JP7134547B2 - herbicide composition - Google Patents

Description

[Cross reference to related applications]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0153278 dated November 16, 2017, and all contents disclosed in the documents of the Korean Patent Application are incorporated herein by reference. included as

The present invention relates to herbicidal compositions containing herbicidally active ingredients exhibiting excellent herbicidal activity.

BACKGROUND ART In crop cultivation technology, it is important to protect crops by controlling weeds that inhibit the growth of crops. In order to reduce damage such as stunted growth or reduced yield of crops caused by weeds grown in crop cultivation areas, herbicidal active substances capable of effectively controlling them and being safe for crops have been developed. A large number of herbicidally active substances developed to date are registered for specific crops and used for controlling weeds. A herbicidal active substance for use in controlling weeds occurring in such specific crop cultivation areas should have high herbicidal activity, a broad herbicidal spectrum, and be safe for the environment and crops. is preferred.

On the other hand, herbicidal compositions containing herbicidally active substances as described above include wettable powders, emulsifiable concentrates, water-dispersible granules, granules, and liquid water. It is developed as a dosage form such as a suspension concentrate and used as a herbicide. However, in the case of wettable powders, emulsified concentrates and granular wettable powders, they are generally diluted with water to a predetermined concentration to produce a spray solution. There is a problem of excessive cost and time required to evenly spread the surface. In the case of granules, since they can be used directly as they are, the problems of wettable powders, emulsifiable concentrates and granular wettable powders have been solved. Auxiliary agents for forming must be included, and the manufacturing process such as pulverization, mixing, kneading, granulation, drying, classification, etc. is complicated, and there is a problem that uneven spraying occurs. . In order to overcome the above-mentioned problems such as the dosage form, a formulation of a liquid suspension concentrate has been developed, which has a relatively simple manufacturing process, is environmentally friendly, and can be simplified and efficiently applied. was done. On the other hand, when used as herbicides in various dosage forms, it is an important issue to ensure the stability of the herbicide composition even during long-term storage.

The compound of the following chemical formula a [ISO proposed name: flucetosulfuron] is a herbicidally active substance belonging to the sulfonylurea family, and has herbicidal activity in Korean Patent No. 10-0399366 (Application No. 10-2000-0059990). Already described as a substance.

The flucetosulfuron is applied to rice, wheat, barley (appropriate dosage: 10-40 g a.i./ha) and lawn (appropriate dosage: 50-200 g a.i./ha) in soil or foliage. It is safe for these crops when treated and is known to be highly herbicidal against a wide range of grass species including broadleaf weeds, grass weeds, cyperaceous weeds, annual and perennial weeds.

However, ensuring the stability of herbicidal compositions containing herbicidally active substances belonging to the sulfonylurea family as described above remains a problem. In particular, in the case of a liquid wettable powder (Suspension Concentrate, SC) dosage form, it is difficult to store for a long period of time because its stability is further deteriorated due to hydrolysis during storage at high temperatures.

Korean Patent No. 10-0399366

The present invention aims to provide a herbicidal composition containing a herbicidally active substance belonging to the sulfonylurea family, which has excellent herbicidal activity and excellent stability and can be stored for a long period of time. is.

The present invention comprises a pyridinesulfonylurea compound represented by the following chemical formula 1 as an active ingredient, the pyridinesulfonylurea compound is included in an isomer mixture of erythro-form and threo-form, A herbicidal composition is provided in which the Erythro-form is present in at least 92% by weight of the isomer mixture.

n represents an integer from 1 to 3,
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R' is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a halogen group or an alkoxy group having 1 to 2 carbon atoms,
X and Y are each independently an alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a haloalkoxy group having 1 or 2 carbon atoms or a halogen group.

According to the present invention, it has excellent herbicidal activity and a low decomposition rate even during long-term high-temperature storage, and in particular, it is possible to ensure excellent stability even in the form of a liquid wettable powder (suspension concentrate, SC). herbicidal compositions can be provided.

Hereinafter, the present invention will be described in more detail in order to facilitate understanding of the present invention. At this time, the terms and words used in the specification and claims should not be construed as being limited to their ordinary and dictionary meanings, and the inventors should use their inventions in the best possible way. For the purpose of explanation, it should be construed to have meanings and concepts that conform to the technical spirit of the present invention, in line with the principle that the concepts of terms can be defined appropriately.

The herbicidal composition of the present invention contains a pyridinesulfonylurea compound represented by the following chemical formula 1 as an active ingredient, and the pyridinesulfonylurea compound is an isomer mixture of erythro-form and threo-form. and the Erythro-form is contained in at least 92% by weight of the isomer mixture.

In Chemical Formula 1, n is an integer of 1 to 3, R is hydrogen or an alkyl group having 1 to 4 carbon atoms, and R' is hydrogen, an alkyl group having 1 to 4 carbon atoms, and 1 carbon atom. is a haloalkyl group having 3 to 3, a halogen group or an alkoxy group having 1 to 2 carbon atoms, and X and Y are each independently an alkyl group having 1 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, or 1 is a haloalkoxy group or a halogen group of 2 from .

More preferably, the pyridinesulfonylurea compound represented by Formula 1 is an integer of 1 or 2, R is hydrogen or a methyl group, and R' is hydrogen or a halogen group. or a methyl group, and X and Y may each be a methoxy group.

More preferably, the pyridinesulfonylurea compound represented by Chemical Formula 1 has n in Chemical Formula 1, where n is an integer of 1 or 2, R is methyl, and R' is hydrogen, Cl, Br, or a methyl group. and each of X and Y may be a methoxy group.

The pyridinesulfonylurea compound represented by Chemical Formula 1 is, for example, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine -3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide, N- [(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-hydroxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4 ,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-methoxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6- Dimethoxypyrimidin-2-yl)aminocarbonyl]-4-methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine-2 -yl)aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, and N-[(4,6-dimethoxypyrimidin-2-yl) It may be at least one selected from the group consisting of aminocarbonyl]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide.

More preferably, the pyridinesulfonylurea compound represented by Formula 1 may be the compound represented by Formula 2 below [ISO proposed name: flucetosulfuron].

Since the compound of Formula 1 contains two asymmetric carbons, it can exist as an erythro-form or threo-form isomer.

The herbicidal composition of the present invention contains the compound represented by Chemical Formula 1 in the form of an erythro-form and threo-form isomer mixture, wherein the erythro-form form) is contained at 92% by weight or more of the total isomer mixture. More preferably, the Erythro-form may comprise 95% by weight or more of the isomer mixture, and even more preferably, the Erythro-form is 95% to 99% by weight of the isomer mixture. % may be included.

Thus, by containing 92% by weight or more of the erythro-form in the isomer mixture of the erythro-form and the threo-form, the herbicidal activity is excellent. In addition, stability can be ensured because the decomposition rate decreases even during long-term high-temperature storage.

When the compound represented by Chemical Formula 1 is not included in the form of a mixture of erythro-form and threo-form isomers, but in the form of an erythro-form alone, production efficiency However, when it is contained in the threo-form alone, the herbicidal activity is lowered and the decomposition rate is greatly increased, so that the stability is lowered. In addition, even though it exists in an isomer mixture of erythro-form and threo-form, when the erythro-form is contained in less than 92% by weight of the isomer mixture, weeding Activity decreases and degradation rate increases. In particular, in the case of a liquid dosage form, hydrolysis further degrades the stability, thus causing a problem of difficulty in long-term high-temperature storage.

In the present invention, the herbicidal composition containing the isomer mixture of the compound represented by Chemical Formula 1 may be used in the usual dosage forms of herbicidal compositions. The herbicidal composition containing the isomer mixture may be used as a herbicide in various formulations by further including a carrier, surfactant, or an additive commonly used in the technical field of formulations, if necessary. obtain. Said carriers and excipients may be solid or liquid and are ingredients useful in the art of dosage forms, such as natural or synthetic inorganic substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders. and so on.

For example, the herbicidal composition includes a suspension concentrate, a spreading oil, a wettable powder, a water-dispersible granule, and a dispersible powder. , dust, granules, granules, and tablets. More preferably, it may be a liquid wettable powder (suspension concentrate), and in the case of the liquid wettable powder (suspension concentrate), it may further include a buffer solution, a surfactant and an antifreeze. In the case of a liquid wettable powder (suspension concentrate), the production process is generally relatively simple, it is environmentally friendly, and it is possible to simplify and improve efficiency when spraying. I had a problem with falling. However, the herbicidal composition of the present invention is stabilized by containing 92% by weight or more of the erythro-form in the isomer mixture of the erythro-form and the threo-form. In addition, even in the case of such a liquid wettable powder (suspension concentrate) dosage form, the decomposition rate due to hydrolysis is lowered, the stability is greatly improved, and long-term storage at high temperatures is possible. .

Various dosage forms of the herbicidal composition can be prepared by known methods, for example, by intimately mixing and/or grinding the active ingredient with solvents, solid carriers, surfactants or other additives. .

Usable as said solvents are aromatic hydrocarbons such as xylene mixtures or substituted naphthalenes; alcohols and glycols and their ethers and esters such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether; ketones such as cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide and epoxidized or non-epoxidized vegetable oils such as epoxidized coconut oil or soybean oil; Or it may be water. Such solvents may be used as solvents for liquid dosage forms or co-solvents for granular formulations.

The solid carriers commonly used in said dusting agents and granular formulations are usually ground natural minerals such as talc, kaolin, montmorillonite, pyrophyllite, bentonite, or calcium carbonate, or adsorbent carriers such as zeolites. , or sand. As well, a number of pre-milled inorganic or organic materials may be used.

The surfactant is selected from nonionic, cationic and/or anionic surfactants exhibiting good dispersing, wetting and lubricating properties according to the properties of the compound of Formula 1 to be formulated. good.

A more preferred method of administering a herbicidal composition comprising an isomeric mixture of the compound of formula 1 is wetting the plant habitat with a liquid formulation or incorporating the active ingredient into the soil in solid form, e.g. in the form of a granular formulation. (soil treatment) is to reach the plant through the soil or water through the roots and stems. Alternatively, herbicidal activity can be exhibited by direct administration to the leaves of plants (foliar application). The frequency and rate of administration may vary depending on the biological characteristics of plants, climate, and soil environment.

The present application will now be described with respect to particular embodiments, which are not intended to limit the scope of the invention. On the contrary, the application covers all alternatives and variations falling within the scope of the claims. Accordingly, the following exemplifies the practice of the present application for purposes of illustration of particular embodiments, and is believed to be a useful and readily understood description of the process and conceptual aspects thereof. presented to serve.

The following examples are presented to provide those skilled in the art with a complete disclosure and description of how to make and evaluate the compounds, compositions, and methods provided herein, and are merely illustrative. intended as Thus, the examples are in no way intended to limit the scope of what the inventors regard as their invention. Many of the conditions that can be used to optimize reaction conditions, such as concentrations of constituents, desired solvents, solvent mixtures, temperature, pressure, and other reaction parameters and product properties such as purity, yield, etc. There are variations and combinations of Such are also considered to be within the scope of this application. Any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or clearly contradicted by context.

Example 1
K ₂ HPO ₄ and KH ₂ PO ₄ were supplemented with water to make a total 1 L solution to prepare a 0.1 M phosphate buffer. Then, CR-DOS70P (Di (2-ethylhexyl) sulfosuccinate, sodium salt, Cas no. 577-11-7) 3.0 parts by weight, NK-SU500 (sucrose laurate, Cas no. 25339-99-5) 1.0 parts by weight and 0.2 parts by weight of antifoaming agent SAG-622 (manufactured by Momentive) are added and thoroughly mixed to form a uniform 1-(3-{[(4, 6-dimethoxy-pyrimidin-2-yl)carbamoyl]sulfamoyl}-2-pyridinyl)-2-fluoropropylmethoxyacetate (Flucetosulfuron, FTS) erythro-form 96% by weight, threo-form ) was added at 4% by weight and thoroughly mixed with a stirrer. Glass beads were added thereto and pulverized until the average particle size reached 1 to 2 μm to prepare a wet part.

Next, P.I. 3.0 parts by weight of G (propylene glycol, cas no. 57-55-6) and X.I. G (Xanthan Gum, cas no. 11138-66-2) 0.1 parts by weight; V [5-chloro-2-methyl-4-isothiazolin-3-one (cas no.26172-55-4) and 2-methyl-4-isothiazolin-3-one (cas no.2682-20-4)] 0.2 parts by weight was added and sufficiently stirred. After that, 16.7 parts by weight of 0.1 M phosphate buffer was added and sufficiently stirred to prepare a thickening part.

Next, 30 parts by weight of the thickening part was added to 70 parts by weight of the wet part, and the mixture was sufficiently stirred to prepare a herbicidal composition in the form of a liquid wettable powder.

Example 2
A liquid wettable powder was obtained in the same manner as in Example 1, except that an isomer mixture containing 92% by weight of Erythro-form and 8% by weight of threo-form as FTS was mixed. A herbicidal composition in dosage form was prepared.

Example 3
After adsorbing 15 parts by weight of CR-PE62 (Polyethylene-Polypropylene glycol, Cas no.9003-11-6) to 20 parts by weight of celite 281 (Calcined Diatomite, Cas no.91053-39-3), 1-(3 Erythro-form of -{[(4,6-dimethoxy-pyrimidin-2-yl)carbamoyl]sulfamoyl}-2-pyridinyl)-2-fluoropropylmethoxyacetate (Flucetosulfuron, FTS) at 96% by weight, 10 parts by weight of an isomer mixture containing 4% by weight of threo-form, 2 parts by weight of NK-EFW (2-Naphthalenesulfonic acid, polymer with formaldehyde, sodium salt, Cas no. 36290-04-7), NK - D425 (2-Naphthalenesulfonic acid, polymer with formaldehyde, sodium salt, Cas no. 36290-04-7) 3 parts by weight, CR-SDS (sodium dodecyl sulfate, Cas no. 151-21-3) 1 part by weight, CR - Mix 10 parts by weight of UF100F (Urea-formaldehyde resin (CAS no. 9011-05-6)), mix the remaining talc so that the total composition is 100 parts by weight, and then air jet Grind using a mill (Air-jet mill). 10 to 12 parts by weight of water is added to the pulverized mixture, kneaded, granulated using a granulator, and dried with hot air at a temperature of about 80° C. to obtain a herbicide in the form of a granular wettable powder. A composition was produced.

Comparative example 1
A liquid wettable powder was obtained in the same manner as in Example 1, except that an isomer mixture containing 88% by weight of Erythro-form and 12% by weight of threo-form as FTS was mixed. A herbicidal composition in dosage form was prepared.

Comparative example 2
A liquid wettable powder was obtained in the same manner as in Example 1 except that an isomer mixture containing 85% by weight of Erythro-form and 15% by weight of threo-form as FTS was mixed. A herbicidal composition in dosage form was prepared.

Comparative example 3
A granular wettable powder was produced in the same manner as in Example 3 except that an isomer mixture containing 88% by weight of Erythro-form and 12% by weight of threo-form as FTS was mixed. A herbicidal composition in dosage form was prepared.

[Experimental example: Evaluation of storage stability of herbicide composition]
In order to evaluate the storage stability of the herbicidal compositions of Examples 1 to 3 and Comparative Examples 1 to 3, plastic bottles made of polyethylene (PE) were filled with the liquid samples, and about 100 g of the granular samples were filled in silver foil envelopes. After sealing and storing in an oven maintained at 54 (±2)° C. for 4 weeks, the area value of the active ingredient was measured by HPLC (manufacturer: Waters) to evaluate the decomposition rate. The results are shown in Table 1 below.

The HPLC analysis conditions are as follows.
Column: 100mm x 4.6mm i. d. "Capcell Pak" C18 column, 3 μm particles
Mobile Phase: acetonitrile/water (0.02M ammonia acetate + 0.1M acetic acid) = 32/68
Flow: 1.0 mL/min.
Column temperature: 30°C
Injection volume: 10 μl
Detector Wavelength: 254nm
Run time: 20min.

Claims (4)

containing a pyridinesulfonylurea compound represented by the following chemical formula 1 as an active ingredient,And
_A liquid _{wettable powder (} A herbicidal composition formed into a Suspension concentrate (SC) dosage form, comprising:
The pyridinesulfonylurea compound includes erythro-form and threo-form isomer mixtures,
a herbicidal composition comprising 95% to 99% by weight of said isomer mixture of said Erythro-form

In the chemical formula 1, n represents an integer of 1 to 3,
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
R' is hydrogen, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a halogen group or an alkoxy group having 1 to 2 carbon atoms;
X and Y are each independently an alkyl group having 1 or 2 carbon atoms, an alkoxy group having 1 or 2 carbon atoms, a haloalkoxy group having 1 or 2 carbon atoms or a halogen group. In the chemical formula 1, n is an integer of 1 or 2,
R is hydrogen or a methyl group;
R' is hydrogen, a halogen group or a methyl group;
2. The herbicidal composition of claim 1, wherein X and Y are each methoxy groups. In the chemical formula 1, n is an integer of 1 or 2,
R is methyl;
R' is hydrogen, Cl, Br or a methyl group;
2. The herbicidal composition of claim 1, wherein X and Y are each methoxy groups. The pyridinesulfonylurea compound represented by Chemical Formula 1 is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3 -sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-hydroxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[( 4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-hydroxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6 -dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3-methoxypropion)oxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidine -2-yl)aminocarbonyl]-4-methyl-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl ) aminocarbonyl]-4-chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, and N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl ]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide, the herbicide according to claim 1, which is at least one selected from the group consisting of Composition.