Specification
Title of the invention: Herbicide composition
Technical field
[One]
Mutual citation with related applications
[2]
This application claims the benefit of priority based on Korean Patent Application No. 10-2017-0153278 filed on November 16, 2017, and all contents disclosed in the documents of the Korean patent application are included as part of this specification.
[3]
Technical field
[4]
The present invention relates to a herbicidal composition comprising a herbicidal active ingredient showing excellent herbicidal activity.
[5]
Background
[6]
In crop cultivation technology, it is important to protect crops by controlling weeds that hinder crop growth. In order to reduce damage such as slow growth or decrease in yield of crops caused by weeds in the cultivation of crops, herbicide active substances that can effectively control them and are safe for crops have been developed. A number of herbicidal active substances developed to date have been registered for specific crops and are used for weed control. The herbicidal active material for use in the control of weeds occurring in the cultivation of such a specific crop has high herbicidal activity and a broad herbicidal spectrum, but it is desirable that it is safe for the environment and crops.
[7]
[8]
On the other hand, as described above, the herbicide composition containing the herbicidal active substance is formulated as a wettable powder, an emulsifiable concentrate, a water-dispersible granule, a granule, and a suspension concentrate. It has been developed and used as a herbicide. However, in the case of hydrating agents, emulsions, and granular hydrating agents, it is generally diluted with water to a predetermined concentration and manufactured as a spraying solution, but the amount of spraying liquid is large and it takes excessive cost and time to evenly spray the entire surface of the target paddy or field. have. In the case of granules, as they can be used directly, the problems of hydrating agents, emulsions, and granular hydrating agents could be solved. , Crushing, mixing, kneading, assembling, drying, classification, etc. The manufacturing process is complicated, and there is a problem that spray stains and the like occur. In order to overcome the problems of the above formulations, the manufacturing process is relatively simple, environmentally friendly, and a liquid hydration formulation (Suspension concentrate) that can be simplified and efficient at the time of spraying has been developed. On the other hand, when used as a herbicide of various formulations as described above, it is an important task to ensure the stability of the herbicide composition even during long-term storage.
[9]
[10]
The compound of the following formula a [ISO proposal name: flucetosulfuron] is a herbicidal active material belonging to the sulfonylurea family, and has herbicidal activity in Korean Patent No. 10-0399366 (Application No. 10-2000-0059990) It has already been described as a substance.
[11]
[Formula a]
[12]

[13]
The flucetosulfuron is safe for these crops when treated with soil or foliage for rice, wheat, barley (appropriate dosage: 10 to 40 g ai/ha) and grass (appropriate dosage: 50 to 200 g ai/ha), It is a substance known to have excellent herbicidal effect on a wide range of weeds such as broadleaf weeds, herbaceous weeds, sedge weeds, annual and perennial weeds.
[14]
[15]
However, there is still a problem in securing the stability of the herbicidal composition containing the herbicidal active material belonging to the above sulfonyl urea system. In particular, in the case of a suspension concentrate (SC) formulation, there is a problem that it is difficult to store for a long time due to its stability due to hydrolysis under high temperature storage conditions.
[16]
Detailed description of the invention
Technical challenge
[17]
The present invention is to provide a herbicidal composition comprising a herbicidal active substance belonging to the sulfonyl urea family, and has excellent herbicidal activity and excellent stability, so that long-term storage is possible.
[18]
Means of solving the task
[19]
The present invention comprises a pyridine sulfonyl urea compound represented by the following formula (1) as an active ingredient, and the pyridine sulfonyl urea compound is included as an isomer mixture of erythro-form and threo-form, It provides a herbicide composition in which the erythro-form is contained in an amount of 92% by weight or more of the isomer mixture.
[20]
[Formula 1]
[21]

[22]
n represents an integer of 1 to 3,
[23]
R is hydrogen or an alkyl group having 1 to 4 carbon atoms,
[24]
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,
[25]
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.
[26]
Effects of the Invention
[27]
According to the present invention, it is possible to provide a herbicide composition that has excellent herbicidal activity, has a low decomposition rate even when stored at high temperature for a long period of time, and in particular, can secure excellent stability even in a formulation of a liquid hydration (Suspension concentrate, SC).
[28]
Mode for carrying out the invention
[29]
Hereinafter, the present invention will be described in more detail to aid understanding of the present invention. At this time, terms or words used in the present specification and claims should not be construed as being limited to a conventional or dictionary meaning, and the inventor appropriately defines the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of ​​the present invention based on the principle that it can be done.
[30]
[31]
The herbicide composition of the present invention comprises a pyridine sulfonyl urea compound represented by the following formula (1) as an active ingredient, and the pyridine sulfonyl urea compound is an isomer mixture of erythro-form and threo-form. And the erythro-form is contained in an amount of 92% by weight or more of the isomer mixture.
[32]
[Formula 1]
[33]

[34]
In Formula 1, n represents 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, a haloalkyl group having 1 to 3 carbon atoms, a halogen group or It is a C1-C2 alkoxy group, X and Y are each independently a C1-C2 alkyl group, a C1-C2 alkoxy group, a C1-C2 haloalkoxy group, or a halogen group.
[35]
More preferably, the pyridine sulfonylurea compound represented by Formula 1 is, 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, and X And Y may each be a methoxy group.
[36]
In addition, more preferably, the pyridinesulfonylurea compound represented by Formula 1 is in Formula 1, n is an integer of 1 or 2, R is methyl, and R'is hydrogen, Cl, Br or a methyl group, Each of X and Y may be methoxy.
[37]
[38]
The pyridinesulfonylurea compound represented by Formula 1 is, for example, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-me Toxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-hydroxy Acetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1-(3- Hydroxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1- (3-methoxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-methyl-2-( 2-Fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-chloro- 2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, and N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]- It may be at least one selected from the group consisting of 4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridine-3-sulfonamide.
[39]
More preferably, the pyridine sulfonyl urea compound represented by Formula 1 may be a compound of Formula 2 [ISO proposal name: flucetosulfuron].
[40]
[Formula 2]
[41]

[42]
[43]
Since the compound of Formula 1 contains two asymmetric carbons, it may exist as an isomer of an erythro-form or a threo-form.
[44]
In the herbicide composition of the present invention, the compound represented by Formula 1 is included as an isomer mixture of erythro-form and threo-form, wherein the erythro-form is the entire isomer mixture. It is contained in 92% by weight or more. More preferably, the erythro-form may be included in an amount of 95% by weight or more of the isomer mixture, and more preferably, the erythro-form is 95% to 99% by weight of the isomer mixture. Can be included as
[45]
As described above, by including more than 92% by weight of erythro-form in the isomer mixture of erythro-form and threo-form, it has excellent herbicidal activity and is stored at high temperatures for a long period of time. Even with low decomposition rate, stability can be secured.
[46]
When the compound represented by Formula 1 is not included in the form of an isomer mixture of erythro-form and threo-form, but is included in the form of erythro-form alone, production efficiency is very poor. There is a problem in that the herbicidal activity is lowered and the decomposition rate is greatly increased, and the stability is lowered when it is included in a threo-form alone form. In addition, it exists as an isomeric mixture of erythro-form and threo-form, but even when the erythro-form is contained in an amount of less than 92% by weight in the isomeric mixture, herbicidal activity decreases and decomposition rate This increases, and in particular, in the case of a liquid formulation, stability is further reduced due to hydrolysis, which makes it difficult to store at high temperature for a long time.
[47]
[48]
In the present invention, the herbicide composition comprising an isomer mixture of the compound represented by Formula 1 may be used as a formulation of a conventional herbicide composition. The herbicide composition comprising the isomeric mixture may be used as a herbicide in various formulations, if necessary, further including a carrier, a surfactant, or an additive commonly used in the formulation technology field. The carrier and additive may be solid or liquid, and may be components useful in the field of formulation technology, such as natural or synthetic inorganic substances, solvents, dispersants, wetting agents, adhesives, thickeners, binders, and the like.
[49]
[50]
For example, the herbicide composition is a liquid wetting agent (Suspension concentrate), a sleeping agent (Spreading oil), a wettable powder (wettable powder), a water-dispersible granule (Water-dispersible granule), a powder (Dispersible powder), a dusting agent, granules, granules ( granule) and tablets (tablet) may be formed in at least one or more formulations selected from the group consisting of. More preferably, it may be a liquid hydrating agent (Suspension concentrate), and in the case of the liquid hydrating agent (Suspension concentrate), it may be formed by further including a buffer solution, a surfactant, and an anti-freezing agent. In the case of suspension concentrate, in general, the manufacturing process is relatively simple, eco-friendly, and simplifies and increases efficiency during spraying, but there is a problem of poor stability due to decomposition due to hydrolysis. However, the herbicidal composition of the present invention contains 92% by weight or more of the erythro-form in the isomer mixture of the erythro-form and the threo-form, thereby greatly improving the stability. In the case of the formulation of Suspension Concentrate, the decomposition rate due to hydrolysis was reduced and stability was greatly improved, so that long-term storage at high temperature was possible.
[51]
[52]
Various formulations of the herbicide composition can be prepared according to known methods, for example, by intimately mixing and/or pulverizing the active ingredient with a solvent, a solid carrier, a surfactant, or other additives.
[53]
[54]
What can be used as the solvent is an aromatic hydrocarbon, such as a xylene mixture or substituted naphthalene; Alcohols and glycols such as ethanol, ethylene glycol, ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, and ethers and esters thereof; Ketones such as cyclohexanone, strong polar solvents such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, and epoxidized or unepoxidized vegetable oils such as epoxidized coconut oil or soybean oil; Or it could be water. Such a solvent can be used as a solvent for a liquid formulation or a co-solvent for a granular formulation.
[55]
The solid carrier generally used in the dusting agent and granular formulation may be a pulverized natural mineral such as talc, kaolin, montmorillonite, pyrophyllite, bentonite, or calcium carbonate, or an adsorbent carrier such as zeolite, or sand. In addition, a number of pre-ground inorganic or organic materials can be used.
[56]
The surfactant may be selected from nonionic, cationic and/or anionic surfactants that exhibit good dispersing, wetting and lubricating properties according to the properties of the compound of formula 1 to be formulated.
[57]
A more preferred method of administering a herbicide composition comprising the isomeric mixture of the compound of Formula 1 is to moisten the habitat of plants with a liquid formulation, or by incorporating the active ingredient into the soil in a solid form, such as a granular formulation (soil treatment). And it can reach the plant through soil or water through the stem. Alternatively, it can also exhibit herbicidal activity by direct administration to the leaves of plants (foliar administration). The frequency and rate of administration may vary depending on the biological characteristics of plants, climate, and soil environment.
[58]
[59]
The present application will now be described with respect to specific embodiments, which are not intended to limit the scope of the invention. Conversely, this application covers all alternatives and variations included within the scope of the claims. Accordingly, the following is presented to illustrate the execution of this application for purposes of illustration of certain embodiments and to provide what is believed to be a useful and readily understood description of the process and conceptual aspects thereof.
[60]
[61]
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 reaction conditions, e.g., constituent concentrations, desired solvents, solvent mixtures, temperatures, pressures, and other reaction parameters and conditions that may be used to optimize 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 invention unless otherwise indicated herein or otherwise clearly contradicted by context.
[62]
[63]
Example 1
[64]
Water was added to K 2 HPO 4 and KH 2 PO 4 to make a total 1L solution to prepare a 0.1M phosphate buffer. Then, 3.0 parts by weight of CR-DOS70P (Di(2-ethylhexyl) sulfosuccinate, sodium salt, Cas no. 577-11-7) 3.0 parts by weight of the buffer solution, NK-SU500 (sucrose laurate, cas no. 25339-99-5) ) 1.0 part by weight, 0.2 parts by weight of antifoaming agent SAG-622 (Momentive Co., Ltd.), and sufficiently mixed, in a uniform state 1-(3-{[(4,6-dimethoxy-pyrimidin-2-yl)carbamoyl ]Sulfamoyl}-2-pyridinyl)-2-fluoropropyl methoxyacetate (Flucetosulfuron, FTS) containing 96% by weight of erythro-form and 4% by weight of threo-form 10.0 parts by weight of the isomer mixture was added and sufficiently mixed using a stirrer. Glass bead was put here and pulverized to produce a wet part by proceeding until the average particle size was 1 to 2 μm.
[65]
Next, PG (propylene glycol, cas no.57-55-6) 3.0 parts by weight XG (Xanthan Gum, cas no. 11138-66-2) 0.1 parts by weight, MV[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 were added and sufficiently stirred. . Then, 16.7 parts by weight of 0.1M phosphate buffer was added and sufficiently stirred to prepare a thickened part.
[66]
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 in a liquid wettable formulation.
[67]
[68]
Example 2
[69]
The herbicide of the liquid wettable formulation was carried out in the same manner as in Example 1, except for mixing an isomer mixture containing 92% by weight of erythro-form and 8% by weight of threo-form as FTS. The composition was prepared.
[70]
[71]
Example 3
[72]
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-fluoropropyl methoxyacetate (Flucetosulfuron, FTS) ) Is 96% by weight, and 10 parts by weight of an isomer mixture containing 4% by weight of a threo-form, NK-EFW (2-Naphthalenesulfonic acid, polymer with formaldehyde, Sodium salt, Cas no. 36290-04-7 ) 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)), mix the remaining Talc so that the sum of the composition is 100 parts by weight, and then use an air-jet mill. And pulverized. After adding 10 to 12 parts by weight of water to the pulverized mixture and kneading, granulation was performed using a granulator, and then dried with hot air at a temperature of about 80°C to prepare a granular wetting agent formulation.
[73]
[74]
Comparative Example 1
[75]
The herbicide of the liquid wettable formulation was carried out 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 a threo-form as FTS was mixed. The composition was prepared.
[76]
[77]
Comparative Example 2
[78]
The herbicide of the liquid wettable formulation was carried out in the same manner as in Example 1, except for mixing an isomer mixture containing 85% by weight of erythro-form and 15% by weight of threo-form as FTS. The composition was prepared.
[79]
[80]
Comparative Example 3
[81]
The herbicide of the granular wettable formulation was carried out 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 a threo-form as FTS was mixed. The composition was prepared.
[82]
[83]
[ Experimental Example : Evaluation of storage stability of herbicide composition]
[84]
In order to evaluate the storage stability of the herbicide compositions of Examples 1 to 3 and Comparative Examples 1 to 3, a liquid sample was filled in a plastic bottle made of polyethylene (PE), and a granular sample was filled with about 100 g in a silver foil bag, and then sealed. After storing for 4 weeks in an oven maintained at (±2)° C., 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.
[85]
HPLC analysis conditions are as follows.
[86]
Column: 100mm×4.6mm id “Capcell Pak” C18 column, 3㎛ particles
[87]
Mobile Phase: acetonitrile/ water (0.02M ammonium acetate + 0.1M acetic acid) = 32/68
[88]
Flow: 1.0 mL/min.
[89]
Column Temperature: 30℃
[90]
Injection Volume: 10µl
[91]
Detector Wavelength: 254nm
[92]
Run time: 20 min.
[93]
[94]
[Table 1]
Decomposition rate (%) after 4 weeks 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
[95]
Claims
[Claim 1]
A pyridine sulfonyl urea compound represented by the following Formula 1 is included as an active ingredient, and the pyridine sulfonyl urea compound is included as an isomer mixture of erythro-form and threo-form, and the erythro-type (Erythro-form) is a herbicidal composition containing 92% by weight or more of the isomer mixture. [Chemical 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, and 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, 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, a haloalkoxy group having 1 to 2 carbon atoms, or a halogen group.
[Claim 2]
The herbicide composition of claim 1, wherein the erythro-form is contained in an amount of 95% by weight or more of the isomer mixture.
[Claim 3]
The herbicide composition of claim 1, wherein the erythro-form is contained in an amount of 95% to 99% by weight of the isomer mixture.
[Claim 4]
The herbicide composition of claim 1, wherein in Formula 1, n is an integer of 1 or 2, R is a hydrogen or a methyl group, R'is a hydrogen, a halogen group or a methyl group, and X and Y are each a methoxy group.
[Claim 5]
The herbicide composition of claim 1, wherein in Formula 1, n is an integer of 1 or 2, R is methyl, R'is hydrogen, Cl, Br or a methyl group, and X and Y are each methoxy.
[Claim 6]
The method of claim 1, wherein the pyridinesulfonylurea compound represented by Formula 1 is N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro- 1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1 -Hydroxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro-1- (3-hydroxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-2-(2-fluoro -1-(3-methoxypropion)oxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4-methyl- 2-(2-Fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, N-[(4,6-dimethoxypyrimidin-2-yl)aminocarbonyl]-4 -Chloro-2-(2-fluoro-1-methoxyacetoxy-n-propyl)pyridin-3-sulfonamide, and N-[(4,6-dimethoxypyrimidin-2-yl)aminocar Bonyl]-4-bromo-2-(2-fluoro-1-methoxyacetoxy-n-propyl) pyridine-3-sulfonamide at least one herbicide composition selected from the group consisting of.
[Claim 7]
The herbicide composition of claim 1, wherein the herbicide composition is 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 agent, a powder, a dusting agent, a granule, a granule, and a tablet.
[Claim 8]
The herbicide composition of claim 1, wherein the herbicide composition is formed in a formulation of a suspension concentrate (SC) further comprising a buffer solution, a surfactant, and a cryoprotectant.