KR100193753B1 - Picolinic acid derivatives, preparations thereof and herbicides - Google Patents

Abstract

The present invention is useful as a herbicide and a novel general formula:

[Wherein R is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, benzyl group, halogen substituted alkyl group, cyanoalkyl group, alkoxyalkyl group, alkoxycarbonyloxyalkyl group, alkoxycarbonylalkyl group, alkylcarbonyloxyalkyl group, cycloalkylcarbon A carbonyloxyalkyl group, a cycloalkylcarbonyloxyalkyl group, a cycloalkylalkyl group, an alkali metal atom; R ¹ and R ² are the same or different and represent an alkyl group, an alkoxy group, a halogen atom, a halogen substituted alkoxy group or an alkylsulfonyl group,

X is an expression

(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, a phenyl group or an acyl group)

Group, cyano group, phenyl group (the group may be substituted with halogen atom, alkyl group or alkyl group), phenoxy group, halogen substituted alkyl group, alkoxy group, alkenyl group, alkynyl group, hydroxyl group, trimethylsilylethynyl group, nitro Group, a 4,6-dimethoxypyrimidin-2-yloxy group or a hydrogen atom, and Y represents an oxygen atom or

(Wherein R ⁵ represents a hydrogen atom or a formyl group)

Represents a group represented by n, and n represents 0 or 1. Provided that when X is a hydrogen atom, Y is Picolinic acid derivatives thereof or salts thereof, and a method for producing the same. And herbicides containing picolinic acid derivatives or salts thereof.

Description

[Name of invention]

Picolinic acid derivatives, their preparation and herbicides

Detailed description of the invention

[Technical Field]

The present invention relates to novel picolinic acid derivatives useful as herbicides and herbicides applicable to rice fields, fields, and non-cropland containing them.

[Background]

As picolinic acid derivatives having herbicidal activity so far, 3- (4,6-dimethoxypyrimidin-2-yl) ethyl oxypicolinate (for example, JP-A No. 64-84 and EP-249707) ), 3- (4,6-dimethoxypyrimidin-2-yl) methylthiopicolinate (for example, Japanese Patent Application Laid-Open No. 2-121973, EP-360163) is known.

[Initiation of invention]

In recent years, a large number of herbicides have been developed and put into practical use, contributing to energy saving in agricultural work and improvement in productivity. However, these herbicides have various problems in terms of their herbicidal effects and crop safety. For example, weeds such as blood, wild buckthorn, cornflower, wheatgrass, and Johnsongrass are very difficult to control, and are widely distributed around the world, and various herbicides have been used to control these weeds. It is not necessarily satisfactory in terms of erosion safety, and the appearance of further improved herbicides is desired.

MEANS TO SOLVE THE PROBLEM In order to solve these problems, the present inventors earnestly researched the picolinic acid derivative, and the compound of this invention which introduce | transduced the substituents, such as a dialkylamine, into the pyridine acid ring of a pyrimidinyl oxy picolinic acid derivative has a 1 year and a perennial picture. And it was found that the herbicidal spectrum which shows the outstanding effect in extremely low dose with respect to broadleaf weed was wide, and completed this invention. That is, the picolinic acid derivative of the present invention is a general formula

[Wherein R is a hydrogen atom, an alkyl (1-4 carbon) group, an alkenyl (2-4 carbon group), an alkynyl (2-4 carbon group), a benzyl group, a halogen-substituted alkyl (1-4 carbon) Group, cyanoalkyl (C1-4) group, alkoxy (C1-4) alkyl (C1-4) group, alkoxy (C1-4) carbonyloxyalkyl (C1-4) group, alkoxy ( C1-C4carbonylalkyl (C1-C4) groups, alkylcarbonyl (C2-C7) oxyalkyl (C4-C4) groups, cycloalkylcarbonyl (C4-C7) oxyalkyl (C1-C4) -4) groups, cycloalkyl (C3-C6) alkyl (C1-C4) groups, alkali metal atoms; for example sodium, potassium, alkaline earth metal atoms; for example cations of calcium or organic amines; lower alkylamines , A lower alkylamine, etc., R ¹ and R ² are the same or different and represent a lower alkyl group, a lower alkoxy group, a halogen-substituted lower alkoxy group, an alkylsulfonyl (C 1-4) group or a halogen atom, X Is

(Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom, a lower alkyl group, a phenyl group or an acyl group)

A group represented by a cyano group, a phenyl group (the group may be substituted with a halogen atom, a lower alkyl group, or a lower alkoxy group), a phenoxy group, a halogen-substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, Alkenyl (C2-4) groups, Alkynyl (C2-4) groups, hydroxyl groups, nitro groups, trimethylsilylethynyl groups, 4,6-dimethoxypyrimidin-2-yloxy groups or hydrogen atoms Indicates,

Y is oxygen atom or formula

(Wherein R ⁵ represents a hydrogen atom or a formyl group)

Represents a group represented by and n represents 0 or 1.

Provided that when X is a hydrogen atom, Y is Represents a group represented by).

As the lower alkyl group, methyl, ethyl, propyl, butyl and the like are methoxy, ethoxy, propoxy, butoxy and the like as the lower alkoxy group, and cyclopropyl, cyclopentyl, cyclohexyl and the like as the cycloalkyl group are the acyl groups. The formyl group and the alkylcarbonyl group and the alkylcarbonyl group include acetyl, propionyl, butyryl, valeryl, pivaloyl, hexane oil, and the like, and halogen atoms include chlorine, bromine, and fluorine.

Examples of the salts of picolinic acid derivatives include hydrochloric acid, sulfuric acid and oxalate.

Next, the compound of the present invention is illustrated in Table 1.

And the compound number is referred to in the following description.

Physical properties of compound 41 in the first table represent the refractive index (20 ° C sodium -D line).

Examples of the method for producing the compound of the present invention include, but are not limited to, the following methods.

Wherein R ¹ , R ² and X have the same meaning as described above, R ⁶ represents R other than a hydrogen atom, L represents a halogen, an alkylsulfonyl group or a benzylsulfonyl group, and Y ¹ represents an oxygen atom or a formula- Represents the group represented by

That is, the compound represented by the formula [I-1] is a compound represented by the formula [II] and the pyrimidine derivative represented by the formula [III] in the presence of a base, preferably in a temperature range of room temperature to the boiling point of the solvent in an inert solvent. It can manufacture by reacting for several minutes to several hours at.

The solvent may be a hydrocarbon solvent such as benzene or toluene, halogenated hydrocarbon solvent such as dichloromethane or chloroform, ether solvent such as tetrahydrofuran or 1,4-dioxane, ketone solvent such as acetone or methyl ethyl ketone, Ether solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as dimethylformamide and dimethylacetamide, and other acetonitrile.

Examples of the base include alkali metals such as metal sodium and potassium metal, hydrogenated alkali metals such as sodium hydride, potassium hydride and calcium hydride and alkali metal hydrides, carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, sodium hydroxide and potassium hydroxide. And metal hydroxides such as calcium hydroxide can be used.

Moreover, the compound whose Y is -NH- is Y It can be prepared by reacting an acid or a base with a compound.

(Wherein R ¹ , R ² , X and Y ¹ represent the same meaning as above, M represents an alkali metal or an alkaline earth metal, and R ⁷ represents an ester forming group in R.)

That is, the compound represented by formula [I-3] is a compound represented by formula [I-2] in the presence of a base within the temperature range of room temperature to the boiling point of the solvent in a polar solvent, water or a mixed solvent of polar solvent and water. It can manufacture by reacting for several hours to several ten hours. When this is analyzed with an organic acid such as quenoic acid or acetic acid or a mineral acid solution such as hydrochloric acid or sulfuric acid, the compound represented by the formula [I-4] can be produced.

As the solvent, alcohol solvents such as methanol and ethanol, ether solvents such as 1,4-dioxane and tetrahydrofuran and amide polar solvents such as dimethylformamide and dimethylacetamide can be used. no.

As the base, carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, metal hydroxides such as sodium hydroxide, potassium hydroxide and calcium hydroxide can be used.

(Wherein R ¹ , R ² , R ⁷ , M, X and Y ¹ have the same meaning as above and L ¹ represents halogen)

That is, the compound represented by the formula [I-5] is a compound represented by the formula [I-3] and the compound represented by the formula [IV] in the presence of a base or in a base with no polar solvent, preferably in an inert solvent. It can manufacture by reacting for several minutes to several hours within the temperature range of a boiling point.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ether solvents such as 1,4-dioxane and tetrahydrofuran, ketone solvents such as acetone and methyl ketone, and methyl acetate. And ester solvents such as ethyl acetate, amide aprotic polar solvents such as dimethylformamide and dimethylacetamide, acetonitrile and the like can be used.

Examples of the base include alkali metals such as metal sodium and potassium metal, hydrogenated alkali metals such as sodium hydride, potassium hydride and calcium hydride and alkali metal hydrides, carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, sodium hydroxide and potassium hydroxide. And organic bases such as metal hydroxides such as calcium hydroxide, triethylamine, diisopropylethylamine and pyridine.

(Wherein R, R ¹ , R ² , X and Y ¹ represent the same meaning as above)

That is, the compound represented by the formula [I-7] can be produced by reacting the compound represented by the formula [1-6] with an acid for several minutes to several hours in an inert solvent within a temperature range of room temperature to the boiling point of the solvent.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ether solvents such as 1,4-dioxane and tetrahydrofuran, ketone solvents such as acetone and methyl ketone, and methyl acetate. Ether solvents such as ethyl acetate, amide aprotic polar solvents such as dimethylformamide and dimethylacetamide, acetonitrile and the like can be used.

Examples of the acid include hydrochloric acid, sulfuric acid, and oxalic acid. An acid may be added directly in an inert solvent, and a gas may be added.

(Wherein R, R ¹ , R ² , X and Y ¹ represent the same meaning as above)

That is, the compound represented by the formula [I-9] can be produced by adding a peroxide to the compound represented by the formula [1-8] within an inert solvent within a temperature range of -20 ° C to the boiling point of the solvent. As the solvent, methanol, water, dichloromethane, chloroform and the like are preferable. As the peroxide, organic peroxides such as hydrogen peroxide, metachloroperbenzoic acid and benzoyl peroxide are used.

Best Mode for Carrying Out the Invention

Next, an example is given and the manufacturing method of the compound of this invention is demonstrated concretely.

Example 1

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (N, N-dimethylamino) methyl picolinate (compound 19)]

1.4 g (7 mmol) methyl 6- (N, N-dimethylamino) -3-hydroxypicolinate, 1.6 g (7 mmol) 4-6-dimethoxy-2-methylsulfonylpyrimidine, 0.6 potassium potassium carbonate g (4 mmol) was added to 100 mL of DMF and reacted at 90 ° C for 2 hours. After completion of the reaction, the oily product obtained by extraction, washing with water, drying and concentration with diethyl ether in water was crystallized with isopropyl ether. The crystals were recrystallized from ethyl acetate / n-hexane to obtain the target compound. Quantity 1.6g (yield 66%), melting point 125-127 degreeC.

Example 2

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-phenylpicolinate (compound 8)]

1.0 g (4.4 mmol) methyl 6-phenyl-3-hydroxypicolinate, 0.8 g (4 mmol) 4-6-dimethoxy-2-methylsulfonylpyrimidine, 0.6 g (4 mmol) potassium carbonate It was added to 20 mL of DMF and reacted at 80 degreeC for 0.5 hour. After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, the organic layer was washed with water and brine, dried and treated with an appropriate amount of proridyl. 20 ml of hexane was added to the residue obtained by distilling ethyl acetate under reduced pressure, and the mixture was left to stand for 3 days, and then crystallized and washed with hexane / isopropyl ether to obtain a target compound. Yield 0.85 g (yield 58%), melting | fusing point 92-94 degreeC.

Example 3

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (N, N-dimethylamino) picolinic acid (compound 20)]

2.5 g (7.7 mmol) of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6- (N, N-dimethylamino) picolinate as a 100 ml methanol solution was added thereto. 6 ml of aqueous potassium hydroxide solution were mixed and stirred overnight at room temperature. After completion of the reaction, the mixture was extracted with ethyl acetate. The aqueous layer was made acidic, the crystals obtained by extraction with chloroform, washed with water, dried and concentrated were washed with isopropyl ether to obtain the target compound. Yield 1.6 g (64% yield), melting point 195-197.5 degreeC.

Example 4

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2-carboxylic acid 1- (ethoxycarbonyloxy) ethyl (compound 40)]

3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2- potassium carbonate 2.0 g (5.6 mmol), 1- (ethoxycarbonyloxy) ethyl 0.8 g (5.7 mmol) of chloride was suspended in 5 ml of dimethylformamide and stirred at room temperature for 6 hours. The reaction mixture was poured into water, extracted twice with ethyl acetate, the organic layer was washed with water and dried, the solvent was distilled off and the viscous body obtained was subjected to column purification to obtain the target compound. Yield 0.5 g (yield 33%), refractive index (Na-D line) 1.5215.

Example 5

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2- potassium carboxylate (compound 48)]

9.2 g (27.5 mmol) of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2-carboxylic acid methyl was dissolved in 30 ml of methanol, and 10 1.55 g (27.5 mmol) of% potassium hydroxide were added, followed by 20 ml of water, followed by stirring at room temperature. The reaction solution was concentrated under reduced pressure, acetone was added, and the precipitated crystals were filtered and washed with hexane to obtain the target compound. Quantity 9.8 g (yield 98%), melting point 240-245 degrees Celsius

Example 6

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2-calcium carboxylate (compound 49)]

1.0 g (3.1 mmol) of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2- potassium carbonate was dissolved in 10 ml of tetrahydrofuran, 0.15 g (1.5 mmol) of precipitated calcium carbonate was added thereto, and 10 ml of water was further added thereto, followed by stirring at room temperature. The reaction solution was concentrated under reduced pressure, acetone was added, and the precipitated crystals were filtered and washed with hexane to obtain the target compound. Yield 1.0 g (91% of yield), melting point 169-182 degrees Celsius

Example 7

[Synthesis of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2-carboxylic acid methoxymethyl (Compound 41)]

0.4 g (1.25 mmol) of 3- (4,6-dimethoxypyrimidin-2-yl) oxy-6-dimethylaminopyrimidine-2-carboxylic acid was dissolved in 15 ml of dichloromethane and cooled therein. 0.17 g (1.31 mmol) of diisopropylethylamine was added thereto and reacted for 15 minutes. 0.12 g (1.49 mmol) of methoxymethyl chloride was further added dropwise at 0 ° C, and the reaction was continued for 4 hours when the temperature was gradually returned to room temperature. After completion of the reaction, 30 ml of dichloromethane was further added, washed with water, washed with 10% aqueous solution of cuic acid and saturated brine, dried, and then concentrated and purified by silica gel column chromatography to obtain the target compound. Yield 0.4 g (yield 84%), melting | fusing point 91-96 degreeC.

Moreover, the raw material compound of the compound of this invention can be manufactured by the following method.

(Wherein R ⁶ ,, L ¹ and X represent the same meaning as above)

That is, the compound represented by formula [II-1] can be led to the compound represented by formula [II-2], and the compound represented by formula [II-3] can be manufactured by the contact addition method with hydrogen. And the manufacturing method of the compound represented by Formula [II-4] and the compound represented by Formula [II-5] from the compound represented by Formula [II-1] is already known [for example, the pharmaceutical journal Vol. 67, p. 51 (1947)].

These methods will be described in detail in the method.

(Wherein R ⁶ represents the same meaning as described above, R ⁸ represents a cyano group, a dimethylamino group, or a diethylamino group, and R ⁹ represents a dimethylamino group, diethylamino group, an alkali group, or a phenyl group.

In other words, the compound represented by the formula [II-1] and the trimethylsilyl derivative represented by the formula [V] or the acid chloride represented by [VI] are reacted for several hours in an inert solvent within a temperature range of room temperature to the point of the solvent. II-6] or the compound shown by [II-7] can be manufactured. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone and methyl ethyl ketone. , Ester solvents such as methyl acetate and ethyl acetate, nonprotonic polar solvents such as dimethylformamide and dimethylacetamide, and other acetonitrile may be used, but chloroform is preferable.

(Wherein R⁶Represents the same meaning as described above, and R¹⁰Represents an alkyl group, a substituted alkyl group, or a 4,6-dimethoxypyrimidinyl group, L²Is Halogen atom or alkylsulfonyl group.) That is, the compound represented by the formula [II-4] and the compound represented by the formula [VI] in the presence of a base in an inert solvent in the temperature range of room temperature to the boiling point of the solvent in the range of several minutes to several By time-reacting, the compound represented by general formula [II-8] can be manufactured. Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chloroform, ether solvents such as tetrahydrofuran and 1,4-dioxane, ketone solvents such as acetone and methyl ethyl ketone. Ester solvents such as methyl acetate and ethyl acetate, aprotic polar solvents such as dimethylformamide and dimethylacetamide, and other acetonitrile. Examples of the base include alkali metals such as metal sodium and potassium metal, hydrogenated alkali metals such as sodium hydride, potassium hydride and calcium hydride and alkali metal hydrides, carbonates such as sodium carbonate, potassium carbonate and calcium carbonate, sodium hydroxide and potassium hydroxide. Metal hydroxides, such as these, can be used.

(Wherein R ⁶ and L ¹ represent the same meaning as described above, and R ¹¹ represents a substituted phenyl group. That is, the compound represented by the formula [II-5] and the compound represented by the formula [VII] are present in the presence of a base and a catalyst). Under the inert solvent, the compound represented by the general formula [II-9] can be produced by reacting for several hours within the temperature range of the boiling point of the solvent, and as the solvent, hydrocarbon solvents such as benzene and toluene, methanol, Alcohol solvents such as ethanol, ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran and ethyl ether, ester solvents such as methyl acetate and ethyl acetate, aprotic properties such as dimethylformamide and dimethylacetamide Polar solvents, other acetonitriles, etc. As a catalyst, tetrax (triphenylphosphine) palladium (0), triphenylphosphine and palladium acetate, tris (0-tril) phosphine and acetic acid Palladium can be used, etc. Further, as the base, carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium hydrogen carbonate or organic bases such as triethylamine and pyridine can be used. can do.

(Wherein R ³ , R ⁴ and R ⁶ represent the same meaning as above)

That is, the compound represented by formula [II-11] can be manufactured by reacting the compound represented by [II-10] and formic acid for several minutes to several hours within the range of room temperature to a boiling point. The compound represented by the formula [II-11] can also be produced by reacting the compound represented by the formula [II-10] with an acetic anhydride-formic acid mixed solution or dicyclohexylcarbodiimide formic acid. However, it is not limited to these methods. Next, the manufacturing method of a raw material compound is demonstrated for a reference example.

Reference Example 1

[Synthesis of 3-benzyloxy-6- (N, N-dimethylamino) methyl picolinate]

15 g (58 mmol) of 3-benzyloxypicolinate-N-oxide, 6.7 g (67 mmol) of trimethylsilylnitrile, 8.3 g (61 mmol) of N, N-dimethylcarbamic acid chloride were added to methylene chloride 100 It was added to ml and left to stir at room temperature. The residue obtained by washing with water, drying and concentrating the organic layer was purified by column chromatography to obtain a target compound. Yield 2.4g (yield 14%), melting point 71.5-73 degreeC.

Reference Example 2

In the same manner, 3-benzyloxy-6-cyanopicolinate methyl was obtained. Yield 3.1g (yield 20%), melting point 103.5-105 degreeC.

Reference Example 3

[Synthesis of 3-benzyloxy-6-ethoxypicolinate methyl]

5.0 g (19 mmol) of methyl 3-benzyloxy-6-hydroxypicolinate, 2.1 g (19 mmol) of ethyl bromide, and 2.9 g (21 mmol) of potassium carbonate were added to 100 ml of DMF and reacted at 80 ° C. for 5 hours. I was. After completion of the reaction, the mixture was poured into water, extracted with ethyl acetate, washed with water, dried and concentrated, and the residue was purified by column chromatography to obtain the target compound. Yield 4.1g (74% of yield), melting | fusing point 45-46 degreeC.

Reference Example 4

[Synthesis of methyl 3-benzyloxy-6-phenylpicolinate]

Into a 100 ml three-necked flask equipped with a thermometer, a cooling tube and a nitrogen introduction tube, 0.6 g (0.5 mmol) of tetralax (triphenylphosphine) palladium (0) and 5 ml of 1,2-dimethoxyethane were added. Under nitrogen stream, 2.7 g (10.0 mmol) of methyl 3-benzyloxy-6-chloropicolinate was dissolved in 1,2-dimethoxyethane (20 mL) and added all at once. After stirring at room temperature for 3 hours, 1.8 g (15.0 mmol) of phenylboric acid was dissolved in 1,2-dimethoxyethane (15 mL), and stirring was continued for 1 hour. Aqueous solution of 2M sodium carbonate (40 ml) was added thereto, and the mixture was heated to reflux for 50 minutes. After cooling, an appropriate amount of water was added, extraction was performed with ethyl acetate, and the organic layer was washed with water and brine, dried and concentrated to obtain a residue, which was purified by column chromatography. Yield 1.9g (59.4% yield).

Reference Example 5

[Synthesis of methyl 3-hydroxy-6-phenylpicolinate]

1.9 g of methyl 3-benzyloxy-6-phenylpicolinate was reduced to 10% palladium carbon / methanol and purified by column chromatography to obtain the target compound. Yield 1.0g (yield 76.9%), melting point 110-101 degreeC.

Reference Example 6

[Synthesis of methyl 6- (N, N-dimethylamino) -3-hydroxypicolinate]

2.3 g (8 mmol) of 3-benzyloxy-6- (N, N-dimethylamino) picholate and 0.3 g of 10% palladium carbon were added to 100 ml of ethyl acetate, and hydrogen was added at normal pressure. After completion of the reaction, the mixture was filtered and concentrated to obtain crystals. Yield 1.4g (yield 92%), melting point 118.5-120 degreeC.

Table 2 lists specific examples of the starting compounds prepared in the same manner as in Reference Examples 1 to 6.

The herbicide of the present invention is composed of the picolinic acid derivative represented by the general formula [I] as an active ingredient. When the compound of the present invention is used as a herbicide in paddy fields, fields, orchards, non-crop lands, and the like, the active ingredient can be used in a suitable formulation according to the purpose. In ordinary cases, the active ingredient may be diluted with an inert liquid or a solid weed, and a surfactant, a dispersing agent, an auxiliary agent, etc. may be blended if necessary, and may be used in various forms such as powders, hydrates, emulsions, and granules. For example, the powder may be prepared by mixing and grinding an active ingredient and a solid carrier.

A hydrating agent may be prepared by mixing an active ingredient, a solid carrier, a surfactant, and a dispersant. The granules are granulated by mixing an active ingredient, a solid carrier, a surfactant, a dispersant, and an auxiliary agent, or a solid carrier, a surfactant, a dispersant, an auxiliary agent, and the like. It can be produced by coating the effective ingredient to the granulated by mixing. Carriers used in these formulations include, for example, talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, burmerite, slaked lime, silica sand, yuan, urea, solid carriers, isopropyl alcohol, xylene, cyclohexanone, isophorone, And liquid carriers such as methylnaphthalene. Examples of the surfactant and dispersant include alcohol sulfate ester salts, alkylaryl sulfonates, naphthalene sulfonates formalin condensates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene sorbitan monoalkylates, and the like. Can be mentioned. Examples of the adjuvant include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like.

The blending ratio of the active ingredient is appropriately selected as necessary, but in the case of powder and granules, 0.01 to 10% (weight), preferably 0.05 to 5% (weight), and 1 to 50% (for emulsions and hydrating agents) Weight), preferably 5-20% (weight), but is not limited thereto.

In use, dilute to a suitable concentration on the foliage, soil or water, or spray or apply directly. The compound of the present invention is applied in an active ingredient of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ars. In addition, when used in a liquid phase such as an emulsion and a wetting agent, it is appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm, but is not limited thereto.

In addition, the compound of the present invention may be mixed with insecticides, fungicides, other herbicides, plant growth regulators, fertilizers and the like as necessary. Next, the formulation method will be described in detail with reference to representative formulation examples. In the following description, "part" means parts by weight.

[Example 1]

[Powder system]

99 parts of diatomaceous earth are mixed and grind | pulverized in the compound (20) 1, and powder is obtained.

[Example 2]

[Hydrating]

0.5 parts of polyoxyethylene alkylaryl ether, 0.5 parts of sodium naphthalene sulfonate formalin condensates, 20 parts of diatomaceous earth, and 69 parts of clay are mixed and ground to obtain a hydrating agent.

[Example 3]

[Hydrating]

0.5 parts of polyoxyethylene alkylaryl ether, 0.5 parts of sodium naphthalene sulfonate formalin condensates, 20 parts of diatomaceous earth, 5 parts of carplex 80, and 64 parts of clay are mixed and ground to obtain a hydrating agent.

[Example 4]

[emulsion]

To 30 parts of the compound (20), 60 parts of an equivalent mixture of xylene and isophorone, 10 parts of a polyoxyethylene alkylaryl ether polymer and an alkylbenzenesulfonic acid metal salt are added, and these are mixed well to obtain an oil agent.

[Example 5]

[Participation]

10 parts of compound (3), 80 parts of an extender in which talc and bentonite were mixed at a ratio of 1: 3, 5 parts of white carbon, 5 parts of polyoxyethylene alkylaryl ether polymer and 5 parts of metal salt of alkylbenzenesulfonic acid were added and mixed well. The paste was pushed into a hole having a diameter of 0.7 mm and dried, and then cut to a length of 0.5 to 1 mm to obtain a granule.

[Effects of the Invention]

Compounds of the present invention represented by the general formula [I] include various weeds that are problematic in the field, such as wild leaf weeds, larvae, tusks, hairy agar, white tusks, chickweeds, tabby and broadleaf weeds such as American metal wormwood, Low-yielding rice and weeds, including perennial and one-year-old Geumbangdongsa, weeds, wheatgrass, Johnson grass, blood, barley, dog grass, sapophore, poisonous grass, etc. Can be effectively controlled. In addition, it has excellent herbicidal effects against Italian weeds, green grass, bandage, chicken eel, purslane, stalk, eel odor, and American bog needles.

In addition, the weeds of annuals such as dolphins, eggs, and cockroaches in rice paddies, algae, beetles, and ladles, tadpoles, and mudstacks are germinated and grown in very low doses. It has an excellent herbicidal effect.

Next, the effect which a compound of this invention shows by a test example is demonstrated. In the test, the following compounds were used as comparative agents.

[Compound A]

3- (4,6-dimethoxypyrimidin-2-yl) ethyl oxypicolinate (compound described in Japanese Patent Application Laid-Open No. 64-84)

[Compound B]

3- (4,6-dimethoxypyrimidin-2-yl) methylthiopicolinate (compound described in Japanese Patent Laid-Open No. 21219 73)

[Test Example 1]

[Test of herbicidal effect by paddy soil treatment]

After filling the paddy soil with a 100 cm 2 plastic pot, it was sown, and then seedlings of dolphins, coots, and tadpoles were sown, and water was washed with 3 cm of water depth. The next day, the hydrating agent prepared according to Formulation Example 2 was diluted with water and treated dropwise with water. The test dose was set to 100 g of 10 active ingredients. Thereafter, the plants were grown in a greenhouse, and the herbicidal effects were examined in accordance with the criteria of Table 3 at 21 days after treatment. The results are shown in Table 4.

[Test Example 3]

[Test of herbicidal effect by field foliage treatment]

Field soils were filled in 100 cm 2 plastic pots, and the seedlings were covered with edible blood, mallow, soybeans, white mallow, and various kinds of true tortoises. After culturing for 2 weeks at room temperature, the hydrating agent prepared according to Formulation Example 2 was diluted in water, and 100 L per 10 ar leaves were sprayed whole from the top of the plant with a small atomizer so that the effective ingredient per 10 ars was 100 g. Thereafter, it was grown in a greenhouse and examined herbicidal effects according to the criteria of Table 3 at 14 days after treatment. The results are shown in Table 6.

[Test Example 4]

[Test of herbicidal effect by field foliage treatment]

Paddy soil was filled in a plastic pot of 600 cm 2, and sown, covered with blood, Johnsongrass, hyacinth, hair amur, white hyacinth, wild jasmine flower, and hawktail. After two weeks of growth in a greenhouse, a predetermined amount (g / 10a) of a hydrating agent prepared according to Formulation Example 2 was diluted with water, and 100 l per 10 ars were sprayed whole from the top of the plant with a small atomizer. Thereafter, it was grown in a greenhouse, and the herbicidal effect was investigated in accordance with the criteria of Table 3 at 14 days after treatment. The results are shown in Table 7.

Claims (9)

General formula [Wherein R is a hydrogen atom, alkyl group, alkenyl group, alkynyl group, benzyl group, halogen substituted alkyl group, cyanoalkyl group, alkoxyalkyl group, alkoxycarbonyloxyalkyl group, alkoxycarbonylalkyl group, alkylcarbonyloxyalkyl group, cycloalkylcarbon A carbonyloxyalkyl group, a cycloalkylcarbonyloxyalkyl group, a cycloalkylalkyl group, an alkali metal atom; R ¹ and R ² are the same or different and represent an alkyl group, an alkoxy group, a halogen atom, a halogen substituted alkoxy group or an alkylsulfonyl group, and X is a formula (Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, a phenyl group or an acyl group) Group, cyano group, phenyl group (the group may be substituted with halogen atom, alkyl group or alkyl group), phenoxy group, halogen substituted alkyl group, alkoxy group, alkenyl group, alkynyl group, hydroxyl group, trimethylsilylethynyl group , A nitro group, a 4,6-dimethoxypyrimidin-2-yloxy group or a hydrogen atom, and Y represents an oxygen atom or a formula (Wherein R ⁵ represents a hydrogen atom or a formyl group) Represents a group represented by and n represents 0 or 1. Provided that when X is a hydrogen atom, Picolinic acid derivatives thereof or salts thereof. The compound according to claim 1, wherein R represents a hydrogen atom or an alkyl group, R ¹ and R ² are the same or different, an alkyl group, an alkoxy group, a halogen atom, a halogen substituted alkoxy group or an alkylsulfonyl group, and X is a formula (Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, a phenyl group or an acyl group) Group, cyano group, phenyl group (the group may be substituted by halogen atom, alkyl group or alkyl group), phenoxy group, alkoxy group, hydroxyl group, nitro group or 4,6-dimethoxypyrimidine-2- Iloxy group, Y represents an oxygen atom or formula (Wherein R ⁵ represents a hydrogen atom or a formyl group) Picolinic acid derivative or its salt which represents group represented by, and n represents 0 or 1. The picolinic acid derivative according to claim 1, wherein Y represents an oxygen atom and n represents zero. A hydrogen atom, a methyl group, an ethoxycarbonylmethyl group, 1-propionyloxyethyl group, 1-ethoxycarbonyloxyethyl group, methoxymethyl group, cyanomethyl group, 2-chloroethyl group, 2- A propynyl group, an aryl group, a benzyl group, sodium or potassium, R ¹ and R ² each represent a methoxy group, X represents a dimethylamino group or a vinyl group, and Y represents an oxygen atom. , picolinic acid derivative wherein n represents 0 or a salt thereof. A herbicide containing an effective herbicidal amount of the picolinic acid derivative of claim 1 or a salt thereof as an active ingredient. A herbicide containing an effective herbicidal amount of the picolinic acid derivative of claim 2 or a salt thereof as an active ingredient. The herbicidal method formed by using the herbicidally effective amount of the picolinic acid derivative of Claim 1, or its salt. General formula [Wherein R ⁶ is an alkyl group, a halogen-substituted alkyl group, an alkylcarbonyloxyalkyl group, an alkoxyalkyl group, an alkoxycarbonylalkyl group, an alkoxycarbonyloxyalkyl group, a cycloalkylcarbonyloxyalkyl group, a cycloalkylalkyl group, a cyanoalkyl group, an alkenyl group, An alkynyl group, a benzyl group, an alkali metal atom, an alkaline earth metal atom or a cation of an organic amine, X represents a halogen-substituted alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or a phenyl group, Good), phenoxy group, hydroxyl group, cyano group, nitro group, trimethylsilylethynyl group, 4,6-dimethoxypyrimidin-2-yloxy group or formula (Wherein R ³ and R ⁴ are the same or different and represent a hydrogen atom, an alkyl group, a phenyl group or an acyl group) Represents a group represented by Y, and an oxygen atom or a formula And a picolic acid derivative represented by General formula: R ¹ and R ² are the same or different and represent a pyrimidine represented by an alkyl group, an alkoxy group, a halogen substituted alkoxy group, an alkylsulfonyl group or a halogen atom, and L ¹ represents a halogen atom, an alkylsulfonyl group or a benzylsulfonyl group). Formula wherein the derivative is reacted in the presence of a base: The manufacturing method of the picolinic acid derivative represented by (wherein, R <^1> , R <^2> , R <^6> , X and Y <^1> have the same meaning as the above.). General formula: Wherein R ¹ , R ² and X have the same meanings as described above, and R ⁷ represents an ester forming group in R. A process for producing a picolinic acid derivative represented by (wherein R ¹ , R ² X and Y ¹ represent the same meaning as described above, and M represents an alkali metal atom or an alkaline earth metal atom).