JPH10291909A - 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 (E,E)-(±)-2[1[[(3-chloro-2-propenyl) oxy]imino][propyl]5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexen-1-one and 2-[1-(ethoxyimino)butyl]-5-[2-(ethylthio)propyl]-3-hydroxy-2-cyclohexe n-1-one 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 (E, E)-(±) -2 [1 [[(3-chloro-2-propenyl) oxy] imino] [propyl] 5-
[2 (ethylthio) propyl] -3-hydroxy-2-
Cyclohexen-1-one (generic name clethodim; hereinafter referred to as clethodim) and 2- [1- (ethoxyimino) butyl] -5- [2- (ethylthio) propyl] -3-hydroxy-2-cyclohexen-1-one A herbicide composition containing, as an active ingredient, a herbicide composition containing one selected from the group consisting of sethoxydim (generic name: sethoxydim) as an active ingredient, and various fossils generated on agricultural or non-agricultural lands by foliar treatment of weeds. Weeds can be effectively weeded, and their herbicidal efficacy is synergistically increased compared to when they are used alone; they can be applied at low doses; and the herbicidal spectrum is further expanded, especially in soybean fields. The present inventors have found that a wide range of weeds can be selectively weeded, leading to the present invention. That is, the present invention relates to 2-chloro-4-fluoro-5- (4-methyl-5-trifluoromethyl-3-pyridazinone-2).
-Yl) a herbicide composition for foliage treatment (hereinafter, referred to as the composition of the present invention) containing, as active ingredients, a phenoxyacetic acid ester derivative and one selected from the group consisting of cletodim and sethoxydim; Provided is a method for weeding by foliage treatment.

[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)

[0007] Cretodim is described in the Farm Chemicals Handbook,
1995 (published by Meister, Publishing Co., 1995
Year) Compound described on page C334. Sethoxydim
Farm Chemicals Handbook, 1995 (Meister, Publ.
ishing Co., published in 1995) C336.

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 derivative as an active ingredient, clethodim and The mixing ratio with one selected from the group consisting of sethoxydim can vary depending on the target weed species, application scenes, application conditions, and the like, but is usually in the range of 1: 1 to 100 by weight.

[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 cletodim and sethoxydim is generally contained in the range of 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. A mixing ratio of the derivative with one selected from the group consisting of clethodim and sethoxydim,
Weather conditions, formulation, application time, application method, application location,
Although it may vary depending on the weeds and crops to be controlled, the total amount of the active ingredient compound per hectare is usually 10 to 2
000 g. Emulsions, wettable powders, suspensions and the like are applied by diluting a predetermined amount thereof with 100 to 1,000 liters of water per hectare.

[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,
10 parts of compound K, compound L, compound M or compound N, 50 parts of clethodim, 3 parts of calcium ligninsulfonate,
2 parts of sodium lauryl sulfate and synthetic hydrous silicon oxide 3
5 parts are well 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,
5 parts of compound K, compound L, compound M or compound N, 25 parts of clethodim, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate, and synthetic hydrous silicon oxide 65
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, 50 parts of sethoxydim, calcium ligninsulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 35 parts of synthetic hydrous silicon oxide are thoroughly 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, clethodim 25 parts, polyoxyethylene sorbitan monooleate 3 parts, CMC (carboxymethylcellulose) 3
And 64 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,
2.5 parts of compound K, compound L, compound M or compound N,
12.5 parts of clethodim, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC (carboxymethyl cellulose) and 79 parts of water are mixed and wet-pulverized until the particle size becomes 5 microns or less, and suspended. Get the agent. Formulation Example 6 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, 25 parts of sethoxydim, 3 parts of polyoxyethylene sorbitan monooleate, CMC (carboxymethyl cellulose)
3 parts and 64 parts of water are mixed and wet-ground to a particle size of 5 microns or less to obtain a suspending agent.

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 Field soil was packed in a plastic pot having an area of 26.5 × 19 cm ² and a depth of 7 cm, soybean, Aquino nokorogosa,
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
A, an emulsion of compound A obtained by thoroughly mixing 35 parts of xylene and 35 parts of cyclohexanone, a clethodim preparation (product name: Select: manufactured by Verent), and a mixture of the compound A emulsion and the clethodim preparation A predetermined amount of each was diluted with water, and sprayed uniformly from above the plant with a small sprayer. Compound E was treated similarly. The plants were grown in a greenhouse for 4 days after the treatment, and the herbicidal efficacy and the safety against soybean were investigated. Table 2 shows the results.

[Table 2]

Test Example 2 Field soil was filled in a plastic pot having an area of 26.5 × 19 cm ² and a depth of 7 cm, soybean, Aquino edulis,
The crabgrass and rice millet 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, a sethoxydim formulation (trade name: Poast: BASF A predetermined amount of each of the mixture of the compound A and the sethoxydim preparation was diluted with water, and the mixture was uniformly sprayed from above the plant with a small atomizer. The plants were grown in a greenhouse for 5 days after the treatment, 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 derivatives, and (E, E)
-(±) -2 [1 [[(3-chloro-2-propenyl)
Oxy] imino] [propyl] 5- [2 (ethylthio)
Propyl] -3-hydroxy-2-cyclohexene-1
-One and 2- [1- (ethoxyimino) butyl] -5
-[2- (ethylthio) propyl] -3-hydroxy-
A herbicidal composition for foliage treatment comprising, as an active ingredient, one selected from the group consisting of 2-cyclohexen-1-one. 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 derivatives, and (E, E)
-(±) -2 [1 [[(3-chloro-2-propenyl)
Oxy] imino] [propyl] 5- [2 (ethylthio)
Propyl] -3-hydroxy-2-cyclohexene-1
-One and 2- [1- (ethoxyimino) butyl] -5
-[2- (ethylthio) propyl] -3-hydroxy-
A herbicidal method comprising foliar treatment of a weed with a herbicide containing, as an active ingredient, one selected from the group consisting of 2-cyclohexen-1-one. 4. A method for treating weeds in a soybean field.
The method for weeding described in 1.