JP2001058909A - Herbicide composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a herbicide composition especially suitable for the control of weeds on corn field. SOLUTION: The objective herbicide composition contains a 2-chloro-4- fluoro-5-(4-methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetic acid ester derivative and 6-chloro-N2-ethyl-N4-isopropyl-1,3,5-triazine-2,4-diamine as active components. Various weeds grown on cultivated field or non-cultivated field can be exterminated in high efficiency by the foliar treatment of the weeds with the herbicide composition. The activity is synergistically increased compared with the separate application of each component. Accordingly, the composition is effective at a low rate of application, has expanded herbicidal spectrum and can selectively exterminate a wide variety of weeds especially on a corn field.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a herbicide composition, and more particularly to a herbicide composition for foliage treatment and a method for herbicide treatment by foliar application of the composition to weeds.

[0002]

2. Description of the Related Art At present, a large number of herbicides are commercially available and used. Therefore, there is a demand for safe herbicides in crops, which have a wide spectrum of herbicides and which have high cropping rates.

[0003]

The present inventors have conducted intensive studies to find an excellent herbicide, and as a result, have found that 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3
-Pyridazinone-2-yl) phenoxyacetic acid ester derivative and 6-chloro-N ² -ethyl-N ⁴ -isopropyl-1,3,5-triazine-2,4-diamine (generic name atrazine, hereinafter referred to as atrazine) are effective. The herbicidal composition contained as an ingredient, by foliar treatment of weeds, can effectively weed various weeds that occur on agricultural lands or non-agricultural lands, and the herbicidal effect is that when they are used alone. The present invention was found to increase synergistically, to be able to be applied at a low dose, to further broaden the herbicidal spectrum, and to be able to selectively remove a wide range of weeds particularly in a corn field, leading to the present invention. That is, the present invention relates to a herbicidal composition for foliage treatment containing a 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and atrazine as active ingredients ( Hereinafter, the present invention is referred to as a composition of the present invention) and a method for foliar application of the composition to weeds.

[0004]

DETAILED DESCRIPTION OF THE INVENTION 2-Chloro-4-fluoro-5- (4-methyl-5) which is one of the active ingredients of the composition of the present invention.
-Trifluoromethyl-3-pyridazinone-2-yl)
In the phenoxyacetic acid ester derivative, the ester means C1 to C7 alkyl ester, C5 to C6 cycloalkyl ester, and C2 to C6 alkenyl ester, and these compounds can be produced by the method shown in the following production examples. . Production Example 1 To a solution obtained by mixing 5.3 g (53.3 mmol) of sodium acetate and about 100 ml of water, 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone was added under ice-cooling. For 20 minutes. The reaction was cooled to room temperature and
5.8 g (21.5 mmol) of -fluoro-4-chloro-5-isopropoxyphenylhydrazine is added to about 20 ml of diethyl ether.
Was added and stirred at room temperature for 1 hour. The ether layer was separated, concentrated, and about 60 ml of THF was added to the residue.
To this, 8.3 g (23.0 mmol) of carboxyethylidenetriphenylphosphorane was added, and the mixture was heated under reflux for 2 hours. After distilling off THF under reduced pressure, the residue was subjected to silica gel column chromatography to give 2- [2-fluoro-4-chloro-5-isopropoxyphenyl] -4-methyl-5-
3.8 g of trifluoromethylpyridazin-3-one (10.5
mmol). Dissolve 3.5 g (9.7 mmol) of 2- [2-fluoro-4-chloro-5-isopropoxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one in about 10 ml of concentrated sulfuric acid under ice-cooling and bring to room temperature. The temperature rose. After 10 minutes, about 100 ml of water was added to the reaction solution, and the resulting crystals were collected by filtration and washed successively twice with 20 ml of water and once with 10 ml of hexane.
The obtained crystals were recrystallized from isopropanol to give 2-
3.2 g (9.9 mmol) of [2-fluoro-4-chloro-5-hydroxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one was obtained. 3.2 g of 2- [2-fluoro-4-chloro-5-hydroxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one
(9.9 mmol) was dissolved in about 50 ml of DMF, and 0.44 g of sodium hydride (60% by weight oil dispersion) was dissolved at room temperature.
(11 mmol), left at room temperature for 30 minutes, cooled on ice, and added with ethyl bromoacetate (1.8 g, 11 mmol). After stirring at room temperature for 1 hour, diethyl ether and water were sequentially added and extracted. The organic layer was washed successively with a 10% aqueous hydrochloric acid solution, a saturated aqueous solution of sodium hydrogen carbonate and a saturated saline solution, and then dried over anhydrous magnesium sulfate. After evaporating the solvent under reduced pressure, the residue was subjected to silica gel column chromatography to give 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3
2.4 g (5.5 mmol) of ethyl -pyridazinone-2-yl) phenoxyacetate (hereinafter referred to as compound A) was obtained. Melting point: 102.0 ° C. Production Example 2 In the above Production Example 1, except that the following reaction reagents were used instead of ethyl bromoacetate, the same operation was carried out to obtain the desired 2-chloro-4-fluoro-5- ( 4
-Methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative can be obtained.

[Table 1] (In the table, i represents iso, t represents tertiary, c represents cyclo) ¹ H-NMR (250 MHz or 300 MH, CDC
l ₃ , TMS, δ (ppm)) Compound E 0.88 (3H, t, J = 7 Hz), 1.2-1.4
(4H, m), 1.55-1.70 (2H, m), 2.
43 (3H, q, J = 2 Hz), 4.19 (2H, t,
J = 7 Hz), 4.68 (2H, s), 6.98 (1
H, d, J = 7 Hz), 7.33 (1H, d, J = 8H)
z), 7.99 (1H, s) Compound H 1.26 (6H, d, J = 6.3 Hz), 2.43 (3
H, q, J = 2 Hz), 4.65 (2H, s), 5.0
5-5.18 (1H, m), 6.98 (1H, d, J =
7 Hz), 7.33 (1H, d, J = 8 Hz), 7.9
8 (1H, s) Compound I 0.90 (6H, d, J = 6.6 Hz), 1.85 −
2.03 (1H, m), 2.42 (3H, q, J = 1.
8 Hz), 3.98 (2H, d, J = 6.5 Hz),
4.70 (2H, s), 6.99 (1H, d, J = 6.
3Hz), 7.33 (1H, d, J = 9.1 Hz),
7.98 (1H, s) Compound J 1.45-1.53 (9H, m), 2.39-2.45
(3H, m), 4.58-4.60 (2H, m), 6.
96-7.00 (1H, m), 7.30-7.36 (1
H, m), 7.96-8.00 (1H, m) Compound K 1.5-1.9 (8H, m), 2.43 (3H, q, J
= 2 Hz), 4.65 (2H, s), 5.2-5.4
(1H, m), 6.97 (1H, d, J = 7 Hz),
7.33 (1H, d, J = 8 Hz), 7.98 (1H, d, J = 8 Hz)
s) Compound M 2.42 (3H, q, J = 1.9 Hz), 4.67-
4.72 (2H, m), 5.23-5.37 (2H,
m), 5.84-5.98 (1H, m), 7.00 (1
H, d, J = 6.3 Hz), 7.33 (1H, d, J =
9.2 Hz), 7.99 (1H, s) Compound N 2.42 (3H, q, J = 1.8 Hz), 4.68−
4.71 (1H, m), 4.77 (2H, s), 4.9
4-5.01 (1H, m), 7.03 (1H, d, J =
6.3 Hz), 7.26-7.31 (1H, m), 7.
34 (1H, d, J = 9.0 Hz), 7.99 (1H, d, J = 9.0 Hz)
s) Atrazine is described in the Farm Chemicals Handbook, 1995 (Me
ister, Publishing Co., 1995) C32.

The composition of the present invention provides an effective herbicidal composition for selectively controlling a wide range of weeds and for applying to new cultivation methods such as no-tillage cultivation. Especially the major weeds in corn fields,
For example, buckwheat, Sanaetada, U.S.
Purslane, Shiroza, Aogaito, Noharagarashi, Utsunotsusanem, Ebisugusa, Ichibi, U.S. stag, U.S. morning glory, Maruba Asagao, Malva U.S. While effectively weeding off dicotyledonous plants and monocotyledonous plants such as barnyardgrass, enokorogosa, Achinonokorogosa, chinoko nokoro, crabgrass, ohishiba, seiban sorghum, barley, corngrass, etc. It does not cause harm to the patient.

In the composition of the present invention, the mixing ratio of 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and atrazine as active ingredients is considered. Although it may vary depending on weed species, application scenes, application conditions and the like, the weight ratio is usually in the range of 1: 5 to 500.

[0007] The composition of the present invention is usually mixed with a solid carrier, a liquid carrier and the like, and if necessary, added with a surfactant and other auxiliaries for the formulation to form an emulsion, wettable powder, suspension and the like. It is used after conversion. In these preparations, the total amount of the 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and atrazine is generally 0.5 to 90% by weight, preferably 0.5 to 90% by weight. Is contained in an amount of 1 to 80% by weight.

[0008] The solid carrier used in the formulation includes, for example, clays (kaolinite, diatomaceous earth, synthetic hydrous silicon oxide, fubasami clay, bentonite, acid clay, etc.), talc, and other inorganic minerals (sericite, quartz powder) , Sulfur powder, activated carbon, calcium carbonate, etc.) fine powders and granular materials such as chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, salt ammonium chloride, urea, etc.). Examples of the liquid carrier include water, alcohols (methanol, Ethanol, etc.), ketones (acetone, methyl ethyl ketone, cyclohexanone, etc.), aromatic hydrocarbons (toluene, xylene, ethylbenzene, methylnaphthalene, etc.), non-aromatic hydrocarbons (hexane, cyclohexane, kerosene, etc.), esters ( Ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile) Etc.), ethers (dioxane, diisopropyl ether), acid amides (dimethylformamide, dimethylacetamide), halogenated hydrocarbons (dichloroethane, trichlorethylene, etc.) and the like.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenates thereof, polyethylene glycol ethers, polyhydric alcohol esters, and sugars. Alcohol derivatives and the like. Other formulation aids include:
Fixing agents and dispersing agents such as casein, gelatin, polysaccharides (starch, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonite, synthetic water-soluble polymers (polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid, etc.), PAP (acidic isopropyl phosphate), BHT (2,6-tert-butyl-4-methylphenol), BHA (2- / 3-tert-butyl-
4-methoxyphenol), vegetable oil, mineral oil, fatty acid,
Stabilizers such as fatty acid esters are included.

[0010] The composition of the present invention can also be prepared by formulating each active ingredient by the above-mentioned formulation technique and then mixing them. The composition of the present invention thus formulated is applied to a plant as it is or diluted with water or the like. The composition of the present invention can further be expected to enhance herbicidal efficacy by being used in combination with other herbicides, and can also be used in combination with insecticides, fungicides, plant growth regulators, fertilizers, soil improvers, and the like. it can.

The application rate of the composition of the present invention is determined by mixing atrazine with an active ingredient compound, 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and atrazine. Although the ratio may vary depending on the ratio, weather conditions, formulation form, application time, application method, application place, weeds to be controlled and target crops, the total amount of the active ingredient compound per hectare is usually 10%.
２０００2000 g. Emulsions, wettable powders, suspending agents and the like are applied by diluting a predetermined amount thereof with water of usually 100 to 1000 liters per hectare.

[0012]

[Examples] Formulation examples are shown below. In the following examples, parts represent parts by weight. Formulation Example 1 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
Compound K, compound L, compound M or compound N2 parts, atrazine 40 parts, calcium ligninsulfonate 3 parts, sodium lauryl sulfate 2 parts and synthetic hydrous silicon oxide 53
The mixture is pulverized and mixed well to obtain a wettable powder. Formulation Example 2 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
5 parts of compound K, compound L, compound M or compound N, 40 parts of atrazine, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 50 parts of synthetic hydrous silicon oxide
The mixture is pulverized and mixed well to obtain a wettable powder. Formulation Example 3 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
10 parts of compound K, compound L, compound M or compound N, 40 parts of atrazine, 3 parts of calcium ligninsulfonate,
2 parts sodium lauryl sulfate and synthetic hydrous silicon oxide 4
5 parts are well pulverized and mixed to obtain a wettable powder. Formulation Example 4 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
Compound K, Compound L, Compound M or Compound N5 parts, Atrazine 40 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC (carboxymethylcellulose) 3
And 49 parts of water and wet milling until the particle size is less than 5 microns to obtain a suspending agent. Formulation Example 5 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
Compound K, Compound L, Compound M or Compound N2 parts, Atrazine 40 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC (carboxymethylcellulose) 3
And 52 parts of water are mixed and wet-ground to a particle size of 5 microns or less to obtain a suspending agent. Formulation Example 6 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
2 parts of compound K, compound L, compound M or compound N, 50 parts of atrazine, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 43 parts of synthetic hydrous silicon oxide
The mixture is pulverized and mixed well to obtain a wettable powder.

Hereinafter, test examples will be described. Evaluation criteria Herbicidal efficacy was evaluated as “0” when the emergence or growth of the test weed at the time of the survey showed no or little difference from that of the untreated one, and the test plant completely died or emerged or "10" indicates that growth is completely suppressed
And divided into 11 stages of 0 to 10, 0, 1, 2,
3, 4, 5, 6, 7, 8, 9, and 10. The evaluation values "7", "8", "9", and "10" of the herbicidal effect indicate excellent herbicidal effects, and the evaluation value "6" or less indicates insufficient herbicidal effect. Evaluation of phytotoxicity is `` harmless '' when little phytotoxicity is found, `` small '' when mild phytotoxicity is found, `` medium '' when moderate phytotoxicity is found, and `` harmless '' when severe phytotoxicity is found Indicated by "Large". Test Example 1 A plastic pot having an area of 26.5 × 19 cm ² and a depth of 7 cm was filled with field soil, and corn, Aquino nokorogosa, and crabgrass were sowed and grown in a greenhouse for 23 days.
An emulsion of compound A obtained by thoroughly mixing 10 parts of compound A, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate, 35 parts of xylene and 35 parts of cyclohexanone, an atrazine preparation (trade name: AAtrex: Ciba. A predetermined amount of each of the mixture of the compound A emulsion and the atrazine preparation was diluted with water, and the mixture was uniformly sprayed from above the plant with a small sprayer. The same operation was performed for compound E. The plants were grown in a greenhouse for 4 days after the treatment, and the herbicidal efficacy and safety to corn were investigated. Table 2 shows the results.

[Table 2]

[0014]

EFFECTS OF THE INVENTION By using the composition of the present invention, a wide range of weeds in a field corn field, particularly in a corn field, can be selectively removed.

Claims (4)

[Claims] (1) 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2
- yl) phenoxyacetic acid ester derivative and 6-chloro-N ² - ethyl-N ⁴ - isopropyl over 1,3,5-triazine-2,4-diamine and foliar herbicides characterized by containing as an active ingredient Composition. 2. The herbicidal composition according to claim 1, for controlling weeds in a corn field. (3) 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2)
- yl) phenoxyacetic acid ester derivative and 6-chloro-N ² - ethyl-N ⁴ - a herbicide containing as an active ingredient and isopropyl over 1,3,5-triazine-2,4-diamine, to foliar treatment to weeds A weeding method characterized by the following. 4. The method according to claim 3, wherein the weeds in the corn field are treated.