KR20110110420A - Herbicidal uracil compounds and a herbicide comprising the derivatives - Google Patents

Abstract

The present invention relates to a herbicidal uracil compound, a method for preparing the compound, and a herbicide containing the compound.

Description

Herbicidal uracil compounds and a herbicide comprising the derivatives}

The present invention relates to a herbicidal uracil compound, a method for preparing the compound, and a herbicide containing the compound.

In general, weed control is very important for improving agricultural productivity, and various kinds of herbicides have been used. For example, corn cultivation has been used triazine herbicides such as atrazine, or anilide herbicides such as Alachlor or Metolachlor. Meanwhile, as non-selective herbicides, herbicides such as Paraquat or Glyphosate have been used. However, there are still many weeds that cause agricultural losses, so the research and development of new herbicides continues.

As a herbicidal compound, Japanese Patent Laid-Open No. 2000-302,764 discloses a compound represented by the following formula (A).

In Formula A, R ¹ is a hydrogen atom or a substituted alkyl group, R ² is an alkyl group, an alkenyl group, or an alkynyl group, and R ³ is a hydrogen atom or a methyl group.

In addition, Japanese Patent Laid-Open No. 2001-172,265 discloses a compound represented by the following general formula (B).

In Formula B, R ¹ is a hydrogen atom or a substituted alkyl group, R ² is a hydrogen atom or an alkyl group, and R ³ is a hydrogen atom or a methyl group.

In addition, US Patent No. 6,403,534 discloses a compound represented by the following formula (C).

In Formula C, R ¹ is a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, or the like, and R ² is a hydrogen atom, an alkyl group, a haloalkyl group, an alkenyl group, an alkynyl group, a phenyl group, a benzyl group, an alkoxy group, an alkyl group. Sulfonyl groups and the like.

However, the compound represented by the formula (A), (B), or (C) is a non-selective herbicide in orchards and non-cultivated lands due to the nature of the drug, which requires high dose treatment for controlling a large number of problem weeds, and when used as a selective herbicide. It is a situation that requires the development of high-performance drugs that can solve these problems because it is weak.

It is an object of the present invention to provide a uracil compound having a novel structure and an agrochemically acceptable salt thereof.

It is another object of the present invention to provide a herbicide comprising as an active ingredient a compound selected from the above-described uracil compound and its agrochemically acceptable salt, or a mixture thereof.

Another object of the present invention is to provide a method for preparing the uracil compound.

The present invention is characterized by the uracil compound represented by the following formula (1).

In Formula 1, R ₁ , R ₂ , R ₄ , and R ₅ is the same as or different from each other, and represents a hydrogen atom or a C _{1 to} C ₆ alkyl group; R ₃ is a hydrogen atom, a hydroxyl group, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkyl group, C _2- C ₆ haloalkenyl group, C ₂ -C ₆ alkoxyalkyl group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryloxy group, C ₆ -C ₁₀ aryl C ₁ -C ₆ alkyl group, C ₆ -C _{A 10} aryl C ₁ -C ₆ alkoxy group; R ₆ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ alkynyl group, C ₁ -C ₆ alkoxycarbo C ₁ -C ₆ alkyl group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryl C ₁ -C ₆ alkyl group, or C ₆ -C ₁₀ aryl C _1- A C ₆ alkoxy group; X represents a halogen atom, a cyano group, CONH ₂ , or CSNH ₂ ; Y represents O, S, NH, or N (C ₁ ~C ₆ alkyl).

The uracil-based compound represented by Chemical Formula 1, which is characterized by the present invention, exhibits a wide range of herbicidal effects from broadleaf weeds as well as flowering and weeds at low concentration. Thus, it is very useful as a non-selective herbicide for foliage treatment in orchards and non-cropland.

In addition, the uracil-based compound represented by Chemical Formula 1, which is characterized by the present invention, does not harm harmful crops such as wheat and corn during soil treatment, and has a high selective herbicidal activity, which shows very excellent herbicidal activity against broadleaf, flowering and weeds. Effect. Thus, the herbicides of the present invention are very useful as herbicides suitable for use in cropland, orchards and non-cropland.

The uracil compounds represented by Formula 1 according to the present invention include agrochemically acceptable salts, racemates, single enantiomers, or diastereomeric compounds of these compounds.

Agrochemically acceptable salts of the uracil compound represented by Formula 1 include, for example, metal salts, salts with organic bases, salts with inorganic acids, salts with organic acids, basic or acidic amino acids, and the like. May be included. Suitable metal salts include, for example, alkali metal salts such as sodium salts, potassium salts and the like; Alkaline earth metal salts such as calcium salts, magnesium salts, barium salts, and the like; Aluminum salts and the like. Salts with organic bases are, for example, trimethylamine, triethylamine, pyridine, picoline, 2,6-lutidine, ethanolamine, diethanolamine, triethanolamine, cyclohexylamine, dicyclohexylamine, N Salts with , N -dibenzylethylenediamine and the like. Salts with inorganic acids may include, for example, salts with hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid and the like. Salts with organic acids may include, for example, salts with formic acid, acetic acid, trifluoroacetic acid, phthalic acid, fumaric acid, oxalic acid, tartaric acid, maleic acid, citric acid, succinic acid, methanesulfonic acid, benzenesulfonic acid, p- toluenesulfonic acid, and the like. . Salts with basic amino acids may include, for example, salts with arginine, lysine, ornithine and the like. Salts with acidic amino acids may include, for example, salts with aspartic acid, glutamic acid and the like.

Hereinafter, the substituents used in the definition of the uracil compound represented by Chemical Formula 1 according to the present invention will be described in more detail.

'Alkyl group' includes all linear or pulverized carbon chains having 1 to 6 carbon atoms, specifically, the alkyl group is methyl, ethyl group, n -propyl group, isopropyl group, n -butyl group, isobutyl group, tert -butyl group, n -hexyl group, etc. are mentioned.

'Alkenyl group' includes at least one or more double bonds, and includes all linear or pulverized carbon chains having 2 to 6 carbon atoms, and specifically, alkenyl groups include vinyl, allyl, 1-butenyl, 2-butenyl group, 1,3-butadienyl group, 1-hexenyl group, 2-hexenyl group, 1,3-hexadienyl group, 1,4-hexadienyl group, 1,5-hexadienyl group, 2,4- Hexadieneyl group, and the like.

'Alkynyl group' includes at least one or more triple bonds, and includes all linear or pulverized carbon chains having 2 to 6 carbon atoms. Specifically, an alkynyl group is an acetylenyl group, a propazyl group, or 1-propine. Diary, 1-butynyl group, 2-butynyl group, 1,3-butadiynyl group, 1-hexynyl group, 2-hexynyl group, 1,3-hexadiynyl group, 1,4-hexadiynyl group, 1 , 5-hexadiynyl group, 2,4-hexadiynyl group, and the like.

"Alkoxy group" means an alkyl group of carbon connected to oxygen, wherein alkyl is as defined above.

'Halo' or 'halogen atom' is used interchangeably with each other to mean chlorine, fluorine, iodine and bromine atoms.

The haloalkyl group includes all alkyl groups in which at least one hydrogen atom of the alkyl carbon chain defined above is substituted with a halogen atom, and specifically, the haloalkyl group is a chloromethyl group, a fluoromethyl group, a dichloromethyl group, a dichloroethyl group, a tri Fluoromethyl group, tetrafluoroethyl group and the like.

The 'haloalkenyl group' includes all alkenyl groups in which at least one hydrogen atom of the alkenyl carbon chain defined above is substituted with a halogen atom, and specifically, the haloalkenyl group is a chlorovinyl group, a fluorovinyl group, or a chloro group. Allyl groups, fluoroallyl groups, and the like.

'Aryl group' means an aromatic ring group, and aryl refers to a ring having at least six atoms resonancely stabilized by a double bond to two rings or adjacent carbon atoms having at least 10 atoms, and aryl The group may include a phenyl group, a naphthyl group, and the like, and the aryl group may be a substituent selected from halogen, hydroxy, carboxylic acid, carboxyester, nitro, amine, thiol, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, and the like. One or more may be substituted.

In the uracil compound represented by Chemical Formula 1 according to the present invention, preferably, R ₁ and R ₂ are the same as or different from each other and are a hydrogen atom, a methyl group, an ethyl group, n- propyl group, isopropyl group, n- Butyl group or tert- butyl group; R ₃ represents a hydrogen atom, a hydroxyl group, a methyl group, an ethyl group, n- propyl group, isopropyl group, n- butyl group, tert- butyl group, vinyl group, allyl group, propazyl group, methoxy group, ethoxy group, n - propoxy group, n- butoxy group, tert- butoxy group, chloromethyl group, dichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, chlorovinyl group, fluorovinyl group, chloroallyl group, fluoro Roallyl group, chloropropazyl group, fluoropropazyl group, methoxymethyl group, ethoxymethyl group, methoxyethyl group, methoxypropyl group, ethoxyethyl group, phenyl group, benzyl group, phenethyl group, phenoxy group, benzyloxy group Or phenethyloxy group; R ₄ and R ₅ are the same as or different from each other and represent a hydrogen atom, a methyl group, an ethyl group, an n- propyl group, an isopropyl group, an n- butyl group, or a tert- butyl group; R ₆ is a hydrogen atom, methyl group, ethyl group, n- propyl group, isopropyl group, n- butyl group, tert- butyl group, chloromethyl group, dichloromethyl group, fluoromethyl group, difluoromethyl group, trifluoromethyl group, Methoxy, ethoxy, n - propoxy, n- butoxy, tert- butoxy, vinyl, allyl, propazyl, chlorovinyl, fluorovinyl, chloroallyl, fluoroallyl, Methoxycarbonylmethyl group, methoxycarbonylethyl group, methoxycarbonylpropyl group, ethoxycarbonylmethyl group, phenyl group, benzyl group, phenethyl group, phenoxy group, benzyloxy group, or phenethyloxy group; X represents a chloro atom, a cyano group, CONH ₂ , or CSNH ₂ Represent; Y is an uracil compound representing O, S, NH, or N (CH ₃ ).

Particularly preferred compounds in the uracil compound represented by Formula 1 are as follows.

{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro Rophenylthio] -1-oxopropyl} amino acetic acid methyl ester;

{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro Rophenylthio] -1-oxopropyl} amino acetic acid ethyl ester;

2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) pyrimidinyl) 4-fluorophenylthio] -1-oxopropyl} amino] propionic acid methyl ester;

2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) pyrimidinyl) 4-fluorophenylthio] -1-oxopropyl} amino] propionic acid ethyl ester.

On the other hand, the present invention includes a method for producing a uracil compound represented by the formula (1).

According to the first production method according to the present invention, as shown in Scheme 1, the carboxylic acid compound represented by the following Chemical Formula 2 is reacted with a chlorination reagent to prepare carboxylic acid chloride, and then the obtained carboxylic acid chloride is represented by the following Chemical Formula 3. It is a method of obtaining the uracil type compound represented by the said General formula (1) by making it react with an ester compound.

Scheme 1

In Reaction Scheme 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X, and Y are as defined in Formula 1, respectively.

The carboxylic acid compound represented by Chemical Formula 2 (X = Cl) used as a raw material in the preparation method of Scheme 1 is a known compound disclosed in WO 03/029226. The amino acid ester compound represented by the formula (3) is a commercially available compound, a known compound, or a person skilled in the art can be easily prepared using known methods.

The chlorination reagent used in Scheme 1 is a conventional chlorination reagent that has been generally used, specifically, thionyl chloride, phosgene, phosphoryl oxychloride, oxaryl chloride, phosphorus trichloride, phosphorus pentachloride, and the like. The chlorination reaction can be carried out in a solvent or can be carried out without a solvent. The reaction solvent that can be used when the solvent is used may be any conventional organic solvent used in the art. Specifically, dichloromethane, chloroform, dichloroethane, ethyl acetate, cyclohexane, benzene, chlorobenzene, toluene, Tetrahydrofuran, diisopropyl ether, 1,4-dioxane and the like can be used. The chlorination reagent is preferably used in an excess of 1 mole or more with respect to 1 mole of the carboxylic acid compound represented by Formula 2, and performs the reaction in the range of 20 ° C to 150 ° C.

When the chlorination reaction is completed, the reaction solution is concentrated under reduced pressure, dissolved in a solvent and reacted with the amino acid ester compound represented by the formula (3). In this case, the reaction is preferably performed under basic conditions, and an organic base such as triethylamine, pyridine, or dimethylaniline, or an inorganic base such as Na ₂ CO ₃ , K ₂ CO ₃ , or Li ₂ CO ₃ may be used. The reaction temperature is preferably in the range of 0 ° C to 100 ° C. The amount of the amino acid ester compound represented by Chemical Formula 3 may vary depending on whether the base is used. Under the reaction conditions without using a base, it is preferable to use 2 moles or more of the amino acid ester compound represented by Formula 3 with respect to 1 mole of the carboxylic acid compound. In the reaction conditions using a base, it is preferable to use 1 mole or more of the amino acid ester compound represented by the formula (3) with respect to 1 mole of the carboxylic acid compound, and 1 mole or more of the base. After completion of the reaction, the mixture was diluted with an organic solvent, washed with acid, and the obtained organic layer was dried, concentrated and purified by column chromatography.

In the second production method according to the present invention, as shown in Scheme 2, the carboxylic acid compound represented by the following formula (2) and the amino acid ester compound represented by the following formula (3) by the amide dehydration reaction using a dehydrating agent to the desired formula (1) It is a method of directly obtaining the displayed uracil compound.

Scheme 2

In Scheme 2, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X, and Y are as defined in Formula 1, respectively.

The dehydrating agent used in the dehydration reaction according to Scheme 2 is a dehydration reagent commonly used in the amide dehydration reaction, N, N -carbonyldiimidazole, N, N- cyclohexyl carbodiimide, N- (3-dimethylamino propyl) - N '- ethylcarbodiimide and (benzotriazol-1-yl) - N, N, N' , N '- it may be selected from borates such as tetramethyl uranium tetrafluoroborate passage, limited to It is not. Dehydration reagent may be used in the range of 1 to 1.5 molar ratio with respect to 1 mole of the carboxylic acid compound represented by Formula 2. In this dehydration reaction, N, N- dimethylaminopyridine may be used as a catalyst if necessary. The catalyst may be used in a range of 0.05 to 0.1 mole ratio with respect to 1 mole of the carboxylic acid compound represented by Formula 2. The dehydration reaction may be carried out within a temperature range of 0 ℃ to 80 ℃, preferably 20 ℃ to 50 ℃. As the reaction solvent, all conventional organic solvents used in the art may be used. Specifically, dichloromethane, dichloroethane, ethyl acetate, acetonitrile, toluene, tetrahydrofuran, diethyl ether, dimethyl formamide, and the like may be used. Can be. After the reaction is completed, the reaction mixture may be diluted in a general separation process, for example, diluted with an organic solvent, washed with an acidic aqueous solution, and then concentrated under reduced pressure, and purified by column chromatography if necessary.

According to the third production method according to the present invention, as shown in Scheme 3, the compound represented by the following formula (4) is subjected to a nucleophilic substitution reaction with the compound represented by the following formula (5) under basic conditions, and the desired uracil represented by the formula (1) It is a method of obtaining a system compound.

Scheme 3

In Reaction Scheme 3, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X, and Y are as defined in Formula 1, respectively, L is a leaving group (leaving group) methanesulfonate group (-OMs), p- toluenesulfonate group (-OTs), halogen atom (for example, Cl, Br), etc. are shown.

In the nucleophilic substitution reaction according to Scheme 3, all conventional organic solvents used in the art as reaction solvents may be used, specifically, dichloromethane, chloroform, dichloroethane, ethyl acetate, cyclohexane, benzene, chlorobenzene, Toluene, cyclohexane, tetrahydrofuran, diisopropyl ether, 1,4-dioxane, acetonitrile and the like can be used. In addition, the base that can be used for the nucleophilic substitution reaction is an organic base such as triethylamine, pyridine, or dimethylaniline, or NaHCO ₃ , KHCO ₃ , Na ₂ CO ₃ , K ₂ CO ₃ , Li ₂ CO _3, or the like. Inorganic base. The base used at this time is preferably used in the range of 1 to 1.1 moles with respect to 1 mole of the compound represented by the formula (5). The nucleophilic substitution reaction is carried out in the range of 0 ℃ to 100 ℃.

Compound (X = Cl) represented by Chemical Formula 4 used as a raw material in the nucleophilic substitution reaction according to Scheme 3 is a known compound of CAS No. 353292-92-9, which is described in US Patent No. 4,859,229. have.

The compound represented by Chemical Formula 5 used as a raw material in the nucleophilic substitution reaction according to Scheme 3 may be prepared by the method of Scheme 4 or Scheme 5 below.

According to the preparation method according to Scheme 4, the carboxylic acid compound represented by the following Chemical Formula 6 is chlorinated by a conventional method using a chlorination reagent, and then reacted by adding an amino acid ester compound represented by the following Chemical Formula 3 to the reactants. To prepare a compound represented by the formula (5).

Scheme 4

In Reaction Scheme 4, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and Y are as defined in Formula 1, respectively, L is a leaving group (leaving group) methanesulfonate group (- OMs), p- toluenesulfonate groups (-OTs), halogen atoms (e.g., Cl, Br) and the like.

Some of the amino compound represented by the formula (3) and the carboxylic acid compound represented by the formula (6) used as a raw material in the reaction of Scheme 4 are known, and some of these compounds are commercially available and can be purchased and used as raw materials. It is easy. In addition, those skilled in the art can also readily prepare these compounds using methods of known literature.

The chlorination reagent in Scheme 5 may be selected from the reagents used in the chlorination reaction according to Scheme 1, and is preferably used in an excess of 1 mol or more with respect to 1 mol of the carboxylic acid compound represented by Formula 6 above. The reaction is carried out in the range of < RTI ID = 0.0 >

When the chlorination reaction is completed, the reaction solution is concentrated under reduced pressure, dissolved in a solvent, and then reacted with the amino acid ester compound represented by Chemical Formula 3. In this case, the reaction is preferably performed under basic conditions, and an organic base such as triethylamine, pyridine, or dimethyl aniline, or an inorganic base such as Na ₂ CO ₃ , K ₂ CO ₃ , or Li ₂ CO ₃ may be used. The reaction temperature is preferably in the range of 0 ° C to 100 ° C. The amount of the amino acid ester compound represented by Chemical Formula 3 may vary depending on whether the base is used. Under the reaction conditions without using a base, it is preferable to use 2 moles or more of the amino acid ester compound represented by Formula 3 with respect to 1 mole of the carboxylic acid compound. In the reaction conditions using a base, it is preferable to use 1 mole or more of the amino acid ester compound represented by the formula (3) with respect to 1 mole of the carboxylic acid compound, and 1 mole or more of the base. After completion of the reaction, the mixture was diluted with an organic solvent, washed with acid, and the obtained organic layer was dried, concentrated and purified by column chromatography.

Another method for preparing a compound represented by Chemical Formula 5 used as a raw material in a nucleophilic substitution reaction according to Scheme 3 may be a carboxylic acid compound represented by Chemical Formula 6, and Chemical Formula 3, as shown in Scheme 5 below. Amide dehydration reaction of the amino acid ester compound represented by using a dehydrating agent to prepare a compound represented by the formula (5).

Scheme 5

In Scheme 5, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and Y are as defined in Formula 1, respectively, L is a leaving group (leaving group) methanesulfonate group (- OMs), p- toluenesulfonate groups (-OTs), halogen atoms (e.g., Cl, Br) and the like.

The dehydrating agent used in Scheme 5 is a dehydrating reagent commonly used in amide dehydration reactions. N, N -carbonyldiimidazole, N, N- cyclohexyl carbodiimide, N- (3-dimethylaminopropyl) -N ' -Ethylcarbodiimide, and (benzotriazol-1-yl) -N, N, N', N' -tetramethyluronium tetrafluoroborate and the like can be used, but not limited thereto. The dehydration reagent may be used in the range of 1 to 1.5 moles based on 1 mole of the carboxylic acid compound represented by Chemical Formula 6. In this dehydration reaction, N, N- dimethylaminopyridine may be used as a catalyst, if necessary. The catalyst may be used in a range of 0.05 to 0.1 molar ratio with respect to 1 mole of the carboxylic acid compound represented by Chemical Formula 6. The dehydration reaction may be carried out within a temperature range of 0 ℃ to 80 ℃, preferably 20 ℃ to 50 ℃. As the reaction solvent, all conventional organic solvents used in the art may be used. Specifically, dichloromethane, dichloroethane, ethyl acetate, acetonitrile, toluene, tetrahydrofuran, diethyl ether, dimethylformamide, and the like may be used. Can be. After the reaction is completed, the reaction mixture may be diluted with a general separation process, for example, diluted with an organic solvent, washed with an acidic aqueous solution, and then concentrated under reduced pressure, and purified by column chromatography if necessary.

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

EXAMPLE

Example 1: {2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluorophenylthio] -1-oxopropyl} aminoacetic acid methyl ester (Compound No. 5)

2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro 200 mg of phenylthio] propionic acid was dissolved in 5 mL of dichloromethane, and 0.05 mL of oxaryl chloride and a drop of DMF were added dropwise. The reaction mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the acid chloride obtained was dissolved in 5 mL of dichloromethane, cooled to 0 ° C., and then slowly added 0.14 mL of triethylamine and 65 mg of glycine methyl ester hydrochloride in sequence. . The reaction mixture was stirred at 5 ° C. or below for 2 hours, washed with water, dried over magnesium sulfate and concentrated, and the concentrate was separated and purified by silica gel column chromatography to obtain 100 mg of the target compound.

^{1 H NMR (300 MHz, CDCl} 3) δ 7.34-7.43 (m, 2H), 6.83 (m, 1H), 6.33 (d, 1H, J = 3.4Hz), 3.98 (d, 2H, J = 5.4 Hz) , 3.75 (m, 1H), 3.69 (s, 3H), 3.53 (s, 3H), 1.60 (d, 3H, J = 7.2 Hz)

Example 2 {2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluorophenylthio] -1-oxopropyl} amino acetic acid ethyl ester (Compound No. 6)

2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro 200 mg of phenylthio] propionic acid was dissolved in 5 mL of dichloromethane, and 0.05 mL of oxaryl chloride and a drop of DMF were added dropwise. The reaction mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the acid chloride obtained was dissolved in 5 mL of dichloromethane, cooled to 0 ° C., and then slowly added 0.14 mL of triethylamine and 72 mg of glycine ethyl ester and hydrochloride in order. . The reaction mixture was stirred at 5 ° C. or below for 2 hours, washed with water, dried over magnesium sulfate and concentrated, and the concentrate was separated and purified by silica gel column chromatography to obtain 124 mg of the target compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.33-7.44 (m, 2H), 6.85 (m, 1H), 6.32 (d, 1H, J = 3.8 Hz), 4.16 (m, 2H), 3.90-3.98 ( m, 2H), 3.76 (m, 1H), 3.53 (s, 3H), 1.60 (d, 3H, J = 7.3 Hz), 1.24-1.29 (t, 3H, J = 7.2 Hz)

Example 3 2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrido Midinyl) -4-fluorophenylthio] -1-oxopropyl} amino] propionic acid methyl ester (Compound No. 24)

2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro 180 mg of phenylthio] propionic acid was dissolved in 5 mL of dichloromethane, and 0.045 mL of oxaryl chloride and a drop of DMF were added dropwise. The reaction mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the acid chloride obtained was dissolved in 5 mL of dichloromethane, cooled to 0 ° C., and 0.13 mL of triethylamine and 64 mg of alanine methyl ester and hydrochloride were added slowly in this order. . The reaction mixture was stirred at 5 占 폚 for 2 hours, washed with water, dried over magnesium sulfate and concentrated, and the concentrate was separated and purified by silica gel column chromatography to obtain 45 mg of the target compound.

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.31-7.40 (m, 2H), 6.92 (m, 1H), 6.33 (s, 1H), 4.50 (m, 1H), 3.80 (m, 1H), 3.71 ( s, 3H), 3.53 (s, 3H), 1.56-1.63 (m, 3H), 1.30-1.43 (m, 3H)

Example 4 2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrido Midinyl) -4-fluorophenylthio] -1-oxopropyl} amino] propionic acid ethyl ester (Compound No. 25)

2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro 180 mg of phenylthio] propionic acid were dissolved in 5 mL of dichloromethane, and 0.045 mL of oxaryl chloride and a drop of DMF were added dropwise. The reaction mixture was stirred at room temperature for 1 hour, concentrated under reduced pressure, and the acid chloride obtained was dissolved in 5 mL of dichloromethane, cooled to 0 ° C., and 0.13 mL of triethylamine and 71 mg of alanine ethyl ester and hydrochloride were slowly added in this order. . The reaction mixture was stirred at 5 占 폚 for 2 hours, washed with water, dried over magnesium sulfate and concentrated, and the concentrate was separated and purified by silica gel column chromatography to obtain the title compound (37 mg).

¹ H NMR (300 MHz, CDCl ₃ ) δ 7.31-7.42 (m, 2H), 6.94 (m, 1H), 6.33 (s, 1H), 4.42-4.51 (m, 1H), 4.08-4.19 (m, 2H ), 3.75-3.82 (m, 1H), 3.53 (s, 3H), 1.56-1.67 (m, 3H), 1.20-1.34 (m, 6H)

To illustrate the uracil-based compound represented by the formula (1) prepared by using or applying the synthesis method exemplified in the above-described exemplary embodiment is shown in Table 1. If the person skilled in the art, the compounds of Table 1 below can be easily synthesized based on the above representative examples.

Compound number R ₁ R ₂ R ₃ R ₄ R ₅ R ₆ X Y ¹ H NMR (300 MHz, CDCl ₃ ) δ One H H H H H Me Cl O 2 H H H H H Et Cl O 3 Me Me H H H Me Cl O 4 Me Me H H H Et Cl O 5 Me H H H H Me Cl O 7.34-7.43 (m, 2H), 6.83 (m, 1H), 6.33 (d, 1H, J = 3.4Hz), 3.98 (d, 2H, J = 5.4 Hz), 3.75 (m, 1H), 3.69 (s , 3H), 3.53 (s, 3H), 1.60 (d, 3H, J = 7.2 Hz) 6 Me H H H H Et Cl O 7.33-7.44 (m, 2H), 6.85 (m, 1H), 6.32 (d, 1H, J = 3.8 Hz), 4.16 (m, 2H), 3.90-3.98 (m, 2H), 3.76 (m, 1H) , 3.53 (s, 3H), 1.60 (d, 3H, J = 7.3 Hz), 1.24-1.29 (t, 3H, J = 7.2 Hz) 7 Me H H H H n-Pr Cl O 8 Me H H H H n-Bu Cl O 9 Me H H H H allyl Cl O 10 Me H H H H propargyl Cl O 11 Me H H H H Me Cl NH 12 Me H H H H Et Cl NH 13 Me H H H H n-Pr Cl NH 14 Me H H H H n-Bu Cl NH 15 Me H H H H Et Cl S 16 Me H Me H H Me Cl O 17 Me H Me H H Et Cl O 18 Me Me OBn H H Me Cl O 19 Me H OBn H H Et Cl O 20 Me H OH H H Me Cl O 21 Me H OH H H Et Cl O 22 Me H H H H Me CN O 23 Me H H H H Et CN O 24 Me H H Me H Me Cl O 7.31-7.40 (m, 2H), 6.92 (m, 1H), 6.33 (s, 1H), 4.50 (m, 1H), 3.80 (m, 1H), 3.71 (s, 3H), 3.53 (s, 3H) , 1.56-1.63 (m, 3H), 1.30-1.43 (m, 3H) 25 Me H H Me H Et Cl O 7.31-7.42 (m, 2H), 6.94 (m, 1H), 6.33 (s, 1H), 4.42-4.51 (m, 1H), 4.08-4.19 (m, 2H), 3.75-3.82 (m, 1H), 3.53 (s, 3H), 1.56-1.67 (m, 3H), 1.20 -1.34 (m, 6H) 26 Me H H Me H n-Pr Cl O 27 Me H H Me H n-Bu Cl O 28 Me H H Me H allyl Cl O 29 Me H H Me H propargyl Cl O 30 Me H H Me H Me Cl NH 31 Me H H Me H Et Cl NH 32 H H H Me H n-Pr Cl NH 33 Me H Me Me H Me Cl O 34 Me H Me Me H Et Cl O 35 Me H H Me H Me CN O 36 Me H H Me H Et CN O 37 Me H H Me Me Me Cl O 38 Me H H Me Me Et Cl O 39 Me H H Me Me Me Cl NH 40 Me H H Et H Me Cl O 41 Me H H Et H Et Cl O 42 Me H H Et H Me CN O 43 Me H H Et H Et CN O 44 Me H Me Et H Me Cl O 45 Me H Me Et H Et Cl O Me: methyl group, Et: ethyl group, n-Pr: normal propyl group, n-Bu: normal butyl group, Bn: benzyl group

[Suggestions]

The uracil compound represented by Chemical Formula 1 of the present invention may be usefully used as a herbicide, and when used as a herbicide, additives such as diluents, surfactants, dispersants, and auxiliary agents commonly used in the formulation of pesticides may be used. In combination with a compound, it can be formulated and used in various forms, such as a hydrating agent, an emulsion, a powder suspension, and a liquid. 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 herbicide composition characterized by the present invention comprises 0.1% to 99.9% by weight of a compound selected from the uracil compound represented by the formula (1) and agrochemically acceptable salts thereof, or a mixture thereof, a surfactant, a solid or liquid diluent, 0.1 wt% to 99.9 wt% of an additive selected from dispersants and auxiliaries. In addition, the herbicide composition characterized by the present invention is formulated into a hydrating agent, a suspending agent, an emulsion, an emulsifying agent, a suspending agent, a liquid preparation, a dispersible liquid preparation, a granular water-forming agent, a granule, a powder, a liquid water-forming agent, a granular water-forming agent, a sleep-injured granule or a tablet. Can be.

Table 2 below is a representative composition of the herbicide composition of the present invention, the herbicide composition of the present invention is not limited thereto.

Formulation Weight ratio (unit: wt%) Active ingredient diluent Surfactants Hydrating agent 10 to 90 0 to 80 1 to 10 Suspension 3 to 50 40 to 95 0-15 Emulsion / Liquid 3 to 50 40 to 95 0-15 Granulation 0.1-95 5 to 98.9 1 to 15

The surfactant used in the present invention is a substance having a high surface activity and is an amphiphilic substance having hydrophilic and lipophilic molecular groups in a molecule, and has a detergency, dispersing ability, emulsifying power, solubilizing power, wetting power, bactericidal power, foaming power, and penetration power. It is excellent in, etc., and acts to wet, collapse, disperse, and emulsify to effectively express the drug. As the surfactant in the surfactant is alkyl (C ₈ ~C ₁₂₎ sulfonate, alkyl (C ₃ ~C ₆₎ naphthalene sulfonate, dialkyl (C ₃ ~C ₆₎ naphthalene sulfonate, dialkyl ( C _8- C ₁₂ ) sulfosuccinate, ligninsulfonate, naphthalenesulfosuccinate formalin condensate, alkyl (C ₈ -C ₁₂ ) naphthalenesulfonate formalin condensate, polyoxyethylene alkyl (C ₈ -C ₁₂ ) Sodium or calcium salts of sulfonates such as phenylsulfonate, alkyl (C ₈ -C ₁₂ ) sulfates, polyoxyethylene alkyl (C ₈ -C ₁₂ ) sulfates, polyoxyethylene alkyl (C ₈ -C ₁₂ ) phenyl sulfates Anionic surfactants such as sodium salts or calcium salts of sulfates, sodium salts or calcium salts of succinates such as polyoxyalkylene succinates, and polyoxyethylene alkyl (C ₈ -C ₁₂ ) ethers, polyoxyethylene alkyl (C ₈ ~C ₁₂₎ phenyl ether, polyoxyethylene al Nonionic surfactants such as the Kiel (C ₈ -C ₁₂ ) phenyl polymer may be used alone or in combination of two or more thereof, and are not limited to the compounds exemplified above.

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

Diluents used in the present invention can be classified into solid diluents and liquid diluents depending on their properties. Highly absorbent diluents as solid diluents are particularly good when making hydrates. The liquid diluent and the solvent are preferably stable without phase separation even at 0 ° C. Liquid diluents include water, toluene, xylene, petroleum ether, vegetable oils, acetone, methyl ethyl ketone, cyclohexanone, acid anhydride, acetonitrile, acetophenone, amyl acetate, 2-butanone, butylene carbonate, chloro Benzene, cyclohexane, cyclohexanol, alkyl esters of acetic acid, diacetone alcohol, 1,2-dichloropropane, diethanolamine, p -diethylbenzene, diethylene glycol, diethylene glycol abietate, diethylene glycol butyl Ether, diethylene glycol ethyl ether, diethylene glycol methyl ether, N, N -dimethylformamide, dimethyl sulfoxide, 1,4-dioxane, dipropylene glycol, dipropylene glycol methyl ether, dipropylene glycol dibenzoate, Diproxytol, alkylpyrrolidone, ethyl acetate, 2-ethyl hexanol, ethylene carbonate, 1,1,1-trichloroethane, 2-heptanone, alpha-pinene, d-limonene , Ethyl lactate, ethylene glycol, ethylene glycol butyl ether, ethylene glycol methyl ether, gamma-butyrolactone, glycerol, glycerol acetate, glycerol diacetate, glycerol triacetate, hexadecane, hexylene glycol, isoamyl acetate, isobor Nyl acetate, isooctane, isophorone, isopropylbenzene, isopropyl myristate, lactic acid, laurylamine, mesityl oxide, methoxypropanol, methyl isoamyl ketone, methyl isobutyl ketone, methyl laurate, methyl octanoate, Methyl oleate, methylene chloride, m -xylene, n -hexane, n -octylamine, octadecanoic acid, octylamine acetate, oleic acid, oleylamine, o -xylene, phenol, polyethylene glycol (PEG 400), propionic acid Propyl lactate, propylene carbonate, propylene glycol, propylene glycol methyl ether, p -xylene, Toluene, triethyl phosphate, triethylene glycol, xylenesulfonic acid, paraffin, mineral oil, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol methyl ether, diethylene glycol methyl ether, methanol, ethanol, Isopropanol, and high molecular weight alcohols such as amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, ethylene glycol, propylene glycol, glycerol, N -methyl-2-pyrrolidone and the like can be used. Solid diluents include talc, titanium dioxide, feldspar clay, silica, attapulgite clay, diatomaceous earth, limestone, calcium carbonate, bentonite, calcium montmorillonite, cottonseed husk, wholemeal, soybean flour, pumice, wood flour, walnut husk, Lignin and the like can be used.

All formulations were added with small amounts of additives to prevent foaming, 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 flour mill. Suspensions can be prepared by admixing in a wet mill and granules can be prepared by spraying an active substance onto the granular carrier.

Examples of preparation of representative formulations using the compounds according to the invention are as follows.

Formulation Example 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% by weight of active compound

Dodecylphenol polyethylene glycol ether 2% by weight

Sodium Lignin Sulfonate 4% By Weight

Sodium silicon aluminate 6% by weight

Montmorillonite 68% by weight

Formulation Example 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% by weight of active compound

Sodium alkyl naphthalene sulfonate 2% by weight

Sodium Lignin Sulfonate 2% By Weight

3% by weight of synthetic amorphous silica

Kaolinite 13 wt%

Formulation Example 3: Emulsion

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

30% by weight of active compound

20% by weight of cyclohesanone

Polyoxyethylene alkylaryl ether 11% by weight

Alkylbenzenesulfonate calcium 4% by weight

Methylnaphthalene 35% by weight

Formulation Example 4: Granulation

The following components were mixed and ground uniformly, 20 parts by weight of water was added to 100 parts by weight of the mixture, mixed, and processed into granules of 14-32 mesh using an extruder, followed by drying to prepare granules.

5% by weight of active compound

Sodium lauryl alcohol sulfate ester salt 2% by weight

Sodium Lignin Sulfonate 5% By Weight

2% by weight of carboxymethyl cellulose

Potassium Sulfate 16% by weight

Gypsum 70% by weight

The formulation of the present invention was sprayed by diluting to an appropriate concentration in actual use.

[Usage]

The uracil-based compound represented by Chemical Formula 1 according to the present invention is very useful as a nonselective foliage treatment-type herbicide for orchards and non-croplands, since the uracil-based compound represented by Formula 1 exhibits a wide range of herbicidal effects to grass weeds as well as broadleaf weeds. In addition, the uracil compound according to the present invention is particularly useful as a herbicide for soil treatment in corn farming because it exhibits high selectivity for cultivated crops such as corn during soil treatment.

The herbicide composition of the present invention can be used up to 10 g to 1 kg per hectare (ha) based on the active ingredient, preferably 10 g to 400 g. The choice of dosage is determined by factors such as weed generation, growth level, and preparation.

In addition, the herbicide composition of the present invention may be used in addition to the compound of the general formula (1) as an active ingredient with a conventional active ingredient having activity as a pesticide. Known active ingredients that can be used together in the herbicide compositions of the invention include acetyl-CoA carboxylase inhibitors (ACC), acetolactate synthase inhibitors (ALS), amides, auxin herbicides, auxin transport inhibitors, carotenoid biosynthesis inhibitors, Nolpyrubilshikimate 3-phosphate synthase inhibitors (ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporpynogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth agents, cell wall biosynthesis inhibitors, and It is also useful to use in admixture with one or more herbicidally active compounds selected from the group consisting of other herbicides.

The acetyl-CoA carboxylase inhibitor (ACC) is a cyclohexenone oxime ether, alkoxydim, cletodim, cloproxidim, cycloxydim, cetoxydim, tralcoxydim, butoxyldim, clepoxydim, Or as tetraphyloxydim, phenoxyphenoxypropionic acid ester, metamipop, sihalofop-butyl, diclofo-methyl, phenoxaprop-ethyl, phenoxaprop-P-ethyl, pentiaprop- Ethyl, Fluazifop-Butyl, Fluazifop-P-Butyl, Haloxifop-Ethoxyethyl, Haloxifop-Methyl, Haloxifop-P-Methyl, Isoxapyrifop, Propacquisapop, Quiz Allopop-ethyl, quizallofo-P-ethyl, or quizallofo-tefuryl can be used.

The acetolactate synthase inhibitor (ALS) is an imidazolinone as imazapyr, imazaquin, imazamethabenz-methyl, imaco, imazapic, imazetapyr, or imazametapyr, as pyrimidyl ether Pyrithiobac-acid, pyrithiobac-sodium, bispyribac-sodium, or pyribenzoxime, florasullam, flumetsulam, or metosullam as sulfonamide, amidosulfuron, azimsulfuron, benzulfur as sulfonylurea Furon-methyl, chlorimuron-ethyl, chlorsulfuron, cynosulfuron, cyclosulfuron, etamethsulfuron-methyl, ethoxysulfuron, plazasulfuron, halosulfuron-methyl, imazosulfuron, metsulfuron -Methyl, nicosulfuron, prisulfuron-methyl, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfumeuron-methyl, thiophensulfuron-methyl, triasulfuron, tribenuron-methyl, triple Rusulfuron-methyl, sulfosulfuron, flucetosul Ron, or you can use IO Dorsal pyuronreul.

As the auxin herbicide, clopyralide or picloram, 2,4-D, or benazolin may be used as the pyridine carboxylic acid.

Naphthalam, or diflufenzopyr may be used as the auxin transport inhibitor, and the carotenoid biosynthesis inhibitor may be benzophenaf, clomazone, diflufenican, fluorochloridone, flulidone, pyrazolinate, Pyrazoxifen, isoxaplutol, isoxaclortol, mesotrione, sulcotrione (chlormethulon), ketospiradox, flutamone, norflurazone, or amitrol can be used.

Glyphosate, or sulfosate, may be used as the enolpyrubilicimate 3-phosphate synthase inhibitor (ESPS), and the glutamine synthetase inhibitor may be villanafos (non-alphafos), or glufosinate-ammonium. Can be used.

The lipid biosynthesis inhibitors include anilophos as anilide or mefenacet, dimethenamid as chloroacetanilide, S-dimethenamid, acetochlor, alachlor, butachlor, buteneaclor, dietathyl-ethyl, di Methachlor, metazachlor, methol achlor, S-methol achlor, pretyl achlor, propacchlor, priaclor, terbuchlor, tenylchlor, or xyl achlor, butylate as thiourea, cycloate, Di-acrylate, dimepiperate, EPTC, esprocarb, molinate, pebulate, prosulfocarb, thiobencarb (benthiocarb), tri-acrylate, or benolate, benfurate, Or perfluidone can be used.

Such mitosis inhibitors include asulam as carbamate, carbetamid, chlorprofam, orbencarb, pronamide (propizamide), profam, or thiocarbazil, benipine as dinitroaniline, butot Raline, dinitramine, etafluralline, fluchlorinline, oryzaline, pendimethalin, prodiamine, or trituraline, dithiopyr as pyridine, or thiazopyr, butamifos, chlortal-dimethyl (DCPA ), Or maleic acid hydrazide can be used.

 The protoporpynogen IX oxidase inhibitors are diphenyl ethers such as asifluorfen, asifluorophene-sodium, acloniphene, biphenox, chlornitropen (CNP), ethoxyphene, fluorodiphene, fluoroglycopene Ethyl, pomesaphene, furyloxyphene, lactofen, nitrophene, nitrofluorophene, or oxyfluorene, oxadiargyl as oxadiazole, or azaphenidine, butafen as oxadione, cyclic imide Acyl, carfentrazone-ethyl, cinidon-ethyl, flumiclolac-pentyl, flumioxazine, flumipropine, flupropacyl, fluthiacet-methyl, sulfentrazone, or thidiazimine, pyrazole Pilaflufen-ethyl can be used as the above.

The photosynthesis inhibitor is propaneyl, pyridate pyridafol, benzothiadiazinone, betazone, bromophenoxime as dinitrophenol, dinocept, dinocept-acetate, dinoterb, or ciper as DNOC, dipyridylene Quat-chloride, dipenquat-methylsulfate, diquat, or paraquat-dichloride, chlorbromuron, chlorotoluron, diphenoxalone, dimefuron, diuron, etidimuron, phenuron, fluorme as urea Touron, Isoproturon, Isouron, Linuron, Metabenzthiazuron, Metazole, Metobenzuron, Metoxuron, Monolinuron, Neburon, Siduron, or Tebutiuron, Bromocinyl as phenol, or Ioxynyl, Chlorida Zone, Triazine as Amethrin, Atrazine, Cyanazine, Desmethrin, Dimethamethrin, Hexazinone, Promethone, Promethrin, Propazine, Simazine, Simethrin, Terbu Metone, Terbutrin, Tervu Triazine, or a percussion to the tree, as yttria Xenon meth US anthrone, or methoxy tree sluggish, bromo drink as uracil, Lena as a yarn, or Terre Basil, bis carbamate used des Medi palm, or palm pen Medi.

Tridiphan may be used as the oxirane as the synergist, and 2,4-DB, clomeprop, dichlorprop, dichlorprop-P (2,4) as aryloxyalkanoic acid as the growth material. -DP-P), fluorooxypyr, MCPA, MCPB, mecoprop, mecoprop-P, or triclopyr, chlorambene as benzoic acid, or dicamba, quinclolac as quinolinecarboxylic acid, or quinmerac And cell wall synthesis inhibitor isoxaben, or diclobenyl.

The other herbicides include Dalapone as dichloropropionic acid, etofumesate as dihydrobenzofuran, chlorfenac (phenac) as phenylacetic acid, or aziprotrin, barban, bensulfide, benzthiazuron, benzofluorine, bumina Phos, butidazole, buturon, carfenstrol, chlorbufam, chlorfenprop-methyl, chloroxalon, cinnamline, cumyluron, cyclluron, ciprazin, ciprazole, dibenzyluron, dipropertrin , Dimron, eglinazine-ethyl, endortal, ethiozin, flucarbazone, fluorbentranil, flupoxam, isocarbamide, isopropaniline, carbutylate, mefluidide, monuron, napropamide , Napropanylide, nitraline, oxacyclomepon, phenisofam, piperophos, prosazine, propluraline, pyributycarb, secbumetone, sulfalate (CDEC), terbucarb, triaziplam , Triaphenamide, Tree can be used Turone methoxy, and their salts in an environmentally sound manner.

The compounds according to the invention have significant herbicidal activity against harmful plants of monocotyledons (flowers and weeds), and dicotyledons (broadleaf weeds). Specifically, some representative examples of weed plants that can be controlled by the compounds according to the present invention are mentioned, but are not limited to specific species.

Specific examples of weed species that may be weeded by the herbicide of the present invention are as follows.

Flower and weed (monolithic weed) species include barley, wheat, blood, American dog breeze, scabbard, king blue grass, dog grass, pulp grass, fall pulp grass, dredge, vine, large bean, larva, poa grass, wangpo grass Can be selected.

As broadleaf weeds (bicotyledonous) species, weeds represented by Bangdongsani, Geumbangdongsani, Hyangbuja, beechbangs, shackles, ovals, barberry; Nasturtium, hairy younger, creeper grass, wormwood hatch, mugwort, American fern, western dandelion, mangosteen, forget-me-not, hairy starfish, locust, barley grass, evergreen mugwort, goblin needle, jindeukchak, maple leaf ragweed, moth, alveolus, king Chrysanthemum weeds, such as horsetail, American mugwort, squirrel, dandelion, ragweed, fat, and red sprout; Larvae and weeds such as nectar and weeds such as scented oil, persimmon grass, perilla grass and motherwort, sesame grass, big grass bed, and baby green bed; Hyunsam and weeds, such as wrinkled leaves and turfgrass; Eggplant and weeds such as crows and American crows; Amaranth and weeds, such as forage and fine hair; Hoe rice and weeds such as hoe rice and sun hoe rice; Mouse grasses and weeds, such as European mouse grasses and dysentery; Mallow and weeds, such as watermelon grass and estuary; Ginseng weeds such as hwansam vine and ginseng; Needle flowers and weeds such as needles and evening primroses; Purslane and weeds such as purslane; Genus and weeds such as horsetail; Tiannan and weeds such as barn; Mountain and weeds, such as casualties; Pomegranate grass and weeds such as pomegranate grass; Chickweed grass and weeds such as chickweed grass; Sedum and weeds such as sedum; Poppy and weeds such as celandine; Weeds, such as weeds; Violets and weeds, such as violets; Sukju and weeds, such as a stellar flower; Nettles and weeds such as ramie; Branch weeds, such as a flower; Plantain and weed, such as plantain; Rosaceae weeds such as croquettes; And the like.

Experimental Example

Test Example: Soil and Foliar Treatment Test

In sterile sand soil (pH 6.1, organics 1.0%, clay 21%, silt 17%, sand 52%), add 1 horticultural yield (N: P: K = 11: 10: 11) per pot (350 cm ² ). The mixture was mixed by g, and then filled in square plastic pots and covered with plants and plants such as corn, American open rice, and barley, and leafy plants such as camellias, larvae, estuaries, and cornflowers. Soil treatment was applied 1 day after sowing, and foliage treatment was sprayed with the test agent prepared 8 to 12 days after sowing. The test agent was 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 an emulsifier, and diluted with water, and sprayed at a rate of 2000 L per hectare. The amount of active compound was chosen to be the specific amount desired.

After weaving for 2 weeks in greenhouse conditions (day temperature 25-35 ℃ / night temperature 20-25 ℃, 14 hours photoperiod), weeding activity of each plant was 0 (uncontrolled) to 100 for weeds. (Complete control) and crops were evaluated according to the 0 (harmless) to 10 (completely tested) grade table and evaluated as the control value for the untreated areas.

The results of the above experiments are shown in Tables 4 to 7, respectively, and the compound represented by the formula (1) according to the present invention exhibited high selectivity in corn, and showed strong herbicidal effect on broadleaf, flowering and weeds.

The control compound is a compound shown in Japanese Patent Laid-Open No. 2000-302764, whose structural formula is as follows.

Foliage treatment herbicidal activity (8 g a.i./ha) Test substance Flower and weed Broadleaf weed Dolphin wire grass Macaw Control compound 65 25 70 Compound 25 100 95 100

Foliar herbicidal activity (II) (8 g a.i./ha) Test substance Flower and weed Broadleaf weed Dolphin wire grass Silkworm Fidget Under the hood Compound 24 100 80 100 100 100 Compound 25 100 95 100 100 100

Soil treatment herbicidal activity (16 g a.i./ha) Test substance Water Flower and weed Broadleaf weed corn wire grass Under the hood Fidget Silkworm Compound 24 0 100 100 100 100 Compound 25 0 100 100 100 100 Control compound 8 100 100 100 100

As can be seen from the above experimental results, the control compound has low activity on broadleaf weeds, flower and weeds when treated with foliage, and in particular, very low activity on barley, which is flower and weeds. It must be dealt with. In addition, the control compound was very severe (8: 0 (harmless) to 10 (completely tested)) for corn, a major crop in soil treatment.

However, the compound represented by Chemical Formula 1, which is characterized by the present invention, is useful as a foliage-treated non-selective herbicide because it exhibits broad activity against broadleaf weeds, plants and weeds during foliage treatment, and is a cultivated crop during soil treatment. It has been found that it is useful as a selective herbicide for corn cultivation because it has very high herbicidal activity against flower beds, weeds and broadleaf weeds.

 Therefore, the compound represented by Chemical Formula 1 of the present invention is expected to have an effect of solving the problem of environmental pollution by greatly reducing the dosage as a high-performance herbicide.

Claims (12)

A uracil compound represented by Formula 1, or an agriculturally acceptable salt thereof:
[Formula 1]

In Chemical Formula 1,
R ₁ , R ₂ , R ₄ , and R ₅ is the same as or different from each other, and represents a hydrogen atom or a C _{1 to} C ₆ alkyl group;
R ₃ is a hydrogen atom, a hydroxyl group, a C ₁ -C ₆ alkyl group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₆ haloalkyl group, C _2- C ₆ haloalkenyl group, C ₂ -C ₆ alkoxyalkyl group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryloxy group, C ₆ -C ₁₀ aryl C ₁ -C ₆ alkyl group, C ₆ -C _{A 10} aryl C ₁ -C ₆ alkoxy group;
R ₆ is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₁ -C ₆ haloalkyl group, a C ₁ -C ₆ alkoxy group, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ haloalkenyl group, C ₂ -C ₆ alkynyl group, C ₁ -C ₆ alkoxycarbo C ₁ -C ₆ alkyl group, C ₆ -C ₁₀ aryl group, C ₆ -C ₁₀ aryl C ₁ -C ₆ alkyl group, or C ₆ -C ₁₀ aryl C _1- A C ₆ alkoxy group;
X represents a halogen atom, a cyano group, CONH ₂ , or CSNH ₂ ;
Y represents O, S, NH, or N (C ₁ ~C ₆ alkyl).
The method according to claim 1,
R ₁ , R ₂ , R ₄ , and R ₅ is the same as or different from each other, and represents a hydrogen atom or a methyl group;
R ₃ represents a hydrogen atom, a hydroxyl group, a methyl group, a methoxy group, or a benzyloxy group;
X represents Cl, or CN;
Y is an uracil compound which represents O or NH.
The method according to claim 1,
{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro Rophenylthio] -1-oxopropyl} amino acetic acid methyl ester;
{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) - pyrimidinyl) -4-fluoro Rophenylthio] -1-oxopropyl} amino acetic acid ethyl ester;
2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) pyrimidinyl) 4-fluorophenylthio] -1-oxopropyl} amino] propionic acid methyl ester; And
2 - [{2- [2-chloro-5- (3,6-dihydro-3-methyl-2,6-dioxo-4-trifluoromethyl -1 (2 H) pyrimidinyl) 4-fluorophenylthio] -1-oxopropyl} amino] propionic acid ethyl ester;
Urasyl compound, characterized in that selected from.
Herbicides, characterized in that the compound selected from the uracil compound represented by the following formula (1) and agrochemically acceptable salts thereof, or a mixture thereof, as an active ingredient:
[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X and Y are as defined in claim 1, respectively.
The method of claim 4,
Foliar herbicide for the removal of flower beds, weeds and broadleaf weeds.
The method of claim 4,
Herbicides for soil treatment for removal of flowering plants, weeds and broadleaf weeds.
0.1 wt% to 99.9 wt% of a compound selected from a uracil compound represented by the following Chemical Formula 1 and an agriculturally acceptable salt thereof, or a mixture thereof, as an active ingredient,
Herbicide composition comprising 0.1% to 99.9% by weight of an additive selected from surfactants, solid or liquid diluents, dispersants, adjuvants:
[Formula 1]

In Formula 1, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X and Y are as defined in claim 1, respectively.
The method according to claim 7,
A herbicide composition characterized in that it is formulated into a hydrating agent, a suspending agent, an emulsion, an emulsion, a suspending agent, a liquid, a dispersible liquid, a granular watering agent, a granule, a powder, a liquid watering agent, a granular watering agent, a sleeping flocculating agent or a tablet.
The method according to claim 7,
The active ingredient is an acetyl-CoA carboxylase inhibitor (ACC), acetolactate synthase inhibitor (ALS), amide, auxin herbicide, auxin transport inhibitor, carotenoid biosynthesis inhibitor, enolpyrubilishmate 3-phosphate synthase inhibitor ( ESPS), glutamine synthetase inhibitors, lipid biosynthesis inhibitors, mitosis inhibitors, protoporpyrogenogen IX oxidase inhibitors, photosynthesis inhibitors, synergists, growth agents, cell wall biosynthesis inhibitors, and known herbicides The herbicidal composition further comprising the above components.
The carboxylic acid compound represented by the following formula (2) is converted to carboxylic acid chloride by chlorination reaction, and then reacted with the amino acid ester compound represented by the following formula (3) to produce a uracil compound represented by the following formula (1) Preparation of Compounds:
(2)

(3)

[Formula 1]

In Formula 1, 2, or 3, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X and Y are as defined in claim 1, respectively.
Method for producing a uracil compound, characterized in that the compound represented by the formula (4) and the compound represented by the formula (5) in the presence of a nucleophilic substitution reaction to prepare a uracil compound represented by the formula (1):
[Chemical Formula 4]

[Chemical Formula 5]

[Formula 1]

In Formula 1, 4, or 5, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , X and Y are as defined in claim 1, respectively, L is a leaving group (leaving group) Indicates.
The method of claim 11,
Compound represented by the formula (5),
A method for preparing the uracil compound represented by Chemical Formula 1, wherein the carboxylic acid compound represented by Chemical Formula 6 is converted to carboxylic acid chloride by chlorination, followed by reaction with an amino acid ester compound represented by Chemical Formula 3 below. :
[Formula 6]

(3)

In Formula 3 or 6, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , Y, and W are as defined in claim 1, respectively, and L represents a leaving group.