WO2000075112A1

WO2000075112A1 - Novel n-(2,2,2-trifluoroethyl)-4-methoxy-6-[(substituted or unsubstituted) m-cyanophenoxy]-2-pyridinecarboxamide derivatives, process for the preparation thereof and herbicides

Info

Publication number: WO2000075112A1
Application number: PCT/JP2000/003666
Authority: WO
Inventors: Hisashi Kanno; Tsutomu Sato; Masato Arahira
Original assignee: Kureha Kagaku Kogyo Kabushiki Kaisha
Priority date: 1999-06-09
Filing date: 2000-06-06
Publication date: 2000-12-14
Also published as: AU2000249545A1

Abstract

N-(2,2,2-Trifluoroethyl)-4-methoxy-6-[(substituted or unsubstituted) m-cyanophenoxy]-2-pyridinecarboxamide derivatives useful as the active ingredient for herbicides exhibiting excellent effects; a process for preparing the derivatives; and herbicides containing the same.

Description

Description Novel N— (2,2,2-trifluoroethyl) 1-4—Methoxy 6 — [(substituted or unsubstituted) methacyanophenoxy] — 2—Pyridine lipoxamide derivative , Its production method and herbicide

The present invention relates to an N- (2,2,2-tritrifluoroethyl) 14-methoxy-16-[(substituted or unsubstituted) metacyanophenoxy] —2-pyridinepyridinecarboxamide derivative, The present invention relates to a production method and a herbicide. Background art

Certain types of 6- (unsubstituted or substituted) phenoxy-l-pyridinecarboxamides are described in Japanese Patent Application Laid-Open No. HEI 4-199085, International Publication WO97 / 24330, etc. Have been. However, the N— (2,2,2-trifluoroethyl) —4—methoxy-6 — [(substituted or unsubstituted) methasanophenoxy] 12-pyridinecarboxamide derivative of the present invention is It is a novel compound that is not described in these documents.

Conventionally, a herbicide that shows low herbicidal effect at low doses that can reduce its abundance in the environment, shows selectivity for crops and weeds regardless of changes in environmental conditions, and is a second crop of double cropping There is a need to provide herbicides that do not cause phytotoxicity. Disclosure of the invention

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a novel compound exhibiting an excellent herbicidal effect, a method for producing the same, and a novel herbicide containing the compound as an active ingredient. It is in. The present inventors have conducted various studies to find a novel pyridine derivative which is industrially useful. As a result, the present inventors have found that a novel compound N- (2,2,2-trifur (4-ethyloxy) 14-methoxy-16-[(substituted or unsubstituted) metacyanophenoxy] -12-pyridinecarboxamide derivative is included in the compound described in the above document, and The present inventors have found that they exhibit higher herbicidal activity than compounds having a close relationship with pyridinecarboxamide derivatives, and have completed the present invention.

That is, N- (2,2,2-trifluoroethyl) _4-methoxy-16- (metacyanophenoxy) -1-pyridine lipoxamide (compound I_1) is compared with the following four compounds. By exhibiting excellent activity, the combination of the pyridine group at the 基! ± 4 position, the methano group on the phenyl ring, and the 2,2,2-trifluoroethyl group in the amide part was excellent. It was found to be a factor indicating herbicidal activity.

1) A compound encompassed in WO 97/24330, which is a compound lacking a cyano group from the above compound I-1 (Α): [Ν- (2,2,2—trifluore) Til) 1-4-Methoxy-6-phenoxy1-2-pyridinecarboxamide].

2) Compounds contained in International Publication WO 97/24330, in which the cyano group of compound I-1 is converted to a methyl group (B): [N- (2, 2, 2) —Trifluoroethyl) 14-Methoxy-6_ (metamethylphenoxy) —2-Pyridine lipoxamide].

3) Compounds included in JP-A-4-1290805, wherein the compound I-11 lacks a methoxy group (C): [N— (2,2,2-trifluoroethyl) One 6_ (metacyanophenoxy) one 2-pyridinecarboxamide].

4) Conversion of 2,2,2-trifluoroethyl group of compound I-1 into ethyl group Compound (D): [N-ethyl-14-methoxy-6- (metathanophenoxy) -12-pyridine-ylboxamide].

According to a first aspect of the present invention, there is provided N- (2,2,2-trifluoroethyl) -14-methoxy-16-[(substituted or unsubstituted) metaciano represented by the following formula (I). Phenoxy] exists in 2-pyridinecarboxamide derivatives.

(In the formula, X represents a _4- alkyl group and a halogen atom. N represents an integer of 0 to _4. )

The second gist of the present invention is that, as represented by the following reaction formula (A), N- (2,2,2-trifluoroethyl) -14-methoxy represented by the general formula (II) A 6-halogeno 2-pyridinecarboxamide derivative is reacted with a (substituted or unsubstituted) metacyanophenol represented by the formula (III), wherein the N— (2, 2, 2—Trifluoroethyl) 1 4—Methoxy

-6-[(substituted or unsubstituted) metacyanophenoxy] —2—pyridinecarboxamide derivatives.

Reaction formula (A)

(Wherein, x is c, to c ₄ alkyl group,. Tau ¹ of a halogen atom is a halogen atom. N is an integer of 0-4.)

The third gist of the present invention is to provide 4-methoxy 6-[(substituted or unsubstituted) methacyanophenoxy represented by the general formula (IV) as represented by the following reaction formula (B). ] — Reacting a 2,2-pyridinecarboxylic acid derivative with a 2,2,2-trifluoroethylamine represented by the formula (V); 2, 4-trifluoromethyl) 6-[(substituted or unsubstituted) metacyanophenoxy] 1-2-pyridine-based method for producing a ruboxamide derivative. Reaction formula (B)

(In the formula, X represents a C i -C ₄ alkyl group and a halogen atom. R represents a leaving group (halogen atom, lower alkoxy group, hydroxyl group). N represents an integer of 0 to _4. ) A fourth gist of the invention is that N— (2,2,2-trifluoroethyl) -14-methoxy-16 — [(substituted or unsubstituted) metacyanphenoxy] -12-pyridine represented by the formula (I) A herbicide characterized by containing a carboxamide derivative as an active ingredient.

(Where X and n are the same as above.)

Hereinafter, the present invention will be described in detail. First, N— (2,2,2-trifluoroethyl) represented by the above general formula (I) —4-methoxy 6 — [(substituted or unsubstituted) methacyanophenoxy] — The 2-pyridinecarboxamide derivative (hereinafter, abbreviated as the present compound (I)) will be described.

The definition of each symbol (X, n) in the compound (I) and the specific contents thereof are described.

Examples of the C! C ^ alkyl group in X include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the above definition, preferred X is a methyl group or a chlorine atom.

n is usually from 0 (meaning unsubstituted) to 4. It is preferably 0 to 2, more preferably 0 to 1, and when n = 1, it is preferable that the compound is bonded to the 4-position of the phenoxy ring. Particularly preferably, η is 0.

Examples of the compound (I) having the combination of the above substituents and integers include the compounds shown in Table 1 below.

Table 1 Compound numbers x ^a) n

I- 1-0

1-2 4- CI 1

1-3 4- Br 1

1-4 5- CI 1

1-5 6- CI 1

1-6 2-F 1

1-7 4-F 1

1-8 5-F 1

1-9 6-F 1

1-10 4-CH 3 1

1-11 5-CH 3 1

1-12 2-CH 3 1

1-13 6-CH 3 1

1-14 4-CH ₂ CH 3 1

1-15 5-CH ₂ CH 3 1

1-16 2,4-F ₂ 2

1-17 4,5- F ₂ 2

1-18 2,4- CI ₂ 2

1-19 2,4- (CH ₃ ) ₂ 2

1-20 2,4,5-F 3 3 a) "One" indicates unsubstituted. When the compound has a substituent, the number before the hyphen indicates the bonding position. Next, a method for producing the present compound (I) will be described. As the solvent used in the reaction step or the separation step of the present invention, usually, aromatic hydrocarbons such as benzene, toluene, xylene and methylnaphthalene, petroleum ether, pentane, hexane, heptane and methylcyclohexane are used. Aliphatic hydrocarbons such as xane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and benzene, dimethylformamide, dimethylacetamide, N-methyl-1-pyrrolidinone, etc. Examples include amides, ethers such as dimethyl ether, dimethyloxetane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane; and alcohols such as methanol and ethanol. Further, water, carbon disulfide, acetonitril, ethyl acetate, pyridine, dimethyl sulfoxide, hexamethylphosphoric amide, or the like may be used as a solvent.

These solvents may be used as a mixture of two or more kinds. All individual reaction steps of the process of the invention are performed in a solvent or solvent mixture. Further, a solvent composition composed of solvents that do not form a uniform layer may be used. In this case, it is preferable to add a phase transfer catalyst, for example, a conventional quaternary ammonium salt or crown ether to the reaction system.

The base used in the reaction step or the separation step of the present invention is usually an alkali metal such as lithium, sodium and potassium, an alkaline earth metal such as magnesium, sodium methoxide, and sodium ethoxide. Alkoxides of alkali metals such as potassium t-butoxide; metal hydride compounds such as sodium hydride and potassium hydride; metal carbonates such as sodium carbonate and sodium carbonate; calcium carbonate and carbonic acid Alkaline earth metal carbonates such as barium, alkaline earth metal hydrogen compounds such as calcium hydride, sodium hydroxide Alkali metal hydroxides such as aluminum and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, magnesium oxide, oxidizing power Alkaline earth metal hydroxides such as lysium, methyl Alkali metal organometallic compounds such as lithium, ethyllithium, n-butyllithium, and phenyllithium; and organics such as methylmagnesium iodide, ethylmagnesium bromide, and n-butylmagnesium bromide Examples include Grignard reagents, organic metal compounds of alkali metals, organic copper compounds prepared from Grignard reagents and monovalent copper salts, and alkali metal amides such as lithium diisopropylamide. The acid used in the reaction step or the separation step of the present invention is usually an inorganic acid such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid or sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid or the like. Organic acids may be mentioned. These acids may be used as a mixture of two or more.

In the production method of the present invention according to the second aspect, the present compound (I) is a compound represented by the following general formula (II): N— (2,2,2-triethylroethyl) _4-methyl The halogen atom at the 6-position on the pyridine ring of the ethoxy-6-halogeno-2-pyridinepyridine compound (hereinafter abbreviated as compound (II)) is represented by the general formula (III) (substituted or unsubstituted). Substitution) It is obtained by substituting an oxygen atom in a hydroxyl group of a metacyanophenol compound (hereinafter abbreviated as compound (III)) to form a carbon-oxygen bond. These are shown by the following reaction formulas.

(In the formula, X. N C! -C ₄ alkyl group, a halogen atom. T ¹ is shown halogen atom is an integer of 0-4.)

The funinoxylation reaction of the compound (II) is generally performed by mixing the compound (II) and the compound (III) in a solvent under basic conditions. In this reaction, the amount of compound (III) to be used is generally 0.8 to 10-fold mol, preferably 1 to 2-fold mol, relative to compound (II). The amount of the base used is the same as or less than the amount of the compound (III), and is usually 0.8 to: L0 mol, preferably 1 to 2 mol. . It is preferable to use a monovalent copper salt such as cuprous chloride as a catalyst. The amount of the monovalent copper salt to be added to compound (III) is usually 0.01 to 10-fold mol, preferably 0.1 to 2-fold mol. The reaction temperature is usually in the range of 20 ° (: to 200 t :, preferably 60T: to 180 C.) The reaction time is usually several minutes to several days.

As the above compound (III), a commercially available product can be used, and a compound produced by an existing technology can also be used. An example is shown below. 1) A compound obtained by diazotizing an amino compound having an amino group at a site corresponding to a hydroxyl group of compound (III) and hydrolyzing the obtained diazo compound can be used. This amino compound can be produced by reducing a compound having a nitro group at the corresponding site.

Examples of the amino compound include 3-amino-6-methylbenzonitrile, 3-amino-6-chlorobenzonitrile, 3-amino-6-bromobenzonitrile,

Examples thereof include 3-amino-6-fluorobenzonitryl and 3-amino-2,6-difluorobenzonitrile, and these compounds are commercially available.

Examples of nitrated ^ include, for example, 2-methyl-5-nitrobenzonitrile, 2-chloro-5-nitrobenzonitrile, 2-bromo-5-nitrobenzonitrile, 2-fluoro-5-nitrobenzonitrile Benzonitrile, 4-methyl-5-nitrobenzonitrile, 4-funoleo-5-nitrobenzonitrile, 4-octorolo-5-nitrobenzonitrile, 2,6-difluoro-3-2- Benzonitrile and the like, and these compounds are commercially available.

2) A compound obtained by dehydrating a compound of the formula (III) having a rubamoyl group at a site corresponding to a cyano group can be used. This carboxylic acid amide compound can be produced by amidating the corresponding carboxylic acid.

— On the other hand, the above compound (II) can be produced as follows. For example, the leaving group (R) in a 2-substituted carbonyl-4-methoxy-16-halogenopyridine derivative (VI) is usually replaced with a 2,2,2,3 represented by the formula (V) in an organic solvent. By substituting with 2-trifluoroethylamine, 4-methoxy-6-halogeno-2-pyridinecarboxamide derivative (II) can be produced. These are shown in the reaction formula below. Reaction formula (C)

(In the formula, R represents a leaving group (halogen atom, lower alkoxy group, hydroxyl group), and T ¹ is the same as described above.)

The reaction conditions are as follows: 4-Methoxy-6-[(substituted or unsubstituted) metacyanopoxy-12-pyridinepyridine represented by the general formula (IV) described below. ) Is replaced by the amino group nitrogen of 2,2,2-trifluoroethylamine represented by the formula (V), and the conditions for forming a carbon-nitrogen bond can be used.

Next, a method for producing compound (VI) as a raw material of compound (II) will be described. The compound (VI-a) in which R is a halogen atom in the compound (VI) can be produced by halogenating the corresponding carboxylic acid compound (VI-b) (the compound in which R is a hydroxyl group in the compound (VI)). For example, in a solvent inert to acid halides such as benzene and toluene, thionyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, bromide It can be produced by halogenating a 4-methoxy-16-halogenopicolinic acid derivative (VI-b) using a halogenating reagent such as phosphoryl. These are shown in the reaction formulas below. Reaction formula (D)

(In the formula, w represents a halogen atom, and τ ¹ is the same as described above.)

The reaction temperature is usually from 0 to 250 ° C, preferably from 30 to 150 ° C. The amount of the halogenating reagent is usually 0.3 to 10 moles, preferably 1 to 5 moles. It is more preferable to use a reaction such as dimethylformamide. The reaction time is usually several minutes to several days.

In compound (VI), compound (VI-c) in which R is a lower alkoxy group substitutes the leaving group (R ¹ ) of the compound represented by compound (VI-d) with a hydroxyl group in lower alcohol. Can be manufactured. These forces are shown in the reaction formula. It is compliant. Reaction formula (E)

BOH

(In the formula, R represents a halogen atom or a hydroxyl group, and T ¹ is the same as described above.) The leaving group (R ¹ ) is a lower alkanol (BOH (B is a lower alkyl group. )) Is a group that is substituted by the hydroxyl oxygen of the above, and is a substituent that is bonded to the carbonyl group in compound (VI-d). The leaving group (R ¹ ) is usually a halogen atom, for example, a chlorine atom, a bromine atom or a hydroxyl group, preferably a halogen atom, particularly preferably a chlorine atom.

When the leaving group (R ¹ ) is a halogen atom, the reaction of substituting a halogen atom using lower alcohol (BOH) is a force that proceeds without the presence of a base. Hydrogen halide generated in the course of the reaction A base such as triethylamine may be coexistent in the reaction solution in order to remove the acid. In this case, a lower class alkanol for compound (VI-d) The amount of the compound used is usually 1.0 to 1000 times mol, preferably 1.0 to 100 times mol. The reaction temperature is usually in the range of 0 to 2001, preferably in the range of 0 to 100. The reaction time is usually several minutes to several days. In addition, a commercial product can be used for the lower alcohol.

When the leaving group (Ri) is a hydroxyl group, the compound (VI-c) can be usually produced by reacting an excess of lower alcohol with the compound (VI-d) in a solvent or without solvent. In this case, the amount of the lower alkynol used for the compound (VI-d) is usually 1.0 to: L000-fold mol, preferably 1.0 to 100-fold mol. The reaction temperature is usually 0 to 250T, preferably 0 to 801C. When the reaction temperature exceeds the boiling point of the lower alcohol used, the reaction vessel is preferably sealed. Further, the reaction can be promoted by using an acid catalyst such as hydrochloric acid or sulfuric acid, or by using a dehydrating agent such as molecular sieves. The reaction time is usually several minutes to several days.

Next, the above compound (VI-b) can be produced as follows. First, as a first method, a compound represented by the general formula (VII) is produced by substituting a metal for the halogen atom (T ² ) of the compound represented by the general formula (VIII). Between the metallized carbon atom of the hydrogenated compound and the carbon atom of carbon dioxide

— A method of producing a compound (VI-b) by forming a carbon bond.

Specifically, the compound (VI-b) is obtained by converting a 2,6-dihalogeno-4-methoxypyridine derivative represented by the general formula (VIII) (hereinafter abbreviated as compound (VIII)) to a metal. Thus, a 2- (metal-substituted) -6-halogeno-4-methoxypyridine derivative (hereinafter abbreviated as compound (VII)) represented by the general formula (VII) is produced. It can be produced by reacting VII) with carbon dioxide, followed by substitution with proton. The power of these is shown in the reaction formula below. Reaction formula (F)

1) C0 ₂

2) H +

(In the formula, T ² represents a halogen atom, M represents a metal (for example, an alkali metal, an alkaline earth metal 'Q (Q represents a halogen atom.)) Or 1/2 (Cu · alkali metal) And T ¹ is the same as above, and T ¹ and T ² may be the same or different.)

The above compound (VII) is obtained by treating compound (VIII) with the following metallating agent. It can be manufactured by Examples of the metallizing agent usually include organometallic compounds of alkali metals such as butyllithium, methyllithium and phenyllithium, alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium. In addition, organic metal compounds of alkali metals prepared with the above-mentioned reagents, organic copper compounds prepared from Grignard reagents and monovalent copper salts, and the like can also be used.

The amount of the metalating reagent to be used is not preferably large because the halogen atom to be further substituted is present in the molecule, and is usually 0.5 to 2 moles, preferably 0.8 to 1.5 moles to the compound (VIII). It is twice the mole. For the amount of carbon dioxide, use a large excess of equivalent or more to make it react sufficiently. The temperature of the treatment with the metallating agent and the reaction with carbon dioxide is usually from -100 to 1001: 100, preferably from -80 to 80. The reaction time is several minutes to several hours, respectively.

Compound (VI-b) can be produced by reacting the obtained compound (VII) with carbon dioxide and then substituting with proton. The proton substitution is performed by treating the reaction solution with an acidic aqueous solution. Examples of the acid generally include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, perchloric acid, and sulfuric acid, and organic acids such as formic acid, acetic acid, and p-toluenesulfonic acid. These acids may be used as a mixture of two or more.

As the solvent used in the reaction for producing the compound (VI-b), a solvent inert to the organometallic compound can be used. For example, aliphatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, and methylcyclohexane; ethers such as dimethyl ether, dimethyloxetane, diisopropyl ether, tetrahydrofuran, diglyme, and dioxane; benzene, toluene, And aromatic hydrocarbons such as xylene and methylnaphthalene. These solvents may be used as a mixture of two or more kinds.

Compound (VIII) can be produced as follows. 2, 6—dihalo As described in Japanese Patent Application Laid-Open No. 8-268808, the two-mouth group of the corresponding 2,6-dihalogeno-4-nitropyridine derivative can be obtained under basicity as described in JP-A-8-268808. It can be produced by substitution with a methoxy group. 2, 6-Dichloro-4—methoxypyridine [compound [VIII, T ¹ = CK T ² = C1]] and 2, 6—dibromo-1-4-methoxypyridine [compound [VIII, T '= Br, T ² = Br]] is described in the above Japanese Patent Publication.

A second method for producing the compound (VI-b) includes a method of hydrolyzing a 2-cyano-16-halogeno-4-methoxypyridine derivative represented by the general formula (IX). These are shown by the following reaction formulas. Reaction formula (G)

(Where τ ¹ is the same as above.)

The above hydrolysis may be performed under any of acidic and basic conditions. In the case of hydrolysis under acidic conditions, catalysts such as hydrochloric acid, hydrobromic acid and sulfuric acid are usually used. Use of the inorganic acid. As a solvent, an aqueous solution of an organic acid such as acetic acid is usually used in addition to water. In the case of hydrolysis under basic conditions, an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base. As the solvent, water or an aqueous alcohol solution is usually used. The hydrolysis temperature is usually from 20 to the reflux point, preferably from 50 to the reflux point. The reaction time is several minutes to several hours.

Compound (D is prepared as follows. 2-Cyanopyridine 4,6-dichropyridine is prepared by chlorinating 2-cyanopyridine according to the method described in British Patent No. 1301724. By subjecting the obtained chlorinated product to a nucleophilic substitution reaction under basic conditions, 2-cyano 6-chloro-14-methoxypyridine [compound [IX, T ^ Cl]] is produced. 2—Cyanone 4—Methoxy 16—Crosin pyridine [Compound [IX, T ¹ = C1]] is 2—Crosin 1—Methoxy— 6-pyridine N-oxide with dimethyl sulfate and N— It can also be produced by alkylating the old oxide part and then reacting with sodium cyanide.

A third method for producing the compound (VI-b) includes a method of hydrolyzing a lower alkyl ester of 6-halogeno-14-methoxypicolinic acid represented by the general formula (X). These are shown in the following reaction formulas.

Reaction formula (H)

(In the formula, B represents a lower alkyl group, and T ¹ is the same as described above.)

The above hydrolysis may be performed under any of acidic and basic conditions. In the case of hydrolysis under acidic conditions, an inorganic acid such as hydrochloric acid, hydrobromic acid or sulfuric acid is usually used as a catalyst. As a solvent, an aqueous solution of an organic acid such as acetic acid is usually used in addition to water. In the case of hydrolysis under basic conditions, an alkali metal base such as sodium hydroxide and potassium hydroxide is usually used as the base. As a solvent, an aqueous alcohol solution is usually used in addition to water. The hydrolysis temperature is usually in the range of 20 to the reflux point, preferably in the range of 50 to the reflux point. The reaction time is several minutes to several hours.

Compound (X) is produced as follows. First, N-methylpyridonic acid and thionyl chloride are reacted to synthesize 4,6-dichloropicolinic acid chloride, and then the obtained 4,6-dichloropicolinic acid chloride and a lower salt are synthesized. 4,6-Dichroic picolinic acid as a raw material for the synthesis of compound (X) Production of alkyl esters (J. Org. Chem., 23, 1030 (1958)). The 4,6-dichloropicolinic acid obtained by oxidizing 4,6-dichloromethyl-2-methylpyridine is converted to an acid halide, and then reacted with lower alkanols to form 4,6-dichloropicolinic acid. —Preparing lower alkyl esters of picolinic acid with diclo mouth. The resulting lower alkyl ester of 4,6-dichloropicolinic acid is subjected to a nucleophilic substitution reaction under basic conditions to give a lower alkyl ester of 6-chloro-4-nitroxpicolinic acid [compound (X, T ' = C1)] can be manufactured.

In the synthesis of substituted picolinic acid by an oxidation reaction, when there is a substituent at the 4-position, 2-picoline N-hydroxy is more effective than a method of directly converting a 2-methyl group of a pyridine ring into a carboxyl group by oxidation. Preferred is a method of synthesizing 2-pyridinemethanol from amides and oxidizing to a carboxyl group via a hydroxymethyl group to generate substituted picolinic acid. For example, by oxidizing the hydroxymethyl group of 6-chloro-4-methoxypyridine-2-pyridine to produce 4-methoxy-16-chloropicolinic acid, which is reacted with thionyl chloride to form 4-Methoxypicolinic acid chloride is synthesized, and then the obtained 6-chloropicolinic acid chloride is allowed to react with lower alkynol chloride to give 6-chloroacetic acid chloride. Toxicolinic acid lower alkyl ester [Compound (X, T ^ Cl)] can be produced.

Next, the manufacturing method of the present invention according to the third aspect will be described. The leaving group (R) in the 4-methoxyethoxy 6-[(substituted or unsubstituted) methacyano-pentoxy-2-pyridinecarboxylic acid derivative represented by the following general formula (IV) is represented by the formula (V) The amino group nitrogen of 2,2,2— trifluoroethylamine represented by the formula (1) forms a carbon-nitrogen bond, and the N— (2,2,2— Trifluoroethyl) —4—Methoxy 6 — [(substituted or unsubstituted) methacyanophenoxy] — Produces 2-pyridinecarboxamide derivatives. These are shown by the following reaction formulas.

(Wherein, R, X, and n are the same as above.)

The leaving group (R) is a group substituted by a nitrogen of the amino group of the compound (V) during the reaction, and means a substituent bonded to the carbonyl group in the compound (IV). The leaving group (R) is usually a halogen atom such as a chlorine atom or a bromine atom, a lower alkoxy group such as a methoxy group or an ethoxy group, or a hydroxyl group, preferably a halogen atom, and particularly preferably a chlorine atom. .

When a compound in which R in compound (IV) is a halogen atom is used, a halogen atom substitution reaction [when a compound in which the amino portion of compound (V) is in a salt form such as a hydrochloride is used. An equivalent amount or more of a base such as triethylamine is added to form a free amine and used. In this case, since hydrogen halide is generated during the reaction, it is preferable to add the compound (V) in excess of one equivalent or more for the purpose of capturing the hydrogen halide. Specifically, the amount of compound (V) to be used is generally 2.0 to 10.0 times, preferably 2.0 to 5.0 | ¾ mol, relative to compound (IV). In addition, a base such as triethylamine may be co-present in the reaction solution instead of adding compound (V) in excess to capture hydrogen halide. In this case, the compound The amount of the compound (V) to be used is generally 1.0 to 5.0 times, preferably 1.0 to 3.0 times, the mole of the compound (IV). The reaction temperature is usually 0 to 150 t, preferably 0 to 80. Commercially available 2,2,2-trifluoroethylamine (compound (V)) can be used.

When a compound in which R in compound (IV) is a lower alkoxy group is used and a base is not used, it is preferable to add compound (IV) in excess of compound (V). The amount of use is usually 1.0 to 1000 times, preferably 1.0 to 100 times. The reaction ¾S is usually 0 to 250, preferably 0 to 180. When the reaction temperature exceeds 38 (boiling point of compound (V)), it is desirable to seal the reaction vessel.

When a compound or a base in which R in the compound (IV) is a lower alkoxy group is used, the reaction for converting an amine to an alkali amide proceeds even under a high temperature condition as described above. The reaction temperature is usually 0 to 150 t :, preferably 0 to 100 t. The amount of compound (IV) to be used is generally 1.0 to 5.0 moles, preferably 1.0 to 3.0 moles, relative to compound (V). The amount of the base used is usually 1.0 to 3.0 times, and preferably 1.0 to 2.0 times.

The reaction time is in each case several minutes to several days.

When a compound in which R in compound (IV) is a hydroxyl group is used, the reaction is usually carried out using an excess of compound (V) in a solvent or without solvent. In this case, the amount of compound (IV) to be used is generally 1.0 to 100-fold mol, preferably 1.0 to 10-fold mol, relative to compound (V). The reaction temperature is generally 0-250, preferably 0-180. In addition, when dehydration such as carposimid is used, the above high temperature is not required. The reaction temperature is usually 0 to 120, preferably 0 to 80, in the presence of a solvent. The amount of compound (IV) to be used is generally 1.0 to 20 moles, preferably 1.0 to 20 moles, relative to compound (V). In any case, if the reaction temperature exceeds 381: (boiling point of compound (V)), it is desirable to seal the reaction vessel. The reaction time is several minutes to several days even in the case of misalignment.

Next, a method for producing compound (IV) will be described. First, as a method for producing compound (IV-a) (a compound in which R is a halogen atom in compound (IV)), the corresponding carboxylic acid compound (IV-b) (compound (IV ), A method in which R is halogenated to form a hydroxyl group ^}). These are shown by the following reaction formulas. Reaction formula (I)

(Where X, W, and n are the same as described above.)

The reaction conditions are the same as in the above-mentioned method for producing the compound (IV-a) by halogenation of the corresponding carboxylic acid compound (IV-b).

Further, the compound (IV-b) used in the above-mentioned production step can be produced by hydrolysis of the compound (XI). These are shown in the following reaction formulas. Reaction formula (J)

(In the formula, Y represents a cyano group or a lower alkoxycarbonyl group, and X and η are the same as described above.)

The above hydrolysis can be performed under any of acidic and basic conditions. When hydrolysis is performed under acidic conditions, an inorganic acid such as hydrochloric acid, hydrobromic acid, or sulfuric acid is usually used as a catalyst. As a solvent, an organic solution such as acetic acid is usually used in addition to water. When the hydrolysis is carried out under basic conditions, an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the base. As a solvent, an aqueous alcohol solution is usually used in addition to water. The hydrolysis temperature is usually in the range from 20 to the reflux point, preferably in the range from 50 ° C to the reflux point. The reaction time is several minutes to several hours.

Compound (XI), which is the starting material for this reaction, can be produced by subjecting compound (XII) to a phenoxylation reaction with compound (III). The reaction conditions are the same as in the method for producing compound (I) by funinoxylation of compound (II) in the second aspect of the present invention. It is. These are represented by the following reaction formulas. The reaction formula (K)

(Where Y, X, and η are the same as described above.)

Compound (XII) means compound (IX) and compound (X). The reaction temperature and reaction time described in each of the above-described reaction steps are all within the range that does not adversely affect the yield because of the necessity of the reaction operation. The time can be long. This compound (I) can be used as it is as a herbicide. Generally, it is used in the form of powders, wettable powders, granules, emulsions, etc. together with formulation auxiliaries. In this case, one or more of the present compounds (I) are usually contained in the drug product. 0.1 to 95 wt%, preferably from 0.5 to 90 wt%, more preferably 2 to 70 weight ^_0/0 containing organic. Carriers used as formulation aids, diluents, and surfactants, for example, solid carriers usually include talc, kaolin, bentonite, diatomaceous earth, white carbon, clay, and the like. Examples of the liquid diluent include water, xylene, toluene, benzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, and alcohol. Surfactants can be used depending on their effects. Examples of the emulsifier usually include polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan monolaurate and the like. Examples of the dispersant usually include lignin sulfonate and dibutyl naphthalene sulfonate. Examples of the wetting agent generally include an alkyl sulfonate and an alkylphenyl sulfonate.

Some of the above preparations are used as they are, and others are used after being diluted to a predetermined concentration with a diluent such as water. When used diluted, the concentration of this compound (I) is usually in the range of 0.001 to 1.0%. The amount of the present compound (I) to be used is usually 0.001 to 10 kg, preferably 0.01 to 5 kg per lha. The concentration and amount used of these may vary depending on the dosage form, the timing of use, the method of use, the place of use, the target crop, and the like, and it is, of course, possible to increase or decrease without being limited to the above range. Further, the present compound (I) can be used in combination with other active ingredients such as fungicides, insecticides, acaricides, herbicides and the like. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the ability to specifically explain the present invention by way of examples The present invention is not limited to the following examples unless it goes beyond the gist. Production Example 1 [Reaction formula (D), reaction formula (C), and reaction formula (A) were combined in this order. Manufacturing example by process]

Synthesis of N- (2,2,2-Trifluoroethyl) -14-Methoxy-16- (3-cyanophenoxy) -12-pyridinecarboxamide (Compound 1-1)

(1) Synthesis of an intermediate, N- (2,2,2-trifluoroethyl) -14-methoxy-6-chloro-1--2-pyridinecarboxamide (compound ΙΙ: Τ "<: ΐ) 〉

4-Methoxy-1-6-picolinic acid (2.5 g, 0.0133 mol) was added to thionyl chloride (3.17 g, 0.0133 X 2.0 mol) and benzene (about 30 ml), and a small amount of dimethylformamide was added. After that, the mixture was refluxed for about 1 hour. After concentrating the reaction mixture, dissolve it in dichloromethane (about 50 ml) and add 2,2,2-Trifluoroethylamine

(1.58 g, 0.0133 x 1.2 mol) and triethylamine (3.37 g, 0.0133 x 2.5 mol). After stirring at room temperature for about 1 hour, the reaction solution was concentrated, dissolved in ethyl acetate, and partitioned between ethyl acetate and saturated aqueous sodium hydrogen carbonate. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated to give the desired product. Yield 3.26 g Yield 91% Solid m.p. 96-98

H-NMR (250MHz, CDC, δ):

3.93 (3H, s), 4.09 (2H, dd, J = 6.8, 9.3 Hz), 6.98 (lH, d, J = 2.3 Hz), 7.68 (lH, d, J = 2.3 Hz), 8.0-8.3 (lH , M).

(2) <Synthesis of N— (2,2,2-trifluoroethyl) -14-methoxy-6— (3—cyanophenoxy) -12-pyridinecarboxamide (compound 1-1)> N— (2 , 2,2-Trifluoroethyl) 1-4-Methoxy-6-chloro-2-pyridincarboxamide (4.5g, 0.0168mol) and 3-cyanophenol

(2.60 g, 0.0168 X 1.3 mol) was dissolved in dimethylformamide (about 50 ml), and sodium hydride (0.80 g, 60% in mineral oil, 0.0168 X 1.2 mol) was added. Further, cuprous chloride (CuCl) (0.25 g, 0.0168 X0.15 mol) was added, and the mixture was stirred at about 110 to 120 for about 5.5 hours. The reaction solution was partitioned with ethyl acetate-saturated aqueous sodium hydrogen carbonate, and the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated. After purification by silica gel column chromatography (eluent: ethyl acetate Zn-hexane), n-hexane was added to a mixed solution of ethyl acetate and getyl ether, followed by reprecipitation to obtain the desired product.

Yield 4.0g Yield 68% Solid m.p.131-132

_{'Η- NMR (60MHz, CDC1 3} , o):

3.87 (3H, s), 3.92 (2H, dq, J = 6,9Hz), 6.52 (lH, d, J = 2Hz), 7.0-7.9 (6H, m). Production Example 2 [According to the reaction formula (A) Manufacturing example]

Synthesis of N- (2,2,2-trifluoroethyl) -14-methoxy-16- (4-chloro-1-3-cyanophenoxy) -12-pyridinecarboxamide (Compound 1-2)

N- (2,2,2-Trifluoroethyl) 1-4-Methoxy-6-Chloro-l-Pyridine-Irboxamide (0.40g, 0.00149mol) and 4-Chloro-l-cyanophenol (0.25 g, 0.00149 X l.lmol) and cuprous chloride (0.022 g, 0.00149 X0.15 mol) were dissolved in dimethylformamide (about 5 ml), and sodium hydride (0.062 g, 60% in mine-ral oil, 0.00149 X 1.04 mol) was added. Then, the mixture was stirred for about 3 hours at about 110 to 20 L; the reaction solution was partitioned between ethyl acetate and saturated aqueous sodium bicarbonate. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated. The residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane) and reprecipitated with getyl ether / hexane to obtain the desired product. Yield 0.20g Yield 35% Solid m.p.i n- 113

_{1 HN R (60MHz, CDC1 3} , o):

3.88 (3H, s), 3.94 (2H, dQ, J = 6,9Hz), 6.53 (lH, d, J = 2Hz), 6.9-7.8 (5H, m). Production Example 3 [According to reaction formula (A) Manufacturing example]

N— (2,2,2—Trifluoroethyl) 1-4—Methoxy 6— (3—Shear Synthesis of 4- (4-methylphenoxy) -12-pyridinecarboxamide (Compound 1-10)

N— (2,2,2—Trifluoroethyl) 1-4-Methoxy-16-Chloro-21-pyridine diboxamide (0.50 g, 0.00186 mol) and 3-Cyanol 4-methylphenol (0.30 g, 0.00186 X 1.2 mol) ) And cuprous chloride (0.025 g, 0.00186 X 0.14 mol) are dissolved in dimethylformamide (about 5 ml), and sodium hydride (0.090 g, 60% in mine-ral oil, 0.00186 X 1.2 mol) is added. did. Then, the mixture was stirred at about 110 to 120 for about 4 hours, the reaction solution was partitioned with ethyl acetate-water, and the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and concentrated. After purification by silica gel column chromatography (eluent: ethyl acetate Zn-hexane), the product was reprecipitated with diethyl ether Z hexane to obtain the desired product.

Yield 0.34g Yield 50% Solid m.p.145-146

'H-NMR (60MHz, CDC1 3, δ):

2.52 (3H, s), 3.88 (3H, s), 3.93 (2H, dQj = 6,9Hz), 6.52 (lH, dJ = 2Hz), 6.7_8.0 (4H, m), 7.50 (lH, d, J = 2Hz). Production example 4 [Production example using reaction formula (B)]

Synthesis of N- (2,2,2-tritrifluoroethyl) 1-4-methoxy-16- (3-cyano 4-methylphenoxy) -12-pyridinecarboxamide (Compound 1-10)

4-Methoxy 6- (3-cyano-1-methylphenoxy) To picolinic acid (0.40 g, 0.0014 mol), add thionyl chloride (0.33 g, 0.0014 X 2.0 mol), benzene (about 10 ml), and add a small amount After addition of dimethylformamide, the mixture was refluxed for about 2 hours. The reaction solution was concentrated and dissolved in dichloromethane. 2,2,2-Trifluoroethylamine (0.21 g, 0.0014 X 1.5 mol) was added, and triethylamine (0.28 g, 0.0014 X 2 mol) was further added. After stirring for about 2 hours at room temperature, the reaction mixture was concentrated. The solution was dissolved in ethyl acetate and partitioned with ethyl acetate-water. The organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated. This was purified by silica gel column chromatography (eluent: ethyl acetate Zn-hexane) to obtain the desired product.

Yield 0.43 g Yield 84% Solid mp145-146 Example 1 [In the following steps, (4) is a production example by S formula (G)]: 4-Methoxy-16-clopicpicolinic acid (Compound VI- txT ^ Cl)

(1) Synthesis of ku intermediate, 2-chloropyridine 4-nitropyridine N-oxide>

To sulfuric acid (64.0 g, 0.102 X 6.4 mol) and fuming nitric acid (36.0 g, 0.102 X 5.3 mol) are added to 2 _ black mouth pyridine N-oxide hydrochloride (17.0 g, 0.102 mol), and Stirred for 2.5 hours. The reaction mixture was added to 800 ml of ice water, and the precipitate was filtered off, washed with water and dried. The aqueous layer was extracted with ethyl acetate, and the extract was recrystallized with ethyl acetate and n-hexane to obtain the desired product.

Yield 14.4g Yield 82.5% Solid m.p.151-153

1 H-NMR (60MHz, CDC1 3, δ):

7.7-8.2 (lH, mult.), 8.2-8.6 (2H, complex)

(2) Synthesis of an intermediate, 2-chloro-1-N-methoxide pyridine 2-synthetic oxide> 2 _cyclopent-4 nitropyridine N-oxide (13.4 g, 0.077 mol) is suspended in 100 ml of methanol. Then, sodium methoxide (14.8 g (Ca. 28% methanol solution), 0.077 X 1.0 mol) was added dropwise, and the mixture was stirred and dissolved at room temperature, and further stirred for 2 days. Methanol was distilled off from the reaction solution under reduced pressure, the solution was dissolved in ethyl acetate, sodium nitrite was filtered off, and then ethyl acetate was distilled off to obtain the desired product.

Yield 12.lg Yield 94% Solid Decomposition point about 90

'H-NMR (60MHz, CDC1 3, 3):

3.80 (3H, s), 6.75 (lH, dd, J = 3.5Hz, 7.5Hz), 6.99 (lH, d, J = 3.5Hz), 8.21 (lH, d, J = 7.5Hz).

(3) Synthesis of the intermediate, 2-chloro-6-cyano-4-methoxypyridine> 2-chloro-4-N-methoxypyridine N-methoxide (ll.lg, 0.070 mol) (8.3 g, 0.072 x imol) was added dropwise. After the mixture was stirred at room temperature to become uniform, the mixture was further stirred overnight. After decanting and washing with Jettlether, it was dissolved in 70 ml of water. Under a nitrogen atmosphere, sodium cyanide (8.3 g, 0.072 × 4 mol) dissolved in 70 ml of water was added dropwise at 10 over about 1 hour. After stirring for 2 hours, the precipitate was separated by filtration and washed with water. The precipitate washed with water was dissolved in ethyl acetate, n-hexane was added, the mixture was treated with silica gel, and the solvent was distilled off to obtain the desired product.

Yield 6.6g Yield 52% Solid m.p.94-96

_{'Η-ΝΜΚίβΟΜΗζ, CDC1 3,} δ):

3.86 (3H, s), 6.94 (lH, d, J = 2Hz), 7.2 (lH, d _I J = 2Hz).

(4) <Synthesis of 4-Methoxy-16-clopicicolinic acid (Compound No. VI-b: T '= C1)>

2-Chloro-6-cyan-4-methoxypyridine (10.0 g, 0.0593 mol) was suspended in about 70 ml of concentrated hydrochloric acid, and stirred at about 100 for about 3 hours. After allowing to cool, water was added to the reaction solution, which was partitioned with ethyl acetate-water. After washing with a saturated saline solution, the extract was dried over anhydrous sodium sulfate, concentrated, and purified by a silica gel column to obtain the desired product. Yield 10.6g Yield 95% Solid m.p.l73-175t:

1 H-NMR (250 MHz, CDCl ₃ + DMSO-d ₆ , o):

3.93 (3H, s), 4.5-6.5 (lH, br), 7.01 (lH, d, J = 2.4Hz), 7.63 (lH, d, J = 2.4Hz). Reference Production Example 2 [Reaction formula (K) Reference production example based on the steps combined in the order of Reaction formula (J)]:

Synthesis of 4-Methoxy 6- (3-cyano 4-methylphenoxy) picolinic acid (1) <Intermediate, 2- Shiano one 4-menu butoxy one 6- (3-Shiano one 4-methyl Fuwenokishi) pyridine (Compound No. _{IX: X = 4 - CH 3} , Y = CN, n = l) of Synthesis)

2-Chloro-6-cyano 4 -Methoxypyridine (1.50 g, 0.0089 mol), 3-cyano-4-methylphenol (1.37 g, 0.0089 X 1.16 mol) and cuprous chloride (0.093 g, 0.0089 XO.lmol) Was dissolved in dimethylformamide (about 10 ml), and sodium hydride (0.41 g, 60% in mine-ral oil, 0.0089 X 1.15 mol) was added. After stirring at about 110 to 120 for about 9 hours, the reaction solution was partitioned with ethyl acetate / water, and the organic layer was washed with brine, dried over anhydrous sodium sulfate, and concentrated. The desired product was obtained after purification by silica gel column chromatography (eluent: ethyl acetate Zn-hexane).

Yield 0.80 g Yield 34% Solid m.p.l80-181t:

_{1H-NMR (250MHz, CDC1 3} , δ):

2.57 (3H, s), 3.93 (3H, s), 6.60 (lH, d, J = 2.4 Hz), 7.02 (lH, d, J = 2 Hz), 7.2-7.4 (3 mm, m).

(2) Synthesis of 4-Methoxy-6- (3-cyano-4-methylphenoxy) picolinic acid (Compound IV: ROH)>

2_cyan-4-methoxy-6- (3-cyan-4-methylphenoxy) pyridine (0.70 g, 0.0026 mol) was suspended in about 20 ml of concentrated hydrochloric acid, and stirred at about 100 for about 3 hours. After cooling, water was added to the reaction solution, and the mixture was partitioned with ethyl acetate / water. After washing with saturated water, the extract was dried over anhydrous sodium sulfate and concentrated to obtain the desired product. Yield 0.72g Yield 96% Solid m.p.164-166

'H-NMR (250MHz, CDC1 3, o):

2.59 (3H, s), 3.96 (3H, s), 6.64 (lH, dJ = 2Hz), 7.2-7.5 (4H, m), 7.53 (lH, d, J = 2Hz). Reference Production Example 3:

Synthesis of 4-chloro-3-cyanophenol (1) <Synthesis of intermediate, 2-chloro-5-hydroxybenzoic acid>

3-Amino-6-chlorobenzoic acid (4.6 g, 0.027 mol) is suspended in a mixed solvent of 30 ml of concentrated sulfuric acid and 20 ml of acetic acid, and sodium nitrite (2.07 g, 0.027 X l. Lmol) is added. The mixture was stirred at room temperature. Thereafter, about 200 ml of water was added, and the mixture was stirred for about 2 hours at about 100 t. After partitioning with ethyl acetate / water, the mixture was washed with saturated saline. After drying over anhydrous sodium sulfate, concentrating and silica gel column chromatography

(Eluent: ethyl acetate Zn-hexane) to obtain the desired product.

Yield 3.59 g Yield 78% Solid m.p. 170-172

1 H-NMR (60 MHz, CDCl ₃ + DMSO-d _6> o):

6.82 (lH, dd, J = 3, 9Hz), 7.15 (lH, d, J = 9Hz), 7.20 (lH, d, J = 3Hz), 9.9-11.3 (2H, br)

(2) 4-Synthesis of Cyanophanol 3->

2-Black mouth-5-Hydroxybenzoic acid (2.0 g, 0.0116 mol), thionyl chloride (4.12 g, 0.0116 x 3 mol) and about 30 ml of benzene are added, and a small amount of dimethylformamide is added. Refluxed for hours. After concentrating the reaction solution, the reaction solution was dissolved in dichloromethane, 20 ml of 29% aqueous ammonia was added, and the mixture was stirred at room temperature for about 2 hours. The reaction solution was partitioned between ethyl acetate and water, and then washed with saturated saline. After drying over anhydrous sodium sulfate, the mixture was concentrated to obtain crude 2-chloro-5-hydroxybenzoic acid amide.

To this was added thionyl chloride (15 ml, 0.0116 × 29 mol), and the mixture was refluxed for about 4 hours. After the reaction solution was concentrated, it was partitioned with ethyl acetate-water. After washing with saturated saline, drying over anhydrous sodium sulfate, iHil, silica gel column chromatography

(Eluent: ethyl acetate Zn-hexane) to obtain the desired product.

Yield 0.52g Yield 32% Solid m.p.164-166

1 H-NMR (60 MHz, CDCl ₃ , o):

6.7- 7.7 (3H, m), 9.67 (lH, s). Reference Production Example 4:

4 Synthesis of monomethyl_3_cyanophenol

(1) Synthesis of ku intermediate, 5-amino-2-methylbenzonitrile>

40 ml of methanol and 30 ml of concentrated hydrochloric acid were added to 5-nitro-2-methylbenzonitrile (10.0 g, 0.0617 mol), iron powder (10.45 g, 0.0617 × 3 mol) was added, and the mixture was stirred at room temperature for about 1 hour. The mixture was poured into about 500 ml of water, and the precipitate was filtered. The precipitate collected by filtration was extracted with ethyl acetate, partitioned with water, and washed with brine. After drying over anhydrous sodium sulfate, the mixture was concentrated to obtain a crude target product of solid ^ K.

Yield 5.0g Yield 61%

(2) <Synthesis of 4-methyl-13-cyanophenol>

To 5-amino-1,2-methylbenzonitrile (4.5 g, 0.034 mol), add 35 ml of acetic acid and concentrated hydrochloric acid (7.2 g, 0.034 X2 mol), and cool in an ice-cooled bath. Dissolved sodium nitrite (2.45 g, 0.034 X lmol) was added, and the mixture was stirred for about 15 minutes except for the ice-cooled bath. Thereafter, about 100 ml of a 50% aqueous sulfuric acid solution was added, and the mixture was stirred at about 100 for about 1 hour. The reaction mixture was partitioned between ethyl acetate-water and washed with saturated saline. After drying over anhydrous sodium sulfate and concentration, the desired product was obtained.

Yield 2.78 g Yield 61% Solid m.p.99-101t:

1 H-NMR (60 MHz, CDCl ₃ , δ):

2.71 (3H, s), 6.43 (lH, s), 6.7-7.3 (3H, m). Next, formulation examples and test examples are shown. Can be changed in a wide range. "Parts" in each of the preparation examples indicates parts by weight. Formulation Example 1 (Wettable powder):

Compound (1-1) 50 parts Sodium lignin sulfonate 5 parts Sodium alkyl sulfonate 3 parts Diatomaceous earth 42 2 parts are mixed and pulverized, used as a wettable powder, and diluted with water. Formulation Example 2 (emulsion):

Compound (1-2) 25 parts Xylene 65 parts Polyoxyethylene alkylaryl ether 10 parts are uniformly mixed to prepare an emulsion, which is diluted with water before use. Formulation Example 3 (granules):

Compound (1-1) 8 parts Bentonite 40 parts Clay 45 5 parts Calcium ligninsulfonate 7 parts are uniformly mixed, further added with water, kneaded, and granulated by an extrusion granulator. Used as an agent. Test Example 1 (Test for herbicidal effect by foliage and soil treatment)

(1) <Preparation of plants used for testing>

A pot filled with horticultural soil (Kureha Chemical Co., Ltd .; same hereafter) is seeded with yamgra, Frasavaso ゥ, Hakobe, and violet. It was cultivated in ~ 10).

(2) Preparation and application of test solution>

The test compound is dissolved or suspended in acetone, and then Tween20 (manufactured by Wako Pure Chemical Industries, Ltd.) and water are added. The concentrations of acetone and Tween20 are 10% (v / v) and 0.5% (v / v, respectively). ) Was prepared. Here, the concentration of the test compound was adjusted so as to have a predetermined amount when sprayed at a ratio of the spraying liquid strength ^ OOLZlha. This was evenly sprayed on the plant prepared in (1) with a sprayer.

(3) <Evaluation of herbicidal activity of test compound>

Plants sprayed with the test solution were cultivated again in an artificial weather vessel (at 5 to 10), and after 34 days, the herbicidal rate of the sprayed plots relative to the non-sprayed plots was evaluated by optimism. This was classified according to the following criteria, and shown in Table 2 as the herbicidal activity of the test compound. Survey criteria 1: Herbicidal rate is less than 30%

2: Herbicidal rate is 30% or more and less than 60%

3: Herbicidal rate is 60% or more and less than 80%

4: Herbicidal rate is 80% or more and less than 90%

5: Herbicidal rate is 90% or more

Table 2

a): Compound (I-11), compound (I-12) and compound (I_10) correspond to the compounds described in Table 1, respectively, and the controls (A) to (D) correspond to the description 2 3 means compounds (A) to (D).

b): SM: Hakobe

VA: Violet

GA: Yaegura

VH: Frasavaso II Industrial applicability

According to the present invention described above, .N— (2,2,2-trifluoroethyl) 1-4-methoxy 6 — [(substituted or unsubstituted) metacyanophenoxy] —2 monopyridinecarboxamide is Since it is a new compound and exhibits high herbicidal properties, it is useful as an active ingredient of a herbicide.

Claims

The scope of the claims

1. N— (2,2,2-trifluoroethyl) —4—methoxy-1 6 — [(substituted or unsubstituted) metacyanphenoxy] represented by the following general formula (I) —2 -Pyridinecarboxamide derivatives.

(In the formula, X represents a C ₄ alkyl group or a halogen atom. N represents an integer of 0 to _4. )

2. N- (2,2,2-trifluoroethyl) —4—methoxy 6 —halogeno 2 —pyridine represented by the following general formula (II) and pyridine-boxyl derivatives represented by the formula (III) N- (2,2,2-trifluoroethyl) represented by the formula (I), characterized by reacting with (substituted or unsubstituted) metacyanphenol. — [(Substituted or unsubstituted) metacyanoxy] —2 Method for producing monopyridinecarboxamide derivatives.

(Wherein, x is c ₄ alkyl group, a halogen atom. Tau ¹ is a halogen atom. N is an integer of 0-4.)

3. 4-Methoxy-6-[(substituted or unsubstituted) methacyanophenoxy-1-pyridinecarboxylic acid derivative represented by the following general formula (IV) and 2,2-methoxypyridine derivative represented by the following formula (V): N— (2,2,2-Trifluoroethyl) — 4—Methoxy 6 represented by the formula (I) characterized by reacting with 2,2-trifluoroethylamine — [(Substituted or unsubstituted) metacyanophenoxy] —2-pyridine lipoxamide derivatives.

(In the formula, X represents C,-(: ₄ alkyl group, halogen atom. R represents a leaving group (halogen atom, lower alkoxy group, hydroxyl group). N represents an integer of 0-4.)

4. N _ (2,2,2-Trifluoroethyl) 1-4 —Methoxy-6— [(substituted or unsubstituted) metacyanophenoxy] —2— represented by formula (I) A herbicide comprising a pyridincarboxamide derivative as an active ingredient.

(Where X and n are the same as above.)