WO2005068430A1 - Pyridylmethyl derivatives of 2,6-dichloroisonicotinic acid, process for production of the same, and disease controllers for agricultural and horticultural use - Google Patents

Abstract

Pyridylmethyl derivatives of 2,6-dichloroisonicotinic acid represented by the general formula (I); a process for the production of the same; and disease controllers for agricultural and horticultural use: (I) (Q1) (Q2) (Q3) (wherein A is oxygen or nitrogen which is unsubstituted or substituted with lower alkyl; Q is a pyridine ring group represented by the general formula: (Q1), (Q2) or (Q3); X is lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkylthio, cyano, hydroxy, phenoxy, phenyl, or halogeno; and m is an integer of 0 to 4, with the proviso that when m is 2 or above, X’s may be the same or different from each other). The derivatives represented by the general formula (I) exhibit excellent control effects against plant diseases.

Description

 Specification

 Pyridylmethyl isonicotinate derivative of 2,6-dicyclomouth, method for producing the same, and agricultural and horticultural disease controlling agent

 Technical field

 [0001] The present invention relates to a pyridylmethyl 2,6-dicyclomouth isonicotinate derivative, a method for producing the same, and an agricultural and horticultural disease control agent containing the pyridylmethyl 2,6-dichloromouth isonicotinate derivative as an active ingredient.

 Background art

 [0002] Hitherto, 2,6-dicyclomouth isonicotinic acid has been known to be used as a plant disease protective composition (see Patent Documents 14 to 14). For pyridylmethyl 2,6-dichloroisonicotinate, 2,2-dichloropyridyl methyl isonicotinate, 2,6-dichloropyridyl isonicotinic acid 3-pyridylmethyl ester, Use of oral isonicotinic acid 4-pyridylmethyl ester as a plant disease protection composition is known (see Patent Document 5).

 [0003] Patent Document 1: JP-A-63-93766

 Patent Document 2: JP-A-1 283270

 Patent Document 3: JP-A-8-208613

 Patent Document 4: JP-A-10-95772

 Patent Document 5: JP-A-1283270

 Disclosure of the invention

 Problems to be solved by the invention

[0004] In view of the above circumstances, the present inventors have developed an agricultural and horticultural disease controlling agent which has low toxicity to humans and animals, has high safety in handling, and has an excellent controlling effect on a wide range of plant diseases. For development, we synthesized pyridylmethyl 2,6-dicyclomouth isonicotinate derivatives represented by formula (I) and examined their disease control effects. Accordingly, an object of the present invention is to provide a pyridylmethyl 2,6-dichloroisonicotinate derivative exhibiting an excellent effect on plant disease control, a method for producing the same, and an agricultural and horticultural disease control agent. Means for solving the problem

[0005] The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a substituted pyridylmethyl ester derivative of 2,6-dicyclomouth isonicotinic acid represented by the formula (I) and 2,2 A substituted pyridylmethyl amide derivative of 6-cyclomouth isonicotinic acid is a novel conjugate, and surprisingly, by introducing a substituent into the pyridine ring, it can be used as an agricultural and horticultural disease controlling agent. It has been found that the present invention exerts more excellent effects, and the present invention has been completed.

 [0006] The present invention has been completed based on the above findings, and a first gist of the present invention is pyridylmethyl 2,6-dicyclomouth isonicotinate represented by the following formula (I). Derivatives exist.

 [0007] [Formula 1]

[0008] (In the formula, A represents an oxygen atom or a nitrogen atom that is unsubstituted or substituted with a lower alkyl group. Q represents a pyridine ring group of Ql, Q2 or Q3. X represents Represents a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a hydroxyl group, a phenoxy group, a phenyl group or a halogen atom, and m is an integer of 0 to 4. When m is 2 or more, X may be the same or different.)

[0009] A second gist of the present invention is to provide a 2,6-dichloroisonicotinic acid derivative represented by the following formula (II) and a substituted pyridylmethyl alcohol, amine or a substituted pyridylmethyl alcohol represented by the following formula (ΠΙ) The present invention relates to a method for producing a pyridylmethyl 2,6-dicyclomouth isonicotinate derivative represented by the formula (I), characterized by reacting with a halide. [0010] [Formula 2]

(In the formula, A represents an oxygen atom or a nitrogen atom which is unsubstituted or substituted with a lower alkyl group. Q represents a pyridine ring group of Ql, Q2 or Q3. X represents Represents a lower alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a hydroxyl group, a phenoxy group, a phenyl group or a halogen atom, and m is an integer of 0 to 4. When m is 2 or more, X may be the same or different Y represents a hydroxyl group, a chlorine atom or a nitrogen atom which is unsubstituted or substituted by a lower alkyl group; Represents a hydroxyl group, a chlorine atom, or a nitrogen atom that is unsubstituted or substituted with a lower alkyl group.)

 A third gist of the present invention resides in an agricultural and horticultural disease control agent containing a pyridylmethyl 2,6-dichloromouth isonicotinate derivative represented by the above formula (I) as an active ingredient.

 The invention's effect

[0013] According to the present invention, the pyridylmethyl 2,6-dicyclomouth isonicotinate derivative of formula (I) can be used as an active ingredient of an agricultural and horticultural disease controlling agent. BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in detail. Of the substituents of the pyridylmethyl isonicotinate derivative (I) of the present invention (I) (hereinafter sometimes abbreviated as “the compound of the present invention”), the substituents defined in the broader concept are included. , A lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group and a lower alkylthio group usually have 116 carbon atoms, preferably 114 carbon atoms. Is included. The lower alkyl group for X includes a methyl group, an ethyl group, a 1-methylethyl group, a 1,1-dimethylethyl group and an n-propyl group, and the lower alkoxy groups include methoxy, ethoxy, 1-methylethyl group. Tiloxy, 1,1-dimethylethyloxy and propyloxy are mentioned. The lower haloalkyl group is a trifluoromethyl group. The lower haloalkoxy group is a difluoromethoxy group and a trifluorooxy group. Examples include a lomethoxy group and a 2,2,2-trifluoroethoxy group, and examples of the lower alkylthio group include a methylthio group. Further, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Preferred integers m are 1 and 2.

 Next, specific examples of the 2,6-dicyclomouth isonicotinic acid derivative (I) are shown in Table 1 and Table 3.

[Table 1]

Compound Compound

AQAQ

 I- 1 O Gas 1 8 0

12 0 Mo 1-9 0

Cl

1-3 0 I 10 o

 , OMe JJ

1-4 o 1-11 o

1-5 0 to 12 NH

j ^cl

1 6 o X ^CF3 1-13 N Me j ^cl

Fight [8 TOO]

lli000 / S00Zdf / X3d 9 0C17890 / S00i OAV

Examples of the diluent used in the production method described above include the following. Water, formic acid Organic acids such as acetic acid, propionic acid, hydrocarbons such as benzene, toluene, xylene, petroleum ether, pentane, hexane, heptane, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, and methanol Alcohols such as ethanol, isopropanol and t-butanol, ethers such as getyl ether, dimethoxyethane, diisopropyl ether, tetrahydrofuran, diglyme and dioxane, carbon disulfide, acetonitrile, acetone and ethyl acetate; Acetic anhydride, pyridine, dimethylformamide, dimethylacetamide, 1-methyl-2-pyrrolidinone, dimethylsulfoxide, hexamethylphosphoric amide and the like.

 [0020] Examples of the base include the following. Alkali metal carbonates such as sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate; alkaline earth metal carbonates such as calcium carbonate and barium carbonate; alkalis such as sodium acetate, potassium acetate and sodium propionate Metal carboxylates, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal oxides such as magnesium oxide and calcium oxide, lithium, sodium, potassium, etc. Alkali earth metals such as magnesium, magnesium, etc., alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium t-butoxide, alkali metal hydrides such as sodium hydride, potassium hydride, methyllithium, ethyllithium, etc. n-Butyllithium, ferric Organic metal compounds of alkali metals, such as organic compounds, organic Grignard reagents such as methyl magnesium iodide, ethyl magnesium bromide, n-butyl magnesium bromide, organic metal compounds of alkali metals or Grignard reagents, and copper (I) salts. Compounds prepared from water, alkali metal amides such as lithium disopropylamide, aqueous ammonia, ammonium hydroxides such as benzyltrimethylammonium hydroxide, tetramethylammonium hydroxide, and methylammonium. And organic amines such as min, ethylamine, n-propylamine, benzylamine, ethanolamine, dimethylamine, benzylmethylamine, dibenzylamine, triethylamine, triethanolamine, pyridine and the like.

[0021] The pyridylmethyl derivative of 2,6-dichloroisonicotinic acid (I) is obtained by substituting the derivative of 2,6-dichloroisonicotinic acid (Π) with the substituted pyridylmethyl alcohol, substituted pyridylmethylamine or substituted pyridylmethylamine of the formula (III). Pyridylmethylnodride can be advantageously produced in a diluent in the presence of a base . In order to carry out the production method of the present invention, for example, a compound prepared by dissolving a 2,6-dichloroisonicotinic acid derivative (II) in the above-mentioned diluent is added, if necessary, to a compound represented by the formula Ability to convert substituted pyridylmethyl alcohol, substituted pyridylmethylamine or substituted pyridylmethyl halide of (III) by 0.5 to 1.5 equivalents, or conversely, substituted pyridylmethyl alcohol, substituted pyridylmethylamine or substituted of formula (III) It is advisable to react a 2,6-dichloroisonicotinic acid derivative (II) with a base dissolved in a solution of pyridylmethyl halide in a diluent. Further, 2,6-dichloroisonicotinic acid pyridylmethyl derivative (I) is a 2,6-dichloroisonicotinic acid derivative (II) and a substituted pyridylmethyl alcohol of formula (III), a substituted pyridylmethylamine or a substituted pyridylmethylnodide. Can be advantageously produced in a diluent in the presence of a condensing agent.

 [0022] In order to carry out the production method of the present invention, for example, 2,3-dichloroisonicotinic acid derivative (II) is dissolved in the above-mentioned diluent, and if necessary, In the presence of a condensing agent such as hexylcarposimide or 1-ethyl-3- (3-dimethylaminopropyl) carposimide, the substituted pyridylmethyl alcohol, substituted pyridylmethylamine or substituted pyridylmethylhalide of the formula (III) is usually added in a concentration of 0.5. — 1.5 equivalents, or conversely, substituted pyridylmethyl alcohol, substituted pyridylmethylamine or substituted pyridylmethyl phenol of formula (III), dissolved in a diluent, added to 2,6-dichloroiso The nicotinic acid derivative (II) and the above-mentioned condensing agent may be added and reacted.

 [0023] The reaction temperature at this time may be any temperature up to the freezing point and boiling point of the diluent as a solvent, but it is practically preferable to carry out the reaction at a temperature in the range of -10 to 100 ° C. . The reaction time is in the range of 0.5 to 10 hours, and it is desirable to carry out the reaction with stirring. After the completion of the above reaction, the reaction mixture obtained by the reaction was cooled, extracted with an organic solvent such as ethyl acetate, chloroform, and benzene to separate an organic layer, and then the obtained organic layer was washed with water. After drying, the solvent is distilled off under reduced pressure, and the obtained residue is purified to give pyridylmethyl 2,6-dichloroisonicotinate derivative (I). The purification treatment can be performed by recrystallization or silica gel column chromatography.

Next, the agricultural properties of the pyridylmethyl 2,6-dichloroisonicotinate derivative of the formula (I) according to the present invention are described. The usefulness of the horticultural disease control agent as an active ingredient will be described. The pyridylmethyl 2,6-dichloromethyl isonicotinate derivative (I) of the present invention exhibits a controlling effect on a wide range of plant diseases described below. For example, rice blast (Pyricularia oryzae), rice sesame leaf blight (Cochliobolus miyabeanus), rice is a power seedling;) hei I ^ KGibberella fujikuroi), 不, J ヽ ヽ (Helminthosporium sigmoideum), ヽRhizoctonia solanu, 3β from various crops (Botrytis cinerea), sclerotium; 丙 ^^ (Sclerotinia sclerotiorum), Sui power vine damage ¹ Fusarium oxysporum f.sp.niveum (1) Fusanum oxysporum f.sp.cucumerinum, P. anthracnose fungus (Colletotnchum lagenarium, Anzai brown 丙 ^^^ K and ercospora beticola, Cercospora 31 斑 (Cercospora ki uchn) ), Peach J fire disease! ¾ (bclerotinia cinerea,

alternata, maili), Nan black ¾ 菌 (Alternaria alternata (kikuchiana)), grape rot (Glomerella cingulata, cucumber and disease (Pseudoperonosora cubensis), tomato throw (Phytophthra infestans), cucumber gray rot (Phytophthora capsici) , Rice seedling blight fungus (Pythium

 aphanidermatum) and E. coli scab (Erisiphe graminis f. sp. tntic).

 [0025] In order to apply the pyridylmethyl 2,6-dichloroisonicotinate derivative (I) of the present invention as an agricultural and horticultural disease controlling agent as described above, the compound can be used as it is, but usually, the compound is used as a preparation. It is formulated and used in various forms such as powders, wettable powders, granules and emulsions together with adjuvants. At this time, one or more pyridylmethyl 2,6-dichloroisonicotinate derivatives (I) are usually 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 0.5 to 90% by weight in the preparation. Preferably, it is formulated so as to contain 2 to 70% by weight.

[0026] Examples of the carriers, diluents, and surfactants used as formulation aids include talc, kaolin, benite, diatomaceous earth, white carbon, and clay as solid carriers, and liquid diluents. Examples thereof include water, xylene, toluene, benzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like. Emulsifiers which can be used properly depending on their effect include polyoxyethylene alkylaryl ether and polyoxyethylene sorbitan monolaurate. Dispersants such as ligne sulfonate and dibutyl naphthalene sulfonate Examples of the wetting agent include alkyl sulfonates and alkyl phenyl sulfonates.

 [0027] The above-mentioned preparations include those used as they are and those used after being diluted to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when diluted and used is preferably in the range of 0.001 to 1.0%. The amount of the compound of the present invention is preferably 20 to 5000 g, more preferably 50 to 100 g per hectare of an agricultural or horticultural land such as a field, a field, an orchard, and a greenhouse. Since the concentration and amount of use vary depending on the dosage form, time of use, method of use, place of use, target crop, and the like, it is of course possible to increase or decrease the amount without being limited to the above range. In addition, the compounds of the present invention can be used in combination with other active ingredients, for example, fungicides, insecticides, acaricides, herbicides.

 Example

 Hereinafter, Production Examples, Preparation Examples, and Test Examples will be shown to specifically describe the present invention. The present invention is not limited to the following Production Examples, Preparation Examples and Test Examples as long as the gist is not exceeded. The NMR spectrum was measured using TMS as an internal standard, and represented by the following symbols or a symbol combining these. s: double line, d: double line, t: triple line, q: quadruple line, m: multiple line, b: broad line, dd: double double line, qq: quadruple line

 Production Example 1:

 Synthesis of Ku (6-bromo-3-pyridyl) methyl 2,6-dichloropyridine 4 carboxylate (I-3)>

5 ml of anhydrous dimethylformamide was suspended in 0.042 g of sodium hydride (oil-based, 60%), and 0.192 g of 2,6-dichloroisonicotinic acid was added. When the generation of hydrogen gas was completed, 0.020 g of potassium iodide and then 0.301 g of 6-bromo-3-picolyl bromide dissolved in 2 ml of dimethylformamide were added, and the mixture was stirred at 75 ° C for 2 hours. After completion of the reaction, the reaction solution was concentrated under reduced pressure, water and ethyl acetate were added to the residue, and the mixture was passed through a diatomaceous earth column and eluted with ethyl acetate. The eluate was concentrated under reduced pressure, and the obtained crude reaction product was separated and purified by silica gel chromatography (manufactured by Merck, hexane Z ethyl acetate = 10 Zl) to obtain 0.346 g of the title compound 3). The physical properties of this compound were measured, and the results were as shown below.o [Table 4]

(1) Melting point: 87 ~ 89.5 ° C

 (2) IR (KBr method, re, cm-1): 3096,3056,1736,1590,1548,1460,1422,1400,1364,1290,1236,1172,1164,1086,1026,994,966,940,922,904,882,836,822,764,742,624

_{(3) NMR (CDC1 3,} δ ppm):. 5.36 (2H, s)) 7.55 (lH, d, J = 8.2Hz)) 7.65 (lH J dd, J = 8 2Hz, 2.5Hz), 7.79 (2H , s) _! 8.47 (lH ₎ d, J = 2.3Hz)

Production Example 2:

 Synthesis of c (6fluoro-3pyridyl) methyl 2,6-dichrolic pyridine 4 carboxylate (I 2)>

 5 ml of anhydrous dimethylformamide was suspended in 0.042 g of sodium hydride (oily, 60%), and 0.192 g of 2,6-dichloroisonicotinic acid was added thereto. At the end of hydrogen gas generation, add 0.020 g of potassium iodide, then add 0.191 g of 6-fluoro-3-picolyl bromide dissolved in 2 ml of dimethylformamide, and stir at 75 ° C for 2 hours. did. After completion of the reaction, the reaction solution was concentrated under reduced pressure, water and ethyl acetate were added to the residue, and the mixture was passed through a diatomaceous earth column and eluted with ethyl acetate. The eluate was concentrated under reduced pressure, and the obtained crude reaction product was separated and purified by silica gel mouth chromatography (manufactured by Merck, hexane Z ethyl acetate = 10Zl) to obtain 0.064 g of the title compound 2). As a result of measuring the physical properties of this compound, it was as shown below.

[Table 5]

 (1) Melting point: 56-58 ° C

 (2) IR (KBr method, ri, cm-ri: 3144,3108,3080,3032,2988,2936,1744,1700,1686,1656,1604,1586,1548,1486,1460,1404,1388,1364, 1272,1174,1158,1124,1090,1030,994,948,932,916,898,870,838,820,784,766,744,732,642,600,534,510,464,456,434,418,406

_{(3) NMR (CDC1 3,} (5, ppm): 5.39 (2H, s), 7.00 (lH, dd, J = 8.4Hz, 3.0Hz), 7.79 (2H, s), 7.90 (lH, ddd, J = 8.1Hz, 8.1Hz, 2,5Hz), 8.34 (lH, s)

Production Example 3:

Synthesis of (6-chloro-3-pyridyl) methyl 2,6-dichloropyridine 4 carboxylate> (1-1): Under an argon atmosphere, 4.55 g of 2,6-dichroic isonicotinic acid was dissolved in 93 ml of anhydrous tetrahydrofuran, followed by 3.09 ml of 6-chloro-3 pyridinemethanol, 0.26 g of 4-dimethylaminopyridine and 4.95 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added, and the mixture was stirred at room temperature for 24 hours. After the completion of the reaction, ethyl acetate was added, and the mixture was washed with 2N hydrochloric acid and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was separated and purified by silica gel chromatography (Wako Pure Chemical Industries, Ltd., Kogel C-300, hexane / ethyl acetate = 5/1) to give the title compound. 6.51 g of (I1) was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

[0034] [Table 6]

 (1) Melting point: 93-94 ° C

 (2) IR (KBr method, v, cm: 3480,3100,1736,1594, 1572, 1550,1466,1418,1400,1362,1286, 1236, 1174,1164,1142, 1110, 1092, 1028,994,966,940,920,904,840,824 , 766,748,732,632

_{(3) NMR (CDC1 3,} δ, ppm):. 5.39 (2H, s)) 7.40 (lH, d, J = 8.2Hz), 7.76 (lH, dd, J = 8 2,2.5Hz), 7.79 ( 2H, s), 8.51 (lH, d, J = 2.5Hz)

Production Example 4:

 [6— (2,2,2-Trifluoroethoxy-3-pyridyl) methyl] 2,6-dichropyridine 4 Synthesis of carboxylate (1-5)>

 0.024 g of sodium hydride (oil-based, 60%) and 0.017 g of potassium salt are suspended in 1 ml of dimethylformamide anhydride, and 2 ml of an anhydrous DMF solution of 0.192 g of 2,6-dichloroisonicotinic acid is stirred for 8 minutes. did. Next, 0.248 g of 6- (2,2,2-trifluoroethoxy-3-pyridyl) methyl chloride dissolved in 2 ml of dimethylformamide was added, and the mixture was stirred at 60 ° C. for 6.5 hours. After completion of the reaction, water was added to the reaction solution, and the mixture was eluted with ethyl acetate. The organic layer was washed sequentially with water and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was separated and purified by silica gel chromatography (manufactured by Merck, hexane Z ethyl acetate = 20 Zl) to give the title compound (1-5). 187 g were obtained. As a result of measuring the physical properties of this compound, it was as shown below.

[0036] [Table 7] (1) Melting point: 78 ~ 79.5 ° C

 (2) IR (KBr method, v> cnr: 3100,2960,1746,1618,1588,1554,1498,1466,1420,1362,1318,1302,1276,1254,1156,1140,1090,1072,994,964,846,806,764,666

_{(3) NMR (CDC1 3,} (5, ppm): 4.77 (2H, q, J = 8.5Hz), 5.34 (2H, s), 6.92 (lH, d, J = 8.4 Hz), 7.74 (lH J dd , J = 8.4,2.3Hz), 7.78 (2H, s) _; 8.25 (lH _> d _J J = 2.3Hz)

Production Example 5:

 <Synthesis of (6-chloro-2-pyridyl) methyl) 2,6-dichropyridine 4 carboxylate> (1-10):

 0.030 g of sodium hydride (oil, 60%) and 0.021 g of potassium salt are suspended in 2 ml of anhydrous dimethylformamide, and 4.5 ml of a solution of 0.238 g of 2,6-dichloroisonicotinic acid in 4.5 ml of anhydrous dimethylformamide is added thereto. Stirred. Next, 0.241 g of 6-chloro-2-pyridylmethyl chloride dissolved in 2.5 ml of DMF was prepared and stirred at 60 ° C. for 2 hours. After completion of the reaction, water was added to the reaction solution, and the mixture was eluted with ethyl acetate. The organic layer was sequentially washed with water and saturated saline, and then dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was separated and purified by silica gel chromatography (manufactured by Merck, hexane Z ethyl acetate = 20 Zl) to obtain 0.316 g of the title compound 10). As a result of measuring the physical properties of this compound, it was as shown below.

[0038] [Table 8]

(1) Melting point: 77.7 to 79.2 ° C

 (2) IR (KBr method, re, cm-i): 3096,3012,2956,1740,1596,1568,1550,1444,1416,1368,1290,1236,1180,1164,1144,1100,1088,998,990,982,916,904,812,786,762,740 , 730,684

_{(3) NMR (CDC1 3,} d ppm.): 5.45 (2H J s) 5 7.34 (2H, d, J = 7.6Hz), 7.72 (lH, tJ = 7.6 Hz), 7.85 (2H, s)

Production Example 6:

 <Synthesis of (5,6-dichloro-3pyridyl) methyl) 2,6-dichloropyridine-4 carboxylate (1-7)>

Dissolve 171 mg of 5,6-dichloro-3-pyridylmethanol in 3 ml of anhydrous tetrahydrofuran, 218 mg of 2,6-dichloroisonicotinic acid, 13 mg of 4-dimethylaminopyridine and WSC2 17 mg was added, followed by vigorous stirring at room temperature for 5.5 hours. After the reaction was completed, 30 ml of ethyl acetate was added to the mixture, which was washed twice with 2N HCl and then twice with a saturated saline solution, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the obtained residue was separated and purified by silica gel column chromatography (manufactured by Merck Ltd., hexane Z ethyl acetate = 10Zl) to obtain 239 mg of the title compound (I 7). . As a result of measuring the physical properties of this compound, it was as shown below.

[0040] [Table 9]

 (1) Melting point: 62.0 to 62.8 ° C

 (2) IR (KBr method, re, cm: 3092,2976,1740,1586,1552,1456,1426,1394,1376,1362,1274,1264,1240,1164,1152,1090,1046,966,896,814,772,728,666

_{(3) NMR (CDC1 3,} <5, ppm): 5.37 (s, 2H), 7.80 (s, 2H), 7.88 (d, lH, J = 2.1Hz), 8.40 (d, lH, J = 2.1Hz )

Production Example 7:

 <Synthesis of <(2-chloro-3-pyridylmethyl) 2,6-dicyclopyridinepyridine-4 carboxylate> (I 8):

 Dissolve 171 mg of 5,6-dichloro-3-pyridylmethanol in 3 ml of anhydrous tetrahydrofuran, and dissolve 440 mg of 2,6-dichloroisonicotinic acid and 270 mg of 2,6-dichloroisonicotinic acid in 15 ml of anhydrous tetrahydrofuran. 600mg of luphosphine was obtained. Subsequently, an anhydrous tetrahydrofuran solution (3 ml) containing 400 mg of getyl azodicarboxylate was added dropwise, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the solvent was distilled off under reduced pressure, and the residue was separated and purified by silica gel column chromatography (manufactured by Wako Pure Chemical Industries, Ltd., Kogel C-300, hexane Z ethyl acetate = 2Zl) to give the title compound. 230 mg of (I8) was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

[0042] [Table 10]

 (1) Melting point: 93-94 ° C

 (2) IR (KBr method, v, cm-: 3092,2976,1740,1586,1552,1456,1426,1394,1376,1362,1274,1264,1240,1164,1152,1090,1046,966,896,814,772,728,666

_{(3) NMR (CDC1 3,} δ, ppm): 5.49 (2H, s), 7.33 (lH, dd, J = 5,8Hz), 7.81 7.84 (1Η, m), 7.83 (2H, s), 8.45 ( (lH, dd, J = 2,5Hz) Production Example 8:

 <Synthesis of N— (6-chloro-3 pyridylmethyl) 2,6-dichloro-4 pyridylcarboxamide (1-1-2)>

 Under an argon atmosphere, 170 mg of 6-methyl-3-pyridylmethylamine was dissolved in 4.6 ml of anhydrous tetrahydrofuran, and 250 mg of 2,6-dichloroisonicotinic acid, 14 mg of 4-dimethylaminopyridinine and 1-ethyl-3 — (3-Dimethylaminopropyl) carbodiimide hydrochloride (237 mg) was added, and the mixture was stirred at room temperature for 2.5 hours. After the completion of the reaction, 40 ml of ethyl acetate was added, washed with a 2M aqueous solution of hydrochloric acid and a saturated saline solution in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure, and the resulting crude reaction product was separated and purified by silica gel column chromatography (Wako Pure Chemical Industries, Ltd., Kogel C300, hexane Z ethyl acetate = 2Zl) to give the title compound (I 12). 611 mg were obtained. The physical properties of this compound were measured, and the results were as shown below.o

 [Table 11]

 (1) Melting point: 165-166 ° C

 (2) IR (KBr method, cm, r: 3308,3092, 1654, 1592,1568,1552,1540,1466, 1456,1394,1364,1300,1222, 1192, 1168,1140,1108,1074.1024, 884,842,812,760,740,666,6 32,520,444

_{(3) NMR (CDC1 3,} δ, ppm): 4.63 (2H, d, J = 6,0Hz), 6.68 (lH, brs) J.34 (lH, dJ = 8 .2Hz), 7.59 (2H, s ) _! 7.69 (lH, dd, J = 8.2,2.5Hz), 8.35 (lH, d, J = 2.5Hz)

The compounds of I4, I6, I9, 1-11 and I13 were synthesized by the operation according to Production Example 18 above. The melting points and NMR data for these compounds are shown in Table 12 along with the data for the compounds 1-1, I5, I7, I8, I10 and I12.

[Table 12]

 [0047] The compounds shown in Tables 2 to 3 were synthesized by the operation according to Production Example 1-18. The melting points and NMR data of these compounds are shown in Table 13-Table 15.

[Table 13] / vu niooosooifcld O 0S890AV

(U [] size ΐ6 size 00

] Compound number Melting point CO NMR

I -37 viscous substance 5.40 (2H, s), 7.78 (2H, s) J.24 (lH _> dd, J = 5, lHz), 7.4

8 (lH, dJ = lHz) _; 8.43 (lH, d, J = 5Hz)

 1 -38 Viscous substance 5.42 (2H, s), 7.79 (2H, s), 7.35 (lH, dd, J = 5Hz), 8.49

(lH, bs), 8.45 (lH _J d, J = 5Hz)

 1 -39 103 2.57 (s, 3H), 5.33 (s, 2H), 7.08 (s, lH), 7.17 (s, lH), 7.

 83 (s, 2H)

I -40 88.5 2.47 (s ₎ 3H), 3.93 (s, 3H), 5.29 (s, 2H), 6.54 (s, lH), 6.

 71 (s, lH), 7.83 (s, 2H)

 I 41 viscous substance 5.44 (s, 2H), 7.26 (dt, J = 2.0, 6.2Hz, 1H), 7.81

 (s, 2H), 7.90 (dt, J = 2.0, 8.2Hz, IH), 8.27 (d, J = 6.2Hz, IH)

 I -42 168-169 4.70 (d, J = 4Hz, 2H), 7.28 (q, J = 4Hz, IH), 7.57

 (s, 2H), 7.83 (dd, J = 2, 8Hz, 1H), 8.37 (dd, J = 2, 4Hz, IH)

 I -43 75-76 (Isomer ①) δ 2.97 (s, 3H), 4.85 (s, 2H), 7.30

 (s, 2H), 7.31 (m, IH), 7.74 (d, J = 8Hz, IH), 8.40 (d, J = 4Hz, IH)

 (Isomer ②) δ 3.07 (s, 3H), 4.53 (s, 2H), 7.31 (s, 2H), 7,38 (m, 1H), 7.54 (d, J = 8Hz, IH), 8.41 (d , J = 4Hz, IH)

 I 44 194-195 4.66 (d, J = 4Hz, 2H), 6.75 (bs, IH), 7.30 (d,

 J = 8Hz, IH), 7.56 (s, 2H), 7.81 (d, J = 8Hz, IH)

1 45 138.4-139.2 4.72 (d, 2H, J = 5, l Hz), 7.27 (d, IH, J = 8.3Hz),

 7.31 (d, 1H, J = 7.9 Hz), 7.39 (bs, IH), 7.65 (s, 2H), 7.69 (t, IH, J = 7.8 Hz).

 1 46 180.2-181.5 4.63 (d, 2H, J = 6.0 Hz), 6.60 (bs, 1H), 7.59 (s, 2H),

 7.82 (d, IH, J = 2.0 Hz), 8.29 (d, IH, J = 2.0 Hz).

I -47 180 ~ 181 4.67 (d, J = 4Hz, 2H), 7.30 (q, J = 4Hz, IH), 7.57 (s,

 2H), 7.80 (dd, J = 2, 8Hz, IH), 8.34 (dd, J = 2, 4Hz, IH)

I -48 viscous substance 4.63 (2H, dJ = 6Hz) _i 6.70 (lH, bs), 7.60 (2H, s), 7.77

(lH, d, J = 8Hz) J.91 (lH, ddJ = 8 _! 1.5Hz), 8.82 (lH, d

, J = 1.6Hz) Formulation Example 1:

 <Powder>

3 parts by weight of the compound of the present invention (I-Danied Compound No. I2), 40 parts by weight of clay and 57 parts by weight of talc Crush and mix and use as a dust.

 Formulation Example 2:

 <Wettable powder>

 50 parts by weight of the compound of the present invention (I-Danied Compound No. 1-3), 5 parts by weight of lignesulfonate, 3 parts by weight of alkylsulfonate and 42 parts by weight of diatomaceous earth were mixed by grinding to obtain a wettable powder, and water was added. Use it after dilution.

Formulation Example 3:

 <Granules>

 5 parts by weight of the compound of the present invention (Compound No. I-4), 43 parts by weight of benite, 45 parts by weight of clay, and 7 parts by weight of lignesulfonate are mixed uniformly, and the mixture is kneaded with water, kneaded, and extruded. It is processed into granules by a granulator and dried to obtain granules.

Formulation Example 4:

 <Emulsion>

 20 parts by weight of the compound of the present invention (I-Danied Compound No. I8), 10 parts by weight of polyoxyethylene alkylaryl ether, 3 parts by weight of polyoxyethylene sorbitan monolaurate and 67 parts by weight of xylene are uniformly mixed and dissolved. To make an emulsion.

[0055] Test example 1:

 <Rice blast control effect test (water application)>

 Transplant rice (variety: Koshihikari) at the 3 leaf stage into a 1/1 Oo Wagner pot filled with paddy soil, and after 20-35 days, the granules adjusted according to Formulation Example 3 have a predetermined concentration (500g / 10a) The surface was applied as shown. Ten to twenty days after the chemical treatment, a spore suspension of the rice blast fungus formed on the rice disease was sprayed and inoculated, and kept at high humidity in a vinyl tunnel in a glass greenhouse. After 10-20 days, the inoculation power was investigated for all seedlings per test plot according to the investigation criteria in Table 16 below (China Agricultural Test Leaf Blast Inspection Standards), and calculated from the average disease incidence per pot: = (1-Degree of disease on treatment plot Z Degree of disease on non-treatment plot) X 100, the control value (%) was calculated. Table 17 shows the results.

[0056] [Table 16] Disease severity Disease area ratio (%)

 0 0

 Greater than 10 and less than 0.5

 20.5 or more and less than 1

 3 1 or more and less than 2

 4 2 or more and less than 5

 5 5 or more and less than 10

 6 1 0 or more and less than 25

 7 2 5 or more and less than 50

 850 or more and less than 80

 9 8 0 or more and less than 100

 10 Withering

[0057] A test was conducted in the same manner as in Test Example 1, using Compound (B) and Compound (C) represented by the following formulas as comparative drugs. Table 17 shows the results.

[0058] [Compound 3] Compound (A)

[0059] Compound (B)

[0060] Compound (C):

 [Table 17]

 [0062] Test example 2:

 <Effect of controlling wheat powdery mildew (foliage application)>

Using a square pot (1.5 cm X 2. Ocm), wheat (cultivar: Norin 61) cultivated in a greenhouse at the tillering stage was mixed with a wettable powder prepared according to Formulation Example 2 at a specified concentration ( The suspension was diluted with water at 125 g / ha) and sprayed at a rate of 100 L / ha. 10 to 20 days after drug treatment, spores of wheat powdery mildew were sprinkled and inoculated. Thereafter, the disease was caused in a glass greenhouse. 10-20 days after inoculation The disease incidence rate (%) in the eyes is examined arbitrarily, and the formula is calculated from the average disease incidence per pot according to the investigation criteria in Table 18 below: Control value = (1-disease incidence in the treated area, non-treated area) X The control value (%) was calculated from 100. The results are shown in Table 19.

 [Table 18]

A test was performed in the same manner as in Test Example 2 using Compound (A), Compound (B) and Compound (C) as comparative drugs. The results are shown in Table 19.

[0065] [Table 19]

Compound number Control value Compound number Control value Compound number Control value

I 1 100 I -15 75 I -32 75

I -2 100 I -16 90 I -33 85

I 3 100 I 17 75 I -34 80

I-4 100 I 18 80 I ~ 35 85

I-5 100 I -19 85 I -36 85

I 6 95 I -20 75 I -37 95

I-7 90 I 21 95 I -38 90

I 8 100 I -22 85 I -39 90

I -9 95 I -23 90 I -40 90

I -10 100 I 24 95 I -41 90

I -11 95 I -25 85 I -42 75

I 12 75 I -26 80 I -43 75

I -13 80 I-27 85 I -44 75

I -14 75 I 28 75 I 45 80 Compound (A) 55 I 29 85 I -46 SO Compound (B) 50 I -30 90 I -47 75 Compound (C) 15 I -31 75 I 48 75 The application is based on the appearance of a Japanese patent filed on January 13, 2004 (Japanese Patent Application No. 2004-00283), which is incorporated by reference in its entirety.

Claims

Claims A pyridylmethyl derivative of 2,6-dicyclomouth isonicotinate represented by the following formula (I).

 [Chemical 1]

(In the formula, A represents an oxygen atom or a nitrogen atom which is unsubstituted or substituted with a lower alkyl group. Q represents the pyridine ring group of the above Q1, Q2 or Q3. X represents a lower group. Represents an alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a hydroxyl group, a phenoxy group, a phenyl group or a halogen atom, and m represents an integer of 0 to 4. When m is 2 or more, Xs may be the same or different.)

 A method characterized by reacting a 2,6-dichloroisonicotinic acid derivative represented by the following formula (Π) with a substituted pyridylmethyl alcohol, amine or halide represented by the following formula (III) ( A process for producing a pyridylmethyl isonicotinate 2,6-diclonate derivative of I).

[Chemical 2]

(In the formula, A represents an oxygen atom or a nitrogen atom which is unsubstituted or substituted with a lower alkyl group. Q represents the pyridine ring group of the above Q1, Q2 or Q3. X represents a lower group. Represents an alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a hydroxyl group, a phenoxy group, a phenyl group or a halogen atom, and m represents an integer of 0 to 4. When m is 2 or more, X may be the same or different, Y represents a hydroxyl group, a chlorine atom, or an unsubstituted or substituted with a lower alkyl group, a nitrogen atom Z represents a hydroxyl group, a chlorine atom Represents an atom or a nitrogen atom that is unsubstituted or substituted with a lower alkyl group.)

[3] A disease control agent for agricultural and horticultural use, comprising an effective component of a pyridylmethyl 2,6-dichroic isonicotinate derivative represented by the following formula (I).

[Formula 3]

(In the formula, A represents an oxygen atom or a nitrogen atom which is unsubstituted or substituted with a lower alkyl group. Q represents the pyridine ring group of the above Q1, Q2 or Q3. X represents a lower group. Represents an alkyl group, a lower haloalkyl group, a lower alkoxy group, a lower haloalkoxy group, a lower alkylthio group, a cyano group, a hydroxyl group, a phenoxy group, a phenyl group or a halogen atom, and m is an integer of 0 to 4. When m is 2 or more, X may be the same or different.)