WO1993012109A1

WO1993012109A1 - Picolinic acid derivative, production thereof, and herbicide

Info

Publication number: WO1993012109A1
Application number: PCT/JP1991/001725
Authority: WO
Inventors: Fumiaki Takabe; Yoshihiro Saito; Masatoshi Tamaru; Shigehiko Tachikawa; Ryo Hanai
Original assignee: Kumiai Chemical Industry Co., Ltd.; Ihara Chemical Industry Co., Ltd.
Priority date: 1991-12-18
Filing date: 1991-12-18
Publication date: 1993-06-24
Also published as: HUT64321A; RU2091380C1; PL295868A1; HU9201294D0; BR9106704A; HU213623B; PL169374B1; RO109848B1

Abstract

A novel picolinic acid derivative represented by general formula (I), salt thereof, production thereof, and a herbicide containing the same as the active ingredient. In formula (I), R represents hydrogen, alkyl, etc.; R?1 and R2¿ may be the same or different from each other and each represents alkyl, alkoxy, etc.; X represents cyano, phenoxy, etc.; Y represents oxygen, sulfur, etc.; and n represents 0 or 1. The derivative and salt have an excellent herbicidal effect even in small doses against a wide variety of weeds; so that they can be used in lowland and upland fields, non-crop lands and the like.

Description

Description: ^Picolinic acid derivative, its production method and herbicide [Technical field]

TECHNICAL FIELD The present invention relates to a novel picolinic acid derivative useful as a herbicide and a herbicide containing the same, which can be applied to paddy fields, fields, non-agricultural lands, and the like.

(Background technology)

Until now, as a picolinic acid derivative having herbicidal activity, 3— (4,6—dimethyloxypyrimidine-1 2—inore) oxopicolin Ethyl acid (for example, JP-A-64-84, JP-A-2497707), 3- (4, 6-dimethyloxypyridine 1-2-yl) There is known methyl thiopicolinate (for example, Japanese Patent Application Laid-Open Nos. 2-11973 and 316-1633).

[Disclosure of Invention]

In recent years, such a large number of herbicides have been developed and put into practical use, and have contributed to labor saving of agricultural work and improvement of productivity. However, these herbicides also have various problems in practical use in terms of herbicidal effect and safety against crops. For example, weeds such as hee, noasagao, bonafami, shipamugi, and jonsonggrass are widely distributed throughout the world as weeds that are extremely difficult to control, and control these weeds. Various herbicides have been used to improve the herbicidal efficacy and safety of crops. However, it is not always satisfactory in terms of sex and the like. ^出現 The emergence of more improved herbicides is desired.

The present inventors have conducted intensive studies on picolinic acid derivatives in order to solve these problems. As a result, dialkylamine was added to pyridin 瑗 of pyrimidinyloxypicopolinic acid derivatives. The compound of the present invention into which the substituents such as described above are introduced has a wide range of herbicidal spectrum which shows an excellent effect on annual and perennial grasses and broadleaf grasses at extremely low doses. And completed the present invention. .

That is, the picolinic acid derivative of the present invention has the general formula

[Wherein R is a hydrogen atom, an alkyl (C 1-4) group, an alkenyl (C 2 -C 4) group, an alkynyl (C 2 -C 4) group, a benzyl group, a phenyl group, C 1 -C 4 groups, cyanoalkyl (C 1 -C 4) groups, alkoxy (C 1 -C 4) alkyl (C 1 -C 4) groups, alkoxy (C 1 -C 4) carponyloxyalkyl ( 1 to ⁴ carbon atoms) Algishi (1 to 4 carbon atoms) carbonyl alkyl (1 to 4 carbon atoms) group, alkylcarbonyl (2 to 7 carbon atoms) oxyalkyl (1 to 4 carbon atoms) group, cyclo Alkyl carbonyl (C 4-7) 4) group, cycloalkyl (C3-6) α / lekyl (C1-4) group, alkali metal atom; for example, alkaline earth metal atom such as sodium, potassium, etc. For example, calcium or organic amine cation; for example, lower alkylamine, di-lower alkylamine, etc .;

R and R ² are the same or different and each represents a lower alkyl group, a lower alkoxy group, a nitrogen-substituted lower alkoxy group, an alkylsulfonyl (C 1 -C 4) group or a halo group; Indicates a halogen atom,

R ³

X is the formula N <

R ⁴

(Wherein, R ³ and R ⁴ are the same or different and each represent a hydrogen atom, a lower alkyl group, a phenyl group or a acyl group.), A cyano group, a phenyl group Group (the group may be substituted by a nitrogen atom, a lower alkyl group or a lower alkoxy group), a phenoxy group, a nitrogen-substituted alkyl (carbon number 1-4) groups, alkoxy (1-4 carbons) groups, alkenyl

(C 2-4) group, alkynyl (C 2-4) group, hydroxyl group, nitro group, trimethylinoresilizoleethynyl group, 4, 6-dimethoxypyridine — Denotes an isoleoxy group or a hydrogen atom,

R ⁵

Y is an oxygen atom, a sulfur atom or a formula

(In the formula, R ⁵ represents a hydrogen atom or a formyl group.) n represents 0 or 1. '

C H 0

However, when X is a hydrogen atom, Y represents a group represented by the formula _N <. )]. Here, lower alkyl groups include methyl, ethyl, propyl, butyl, etc., and lower alkoxy groups include methoxyethoxy, propoxy, butoxy, etc., and cycloalkyl. Examples of the group include cyclopropinole, cyclopentisole, and cyclohexyl.Examples of the acyl group include a formyl group and an alkyl carbonyl group, and an example of an azole carbonyl group. Examples include acetinole, propionole, petilyl, norrelyl, pinolyl, hexamyl, and the like, and further, as nitrogen atoms, kurozole, brom, Fluoro and the like. Examples of the salt of the picolinic acid derivative include hydrochloric acid, sulfuric acid, and oxalate. Next, the compounds of the present invention are shown in Table 1. The compound number will be referred to in the following description.

1 Table

1 table continued

1 table continued

1 table continued

The physical properties of compound 41 in Table 1 indicate the refractive index (20 ° C sodium-D line).

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

[Π] [m] [I-1]

(Wherein, R ', R ²及beauty X is indicates the same one meaning, R ^s is shows the R other than a hydrogen atom, L is Nono b gain down, alkyl Rususoreho Ninore group or Represents a benzylsulfonyl group, and Y ′ represents

C H 〇

It represents an oxygen atom, a sulfur atom, or a group represented by the formula: N <. That is, the compound represented by the formula [I-11] is obtained by converting a compound represented by the formula [と] and a pyrimidine derivative represented by the formula [m] to a base. In an inert solvent, preferably at room temperature or within the temperature range of the boiling point of the solvent, for a few minutes to several hours. . Examples of the solvent include hydrocarbon solvents such as benzene and toluene, and halogenated hydrocarbons such as dichloromethane and chlorohonolem. Solvents, ether solvents such as tetrahydrofuran, 1,4-dioxane, etc., ketone solvents such as aceton, methylethyl ketone, etc., methyl acetate, acetic acid Estel solution such as ethyl Solvents, non-protonic polar solvents such as dimethylformamide, dimethylacetamide, etc., and acetate nitrile can be used. Examples of the base include alkali metals such as sodium metal and potassium metal, and alkali metal hydride such as sodium hydride and potassium hydride calcium hydride. Metals and hydrogenated alkaline earth metals, sodium carbonate, potassium carbonate, calcium carbonate and other carbonates, sodium hydroxide, potassium hydroxide, Metal hydroxides such as calcium hydroxide can be used.

A compound in which C H 〇 or Y is —N H — can be produced by reacting a compound in which Y is —N <with an acid or a base.

Γ I-2] [I-1 3] C I-4)

(Wherein, R ′ ^ R ² X and Y ¹ have the same meanings as described above, M represents an alkali metal or an alkaline earth metal, and R ⁷ represents an ester of R. In other words, the compound represented by the formula [I-13] is obtained by mixing a compound represented by the formula [I-13] with a polar solvent, water or a mixture of a polar solvent and water in the presence of a base. The reaction is carried out in a solvent at room temperature or within the temperature range of the boiling point of the solvent for several hours to tens of hours. Can be built

By subjecting this to acid precipitation with an organic acid such as citric acid or acetic acid or a mineral acid aqueous solution such as hydrochloric acid or sulfuric acid, the compound represented by the formula [I-14] can be produced.

Examples of the solvent include alcohol solvents such as methanol and ethanol, and 1,4-dioxane and tetrahydrofuran.

—Amide polar solvents such as ter polar solvents, dimethylformamide and dimethylacetamide can be used, but are not limited thereto. As the base, carbonates such as sodium carbonate, potassium carbonate, calcium carbonate and the like, sodium hydroxide, potassium hydroxide, calcium hydroxide Metal hydroxides such as rubber can be used.

C method>

C〇 0 MRC 0 OR ⁷ R

RR

[I-1 3] [I-1 5]

(In the formula, R ′, R ² , R ′, M, X and Y ^1. Have the same meanings as described above, and L ¹ represents no and logen.)

That is, the compound represented by the formula [I-15] can be prepared by converting the compound represented by the formula [1-3] and the compound represented by the formula [IV] into a polar compound in the presence of a base or in the absence of a base. In a solvent, preferably an inert solvent, at room temperature or within a temperature range of the boiling point of the solvent for several minutes. By reacting for several hours, it can be re-manufactured.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as chloromethane and chloro-form, 1,4-dioxane, and tetrahydrofuran. Ether solvents, such as acetone, methyl ketone, etc .; ester solvents, such as methyl acetate, ethyl acetate; etc., such as dimethyl phenol amide, dimethyl acetate amide, etc. Mid-based non-protonic polar solvents, acetonitrile, etc. can be used. Examples of the base include alkali metals such as sodium metal and potassium metal, and alkali metal hydrides such as sodium hydride, potassium hydride and hydrogen sulfide. And hydrogenated alkaline earth metals, sodium carbonate, carbonates such as calcium carbonate and calcium carbonate, sodium hydroxide, lithium hydroxide, calcium hydroxide Metal hydroxides such as aluminum, and organic bases such as triethylamine, diisopropylethylamine, pyridine and the like can be used.

D method>

〔acid〕

[I-1 6] [I-1 7]

^{^{(Wherein, R, R l, R z}} , X and Y ¹ represents the same BARA or BARB.) That is, the compound represented by the formula [I-17] is different from the compound represented by the formula [I-17] in an inert solvent at room temperature or within a temperature range of the boiling point of the solvent for several minutes. It can be produced by reacting with acid for several hours.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, dichloromethane, and nitrogenated hydrocarbon solvents such as chloro-form, 1,4-dioxane, Ether solvents such as transhydran, ketone solvents such as aceton and methyl ketone, ester solvents such as methyl acetate and ethyl acetate, dimethylformamide, dimethyla Amide-based non-protonic polar solvents such as cetamide and acetate nitrile can be used. Examples of the acid include hydrochloric acid, sulfuric acid, and oxalic acid. The acid may be added directly to the inert solvent or a gas may be added.

Ε method

[I-18] [I-19]

^{(Wherein, R, R ', R 2} , X and Y ¹ are the same meaning as described above.)

That is, the compound represented by the formula [I-19]

8) Dissolved in the inert solvent at -20 ° C By adding peroxide within the temperature range of the boiling point of the medium, it can be produced again.

As the solvent, methanol, water, dichloromethane, orifice form and the like are preferable. As the peroxide, an organic peroxide such as hydrogen peroxide, methanol perbenzoic acid, or benzoyl peroxide is used.

[Best mode for carrying out the invention]

Next, the production method of the compound of the present invention will be specifically described with reference to Examples.

Example 13 3 — (4, 6 — dimethoxypyridine 2 — yl) oxy 6 — (N, N — dimethizoleamino) methyl picolinate (compound 19) Synthesis of

6- (N, N-dimethylamino) 13-Hydroxypicolinic acid 1.4 g (7 ιαmol), 4, 6-dimethyloxy 2-methylsulfonylpyri 16 g (7πι mozole) of the midine and 0.6 g (4 m mozole) of potassium carbonate were added to 100 mJ of DMF, and reacted at 90 ° C for 2 hours. After completion of the reaction, the mixture is poured into water, extracted with getyl ether, washed with water, dried and concentrated.

The oil was crystallized from isopropyl ether. The reconciled day was recrystallized with ethyl acetate Zn-hexane to obtain the target compound. Example 23 with a yield of 1.6 g (yield 66%) and a melting point of 125 to 127. Example 2 3 — (4,6 — dimethyloxypyridine 2 -yl) oxy 6 — Methizole phenylpicolinate (Compound 8) , °

Synthesis of

6 — Phenylamine 3 .— Hydroxypicolinic acid methyl ester 1.0 g (4.4 mmol), 4, 6 — dimethyloxy-1'-methyl-2-sulfonylpi Add 0.8 g of rimidine (4 m mosole) and 0.6 g of potassium carbonate (4 m monole) to 20 mJ of DMF, and react at 80 ° C for 0.5 hours. Was After completion of the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with water and saturated saline, dried, and treated with an appropriate amount of fluoridyl. Diethyl acetate was distilled off under reduced pressure, and hexane was added to the residue obtained by adding 2 O rn fi, left for 3 days to crystallize, and washed with hexane diisopropyl ether. As a result, a target compound was obtained. The yield was 0.85 g (yield 58%), melting point 92-94 ° C.

Example 3 3 — (4, 6 — dimoxirimidine 1 2 — yl) oxo 1 6 — (N, N — dimethylinomino) picolinic acid

Synthesis of (Compound 20)

2.5-3-(4, 6-dimethoxypyridine 2-yl) oxy 6-(N, N-dimethylamino) methyl picolinate 2.5 g (7.7 mmol) as a 100 mJ methanol solution, mixed with 10% aqueous potassium hydroxide solution 6πι, and stirred at room temperature overnight. Was After completion of the reaction, the reaction mixture was poured into water and extracted with ethyl acetate. The aqueous layer was acidified, extracted with a black hole holm, washed with water, dried and concentrated, and the obtained crystals were washed with isopropropyl ether to obtain the target compound. Yield 1.6 g (yield 64%), Melting point 1995-197.5 ° C.

Example 4 3-(4, 6 — dimethyl pyrimidine 1-2-yl) oxy 6-dimethylaminopyrimidine 12-carboxylic acid 1-(ethoxy Synthesis of Cycarbonyloxy) ethyl (Compound 41)

3 — (4, 6 — Dimethyl oxirimidine-1 2 — dinore) oxie 6 — Dimethyltinoleaminopyridine 1 2 — Caffervic acid reamer 2,0 g (5.6 0.8 g (5.7 mmol) of 11 (ethoxycarbonyloxy) ethyl chloride are suspended in dimethylformamide (5ππ £) and stirred at room temperature for 6 hours. Was.

The reaction mixture was taken in water and extracted twice with ethyl acetate. After the organic layer was washed with water and dried, the solvent was distilled off, and the obtained viscous substance was subjected to column purification to obtain a target compound. The yield was 0.5 g (yield 33%) and the refractive index (Na-D line) was 1.5215.

Example 5 3 — (4, 6 — dimethyl pyrimidine 1-2 — yl) oxy 6 — dimethylaminopyridine 12 — potassium carboxylate (compound 49) Synthesis of

3-(4, 6-dimethyl ketone pyrimidine 1-2-dizole) oki-sea 6-dimethylamine pyrimidine-2-methionolemate 9.2 g (27 5 mmol) was dissolved in 30 ml of methanol, and 1.55 g (27.5 πιmol) of 10% potassium hydroxide was added thereto. Add m £ and stir at room temperature. After concentrating the reaction solution under reduced pressure, acetate was added and the precipitated crystals were filtered. 丄 7

*.

Separately, hexane washing was performed to obtain the target compound. Yield 9.8 g

(98% yield), melting point 240-245.

Example 6 3-(4, 6-dimethoxypyridine 2-yl) oxide 6-dimethylaminopyrimidine 12-carboxylate calcium Synthesis of Palladium (Compound 50)

3 — (4, 6 — dimethoxy pyrimidine 1 2 — isole) 1 6 — dimethinorea minopyridine 1 2 — power g (3.1 mmol) was dissolved in tetrahydrofuran (10 mJ2), and 0.15 g (1.5 mmol) of precipitated calcium carbonate was added thereto. In addition, 10 m of water was further added, and the mixture was stirred at room temperature. After the reaction solution was concentrated under reduced pressure, acetate was added, and the precipitated crystals were separated by filtration and washed with hexane to obtain the target compound. Yield l.Og (91% yield), mp 169-: I82.

Example 7 3 — (4, 6 — dimethyl pyrimidine — 2 — yl) oxy 1 6 — dimethylaminopyridin 1 2 — methoxycarboxylate Synthesis of methyl (compound 42)

3-(4, 6-dimethyl pyrimidin 1 2-dinole) ox 6-dimethyl pyramino pyridine 1 2-zolevonic acid 0.4 g (1. 25 mmol) in 15 ml of dichloromethan, and 0.17 g (1.31 mmol) of disopropyruetylamine is added under cooling. The reaction was carried out for 15 minutes. At 0 ° C., 0.12 g (1.49 m monole) of methoximethicolechloride was further dropped, and the mixture was allowed to react for 4 hours while gradually returning to room temperature. End of reaction Thereafter, dichloromethane 3Οβ is further added, washed with water, washed with a 10% aqueous solution of citric acid and saturated saline, dried, concentrated, and concentrated to obtain silica gel chromatographic graphite. Purification was performed to obtain the target compound. Yield 0.4 _g (84% yield), mp 91-

96 ° C.

In addition, the starting compound of the present compound can be produced according to the following method.

0R '

]

[Π-5]

(Wherein, R ^s , L ′ and X have the same meanings as described above.) That is, from the compound represented by the formula [Π—1] to the compound represented by the formula [Π—2] The compound represented by the formula [III-3] can be produced by a derivation and catalytic addition method using hydrogen. Methods for producing the compound represented by the formula [式 -4] and the compound represented by the formula [Π-5] from the compound represented by the formula [Π-1] are already known. (E.g. Pharmaceutical Journal 6 7 51 1

(19447) Can be manufactured according to that method

Next, these methods will be described in detail. F method>

[Π-1] [VI] [Π-6]

C〇〇 R ¹ or I

[11-7]

(Wherein, R ^s is shows the the same meaning, R ⁸ is shows the Xia amino group dimethyl Chirua Mi amino group or Jechirua Mi amino group, R ^s is dimethyl Chirua Mi amino group, Jechirua Mi Represents a no group, an alkyl group or a phenyl group.)

That is, the compound represented by the formula [11-1] and the trimethylsilyl derivative represented by the formula [V] or the acid chloride represented by the formula CVI] are not heated at room temperature in an inert solvent. By reacting for several hours within the temperature range of the boiling point of the solvent, the compound represented by the formula [Π-6] or the formula [H-7] can be produced.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, halogenated hydrocarbon solvents such as dichloromethane and chlorofozolem, tetrahydrofuran, 1 , 41-Dioxane and other ether solvents, Acetone and methyl ethyl ketone and other ketone solvents, methyl acetate and ethyl acetate and other ester solvents, dimethyl formamide, dimethyl acetate Non- -Protonic polar solvents, other acetonitriles, etc. can be used, but chlorophonolem is preferred.

G method>

H O

[Π—4] [Π-8

(In the formula, R ^s has the same meaning as described above, and R ′ represents an alkyl group, a substituted alkyl group or a 4,6-dimethoxypyrimidinyl group, L ² represents a halogen atom, provided that when R ¹ ° is a 4,6-dimethoxypyrimidinyl group, L ² represents a nitrogen atom or an alkylsulfonyl group; That is, the compound represented by the formula [〔-4] and the compound represented by the formula [VI] are mixed in the presence of a base in an inert solvent at room temperature or within the temperature range of the boiling point of the solvent. By reacting for several minutes to several hours, the compound represented by the general formula [I [18]] can be produced.

Examples of the solvent include hydrocarbon solvents such as benzene and toluene, dichloromethane and nitrogen-containing hydrocarbon solvents such as cross-hole form, and tetrahydrocarbons. Ether solvents such as drofuran and 1,4-dioxane; ketone solvents such as acetone and methyl ethyl ketone; ester solvents such as methyl acetate and ethyl acetate; Non-standards such as chill formamide and dimethylacetamide Protonic polar δ solvents, other acetonitrile, etc. can be used. Examples of the base include alkali metals such as sodium metal and potassium metal, and alkali metal hydrides such as sodium hydride and potassium hydride calcium hydride. Metals and hydrogenated Alkaline earth metals, sodium carbonate, potassium carbonate, carbonates such as caneoleum carbonate, sodium hydroxide, sodium hydroxide, calcium hydroxide Metal hydroxides such as aluminum can be used.

Η method

C〇 0 R ¹ R ^{1 1} Β (0 Η) ₂ C 00 R '

L

[2-5] [H-9)

(In the formula, R ^s and L ¹ have the same meanings as described above, and R ¹¹ represents a substituted phenyl group.)

That is, the compound represented by the formula [Π-5] and the compound represented by the formula [VI] are reacted for several hours in the presence of a base and a solvent in an inert solvent within a temperature range from room temperature to the boiling point of the solvent. By reacting, the compound represented by the general formula [H-9] can be produced.

Examples of the solvent include a hydrocarbon solvent such as benzene and toluene, an after-recording solvent such as methanol and ethanol, and 1,2-dimethoxetane and tetramer. Hid EI Franc, Ethil Ether solvents such as ether, ester solvents such as methyl acetate and ethyl acetate, non-protonic polar solvents such as dimethyl reformamide and dimethinorea set amide, and other solvents Trinitrile can be used. Tetrax (triphenylphosphine) is used as a catalyst. Radium (0), triphenylinolefos fin and acetate acetate are used, tris (0-tolyl) phosphine and palladium acetate are used. it can. Examples of the base include carbonates such as sodium carbonate and potassium carbonate, bicarbonates such as sodium hydrogen carbonate, and triethylamine and pyridin. Organic bases can be used.

Furthermore, the starting compound can be produced by the following method.

H 0

[Π-1 0] [Π-1 1]

(Wherein, 1 ^3, 1 ⁴ and 1 ^ are are of the same meaning.) To snare Chi formula [[pi - 1 1] compound Ru represented by the formula [pi

[10] can be produced by reacting the compound of formula [10] with formic acid at room temperature or within the boiling range for several minutes or several hours.

Further, the compound represented by the formula Π Π — 11] has the formula [Π — 1

0] and acetic anhydride-formic acid mixed solution or diformate It can also be produced by reacting with cyclohexylcarbodiimide.

K method>

[Π-1 2] [Π-1 31

(Wherein, R ³ and R ^s have the same meanings as described above.) That is, the compound represented by the formula [H—13] is a compound represented by the formula [Π 12] It can be produced by reacting with sodium nitrite at around 0 ° C in the presence of a mineral acid to form a diazonium salt, and then treating with sulfuric acid or a sulfur compound. it can.

Examples of the sulfur compound include inorganic compounds such as sodium sulfide and sodium hydrosulfide, and organic compounds such as benzylmelkabutane and diethyl carbonate. However, it is not limited to these methods.

Next, a method for producing a starting compound will be described with reference to Reference Examples. Reference Example 13 3 _ Benzizoleoxy 6-(N, N-dimethylamino-) Synthesis of methyl picophosphate-

3 — Benzinolexic picophosphate N-oxod 1

5 g (58 mmol), trimethylsilyl nitrile 6.7 g

(67 mmol),, X — dimethyl carnomic acid chloride 8.3 g (6 fπιmol) was added to 100 m of Shiojiri methylene, and the mixture was allowed to stir at room temperature. The residue obtained by washing, drying and concentrating the organic layer with water was purified by column chromatography to obtain a target compound. Yield: 2.4 g (Yield: 14%), melting point: 71.5 to 73 ° C Reference Example 2 Similarly, 3—benzyloxy 16-methyl methyl cyanovicocholinate Was obtained. Yield: 3.1 g (20% yield), melting point: 103.5 to 105 ° (.

Reference Example 3 3—Synthesis of Benzizoleoxy 1-6—Methinole picolinate

3 — Penzinoleoxyhydroxymethyl picolinate

5.0 g (19 m mol), 2.1 g (19 m mol) of bromide chill and 2.9 g (21 m mol) of potassium carbonate were added to DMF lOOmβ. In addition, the reaction was carried out at 80 ° C for 5 hours. After the reaction is completed, the residue is poured into water, extracted with ethyl acetate, washed with water, dried and concentrated.The residue obtained is purified by column chromatography to purify the target compound. Was obtained. Yield 4.1 g (74% yield), mp 45-46 ° C. Reference Example 4 Synthesis of 3-benzyloxy 6-methynole phenyl picolinate

A 100-111 £ capacity 3-port flask with thermometer, cooling pipe and nitrogen inlet pipe is equipped with a tedrox (tri-enisole phos fin). 0.6 g (0.5 mmol) and 1, 2-dimethoxybenzene 5 mJ2, and under a nitrogen stream, 3-benzyloxy 16-black mouth 2.7 g of methyl picolinate (10.0 m 1,2 ”dimethoxhetane (20 πι)

— Added at each time. After stirring at room temperature for 3 hours, 1.8 g (15.0 mmol) of phenylboric acid is dissolved in 1,2-dimethylxethan (15 mβ) and added. Stirring was continued for hours. An aqueous solution of sodium carbonate (40 m £) was added, and the mixture was heated under reflux for 50 minutes. After cooling, add an appropriate amount of water, extract with ethyl acetate, wash the organic layer with water and saturated saline, dry, and concentrate.The residue obtained is purified by column chromatography. Thus, the target compound was obtained. Yield 1.9 g (yield 59.4%).

Reference Example 5 Synthesis of 3-hydroxy-6-methyl phenizolepicolinate

1.9 g of methyl 3-benzyloxyphosphate 6-phenylpicolinate is reduced with 10% palladium on carbon Z-methanol and purified by power chromatography. The target compound was obtained. Yield 1.0 g (76.9% yield), melting point 100-: L 0 1 ° C. Reference Example 6 Synthesis of methyl 6- (N, N-dimethylamino) -3-hydroxymethyl picolinate

3—Benzyroxy 6- (N, N—Dimethylamino) picolate 2.3 g (8 mM), 10% noradium charcoal 0.3 g and ethyl acetate 10 In addition to 0 m £, hydrogen was added at normal pressure. After completion of the reaction, the mixture was filtered and concentrated to obtain crystals. Yield 1.4 g (92% yield), mp 118.5-1200 ° C.

Specific examples of raw material compounds produced in the same manner as in Reference Examples 1 to 6 Are listed in Table 2

Table 2

Intermediate XR ¹² Melting point (° c) No.

_{_{1 N (CH 3) 2 CH}} 2 - 71.5~73

2 N (CH ₃ ) ₂ H 118.5-120

3 CN 103.5 ~ 105

4 CN H

5H 100-101

6 0CH ₃ H

7 0C ₂ H ₆ H

8 H ₃ CH ₂ - 140~143

9H 84.5-86

1 0 CI CH ₂ - 127~130

1 1 1 CI H 142〜145

• 1 2. '—Ή. 124.5 to 127

1 3-0CH ₃ H 82-85 Removing agent of the present invention, ing formula pico-phosphate derivative represented by [i] and a chromatic效成min ₌

When the compound of the present invention is used as a herbicide in a paddy field, a field, an orchard, a non-agricultural land, or the like, the active ingredient can be used in an appropriate dosage form according to the purpose. In ordinary cases, it is impeached, and the component is diluted with an inert liquid or solid carrier and, if necessary, mixed with a surfactant, dispersant, scavenger, etc. to form a powder, wettable powder, It can be used after being formulated into various forms such as emulsions and granules.

For example, a powder can be produced by mixing and grinding an active ingredient and a solid carrier. A wettable powder can be produced by mixing and grinding an active ingredient, a solid carrier, a surfactant and a dispersant. Emulsions can be prepared by mixing the active ingredient, a liquid carrier, a surfactant and a dispersant. Granules may be granulated by mixing an erect ingredient, a solid carrier, a surfactant, a dispersant, an auxiliary agent, or the like, or may be mixed by mixing a solid carrier, a surfactant, a dispersant, an auxiliary agent, and the like. It can be manufactured by coating the active ingredient _c

Carriers used in these formulations include, for example, talc, bentonite, cray, kaolin, diatomaceous earth, white carbon, nomi-kiurarite, Solid carriers such as slaked lime, silica sand, ammonium sulfate, urea, etc., and liquid carriers such as i-V propizole alcohol, xylene, sicc hexoxanone, isophorone, methizolenaphthalene, etc. -As surfactants and dispersants, for example, alcohol monoester sulfate, alkyl aryl sulfone Acid salt, naphthalene sulfonate formalin condensate, lignosolephonate, polyoxyethylene glycol ether ether, polyoxyethylene Anorexoleately soleret, polyoxyethylene solesoltantan monofluorate, and the like can be mentioned. Examples of adjuvants include lipoxymethyl cellulose, polyethylene glycol, and gum arabic.

The mixing ratio of the active ingredient is appropriately selected according to need, but in the case of powders and granules, it is 0.01 to 10% (weight), preferably 0.05 to 5%. (Weight), in the case of emulsions and wettable powders, 1 to 50% (weight), preferably 5 to 20% (weight), but is not limited thereto. It will not be done.

For use, dilute to appropriate concentration on foliage, soil or water surface and spray, or apply directly. The compound of the present invention is applied in an amount of 0.1 g to 5 kg, preferably 1 g to 1 kg, per 10 are active ingredients. When used in the form of very liquid emulsions and wettable powders, the range is 0.1 to 50,000 ppm, preferably 10 to 100,000 ppm. However, the present invention is not limited to this.

The compounds of the present invention may be mixed with pesticides, fungicides, other herbicides, plant growth regulators, fertilizers, and the like, if necessary.

Next, the formulation method will be specifically described with reference to typical formulation examples. In the following description, “parts” means parts by weight.

Formulation Example 1 Powder One part of the compound (2) and 99 parts of diatomaceous earth are mixed and ground to obtain a powder.

Formulation Example 2 wettable powder

To 10 parts of the compound (19), 0.5 parts of a polyoxyethylene alkylaryl ether, 0.5 parts of a sodium formalin naphthalenesulfonate condensate, and 0.5 parts of a diatomaceous earth 20 parts and 69 parts of the clay are mixed and ground to obtain a wettable powder.

Formulation Example 3 wettable powder

To 10 parts of the compound (I) were added 0.5 parts of polyoxyethylene phenol, 0.5 parts of sodium naphthalenesulfonate condensate, and 20 parts of diatomaceous earth. Parts, 5 parts of carplex 80 and 64 parts of clay are mixed and ground to obtain a hydrating agent.

Formulation Example 4 Emulsion

60 parts of an equivalent mixture of xylene and isophorone in 30 parts of the compound (20), 60 parts of a polyoxyethylene azorealkyl aryl ether polymer and metal salt of asoalkyl benzene sulfonate Add 10 parts of the mixture and stir the mixture well to obtain an emulsion.

Formulation Example 5 'Granule

10 parts of the compound (3), 80 parts of a bulking agent obtained by mixing talc and bentonite in a ratio of 1: 3, 5 parts of white carbon, and polyoxyethylene benzoquinone One Terpo Lima First and Water 1 0 parts was added to 5 parts of ^¾ of alkylene base Nze down Tsu sulfo phosphate metal salts, good Ku kneaded diameter 0. The was a pace preparative shape. 7 mm of Fu that les, the holes After being extruded and dried, it is cut to a length of 0.5 to 1 mm to obtain granules.

[The invention's effect ]

The compound of the present invention represented by the general formula [I] can be used for various kinds of weeds which are problematic in the field, such as Asagao, Onamimi, Ooinutade, Aobu, Siroza, Perennial such as broadleaf weeds such as wildflowers, kobe, ichibi, americana chinenka, and other perennials such as horseshoe sedge, yellow sedge, kimegugu, caligrasa, kogomegalari, etc. Grassicaceae Weeds, grasses, jungsongrass, hee, mehsino, enocologusa, suzumenokatabira, suzumenotetsubo, etc. It can effectively control grass weeds at low doses.

In addition, the problem weeds on non-agricultural lands, such as japonica, cedar, poppy, oak, and oak reticulum, american clover, etc. It has an excellent herbicidal effect.

In addition, perennial weeds and perennials such as Tainubie, Tamagayalli, Konagi, etc., which occur in paddy fields, such as perennial weeds, Perica, Mizugayari, Krogui, Hotarui, Heramodaka etc. It exhibits excellent herbicidal effects at extremely low doses over a wide range from the germination of the weed to the growing season. Next, the effects of the compound of the present invention will be described with reference to test examples.

In the test, the following compound was used as a comparative compound: Compound A3 — (4, 6 — dimethylpyrimidine 12-yl) oxypicolinate (ethyl) Compounds described in JP-A-64-84)

Compound B 3-(4, 6-dimethoxypyridine 1-2-yl) methyl thiopicolinate (compound written in Japanese Patent Application Laid-Open No. 211,973)

Test example 1 (weed control by paddy soil treatment)

100 cm ² plastic pots are filled with paddy soil, and seedlings of soybean (Ec), konagi (Mo) and firefly (Sc) are sown after the paddy field. It was submerged at a depth of 3 cm. The next day, the wettable powder prepared according to Formulation Example 2 was diluted with water and dropped on the water surface. The application amount is 100 g per 100 ares for the yo components. After that, the plants were grown in a greenhouse, and on the 21st day after the treatment, the herbicidal efficacy was investigated according to the criteria in Table 3. The results are shown in Table 4.

Table 3

Index Weeding effect (growth suppression)

Herbicidal effect of 590% or more suppression

4 70% or more, less than 90%

350% or more and less than 70% herbicidal effect

230% or more and less than 50% herbicidal effect

110% or more and less than 30% herbicidal effect

0% or more and less than 10% herbicidal effect Table 4

House number Weeding effect

Ec Mo Sc

1 5 5 5

2 5 5 5

3 5 5 5

4 5 5 5

1 9 5 5 5

2 0 5 5 5

2 1 5 5 4

2 2 5 5 4

2 3 5 5 5

2 4 5 5 5

2 7 5 5.5. 5

3 6 5 5 5

3 7 5 5 5

• 3 8 '· 5.5-5

3 9 5 5 5

4 0 5 5 5 1 5 5 5

4 2 5 '5''5 4 4 5 5 5

4 5 5 5 5

4 6 5 5 5

4 7 5 5 5

4 8 5 5 5

4 9 5 5 5

5 0 5 5 5

5 7 5 5 5

5 8 5 5 5

6 7 5 5 5 Test example 2 (weed removal test by upland soil treatment)

100 cm ² plastic pots are filled with field soil, and edible flies (Ec :), ooi nutade (Po), ao bye (Am), shiroza (Ch), Kogome galli The seeds of (Ci) were sown and covered with soil. The wettable powder prepared according to Formulation Example 2 was diluted with water, and the size was reduced to 100% per 100 ares and 100 g per 100 ares. It was evenly sprayed on the soil surface with a sprayer. After that, the plants were grown in a greenhouse, and on the 20th day after the treatment, weeds were examined according to the criteria shown in Table 3. Table 5 shows the results.

Compound number Herbicide 劲

Ec Ρο Am Ch Ci

1 5 5 5 D 5

2 5 5 5 0 5

1 9 δ 0 0 D 5

2 0 5 0 DO 5 2 1 5 5 5 5 5

. 2 2 5 5 5 5 5

2 4 5 5 5 5 5

2 5 4 5 5 5 4

2 7 5 5 5 5 5

3 6 5 4 5 5 5

3 7 5 5 4 5 5

3 8 4 4 4 5 5

3 9 5 5 5 5 5

4 0 5 5 5 5 5

4 1 5 5 5 5 5

4 2 5 5 5 5 5

4 3 5 5 5 5 5

4 4 5 5 5 '5 5

4 5 5 5 5 5 5

4 6 5 5 5 5 5

4 7 5 5 5 5 5

4 9 5 5 5 5 5

5 0 5 5 5 5 5

5 7 5 5 δ 5 5

5 8 5 5 5 5 5

6 7 5 δ 5 5 5 Test Example 3 (Test of herbicidal effect by upland foliage treatment)

A 100 cm ² plastic pot is filled with field soil, and is used for edible vegetation (E'c), o-nutata (Po), ao bu (Am), and siroza. (Ch) and various seeds of Kogome gallari (Ci) were sown and covered with soil. After cultivation in a greenhouse for 2 weeks, the wettable powder prepared according to Formulation Example 2 is diluted with water so that the active ingredient becomes 100 g per 100 oz. Then, 100 pieces per 100 rounds were sprayed with foliage from above the whole plant using a small sprayer. After that, the plants were grown in a greenhouse, and on the 14th day after the treatment, the herbicidal effect was investigated according to the criteria in Table 3. Table 6 shows the results. ^ ο 化合物 Compound number Weeding 果 Fruit

Ec Ρο Am Ch C i

1 5 5 5 5 5

2 5 ο δ 5 5

1 9 0 δ 5 5 5

2 0 5 0 5 5 0

2 1 0 4 5 5 5

2 2 D 4 4 5 5

2 3 4 5 4 5 5

2 4 5 5 δ 5 5

2 7 δ 5 5 5 5

3 6 5 5 5 5 0

3 7 0 5 0 δ δ

3 8 D 5 5 δ 5

3 9 o 5 5 5 δ

4 0 0 5 5 5 δ

4 1 0 5 5 5 5

4 2 δ 0 δ 5 5

4 3 5 ο 5 5 δ

4 4-5 ^ 5 * 0 0 5

4 5 δ 0 5 5 5

4 6 5 δ 5 5 5

4 7 5 5 5 5

4 9 0 0 5 δ 0

5 0 δ δ δ 5 δ 5 7 5 5 4 δ 5

5 8 5 5 5 4 5

6 7 5 5 5 5 5 Test Example 4 (Test of herbicidal effect at low dose by field foliar treatment) 600 cm ² plastic pot is filled with field soil, , Jeon Son-Grass (So), Pseudo-Nutade (Po), A-Vo (Am), Siroza (Ch), No-Asagao (Ip) and Ponata (Xa) And covered the soil. After growing for 2 weeks in a greenhouse, a predetermined amount of a wettable powder prepared according to Formulation Example 2 is diluted with water, and the mixture is added to a small atomizer at a rate of 100 β per 100 ares. Then, foliage application was performed on the whole plant from above. After that, they were raised in a greenhouse, and on the 14th day after the treatment, the herbicidal effect was investigated according to the criteria in Table 3. Table 7 shows the results.

Table 7

8 .3 5 5 5 5 5 5 5 9 6 .3 5 5 5 5 5 5 D 0 6 .3 5 5 5 5 5 5 5 8 6 .3 5 5 5 5 5 5 5 7 6 .3 5 5 5 5 5 5 5

A 6. 3 1 4 4 5 4 1 1

B 6. 3 0 2 3 1 3 0 0-

Claims

Range of request

(1) General formula

(In the formula, R represents a hydrogen atom, an azoalkyl group, an azorecenyl group, an alkynyl group, a benzyl group, a benzoyl group, a halogen-substituted alkyl group group, a cyano aphlequinol group, an azo alkynoxy group, Flexo cannole ponyloxy alkynole group, alkynoxy sol bonyl alkynole group Alkyl carbonyl carbonyl cane quinolene group, silk mouth Alkizole force Group, a cycloalkylanoloxy group, an alkali metal atom, an alkaline earth metal atom, or a cation of an organic amine,

R ¹ and R ² are the same or different and each represents an alkyl group, an alkoxy group, a halogen atom, a nitrogen atom, a halogen-substituted flexoxy group or an alkyl group; Represents a rudino group;

R ³

X is the formula

R ⁴

(Wherein, R ³ and R ⁴ are the same or different and each represent a hydrogen atom, an alkenyl group, a phenyl group, or an acyl group.) Group, a cyano group, a phenyl group (the group may be substituted by a halogen atom, an alkyl group or an alkoxy group), a phenoxy group , A halogen-substituted alkynole group, a flexioxy group, a Lucenyl group, "y flexinyl group, hydroxyl group, trimethylsilylethynyl group, nitro group, 4, 6-dimethoxypyrimidine-21-yloxy group or hydrogen atom;

R ⁵

Y represents an oxygen atom, a sulfur atom or a group represented by the formula —N (wherein, R ^s represents a hydrogen atom or a formyl group), and n represents 0 or 1.

C H 0

However, when X is a hydrogen atom, Y represents a group represented by the formula —N <. ] The picolinic acid derivative represented by these, or its salt.

(2) R represents a hydrogen atom or an alkyl group,

R ¹ and R ² are the same or different and each represent an alkyl group, an alkoxy group, a halogen atom, a nitrogen-substituted alkoxy group or a phenolic sole phenol group;

R ³

X is the formula N <

R ⁴

Wherein R ³ and R ³ are the same or different, and each represents a hydrogen atom, an alkyl group, a phenyl group or a acyl group.), A cyano group, a phenyl group (the The group may be substituted with a halogen atom, an alkyl group or an azoreoxy group.), A phenyl group, an alkoxy group, a hydroxyl group, a nitro group or a 4,6- Dimethoxypyrimidine 1- 2 — represents an inoleoxy group,

R ⁵

Y is an oxygen atom, a sulfur atom, or a group represented by the formula (wherein, R ⁵ represents a hydrogen atom or a formyl group). Pin co Li down San誘conductor or salts of that range囲第1 wherein according showing the shows and ^beta n is 0 or 1 Re that group.

(3) Y represents an oxygen atom;

2. The picolinic acid derivative or a salt thereof according to claim 1, wherein n represents 0.

(4) R is a hydrogen atom, a methyl group, an ethoxycarbonylmethyl group, a 1-propioninoleoxyshethyl group, an 11-ethoxycarbonylcarbonyloxy group, a methoxy group Symtisole group, cyanomethyl group, 2—chloroethyl group, 2—propynyl group, aryl group, benzyl group, sodium or potassium Show

R ¹ and R ² each represent a methoxy group,

X represents a dimethylamino group or a vinyl group;

Y represents an oxygen atom. ) Represents a group represented by

(5) A herbicide comprising, as an active ingredient, an effective herbicidal amount of the picolinic acid derivative or a salt thereof according to Claim 1.

(6) A herbicide comprising, as an active ingredient, a herbicidally effective amount of the picolinic acid derivative or a salt thereof according to claim 2. '

(7) A herbicidal method comprising applying the impeached amount of the picolinic acid derivative or a salt thereof according to claim 1 in the claim. C 8) General formula

(In the formula, R ^ε is an azolekyl group, a halogen-substituted alkyl group, an aralkylcarbonylcarbonyl group, an anoxycarbonyl group, an alkoxycarbonylalkynole group, an alkoxybonisolexoxazole group, Alkyl force Bonizoleoxy thiazole group, cycloazoleky azorexole group, cyanoalkyl group, alkenyl group, alkynyl group, benzyl group, alkaline metal atom, alkaline earth metal atom Or indicates the category of organic amine,

X represents a hydrogen, a halogen-substituted alkyl group, an alkoxy group, an alkenyl group, an alkynyl group, or a phenyl group (the group is a halogen atom, an azoalkyl group or an alkoxy group; ), A phenoxy group, a hydroxyl group, a cyano group, a nitro group, a trimethylsilylleletinyl group, a 4,6—dimethoxypyrimidine 12 —

R ³

ルキ <

R ⁴

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

Υ represents an oxygen atom, a sulfur atom or a group represented by the formula> NCHO. ) Represents a group represented by. A picolinic acid derivative represented by the formula • r

General formula

R '

L

(In the formula, R ¹ and R ² are the same or different and each represents an alkyl group, an alfoxy group, a nitrogen-substituted phenol group, an alkylsulfonyl group, Indicates a nitrogen atom,

L ¹ represents a nitrogen atom, a phanolequillsulfonisole group or a benzylsulfonyl group. ) With the pyrimidine derivative represented by the formula (1) in the presence of a base.

General formula

^{(Wherein, R ', R z, R} B, X及Beauty Y ^1, said a. Showing the same taste meaning) preparation of pin co-phosphate derivative that will be table in.

(9) General formula

1

R

(Wherein, R ′, R ² and X have the same meaning as described above, and represent an ester-forming group of R ⁷ R) and a base represented by the following formula: A general formula characterized by reacting

(Wherein, R ′, R ² , X and Y ¹ have the same meanings as described above;

Μ indicates Al-Li metal atom or Al-Li earth metal atom

Method for producing picolinic acid derivative represented by)