JPH07285942A - Phenoxyalkylamine derivative, its production and agricultural and horticultural germicide - Google Patents

Abstract

PURPOSE:To obtain a new compound, useful as an agricultural and horticultural germicide and capable of controlling pests. CONSTITUTION:This compound is expressed by formula I [R<1> is a 1-4C alkyl or H; R<2> is a 1-4C alkyl; R<3> is a l-6C alkyl or H; R<4> is a 1-4C alkyl, H or a halogen; R<5> is A-O-R<7> (A is a 1-4C alkylene; R<7> is a 1-6C alkyl, a 3-6C alkenyl or a 3-6C alkynyl), a 1-10C alkyl, H, a halogen, etc.; R<6> is H, a 1-4C alkyl or a halogen], e.g. methyl N-{2-[4-(2-ethoxyethyl)-2-methylphenoxylethyl}-l,3- dimethylpyrazole-5-carboxamide-4-carboxylate. The compound expressed by formula I is obtained by reacting a pyrazoledicarboxylic acid derivative expressed by formula II (R<8> is a 1-6C alkyl) with phenoxvalkylamines expressed by formula III, preferably in the presence of a base (e.g. sodium methoxide). This compound is effective against blast of rice plant, downy mildew of cucumber, red rust of wheat, powdery mildew of barley, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel phenoxyalkylamine derivative useful as a fungicide for agriculture and horticulture.

[0002]

2. Description of the Related Art The following are known as phenoxyalkylamine derivatives. (1) Japanese Patent Laid-Open No. 3-27360 discloses the following formula

[0003]

[Chemical 4]

(Where A is¹Is an alkyle having 2 to 5 carbon atoms
Represents a group; R¹And R²Are hydrogen atom or carbon respectively
Represents an alkyl group of 1 to 5; R³, R^FourAnd R^FiveIs
Hydrogen atom, alkyl group having 1 to 5 carbon atoms or ha
Rogen atom; R⁶Is a hydrogen atom, having 1 to 5 carbon atoms
Alkyl group, alkenyl group having 3 to 5 carbon atoms or group-A
²-X-R⁷Represents; A²Is an alkyle having 1 to 5 carbon atoms
Represents an oxygen group; X represents an oxygen atom or a sulfur atom; R⁷Is
Alkyl group with 1 to 5 carbon atoms, Alke with 3 to 5 carbon atoms
Nyl group, alkynyl group having 3 to 5 carbon atoms or substituted or
Represents an unsubstituted aralkyl group. )
Described as effective as an insecticide, acaricide and fungicide
Has been done. (2) Japanese Patent Laid-Open No. 5-59011 discloses the following formula

[0005]

[Chemical 5]

[0006] wherein, R ¹ represents a lower alkyl group or a lower haloalkyl group; R ² represents a hydrogen atom or a lower alkyl group; R ³ is a hydrogen atom, a lower alkyl group or a halogen atom; R ⁴ is Lower alkenyl group or -A-O-
R ⁶ (wherein A represents a lower alkylene group; R ⁶ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group); R ⁵ represents a hydrogen atom, a lower alkyl group or a halogen atom. ] It is described that the compound shown by these is effective as an insecticide, an acaricide, and a bactericide. (3) Japanese Patent Laid-Open No. 5-125054 discloses the following formula

[0007]

[Chemical 6]

[Wherein R ¹ represents a lower alkyl group or a lower haloalkyl group; R ² represents a hydrogen atom, a lower alkyl group or a halogen atom; R ³ represents a lower alkenyl group or —A—O—R ⁵ ( However, A represents a lower alkylene group;
R ⁵ represents a lower alkyl group, a lower alkenyl group or a lower alkynyl group. R ⁴ represents a hydrogen atom, a lower alkyl group or a halogen atom. ] It is described that the compound shown by these is effective as an insecticide, an acaricide, and a bactericide.

However, the pyrazole-like compounds of the present invention
There are no reports of 5-carboxamide derivatives. Therefore, it is not known that the phenoxyalkylamide derivative as in the present invention is useful as a fungicide.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel phenoxyalkylamine derivative, a method for producing the same, and an agricultural and horticultural fungicide containing the same as an active ingredient.

[0011]

The present inventors have found that a novel phenoxyalkylamine derivative has a remarkable controlling activity as a fungicide for agricultural and horticultural use, and completed the present invention. That is, the present invention is as follows. The first invention is
Formula (I):

[0012]

[Chemical 7]

[Wherein R¹Is an alkyl having 1 to 4 carbon atoms
Represents a group or a hydrogen atom; R²Is an alky having 1 to 4 carbons
Represents a radical; R³Is an alkyl group having 1 to 6 carbon atoms or water
Represents an elementary atom; R^FourIs an alkyl group having 1 to 4 carbon atoms, water
Represents an elementary atom or a halogen atom; R^FiveIs -A-O-R⁷
(However, A represents an alkylene group having 1 to 4 carbon atoms; R
⁷Is an alkyl group having 1 to 6 carbon atoms and an alkyl group having 3 to 6 carbon atoms.
Represents a alkenyl group or an alkynyl group having 3 to 6 carbon atoms.
You ), An alkyl group having 1 to 10 carbon atoms, a hydrogen atom,
Represents a logen atom or an alkenyl group having 3 to 6 carbon atoms;
R⁶Is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or halo
Represents a gen atom. ] Phenoxyalkylamido
The present invention relates to a derivative thereof. The second invention is the following formula (I
I):

[0014]

[Chemical 8]

(Wherein R ¹ and R ² are as defined above; R ⁸ represents an alkyl group having 1 to 6 carbon atoms) and a pyrazole dicarboxylic acid derivative represented by the following formula (III):

[0016]

[Chemical 9]

(Wherein R ^{4 to} R ⁶ have the same meanings as described above), and a phenoxyalkylamine derivative represented by the above formula (I) is reacted. It relates to the manufacturing method of. A third invention relates to a pest control agent for agricultural and horticultural use, which comprises the phenoxyalkylamine derivative represented by the formula (I) as an active ingredient.

The present invention will be described in detail below. Regarding the target compound and the starting material compound, R ^{1 to} R ⁸ and A represented by the novel phenoxyalkylamine derivative [compound (I)] in the present invention and the starting materials thereof [compound (II), compound (III), etc.] are as follows. Is the street.

Examples of R ¹ include an alkyl group having 1 to 4 carbon atoms and a hydrogen atom. Examples of the alkyl group for R ¹ include linear and branched ones; preferably a methyl group and an ethyl group. Examples of R ² include a linear or branched alkyl group having 1 to 4 carbon atoms; a methyl group and an ethyl group are preferable.

Examples of R ³ include an alkyl group having 1 to 6 carbon atoms and a hydrogen atom. Examples of the alkyl group in R ³ include linear or branched ones; preferably those having 1 to 4 carbon atoms; more preferably those having 1 to 3 carbon atoms. Is.

Examples of R ⁴ include an alkyl group having 1 to 4 carbon atoms, a hydrogen atom and a halogen atom. Examples of the alkyl group for R ⁴ include linear or branched ones; preferably those having 1 to 3 carbon atoms. Examples of the halogen atom in R ⁴ include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom, but a chlorine atom is preferable.

R ⁵ is -A-O-R ⁷ , carbon number 1
Examples thereof include an alkyl group having 10 carbon atoms, a hydrogen atom, a halogen atom, and an alkenyl group having 3 to 6 carbon atoms.
Examples of A in —A—O—R ⁷ include an alkylene group having 1 to 4 carbon atoms; R ⁷ includes an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 3 to 6 carbon atoms. Group, an alkynyl group having 3 to 6 carbon atoms, and the like. Examples of A include a linear or branched alkylene group; preferably an ethylene group.

Examples of the alkyl group for R ⁷ include linear or branched ones; preferably those having 1 to 4 carbon atoms; more preferably 1 to 3 carbon atoms. belongs to. Examples of the alkenyl group for R ⁷ include linear or branched ones; preferably those having 3 to 4 carbon atoms; and more preferably allyl group. Examples of the alkynyl group for R ⁷ include linear or branched ones; preferably those having 3 to 4 carbon atoms (for example,
1-propynyl group, 2-propynyl group, 2-butynyl group, etc.); and more preferably 2-propynyl group.

Examples of the alkyl group for R ⁵ include linear or branched ones; preferably those having 1 to 8 carbon atoms; and more preferably 1 to 5 carbon atoms. belongs to. Examples of the halogen atom for R ⁵ include a chlorine atom, an iodine atom, a bromine atom, a fluorine atom and the like; preferably a chlorine atom. Examples of the alkenyl group for R ⁵ include linear or branched ones; preferably those having 3 to 4 carbon atoms; and more preferably allyl group.

Examples of R ⁶ include a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a halogen atom and the like. Examples of the alkyl group for R ⁶ include linear and branched ones; preferably a methyl group. The position of the substituent is not particularly limited; it is preferably 3-position and 6-position.

Examples of the halogen atom for R ⁶ include a chlorine atom, an iodine atom, a bromine atom and a fluorine atom; preferably a chlorine atom. And
The position of the substituent is not particularly limited; preferably 6
-It is the place. Examples of R ⁸ include a linear or branched alkyl group having 1 to 6 carbon atoms; preferably the alkyl group described as R ¹ is used.

Examples of the compound (I) include those in which the above various substituents are combined, and from the viewpoint of efficacy, R ^{1 to} R ⁴ are linear chains having 1 to ⁴ carbon atoms. A branched or branched alkyl group, R ⁵ is —A—O
-R ⁷ (A is a linear or branched alkylene group having 1 to 4 carbon atoms, and R ⁷ is a linear or branched alkyl group having 1 to 6 carbon atoms), hydrogen An atom or a halogen atom, R ⁶ is a hydrogen atom; more preferably R ^{1 to} R ⁴ are methyl groups, R ⁵ is a 2-ethoxyethyl group, a hydrogen atom or a chlorine atom, R ⁶ is a hydrogen atom. Specific compounds (I) among these include compounds 1, 3, 5, 9, 10, 17 to 20 described in Tables 1 to 4 below.

Synthesis of Compound (I) Compound (I) can be synthesized by the method shown below. Compound (I-1) [In compound (I), R ³
The compound represented by R ⁸ in which is an alkyl group having 1 to 6 carbon atoms] is prepared by reacting compound (II) with compound (III) in a solvent or without a solvent, as shown below. Can be carried out; preferably, the reaction is carried out in the presence of a base to accelerate the reaction.

[0029]

[Chemical 10]

(Wherein R ¹ , R ² , R ^{4 to} R ⁶ and R ⁸
Is as defined above. ) The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, ligroine, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, Chlorinated or unchlorinated aromatic, aliphatic, alicyclic hydrocarbons such as dichloroethane, trichloroethylene, cyclohexane; ethers such as diethyl ether, tetrahydrofuran, dioxane; methanol, ethanol, propanol, Alcohols such as butanol; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; triethylamine, pyridine,
Organic bases such as N, N-dimethylaniline; 1,
3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents, and the like.

The amount of the solvent used is the compound (I
The compound (II) can be used in a concentration range of 5 to 80% by weight, but the compound (II) is preferably used in a concentration range of 10 to 70% by weight.

The base is not particularly limited and includes, for example,
Organic bases such as triethylamine, pyridine, N, N-dimethylaniline and DBU; alkali metal alkoxides such as sodium methoxide and sodium ethoxide;
Mention may be made of inorganic bases such as sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate; alkali metal alkoxides are preferred.

The amount of the base used is the compound (I
It can be used in a molar amount of 0.001 to 5 times, preferably 0.5 to 2 times, the molar amount of I).
The reaction temperature is not particularly limited, but is within a temperature range from the ice cooling temperature to the boiling point of the solvent used or less, and 80 to 120 ° C.
Is preferred. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 1 to 5 hours. The amount of the raw material compound used is 0.5 to 2 times mol of the compound (III) with respect to the compound (II), but preferably 1.0 to 1.5.
It is preferable that the molar ratio is double.

The compound (II) can be produced, for example, according to the method described in Chem. Ber., 93 , 1859 (1960) as shown below.

[0035]

[Chemical 11]

(In the formula, R¹, R²And R⁸Is the same as above
Righteous. ) As the compound (II), for example, the compounds described in Tables 1 to 4 below are given.
Listed R¹, R², R ⁸(However, R⁸Is R³Charcoal in
It represents an alkyl group having a prime number of 1 to 6. ) Has
Can be mentioned each compound [compound (II)₁~
Compound (II)₃₂Called. For example, compound (II)₁Is R
¹, R²And R⁸Is a methyl group. ].

The compound (III) can be produced, for example, according to the method described in the following.

[0038]

[Chemical 12]

[In the formula, R ^{4 to} R ⁶ have the same meanings as described above; Y represents a halogen atom (eg, chlorine atom, bromine atom, fluorine atom, iodine atom). As the compound (III), for example, each compound having R ^{4 to} R ⁶ described in Tables 1 to 4 below can be mentioned [compound (III) ₁ to compound (III) _32] . For example, in compound (III) ₁ , R ⁴ is a methyl group, R ⁵ is a 2-ethoxyethyl group, and R ⁶ is a hydrogen atom. ]. Compound (I-1) [Compound (I), wherein R ³ is a hydrogen atom] is synthesized by the following method as follows: compound (I-1) and compound (IV) in a solvent or The reaction can be carried out in the absence of a solvent; however, the reaction is preferably carried out in the presence of a base in order to accelerate the reaction.

[0040]

[Chemical 13]

(In the formula, R ¹ , R ² , R ^{4 to} R ⁶ and R ⁸
Has the same meaning as above; M represents an alkali metal. The solvent is not particularly limited as long as it does not directly participate in this reaction, and examples thereof include water; ethers such as tetrahydrofuran and dioxane; alcohols such as methanol, ethanol, propanol and butanol; acetone, Ketones such as methyl ethyl ketone; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; mixtures of the above solvents and the like. be able to.

The amount of the solvent used is the compound (I-
The compound (1) can be used in a concentration range of 5 to 80% by weight, and preferably the compound (I-1) is used in a concentration of 10 to 70% by weight.

Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; sodium hydroxide and potassium hydroxide are preferred.

The amount of the base used is the compound (I
It can be used in an amount of 0.001 to 5 times by mole with respect to I), but preferably 0.5 to 2 times by mole. The reaction temperature is not particularly limited, but is within a temperature range from the ice cooling temperature to the boiling point of the solvent used or less, and preferably 50 to 100 ° C. The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be 1 to 5 hours. The amount of the raw material compound used is 0.5 for the compound (IV) relative to the compound (I-1).
˜2 times the molar amount, but preferably 1.0 to 1.5 times the molar amount.

As the compound (IV), the following commercial products can be obtained.・ Sodium hydroxide (Wako Pure Chemical Industries, Ltd., product number 194-02135) ・ Potassium hydroxide (Wako Pure Chemical Industries, Ltd., product number 165-03865) ・ Sodium carbonate (Wako Pure Chemical Industries, Ltd., Product number 199-01585) -Sodium hydrogen carbonate (Wako Pure Chemical Industries, Ltd., product number 191-01305) -Potassium carbonate (Wako Pure Chemical Industries, Ltd., product number 165-03505)

The desired compound (I) produced as described above is subjected to usual post-treatments such as extraction, concentration and filtration after the completion of the reaction, and if necessary, known methods such as recrystallization and various chromatographies. It can be appropriately purified by the above method.

Examples of the compound (I) include compounds 1 to 32 having R ^{1 to} R ⁶ shown in Tables 1 to 4 below (for example, the compound 1 is R ^{1 to} R ^4).
Is a methyl group, R ⁵ is a 2-ethoxyethyl group, and R ⁶ is a hydrogen atom. ].

Pest control agent for agricultural and horticultural use [Controlling effect] Examples of agricultural and horticultural pathogens which have a controlling effect with the compound (I) of the present invention include rice blast,
Those that cause cucumber downy mildew, barley powdery mildew, and wheat leaf rust can be mentioned.

[Pest Control Agent] The pest control agent of the present invention has a remarkable bactericidal effect against agricultural and horticultural pathogens, and contains at least one compound (I) as an active ingredient. Is. The compound (I) may be used alone, but is usually mixed with a carrier, a surfactant, a dispersant, an auxiliary agent, etc. by a conventional method (eg, powder, emulsion, fine granule, granule, hydrate, etc.). It is preferably prepared as a composition such as an agent, an oily suspension, or an aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbonization. Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene) Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethylsulfoxide, etc.), water; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection), and the like.

Examples of surfactants and dispersants that can be used to improve the performance of this agent such as adhesion to animals and plants, improvement of absorption, dispersion of drug, emulsification, spreading and the like include, for example, alcohol sulfates and alkyls. Examples thereof include sulfonate, lignin sulfonate, polyoxyethylene glycol ether and the like. In order to improve the properties of the preparation, for example, carboxymethyl cellulose, polyethylene glycol, gum arabic or the like can be used as an auxiliary agent.

In the preparation of the present agent, the above-mentioned carrier, surfactant, dispersant and auxiliary agent can be used alone or in suitable combination according to the purpose.
The concentration of the active ingredient when the compound (I) of the present invention is formulated is usually 1 to 50% by weight in the case of emulsion and 0.3 in the case of powder.
-25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, usually 0.5 to 5% by weight for oil formulations, and usually 0.1 to 5% by weight for aerosols. is there. These formulations can be diluted to an appropriate concentration and sprayed on the surface of plant foliage, soil, water surface of paddy fields or directly applied to various applications depending on the purpose.

[0053]

EXAMPLES The present invention will be specifically described below with reference to examples. It should be noted that these examples do not limit the scope of the present invention. Example 1 [Synthesis of Compound (I)] (1) N- {2- [4- (2-ethoxyethyl) -2-methylphenoxy] ethyl} -1,3-dimethylpyrazole-5-carboxamide-4- Synthesis of carboxylic acid methyl ester [Compound 1]

1,3-Dimethylpyrazole-4,5-dicarboxylic acid dimethyl ester (2.4 g) and 2- [4-
(2-Ethoxyethyl) -2-methylphenoxy] ethylamine (2.5 g) was dissolved in toluene (20 ml), 28% sodium methoxide methanol solution (3.0 g) was added, and the mixture was heated under reflux for 1 hr. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, the toluene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The oily substance thus obtained was isolated by a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 2.7 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.20 (t, 3H), 2.25 (s, 3H), 2.4
1 (s, 3H), 2.80 (t, 2H), 3.50
(Q, 2H), 3.59 (t, 2H), 3.85-3.
90 (m, 5H), 4.12 (t, 2H), 4.18
(S, 3H), 6.75 (d, 1H), 6.99 (d,
1H), 7.00 (s, 1H), 10.18 (s, 1
H)

(2) Synthesis of N- {2- [4- (2-ethoxyethyl) -2-methylphenoxy] ethyl} -3-methylpyrazole-5-carboxamide-4-carboxylic acid methyl ester [compound 2]

3-Methylpyrazole-4,5-dicarboxylic acid dimethyl ester (0.8 g) and 2- [4- (2-
Ethoxyethyl) -2-methylphenoxy] ethylamine (0.9 g) was dissolved in toluene (10 ml), and 2
8% sodium methoxide in methanol (1.0
g) was added and the mixture was heated under reflux for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, and the toluene layer was separated,
After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oily substance was isolated with a silica gel column (Wakogel C-200, toluene: ethyl acetate = 1: 1) and then washed with n-hexane to obtain 1.0 g of the desired product as colorless powdery crystals. Obtained.

¹ H-NMR (CDCl ₃ , δppm) 1.20 (t, 3H), 2.28 (s, 3H), 2.5
0 (s, 3H), 2.80 (t, 2H), 3.50
(Q, 2H), 3.59 (t, 2H), 3.88-3.
95 (m, 5H), 4.12 (t, 2H), 6.74
(D, 1H), 6.79 to 7.02 (m, 2H), 1
0.61 (s, 1H), 12.21 (s, 1H)

(3) Synthesis of N- {2- [4- (2-ethoxyethyl) -2-methylphenoxy] ethyl} -1,3-dimethylpyrazole-5-carboxamide-4-carboxylic acid [compound 3]

Compound 1 (1.2 g) obtained in the above (1) was mixed with 3
Aqueous sodium hydroxide solution (5 ml) was added, and the mixture was heated under reflux for 1 hr. After completion of the reaction, the mixture was cooled to room temperature, weakly acidified with dilute hydrochloric acid, and the precipitated crystals were collected by filtration. The obtained crystals were washed with water and then with n-hexane to obtain 1.1 g of the target substance as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 1.20 (t, 3H), 2.19 (s, 3H), 2.4
0 (s, 2H), 2.79 (t, 2H), 3.50
(Q, 2H), 3.60 (t, 2H), 3.82 (t,
d, 2H), 4.11 (t, 2H), 4.19 (s, 3)
H), 6.71 (d, 1H), 6.92 to 7.00
(M, 2H), 10.03 (s, 1H)

(4) N- {2- [4- (2-methoxyethyl) -2-methylphenoxy] ethyl} -1,3-dimethylpyrazole-5-carboxamide-4-carboxylic acid methyl ester [Compound 9] Synthesis of

1,3-Dimethylpyrazole-4,5-dicarboxylic acid dimethyl ester (0.8 g) and 2- [4-
(2-Methoxyethyl) -2-methylphenoxy] ethylamine (0.8 g) was dissolved in toluene (10 ml), 28% sodium methoxide methanol solution (0.9 g) was added, and the mixture was heated under reflux for 2 hr. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, the toluene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was isolated by a silica gel column (Wakogel C-200, toluene: ethyl acetate = 9: 1 elution) to obtain 0.9 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 2.26 (s, 3H), 2.42 (s, 3H), 2.7
9 (t, 2H), 3.34 (s, 3H), 3.57
(T, 2H), 3.80 to 3.88 (m, 5H), 4.
12 (t, 2H), 4.18 (s, 3H), 6.75
(D, 1H), 6.95 to 7.00 (m, 2H), 1
0.18 (s, 2H)

(5) N- (2-phenoxyethyl) -1,
Synthesis of 3-dimethylpyrazole-5-carboxamide-4-carboxylic acid methyl ester [compound 17]

1,3-Dimethylpyrazole-4,5-dicarboxylic acid dimethyl ester (1.0 g) and 2-phenoxyethylamine (0.65 g) were added to toluene (10 m).
It was dissolved in 1), 28% sodium methoxide in methanol (1.1 g) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, the toluene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The oily substance thus obtained was isolated by a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 0.8 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 2.41 (s, 3H), 3.80 to 3.86 (m, 5
H), 4.21 to 4.18 (m, 5H), 6.92 to
7.00 (m, 3H), 7.24 to 7.32 (m, 2
H), 10.03 (s, 1H)

(6) N- [2- (2-methylphenoxy)
Ethyl] -1,3-dimethylpyrazole-5-carboxamide-4-carboxylic acid methyl ester [Compound 18]
Synthesis of

1,3-Dimethylpyrazole-4,5-dicarboxylic acid dimethyl ester (0.7 g) and 2-phenoxyethylamine (0.5 g) were added to toluene (10 m).
1), 28% sodium methoxide in methanol (0.8 g) was added, and the mixture was heated under reflux for 2 hours. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, the toluene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The oily substance thus obtained was isolated by a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 6: 1) to obtain 0.7 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 2.82 (s, 3H), 2.43 (s, 3H), 3.8
2 to 3.91 (m, 5H), 4.11 to 4.19 (m,
5H), 6.80 to 6.91 (m, 2H), 7.10
7.19 (m, 2H), 10.20 (s, 1H)

(7) N- [2- (4-chlorophenoxy)
Ethyl] -1,3-dimethylpyrazole-5-carboxamide-4-carboxylic acid methyl ester [Compound 19]
Synthesis of

1,3-Dimethylpyrazole-4,5-dicarboxylic acid dimethyl ester (1.1 g) and 2- (4-
Chlorophenoxy) ethylamine (0.9 g) was dissolved in toluene (10 ml), 28% sodium methoxide methanol solution (1.2 g) was added, and the mixture was heated under reflux for 2 hr. After completion of the reaction, the mixture was cooled to room temperature, water (10 ml) was added, the toluene layer was separated, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The oily substance thus obtained was isolated by a silica gel column (Wakogel C-200, eluted with toluene: ethyl acetate = 9: 1) to obtain 1.1 g of the desired product as colorless powdery crystals.

¹ H-NMR (CDCl ₃ , δppm) 2.41 (s, 3H), 3.28 (t, d, 2H),
3.88 (s, 3H), 4.12 (t, 2H), 4.1
8 (s, 3H), 6.89 (d, 2H), 7.22
(D, 2H), 10.11 (s, 1H)

(9) Synthesis of other compounds (I) in Tables 1 to 4 Other compounds (I) in Tables 1 to 4 were synthesized according to the methods described in (1) to (8) above. did. The compounds synthesized as described above are shown in Tables 1 to 4.

[0075]

[Table 1]

[0076]

[Table 2]

[0077]

[Table 3]

[0078]

[Table 4]

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium lignin sulfonate were uniformly mixed, and then a small amount of water was added and kneaded, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 67.5 parts by weight of kaolin, 20 parts by weight of white carbon, 2 parts by weight of neoperex powder (trade name; manufactured by Kao Corporation) and demol (product) Name; made by Kao Co., Ltd.) and 0.5 parts by weight, and
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of Compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Kasei Co., Ltd.) were added and mixed uniformly to obtain an emulsion. .

(4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and 4 of kaolin
A powder was obtained by uniformly mixing 5 parts by weight.

Example 3 [Efficacy test] (1) Efficacy test against rice blast (stem and leaf spraying test) Ten rice plants (cultivar: Nihonbare) were cultivated in a plastic flower pot with a diameter of 6 cm and grown at the three-leaf stage. Compounds (I) shown in Tables 1 to 4 prepared according to Example 2 in plants
Each wettable powder of 1 with 1% water containing surfactant (0.01%)
It was diluted to 000 ppm and sprayed at 20 ml per pot. The day after the spraying, a conidial suspension of rice blast fungus (3 × 10 ⁵ spores / ml) prepared from diseased leaves was uniformly spray-inoculated onto plant leaves. After inoculation, the plants were kept in a moist chamber for 1 day and then grown in a glass greenhouse to examine the degree of rice blast lesions appearing on the third leaf. The evaluation of the bactericidal effect was carried out in 6 stages (0: the entire diseased,
1: Lesion area is about 60%, 2: Lesion area is about 40%, 3: Lesion area is about 20%, 4: Lesion area is 10%
Hereinafter, 5: no lesions). The results are shown in Table 5.

[0084]

[Table 5]

(2) Efficacy test against rice blast (hydroponic test) Each wettable powder of the compound (I) shown in Tables 1 to 4 prepared according to Example 2 was treated with a surfactant (0.01 %) To 50 ppm. This is a test tube (φ18mm
Xh110 mm), and after cultivating 3-leaf stage rice (cultivar; Nihonbare) in this for 3 days, a conidial suspension of rice blast fungus (3 × 10 ⁵ ) prepared from diseased leaves was prepared.
Spores / ml) were uniformly spray-inoculated onto plant leaves. After inoculation,
After keeping the plants in the humid chamber for 1 day, grow them in a glass greenhouse,
The extent of the rice blast lesion that appeared on the third leaf was investigated. The results of the evaluation of the bactericidal effect are shown in Table 6 by the 6-step evaluation method described in (1) above.

[0086]

[Table 6]

(3) Control efficacy test against cucumber downy mildew One cucumber (cultivar: Sagamihanjiro) was grown in a plastic flower pot with a diameter of 6 cm, and the plant at the time of 1.5 leaves was treated with Table 1. To the target compound (I) shown in
Wettable powder prepared according to
Diluted to 1000ppm with water containing
Sprayed with 0 ml. The day after the spraying, a suspension of cucumber downy mildew zoosporangium (1 × 10 ⁵ spores / ml) was uniformly spray-inoculated on the plants. After inoculation, the plants were kept in the dark at 20 ° C. for 1 day and then grown in a glass greenhouse to examine the degree of rice blast lesions appearing on the first leaves. The results of evaluation of the bactericidal effect are shown in Table 7 by the 6-step evaluation method described in (1) above.

[0088]

[Table 7]

(4) Efficacy test against barley powdery mildew 10 barleys (cultivar: Kromugi) were cultivated in a plastic flower pot having a diameter of 6 cm, 10 plants per pot, and planted at 1.5 leaf stage, according to Example 2. Each of the wettable powders of compound (I) shown in Tables 1 to 4 prepared by
Each of them was diluted to 1000 ppm with water containing water, and 20 ml of each chemical solution was sprayed per pot. The day after the spraying, the conidia of barley powdery mildew fungi prepared from the diseased leaves were sprinkled evenly on the plants to inoculate them. After inoculation, it was grown in a glass greenhouse for 1 week, and the degree of barley powdery mildew lesions appearing on the first leaf was examined. The result of the evaluation of the bactericidal effect is
Table 8 shows the 6-step evaluation method described in (1).

[0090]

[Table 8]

(4) Efficacy test against wheat leaf rust Wheat (cultivar: Kobushi wheat) was cultivated in a plastic flower pot having a diameter of 6 cm, 10 plants per pot, and the plant body at 1.5 leaf stage was treated according to Example 2. The prepared wettable powder of the compound (I) shown in Tables 1 to 4 was used as a surfactant (0.01%).
Dilute to 1000ppm with water containing 20
sprayed with ml. The day after the spraying, a spore suspension of wheat rust (5 × 10 ⁵ spores / ml) was uniformly spray-inoculated on the plants. After inoculation, the plants were grown in a glass greenhouse for 1 week, and the degree of wheat leaf rust lesions appearing on the first leaf was investigated. The results of evaluation of the bactericidal effect are shown in Table 9 by the 6-step evaluation method described in (1) above.

[0092]

[Table 9]

[0093]

The novel phenoxyalkylamine derivative of the present invention has an excellent bactericidal effect.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Koichi Morikuni 5 1978, Koujigushi, Ube City, Yamaguchi Prefecture 5 1978, Ube Laboratory, Ube Industries, Ltd. Ube Institute, Ube Institute

Claims (3)

[Claims] 1. The following formula (I):[In the formula, R¹Is an alkyl group having 1 to 4 carbon atoms or a hydrogen source
Represents a child; R²Represents an alkyl group having 1 to 4 carbon atoms;
R³Represents an alkyl group having 1 to 6 carbon atoms or a hydrogen atom.
Do; R^FourIs an alkyl group having 1 to 4 carbon atoms, a hydrogen atom or
Represents a halogen atom; R^FiveIs -A-O-R⁷(However, A
Represents an alkylene group having 1 to 4 carbon atoms; R ⁷Is the carbon number
1 to 6 alkyl groups and 3 to 6 carbon alkenyl groups
Alternatively, it represents an alkynyl group having 3 to 6 carbon atoms. ), Carbon number
1 to 10 alkyl groups, hydrogen atoms, halogen atoms or
Represents an alkenyl group having 3 to 6 carbon atoms; R⁶Is hydrogen
Child, alkyl group having 1 to 4 carbon atoms or halogen atom
You ] The phenoxy alkylamine derivative shown by these. 2. The following formula (II): (Wherein R ¹ and R ² have the same meanings as described in claim 1; R ⁸ represents an alkyl group having 1 to 6 carbon atoms) and a pyrazole dicarboxylic acid derivative represented by the following formula (III) : [Chemical 3] (Wherein R ^{4 to} R ⁶ have the same meanings as described in claim 1) and are reacted with phenoxyalkylamines represented by the formula (I) in claim 1. Process for producing phenoxyalkylamine derivative. 3. An agricultural and horticultural fungicide containing the phenoxyalkylamine derivative represented by the formula (I) according to claim 1 as an active ingredient.