JPH10291907A - Herbicidal composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a herbicidal composition, especially the one suitable for controlling weeds in soybean fields. SOLUTION: This herbicidal composition contains a 2-chloro-4-fluoro-5-(4- methyl-5-trifluoromethyl-3-pyridazinon-2-yl)phenoxyacetic acid ester derivative and one selected from the group consisting of ethyl 2-[[[[(4-chloro-6-methoxy-2- pyrimidin-2-yl)amino]carbonyl]amino]sulfonyl]benzoate and methyl 3-[[[[(4- methoxy-6-methyl-1,3,5-triazin-2-yl)amino]sulfonyl]-2-thiophenecarboxy late as active ingredients. The foliar treatment of weeds can be carried out by using the herbicidal composition to thereby effectively kill various weeds growing in crop or non-crop lands. The herbicidal efficacies thereof are synergistically increased as compared with those of the single use thereof and application can be performed in a low dose. The weeding spectrum can further be enlarged to selectively kill a wide range of the weeds especially in soybean fields.

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 ethyl 2-[[[[(4-chloro-6-methoxy-2-pyrimidindinyl) amino] carbonyl] amino] sulfonyl] benzoate (generic name chlorimuron −
Ethyl, hereinafter referred to as chlorimuron-ethyl) and methyl 3-[[[[(4-methoxy-6-methyl-1,3,5
-Triazin-2-yl) amino] carbonyl] amino] sulfonyl] -2-thiophenecarboxylate (generic name thifensulfuron-methyl, hereinafter referred to as thifensulfuron-methyl); By treating the weeds with foliage, the herbicidal composition containing as an active ingredient can effectively weed various weeds that occur in agricultural land or non-agricultural land, and the herbicidal efficacy uses them alone. The present invention has been found to be synergistically increased as compared with the case, can be applied at a low dose, and has a broader herbicidal spectrum, and can selectively remove a wide range of weeds, particularly in a soybean field, and have reached the present invention. That is, the present invention provides 2-chloro-4-fluoro-5- (4-methyl-5-
A herbicidal composition for foliage treatment comprising as an active ingredient a trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and one selected from the group consisting of chlorimuron-ethyl and thifensulfuron-methyl ( 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 6.6 g (24.3 mmol) of 1,1-dibromo-3,3,3-trifluoroacetone was added to a mixture of 5.3 g (53.3 mmol) of sodium acetate and about 100 ml of water under ice-cooling. 2 at ℃
Stirred for 0 minutes. The reaction was cooled to room temperature and
A solution of 5.8 g (21.5 mmol) of fluoro-4-chloro-5-isopropoxyphenylhydrazine dissolved in about 20 ml of diethyl ether was added, and the mixture was stirred at room temperature for 1 hour. The ether layer was separated and concentrated, and about 60 ml of tetrahydrofuran (hereinafter referred to as "THF") was added to the residue, and 8.3 g (23.0 mm) of carbethoxyethylidenetriphenylphosphorane was added thereto.
ol) and heated to reflux for 2 hours. After the THF was distilled off under reduced pressure, the residue was subjected to silica gel column chromatography.
To give 3.8 g (10.5 mmol) of 2- [2-fluoro-4-chloro-5-isopropoxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one. 2
3.5 g (9.7 mmol) of-[2-fluoro-4-chloro-5-isopropoxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one was added under ice-cooling to about 10 m of concentrated sulfuric acid.
l and warmed to room temperature. After 10 minutes, about 1
00 ml of water was added, and the resulting crystals were collected by filtration and twice with 20 ml of water.
Washing was sequentially performed once with 10 ml of hexane. The obtained crystals were recrystallized from isopropanol to give 2- [2-fluoro-4
-Chloro-5-hydroxyphenyl] -4-methyl-5
3.2 g of trifluoromethylpyridazin-3-one (9.9 m
mol). 2- [2-fluoro-4-chloro-5-
Hydroxyphenyl] -4-methyl-5-trifluoromethylpyridazin-3-one 3.2 g (9.9 mmol) in DMF
Dissolve in about 50 ml and add sodium hydride (60 wt%
Add 0.44 g (11 mmol) of oil dispersion and add 30
After leaving at room temperature for 10 minutes, the mixture was cooled on ice, and ethyl bromoacetate (1.8 g, 11 g) was added.
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 purified by silica gel column chromatography.
And ethyl 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetate (hereinafter referred to as compound A).
2.4 g (5.5 mmol) were obtained. Melting point 102.0 ° C

Production Example 2 The same procedure as in Production Example 1 was carried out except that the following reaction reagents were used instead of ethyl bromoacetate, whereby 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, and c represents cyclo.)

[0006] ¹ H-NMR (250 MHz or 300 MHz)
MHz, CDCl 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)

Chlorimuron-ethyl is obtained from Farm Chemicals H
andbook, 1995 (Meister, Publishing Co., 1995), page C91. Thifensulfuron-methyl is available from the Farm Chemicals Handbook,
1995 (published by Meister, Publishing Co., 1995
Year) C293.

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. In particular, major weeds in soybean fields, such as buckwheat, Sanaetada, Sasaetada, Purslane, Shiroza, Aogetou, Noharagarashi, Tsunoxanem, Ebisugusa, Ichibi, American dragon deer, American morning glory, Malva morning glory, Malva American Dicotyledonous plants such as morning glory, artichoke mackerel, dogwood, onamimomi, sunflower, medaka, mulberry, euphorbia americana, ragweed, etc. Yatta - Ke - while effectively herbicidal monocotyledons such emissions, no phytotoxicity, such as a problem with respect to maize crop after soybeans and soybean crop.

In the composition of the present invention, 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester derivatives as active ingredients and chlorimuron- The mixing ratio with one selected from the group consisting of ethyl and thifensulfuron-methyl can vary depending on the target weed species, application scenes, application conditions and the like, but is usually 1: 0.2 by weight.
-20.

[0010] 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 formulation, etc., to form an emulsion, a wettable powder, a suspension and the like. It is used after conversion. In these formulations, 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-
The total amount of the 3-pyridazinone-2-yl) phenoxyacetic acid ester derivative and one selected from the group consisting of chlorimuron-ethyl and thifensulfuron-methyl is generally 0.5 to 90% by weight, preferably 1 to 80% by weight. %.

[0011] The solid carrier used in the preparation includes, for example, clays (kaolinite, diatomaceous earth, synthetic hydrous silicon oxide, fubasamikure, bentonite, acid clay, etc.), talc, and other inorganic minerals (sericite, quartz) Powder, sulfur powder, activated carbon, calcium carbonate, etc.) and fine powders and granular materials such as chemical fertilizers (ammonium sulfate, ammonium phosphate, ammonium nitrate, salt ammonium salt, urea, etc.). Examples of the liquid carrier include water, alcohol and the like. (E.g., methanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone), aromatic hydrocarbons (e.g., toluene, xylene, ethylbenzene, methylnaphthalene), non-aromatic hydrocarbons (e.g., hexane, cyclohexane) , Kerosene, etc.), esters (ethyl acetate, butyl acetate, etc.), nitriles (acetonitrile, isobutyronitrile) Le etc.), e - ethers (dioxane, diisopropyl et - ether, etc.), 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, and polyethylene glycol ethers.
Examples include ters, polyhydric alcohol esters, and sugar alcohol derivatives. Other formulation aids include:
For example, fixing 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.). And dispersant, PAP (isopropyl 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.

The composition of the present invention can also be prepared by formulating each of the active ingredients 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 as follows: 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2-yl) phenoxyacetic acid ester which is an active ingredient compound. Derivative and chlorimuron-
The mixing ratio with one selected from the group consisting of ethyl and thifensulfuron-methyl, weather conditions, formulation form, application time, application method, application place, weeds to be controlled, and 1 hectare Usually, the total amount of the active ingredient compounds is 5 to 500 g. Emulsions, wettable powders,
The predetermined amount of the suspension or the like is usually 100 per hectare.
Dilute with ~ 1000 liters of water and apply.

[0015]

[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 N (10 parts), chlorimuron-ethyl (5 parts), calcium ligninsulfonate (3 parts), sodium lauryl sulfate (2 parts) and synthetic hydrous silicon oxide (80 parts) are thoroughly pulverized and mixed 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,
30 parts of compound K, compound L, compound M or compound N, 15 parts of chlorimuron-ethyl, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 50 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed 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, 2.5 parts of thifensulfuron-methyl, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 82.5 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed. Obtain 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,
10 parts of compound K, compound L, compound M or compound N, 5 parts of chlorimuron-ethyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethyl cellulose) and 79 parts of water were mixed, To 5 microns or less to obtain a suspension. 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 N 5 parts, chlorimuron-ethyl 2.5 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC (carboxymethyl cellulose) 3 parts and water 86.5 parts Mixed, particle size 5
The suspension is obtained by wet milling to submicron size. Formulation Example 6 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
20 parts of compound K, compound L, compound M or compound N, 5 parts of thifensulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethyl cellulose) and 69 parts of water were mixed. , Particle size is 5
The suspension is obtained by wet milling to submicron size. Formulation Example 7 Compound A, Compound B, Compound C, Compound D, Compound E,
Compound F, Compound G, Compound H, Compound I, Compound J,
30 parts of compound K, compound L, compound M or compound N, 7.5 parts of thifensulfuron-methyl, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethylcellulose) and 56.5 water Mix the parts,
The suspension is obtained by wet grinding until the particle size is less than 5 microns.

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".

[0018] Test Example 1 area 26.5 × 19cm ^2, soybean filled with upland soil in a plastic pot of depth 7 cm, giant foxtail,
The crabgrass was sowed and grown in a greenhouse for 23 days. Compound A 10 parts, polyoxyethylene styryl phenyl ether 14 parts, calcium dodecylbenzenesulfonate 6
Part A, an emulsion of compound A obtained by thoroughly mixing 35 parts of xylene and 35 parts of cyclohexanone;
A predetermined amount of each of an ethyl preparation (Classic: manufactured by DuPont) and a mixture of the compound A emulsion and the chlorimuron-ethyl preparation was diluted with water, and the mixture was uniformly sprayed from above the plant with a small sprayer. . The plants were grown in a greenhouse for 4 days after the treatment, and the herbicidal efficacy and the safety against soybean were investigated.
In addition, the same test was performed for compound E. Table 2 shows the results.

[Table 2]

Test Example 2 A field pot was filled with field soil in a plastic pot having an area of 26.5 × 19 cm ² and a depth of 7 cm, soybean, Aquino nokorogosa,
The crabgrass and rice millet were sowed and grown in a greenhouse for 23 days. Emulsion of compound A obtained by well 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, thifensulfuron-methyl preparation (product) Name Pinnacl
e: manufactured by DuPont), a predetermined amount of each of the compound A and the mixed agent of thifensulfuron-methyl preparation was diluted with water,
The plant was evenly sprayed from above the plant with a small sprayer. After processing 5
The plants were bred in a greenhouse for a day and their herbicidal efficacy and safety against soybean were investigated. Table 3 shows the results.

[Table 3]

[0020]

EFFECT OF THE INVENTION By using the composition of the present invention, a wide range of weeds in a soybean field, particularly in a soybean 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 ethyl 2-
[[[[(4-Chloro-6-methoxy-2-pyrimidindinyl) amino] carbonyl] amino] sulfonyl] benzoate and methyl 3-[[[[(4-methoxy-6
-Methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] -2-thiophenecarboxylate as an active ingredient. Herbicide composition for foliage treatment. 2. The herbicidal composition according to claim 1, for controlling weeds in a soybean field. (3) 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2)
-Yl) phenoxyacetic acid ester derivative and ethyl 2-
[[[[(4-Chloro-6-methoxy-2-pyrimidindinyl) amino] carbonyl] amino] sulfonyl] benzoate and methyl 3-[[[[(4-methoxy-6
-Methyl-1,3,5-triazin-2-yl) amino] carbonyl] amino] sulfonyl] -2-thiophenecarboxylate as an active ingredient; A method for weeding, characterized in that weeds are treated with foliage. 4. A method for treating weeds in a soybean field.
The method for weeding described in 1.