WO2001000580A1 - 2-(optionally substituted benzoylamino)-6-(optionally substituted phenoxy)pyridine derivatives, process for the preparation thereof and herbicides - Google Patents

Abstract

2-Benzoylamino-6-phenoxypyridine derivatives of general formula (I); a process for the preparation thereof; and herbicides containing the derivatives as the active ingredient.

Description

 2 — (unsubstituted or substituted) benzoylamino-6— (unsubstituted or substituted) fuunoxypyridine derivative, its production method and herbicide

Technical field

 The present invention relates to 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or

Is substituted) phenoxypyridine derivative, its production method and its derivative

And herbicides.

Background art

 Certain types of 6- (unsubstituted or substituted) phenoxypicolinic acids are disclosed in Japanese Patent Application Laid-Open Nos. Hei 1991-1985, Hei 4-2-17959, and International Publication WO98. / 29391 publication. However, the 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative of the present invention is not described in the literature and is a novel compound.

 Conventionally, herbicides that can reduce the abundance in the environment, show low herbicidal efficacy at low doses, herbicides that show selectivity between crops and weeds regardless of changes in environmental conditions, after double cropping There is a need to provide herbicides that do not cause harm to crops.

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, and as a result, it is a novel compound which is not described in the above literature. The inventors have found that a 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative has high herbicidal properties, and have completed the present invention.

 A first gist of the present invention resides in a 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the general formula (I).

(Wherein, X is a halogen atom, C ^ ^ alkyl group, mouth alkyl group, (:.) ~ Alkoxy, C ₄ haloalkoxy group, (^ ~ <3 ₄ alkyl Chiomoto, C i to Ji ₄ haloalkylthio group, a nitro group, a Shiano group, m. Y is a halogen atom represents an integer of 0 - 5, C! CA alkyl group, (~ Jiヽport alkyl groups, C] -C ₄ alkoxy group, CCA haloalkoxy group, Ci～C ₄ alkylthio groups, C ~ Ji, Roarukiruchio group, ^ C ^ alkylamino groups, C] - (- ₄ dialkylamino group, a nitro group, a Shiano group, n represents an integer of 0 to 3 are shown. Z represents a halogen atom, C! C ^ alkyl group, CC ^ a Haroaruki Le group, Ci～C ₄ alkoxy groups, _C} ~ ₍₄ C port alkoxy group, a nitro group, a Xia amino group, p is Represents an integer of 0 to 5. When m, n, and p are 2 or more, X, Y, and Ζ are the same or different. And it may be.)

A second gist of the present invention is to provide a 2-amino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the general formula (Π) as represented by the following reaction formula: 2- (unsubstituted or substituted) benzol represented by the general formula (I) characterized by reacting with (unsubstituted or substituted) benzoyl halide represented by (III) Ylamino-6- (unsubstituted or substituted) phenoxypyridine derivative.

(In the formula, X is a halogen atom, cc ^ alkyl group, c:!!] - ₍₄ cutting edge alkyl group, C C alkoxy group, C ₄ cutting edge alkoxy group, Ji-Ji alkyl Chiomoto, C丄～〇 ₄ haloalkylthio group, a nitro group, a Shiano group, m is an integer of 0 - 5. Y is a halogen atom, C] -C ₄ alkyl group, (^ - (ヽport alkyl group,

Alkylthio, C to, loalkylthio, C to ( ₄ alkylamino, C to ₄ dialkylamino, nitro, and cyano; n is an integer of 0 to 3; Z is a halogen atom; C ^ C ^ alkyl group, (^ - (^ haloalkyl group, (^ ~ Ji ₄ alkoxy groups, C I～C ₄ Ha port alkoxy group, a nitro group, a Shiano group, p is an integer of 0-5 When m, n, and p are 2 or more, X, Y, and よ い may be the same or different from each other, and W represents a halogen atom.) A third gist of the present invention is that of general formula (I) 2 — (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative Herbicide characterized by containing as an active ingredient.

(Where X, Y, Z, W, m, n and p are the same as described above.) Hereinafter, the present invention will be described in detail.

 First, 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the above general formula (I) of the present invention [hereinafter abbreviated as the present compound (I)]. ] Will be described. .

 The definition of each symbol (X, Y, Z, W, m, n and p) of the present compound (I) and the contents specifically included are described.

Halogen atom for X, chlorine atom, bromine atom, fluorine atom, the -C ₄ alkyl group, a methyl group, Echiru group, (! ~ Ji, as the mouth alkyl group, triflate Ruo b methyl group, C to ( ₄ alkoxy groups include methoxy groups and ethoxy groups, etc .; C to C ₄ halo alkoxy groups include difluoromethoxy groups and trifluoromethoxy groups; C! To ₄ alkylthio groups; main Chiruchio group, etc. Echiruchio group, the C ～〇 ₄ haloalkylthio group, etc. Application Benefits full O b methyl thio group, further, a nitro group, Shiano group ^forces? like.

 More preferable X in the above definition includes a halogen atom (a chlorine atom and a bromine atom), a methyl group, a difluoromethyoxy group, a trifluoromethyl group, a trifluoromethoxy group and the like, and among them, a trifluoromethyl group is particularly preferable. preferable.

The range of m is usually from 1 to 5, and more preferably from 1 to 2. Among them, those having a substituent at Fuwenokishi ring 3-position with m = 1 the force ⁵ 'particularly preferred.

Next, Y will be described. Examples of the halogen atom in Y include a chlorine atom, a bromine atom, a fluorine atom, and the like.

The C! C ^ alkyl group, a methyl group, Echiru group, (~. ^, As the Roaruki group, triflate Ruo b methyl group, C丄-c ₄ The alkoxy group main butoxy group, an ethoxy group, etc. as the C i to ₍₄ C port alkoxy group, Torifuruo Lome butoxy group, etc., as the Ci～ c ₄ alkylthio group, a methylthio group, Echiru Chio group, C i to (: as ₄ haloalkylthio group, Torifuruo C- (: ₄ alkylamino groups include methylamino group, ethylamino group, etc .; di (c ^ c ^ alkyl) amino groups include dimethylamino group, ethylmethylamino group, etc., and nitro group, cyano group, etc. Power.

 More preferable Y in the above definition includes a chlorine atom, a methyl group, a methoxy group, a methylthio group, a dimethylamino group, a methylamino group and the like, and among them, the methoxy group S is particularly preferable.

 The range of η is usually from 0 to 3, and more preferably from 0 to 1. Among them, those having a substituent at the 4-position on the pyridine ring are particularly preferred.

The halogen atom in Ζ is a chlorine atom, a bromine atom, a fluorine atom, etc., the C alkyl group is a methyl group, an ethyl group, etc. (: ：-丄, the loalkyl group is a trifluoromethyl group, etc. Examples of the i-C ₄ alkoxy group include a methoxy group and an ethoxy group, and the like, and examples of the C 丄-(: _4- halo alkoxy group include a trifluoromethoxy group and the like, and further, a nitro group and a cyano group.

 More preferable Z in the above definition includes a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a trifluoromethyl group, a methoxy group and the like. Halogen atoms such as chlorine atom, fluorine atom and bromine atom are particularly preferred.

 The range of p is usually from 0 to 5, and more preferably from 0 to 2.

In preferred combinations of the substituents (X, Y, Ζ) and the integers of m, n, and p, the compounds of the following Tables 1 to 3 can be exemplified as the present compound (I). table 1

o / s o -lud fcv

糊

CO

Three

a): Hyphen (1) means unsubstituted (m = 0). X represents a substituent on the phenoxy ring. When a substituent is present on the fuoxy ring, the number preceding the substituent indicates the bonding position. For example, 3-CF ₃ in compound (1-1) indicates that CF ₃ is bonded to the _third carbon atom on the phenoxy ring.

b): Hyphen (1) means unsubstituted (n = 0). Y represents a substituent on the pyridine ring. When the pyridine ring has a substituent, the number before the substituent indicates the bonding position. For example, 4-〇CH ₃ in compound number (1-4) indicates that 〇CH ₃ is bonded to the carbon atom at the 4-position on the pyridin ring.

c): A hyphen (1) means unsubstituted (p = 0). Z represents a substituent on the benzoyl ring. When the benzoyl ring has a substituent, the number preceding the substituent indicates the bonding position. For example, 2,4-Cl ₂ in compound (1-17) indicates that the chlorine atom is bonded to the carbon atom at the 2- and 4-positions on the benzoyl ring. Next, a method for producing the compound (I) of the present invention will be described. As the solvent used, usually, aromatic hydrocarbons such as benzene, toluene, xylene, and methylnaphthalene, aliphatic hydrocarbons such as petroleum ether, pentane, hexane, heptane, methylcyclohexane, methylene chloride, and chloroform Halogenated hydrocarbons such as oral form, carbon tetrachloride, and chlorobenzene, amides such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, getyl ether, dimethyloxetane, diisopropyl ether, Ethers such as tetrahydrofuran, diglyme, and dioxane; and alcohols such as methanol and ethanol.

Other solvents used include water, carbon disulfide, acetonitrile, ethyl acetate, pyridine, dimethyl sulfoxide, hexamethylphosphoramide, and the like. These solvents may be used as a mixture of two or more kinds. The individual reaction steps of the process according to the invention are advantageously carried out in a solvent or a mixture of solvents. Further, a solvent composition composed of solvents that do not form a uniform layer with each other can also be used. In this case, a phase transfer catalyst to the reaction system, for example, the ^force? Is suitable to add a fourth ammonium two © beam salts or Kuraun'eteru customary.

 This compound (I) is obtained by converting a 2-amino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the following general formula (II) into a compound represented by the following general formula (III) (unsubstituted or substituted). Substitution) Obtained by reacting with benzoyl chloride. This is represented by the following reaction formula.

(Where X, Y, Z, W, m, n and p are the same as described above).

 The reaction is usually carried out by mixing compound (Π) and compound (ΙΠ) in a solvent. It is very effective to use the following bases as catalysts. The amount of compound (III) to be used is generally 0.5 to 5 moles, preferably 0.8 to 1.5 moles, relative to compound (II). The reaction temperature is usually 0 to 200 ° C, preferably 10 to 150 ° C. The reaction time is a few minutes to a few days.

In the above reaction, tertiary amines, dialkylamido Organic bases of noanilines and pyridines, for example, triethylamine, N, Ν,, ′, N′-tetramethylethylenediamine (TMEDA), Ν, Ν-dimethylaniline, Ν, ジ ェ -jetylaniline, pyridine , 4-dimethylaminopyridine

(DMAP), etc., inorganic bases such as alkali metal and alkaline earth metal hydroxides, carbonates and bicarbonates, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, water Examples thereof include sodium oxide, potassium hydroxide, and calcium hydroxide.

 As the compound (ΠΙ), a commercially available carboxylic acid halide can be used. Carboxylic acid halides are derived, for example, by deriving (unsubstituted or substituted) benzoic acid compounds from carboxylic acids using halogenating reagents such as thionyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, and phosphoryl bromide. Compounds that can be manufactured using existing technologies, such as the above, can be used.

Compound (Π) can be produced by the following method. That is, the compound represented by the general formula (II) is easily converted to a compound represented by the general formula (II) by subjecting the compound represented by the general formula (V) to Lossen rearrangement in the presence of a base and subjecting the resulting isocyanate compound (IV) to water addition and decarboxylation. Can be obtained. These are shown by the following reaction formulas.

l_oss6n transition

 Water addition and decarbonation

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

 The production method for obtaining the compound (Π) is shown below. First, the reaction for obtaining compound (IV) will be described. The reaction is usually carried out by mixing compound (V) in an organic solvent and using a base as a catalyst. The amount of the base to be used is generally 1 to 2 moles, preferably 1 to 1.5 moles, per 1 mole of Compound (V). The reaction temperature is 0 to 200 ° C, preferably 10 to 150 ° C. The reaction time is several minutes to several days.

In the above, examples of the base used include hydrides, hydroxides, carbonates and bicarbonates of alkali metals and alkaline earth metals, such as sodium hydride, Examples thereof include lithium hydride, sodium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, and potassium carbonate. Particularly preferred bases are sodium hydride and potassium carbonate. Next, a production method for obtaining the compound (II) by adding water and decarboxylating the compound (IV) will be described below. First, the reaction is usually performed in a mixed solvent obtained by mixing water with the reaction solution used in the reaction for obtaining the compound (IV) without isolating the compound (IV). These do not have to form a uniform layer with each other. The reaction can proceed sufficiently without adding a catalyst, and of course, an acid or a base may be added as a catalyst. When an acid is added as a catalyst, an inorganic acid such as hydrochloric acid, hydrobromic acid or sulfuric acid is usually used as the catalyst. When adding basicity as a catalyst, an alkali metal base such as sodium hydroxide or potassium hydroxide is usually used as the catalyst.

 The hydrolysis temperature is usually in the range of 0 to the reflux point. The reaction time is several minutes to several hours.

 Next, a method for producing the compound (V) will be described.

The compound of the formula (V) can be easily obtained by mixing the compound of the formula (VI) with hydroxyamine. These are represented by the following reaction formulas.

HO '

(In the formula, X, Y, m, and n are the same as described above. W ¹ represents a halogen atom or a CC ^ lower alkoxy group.)

The reaction is usually carried out in an organic solvent, and the compound (VI) is treated with hydroxylamine (when a compound in the form of a salt such as hydrochloride is used as the source of hydroxylamine, an equivalent amount or more of a base such as triethylamine is added to free And then use hydroxylamine). When W ¹ is a halogen atom, hydrogen halide is generated in the course of the reaction. Therefore, it is preferable to add a base such as triethylamine in excess of one equivalent or more for the purpose of capturing the hydrogen halide. The amount of hydroxyamine to be used is generally equimolar to 10-fold molar, preferably equimolar to 3-fold molar, relative to compound (V). The amount of the base used is equimolar to 10-fold molar, preferably equimolar to 3-fold molar. The reaction temperature is 0 to 200 ° C, preferably 10 to 150 ° C. The reaction time is several minutes to several days. In the above, as the base to be used, tertiary amines such as triethylamine, carbonates of alkaline earth metal such as lithium carbonate and the like are preferable.

The compound (VI) used above is produced by halogenating or esterifying the compound represented by the general formula (VII). Is

(Where X, Y, m, n and W ¹ are the same as described above.)

Compound (VI) in which W ¹ is a halogen atom can be obtained by converting the compound represented by formula (VII) to a halogenating reagent such as thionyl chloride, phosphoryl chloride, phosphorus pentachloride, phosphorus trichloride, and phosphoryl bromide. And can be obtained by halogenation. Compound (VI) in which W ¹ is a C] to C ₄ lower alkoxy group is a compound represented by the general formula (VII): Or by producing an alkali carboxylate of compound (VII), followed by esterification such as reaction with dialkyl sulfate or alkyl halide to produce the compound.

 The compound (VI) used in the present invention can be derived, for example, from the following compound (VII).

4-Methoxy 6-[(3-trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = 4-OCH ₃ ]],

4-Methoxy-1-6-((3-trifluoromethoxy) phenoxy] picolinic acid [Compound [VII, X = 3-OCF ₃ , Y = 4-OCHj], 4-menu butoxy one 6- [(3-triflate Ruo b methylthio) phenoxy] picolyl phosphate [compound _{[VII, X = 3- SCF 3} , Y = 4-OCH 3]],

4—Methoxy 6 — [(3-Trifluoromethoxy) phenoxy] picolinic acid [Compound [VII, X = 3-OCF ₃ , Y = 4-OCH ₃ ]],

4-methyl-6-[(3-trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = 4-CH ₃ ]],

4 Mechirua Mi No 6- [(3-tri Furuo port methyl) phenoxy] picolyl phosphate [compound _{[VII, X = 3- CF 3} , Y = 4-NH (CH 3)]],

4-dimethylamino-6-[(3-trifluoromethyl) phenoxy] picolinic acid [compound [VII, Χ = 3-CF ₃ , Y = 4-N (CH ₃ ) ₂ ]],

4-methylthio-6-[(3-trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = SCH ₃ ]],

6-[(3-Trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = 4-C1]],

6-[(3-Trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = 3-C1]],

6 — [(3—Trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = unsubstituted]],

4— (2,2,2-trifluorotrifluoro) _ 6 — [(3-trifluoromethyl) phenoxy] picolinic acid [Compound [VII, X = 3-CF ₃ , Y = 4-OCH ₂ CF ₃ ]], 4-Methoxy-6-[(3-Methoxy) phenoxy] picolinic acid [Compound [VII, X = 3-OCH ₃ , Y = 4-OCH ₃ ]],

4-Methoxy 6-[(3-methyl) phenoxy] picolinic acid [Compound [VII, X = 3-CH ₃ , Y = 4-OCH ₃ ]],

4-Methoxy-6-[(3-chloro) phenoxy] picolinic acid [Compound [VII, X = 3-Cl, Y = 4-OCH ₃ ]], 4-main Tokishi 6- [(2 - chloro port one 5 - triflate Ruo B methyl) phenoxy] Pico phosphate [compound [VII, X = 2-C1, 5- CF 3, Y = 4-OCH 3]],

4-Methoxy-1-6-((2-fluoro-3-trifluoromethyl) picolinic acid [Compound [VII, X = 2-F, 3-CF ₃ , Y = 4-OCH ₃ ]],

4 main butoxy one 6- [(4-chloro-3-triflate Ruo ii methyl) phenoxy] Pico phosphate [compound [VII, X = 4-C1, 3- CF 3, Y = 4-OCH 3]].

 Compound (VII) can be produced, for example, by the method described in International Patent Publication No. 98/29391.

The reaction temperature and reaction time 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. It can be longer. This compound (I) can be used as it is as a herbicide. Usually, it is formulated into various forms such as powders, wettable powders, granules and emulsions together with formulation aids. In this case, one or more of the present compounds in the formulation (I), usually 0.:!～ 95 wt%, preferably from 0.5 to 90 wt%, more preferably is 2 to 70 weight _^0/0 containing organic You.

Examples of carriers, diluents, and surfactants used as formulation aids include solid carriers, such as talc, kaolin, bentonite, diatomaceous earth, white power—bon, clay, and the like ^. Examples of the diluent include water, xylene, toluene, benzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, and alcohol. It is better to use different surfactants depending on their effects. For example, emulsifiers generally include polyoxyethylene alkylaryl ether, polyoxyethylene alkyl ether, polyoxyethylene sorbitan monolaurate, and the like.Dispersants include lignin sulfonate, Dibutyl naphthalene sulfonate No. Examples of the wetting agent generally include an alkyl sulfonate and an alkylphenyl sulfonate.

 Some of the above preparations are used as is, and others are used after being diluted to a predetermined concentration with a diluent such as water. When diluted and used, 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: L0 kg, preferably 0.01 to 5 kg per lha. Since the concentration and amount of use differ depending on the dosage form, time of use, method of use, place of use, target crop, etc., it is 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 power to specifically explain the present invention by the examples, and the present invention is not limited to the following examples unless it exceeds the gist. Production Example 1:

 Synthesis of 2- (2-cyclobenzoyl) amino-6-[(3_trifluoromethyl) phenoxy] pyridine (Compound No. I-2)

(1) <Intermediate, 2-—Cross-Carbonyl 6 — [(3—Trifluoromethyl) phenoxy] pyridine Synthesis (Compound (VI): X = 3-CF ₃ , Y = Unsubstituted, E>

 6— [(3-Trifluoromethyl) phenoxy] picolinic acid (2.83 g, O.OlOmol) is suspended in benzene (about 50 ml), and thionyl chloride (2.38 g, 0.010 X 2.1 ml) and catalyst are suspended. An amount of Ν, Ν-dimethylformamide was added and refluxed for about 3 hours. After cooling, the insolubles were filtered off and the solvent was concentrated to give the desired product.

Yield 3.10 g, 103% yield, oil. _{^{J H- NMR (60MHz, CDC1 3}} , δ): 6.88- 7.87 (7H, m).

(2) <Synthesis of Intermediate, N-Hydroxy-1-6-[(3-trifluoromethyl) phenoxy] -12-pyridine-ylboxamide (Compound (V): X = 3-CF ₃ , Y = No replacement)>

 Hydroxylamine hydrochloride (1.04 g, 0.0099 XI.5 mol) was suspended in dichloromethane (about 50 ml), and triethylamine (3.1 g, 0.0099 X3.1 mol) was added thereto. — A solution of [(3-trifluoromethyl) phenoxy] pyridine (3.0 g, 0.0099 mol) in dichloromethane (about 20 ml) was added dropwise. After stirring at room temperature for 1 hour, the reaction solution was concentrated, then dissolved in ethyl acetate, washed with water, washed with brine, and dried over anhydrous sodium sulfate. The solvent was concentrated and purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 1Z1) to obtain the desired product.

Yield 1.92g, 65% yield, solid, m.p .: 159-161 ° C.

_{NMR (60MHz, CDC1 3, δ} ): 6.93- 8.07 (7H, m), 6.78 - 9.35 (lH, br), 10.23 (lH, brs).

(3) <Intermediate, 2- amino-6- [(3-triflate Ruo ii methyl) Fuenoki sheet] pyridine (Compound (II): X = 3- CF 3, Y = unsubstituted)>

In a solution of sodium hydride (0.27 g, 60% in mineral oil, 0.0064 x 1.05 mol) suspended in N, N-dimethylformamide (about 10 ml), N-hydroxy-6-[(3 —Trifluoromethyl) phenoxy] —2-N-pyridinecarboxamide (1.9 g, 0.0064 mol) dissolved in N, N-dimethylformamide (about 15 ml) was added. Thereafter, the mixture was stirred at about 100 ° C. for 0.5 hour. After cooling, the reaction solution was poured into ice water and extracted twice with ethyl acetate. The ethyl acetate layers were combined, washed with water, washed with saturated saline, and dried over anhydrous sodium sulfate. Concentrate the solvent, PC drawing IS

20 Purification by silica gel column chromatography (eluent: n-hexane / ethyl acetate = 2/1) gave the desired product.

Yield 1.39g, 86% yield, oil.

_{- NMR (60MHz, CDC1 3,} δ): 4.47 (2H, brs), 6.06 (2H, d, J = 8Hz),

7.02-7.47 (5H, m).

(4) <Synthesis of 2- (2-cyclobenzoyl) amino-6-[(3-trifluoromethyl) phenoxy] pyridine (Compound No. 1-2)>

 2—Amino 6 — [(3-Trifluoromethyl) phenoxy] pyridine

(0.25 g, 0.00098 mol) in dry benzene (approx. 25 m 1), and benzoyl chloride 2-chloride (0.192 g, 0.00098 XI. Imol) and triethylamine

(0.13 g, 0.00098 X1.2 mol) and refluxed for 2 hours. After cooling, ethyl acetate was added to the reaction solution, which was then washed with water, and the organic layer was washed with saturated saline. After drying over anhydrous sodium sulfate, the solvent was concentrated, and the residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 5Z1) to obtain the desired product.

Yield 0.33g, 85% yield, oil.

_{^{J H- NMR (60MHz, CDC1 3}} , δ):. 6.63 (lH, d, J = 7Hz), 7.10- 8.15 (10H, m), 8.30 (lH, brs) Preparation Example 2:

 Synthesis of 2-benzoylamino 4-methoxy 6-[(3-trifluoromethyl) phenoxy] pyridine (Compound No. I-4)

(1) Synthesis of ku intermediate, 2-cyclobutane-2-4-methoxy-6-[(3-trifluoromethyl) phenoxy] pyridine (Compound (VI): X = 3-CF 3, Y = 4- OCH ₃ , W] = C1)>

4-Methoxy 6 — [(3-Trifluoromethyl) phenoxy] picolinic acid (lO.Og, 0.032 mol) was suspended in benzene (about 125 ml), and thionyl chloride (7.6 g, 0.032X2.0 mol) and a catalytic amount of N, N-dimethylformamide were added. Refluxed for about 4 hours. After cooling, the mixture was filtered off, and the solvent was concentrated to obtain the desired product. Yield 10.3g, 97% yield, solid, mp 66-69 ° C.

^{1 H - NMR (60MHz, CDC1} 3, δ): 3.83 (3H, s), 6.57 (lH, d J = 2Hz),

 7.13- 7.62 (5H, m).

(2) <Intermediate, synthesis of N-hydroxy-14-methoxy-6-[(3-trifluoromethyl) phenoxy] —2-pyridinecarboxamide (Compound (V): X = 3-CF ₃ , Y = 4-OCH ₃ )>

 Hydroxylyamine hydrochloride (3.27 g, 0.031 XI.5 mol) was suspended in dichloromethane (about 70 ml), and triethylamine (9.40 g, 0.031 X3 mol) was added to the suspension. A solution of 6-[(3-trifluoromethyl) phenoxy] pyridine (10.3 g, 0.031 mol) in dichloromethane (about 40 ml) was added dropwise. After stirring at room temperature for 2 hours, the reaction solution was concentrated, transferred to ethyl acetate, washed with water, washed with saturated saline, and dried over anhydrous sodium sulfate. The solvent was concentrated and purified by silica gel column chromatography (eluent: n-hexaneethyl acetate = purified to obtain the desired product.

Yield 8.12 g, 80% yield, solid, m.p. 120-122 ° C.

_{- NMR (60MHz, CDC1 3,} δ): 3.80 (3H, s), 6.40 (lH, d, J = 2Hz),

7.03- 7.50 (5H, m), 9.00 (2H, brs).

(3) <Synthesis of Intermediate, 2-Amino-4-Methoxy-6 — [(3-Trifluoromethyl) phenoxy] pyridine (Compound (Π): X = 3-CF ₃ , Y = 4-OCH ₃ )> Hydrogen A solution of sodium chloride (0.61 g, 60% in mineral oil, 0.0145 X 1.05 mol) in Ν, Ν-dimethylformamide (about 30 m 1) was added with N-hydroxyl. A solution of N, N dimethylformamide (approximately 35 ml) in which 4-pyroxyl 6 — [(3 trifluoromethyl) phenoxy] 2 pyridinecarboxamide (4.75 g, 0.0145 mol) was dissolved was added. Thereafter, the mixture was stirred at about 100 ° C for 0.5 hour. After cooling, the reaction solution was poured into ice water and extracted twice with ethyl acetate. The ethyl acetate layers were combined, washed with water, washed with brine, and dried over anhydrous sodium sulfate. The solvent was concentrated, and the residue was purified by silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 2: 1) to obtain the desired product.

Yield 3.26 g, 79% yield, oil.

] _{H- NMR (60MHz, CDC1 3,} δ): 3.67 (3H, s), 4.38 (2H, brs), 5.63 (lH, d, J = 2Hz), 5.70 (lH, d, J = 2Hz), 7.02 -7.42 (4H, m).

(4) <Synthesis of 2-benzoylamino-4-methoxy-6-[(3 trifluoromethyl) phenoxy] pyridine (Compound No. I-4)>

 2-Amino-4-methoxy-1-6-((3 trifluoromethyl) phenoxy] pyridine (0.33 g, 0.00116 mol) was dissolved in ethyl acetate (about 50 ml), and benzoyl chloride (0.18 g, 0.00116 X l.lmol) and triethylamine (0.14 g, 0.00116X1.2 mol) were added, and the mixture was stirred at about 50 ° C for 0.5 hour. After cooling, the solution is washed with water, and the organic layer is saturated: washed with water, dried over anhydrous sodium sulfate, concentrated, and concentrated on a silica gel column chromatography (eluent: n-hexane Z ethyl acetate = 5 / Purification by 1) gave the desired product.

Yield 0.35g, 78% yield, oil.

_{NMR (60MHz, CDC1 3, δ} ): 3.83 (3H, s), 6.07 (lH, d, J = 2Hz),

7.00-7.50 (7H.m), 7.60-7.85 (3H, m), 8.43 (lH, brs). Production Example 3:

2- (3-bromobenzoyl) amino 4- (methoxy) 6- [(3 Synthesis of (Oromethyl) phenoxy] pyridine (Compound No. 1-6)

 2-Amino-4-methoxy-6-[(3-trifluoromethyl) phenoxy] pyridine (0.20 g, 0.00070 mol) was dissolved in benzene (about 20 ml), and 3-bromobenzoyl chloride (0.17 g, 0.00070 XI. Lmol) and triethylamine (0.084 g, 0.00070 XI.2 mol) were added, and the mixture was refluxed for about 2 hours. After cooling, ethyl acetate was added to the reaction mixture, followed by washing with water. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, concentrated, and concentrated on a silica gel column chromatography (eluent: n- Purification with hexane Z-ethyl acetate = 5/1) gave the desired product. Yield 0.28g, 85% yield, oil.

_{NMR (60MHz, CDC1 3, δ} ): 3.82 (3H, s), 6.12 (lH, d, J = 2Hz),

7.03- 7.98 (8H.m), 7.70 (lH, d, J = 2Hz), 8.52 (lH, brs). Production Example 4:

 Synthesis of 2- (4-chlorobenzoyl) amino-4-methoxy-6-[(3-trifluoromethyl) phenoxy] pyridine (Compound No. 1-10)

 2-Amino-4-methoxy-6 _ [(3-trifluoromethyl) phenoxy] pyridine (0.20 g, 0.00070 mol) is dissolved in benzene (about 20 ml), and 4-chlorobenzoyl chloride (0.135 g) is dissolved. , 0.00070 Xl.lmol) and triethylamine (0.084 g, 0.00070 XI.2 mol) were added, and the mixture was refluxed for about 2 hours. After cooling, ethyl acetate was added to the reaction mixture, followed by washing with water. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, concentrated, and concentrated on a silica gel column chromatography (eluent: n- Purification with hexane Z ethyl acetate = 5Z1) gave the desired product. Yield 0.26 g, 87% yield, solid, m.p. 117-119 ° C.

_{NMR (60MHz, CDC1 3, δ} ): 3.83 (3H, s), 6.10 (lH, d, J = 2Hz),

7.10-7.47 (6H.m), 7.53--7.80 (3H, m), 8.40 (lH, brs). Production Example 5:

 Synthesis of 2- (2-fluorobenzoyl) amino-4-methoxy-6 _ [(3-trifluoromethyl) phenoxy] pyridine (Compound No. 1-11)

 2-Amino 4-Methoxy-6-[(3-Trifluoromethyl) phenoxy] pyridine (0.29 g, O.OOlOmol) is dissolved in benzene (about 25 m 1), Nzoyl chloride (0.18 g, O.OOlOXl.lmol) and triethylamine (0.12 g, 0.0010 X1.2 mol) were added, and the mixture was refluxed for about 2.5 hours. After cooling, ethyl acetate was added to the reaction solution, followed by washing with water. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, concentrated, and concentrated on a silica gel column chromatograph (eluent: n- Purification by hexane / ethyl acetate = 5Z1) gave the desired product. Yield 0.38g, 92% yield, solid, m.p. 73-76 ° C.

_{iH - NMR (60MHz, CDC1 3} , δ): 3.82 (3H, s), 6.05 (lH, d, J = 2Hz),

6.70-7.48 (7H.m), 7.67 (lH, d, J = 2Hz), 7.93 (lH, dt, J = 2Hz, 8Hz),

8.60 (lH, brs). Production Example 6:

 Synthesis of 2- (2,4-dibenzobenzoyl) amino-4-methoxy-1 6-[(3-trifluoromethyl) phenoxy] pyridine (Compound No. 1-22)

2-Amino-4-methoxy-6-[(3-trifluoromethyl) phenoxy] pyridine (0.30 g, 0.00106 mol) is dissolved in ethyl acetate (approximately 30 m 1). He was given calories of benzoyl chloride (0.20 g, 0.00106 XI. Lmol) and triethylamine (0.13 g, 0.00106 XI.2 mol) and was treated for 2.5 hours at room temperature. After cooling, the reaction solution is washed with water, the organic layer is washed with saturated saline, dried over anhydrous sodium sulfate, concentrated, and the solvent is concentrated. Silica gel column chromatography (eluent: n-ethylhexanoacetate = 5/1) Purified. This was recrystallized from n-hexane Z ethyl acetate (5Z1) to obtain a compound. Yield 0.21 g, 47% yield, solid, mp 92-94 ° C.

 1H-NMR (60MHz, CDC1,, δ): 3.82 (3H, s), 6.10 (lH, d, J = 2Hz),

6.58- 7.50 (6H.m), 7.70 (lH, d, J = 2Hz), 7.83- 8.27 (lH, m), 8.70 (lH, brs). Tables 4 to 6 show the properties and NMR data of the synthesized compounds.

Table 4 Compound properties NMR (60MHz, CDC ", d)

Turn

1-1 Oil 6.63 (lH, d, J = 7Hz), 7.00-7.90 (10H.m), 8.07 <lH, d, J = 7Hz), 8.70 (lH, bs).

<m -1Λ. vn, / m /,

 7.05-8.15 (10H.m), 8.30 (lH, bs).

1-5 Oil 3.83 (3H, s), 6.10 (1H, d, J = 2Hz),

 7.00-7.63 (8H.m), 7.63 (lH, d, J = 2Hz), 8 1 n n H bs)

1-7 Solid 3.83 (3H _f s), 6.08 (lH, d, J = 2Hz),

 Di.ρ 125-127 "C 7.10-7-43 (4H.m), 7.47 (2H, d, J = 9Hz),

 7.63 (2H, d, J = 9Hz), 7.70 (1H, d, J = 2Hz), 8.23 (1H, rs).

1-8 Oil 3.82 (3H, s), 6.07 (lH, d, J = 2Hz),

 7.05-7.63 (8H.m), 7.68 (lH, d, J = 2Hz), 8.35 (1H, brs).

1-9 Oil 3.83 (3H, s), 6.10 (lH, d, J = 2Hz),

7.05-7.80 (9H.m), 8.47 (lH, brs). Table 5 I k compound Typical Properties _{NMR (60MHz, CDC1 3, d} )

Number

1-12 Oil 3.83 (3H, s), 6.10 (lH, d, J = 2Hz),

 7 07-7.65 (8H.m), 7.70 (lH, d, J = 2Hz).

8.45 (lH, brs).

1-13 Solid 3.83 (3H, s), 6-08 (lH, d, J = 2Hz),

mr, 1 1 _ 1 IK ⁰ c 77-7 ΛΡ; (am 7 R— 7 H m,

 8.37 (lH, brs).

1-14 Oil 3.83 (3H, s), 6.10 (1H, d, J = 2Hz),

 β 83-7 | · 4 * "| 7 | (7H m), 765 (1H, d, J = 2Hz)

7.60-8.42 (2H.m).

1-17 Oil 3.83 (3H, s), 6.10 (1H, d, J = 2Hz),

 7.07-7.63 (7H.m), 7.65 (lH, d, J = 2Hz), 8.37 (lH, brs).

1-18 Solid 3.83 (3H, s), 6.10 (lH, d, J = 2Hz),

 Di.p 123-126 ° C 7.07-7.43 (7H.m), 7.70 (lH, d, J = 2Hz),

 8.lOUH'brs).

1-19 Solid 3.83 (3H, s), 6.10 (lH, d, J = 2Hz),

 m.p 104-106 ° C 7.07-7.47 (6H.m), 7.67 (lH, d, J = 2Hz),

7.93 (lH, d, J = 2Hz), 8.40 (1H, brs). Table 6

製造例及び表 4〜 6中の NM Rデータの略号は下記を表す。

Abbreviations of NMR data in Production Examples and Tables 4 to 6 represent the following.

s: singlet, d: doublet, m: multiplet, br: broad signal Next, formulation examples and test examples are shown. Carriers (diluents) and auxiliaries, mixing ratios are wide. It can be changed within a range. "Parts" in each of the preparation examples indicates parts by weight. Formulation Example 1 (Wettable powder):

 Compound (1-4) 50 parts Sodium ligninsulfonate 5 parts Sodium alkylsulfonate 3 parts Diatomaceous earth 42 2 parts are mixed and pulverized. Formulation Example 2 (emulsion):

 Compound (1-5) 25 parts xylene 65 parts

 Mix 10 parts uniformly to form an emulsion, and dilute with water before use. Formulation Example 3 (granules):

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

 (1) Preparation of plants to be used for testing>

 Seeds of Aogayto, Noharagarashi, Hakobe, Shiroza and Furazabaso are uniformly seeded in a planter filled with granular cultivation soil for horticulture [Kureha Chemical Co., Ltd .; C). Two germinated plants per plant species are transplanted to pots with a diameter of 10 cm filled with horticultural granulated soil, and greenhouses are used from the cotyledon stage to the two-leaf stage, which is the optimal stage for foliage and soil treatment (19 to 25 °) C).

(2) <Preparation and spraying of test solution>

 An aqueous solution containing 10% (v / v) acetone and 0.5% (ν / ν) of Tween 20 (Tween 20, manufactured by Wako Pure Chemical Industries, Ltd.) was added to an aqueous solution containing lmg / ml of the test compound. The test compound was dissolved or suspended in acetone using the above amounts, and then Tween 20 and water were added to prepare a test solution. Next, the plant prepared in (1) was placed in a frame having a predetermined area, and the plant compound was uniformly sprayed on the frame using a sprayer so that the applied amount of the test compound became a predetermined amount.

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

 The plants to which the test solution was sprayed were grown again in a greenhouse (19 to 25 ° C), and 14 days later, the growth of the plants in the treated plot relative to the unsprayed plot was evaluated based on the following criteria. Herbicidal activity. Table 7 shows the results.

1 Herbicidal rate is less than 20%

 2 Herbicidal rate is 20% or more and less than 40%

3 Herbicidal rate is 40% or more and less than 60% 4: Herbicidal rate is 60% or more and less than 80%

 5: Herbicidal rate is 80% or more

Table 7 Grass species a)

 Compound

 Number & a i AR SA SM CH VH

 / 10a

1-4 100 5 5 5 5 5

1-5 100 5 5 5 5 5

1-7 100 5 5 5 5 5

1-8 100 5 5 5 5 5

1-9 100 5 5 5 5 5

1-11 100 5 5 5 5 5

[-12 100 5 5 5 5 5 G 22 100 5 5 5 5 5 In the table, AR Age Toe;

 S A: Noharagarashi;

 S M: Hakobe;

 C H: Shiroza;

 V H: Furasabaso II. Industrial applicability

 According to the present invention described above, 2- (unsubstituted or substituted) benzoylamino 16- (unsubstituted or substituted) phenoxypyridine derivative (general formula (I)) is a new compound and has high herbicidal properties. It is useful as an active ingredient of herbicides.

Claims

The scope of the claims 1. 2- (unsubstituted or substituted) benzoylamino-1 6- (unsubstituted or substituted) phenoxypyridine derivative represented by the following general formula (I).

(In the formula, X is a halogen atom, C ^ C ^ alkyl group, (^ ~ (, mouth alkyl group, C C ^ alkoxy group, C ~C ₄ cutting edge alkoxy group, (:!丄~ Ji alkyl Chiomoto, C represents a _4- haloalkylthio group, a nitro group, or a cyano group, and m represents an integer of 0 to 5. Y represents a halogen atom, a C! C ^ alkyl group, (^ ~ (ヽ 口 ア ル キ ル 基 、 じ ～ 〜)ア ル コ キ シ alkoxy group, C 丄-じ haloalkoxy group, C ^ C alkylthio group, 〜- ロ, loalkylthio group, C -alkylamino group, C〜- ( _4- dialkylamino group, nitro group, cyano group , n represents shows the integer of 0 to 3. Z represents a halogen atom, C ^ C ^ alkyl, C! C haloalkyl group, C ^ C ^ alkoxy, C -C ₄ Ha port alkoxy group, a nitro group, Shiano Represents a group, and p represents an integer of 0 to 5. When m, n, and p are 2 or more, X, Y, and Z are the same, respectively. The other may be different.) 2. A 2-amino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the following general formula (II) and a (unsubstituted or substituted) benzoyl halide represented by the following general formula (III) A method for producing a 2- (unsubstituted or substituted) benzoylamino-6- (unsubstituted or substituted) phenoxypyridine derivative represented by the general formula (I), characterized by reacting.

(Wherein, X is a halogen atom, Ci C alkyl group, cc ^ haloalkyl group, CC alkoxy, C, -C ₄ haloalkoxy group, C ^ C ^ alkyl Chiomoto, C ~ (: ₄ haloalkylthio group, nitro B represents a cyano group, m is 0 Indicates an integer from 5 to 5. Y is a halogen atom, C ^ C alkyl group, (~ Jiヽopening alkyl group, C ^ C ^ alkoxy group, C, ~C ₄ haloalkoxy groups, C] ~C ₄ alkylthio group, C! ~ Ji, Roarukiruchio .! group, C ~ Ji alkylamino group, C ₄ dialkylamino group, a nitro group, a Shiano radical, n represents an integer of 0 to 3 Z is halogen atom, C ^ C ^ alkyl group, (: ! ~ Ji, mouth alkyl group, (:. ~ Ji alkoxy group, C i~C ₄ haloalkoxy group, a nitro group, a Shiano group, p is 0 to m represents an integer of 5, n, p is 2 or more In the case of, X, Y, and Ζ may be the same or different. W represents a halogen atom.) 3. A herbicide characterized by containing a 2- (unsubstituted or substituted) benzoylamino represented by the general formula (I) 6- (unsubstituted or substituted) phenoxypyridine derivative as an active ingredient.

(Wherein, X is a halogen atom, c ^ c ^ alkyl, cc ^ haloalkyl group, C! C ^ alkoxy group, C ~ Ji ₄ Ha port alkoxy, cc ^ alkyl Chiomoto, C ~ C ₄ haloalkylthio group , A nitro group, a cyano group, and m represents an integer of 0 to 5. Y represents a halogen atom, a CC ^ alkyl group, a C! C ^ haloalkyl group, a CC ^ alkoxy group, a C-alkoxy group, a ()- C ₄ alkylthio groups, (:.] -C ₄ haloalkylthio group, C, ~ ₍₄ alkylamino group, C ₄ dialkylamino group, a nitro group, a Shiano radical, n represents an integer of 0 to 3 Z a halogen atom, CC ^ alkyl, mouth alkyl, C ^ C ^ alkoxy, C i~C ₄ haloalkoxy group, a nitro group, a Shiano group, p is an integer of 0 to 5. m, n , P is 2 or more, each of X, Y, and そ れ ぞ れ may be the same or different.