KR20010106604A - Herbicidal haloxyfop amides - Google Patents

Abstract

The present invention relates to a halooxypop amide compound represented by the following formula (1), a method for producing the same, a use for controlling blood generated in rice farming, and a herbicide composition comprising these compounds.

In Formula 1 above:

R represents a methyl group or an ethyl group; X is a hydrogen atom, a halogen atom, a cyano group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ alkoxy group, a C ₁ to C ₃ haloalkyl group substituted with _{1 to 3} halogen atoms, 1 to 3 halogens A C ₁ to C ₃ haloalkoxy group substituted with an atom, a C _{2 to} C ₄ alkoxyalkoxy group, a C _{2 to} C ₆ alkenyl group, or a C _{2 to} C ₆ alkenyloxy group; Y represents a hydrogen atom or a fluoro atom; n represents an integer of 1 or 2, and when n is 2, X may be a combination of different substituents.

Description

Herbicidal haloxyfop amides

The present invention relates to a halooxypop amide compound represented by the following formula (1), a method for producing the same, a use for controlling blood generated in rice farming, and a herbicide composition comprising these compounds.

Formula 1

In Formula 1 above:

R represents a methyl group or an ethyl group; X is a hydrogen atom, a halogen atom, a cyano group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ alkoxy group, a C ₁ to C ₃ haloalkyl group substituted with _{1 to 3} halogen atoms, 1 to 3 halogens A C ₁ to C ₃ haloalkoxy group substituted with an atom, a C _{2 to} C ₄ alkoxyalkoxy group, a C _{2 to} C ₆ alkenyl group, or a C _{2 to} C ₆ alkenyloxy group; Y represents a hydrogen atom or a fluoro atom; n represents an integer of 1 or 2, and when n is 2, X may be a combination of different substituents.

US Patent No. 4,531,969 discloses a compound represented by the following formula (2).

In Formula 2: R _a (Wherein R _b is a hydrogen atom, a halogen atom, a trifluoromethyl group or the like, R _c is a hydrogen atom, an alkyl group of C _{1 to} C ₄ , a halogen atom, a nitro group or the like), or the like; Z is among many (Wherein R _d and R _e are the same as or different from each other and are a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ hydroxyalkyl group, a C ₃ -C ₆ cycloalkyl group, a C ₁ -C ₄ It represents an alkoxy group, a phenyl group or an alkyl group of C ₁ ~C _4, an alkoxy group, a will) substituted with 1 to 3 substituents selected from the group of a halogen atom and trifluoromethyl the C ₁ ~C _6.

U.S. Patent 5,254,527 discloses a compound represented by the following formula (3).

In Chemical Formula 3, R _a and Z are as defined in Chemical Formula 2, respectively.

U.S. Patent 4,325,729 discloses a compound represented by the following formula (4).

In Formula 4, R _f and R _g are the same as or different from each other, and represent a hydrogen atom, a halogen atom, a cyano group, or an alkyl group having _{1 to 4} carbon atoms; Z is as defined in the formula (2).

WO 82/00400 discloses a compound represented by the following formula (5).

In Chemical Formula 5: T represents an oxygen atom or a sulfur atom; X ₁ represents a hydrogen atom, a bromine atom, or a chlorine atom; Z represents NR _h Ar (wherein R _h represents a hydrogen atom, a C _{1 to} C ₃ alkyl group; Ar is a nitrile group having one or two halogen atoms or a benzyl group, or a phenyl ring as a phenyl group). A valent halogen atom, a C ₁ -C ₄ alkyl group, a C ₁ -C ₄ thioalkyl group, a C ₁ -C ₃ alkoxy group, a hydroxy group, a C ₁ -C ₂ mono or dialkyl amino group, an amino group, a trifluoromethyl group 1 to 3 substituents selected from a cyano group, a thioamide group, and a nitro group may be substituted.

British Patent No. 1,599,121 discloses a compound represented by the following formula (6).

In Chemical Formula 6, X ¹ represents a fluoro atom or a chlorine atom; X ² represents a hydrogen atom or a chlorine atom; R _i represents a hydrogen atom, a methyl group or an ethyl group; Z ¹ represents an aniline group in which one to three halogen atoms are substituted.

In addition to the patents described above, US Pat. No. 4,479,001, European Patent Publication No. 00483 (1979) and European Patent No. 28,870 describe that halooxypopamide derivatives have herbicidal activity.

However, although some of the compounds represented by Formula 1 according to the present invention may be included in the general range of the conventional preparations described above, the patent has not synthesized the compounds of Formula 1 or the specific herbicidal activity of these compounds has not been tested. In particular, as shown in the present invention has excellent stability against rice and at the same time has not been reported to be excellent in the control properties generated in rice farming and has never been developed as a herbicide until now.

Although various herbicides are currently being developed and used, the most problematic weed in paddy farming is Barnyard grass.

Therefore, the development of medicines that control blood effectively is the greatest desire for rice farmers. In particular, single herbicides treated after seedling transplanting do not effectively suppress the development of rice blood, and the rice blood is regenerated in the middle of growing rice, causing great damage to rice harvest. Blood from rice fields has a significant effect on the yield of rice. For example, a decrease in rice yield is about 2 per 1 m 2, and a decrease in rice yield is about 10 when 5 per 1 m 2 is produced. At 10 weeks, it is reported to be about 19, and at 20 weeks, it is reported that the rice yield is reduced by about 35.

This phenomenon, despite the fact that many herbicides have been known in recent years, prevented the problem of blood avoidance, which is still a big problem, and is also a decisive factor in reducing the yield of rice. There is a great need for herbicides for control.

The present inventors studied to find a herbicide capable of effectively controlling the blood of the present discussion. As a result, the present inventors have completed the present invention by finding a derivative having a high stability against rice while showing a high stability among the halooxypopamide compounds. Reached. The present invention showing such performance is remarkably distinguished from the conventional inventions.

The present invention is characterized by a halooxypop amide compound represented by the following formula (1) which is extremely safe against rice and excellent in barnyard grass control activity.

Formula 1

In Formula 1, R, X, Y, and n are the same as defined above.

In more detail, the compounds represented by Formula 1 according to the present invention are shown in Tables 1a, 1b, and 1c.

R Y X CH ₃ H H CH ₂ CH ₃ H H CH ₃ H 4-CN CH ₃ H 4-F CH ₃ H 3-F CH ₃ H 5-F CH ₃ H 4-Cl CH ₃ H 4-F, 5-F CH ₃ H 4-Br CH ₃ H 4-CH ₃ CH ₃ H 4-CH ₂ CH ₃ CH ₃ H 4-profile CH ₃ H 4-isopropyl CH ₃ H 4-butyl CH ₃ H 4-isobufil CH ₃ H 3-CN CH ₃ H 4-OCH ₃ CH ₃ H 4-OCH ₂ CH ₃ CH ₃ H 4-O-isopropyl CH ₃ H 3-O-allyl CH ₃ H 4-O-propyl CH ₃ F H CH ₃ F 3-F CH ₃ F 4-F CH ₂ CH ₃ F 4-F CH ₃ F 4-Cl CH ₃ F 4-Br CH ₃ F 4-CH ₃ CH ₃ F 4-CH ₂ CH ₃ CH ₃ F 4-profile CH ₃ F 4-isopropyl CH ₃ F 4-butyl CH ₃ F 4-isobutyl

R Y X CH ₃ F 4-OCH ₃ CH ₃ F 4-OCH ₂ CH ₃ CH ₃ F 4-O-isopropyl CH ₃ F 4-O-propyl CH ₃ H 3-F, 5-F CH ₃ H 5-F CH ₃ H 5-Cl CH ₃ H 5-Br CH ₃ H 5-CN CH ₃ H 5-CH ₃ CH ₃ H 5-CH ₂ CH ₃ CH ₃ H 5-profile CH ₃ H 5-isopropyl CH ₃ H 5-butyl CH ₃ H 5-isobutyl CH ₃ H 5-OCH ₃ CH ₃ H 5-OCH ₂ CH ₃ CH ₃ H 5-O-isopropyl CH ₃ H 5-O-propyl CH ₃ H 5-O-allyl CH ₃ F 5-H CH ₃ F 5-F CH ₃ F 5-Cl CH ₃ F 5-Br CH ₃ F 5-CH ₃ CH ₃ F 5-CH ₂ CH ₃ CH ₃ F 5-profile CH ₃ F 5-isopropyl CH ₃ F 5-butyl CH ₃ F 5-isobutyl CH ₃ F 5-OCH ₃ CH ₃ F 5-OCH ₂ CH ₃ CH ₃ F 5-O-isopropyl CH ₃ F 5-O-propyl

As described above, the compound represented by Chemical Formula 1 according to the present invention is subjected to the coupling reaction between the compound represented by Chemical Formula 7 and the compound represented by Chemical Formula 8, as shown in the following Scheme 1 by applying a conventional organic synthesis method Can be prepared.

In Scheme 1: X 'represents a chlorine atom, bromine atom, hydroxy group, or phenoxy group; R, X, Y, n are as defined in the formula (1), respectively.

In the production method according to Scheme 1, it is preferable to use a binder such as triphenylphosphine and an organic base such as triethylamine and pyridine, and the reaction temperature is maintained at a suitable temperature of 0 to 100 ° C., with a diluting solvent. After reacting in an inert solvent such as ethers such as tetrahydrofuran, ethyl acetate, acetonitrile, toluene, xylene, hexane, dichloromethane, carbon tetrachloride and dichloroethane, the product was evaporated the solvent and the residue was chromatographed. It can be obtained by separation and purification by the method.

As another preparation method, the compound of Formula 1 may be obtained by alkylating the compound represented by Formula 9 with the compound represented by Formula 10, as shown in Scheme 2 below.

In Scheme 2, X ″ represents a chlorine atom, a bromine atom, an iodo atom, a benzenesulfonyloxy group, a toluenesulfonyloxy group, a methanesulfonyloxy group, or a lower alkyl sulfate group; R, X, Y and n each represent As defined in the formula (1).

The reaction according to Scheme 2 is preferably carried out in the presence of a strong base capable of extracting NH hydrogen of the anilide, for example, a strong base such as NaOH, KOH, LiOH, NaH, n-BuLi, LDA, and the like. The reaction temperature is maintained in the range of −78 to 50 ° C., and an inert solvent that does not affect the reaction, such as ethers such as ethyl ether, dioxane, tetrahydrofuran, and a hydrocarbon solvent such as hexane, is preferable.

As another method, the compound of Formula 1 may be prepared by reacting the compound of Formula 11 with the compound of Formula 12 in the presence of a base, as shown in Scheme 3 below.

In the above Scheme 3: Y 'represents a halogen atom, an alkylsulfonyloxy group, a haloalkylsulfonyloxy group, a benzenesulfonyloxy group, or a toluenesulfonyloxy group; R, X, Y, n are as defined in the formula (1), respectively.

In the production method according to Scheme 3, for example, the base includes alkali metal hydroxides such as hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Inorganic bases such as bicarbonates, or organic bases such as triethylamine, N, N-dimethylaniline, pyridine, and 1,8-diazabicyclo [5,4,0] unde-7-cene.

In addition, if necessary, by adding a phase transfer catalyst such as tetra-n-butylammonium bromide and 18-crown-6 [1,4,7,10,13,16-hexaoctacyclooctadecane], a desired reaction is carried out. It can also be terminated quickly. The reaction may be carried out in the presence of one kind or two or more kinds of suitable solvents, if necessary. Examples of solvents that can be used include inert organic solvents such as ketones such as acetone; Aromatic hydrocarbons such as toluene, xylene and chlorobenzene; Aliphatic hydrocarbons such as petroleum ether and ligroin; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Nitriles such as acetonitrile and propionitrile; Or amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like can be used. The reaction temperature is any temperature range from 0 deg. C to reflux temperature at which the reaction proceeds, and is preferably in the range of 5 to 50 deg. Reaction time can be carried out for 1 to 24 hours to obtain the target product in a good yield.

As another preparation method, the compound represented by Chemical Formula 1 may be prepared by reacting the compound represented by Chemical Formula 13 with the compound represented by Chemical Formula 14 in the presence of a base, as shown in Scheme 4 below.

In Scheme 4: X, Y, Y ', R and n are the same as defined in Chemical Formula 1.

In the production method according to Scheme 4, for example, alkali bases include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate and potassium hydrogen carbonate. Inorganic salts such as bicarbonates, or organic such as triethylamine, N, N-dimethylaniline, pyridine, picoline, quinoline, 1,8-diazabicyclo [5,4,0] unde-7-cene Bases are good.

If necessary, the reaction may be accelerated by adding a phase transfer catalyst such as tetra-n-butylammonium bromide and 18-crown-6 [1,4,7,10,13,16-hexaoctacyclooctadecane]. Can be.

The reaction may be carried out in an appropriate one or two or more diluent solvents as necessary. Examples of the solvent that can be used include ketones such as inert organic solvents such as acetone and butanone; Aromatic hydrocarbons such as benzene, toluene, xylene and chlorobenzene; Aliphatic hydrocarbons such as petroleum ether and ligroin; Ethers such as diethyl ether, tetrahydrofuran and dioxane; Nitriles such as acetonitrile and propionitrile; Or amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone. Reaction temperature is arbitrary temperature from 0 degreeC to the reflux temperature of a reaction solvent, Preferably it is 20-100 degreeC. The reaction time is somewhat different depending on the compound, but the reaction can be obtained in a good yield if the reaction for 1 to 24 hours.

Such a present invention will be described in more detail based on the following examples, but the present invention is not limited thereto.

Example 1 Synthesis of (S) -2-bromopropionic acid-N- (2-fluorophenyl) -N-methylamide

(S) -2-bromopropionic acid (3.4 g, 0.022 mol) and 2-fluoroaniline (3 g, 0.024 mol) were dissolved in 50 mL of chloroform and the reaction was cooled to 0 ° C. A solution of dicyclohexylcarbodiimide (5 g, 0.024 mol) in 10 mL of CHCl ₃ was slowly injected using a syringe. The temperature of the reaction mixture was slowly raised to room temperature and then stirred at room temperature for 1 hour. The insoluble solid in the reaction mixture was filtered, and then the solid filtrate was washed twice with 20 mL of CHCl ₃ . The filtrate was distilled under reduced pressure and purified by column chromatography (eluent: ethyl acetate / n-hexane = 1/3) to obtain 5 g of pure target product.

¹ H-NMR (CDCl ₃ ): δ 1.7 (3H, d), 3.24 (3H, s), 4.16 (0.7H, q), 4.34 (0.3H, q), 7.13-7.48 (4H, m)

Example 2 Synthesis of (R) -2- (4-hydroxyphenoxy) propion-N- (2-fluorophenyl) -N-methylamide

(S) -2-bromopropionic acid-N- (2-fluorophenyl) -N-methylamide (18.2 g, 0.07 mol) with hydroquinone (7 g, 0.064 mol), K ₂ CO ₃ (10.54 g, 0.076 mol) and tetran-butylammonium bromide (1 g) were dissolved in 350 ml of acetonitrile and refluxed for 6 hours. After lowering the temperature of the reaction mixture to room temperature, the insoluble solids in the reaction mixture were removed by filtration, and the filtrate was distilled under reduced pressure and purified by column chromatography (eluent solvent: ethyl acetate / n-hexane = 1/2). 16 g of pure target product was obtained.

¹ H-NMR (CDCl ₃ ): δ 1.42 (3H, t), 3.25 (3H, s), 4.56 (1H, q), 6.5 to 7.4 (8H, m)

Example 3: (R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2-fluorophenyl)- Synthesis of N-methylamide

(R) -2- (4-hydroxyphenoxy) propionic acid-N- (2-fluorophenyl) -N-methylamide (11.5 g, 0.04 mol) and 2,3-dichloro-5- (trifluoro Methyl) pyridine (7.74 g, 0.036 mol), K ₂ CO ₃ (6 g, 0.043 mol) and tetran-butylammonium bromide (1 g) were dissolved in 300 ml of acetonitrile and refluxed for 7 hours. After lowering the temperature of the reaction mixture to room temperature, the insoluble solids in the reaction mixture were removed by filtration, and the filtrate was distilled under reduced pressure and purified by column chromatography (eluent solvent: ethyl acetate / n-hexane = 1/3). 12.5 g of pure target product was obtained.

¹ H-NMR (CDCl ₃ ): δ 1.47 (3H, t), 3.28 (3H, s), 4.65 (1H, m), 6.7-7.35 (8H, m), 7.95 (1H, d), 8.25 ( 1H, d)

Example 4: (R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2-fluorophenyl) amide Synthesis of

(R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid (361.7 mg, 1 mol) was added to 200 mL of anhydrous dichloromethane. It was dissolved, 2-fluoroaniline (111.12 mg, 1 mmol) was added thereto, and then cooled to 0 ° C under nitrogen. Dicyclohexylcarbodiimide (226.6 mg, 1.1 mmol) dissolved in 10 ml of CHCl ₃ was slowly injected into the reaction mixture using a syringe. The temperature of the reaction mixture was slowly raised to room temperature and then stirred at room temperature for 3 hours. The insoluble solid in the reaction mixture was filtered, and then the solid filtrate was washed twice with 20 mL of CHCl ₃ . The filtrate was distilled under reduced pressure and purified by column chromatography (eluent: ethyl acetate / n-hexane = 1/4) to obtain 370 mg of the pure target product.

m.p: 129-130 ° C

¹ H-NMR (CDCl ₃ ): δ 1.69 (3H, t), 4.84 (1H, q), 7.03 to 7.26 (7H, m), 7.98 to 8.39 (3H, m), 8.56 (1H, br)

Example 5: (R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2-fluorophenyl)- Synthesis of N-methylamide

(R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2-fluorophenyl) amide (104 mg, 0.24 mol) was dissolved in 10 ml of anhydrous tetrahydrofuran and lowered to 0 ° C. Then, 60 NaH (10 mg, 0.24 mmol) and CH ₃ I (34 mg, 0.24 mmol) were added sequentially and stirred at room temperature for 4 hours. Ice-water was added to the reaction mixture, extracted three times with ethyl acetate, dried over MgSO ₄ , filtered, and distilled under reduced pressure, and then purified by column chromatography (eluent: ethyl acetate / n-hexane = 1/2) to obtain 80 mg of pure target product. Got.

Example 6: (R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2,5-difluoro Synthesis of Phenyl) -N-methylamide

(R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid (0.728 g, 2 mmol) in 10 ml of thionylchloride Then refluxed for 4 hours. Excess thionylchloride was removed by distillation under reduced pressure and 3 ml of anhydrous tetrahydrofuran was added. In another reaction vessel, N-methyl-2,5-difluoroaniline (0.58 g, 2 mmol) and triethylamine (0.42 mL) were mixed with anhydrous tetrahydrofuran (10 mL) and maintained at 0 ° C. One solution was slowly added dropwise. The reaction mixture was stirred at room temperature for 4 hours, then water was added and extracted three times with ethyl acetate. The extracted organic layer was dried over MgSO ₄ , filtered, and distilled under reduced pressure, and then purified by column chromatography (eluent: ethyl acetate / n-hexane = 1/2) to obtain 650 mg of the pure target compound.

¹ H-NMR (CDCl ₃ ): δ 1.47 (3H, d), 3.27 (3H, s), 4.63 (1H, m), 6.74 to 7.3 (7H, m), 7.95 (1H, d), 8.25 ( 1H, d)

Example 7: (R) -2- [4-((3-chloro-5- (trifluoromethyl) -2-pyridyl) oxy) phenoxy] propionic acid-N- (2,6-difluoro Synthesis of Phenyl) -N-methylamide

The same procedure as in Example 6, except that N-methyl-2,5-difluoroaniline (0.58 g, 2 mmol) was used instead of N-methyl-2,5-difluoroaniline. 675 mg were obtained.

¹ H-NMR (CDCl ₃ ): δ 1.46 (3H, d), 3.27 (3H, s), 4.62 (1H, q), 6.74-7.29 (7H, m), 7.95 (1H, d), 8.25 ( 1H, d)

Formulation

When the compound of the present invention is used as a herbicide, it is formulated into various forms such as a hydrating agent, an emulsion, a granule, a powder suspension and a liquid by combining the compound of the present invention with a carrier, a surfactant, a dispersant, and an auxiliary agent commonly used in the preparation of agrochemicals. Use it. These formulations can be used directly and can be processed by dilution in appropriate media. The spray volume can be used from several hundred liters to several thousand liters per hectare. The formulations may contain from about 0.1 to 99 by weight of the active ingredient, with the surfactant in the range of about 0.1 to 20, or in the range of 0 to 99.9 of the solid or liquid diluent. A summary of this is shown in Table 2 below.

The proportion of the active ingredient can be adjusted according to the application and it is sometimes necessary to use a larger proportion of the surfactant than the active ingredient, and it can be added in the preparation or used in tank mixing.

When using a solid diluent, a highly absorbent diluent is good for making a hydrate. Liquid diluents and solvents should be stable without phase separation at 0 ° C. All formulations are added with small amounts of additives to prevent antifoam cakes, corrosion and microbial growth.

The method of making the composition is a conventional method, and the liquid preparation only needs to mix the components, and the fine solid composition may be mixed and ground in a hammer or a flow mill. Suspensions are compounded in a wet mill and granules are made by spraying an active substance onto the granular carrier.

Representative formulation preparation examples are as follows.

Formulation 1: Hydration

The following components were thoroughly mixed and the liquid surfactant was mixed while spraying onto the solid components. Grinding in a hammer mill brought the particle size to 100 μm or less.

20 weight of compound (Example 3 compound)

Dodecylphenol Polyethylene Glycol Ether 2 Weight

Sodium Lignin Sulfonate 4 Weight

Sodium Silicone Aluminate 6 Weight

Montmorillonite 68 Weight

Formulation 2: Hydration

The following ingredients were mixed and ground in a hammer mill until the particle size was 25 μm or less and packaged.

80 weight of compound (Example 3 compound)

Sodium Alkyl Naphthalene Sulfonate 2 Weight

Sodium Lignin Sulfonate 2 Weight

Synthetic Amorphous Silica 3 Weight

Kaolinite 13 weight

Formulation 3: Emulsion

The following components were mixed and uniformly dissolved to give an emulsion.

30 weight of compound (Example 3 compound)

20 cyclohexanone

Polyoxyethylene alkylaryl ether 11 weight

Alkylbenzenesulfonate calcium 4 weight

Methylnaphthalene 35 weight

Formulation 4: granulation

The following components are mixed and ground uniformly, 20 parts by weight of water is added to 100 parts by weight of the mixture, mixed, processed into granules of 14 to 32 mesh using an extruder, and dried to form granules.

Compound 5 Example 3 Weight

Sodium Lauryl Alcohol Sulfate Ester Salt 2 Weight

Sodium Lignin Sulfonate 5 Weight

Carboxymethyl Cellulose 2 Weight

Potassium sulfate 16 weight

Gypsum 70 weight

In actual use, the formulations of the present invention are diluted and applied at appropriate concentrations.

[Usage]

The compound of the present invention is particularly useful for rice farming because it exhibits high stability against rice during foliage treatment, and at the same time shows excellent control of young blood as well as grown blood.

The herbicide of the present invention can be used as an active ingredient up to 10 g to 4 kg per hectare (ha), preferably using about 50 g to 400 g. The choice of dosage is determined by factors such as weed generation, growth level, and preparation. In addition, the herbicide of the present invention can be used alone or in combination with other herbicides, insecticides or fungicides. Especially bentazone, quinclolac, furofanyl, cetmethrin, 2,4-D, phenoxapuroethyl, linyuron, MCPA, azaphenidine, carfentrazone, molinate, thiobencarb, pendimethalin, Bensulfuronmethyl, pyrazosulfuronethyl, metsulfuronmethyl, thifensulfuronmethyl, tribenuronmethyl, trifluurine, amidosulfuron, brooxynyl, butaclo, mecofurop, metreuxin, biphenox, ben Mixed with one or more agents such as purazate, isopururoron, thihalopopbutyl, mefenacet, pentrazamide, pyriminobac methyl, bispyribac sodium, azisulfuron, cyclosulfamuron, peanker and the like It is also useful to use.

The following describes an example of testing the weed control effect exhibited by the compounds of the present invention.

Test Example 1: Foliage Treatment Test

Soil-filled 600 cm 2 pots were planted with seeds of each plant, such as rice, wheat, barley, corn, cotton, blood, sorghum, and barley, and covered with 0.1-1 cm. Pot is dissolved in a mixture of 1 part by weight of the test agent, 5 parts by weight of acetone and 1 part by weight of emulsifier when grown in a greenhouse at 20 to 30 ℃, and diluted with water. 2000 L per hectare (ha) The plant foliage surface was sprayed at a ratio of. The amount of active compound was chosen to be the specific amount desired. The drug efficacy test was assessed as damage by visually comparing the degree of damage of the plant with the control group not treated with the drug on the 14th day after treatment. Evaluation values are shown as follows.

Zero effect (same as no medication)

20 slight effects

70 Herbicide effect

100 annihilation (completed test)

As a result of the experiment, the compound represented by Chemical Formula 1 according to the present invention showed high selectivity in crops and strong herbicidal effect in weeds.

The plant names used in this test are shown in Table 3 below.

Abbreviation Scientific name Tube ZEAMX Zea mays L. Corn TRZAW Triticum aestivum L. Wheat ORYSA Oryza sativa cv. Dongjin Rice SORBI Andropogon sorghum Common sorgum ECHCG Echinoch crus-galli Beauv. var. caudata Kitagawa Barnyard grass DIGSA Digitaria Sanguinalis (L.) SCOP Large crabgrass PANDI Panicum dichotomiflorum Michx Fall panicum

Among the compounds represented by Formula 1 according to the present invention, the herbicidal activity of the compounds exemplified in Table 4 below was evaluated and shown in Table 5 below.

division R Y X Compound number 1 CH ₃ H H Compound number 2 CH ₃ F H Compound number 3 CH ₃ H 5-F Comparator 1 Reference Drug 2

division Botanical name Foliage treatment amount (Kg / ha) 0.16 0.04 Compound number 1 ZEAMX 40 0 TRZAW 30 0 ORYSA 0 0 SORBI 100 100 ECHCG 100 100 DIGSA 100 100 PANDI 100 50 Compound number 2 ZEAMX 10 0 TRZAW 20 0 ORYSA 0 0 SORBI 100 100 ECHCG 100 90 DIGSA 100 100 PANDI 100 30 Compound number 3 ZEAMX 30 0 TRZAW 20 0 ORYSA 0 0 SORBI 100 100 ECHCG 100 80 DIGSA 100 100 PANDI 100 60 Comparator 1 ZEAMX 100 100 TRZAW 100 100 ORYSA 100 100 SORBI 100 100 ECHCG 100 100 DIGSA 100 100 PANDI 100 100 Reference Drug 2 ZEAMX 100 30 TRZAW 100 80 ORYSA 80 0 SORBI 100 100 ECHCG 100 80 DIGSA 100 100 PANDI 100 90

According to the results of Table 5, the compounds according to the present invention as a compound having a stereospecificity can show excellent stability for rice and excellent control ability for three-leaf paddy field in the foliage treatment test.

On the contrary, the control agent 1 and the control agent 2, which are one of the compounds having the most excellent herbicidal activity shown in WO 82/00400, are racemic compounds. There was no hepatic selectivity, and Control 2 was found to have poor control of trifoliate bast.

Based on the above results, it was found that even the halooxypop derivatives showed a great difference in the herbicidal activity depending on the substituents.

As described above, the selectivity and herbicidal activity of the compound according to the present invention was found in the greenhouse test. The excellent skin control effect of the compound of the present invention increases the utility, especially in rice farming. In addition, wheat, barley, soybeans and corn also shows high safety, so it is useful for weed control in agriculture other than rice farming.

Claims (11)

Haloxypop compound represented by the following formula (1), characterized in that the stability to rice and the ability to control the paddy field. Formula 1 In Formula 1 above: R represents a methyl group or an ethyl group; X is a hydrogen atom, a halogen atom, a cyano group, a C _{1 to} C ₆ alkyl group, a C _{1 to} C ₆ alkoxy group, a C ₁ to C ₃ haloalkyl group substituted with _{1 to 3} halogen atoms, 1 to 3 halogens A C ₁ to C ₃ haloalkoxy group substituted with an atom, a C _{2 to} C ₄ alkoxyalkoxy group, a C _{2 to} C ₆ alkenyl group, or a C _{2 to} C ₆ alkenyloxy group; Y represents a hydrogen atom or a fluoro atom; n represents an integer of 1 or 2, and when n is 2, X may be a combination of different substituents. The compound of claim 1, wherein R is CH ₃ ; X is H, F, Cl, Br, CN, CH ₃ , or OCH ₃ ; Y is H, or F; noxyhalo compound, characterized in that n = 1. The compound of claim 1, wherein R is CH ₃ ; X is H; Y is H, haoxypop compound, characterized in that. The compound of claim 1, wherein R is CH ₃ ; X is 5-F; Y is H, herbicidally active compound, characterized in that. The compound of claim 1, wherein R is CH ₃ ; X is H; Y is F herbicidally active compound, characterized in that. The method of spraying an effective amount of the compound represented by the following formula (1) to control Barnyard grass generated in the paddy field in which the rice is growing, without causing substantial damage to the rice. Formula 1 In Formula 1: R, X, Y and n are as defined in claim 1, respectively. A herbicide composition characterized by containing a compound represented by the following formula (1) and a carrier, adjuvant, surfactant or other herbicide compound which can be used agriculturally. Formula 1 In Formula 1: R, X, Y and n are as defined in claim 1, respectively. A method for producing a compound represented by the following Chemical Formula 1, comprising using the compound represented by the following Chemical Formula 7 and the compound represented by the following Chemical Formula 8. Formula 1 Wherein R, X, Y and n are as defined in claim 1, respectively; X 'represents OH, Cl, Br, or a phenoxy group. A method for preparing a compound represented by the following Chemical Formula 1, comprising using the compound represented by the following Chemical Formula 9 and the compound represented by the following Chemical Formula 10: Formula 1 Wherein R, X, Y and n are as defined in claim 1, respectively; X "represents Cl, Br, I, benzenesulfonyloxy group, toluenesulfonyloxy group, methanesulfonyloxy group, or lower alkyl sulfate group. A method for producing a compound represented by the following Chemical Formula 1, comprising using the compound represented by the following Chemical Formula 11 and the compound represented by the following Chemical Formula 12: Formula 1 Wherein R, X, Y and n are as defined in claim 1, respectively; Y 'represents a halogen atom, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy group, or toluenesulfonyloxy group. A method for preparing a compound represented by the following Chemical Formula 1, comprising using the compound represented by the following Chemical Formula 13 and the compound represented by the following Chemical Formula 14. Formula 1 Wherein R, X, Y and n are as defined in claim 1, respectively; Y 'represents a halogen atom, alkylsulfonyloxy, haloalkylsulfonyloxy, benzenesulfonyloxy group, or toluenesulfonyloxy group.