KR102059979B1 - Herbicidal composition - Google Patents

Abstract

상기 화학식 1에서, n은 1 내지 3의 정수를 나타내고, R은 수소 또는 탄소수 1 내지 4의 알킬기이며, R’은 수소, 탄소수 1 내지 4의 알킬기, 탄소수 1 내지 3의 할로알킬기, 할로겐기 또는 탄소수 1 내지 2의 알콕시기이고, X 및 Y는 각각 독립적으로 탄소수 1 내지 2의 알킬기, 탄소수 1 내지 2의 알콕시기, 탄소수 1 내지 2의 할로알콕시기 또는 할로겐기이다.The present invention comprises a pyridinesulfonylurea compound represented by the following formula (1) as an active ingredient, the pyridinesulfonylurea compound is included as an isomer mixture of erythro-form and threo-form, The erythro-form relates to a herbicide composition comprising not less than 92% by weight of the mixture of isomers.
[Formula 1]

In 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 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a haloalkoxy group having 1 to 2 carbon atoms, or a halogen group.

Description

Herbicide composition {HERBICIDAL COMPOSITION}

The present invention relates to a herbicide composition comprising a herbicidal active ingredient exhibiting excellent herbicidal activity.

In crop cultivation technology, it is important to protect crops by controlling weeds that inhibit crop growth. In order to reduce damages such as poor growth or yield reduction of crops caused by weeds in crop plantations, safe herbicides have been developed that can effectively control them and to crops. Many herbicides developed to date have been registered for specific crops and used for weed control. The herbicidal active substance for use in the control of weeds occurring in the cultivation of such specific crops has high herbicidal activity and has a broad herbicidal spectrum, but is safe for the environment and crops.

On the other hand, the herbicide composition comprising the herbicidal active material as described above is a formulation such as wettable powder, emulsion (emulsifiable concentrate), water-dispersible granule, granules, liquid concentrate (Suspension concentrate) Developed and used as herbicide. However, in the case of a hydrating agent, an emulsion, and a granulating agent, it is generally diluted to a predetermined concentration with water and manufactured as a spraying solution. However, a large amount of spraying liquid requires excessive cost and time to uniformly spray the entire surface of the paddy field or field. have. In the case of granules, it can be used directly as it is, the problem of the hydrating agent, emulsion and granulating agent could be solved, but the herbicidal active substance content is relatively small on the basis of the total herbicide, and supplementary agents for forming herbicides must be included. There is a problem that the manufacturing process such as crushing, mixing, drawing, granulation, drying, classification, etc. is complicated, and spray stains occur. In order to overcome the problems of the formulations, a liquid concentrate formulation has been developed that is relatively simple, environmentally friendly, and can be simplified and efficient at the time of application. On the other hand, when used as a herbicide of various formulations, it is an important task to ensure the stability of the herbicide composition even during long-term storage.

The compound of formula a [ISO Proposal Name: flucetosulfuron] is a herbicidal active substance belonging to sulfonylurea system and is herbicidally active in Korean Patent No. 10-0399366 (Application No. 10-2000-0059990). It has already been described as a substance.

[Formula a]

The flucetosulfuron is safe for these crops when treated with soil or foliage against rice, wheat, barley (appropriate dosage: 10-40 g ai / ha) and grass (appropriate dosage: 50-200 g ai / ha), It is known to have excellent herbicidal effect on a wide range of herb species, including broadleaf weeds, flowering and weeds, forage weeds, annual and perennial weeds.

However, it is still a problem to ensure the stability of the herbicide composition comprising the herbicidal active substance belonging to the sulfonylurea system as described above. In particular, in the case of liquid concentrate (Suspension concentrate, SC) formulation there is a problem that is difficult to be stored for a long time because the stability is further reduced by hydrolysis at high temperature storage conditions.

Republic of Korea Patent Publication No. 10-0399366

The present invention is to provide a herbicide composition comprising a herbicidal active substance belonging to the sulfonylurea system, having excellent herbicidal activity and excellent stability and long term storage.

The present invention comprises a pyridinesulfonylurea compound represented by the following formula (1) as an active ingredient, the pyridinesulfonylurea compound is included as an isomer mixture of erythro-form and threo-form, The erythro-form provides a herbicide composition comprising not less than 92% by weight of the mixture of isomers.

[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 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a haloalkoxy group having 1 to 2 carbon atoms or a halogen group.

According to the present invention, it is possible to provide a herbicide composition having excellent herbicidal activity, low decomposition rate even at high temperature storage for a long time, and in particular, excellent stability can be secured even in the formulation of a liquid concentrate (Suspension concentrate, SC).

Hereinafter, the present invention will be described in more detail to aid in understanding the present invention. At this time, the terms or words used in the present specification and claims should not be construed as being limited to the ordinary or dictionary meanings, and the inventors appropriately define the concept of terms in order to explain their invention in the best way. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that it can.

The herbicide composition of the present invention comprises a pyridinesulfonylurea compound represented by the following formula (1) as an active ingredient, and the pyridinesulfonylurea compound is an isomeric mixture of erythro-form and threo-form. The erythro-form is included in at least 92% by weight of the mixture of isomers.

[Formula 1]

In 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 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a haloalkoxy group having 1 to 2 carbon atoms, or a halogen group.

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

Further, more preferably, the pyridinesulfonylurea compound represented by Formula 1 is represented by Formula 1, n is an integer of 1 or 2, R is methyl, R 'is hydrogen, Cl, Br or methyl group, X and Y may each be methoxy.

The pyridinesulfonylurea compound represented by the formula (1) is, for example, N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-meth Methoxyacetoxy-n-propyl) pyridine-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -2- (2-fluoro-1-hydroxy Acetoxy-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-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-chloro- 2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sul Vonamide, and N-[(4,6-dimethoxypyrimidin-2-yl) aminocarbonyl] -4-bromo-2- (2-fluoro-1-methoxyacetoxy-n-propyl ) At least one selected from the group consisting of pyridine-3-sulfonamide.

More preferably, the pyridinesulfonyl urea compound represented by Chemical Formula 1 may be a compound of Chemical Formula 2 (ISO proposal name: flucetosulfuron).

[Formula 2]

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

The herbicide composition of the present invention includes the compound represented by Formula 1 as an isomeric mixture of erythro-form and threo-form, wherein the erythro-form is an isomeric mixture as a whole. It comprises at least 92% by weight of. More preferably, the erythro-form may be included in at least 95% by weight of the isomeric mixture, and more preferably, the erythro-form is in the range of 95% to 99% by weight of the isomeric mixture. It may be included as.

As such, by including more than 92% by weight of the erythro-form in the mixture of erythro-form and threo-form isomers, it has not only excellent herbicidal activity but also long-term storage at high temperature. Even though the decomposition rate is low, stability can be ensured.

When the compound represented by Chemical Formula 1 is not included in the form of an isomeric mixture of erythro-form and threo-form, but in erythro-form alone, the production efficiency is very low. In addition, when included in the threo-type (threo-form) alone form herbicidal activity is lowered, there is a problem that the degradation rate is very increased and the stability is lowered. In addition, although present as an isomeric mixture of erythro-form and threo-form, even when the erythro-form is less than 92% by weight in the isomeric mixture, herbicidal activity is lowered and the degradation rate is reduced. In this case, in particular, in the case of liquid formulations, the stability is further decreased due to hydrolysis, which makes it difficult to store high temperature for a long time.

In the present invention, the herbicide composition comprising an isomer mixture of the compound represented by Formula 1 may be used in the formulation of a conventional herbicide composition. Herbicide compositions comprising such isomer mixtures may be utilized as herbicides in various formulations, if desired, further comprising additives commonly used in the carrier, surfactant or formulation art. The carriers and additives may be solid or liquid and may be useful ingredients in the formulation art, such as natural or synthetic inorganic materials, solvents, dispersants, wetting agents, adhesives, thickeners, binders and the like.

For example, the herbicide composition may be used as a liquid concentrate (Spspension concentrate), Spreading oil (wettable powder), Wettable powder, Water-dispersible granule (Dispersible powder), Spraying agent, Granules, Granules ( granule) and tablet (tablet) may be formed of at least one or more formulations selected from the group consisting of. More preferably, it may be a liquid concentrate (Suspension concentrate), in the case of the liquid concentrate (Suspension concentrate) may be formed by further comprising a buffer, a surfactant and a cryoprotectant. In the case of a liquid concentrate (Suspension concentrate) in general, the manufacturing process is relatively simple, environmentally friendly, there is an advantage that can be simplified, efficient at the time of spraying, there was a problem that the stability is poor due to decomposition due to hydrolysis. However, the herbicide composition of the present invention contains more than 92% by weight of the erythro-form in the mixture of the erythro-form and threo-form isomers, thereby greatly improving the stability of such liquid phase. In the case of Suspension concentrate formulations, the degradation rate due to hydrolysis was lowered, and stability was greatly improved to allow long-term storage at high temperatures.

Various formulations of the herbicide composition can be prepared according to known methods, for example by intimately mixing and / or grinding the active ingredient with a solvent, solid carrier, surfactant or other additives.

Usable as the solvent include aromatic hydrocarbons such as xylene mixtures or substituted naphthalenes; Esters with alcohols such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether and glycols and ethers thereof; Ketones such as cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide and vegetable oils such as epoxidized or unepoxidized vegetable oils such as epoxidized coconut or soybean oil; Or water. Such solvents may be used as solvents for liquid formulations or as cosolvents for particulate formulations.

Solid carriers commonly used in the dispersants and particulate preparations are typically ground natural minerals such as talc, kaolin, montmorillonite, pyrophyllite, bentonite, or calcium carbonate, or adsorbent carriers such as zeolites, or sand. In addition, many pre-pulverized inorganic or organic materials can be used.

The surfactant may be selected from nonionic, cationic and / or anionic surfactants that exhibit good dispersion, wetting and lubricating properties depending on the nature of the compound of formula 1 to be formulated.

A more preferred method of administering a herbicide composition comprising an isomeric mixture of compounds of Formula 1 is to wet the plant's habitat with a liquid formulation, or to incorporate the active ingredient into the soil in solid form, eg in the form of a granular formulation (soil treatment). And through the stem to reach the plant via soil or water. Alternatively, the herbicidal activity can also be exhibited by directly administering to the leaves of plants (foliar administration). Frequency and rate of administration may vary depending on the plant's biological characteristics, climate and soil environment.

The present application will now be described with reference to specific embodiments, which are not intended to limit the scope of the invention. On the contrary, the present application covers all alternatives and modifications included within the scope of the claims. Accordingly, the following is intended to illustrate the implementation of the present application for purposes of illustration of certain embodiments and is presented to provide those that are believed to be useful and readily understood descriptions of its process and conceptual aspects.

The following examples are presented to provide those skilled in the art with a complete disclosure and description of how the compounds, compositions, and methods provided herein are made and evaluated, and are intended to be purely illustrative. Thus, the examples are by no means intended to limit the scope of what the inventors regard as their invention. There are many variations and combinations of conditions that may be used to optimize reaction conditions such as component concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction parameters and product properties such as purity, yield, etc. . These are also considered to be within the scope of this application. In all possible variations any combination of the above described elements is encompassed by the present invention unless otherwise indicated herein or otherwise specifically disclaimed in context.

Example  One

K ₂ HPO ₄ and KH ₂ PO ₄ were supplemented with water to make a total 1 L solution to prepare 0.1 M phosphate buffer. Then, 65.8 parts of buffer, 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, defoaming agent SAG-622 (momentive) 0.2 parts by weight of the mixture thoroughly mixed 1- (3-{[(4,6-dimethoxy-pyrimidin-2-yl) carbamoyl in a uniform state ] Sulfamoyl} -2-pyridinyl) -2-fluoropropyl methoxyacetate (Flucetosulfuron, FTS) containing 96% by weight of the erythro-form (threo-form), 4% by weight 10.0 parts by weight of the isomeric mixture was added and mixed well using a stirrer. A glass bead was put therein and pulverized, and the wet portion was prepared until the average particle size became 1 to 2 μm.

Next, 0.1 parts by weight of XG (Xanthan Gum, cas no. 11138-66-2), 3.0 parts by weight of PG (propylene glycol, cas no. 57-55-6), and MV [5-chloro-2-methyl-4 0.2 parts by weight of isothiazolin-3-one (cas no.26172-55-4) and 2-methyl-4-isothiazolin-3-one (cas no.2682-20-4) were sufficiently stirred. . Then, 16.7 parts by weight of 0.1M phosphate buffer was added thereto, and the mixture was sufficiently stirred to prepare a thickener.

Next, 30 parts by weight of the thickening part was added to 70 parts by weight of the wet part, and sufficiently stirred to prepare a herbicide composition of the liquid hydration formulation.

Example  2

The herbicide of the liquid hydration formulation was carried out in the same manner as in Example 1 except that an isomeric mixture containing 92 wt% of erythro-form and 8 wt% of threo-form was mixed as FTS. The composition was prepared.

Example  3

15 parts by weight of CR-PE62 (Polyethylene-Polypropylene glycol, Cas no.9003-11-6) was adsorbed on 20 parts by weight of celite 281 (Calcined Diatomite, Cas no.91053-39-3), followed by 1- (3- { Erythro-form of [(4,6-dimethoxy-pyrimidin-2-yl) carbamoyl] sulfamoyl} -2-pyridinyl) -2-fluoropropyl methoxyacetate (Flucetosulfuron, FTS) ), 10 parts by weight of an isomeric mixture containing 4% by weight of threo-form (threo-form), NK-EFW (2-Naphthalenesulfonic acid, polymer with formaldehyde, Sodium salt, Cas no. ) 2 parts by weight, 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, 10 parts by weight of CR-UF100F (Urea-formaldehyde resin (CAS no.9011-05-6)) is mixed, and the remaining Talc is mixed so that the sum of the composition is 100 parts by weight, followed by using an air-jet mill. And crushed. 10 to 12 parts by weight of water was kneaded into the pulverized mixture, and then granulated using a granulator, followed by hot air drying at a temperature of about 80 ° C. to prepare a herbicide composition of a granular wetting agent formulation.

Comparative example  One

The herbicide of the liquid hydration formulation was carried out in the same manner as in Example 1 except that an isomeric mixture containing 88% by weight of erythro-form and 12% by weight of threo-form was mixed as FTS. The composition was prepared.

Comparative example  2

The herbicide of the liquid hydration formulation was carried out in the same manner as in Example 1 except that an isomeric mixture containing 85 wt% of erythro-form and 15 wt% of threo-form was mixed as FTS. The composition was prepared.

Comparative example  3

The herbicide of the granular wetting agent formulation was carried out in the same manner as in Example 3, except that an isomeric mixture containing 88% by weight of erythro-form and 12% by weight of threo-form was mixed as FTS. The composition was prepared.

[ Experimental Example : Storage Stability Evaluation of Herbicide Composition]

In order to evaluate the storage stability of the herbicide compositions of Examples 1 to 3 and Comparative Examples 1 to 3, the liquid sample was filled in a plastic bottle made of polyethylene (PE), and the granular sample was filled in a silver foil bag, and then sealed. After 4 weeks of storage in an oven maintained at (± 2) ℃, the degradation rate was evaluated by measuring the area value of the active ingredient by HPLC (manufacturer: Waters). The results are shown in Table 1 below.

HPLC analysis conditions are as follows.

Column: 100mm × 4.6mm i.d. “Capcell Pak” C18 column, 3㎛ particles

Mobile Phase: acetonitrile / water (0.02M ammonium acetate + 0.1M acetic acid) = 32/68

Flow: 1.0 mL / min.

Column Temperature: 30 ℃

Injection Volume: 10µl

Detector Wavelength: 254nm

Run time: 20 min.

Degradation rate after 4 weeks of storage at 54 ℃ Example 1 6.89 Example 2 9.82 Example 3 13.63 Comparative Example 1 9.94 Comparative Example 2 12.24 Comparative Example 3 17.85

Claims (8)

To include a pyridinesulfonyl urea compound represented by the formula (1) as an active ingredient,
The pyridinesulfonyl urea compound is included as an isomer mixture of erythro-form and threo-form,
Herbicide composition comprising the Erythro-form (95% to 99% by weight of the isomer mixture).
[Formula 1]

In 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 to 2 carbon atoms, an alkoxy group having 1 to 2 carbon atoms, a haloalkoxy group having 1 to 2 carbon atoms or a halogen group.
delete delete The method of claim 1,
In 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,
A herbicide composition wherein X and Y are each a methoxy group.
The method of claim 1,
In Formula 1, n is an integer of 1 or 2,
R is methyl,
R 'is hydrogen, Cl, Br or a methyl group,
X and Y are each methoxy herbicide composition.
The method of claim 1,
Pyridinesulfonyl urea compound represented by the formula (1),
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-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 At least one herbicide composition selected from the group consisting of 2- (2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide.
The method of claim 1,
The herbicide composition is a herbicide composition formed of at least one formulation selected from the group consisting of a liquid hydrating agent, a sleep developing agent, a hydrating agent, a granular hydrating powder, a powder, a spraying agent, granules, granules and tablets.
The method of claim 1,
The herbicide composition is a herbicide composition formed in the form of a liquid concentrate (SC) containing a buffer, a surfactant and a cryoprotectant.