula [] has a significant synergistic effect with the herbicidal power. The present invention relates to a herbicidal composition comprising an isonicotinic acid anilide compound represented by the general formula [] and a triazine compound represented by the general formula [], as described above, and which has a synergistic effect based on the combination of active ingredients. It is characterized by its markedly improved performance as a herbicide due to its chemical effects. The compound represented by the general formula [] is new and can be produced by the method shown below. (1) General formula [] (In the formula, Y represents a halogen atom) isonicotinic acid halide represented by the general formula [] (In the formula, R ₁ , R ₂ , X, n and Z have the same meanings as above.) A compound represented by the general formula [] is produced by reacting with an aniline derivative represented by the formula []. In this case, the reaction will proceed more smoothly if a suitable deoxidizing agent is used. Suitable solvents include pyridine, methanol, acetone, benzene, toluene, xylene, dichloromethane, chloroform, tetrahydrofuran, dioxane, dimethylformamide, and the like. As a deoxidizing agent, pyridine, triethylamine, caustic soda,
Examples include caustic potash, carbonated soda, and carbonated potash. Although the reaction proceeds at room temperature, it may be carried out with cooling or heating as the case may be.
The temperature is preferably 0 to 60°C. Although the reaction time depends on the selection of conditions, the reaction is completed in 1 to 8 hours. After the reaction is completed, the desired product can be obtained by separation and purification using conventional methods. (2) General formula [] The compound represented by the general formula [] can be easily produced by reducing the isonicotinic acid derivative represented by the formula (in which R ₁ , X, n and Z have the same meanings as above) with an appropriate reducing agent. can do. Examples of the reducing agent include lithium aluminum hydride and sodium borohydride. In practice, each reducing agent can be easily produced by using conventional methods. A manufacturing example will be given and explained below. Production example 1 N-methyl-isonicotinic acid-{4-chloro-
2-(α-Hydroxybenzyl)}anilide (Compound No. 3) Dissolve 1.5 g of 2-methylamino-5-chlorobenzhydrol in 30 ml of pyridine, cool the solution with ice while stirring, and dissolve isonicotinic acid chloride. Add 1.4 g of hydrochloride little by little. This takes about 30 minutes. After further stirring at room temperature for 3 hours, 200 ml of water was added to the reaction solution, and crystals were precipitated. When these crystals are collected and recrystallized from a methanol-acetone mixed solvent, N-methyl-isonicotinic acid-{4
1.7 g of -chloro-2-(α-hydroxybenzyl)}anilide is obtained. Melting point 199-201℃ Elemental analysis value: C ₂₀ H ₁₇ ClN ₂ O ₂ (as molecular weight 351.81) C H N Calculated value (%) 68.08 4.86 7.94 Actual value (%) 67.96 4.98 7.79 Production example 2 Isonicotinic acid - {4 -Chloro-2-(α-hydroxybenzyl)}anilide (Compound No. 4) Add 0.2 g of sodium borohydride to a solution of 1.9 g of isonicotinic acid-(4-chloro-2-benzoyl)anilide dissolved in 20 ml of methanol with stirring. Add little by little. This will take approximately 30 minutes. Stirring was continued for an additional 2 hours at room temperature. After the reaction was completed, 200 ml of water was added to precipitate crystals. When this crystal is collected and recrystallized from a dimethylformamide-methanol mixed solvent, isonicotinic acid-{4-chloro-2-
1.8 g of (α-hydroxybenzyl)anilide is obtained. Melting point 210-212℃ Elemental analysis value: C ₁₉ H ₁₅ ClN ₂ O ₂ (as molecular weight 338.79) C H N Calculated value (%) 67.36 4.46 8.27 Actual value (%) 67.18 4.56 8.29 Production example 3 Isonicotinic acid - (4 -Chloro-2-benzyl)anilide (Compound No. 1) Dissolve 1.3 g of 4-chloro-2-benzylaniline in 30 ml of pyridine, cool the solution with ice, and add a small amount of 1.4 g of isonicotinyl chloride hydrochloride while stirring. Add one by one. This will take approximately 30 minutes. Stirring was further continued at room temperature for 3 hours to complete the reaction. When 200 ml of water was added to this reaction solution, crystals were precipitated. When these crystals are collected and recrystallized with ethanol, isonicotinic acid-(4-chloro-2-benzyl)anilide 1.6
get g. Melting point 178-179°C Elemental analysis value: C ₁₉ H ₁₅ ClN ₂ O (as molecular weight 322.79) C H N Calculated value (%) 70.70 4.68 8.68 Actual value (%) 70.75 4.79 8.65 Next, the thus obtained Representative examples of compounds represented by the general formula [] are shown in Table 1. The present invention is not limited only to these exemplified compounds. Note that the compound numbers are also referred to in the following Examples and Experimental Examples.

【table】

【table】

【table】

[Table] When blending the composition of the present invention, general formula []
Isonicotinic acid anilide compound 5 represented by
1 to 20 of the triazine compound represented by the general formula [ ] to 100, preferably 2 to 20 to 10 to 50.
A ratio of 5 is an appropriate range. The composition of the present invention usually has a concentration of 80 to 600 per 10 ares.
Although it is appropriate to use preferably at a ratio of 120 to 450 g, it goes without saying that the dosage can be adjusted as appropriate depending on the situation of the plant. In addition, for formulation, it can be mixed with various solid and liquid carriers used in the formulation of general agricultural chemicals to produce wettable powders, emulsions, powders, granules, etc. Furthermore, auxiliary agents such as dispersants, diluents, emulsifiers, penetrants, and binders may be added to the drug. Also,
Depending on the purpose of use, the above components can be used in combination with other herbicides, fungicides, insecticides, plant growth regulators, fertilizers, etc. The carrier referred to herein may be either solid or liquid, or a combination thereof. Examples of these include talc, clay, kaolin, diatomaceous earth,
Calcium carbonate, wood flour, starch, gum arabic,
Water, alcohol, kerosene, naphtha, xylol, xylene, cyclohexanone, methylnaphthalene, benzene, acetone, etc., as well as adjuvants used in drug formulations, such as spreading agents, emulsifiers, dispersants, wetting agents, etc. as non-ionic (polyoxyethylene alkyl phenyl ether, ethylene oxide propylene oxide copolymer, lignin sulfonate, sorbitan esters, etc.),
Anionic (soaps, sulfated oils, alkyl sulfate ester salts, petroleum sulfonates, dioctyl sulfosuccinate salts, alkylaryl sulfonates, etc.), cationic (fatty acid amine salts,
Examples include surfactants of quaternary ammonium salts, alkylpyridinium salts, etc.) and amphoteric surfactants (alkylaminoethylglycine, alkyldimethylbetaine, polyglycol sulfate, alkylamine sulfonic acid, etc.). However, it goes without saying that the embodiments of the present invention are not necessarily limited to the above-mentioned dosage form. In addition, when formulating the formulation, the mixing ratio is determined by the general formula []
The optimum ratio is 10 to 50% of the compound represented by the following: Compounds 1 to 10 represented by the general formula []: 0 to 10% of the surfactant: 45 to 89% of the carrier. In addition, in the present invention, various insecticides, fungicides,
Herbicides, plant growth regulators, acaricides, nematicides,
By using it in combination with attractants, repellents, plant nutrients, fertilizers, etc., a wider range of effects can be expected. Next, an experimental example will be shown and the effects of the present invention will be explained in detail. Experimental Example 1 A 1/2000 are plastic pot was filled with sandy loam soil (black soil) containing a large amount of weed seeds such as crabgrass, cyperus, and wild grass, and after sowing soybeans, water was added using the formulation method shown in Example 1 below. Compounds and additives (Isonicotinic acid anilide compounds represented by the general formula [ ] and simazine alone were formulated in the same way, and the concentration of the active ingredient in the composition was made constant by increasing or decreasing with clay.) was uniformly applied to the soil surface using a glass spray gun. Thereafter, they were kept in a glass greenhouse until the day of the survey. To investigate the effectiveness, the fresh weight of surviving weeds was measured 30 days after treatment, and at the same time, chemical damage to soybeans was also observed. The results are shown in Table 2. Furthermore, when an efficacy test was conducted using trietadine in a similar manner, the same level of efficacy as when using simazine was obtained.

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[Table] Experimental example 2 Japanese crabgrass, Japanese cyperus, Japanese wildflower, Japanese wildflower,
A field with a lot of weeds such as purslane, 5 m ² in one section.
Corn (golden cross,
Vandam) was sown, and when the weeds had grown to a height of 2 to 5 cm, an emulsion was prepared using the formulation method shown in Example 2 below, and an isonicotinic acid anilide compound represented by the general formula [ ], atrazine was sown. For single use, the formulation was prepared in the same way, and the concentration of the active ingredient in the composition was kept constant by increasing or decreasing it with xylene.
The weed foliage and soil surface were uniformly treated using a small sprayer. The test section consisted of 1 section and 2 repetitions. To investigate the effectiveness, the fresh weight of surviving weeds was measured 25 days after treatment with the chemical, and at the same time, chemical damage to corn was also observed. The results are shown in Table 3. In addition, propazine, ametrine,
When an efficacy test was conducted using chlorazine and atratone, the same level of efficacy was obtained as when using atranzine.

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[Table] Experimental Example 3 The following test was conducted in a rice field partitioned into ^10m2 sections, with 3 repetitions per test section. First, paddy fields where weeds grow uniformly are plowed,
Rice seedlings at the 2.5 leaf stage were transplanted under flooded conditions and cultivated using conventional methods. Next, drug treatment is carried out in rice transplantation 7.
After a few days (the height of the wild grass plant is 5 to 7 cm), it is formulated into granules according to the formulation method shown in Example 3 below. The concentration of active ingredients in the composition was kept constant by adjusting the amount of bentonite.) The mixture was uniformly rolled by hand. Thereafter, the area was flooded to a depth of 3 to 4 cm and maintained until the day of the survey. To investigate the effectiveness, we measured the fresh weight of surviving weeds 30 days after treatment, and at the same time observed the chemical damage to rice.
The results are shown in Table 4. Furthermore, when an efficacy test was conducted using promethrin and desmetrin in a similar manner, the same level of efficacy as when using simetrin was obtained.

【table】

[Table] Examples of the present invention are shown below, but the compounds, carriers, and proportions used are not limited to these examples. Example 1 (Wettable powder) Compound No. 4 50 parts by weight Simazine 5 Sodium alkyl sulfate 5 Clay 40 These are thoroughly mixed until homogeneous and pulverized to obtain a wettable powder. When using this, dilute it with water to a predetermined concentration and spray it. Example 2 (emulsion) Compound No. 6 20 parts by weight Atrazine 2 Polyoxyethylene alkyl phenyl ether 7 Calcium alkylbenzene sulfonate
3 xylene 48 cyclohexanone 20 Mix and dissolve these thoroughly until uniform to obtain an emulsion. When using this, dilute it with water to a predetermined concentration and spray. Example 3 (granules) Compound No. 13 10 parts by weight Simetrine 2 Bentonite 43 Diatomaceous earth 45 These are mixed until homogeneous, pulverized, and granulated by a conventional method to be used as a granule.

Claims (1)

[Claims] 1.1 General formula (In the formula, R ₁ represents a hydrogen atom or a lower alkyl group, R ₂ represents a hydrogen atom or a hydroxyl group, X represents a halogen atom or a lower alkyl group, n represents an integer from 0 to 2, and Z represents a hydrogen atom or One or two of the compounds represented by (representing a halogen atom)
More than species and general formula (In the formula, R ₃ represents a halogen atom, a methoxy group, or a methylthio group, and R ₄ and R ₅ represent a mono- or dialkylamino group, which may be the same or different.) A herbicidal composition comprising a mixture of as an active ingredient.