JPWO2006004062A1 - 2,6-dichloro-4-pyridylmethylamine derivative and agricultural and horticultural disease control agent - Google Patents

Abstract

The present invention provides a 2,6-dichloro-4-pyridylmethylamine derivative and an acid addition salt thereof, and an agricultural and horticultural disease control agent containing the same. A 2,6-dichloro-4-pyridylmethylamine derivative of the formula (I) is a novel compound and can be used as an active ingredient of an agricultural and horticultural disease control agent. Wherein R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 3 carbon atoms. R 4 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 4 carbon atoms. Represents an alkoxy group, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. When n is 2 or more, , X may be the same or different.) [Selection figure] None

Description

  The present invention relates to agricultural and horticultural disease control comprising 2,6-dichloro-4-pyridylmethylamine derivative and acid addition salt thereof, and 2,6-dichloro-4-pyridylmethylamine derivative and acid addition salt thereof as active ingredients. It relates to the agent.

Conventionally, 2,6-dihalogenated isonicotinic acid ester derivatives and 2,6-dichloroisonicotinic acid benzylamide derivatives are known as agricultural fungicides for isonicotinic acid derivatives.
JP-A-1-283270 JP-A-8-208615

  In order to develop an agricultural and horticultural disease control agent that has low toxicity to human livestock and high safety in handling, and exhibits an excellent control effect against a wide range of plant diseases, the following formula ( I) 2,6-dichloro-4-pyridylmethylamine derivatives and acid addition salts thereof were synthesized and their disease control effects were examined. Accordingly, an object of the present invention is to provide 2,6-dichloro-4-pyridylmethylamine derivatives and acid addition salts thereof that can be used as active ingredients of agricultural and horticultural disease control agents, and agricultural and horticultural disease control agents containing the same. Is to provide.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents a haloalkyl group, a cyano group, COOR ⁴ or CONHR ⁴ , wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom; Represents an alkoxy group of -4, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. n is 2 or more. X may be the same or different.)

  As a result of intensive studies to solve such problems, the present inventors have found that the 2,6-dichloro-4-pyridylmethylamine derivative represented by the formula (I) and its acid addition salt are novel compounds, As a result, the present invention was found to be excellent as a horticultural disease control agent.

  The first gist of the present invention resides in a 2,6-dichloro-4-pyridylmethylamine derivative represented by the following formula (I) and an acid addition salt thereof.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents a haloalkyl group, a cyano group, COOR ⁴ or CONHR ⁴ , wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom; Represents an alkoxy group of -4, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. n is 2 or more. X may be the same or different.)

  The second gist of the present invention resides in an agricultural and horticultural disease control agent containing a 2,6-dichloro-4-pyridylmethylamine derivative of the following formula (I) and an acid addition salt thereof as active ingredients.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents a haloalkyl group, a cyano group, COOR ⁴ or CONHR ⁴ , wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom; Represents an alkoxy group of -4, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. n is 2 or more. X may be the same or different.)

  According to the present invention, the 2,6-dichloro-4-pyridylmethylamine derivative represented by the formula (I) and acid addition salts thereof can be used as active ingredients of agricultural and horticultural disease control agents.

Hereinafter, the present invention will be described in detail. Substituents (R ¹ , R ² , R ³ , R ⁴ , X) of the 2,6-dichloro-4-pyridylmethylamine derivative (I) of the present invention (hereinafter sometimes abbreviated as “the present compound”) In the definition of), the substituents shown in the general concept include the following preferred substituents.

R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and, as the alkyl group having 1 to 4 carbon atoms of R ^1, may be cyclic also be straight-chain or branched, such as methyl group, Examples include an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, and a cyclobutyl group, preferably a hydrogen atom or a methyl group. It is.

R ² and R ³ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 3 carbon atoms, a cyano group, COOR ⁴ or CONHR ⁴ , and R ² and R ³ The alkyl group having 1 to 4 carbon atoms may be linear, branched or cyclic. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, A sec-butyl group, a tert-butyl group, a cyclopropyl group, and a cyclobutyl group are included. R ² is preferably a methyl group, an ethyl group, an n-propyl group, or COOR ⁴ . R ³ is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and, as the alkyl group having 1 to 4 carbon atoms R ^4, may be cyclic also be straight-chain or branched, such as methyl group, Ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, cyclopropyl group, cyclobutyl group are included.

  X represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms. And the alkyl group having 1 to 4 carbon atoms of X may be linear, branched or cyclic. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n- A butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group, a cyclopropyl group, and a cyclobutyl group are included. Examples of the alkoxy group having 1 to 4 carbon atoms of X include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an i-propoxy group, an i-butoxy group, a sec-butoxy group, and a tert-butoxy group. The halogen atom of X includes chlorine, fluorine, bromine and iodine, and the haloalkyl group having 1 to 4 carbon atoms of X includes a trifluoromethyl group, a trichloromethyl group, a difluoromethyl group and a pentafluoroethyl group. The haloalkoxy group having 1 to 4 carbon atoms of X includes a trifluoromethoxy group. n is an integer of 0 to 5, preferably 0 to 3, more preferably 1 or 2. .

  In addition, as this invention compound shown by general formula (I), the compound of Tables 1-2 can be illustrated.

A) and B) shown in Tables 1 and 2 show the following contents.
A): Indicates the following contents. 4-Cl in the compound (I-3) of the present invention represents a chlorine atom bonded to the 4-position. 3,4-Cl ₂ in the compound (I-27) of the present invention indicates that a chlorine atom is bonded to the 3-position and the 4-position. That is, the number before "-" indicates the bonding position, and the number after "-" indicates the number when there are two or more substituents and the same kind of substituents. In the compound (I-19) of the present invention, H represents unsubstituted.
B): Indicates hydrochloride.

  Although the manufacturing method of the compound shown by the said general formula (I) in this invention is not specifically limited, For example, it can manufacture with the following two methods.

That is, the amine derivative represented by the formula (II) and the 2,6-dichloro-4-halogenomethylpyridine derivative represented by the formula (III) are reacted in an appropriate solvent in the presence of a base, or the formula The α-halogenomethylbenzene derivative represented by (IV) is reacted with the 2,6-dichloro-4-aminomethylpyridine derivative represented by the formula (V) in the presence of a base in a suitable solvent. A 2,6-dichloro-4-pyridylmethylamine derivative represented by (I) can be produced (wherein X, R ¹ , R ² and R ³ have the same definition as above, Y represents a halogen atom) For example, chlorine, bromine or iodine.

Other methods include an amine derivative represented by the formula (II) and 2,6-dichloro-4-pyridylaldehyde represented by the formula (VI), or a ketone derivative represented by the formula (VII) and the formula ( The 2,6-dichloro-4-aminomethylpyridine derivative represented by V) is subjected to a reductive amination reaction in a suitable solvent in the presence of a reducing agent to produce 2,6- A dichloro-4-pyridylmethylamine derivative can be produced (wherein X, R ¹ , R ² and R ³ have the same definition as above, and R ⁵ has the same definition as R ² or R ³ ). .)

  The reaction solvent is not particularly limited as long as it does not participate in the reaction, but preferably an aprotic polar solvent such as N, N-dimethylformamide and dimethyl sulfoxide, ethers such as tetrahydrofuran and dioxane, chloroform, dichloroethane and the like. And halogenated hydrocarbons, acetone, acetonitrile and the like. Bases include alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate and potassium hydrogen carbonate, alkaline earth metal carbonates such as calcium carbonate and barium carbonate, and alkalis such as sodium hydroxide and potassium hydroxide. Metal hydroxide, alkali metal such as lithium, sodium and potassium, alkali alkoxide such as sodium methoxide, sodium ethoxide and potassium t-butoxide, alkali metal hydride such as sodium hydride and potassium hydride, methyl Alkali metal organometallic compounds such as lithium, ethyl lithium, n-butyl lithium, and phenyl lithium can be used. While the reaction temperature varies depending on the solvent, base and the like, it is generally 0 to 100 ° C, preferably 20 to 80 ° C. While the reaction time varies depending on the reaction temperature, solvent, base and the like, it is generally 0.1 to 10 hours, preferably 0.5 to 5 hours.

  The reaction solvent used in the reductive amination reaction is not particularly limited as long as it does not participate in the reaction, but preferably alcohols such as methanol and ethanol, ethers such as tetrahydrofuran and dioxane, 1,2-dichloroethane, and the like. And halogenated hydrocarbons such as water, acetonitrile and the like. These solvents can be used alone, or can be used as a mixed solvent containing at least one of these solvents. The reducing agent used in the reductive amination reaction is preferably a complex hydrogen compound such as sodium triacetoxyborohydride or sodium cyanoborohydride. In addition to the complex hydrogen compound, for example, a combination of hydrogen gas and a hydrogenation catalyst such as palladium / charcoal or Raney nickel can be suitably used. The amount of the reducing agent used is preferably 1.0 to 20.0 moles, more preferably 1.0 to 3.0 moles, relative to the aldehyde derivative (VI) or ketone derivative (VII). preferable. While the reaction temperature varies depending on the solvent, base and the like, it is generally 0-80 ° C, preferably 20-50 ° C. While the reaction time varies depending on the reaction temperature, solvent, base and the like, it is generally 0.1 to 48 hours, preferably 1 to 24 hours.

In the 2,6-dichloro-4-pyridylmethylamine derivative (I) thus obtained, the carbon to which R ² and R ³ are bonded may have an asymmetric carbon. Optical isomers can exist with or without dots. In the present invention, the 2,6-dichloro-4-pyridylmethylamine derivative (I) includes all single isomers as well as mixtures of each isomer in any ratio.

  Furthermore, since the 2,6-dichloro-4-pyridylmethylamine derivative (I) can easily form an acid addition salt, it may be used in the form of an inorganic acid salt or an organic acid salt. Examples of acids that form acid addition salts include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, and phosphoric acid, formic acid, acetic acid, butyric acid, p-toluenesulfonic acid, and dodecylbenzenesulfone. Examples thereof include organic acids such as acid, camphorsulfonic acid, maleic acid, palmitic acid, stearic acid, oxalic acid, succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid, and saccharin.

  Next, the usefulness of the 2,6-dichloro-4-pyridylmethylamine derivative of the formula (I) according to the present invention as an active ingredient of an agricultural and horticultural disease control agent will be described.

  The 2,6-dichloro-4-pyridylmethylamine derivative (I) of the present invention exhibits a controlling effect against a wide range of plant diseases shown below. For example, rice blast (Pyricularia grisea), rice sesame leaf blight (Cochliobolus miyabeanus), rice white blight (Xanthomonas oryzae), rice blight (Rhizoctonia solani), rice small black rot (Helminthosporium sigmoideun), rice Seedling disease (Gibberella fujikuroi), rice seedling blight (Pythium aphanidermatum), apple powdery mildew (Podosphaera leucotricha), apple black spot disease (Venturia inaequalis), apple morinia disease (Monilinia mali), apple spotted leaf disease (Alternaria alternata), Apple rot (Valsa mali), pear black spot (Alternaria kikuchiana), pear powdery mildew (Phyllactinia pyri), pear scab (Gymnosporangium asiaticum), pear black scab (Venturia nashicola), grape powdery mildew (Uncinula necator) , Grape mildew (Plasmopara viticola), grape late rot (Glomerella cingulata), barley powdery mildew (Erysiphe graminis f. Sp hordei), barley blackness Diseases (Puccinia graminis), barley yellow rust (Puccinia striiformis), barley leaf (Pyrenophora graminea), barley cloud (Rhynchosporium secalis), wheat powdery mildew (Erysiphe graminis f. Sp tritici), wheat red rust recondita), wheat yellow rust (Puccinia striiformis), wheat eyespot (Pseudocercosporella herpotrichoides), wheat red mold (Microdochium nivale), wheat blight (Leptosphaeria nodorum), wheat leaf blight (Septoria tritici), cucurbits Powdery mildew (Sphaerotheca fuliginea), cucumber anthracnose (Colletotrichum lagenarium), cucumber downy mildew (Pseudoperonospora cubensis), cucumber gray plague (Phytophthora capsici), tomato powdery mildew (Erysiphe cichoracearum), tomato ring disease (Alternary rot) solani), eggplant powdery mildew (Erysiphe cichoracearum), strawberry powdery mildew (Sphaerotheca humuli), tobacco powdery mildew (Er ysiphe cichoracearum), sugar beet brown spot (Cercospora beticola), corn smut (Ustillaga maydis), fruit tree gray scab (Monilinia fructicola), gray mold (Botrytis cinerea), fungal sclerosis ( Sclerotinia sclerotiorum) and the like.

  In order to apply the compound of the present invention as an active ingredient of an agricultural and horticultural disease control agent, it may be left as it is without adding any other components, but usually mixed with a solid carrier, a liquid carrier, a surfactant, and other formulation adjuvants. Then, it is formulated and used in various forms such as powders, wettable powders, granules, and emulsions. These preparations are formulated so that the compound of the present invention is usually contained in an amount of 0.1 to 95% by weight, preferably 0.5 to 90% by weight, more preferably 2 to 80% by weight.

  Examples of carriers, diluents, and surfactants used as formulation adjuvants include solid carriers such as talc, kaolin, bentonite, diatomaceous earth, white carbon, and clay, and liquid diluents include water. Xylene, toluene, chlorobenzene, cyclohexane, cyclohexanone, dimethyl sulfoxide, dimethylformamide, alcohol and the like. Surfactants should be properly used depending on their effects. Examples of emulsifiers include polyoxyethylene alkyl aryl ethers and polyoxyethylene sorbitan monolaurate. Dispersants include lignin sulfonate and dibutyl naphthalene sulfonate. Examples of the wetting agent include alkyl sulfonates and alkylphenyl sulfonates.

  The above preparations include those used as they are and those diluted to a predetermined concentration with a diluent such as water. The concentration of the compound of the present invention when diluted is preferably in the range of 0.001 to 1.0%. Moreover, the usage-amount of this invention compound becomes like this. Preferably it is 20-5000g, More preferably, it is 50-1000g per 1 ha of agricultural and horticultural lands, such as a field, a rice field, an orchard, and a greenhouse. Since these use concentrations and amounts differ depending on the dosage form, use time, use method, use place, target crop, etc., it is of course possible to increase or decrease without sticking to the above range. Furthermore, the compound of the present invention can be used in combination with other active ingredients such as fungicides, insecticides, acaricides and herbicides.

  Hereinafter, the present invention will be specifically described with reference to production examples, formulation examples, and test examples. In addition, this invention is not limited to the following manufacture examples, formulation examples, and test examples, unless the summary is exceeded.

Production Example 1:
<Production of N- (2,6-dichloro-4-pyridylmethyl)-(R) -1- (4-chlorophenyl) ethylamine (I-4)>
(1) 2,6-dichloroisonicotinic acid chloride (32.0 g) was added dropwise to a solution of sodium borohydride (10.2 g) dissolved in 200 ml of 40% ethanol aqueous solution and stirred for 2 hours. After the reaction, extraction with dichloromethane was performed, and the organic layer was washed with water and brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the obtained solid was recrystallized from acetone / hexane to obtain 15.5 g of 2,6-dichloro-4-pyridylmethanol. As a result of measuring the physical properties of this compound, it was as shown below.

  Next, 15.0 g of 2,6-dichloro-4-pyridylmethanol was suspended in 350 ml of benzene, 1.0 ml of pyridine and 10 ml of thionyl chloride were added, and the mixture was refluxed for 3 hours. After thionyl chloride was distilled off under reduced pressure, the residue was partitioned by adding water and ethyl acetate. The organic layer was washed successively with aqueous hydrochloric acid, aqueous sodium hydroxide solution and saturated brine, and dried over anhydrous sodium sulfate. The resulting oily product was distilled under reduced pressure to obtain 15.8 g of 2,6-dichloro-4-pyridylmethyl chloride (which solidified on standing). As a result of measuring the physical properties of this compound, it was as shown below.

  (2) 0.39 g of 2,6-dichloro-4-pyridinemethyl chloride obtained in (1) above was added together with 0.27 g of (R) -1- (4-chlorophenyl) ethylamine and 0.36 g of anhydrous potassium carbonate, and N , N-dimethylformamide dissolved in 6 ml and stirred at 75 ° C. for 1.5 hours. After cooling, the solvent was distilled off under reduced pressure, water and ethyl acetate were added to the residue, and the mixture was passed through a diatomaceous earth column. After elution with ethyl acetate, the eluate was concentrated under reduced pressure and purified by silica gel chromatography to give N- (2,6-dichloro-4-pyridylmethyl)-(R) -1- (4-chlorophenyl) ethylamine. 0.42 g of (I-4) was obtained as an oily substance. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 2:
<Production of 2- [2,6-dichloro-4-pyridylmethyl) amino] -2-phenylacetic acid methyl ester (I-19)>
Under ice-cooling, a hydrogen chloride-methanol solution was added to 1.5 g of phenylglycine, and the mixture was stirred overnight at room temperature. The solvent was distilled off to obtain 2.0 g of 2-amino-2-phenylacetic acid methyl ester hydrochloride as a white solid. As a result of measuring the physical properties of this compound, it was as shown below.

  Next, 0.21 g of 2-amino-2-phenylacetic acid methyl ester hydrochloride and 0.24 g of 2,6-dichloro-4-pyridylmethyl bromide were dissolved in 5 ml of dehydrated dimethylformamide, and 0.36 g of anhydrous potassium carbonate was added. , And stirred at 70 ° C. for 3 hours. After cooling, the mixture was concentrated under reduced pressure, water and ethyl acetate were added to the residue, and the mixture was passed through a diatomaceous earth column. After elution with ethyl acetate, the eluate was concentrated under reduced pressure and purified by silica gel chromatography to give 2-[(2,6-dichloro-4-pyridylmethyl) amino] -2-phenylacetic acid methyl ester (I- The white solid 0.17g of 19) was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 3:
<Production of 2- (2-methylphenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester (I-34)>
(1) To 2.25 g of 2-methylphenylacetic acid, 2 ml of carbon tetrachloride and 4.25 ml of thionyl chloride were added and stirred at 65 ° C. for 1 hour. After cooling, 7.5 ml of carbon tetrachloride and 3.13 g of N-bromosuccinimide were added, 48% hydrobromic acid was further added, and the mixture was heated to 85 ° C. and stirred for 2 hours. After cooling, the oil obtained by filtration and concentration under reduced pressure was added to 50 ml of methanol, stirred for 30 minutes, and then concentrated under reduced pressure to obtain 3.80 g of a crude reaction product. The crude reaction product was purified by silica gel chromatography to obtain 2.99 g of α-bromo-4-methylphenylacetic acid methyl ester as a colorless oil. As a result of measuring the physical properties of this compound, it was as shown below.

  (2) 6.6 g of 2,6-dichloro-4-pyridylmethyl chloride obtained in the same manner as in (1) of Production Example 1 was dissolved in 60 ml of N, N-dimethylformamide, and 7.1 g of potassium phthalimide was added. The mixture was stirred at 70 ° C. for 2 hours. After cooling, the reaction solution was poured into water, and the precipitate was filtered under reduced pressure. The precipitate was suspended in 150 ml of water, 7.2 g of 25% aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 3 hours. Further, 32 g of a 10% hydrochloric acid aqueous solution was added and stirred at reflux for 3 hours. After cooling, the pH was adjusted to 10-11 using an aqueous sodium hydroxide solution, followed by extraction with chloroform. The organic layer was washed successively with 2% aqueous sodium hydroxide solution, water and brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the obtained solid was recrystallized with ethyl acetate / hexane to obtain 3.5 g of 2,6-dichloro-4-pyridylmethylamine. As a result of measuring the physical properties of this compound, it was as shown below.

  (3) 0.54 g of α-bromo-4-methylphenylacetic acid methyl ester obtained in (1) above and 0.27 g of 2,6-dichloro-4-pyridylmethylamine obtained in (2) were dehydrated acetonitrile. It melt | dissolved in 7 ml, the anhydrous potassium carbonate 0.23g was added, and it recirculate | refluxed for 1.5 hours. After cooling, water and ethyl acetate were added to the residue obtained by concentration under reduced pressure and passed through a diatomaceous earth column. After elution with ethyl acetate, the eluate was concentrated under reduced pressure, purified by silica gel chromatography, and recrystallized to give 2- (2-methylphenyl) -2-[(2,6-dichloro-4-pyridylmethyl). ) Amino] acetic acid methyl ester (I-34) 0.38 g of white powder crystal was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 4:
<Production of 2- (4-methoxyphenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester (I-37)>
Dissolve 1.55 g of 4-methoxymandelic acid in 10 ml of acetonitrile, add 1.29 g of 1,8-diazabicyclo [5.4.0] -7-undecene and 1.57 g of methyl iodide, and stir at room temperature for 20 hours. did. The solvent was distilled off and the residue was purified by silica gel chromatography to obtain 1.41 g of α-hydroxy-4-methoxyphenylacetic acid methyl ester. As a result of measuring the physical properties of this compound, it was as shown below.

  1.25 g of the resulting α-hydroxy-4-methoxyphenylacetic acid methyl ester was dissolved in 50 ml of dichloromethane, 2.00 g of triphenylphosphine and 3.16 g of carbon tetrabromide were added, and the mixture was stirred at room temperature for 13 hours. The reaction solution was concentrated to dryness and purified by silica gel chromatography to obtain 1.05 g of α-bromo-4-methoxyphenylacetic acid methyl ester. As a result of measuring the physical properties of this compound, it was as shown below.

  Next, 0.57 g of this α-bromo-4-methoxyphenylacetic acid methyl ester and 0.27 g of 2,6-dichloropyridine-4-methylamine were dissolved in dehydrated acetonitrile, and then 0.23 g of anhydrous potassium carbonate was added. Reflux for 5 hours. After cooling, water and ethyl acetate were added to the residue obtained by concentration under reduced pressure and passed through a diatomaceous earth column. After elution with ethyl acetate, the eluate was concentrated under reduced pressure and purified by silica gel chromatography to give 2- (4-methoxyphenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid. 0.17 g of methyl ester (I-37) was obtained as a pale yellow oil. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 5:
<Production of 2- (2-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] -N-methylacetamide (I-41)>
Dissolve 0.31 g of 2- (2-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester (I-25) in methanol and add 40% methylamine methanol solution. , Stirred overnight. The solvent was distilled off and the residue was purified by silica gel chromatography to give 2- (2-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] -N-methylacetamide (I-41). 0.31 g of oil was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 6:
<Production of 2- (4-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester (I-21)>
(1) A hydrogen chloride-methanol solution was added to 8.0 g of 4-chlorophenylglycine under ice cooling, and the mixture was allowed to stand at room temperature for 2 days. After distilling off methanol, the residue was made basic by adding aqueous sodium hydrogen carbonate solution. Extraction was performed with dichloromethane, and the organic layer was washed successively with water and brine and dried over anhydrous sodium sulfate. Concentration under reduced pressure yielded 5.0 g of 2-amino-2- (4-chlorophenyl) acetic acid methyl ester as a reddish brown oil. As a result of measuring the physical properties of this compound, it was as shown below.

  (2) Suspend 5.0 g of 2,6-dichloro-4-pyridylmethanol obtained in the same manner as in Production Example 1 (1) in 150 ml of dehydrated dichloromethane, add 12.1 g of pyridinium chlorochromate, and And stirred vigorously for 4.5 hours. The reaction solution was filtered, and the residue was washed with chloroform. The filtrate and washings were combined and concentrated under reduced pressure to give a dark brown oily crude reaction solution. This crude reaction solution was purified by silica gel chromite to obtain 4.1 g of a yellow oily substance of 2,6-dichloro-4-pyridylaldehyde (this oily substance solidified on standing). As a result of measuring the physical properties of this compound, it was as shown below.

  (3) 3.12 g of 2-amino-2- (4-chlorophenyl) acetic acid methyl ester obtained in (1) above and 2.5 g of 2,6-dichloro-4-pyridylaldehyde obtained in (2) above Was dissolved in 35 ml of 1,2-dichloroethane, 3.3 g of sodium triacetoxyborohydride was added, and the mixture was stirred at room temperature for 14 hours. Saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was stirred for 30 min and extracted with dichloromethane. The organic layer was washed successively with water and brine and dried over anhydrous sodium sulfate. After concentration under reduced pressure, the resulting crude reaction product was purified by silica gel chromatography, and further crystallized from ethyl acetate / hexane to give 2- (4-chlorophenyl) -2-[(2,6-dichloro-4-pyridyl). 1.62 g of methyl) amino] acetic acid methyl ester (I-21) was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 7:
<Production of N- (2,6-dichloro-4-pyridylmethyl) -1-phenylethylamine (I-2)>
0.123 g of acetophenone and 0.20 g of 2,6-dichloro-4-pyridylmethylamine obtained in the same manner as in Production Example 3 (2) were dissolved in 7 ml of 1,2-dichloroethane, and sodium triacetoxyborohydride 0.261 g was added and stirred at room temperature for 20 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, and the mixture was stirred for 30 minutes, and then the solvent was distilled off under reduced pressure. Water and ethyl acetate were added to the residue and passed through a diatomaceous earth column. Elution with ethyl acetate was performed, and the eluate was concentrated under reduced pressure to obtain a crude reaction product. This crude reaction product was purified by silica gel chromatography to obtain 0.20 g of a colorless oily substance of N- (2,6-dichloro-4-pyridylmethyl) -1-phenylethylamine (I-2). As a result of measuring the physical properties of this compound, it was as shown below.

Production Example 8:
<Production of 2- (4-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester hydrochloride (I-46)>
After dissolving 1.50 g of 2- (4-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester (I-21) in anhydrous diethyl ether, 1 molar hydrochloric acid diethyl ether 4.2 ml was added dropwise. The precipitated crystals were filtered, washed and dried to give a white solid of 2- (4-chlorophenyl) -2-[(2,6-dichloro-4-pyridylmethyl) amino] acetic acid methyl ester hydrochloride (I-46) 1.60 g of product was obtained. As a result of measuring the physical properties of this compound, it was as shown below.

  The compounds in Table 1 were synthesized by operations according to the above Production Examples 1-8. Properties and NMR data of these compounds are shown in Tables 20 to 31.

The symbols in the table indicate the following contents.
s: single line, d: double line, t: triple line, q: quadruple line, m: multiple line, br: broad line, dd: double double line, qq: quadruple line

Formulation Example 1:
<Dust>
Compound (I-4): 3 parts by weight Clay: 40 parts by weight Talc: 57 parts by weight are ground and mixed and used as dust.

Formulation Example 2:
<Wettable powder>
Compound (I-21): 50 parts by weight lignin sulfonate: 5 parts by weight Alkyl sulfonate: 3 parts by weight Diatomaceous earth: 42 parts by weight are ground and mixed to obtain a wettable powder and diluted with water for use.

Formulation Example 3:
<Granule>
Compound (I-29): 5 parts by weight Bennite: 43 parts by weight Clay: 45 parts by weight Lignin sulfonate: 7 parts by weight are mixed uniformly, kneaded with water, processed into granules by an extrusion granulator, and dried. To make granules.

Formulation Example 4:
<Emulsion>
Compound (I-32): 20 parts by weight polyoxyethylene alkylaryl ether: 10 parts by weight polyoxyethylene sorbitan monolaurate: 3 parts by weight Xylene: 67 parts by weight are uniformly mixed and dissolved to prepare an emulsion.

Test Example 1:
<Rice blast control effect test (water surface application)>
Grain prepared in accordance with Formulation Example 3 to a predetermined concentration (500 g / 10a) after transplanting rice (variety: Koshihikari) at the 3-leaf stage into a 1 / 10000a Wagner pot filled with paddy soil. Applied to the water surface. 10 to 20 days after the drug treatment, a spore suspension of rice blast fungus formed on rice disease was spray-inoculated and kept under high humidity in a vinyl tunnel in a glass greenhouse. 10 to 20 days after the inoculation, the following survey criteria (Chinese agricultural trial leaf potato survey criteria) are used to investigate the disease severity for all seedlings per test area, and from the average disease severity per pot, formula: control value = The control value (%) was calculated by (1-treated area disease severity / untreated area disease severity) × 100. The survey criteria are shown in Table 31 and the results are shown in Table 32.

Test example 2:
<Wheat powdery mildew control effect (stem and leaf spray)>
Using a square-shaped pot (1.5 cm × 2.0 cm), a wet concentration prepared in accordance with Formulation Example 2 was added to wheat (cultivar: Norin 61) grown in a tillering greenhouse. 90 g / ha) was diluted with water and suspended at a rate of 1000 L / ha. 10 to 20 days after drug treatment, spores of wheat powdery mildew were sprinkled and inoculated. After that, she was sick in a glass greenhouse. On the 10th to 20th day after the inoculation, the disease area ratio (%) was investigated objectively, and the following calculation criteria was used to calculate the following formula: control value = (1−treatment area disease severity / The control value (%) was calculated by (non-treated morbidity) × 100. The survey criteria are shown in Table 24 and the results are shown in Table 25.

Claims (2)

2,6-dichloro-4-pyridylmethylamine derivatives represented by the following formula (I) and acid addition salts thereof.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents a haloalkyl group, a cyano group, COOR ⁴ or CONHR ⁴ , wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom; Represents an alkoxy group of -4, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. n is 2 or more. X may be the same or different.) An agricultural and horticultural disease control agent comprising a 2,6-dichloro-4-pyridylmethylamine derivative of the following formula (I) and an acid addition salt thereof as active ingredients.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ² and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkyl group having 1 to 3 carbon atoms. Represents a haloalkyl group, a cyano group, COOR ⁴ or CONHR ⁴ , wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Xn represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 carbon atom; Represents an alkoxy group of -4, a cyano group, a nitro group, a halogen atom, a haloalkyl group having 1 to 4 carbon atoms, or a haloalkoxy group having 1 to 4 carbon atoms, n represents an integer of 0 to 5. n is 2 or more. X may be the same or different.)