Composition comprising r-type pyridine carboxylic acid compound and safeners and use thereof

Abstract

The application belongs to the field of pesticides, and particularly relates to a composition containing R-type pyridine oxycarboxylic acid compound and a safener and application thereof. The active ingredient R-type pyridine oxycarboxylic acid compound in the herbicidal composition is at least one selected from the following compounds: a) dichlorophenyl pyrazoline-3-carboxylic acid compound; b) 5-benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid compound; c) 8-quinolinyloxy acetic acid compound; d) pyrimidine compound; e) acyl sulfonamide compound; f) metcamifen and the like. The composition has obviously improved compatibility with important crops while maintaining high herbicidal activity, has excellent selectivity, and has great economic and social benefits in popularization and application.

Description

Technical Field

[0001] This invention belongs to the field of pesticides, specifically relating to a composition comprising an R-type pyridineoxycarboxylic acid compound and a safener, and its application. Background Technology

[0002] Keeping crops away from weeds and other vegetation that inhibit crop growth is of paramount importance in agriculture. To help address this issue, researchers in the field of synthetic chemistry have developed a variety of chemicals and chemical agents that can effectively control these unwanted weeds and other vegetation. Many types of chemical herbicides have been disclosed in the literature; for example, DE2335349A1, GB1418979A, and US3761486 disclose certain pyridineoxycarboxylic acid compounds, and many are already in commercial use. However, in addition to controlling the weeds and other vegetation, these herbicides can sometimes damage the protected crops. Summary of the Invention

[0003] To address the aforementioned problems in the prior art, this invention provides a composition comprising an R-type pyridineoxycarboxylic acid compound and a safener, and its application. This composition maintains high herbicidal activity while significantly improving compatibility with important crops and exhibiting excellent selectivity. Its widespread application offers substantial economic and social benefits.

[0004] A composition comprising an R-type pyridineoxycarboxylic acid compound and a safener, wherein the active ingredient, the R-type pyridineoxycarboxylic acid compound (A), is... The safer agent (B) is selected from at least one of the following compounds:

[0005] a) Dichlorophenylpyrazoline-3-carboxylic acid compounds, preferably, for example, mefenpyr-diethyl pyrazoline (CAS No.: 135590-91-9), and related compounds described, for example, in WO91 / 07874;

[0006] b) 5-Benzyl- or 5-phenyl-2-isoxazoline-3-carboxylic acid or 5,5-diphenyl-2-isoxazoline-3-carboxylic acid compounds, preferably compounds such as ethyl 5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylic acid or ethyl 5-phenyl-2-isoxazoline-3-carboxylic acid and related compounds described in WO91 / 08202, or isoxadifen-ethyl, n-propyl 5,5-diphenyl-2-isoxazoline-3-carboxylic acid or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylic acid described in patent application (WO95 / 07897);

[0007] c) 8-quinolinoxyacetic acid compounds, preferably cloquintocet-mexyl (CAS No.: 99607-70-2), (1,3-dimethylbut-1-yl)(5-chloro-8-quinolinoxy)acetate, 4-allyloxybutyl(5-chloro-8-quinolinoxy)acetate, 1-allyloxypropyl-2-yl(5-chloro-8-quinolinoxy)acetate, and (5-chloro-8-quinolinoxy)acetic acid ethyl Esters, methyl (5-chloro-8-quinolinoxy)acetate, allyl (5-chloro-8-quinolinoxy)acetate, 2-(2-propyliminooxy)-1-ethyl(5-chloro-8-quinolinoxy)acetate, 2-oxopropyl-1-yl(5-chloro-8-quinolinoxy)acetate, and related compounds described in EP-A-86750, EP-A-94349 and EP-A-191736 or EP-A-0492366;

[0008] d) Pyrimidine compounds, such as fenclorim (CAS No.: 3740-92-9);

[0009] e) Acylsulfonamide compounds, such as cyprosulfonamide (CAS No.: 221667-31-8) and 2-methoxy-N-{[4-(3-methylureido)phenyl]sulfonyl}benzamide (CAS No.: 129531-12-0) (metcamifen, “CGA246783”);

[0010] f)metcamifen (CAS No.: 129531-12-0).

[0011] The weight ratio of the active ingredient to the safener can vary within a wide range, such as 1:1000 to 1000:1, and is preferably 1:100 to 100:1 or 1:50 to 50:1; more preferably 1:30 to 30:1 or 1:20 to 20:1; more preferably 1:10 to 10:1 or 1:8 to 8:1; and even more preferably 1:5 to 5:1, 1:1 to 2:1 or 2:1 to 1:1.

[0012] The active ingredient in the composition accounts for 1-95% of the total mass, preferably 10-80%.

[0013] The application rate of the active ingredient can vary over a wide range depending on outdoor conditions such as temperature and humidity, as well as the type of herbicide used, typically between 0.001 and 1.0 kga.i. / ha, preferably between 0.1 and 750 ga.i. / ha, particularly between 1 and 500 ga.i. / ha, even more particularly between 5 and 300 ga.i. / ha, and especially between 10 and 100 ga.i. / ha.

[0014] The application rate of the safety agent is typically between 0.001 and 1.0 kga.i. / ha, preferably between 0.1 and 750 ga.i. / ha, particularly between 1 and 500 ga.i. / ha, even more particularly between 5 and 300 ga.i. / ha, and especially between 10 and 100 ga.i. / ha.

[0015] The composition also contains conventional additives, including carriers and surfactants.

[0016] The term "carrier" in this article refers to an organic or inorganic, natural or synthetic substance. These facilitate the application of the active ingredient and are generally inert and must be agriculturally acceptable, particularly to the plant being treated. Carriers can be solid, such as clay, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.; or liquid, such as water, alcohols, ketones, petroleum fractions, aromatic or waxy hydrocarbons, chlorinated hydrocarbons, liquefied gas, etc.

[0017] Surfactants can include emulsifiers, dispersants, or wetting agents, and can be ionic or nonionic. Examples that may be mentioned include salts of polyacrylic acid, lignin sulfonates, salts of phenol sulfonic acid or naphthalene sulfonic acid, polymers of ethylene oxide with aliphatic alcohols or with aliphatic acids or with aliphatic amines and substituted phenols (especially alkylphenols or arylphenols), sulfosuccinates, taurine derivatives (especially alkyl taurine esters), and phosphate esters of alcohols or polyhydroxyethylated phenols, alkyl sulfonates, alkyl aryl sulfonates, alkyl sulfates, lauryl ether sulfates, fatty alcohol sulfates, and sulfated hexadecyl, heptadecanols, and octadecyl alcohols, as well as sulfated fatty alcohol glycol ethers, and naphthalene or naphthalene sulfonic acid with phenol and formaldehyde. Condensations, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol or nonylphenol, alkylphenyl polyethylene glycol ether, tributylphenyl polyethylene glycol ether, tripearylphenyl polyethylene glycol ether, alkylaryl polyether alcohol, alcohols and fatty alcohols / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl polyethylene glycol ether acetal, sorbitan ester, lignin sulfite waste liquid, and proteins, denatured proteins, polysaccharides (e.g., methylcellulose), hydrophobically modified starch, polyvinyl alcohol, polycarboxylates, polyalkoxylated compounds, polyethyleneamine, polyvinylpyrrolidone and copolymers thereof. At least one surfactant is required to facilitate the dispersion of the active ingredients in water and to facilitate their proper application to plants.

[0018] The above composition may also contain various other components, such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, chelating agents, dyes, colorants, and polymers.

[0019] In addition, the compositions of the present invention can be mixed with known herbicidal active substances, such as those in the "World Encyclopedia of New Pesticide Varieties Technology", China Agricultural Science and Technology Press, 2010.9 and the literature cited therein.

[0020] In the context of this specification, if the abbreviation of the common name of the compound is used, it includes, in each case, all conventional derivatives, such as esters and salts, and isomers, particularly optical isomers, especially one or more commercially available forms. If the common name indicates an ester or salt, it also includes, in each case, all other conventional derivatives, such as other esters and salts, free acids and neutral compounds, and isomers, particularly optical isomers, especially one or more commercially available forms. The chemical name of the compound given indicates at least one compound covered by the common name, which is generally preferred. In the case of sulfonamides such as sulfonylureas, the salt also includes salts formed by the exchange of hydrogen atoms in the sulfonamide group with a cation. For example, 2,4-chloro derivatives include, but are not limited to: sodium salt, potassium salt, dimethylammonium salt, isopropylamine salt, etc., as well as methyl 2,4-chloro, ethyl 2,4-chloro, isooctyl 2,4-chloro, ethyl 2,4-chloro, etc.; 2,4-D derivatives include, but are not limited to: 2,4-D salts such as sodium salt, potassium salt, dimethylammonium salt, triethanolamine salt, isopropylamine salt, choline, etc., as well as 2,4-D esters such as methyl 2,4-chloro, ethyl 2,4-chloro, butyl 2,4-chloro, isooctyl 2,4-chloro, etc.

[0021] In the context of this invention, the salt of the compound is preferably in the form of its respective alkali metal salt, alkaline earth metal salt or ammonium salt, more preferably in the form of its respective alkali metal salt, more preferably in the form of its respective sodium salt or potassium salt, and most preferably in the form of its respective sodium salt.

[0022] The herbicide-safety agent composition of the present invention can be prepared by known methods, for example as a mixture of each component optionally with other active ingredients, additives and / or conventional formulation adjuvants, which is then applied after being diluted with water in a conventional manner, or as a so-called tank mix obtained by co-dilution of separately formulated or partially separately formulated components with water. Similarly, the separately formulated or partially separately formulated components can be applied at different times (separate application). The components or the herbicide-safety agent composition can also be applied in several portions (sequential application), for example, pre-emergence application followed by post-emergence application, or early post-emergence application followed by mid- or late post-emergence application. Preferably, the active ingredients in the respective compositions are applied together or continuously.

[0023] In one specific embodiment, the composition of the present invention can be diluted or used directly by the user before use. Its formulation can be prepared by conventional processing methods, namely, mixing the active substance with a liquid solvent or solid carrier, and then adding one or more surfactants such as dispersants, stabilizers, wetting agents, binders, defoamers, etc.

[0024] For application, commercially available formulations are diluted in a conventional manner, if appropriate, such as with water in the case of wettable powders, emulsifiable concentrates, dispersants, and water-dispersible granules. Powders, soil granules, or granules for broadcasting, as well as sprayable solutions, are generally not further diluted with other inert substances before application.

[0025] Specific formulations of the composition include, for example, dispersible oil suspensions, aqueous suspensions, emulsions, wettable powders, emulsifiable concentrates, water-dispersible granules (dry suspensions), water emulsions, or microemulsions.

[0026] In short, the compositions of the present invention can be mixed with solid and liquid additives conventionally used in prior art formulations.

[0027] In addition, the composition of the present invention can be applied to the leaves of the plant to be treated by spraying, i.e., applied to weeds, especially to surfaces that are infested or susceptible to weed infestation.

[0028] Depending on their properties, the safeners present in the herbicide-safener compositions of the present invention can also be used for pretreatment of crop seeds (e.g., for seed dressing), introduced into the sowing furrows before sowing, or applied together with the herbicide before or after emergence. Pre-emergence treatment includes not only treatment of the planting area before sowing (including any water present in the planting area, e.g., in the case of rice), but also treatment of planting areas where seeds have been sown but not yet covered by growing plants. Preferably, it is applied together with the herbicide. For this purpose, tank mixes or ready-to-use formulations can be used.

[0029] In one specific embodiment, seeds (e.g., grains, seeds, or vegetative propagators, such as the germination site of tubers or buds) or seedlings are pretreated with a safener—optionally in combination with other active agricultural chemicals. For seed pretreatment, the active ingredient may be applied to the seeds, for example, by seed dressing, or the active ingredient and seeds may be added to water or other solvents, and the active ingredient may be absorbed by adsorption or diffusion during, for example, soaking, or by swelling or germination. For seedling pretreatment, the seedlings may be contacted with the safener—optionally in combination with other active agricultural chemicals—by, for example, spraying, soaking, or irrigating, and subsequently transplanted, and optionally post-treated with a herbicide.

[0030] Safeners can be used alone or in combination with other active agricultural chemicals, such as fungicides, insecticides, plant fortifiers, fertilizers, or swelling and emergence promoters, to treat seeds or seedlings. Following pretreatment, the safener can be applied again before, after, or with one or more herbicides—or in combination with other known herbicides. Pretreatment of seeds or seedlings can improve the long-term effectiveness of the safener.

[0031] Furthermore, the present invention also provides a method for making the active ingredient A safe against the phytotoxicity of crops, comprising applying a combination of the herbicidal active ingredient A and a detoxifying safer B.

[0032] The present invention also provides an application of the composition in preventing unwanted plant growth.

[0033] The present invention also provides a method for preventing unwanted plant growth, comprising applying the composition to a plant, plant part, plant seed or area of ​​plant growth.

[0034] Preferably, the composition is used to selectively control weeds in useful crops; more preferably, the useful crops are genetically modified crops, crops treated with genome editing technology, or herbicide-tolerant crops.

[0035] The term "safener" in this invention should be understood to mean a compound suitable for reducing the phytotoxic effects of an active ingredient, such as a herbicide, in a crop protection composition on crop plants (useful crops). In the context of this invention, "weed-effective amount" means an amount suitable for one or more herbicides that have an adverse effect on plant growth. In the context of this invention, "detoxifying active amount" means an amount of one or more safeners suitable for reducing the phytotoxic effects of an active ingredient (e.g., a herbicide) in a crop protection composition on crop plants.

[0036] The term "useful crop" or "crop plant" refers to, for example, economically important crops, such as monocotyledonous crops like cereals (e.g., wheat, barley, rye, oats), rice, corn, millet, sorghum / millet; or dicotyledonous crops like sugar beets, rapeseed, cotton, sunflowers, and legumes such as *Glycine* (e.g., *Glycine max.(soya)*) such as non-GMO soybeans (e.g., conventional varieties like STS) or GMO soybeans (e.g., RR soybeans or LL soybeans) and their hybrids), *Phaseolus*, *Pisum*, *Vicia*, *Sesamum*, and *Arachis*; or vegetable crops from different plant groups, such as potatoes, leeks, cabbage, carrots, tomatoes, onions, and permanent crops. Crops and plantation crops, such as pome and stone fruit, berries, grapes, hevea, bananas, sugarcane, coffee, tea, citrus, nut cultivation, lawns, palm crops and forestry crops.

[0037] The term "unwanted plants" should be understood to mean all plants that grow where they are not desired. For example, these can be harmful plants (such as monocot or dicot weeds or unwanted crop plants), including those that are resistant to certain active herbicidal compounds—such as glyphosate, atrazine, glufosinate, or imidazolinone herbicides.

[0038] The compounds of this invention can be used to treat all plants and plant parts. Plant varieties and cultivars can be obtained through conventional propagation and breeding methods or through genetic engineering methods. Genetically modified plants (transgenic plants) are those in which a heterologous gene (transgenic gene) has been stably integrated into the plant's genome. The transgenic event defined by its specific location in the plant genome is called a transformation event or transgenic event.

[0039] Genetically modified plant cultivars that can be treated according to the present invention include those resistant to one or more biotic stresses (pests, such as nematodes, insects, mites, fungi, etc.) or abiotic stresses (drought, low temperature, soil salinization, etc.), or those containing other desired characteristics. Plants can be genetically modified to express traits such as herbicide tolerance, insect tolerance, modified oil characteristics, or drought tolerance.

[0040] When the herbicide-safety agent composition of the present invention is used on genetically modified crops, it not only has an effect on harmful plants observed in other crops, but also often reveals special effects when applied to specific genetically modified crops, such as altered or particularly broadened spectrum of controllable weeds, altered application rates, better compatibility with herbicides to which the genetically modified crops are resistant, and effects on the growth and yield of the genetically modified crop plants.

[0041] The present invention has the following excellent effects: compared with the use of various herbicides that do not contain a safener, the use of the herbicide-safener composition of the present invention significantly reduces damage to crop plants and can maintain excellent herbicidal activity. Detailed Implementation

[0042] The following embodiments are not intended to limit the invention, but are merely illustrative of how the invention is implemented. Examples are as follows:

[0043] Bioactivity evaluation:

[0044] Seeds or rhizomes of monocot and dicotyledonous plants were placed in plastic seedling pots filled with sandy loam, covered with soil, and grown at room temperature under favorable conditions (aquatic plants such as rice were planted in plastic square boxes containing water, with the water level reaching 3 cm above the soil surface). Ten to twenty days after sowing, the test plants at the one- to six-leaf stage were treated. The herbicide-safety agent composition of this invention, formulated as a water-soluble powder or suspension, along with the corresponding active ingredients prepared in parallel experiments, were sprayed onto the green plant parts at different doses, with a spray volume of 450 L / ha (converted value). The test plants were then placed in a greenhouse for 3-6 weeks, and the efficacy of the formulation was evaluated according to the following rating criteria, as shown in Tables 1-24. The experiments showed that, compared with the use of herbicides without a safener, the use of the herbicide-safety agent composition of this invention significantly reduced crop damage and maintained or improved weed control efficacy.

[0045] The absolute number method was used. Surviving weed seedlings were cut along the soil surface with a blade, and their fresh weight was measured using an analytical balance. Dead weeds were counted as having a fresh weight of zero.

[0046]

[0047]

[0048] Table 1 The safety activity and weed control efficacy of pyrazole herbicides in crops.

[0049]

[0050] Table 2 Safety activity of pyrazole herbicides in crops

[0051]

[0052] Table 3 The safety activity of quinoline in crops and its efficacy against weeds.

[0053]

[0054] Table 4 Safety activity of quinolone in crops

[0055]

[0056] Table 5 Safety activity and weed control efficacy of dibenzoxazolidine in crops

[0057]

[0058] Table 6 Safety activity of bis(oxazolyl) in crops

[0059]

[0060] Table 7 Safety activity and weed control efficacy of cyclopropanesulfonamide in crops.

[0061]

[0062]

[0063] Table 8 Safety and activity of cyclopropanesulfonamide in crops

[0064]

[0065] Table 9 Safety and weed control efficacy of glyphosate in crops

[0066]

[0067] Table 10 The safety activity of glyphosate in crops

[0068]

[0069]

[0070] Table 11 The safety activity and weed control efficacy of metcamifen in crops.

[0071]

[0072] Table 12 and the safety activity of metcamifen in crops

[0073]

[0074] Table 13 The safety activity and weed control efficacy of pyrazole herbicides in crops.

[0075]

[0076]

[0077] Table 14 Safety activity of pyrazole herbicides in crops

[0078]

[0079] Table 15 The safety activity of quinoline in crops and its efficacy against weeds.

[0080]

[0081] Table 16 Safety activity of quinolone in crops

[0082]

[0083] Table 17 Safety activity and weed control efficacy of dibenzoxazolidine in crops

[0084]

[0085] Table 18 Safety activity of bis(oxazolyl) in crops

[0086]

[0087] Table 19 Safety activity and weed control efficacy of cyclopropanesulfonamide in crops.

[0088]

[0089] Table 20 Safety and activity of cyclopropanesulfonamide in crops

[0090]

[0091] Table 21 Safety and weed control efficacy of glyphosate in crops

[0092]

[0093] Table 22 The safety activity of glyphosate in crops

[0094]

[0095] Table 23 The safety activity and weed control efficacy of metcamifen in crops.

[0096]

[0097]

[0098] Table 24 and the safety activity of metcamifen in crops

[0099]

[0100] Through extensive experimentation and exploration, this invention unexpectedly discovered that the composition not only effectively controls grasses, broadleaf weeds, and other weeds, but also significantly improves crop safety, and can be developed into a herbicide mixture with broad market value.

Claims

1. A composition comprising an R-type pyridineoxycarboxylic acid compound and a safener, characterized in that, The active ingredient, an R-type pyridineoxycarboxylic acid compound, is... The safety agent is selected from at least one of the following compounds: a) Dichlorophenylpyrazoline-3-carboxylic acid compounds; b) 5-Benzyl- or 5-phenyl-2-isooxazoline-3-carboxylic acid compounds or 5,5-diphenyl-2-isooxazoline-3-carboxylic acid compounds; c) 8-quinolinooxyacetic acid compounds; d) Pyrimidine compounds; e) Compounds of the acylsulfonamide class.

2. The composition comprising an R-type pyridineoxycarboxylic acid compound and a safener according to claim 1, characterized in that, The safety agent is selected from at least one of the following compounds: a) Pyrazole herbicide; b) Ethyl 5-(2,4-dichlorobenzyl)-2-isooxazoline-3-carboxylate, ethyl 5-phenyl-2-isooxazoline-3-carboxylate, bis(benzoxazolyl) acid, n-propyl 5,5-diphenyl-2-isooxazoline-3-carboxylate, or ethyl 5-(4-fluorophenyl)-5-phenyl-2-isooxazoline-3-carboxylate; c) Detoxifying quinone, (1,3-dimethylbut-1-yl)(5-chloro-8-quinolinoxy) acetate, 4-allyloxybutyl(5-chloro-8-quinolinoxy) acetate, 1-allyloxypropyl-2-yl(5-chloro-8-quinolinoxy) acetate, (5-chloro-8-quinolinoxy) ethyl acetate, (5-chloro-8-quinolinoxy) methyl acetate, (5-chloro-8-quinolinoxy) allyl acetate, 2-(2-propyliminooxy)-1-ethyl(5-chloro-8-quinolinoxy) acetate or 2-oxopropyl-1-yl(5-chloro-8-quinolinoxy) acetate; d) Detoxify glyphosate; e) Cyclopropanesulfonamide or 2-methoxy-N-{[4-(3-methylureo)phenyl]sulfonyl}benzamide; f)metcamifen.

3. A composition comprising an R-type pyridineoxycarboxylic acid compound and a safener according to claim 1 or 2, characterized in that, The weight ratio of the active ingredient to the safener is 1:1000 to 1000:1, preferably 1:100 to 100:1 or 1:50 to 50:1; more preferably 1:30 to 30:1 or 1:20 to 20:1; more preferably 1:10 to 10:1 or 1:8 to 8:1; and even more preferably 1:5 to 5:1, 1:1 to 2:1 or 2:1 to 1:

1.

4. A composition comprising an R-type pyridineoxycarboxylic acid compound and a safener according to claim 1 or 2, characterized in that, The composition also contains conventional adjuvants and / or other active ingredients.

5. The use of a composition comprising an R-type pyridine oxycarboxylic acid compound and a safener as described in any one of claims 1-4 in the prevention of unwanted plant growth.

6. A method for making the active ingredient of any one of claims 1-4 safe to phytotoxicity in crops, comprising applying a combination of the herbicidal active ingredient of any one of claims 1-4 and a safener of detoxifying activity.

7. A method for preventing unwanted plant growth, comprising applying a composition comprising an R-type pyridineoxycarboxylic acid compound and a safener as described in any one of claims 1-4 to a plant, plant part, plant seed or area of ​​plant growth.

8. The method according to claim 7, characterized in that, Apply the composition before, during, and / or after unwanted plant germination.

9. The application according to claim 5 or the method according to claim 6, 7 or 8, characterized in that, The composition is used to selectively control weeds in useful crops.

10. The application or method according to claim 9, characterized in that, The useful crops are genetically modified crops, crops treated with genome editing technology, or herbicide-tolerant crops.

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