KR20090051237A - Herbicide composition with reduced phytotoxicity - Google Patents

Abstract

(a) 2- {2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy) methyl] benzoyl} -cyclohexane-1,3-dione; And (b) benzoisothiazolinone derivatives, benzamide derivatives, benzothiazole derivatives, benzoxazolinone derivatives, benzoxazine derivatives, thiazinyl, isoprothiolane, hexamethylenetetramine, potassium oxalate and vanillin derivatives Provided are herbicide compositions having reduced phytotoxicity, comprising as a combination at least one phytotoxicity reducing substance selected from the group.

Description

Herbicide composition with reduced phytotoxicity {HERBICIDAL COMPOSITIONS WITH REDUCED PHYTOTOXICITY}

The present invention relates to herbicide compositions with reduced plant toxicity. In particular, the present invention relates to a herbicide composition having reduced phytotoxicity, which contains a compound having herbicidal activity and a specific compound having phytotoxicity reducing action.

Herbicide benzoylcyclohexadione is known from several documents (eg, WO 98/29406, WO 00/21924, WO 01/07422 and WO 2004/063187). Also, 2- {2-chloro-4-methyl-3-[(tetrahydrofuran-2-ylmethoxy) -methyl] benzoyl} cyclohexane-1,3-dione, which is one of the benzoylcyclohexadiones (common name) : Abbreviated as Tefuryltrione) has excellent herbicidal activity, but has a problem of causing significant plant toxicity to the crop depending on the conditions of use, the stage of use, the amount of use, the target crops. Therefore, it is required to investigate and find a compound having a phytotoxicity reducing action for suppressing such phytotoxicity.

The inventors have found that the combinations shown below reduce the phytotoxic action on crops produced by the herbicidally active compounds and exhibit the desired herbicidal effect, thus completing the present invention. Thus, according to the present invention,

(a) 2- {2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy) methyl] benzoyl} -cyclohexane-1,3-dione; And

(b) a group consisting of benzoisothiazolinone derivatives, benzamide derivatives, benzothiazole derivatives, benzoxazolinone derivatives, benzoxazine derivatives, thiazinyl, isoprothiolane, hexamethylenetetramine, potassium oxalate and vanillin derivatives Provided is a herbicidal composition with reduced plant toxicity, comprising as a combination at least one compound selected from.

Surprisingly, according to the present invention, when the above-mentioned herbicide compound (a) and compound (b) are used in combination, the compound (b) can reduce the phytotoxic action of the herbicide compound (a). It can be used in crop cultivation areas where the use of herbicide compounds is difficult, which has a very beneficial effect. In addition, it was found that the action of reducing the phytotoxicity of this compound (b) is a very useful action which is new and unknown so far.

Among the compounds (b), examples of the benzoisothiazolinone derivatives include 1,2-benzoisothiazolin-3-one and its sodium salts, probenazole and saccharin.

Examples of benzamide derivatives include phthalimide and benzamide.

Examples of benzothiazole derivatives include 2-hydroxybenzothiazole.

Examples of benzoxazolinone derivatives include 2-benzoxazolinone.

Examples of benzoxazine derivatives include 2H-1,4-benzoxazine-3 (4H) -one and isatoic anhydride.

Examples of vanillin derivatives include vanillin, vanillic acid, vanylyl alcohol and ethylvanillin.

Compound (b) is those known in the field of organic chemistry. Compound (b) itself has a phytotoxic effect, and in the herbicide composition of which the phytotoxicity of the present invention is reduced, the mixing ratio of the herbicide compound (a) and the compound (b) is the kind of herbicide compound, and the use of the composition. It may vary relatively widely depending on the stage, the zone of use and the method of use. In general, compound (b) may be used in a proportion of 0.001 to 5 parts by weight, preferably 0.004 to 3 parts by weight, per weight part of herbicide compound (a).

Herbicide compositions of reduced phytotoxicity of the present invention are most preferably characterized by being capable of exhibiting selective herbicidal activity between crops and weeds. This selective herbicidal action makes the composition useful in the following plants.

Dicotyledonous weed varieties such as Mustapis, Crepidium, Gallium, Stellaria, Chinenopodium, Urtica, Senecio, Hairy Purse ( Amaranthus, Purslane (Portulaca), Xanthium, Morning Glory (Ipomoea), Burdock (Polygonum), Shamrock (Ambrosia), Milk Thistle (Cirsium), Seaweed (Sonchus), Horsecress (Rorippa), Lamium ), Veronica, Datura, Viola, Galeopsis, Papaver, Centaurea, Garlinsoga, Nodeul, Lindermia et al .;

Dicotyledonous crops such as Gossypium, Glycine, Beetroot, Beet, Carrot (Daucus), Beans (Phaseolus), Peas (Pisum), Potatoes (Solanum), Flax (Linum), Sweet Potatoes / Morning Glory (Ipomoea), Vicia, Tobacco (Nicotiana), Tomato (Lycopersicon), Peanut (Arachis), Turnip / Chinese / Red / Cabbage (Brassica), Lettuce (Lactuca), Cucumber / Melon (Cucumis) and Pumpkin (Cucurbita) );

Monocotyledonous weed varieties such as Echinochloa, Setaria, Panicum, Digitaria, Pleleum, Poa, Feduca, Festuca, Rake Eleusine, Lolium, Bromus, Oat, Avena, Papyrus / Cyperus, Sorghum, Agropyron, Aqualily, Skykeeper (Fimbristylis) ), Sagittaria, Eleocharis, Reed (Scirpus), Sparrow (Paspalum), Barley, Agrostis, Alopecurus and Cynodon; And

Monocotyledonous crops such as rice (Oryza), corn / popcorn (Zea), wheat (Triticum), barley (Hordeum), oats (Avena), rye (Secale), sorghum (Sorghum), millet (Panicum), sugar cane ( Saccharum), pineapple (Ananas), asparagus and onion (Allium).

In addition, the composition of the present invention is by no means limited to these plants, and likewise includes other plants.

Compositions of the present invention are perennial plant cultivation, such as arbors, ornamentals, orchards, vineyards, citrus orchards, nut orchards, banana arable land, coffee arable land, tea arable land, rubber arable land, guinean oil palm arable land, cocoa arable land, It can be used to control weeds in small orchards and hop fields. In addition, the compositions of the present invention can be used to selectively control weeds in annual plant cultivation.

The compositions of the present invention may be formulated in conventional formulations used to control weeds. Examples of formulation forms include dust, granules, hydrating agents, water dispersible granules, emulsifiable concentrates, flowable formulations or aqueous suspensions, emulsions, jumbo package, suspended granules and the like.

These formulations may be prepared in a manner known per se, for example by mixing the herbicide compound (a) and compound (b) with a liquid or solid diluent or carrier, optionally with a surfactant or formulation aid, to prepare the formulation. Can be.

Examples of solid carriers and / or solid diluents that can be used in formulating the compositions of the present invention are:

Minerals of minerals such as clay, kaolin, talc, calcium carbonate, diatomaceous earth, zeolite, bentonite, acidic clay, activated clay, attapulgite clay, vermiculite, pearlite, pumice, silica sand, silica and the like;

Synthetic products such as hydrophilic silica, hydrophobic silica, white carbon such as calcium silicate, synthetic zeolites, titanium dioxide and the like;

Vegetable organics such as soybean powder, tobacco powder, corncob meal, walnut powder, flour, wood flour, starch, crystalline cellulose and the like;

Synthetic or natural polymer compounds such as coumarone resins, petroleum resins, alkyd resins, polyalkylene glycols, ketone resins, ester gums and the like;

Waxes such as carnauba wax, beeswax and the like; And

Water-soluble substances such as urea, lactose, sucrose, ammonium sulfate, potassium chloride and the like.

Examples of suitable liquid carriers and / or liquid diluents are:

Fats and oils such as palm oil, rapeseed oil, corn oil, soybean oil, rice bran oil and the like;

Paraffinic or naphthenic hydrocarbon-based solvents such as kerosene, mineral oil, spindle oil, white oil, n-paraffin, isoparaffin, naphthene and the like;

Aromatic hydrocarbon solvents such as xylene, alkylbenzenes, alkylnaphthalenes, and the like;

Alcohols such as ethanol, benzyl alcohol, isopropanol, cyclohexanol and the like;

Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, polyethylene glycol and the like;

Ether alcohols such as ethylene glycol ethyl ether, ethylene glycol phenyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether and the like;

Ketones such as methyl ethyl ketone, diisobutyl ketone, cyclohexanone, acetophenone, isophorone, γ-butyrolactone and the like;

Fatty acid methyl esters such as palm oil fatty acid methyl esters, dibasic acid methyl esters such as succinic acid dimethyl esters, glutamic acid dimethyl esters, adipic acid dimethyl esters, and the like, and ethyl acetate, amyl acetate, ethylene glycol acetate, diethylene glycol acetate, and the like. Esters containing;

Ethers such as dioxane, tetrahydrofuran and the like;

Polar solvents such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-alkylpyrrolidone and the like, or water.

In addition, surfactants, for the emulsification, dispersion, wetting, diffusion, disintegration of the active ingredient, prevention of effects, enhancement of the effect, and / or improvement of the physical properties of the preparation (control of collapse properties, improvement of fluidity, inhibition of freezing, imparting rainfall resistance, etc.), Binders and other auxiliaries may be used. As surfactants, all types of compounds can be used, such as nonionic, anionic, cationic and amphoteric compounds, and usually nonionic and / or anionic compounds can be used. Suitable nonionic surfactants include, for example, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters, sucrose fatty acid esters; Polyoxyalkylene fatty acid esters, polyoxyalkylene resin acid esters, polyoxyalkylene fatty acid esters; Polyoxyalkylene castor oil, polyoxyalkylene hardened castor oil; Polyoxyalkylene alkyl ethers; Polyoxyalkylene alkylphenyl ethers, polyoxyalkylene dialkylphenyl ethers, polyoxyalkylene alkylphenyl ether formalin condensates; Polyoxyethylene / polyoxypropylene block polymers, alkylpolyoxyethylene / polyoxypropylene block polymer ethers, alkylphenylpolyoxyethylene / polyoxypropylene block polymer ethers; Polyoxyalkylenealkylamines, polyoxyalkylene fatty amides; Polyoxyalkylene benzylphenyl (or phenylphenyl) ether, polyoxyalkylene styrylphenyl (or phenylphenyl) ether; Polyoxyalkylene ethers and ester type silicon-based and fluorine-based surfactants and the like can be mentioned.

Examples of suitable anionic surfactants include alkylsulfate salts, polyoxyalkylene alkyl ether sulfate salts, polyoxyalkylene alkylphenyl ether sulfate salts, polyoxyalkylene benzyl (or styryl) phenyl (or phenylphenyl) Ether sulfate salts, polyoxyethylene / polyoxypropylene block polymer sulfate salts; Paraffin (alkane) sulfonate salts, α-olefin sulfonate salts, dialkyl sulfosuccinate salts, alkylbenzene sulfonate salts, mono or dialkylnaphthalene sulfonate salts, naphthalene sulfonate-formalin condensate salts, alkyldiphenyls Ether disulfonate salts, ligninsulfonate salts, polyoxyalkylene alkylphenyl ether sulfonate salts, polyoxyalkylene ether sulfosuccinic acid half ester salts; Fatty acid salts, N-methylfatty acid sarcosinate, resin acid salts; Polyoxyalkylene alkyl ether phosphate salts, polyoxyalkylene mono or dialkylphenyl ether phosphate salts, polyoxyalkylene benzylated (or styrylated) phenyl (or phenylphenyl) ether phosphate salts, polyoxyethylene / polyoxypropylene Block polymer phosphate salts; Polyacrylic acid salt, polycarboxylic acid salt, etc. are mentioned.

Cationic surfactants include ammonium types such as alkyltrimethyl ammonium chloride, methyl-polyoxyethylene-alkyl ammonium chloride, alkyl-N-methylpyridinium bromide, mono or dialkylmethylated ammonium chloride, alkylpentamethylpropylenediamine dichloride, and the like. ; Benzalkonium types such as alkyldimethylbenzalkonium chloride, benzetonium chloride and the like.

Amphoteric surfactants include betaines such as dialkyldiaminoethyl betaine, alkyldimethylbenzyl betaine and the like.

Examples of the binder include bentonite, casein, gelatin, starch, dextrin, lignin sulfonate, alginate, gum arabic, xanthan gum, carboxymethylcellulose, methylcellulose, polyvinyl alcohol, polyvinylpyrrolidone and the like.

Other auxiliaries include disintegration modifiers, cryoprotectants, preservatives, rheology improvers, antifoams, wetting agents, electrodeposition agents, and imparting rainfall resistance.

The above-mentioned carriers and surfactants, binders and various auxiliaries may be appropriately used alone or in combination depending on the object in consideration of the form of the preparation, the steps of use, and the like.

The formulations may usually contain herbicide compounds (a) and compounds (b) having a total concentration of 0.1 to 95 wt%, preferably 0.5 to 90 wt%.

The compositions of the present invention may be used as such or in the form of a formulation thereof to prevent or control weeds, or may be mixed in a tank in use. In addition, the compositions can be mixed with other known active compounds, especially those commonly used, such as fungicides, insecticides, plant growth regulators, plant nutritional supplements, soil improvers, fertilizers and the like.

The compositions of the invention can be used as such or in the form of their preparations, or in the form of use prepared by further dilution of the preparations, for example in the form of solutions, emulsions, suspensions, dusts, hydrating agents or granules ready for use. These forms can be used in rice fields by conventional methods such as spraying, spraying, atomizing, dusting, granulating spraying and the like.

The composition of the present invention can be used before and after plant germination. According to the invention, plant toxicity can also be reduced by using compound (b) before and after use of herbicide compound (a).

According to the present invention, the amount of the composition used can vary widely. The amount used may be, for example, 0.01 to 10 kg / ha, preferably 0.5 to 5 kg / ha, with respect to the total amount of the herbicide compound (a) and the compound (b).

The excellent effects of the compositions of the present invention will be more specifically illustrated by the following examples. However, the present invention should not be limited only to these examples.

Biological test and preparation

(Test compound)

(a): Tefuryltrion

(b-1): sodium salt of 1,2-benzoisothiazolin-3-one

(b-2): probenazole

(b-3): phthalimide

(b-4): benzamide

(b-5): 2-hydroxybenzothiazole

(b-6): 2-benzoxazolinone

(b-7): 2H-1,4-benzoxazine-3 (4H) -one

(b-8): isatoic anhydride

(b-9): hexamethylenetetramine

(b-10): potassium oxalate

(b-11): vanillin

(b-12): vanyl acid

(b-13): ethylvanillin

Test Example 1:

Plant toxicity reduction effect test (I)

Test Methods:

30 ml of the pharmaceutical solution containing 1 ppm of compound (a) and 20 ppm of test compound belonging to compound (b), respectively, were injected into a standard bottle having a volume of 50 ml.

After cutting the root portions of rice to 1 cm at 2.0-2.2 blade stages, they were immersed in the pharmaceutical solution and placed in growth cabinets (at 25 ° C, 80% humidity, 6 KLx irradiation light and 12 hours light cycle). It was left for 3 days. Water was evaporated upon standing so that the moisture content was maintained at 30 ml. After 3 days, the rice was taken out and the medicinal solution attached to the rice was rinsed with water, and then transferred to a hydroponic solution containing a fertilizer (30 ml), and the growth cabinet (temperature of 25 ° C., 80% humidity, 6 KLx irradiation dose) And in a light cycle of 12 hours).

For evaluation, after immersion in the drug solution for 12 days, the leaf part and root part of the rice treated in each treatment compartment marked by the kind of compound (b) contained in the drug solution were visually observed.

Evaluation was performed according to the following evaluation criteria.

+++; No longer grow Rooting of the roots and growth of the leaf and root portions were promoted.

++; Compared with a single agent of compound (a), rooting of roots and growth of leaf parts and root parts were promoted.

+; These were at similar levels to a single agent of compound (a).

-; These were more inhibited than a single agent of compound (a).

The test results are shown in Table 1.

TABLE 1

 Compound (b) Visual observation Leaf part Root part (b-1) ++ +++ (b-2) - +++ (b-3) +++ ++ (b-4) ++ ++ (b-5) ++ ++ (b-6) +++ +++ (b-7) +++ - (b-8) ++ - (b-9) ++ +++ (b-10) ++ +++ (b-11) +++ +++ (b-12) +++ - (b-13) +++ ++

Test Example 2:

Plant toxicity reduction effect test (II)

Test Methods:

A 1/500 Oa Wagner's pot filled with paddy soil was provided to KOITOTRON and the greenhouse. The temperature setting of Coitotron was at one crossing of 13 ° C. (12 hours) to 15 ° C. (12 hours) until 14 days after implantation, and at one crossing of 20 ° C. (12 hours) to 25 ° C. (12 hours) after 14 days. It was done. The water on the bench provided with the pot was cooled so that the temperature in the greenhouse was set at an average of 12.5 ° C. until 14 days after transplantation. Cooling was stopped after 14 days with an average temperature of 21.8 ° C.

Three rice (brand; NIHONBARE, 2.2-2.6 blade) per port were transplanted to a transplant depth of 2 cm. After implantation, the ports were kept under 3 cm irrigation and the water level was maintained for the duration of the test. After 5 days of implantation, a fixed amount of each of granules having compound (a) 3% and granules of compound (a) and compound (b) having a fixed concentration was added to each pot on the irrigation surface.

A 0.5 cm / day leak treatment was performed for 7 days from the next day after the treatment.

For evaluation, measurements of stem number, root weight and leaf weight were made 5 weeks after treatment with the compound.

Evaluation was performed according to the following evaluation criteria.

It is expressed as 100% as a% comparative rate with respect to a single agent treated with compound (a).

Greater than 100%; Compared to single drug treatment of compound (a), plant toxicity was reduced.

100 to 90%; Compared with the single drug treatment of compound (a), the effect was observed, but recovery is expected but little effect on the yield.

90 to 80%; Compared with single drug treatment of compound (a), a large effect was observed.

Less than 80%; Compared with the single agent treatment of compound (a), an apparently large effect was observed.

The test results are shown in Table 2.

TABLE 2

Throughput (kg / ha) Koitoron greenhouse Stem Number Root weight Leaf weight Stem Number Root weight Leaf weight Granules with Compound (a) 3%  15  13.0  0.63 g  3.30 g  3.5  0.29 g  3.90 g Add 0.1% of compound (b-9)  15  -  -  -  135.7%  104.4%  113.3% Add 0.5% of compound (b-9)  15  148.0%  160.0%  134.6%  128.6%  106.1%  118.6% Add 1.0% of compound (b-9)  15  132.0%  146.4%  132.9%  -  -  - Add 0.1% of compound (b-1)  15  164.0%  168.8%  184.5%  157.1%  112.3%  111.0% Add 0.5% of compound (b-1)  15  156.0%  186.4%  177.7%  142.9%  98.2%  102.7% Add 0.2% of compound (b-1) and 0.2% of compound (b-9)   15   132.0%   145.6%   174.5%   142.9%   100.0%   111.0% Untreated - 31 2.23 g 10.3 g 7.3 0.38 g 5.57 g

Preparation Example 1 (Extruded Granules)

3 parts by weight of compound (a), 0.1 parts by weight of compound (b-2), 30 parts by weight of sodium bentonite (montmorillonite), 1 part by weight of sodium tripolyphosphate, 3 parts by weight of ligninsulfonate and 61.4 parts by weight of calcium carbonate To the mixture, 25 parts by weight of water containing 0.5 parts by weight of sodium dialkylsulfosuccinate salt and 1 part by weight of sodium polycarboxylic acid salt were added, the mixture was kneaded well, and processed into granules of 500 to 1700 µm by an extrusion granulator. It dried at ° C and obtained granules.

Preparation Example 2 (Extruded Granules)

Sodium dialkylsulfosuccinate in a mixture of 3 parts by weight of compound (a), 0.1 part by weight of compound (b-2), 30 parts by weight of sodium bentonite (montmorillonite), 2 parts by weight of hexamethaphosphate and 60.2 parts by weight of clay 22 parts by weight of water containing 0.2 parts by weight of salt, 4 parts by weight of polyoxyalkylene tristyrylphenyl ether sodium sulfate salt and 0.5 parts by weight of sodium polycarboxylic acid salt were added, and the mixture was kneaded well by an extruded granulator for 500-1700 μm. Was processed into granules and dried at 80 ° C. to obtain granules.

Preparation Example 3 (Fine Granules)

73.2 parts by weight of clay mineral particles having a particle diameter distribution of 0.2 to 0.7 mm were injected into a container rotary mixer, and 15 parts by weight of compound (a) and 0.3 parts by weight of compound (b-2) were sprayed together with 10 parts by weight of the liquid diluent under rotation, 1.5 parts by weight of white carbon was added to obtain fine particles.

Preparation Example 4 (Fluid Formulation)

6 parts by weight of compound (a), 0.1 part by weight of compound (b-2), 10 parts by weight of propylene glycol, 5 parts by weight of polyoxyalkylene tristyrylphenyl ether, 1 part by weight of xanthan gum, 0.1 part by weight of silicone oil emulsion And 77.8 parts by weight of the water were stirred well and then milled using DYNO-MILL (type KDL) to give a liquid wetting agent.

Claims (2)

(a) 2- {2-chloro-4-mesyl-3-[(tetrahydrofuran-2-ylmethoxy) methyl] benzoyl} -cyclohexane-1,3-dione; And (b) a group consisting of benzoisothiazolinone derivatives, benzamide derivatives, benzothiazole derivatives, benzoxazolinone derivatives, benzoxazine derivatives, thiazinyl, isoprothiolane, hexamethylenetetramine, potassium oxalate and vanillin derivatives A herbicide composition with reduced plant toxicity, comprising as a combination at least one compound selected from. The compound (b) according to claim 2, wherein the compound (b) according to claim 1 is 1,2-benzoisothiazolin-3-one and its sodium salt, probenazole, saccharin, phthalimide, benzamide, 2-hydroxy Benzothiazole, 2-benzoxazolinone, 2H-1,4-benzoxazin-3 (4H) -one, isatoic anhydride, thiazinyl, isoprothiolane, hexamethylenetetramine, potassium oxalate, vanillin, vanillic acid And at least one compound selected from the group consisting of vanylyl alcohol and ethylvanillin.