JPH11263776A - Pyridyloxy(thio)alkanoic acid amide derivative and agricultural/horticultural germicide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound having high controlling effect against rice blast and the like while having no chemical injury on crops, excellent in residual activity and resistance to rain, therefore useful as an agricultural/ horticultural germicide. SOLUTION: This new compound is shown by formula I (X is H or the like; (n) is 1-4; R<1> is H or the like; R<2> and R<3> are each a 1-6C alkyl or the like; Q is a 2-6C alkyl or the like; A is an oxygen atom or the like), e.g. 2-(4,5- ditrifluoromethylpyridin-2-y]-oxy)-N-(1-isopropyl-1-methyl-2-oxopropyl) propionamide. The compound of formula I is obtained, for example, by reaction of a pyridyloxy(thio)alkanoic acid derivative of formula II [e.g. 2-(4,5- ditrifluoromethylpyridin-2-yloxy)propionic acid] with an amine of formula III (e.g. 3-amino-3,4-dimethyl-2-pentanone hydrochloride) normally in a solvent, as necessary in the presence of a catalyst and/or base, using a condensation agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a pyridyloxy (thio) alkanoic acid amide derivative which is a novel compound not described in any literature, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

[0002]

2. Description of the Related Art JP-A-5-286937 and JP-A-6-306050 disclose that pyridyloxycarboxylic acid amide derivatives have bactericidal activity. However, the compound of the present invention is not described at all.

[0003]

In recent years, due to the heavy use of fungicides for agricultural and horticultural use, resistant bacteria have emerged, and existing drugs may not show sufficient bactericidal activity. In addition, a new disinfectant capable of efficiently controlling harmful bacteria at a low concentration is demanded due to environmental problems. Accordingly, the present invention provides a pyridyloxy (thio) alkanoic acid amide derivative having a novel and excellent bactericidal activity.

[0004]

Means for Solving the Problems The present inventors have synthesized various pyridyloxy (thio) alkanoic acid amide derivatives,
Examination of its physiological activity revealed that the compound of the present invention has a broad bactericidal spectrum, has particularly excellent bactericidal activity against blast, and does not cause any harm to useful crops. Was completed. That is, the present invention relates to (1) a compound represented by the general formula [I]:

[0005]

Embedded image [Wherein, X is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C _1-
C ₄ haloalkyl group, C ₁ -C ₆ alkoxy group, C _1-
A C ₄ haloalkoxy group, a C ₂ -C ₆ alkenyloxy group, a C ₂ -C ₆ alkynyloxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₄ haloalkylthio group, a halogen atom, an amino group, a nitro group, A cyano group, a phenyl group (the group is a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ haloalkyl group,
It may be substituted by a C ₁ -C ₆ alkoxy group or a halogen atom. ) Or a phenoxy group, which is a C ₁ -C
C ₆ alkyl group, C ₁ -C ₄ haloalkyl group, C ₁ -C
_It may be substituted by a ₆ alkoxy group or a halogen atom. N represents an integer of 1 to 4, R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group or a C ₁ -C ₄ haloalkyl group, and R ² and R
³ each independently represent a C ₁ -C ₆ alkyl group, C _2-
A C ₆ alkenyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group), a C ₃ -C ₆ cycloalkyl C ₁
Represents a C ₆ -alkyl group or a C ₁ -C ₄ haloalkyl group, or R ² and R ³ together with the carbon atom to which they are attached are a 5- to 7-membered cycloalkyl group (the C ₁
It may be substituted by -C ₆ alkyl group. ) To form, Q is _C 2 -C ₆ alkyl group, ethynyl group, group -
COR ⁴ (R ⁴ is a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group) or C ₁ -C ₄ Represents a haloalkyl group) or a group —CH (OH) R ⁵ (R
⁵ represents a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted with a halogen atom or a C ₁ -C ₆ alkyl group) or a C ₁ -C ₄ haloalkyl group. . A represents an oxygen atom or a sulfur atom. ] The pyridyloxy (thio) alkanoic acid amide derivative represented by these.

(2) A fungicide for agricultural and horticultural use containing the pyridyloxy (thio) alkanoic acid amide derivative as an active ingredient.

First, terms used in the present specification will be described below. In this specification, for example, a notation such as “C _{1 to} C ₆ ” indicates that the number of carbon atoms of the substituent following the substituent is 1 to 6 in this case.

The C ₁ -C ₆ alkyl group means a linear or branched alkyl group, for example, a methyl group, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
-Pentyl group, isopentyl group, neopentyl group, n-
Examples include a hexyl group, an isohexyl group, and a 3,3-dimethylbutyl group.

The C ₃ -C ₆ cycloalkyl group includes, for example, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like.

The C ₃ -C ₆ cycloalkyl C ₁ -C ₆ alkyl group includes, for example, a cyclopropylmethyl group, a cyclopentylmethyl group, a cyclohexylmethyl group and the like.

The C ₁ -C ₄ haloalkyl group refers to a linear or branched alkyl group substituted by a halogen atom, such as a fluoromethyl group, a chloromethyl group, a bromomethyl group, a difluoromethyl group, a dichloromethyl group. Group, dibromomethyl group, trifluoromethyl group, chlorodifluoromethyl group, pentafluoroethyl group and the like.

The halogen atom means a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The C ₁ -C ₆ alkoxy group means a linear or branched alkoxy group, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec -Butoxy group, te
Examples thereof include an rt-butoxy group, an n-pentyloxy group, an isopentyloxy group, and an n-hexyloxy group.

The C ₂ -C ₆ alkenyloxy group refers to a linear or branched alkenyloxy group, such as an allyloxy group, an isopropenyloxy group, or a 2-butenyloxy group.

The term "C ₂ -C ₆ alkynyloxy group" refers to a linear or branched alkynyloxy group.
Examples thereof include a propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group.

The C ₁ -C ₄ haloalkoxy group refers to a straight-chain or branched-chain alkoxy group substituted by a halogen atom, for example, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, a pentafluoroethoxy group. And the like.

The C ₁ -C ₆ alkylthio group means a linear or branched alkylthio group, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec
-Butylthio group, tert-butylthio group, n-hexylthio group and the like.

The C ₁ -C ₄ haloalkylthio group is a straight or branched alkylthio group substituted by a halogen atom, such as fluoromethylthio, difluoromethylthio, trifluoromethylthio, and pentafluoroethyl. And thio groups.

Some of the compounds of the present invention represented by the general formula [I] have one or two or more asymmetric carbon atoms in the molecule. There are isomers. Pure individual diastereomers, enantiomers and mixtures thereof are also included in the compounds of the present invention.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred compounds of the compound of the present invention represented by the general formula [I] are those wherein X is a methyl group, a trifluoromethyl group, a chlorine atom, a bromine atom or an iodine atom, R ¹ is a hydrogen atom, R ² is a hydrogen atom, a methyl group, an ethyl group or an n-propyl group, and R ^{3 is a} methyl group or an ethyl group;
Is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group or a dichloromethyl group, Q is an ethynyl group,
Examples of the compound include an acetyl group, a propionyl group, a cyclopropylcarbonyl group, and a 1-hydroxyethyl group.

Next, specific examples of the compound of the present invention represented by the general formula [I] are shown in Tables 1 to 6, but are not limited thereto.

The symbols in the table have the following meanings.
Me represents a methyl group, Et represents an ethyl group, and P
r represents an n-propyl group, Pr-i represents an isopropyl group, Bu represents an n-butyl group, Bu-i represents an isobutyl group, and Bu-t represents a tert-butyl group. And Pr-cyc represents a cyclopropyl group;
Pen-cyc indicates a cyclopentyl group, and Ph indicates a phenyl group. Further, for example, Ph (4-Cl) indicates a 4-chlorophenyl group.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

[0027]

[Table 5]

[0028]

[Table 6]

[0029]

[Table 7]

[0030]

[Table 8]

[0031]

[Table 9]

[0032]

[Table 10]

[0033]

[Table 11]

[0034]

[Table 12] The compound of the present invention represented by the general formula [I] can be produced, for example, according to the following production method. Manufacturing method 1

[0035]

Embedded image (In the formula, R ¹ , R ² , R ³ , Q, X, n and A represent the same meaning as described above.)

The compound [I] of the present invention comprises a pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II]:
If necessary, it can be produced by reacting with an amine represented by the general formula [III] using a condensing agent in the presence of a catalyst and / or a base. This reaction is usually performed in a solvent. As a solvent that can be used, a solvent that does not inhibit the reaction may be used, for example, hydrocarbons such as pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene or xylene, dichloromethane, dichloroethane, chloroform, and carbon tetrachloride , Halogenated hydrocarbons such as chlorobenzene or dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, methyl acetate or Acetates such as ethyl acetate; nitriles such as acetonitrile or propionitrile; dimethyl sulfoxide; N, N-dimethylformamid Or aprotic polar solvents such as sulfolane, or may be a mixed solvent combining solvents selected from these.

As the condensing agent, for example, 1-ethyl-3-
(3-Dimethylaminopropyl) carbodiimide hydrochloride, N, N'-dicyclohexylcarbodiimide, carbonyldiimidazole, 2-chloro-1,3-dimethylimidazolium chloride and the like.

Examples of the catalyst include 4-dimethylaminopyridine, 1-hydroxybenzotriazole, dimethylformamide and the like.

As the base, those generally used in this type of reaction can be used. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkaline earth metal hydroxide such as calcium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, or triethylamine, trimethylamine, N, N- Dimethylaniline, pyridine, N-methylpiperidine, 1,5-
Diazabicyclo [4.3.0] non-5-ene (DB
N) or 1,8-diazabicyclo [5.4.0] -7-
Organic bases such as undecene (DBU) and the like are preferable, and tertiary amines such as triethylamine, pyridine and N-methylpiperidine are preferable.

The reaction temperature ranges from -50 ° C to 150 ° C,
It is preferably carried out in the range of 0 ° C to 100 ° C. The reaction time is preferably 1 to 30 hours.

Next, a method for producing a starting compound used in this production method will be described.

First, the compound represented by the general formula [II] can be produced, for example, according to the following production method.

[0043]

Embedded image (Wherein, R ¹ , X, n and A represent the same meaning as described above,
R ⁶ represents a C ₁ -C ₆ alkyl group, and Z represents a leaving group such as a halogen atom. )

The pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II] can be obtained, for example, by converting a pyridine derivative represented by the general formula [IV] or [VII] in the presence of a base into the general formula [V] Reaction with an alkanoic acid ester derivative represented by [VIII] leads to a pyridyloxy (thio) alkanoic acid ester derivative represented by the general formula [VI], followed by hydrolysis of the pyridyloxy (thio) alkanoic acid ester derivative It can be manufactured by the following.

In the above reaction formula, the general formula [IV] or [VI
I] and a pyridine derivative represented by the general formula [V] or [V
The reaction with the ester derivative represented by III] is usually performed in a solvent. The solvent that can be used may be any solvent that does not inhibit the reaction, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, hydrocarbons such as toluene or xylene, dichloromethane, dichloroethane, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, chlorobenzene or dichlorobenzene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether,
Ethers such as tetrahydrofuran or dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acetates such as methyl acetate or ethyl acetate, nitriles such as acetonitrile or propionitrile, or dimethyl sulfoxide, N , N-dimethylformamide or sulfolane, or a mixed solvent obtained by combining solvents selected from these.

As the base, those generally used in this type of reaction can be used. For example, sodium hydroxide,
Examples thereof include inorganic bases such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, and potassium hydride; and organic bases such as triethylamine, trimethylamine, N, N-dimethylaniline, and pyridine.

The reaction temperature ranges from -50 ° C. to 150 ° C.
It is preferably carried out in the range of 0 ° C to 100 ° C. The reaction time is preferably 1 to 30 hours.

The pyridyloxy (thio) alkanoic acid ester derivative represented by the general formula [II] is hydrolyzed in the presence of an acid or an alkali to hydrolyze the pyridyloxy (thio) alkanoic acid ester derivative represented by the general formula [VI]. The reaction for obtaining the derivative is usually performed in a solvent. The solvent that can be used may be any solvent that does not inhibit the reaction, for example, water, alcohols such as methanol, ethanol or 2-propanol, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, ethers such as tetrahydrofuran or dioxane, or A ketone such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, or a mixed solvent obtained by combining solvents selected from these can be used.

The compound represented by the general formula [III] can be prepared by a known method [for example, Journal of the Chemical.
Society. Perkin Transactions. 1 (J
own of the Chemical So
ciety. PerkinTransactions.
1), Vol. 8, p. 1645 (1985); The Journal of Organic Chemistry (The J.
ownnal of Organic Chemistr
y), Vol. 49, p. 1208 (1984)] or a method analogous thereto. Manufacturing method 2

[0050]

Embedded image (In the formula, R ¹ , R ² , R ³ , Q, X, n, A and Z represent the same meaning as described above.)

The compound [I] of the present invention has the general formula [VII]
Can be produced by reacting a pyridine derivative represented by the formula with an alkanoic acid amide derivative represented by the general formula [IX] in the presence of a base. This reaction is usually
Performed in a solvent. As a solvent that can be used, a solvent that does not inhibit the reaction may be used, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, hydrocarbons such as toluene or xylene, dichloromethane, dichloroethane, chloroform,
Halogenated hydrocarbons such as carbon tetrachloride, chlorobenzene or dichlorobenzene, diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether,
Ethers such as tetrahydrofuran or dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone, acetates such as methyl acetate or ethyl acetate, nitriles such as acetonitrile or propionitrile, or dimethyl sulfoxide, N , N-dimethylformamide or sulfolane, or a mixed solvent obtained by combining solvents selected from these.

As the base, those generally used in this type of reaction can be used. For example, sodium hydroxide,
Examples thereof include inorganic bases such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium hydride, and potassium hydride; and organic bases such as triethylamine, trimethylamine, N, N-dimethylaniline, and pyridine.

The reaction temperature ranges from -50 ° C to 150 ° C,
It is preferably carried out in the range of 0 ° C to 100 ° C. The reaction time is preferably 1 to 30 hours.

In this reaction, the compound represented by the general formula [IX] can be produced, for example, by reacting a halogenated alkanoic acid halide with an amine derivative represented by the general formula [III]. Manufacturing method 3

[0055]

Embedded image (In the formula, R ¹ , R ² , R ³ , Q, X, n and Z represent the same meaning as described above.)

The compound [I] of the present invention can be produced by reacting a pyridine derivative represented by the general formula [IV] with an alkanoamide derivative represented by the general formula [X] in the presence of a base. Can be. This reaction is usually performed in a solvent. As a solvent that can be used, any solvent that does not inhibit the same reaction as in Production Method 2 may be used.

As the base, those generally used as in Production method 2 can be used.

The reaction temperature ranges from -50 ° C to 150 ° C,
It is preferably carried out in the range of 0 ° C to 100 ° C. The reaction time is preferably 1 to 30 hours.

In this reaction, the compound represented by the general formula [X] is, for example, an acetoxyalkanoic acid amide derivative obtained by reacting a halogenated alkanoic acid amide derivative represented by the general formula [IX] with sodium acetate. Can be produced by deacylation of Manufacturing method 4

[0060]

Embedded image (In the formula, R ¹ , R ² , R ³ , X, n and A represent the same meaning as described above.)

The compound [I-II] of the present invention has the general formula [I-
The pyridyloxy (thio) alkanoic acid amide derivative represented by I] can be produced by performing a hydration reaction in the presence of an acid. This reaction is performed without a solvent or in a solvent. As a solvent that can be used, any solvent that does not inhibit the reaction may be used, for example, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone or methyl isobutyl ketone. Acetic acid esters such as methyl acetate or ethyl acetate, nitriles such as acetonitrile or propionitrile, or aprotic polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide or sulfolane, or a solvent selected from these. Mixed solvent mixtures can be used.

Examples of the acid include sulfuric acid, hydrochloric acid, formic acid and the like.

The reaction is carried out at a temperature ranging from 0 ° C. to 150 ° C., preferably from 20 ° C. to 100 ° C. The reaction time is preferably 1 to 10 hours. Manufacturing method 5

[0064]

Embedded image (In the formula, R ¹ , R ² , R ³ , R ⁵ , X, n and A represent the same meaning as described above.)

The compound [I-IV] of the present invention has the general formula [I
-III] and reacting the pyridyloxy (thio) alkanoic acid amide derivative with a reducing agent. This reaction is usually performed in a solvent.
As a solvent that can be used, any solvent that does not inhibit the reaction may be used, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene and other hydrocarbons, dichloromethane, dichloroethane, chloroform, tetrachloride Carbon, halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, ethers such as diethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, methanol, ethanol, 2-
An alcohol such as propanol or a mixed solvent of water and an alcohol can be used.

As the reducing agent, those generally used in this type of reaction can be used. For example, lithium borohydride, sodium borohydride, potassium borohydride, lithium trialkyl borohydride, sodium trialkyl borohydride, sodium cyanoborohydride and the like, preferably sodium borohydride .

The reaction temperature ranges from -70 ° C to 150 ° C,
Preferably, it is carried out in the range of -20 ° C to 50 ° C.
The reaction time is preferably 1 to 30 hours.

[0068]

Next, the process for producing the compound of the present invention will be described specifically. <Production Example 1> 2- (4,5-ditrifluoromethylpyridin-2-yloxy) -N- (1-isopropyl-1)
Preparation of -Methyl-2-oxopropyl) propionamide (Compound No. A-10) 2- (4,5-Ditrifluoromethylpyridin-2-yloxy) propionic acid 1 in 50 ml of dichloromethane.
0 g and 1.1 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride were added. After stirring at room temperature for 30 minutes, 3-amino-3,4-dimethyl-2-
Pentanone hydrochloride 0.8 g, triethylamine 0.5
g was added. The mixture was stirred at room temperature for 12 hours, poured into water and extracted with dichloromethane. The dichloromethane layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired product (0.5 g). Melting point 127-1
30 ° C

<Reference Example 1-a> Methyl 2- (4,5-
Preparation of ditrifluoromethylpyridin-2-yloxy) propionate 1.1 g of 60% sodium hydride was washed with hexane,
It was suspended in 50 ml of tetrahydrofuran. To this suspension, 2.9 g of methyl lactate was added dropwise under ice cooling. After stirring at room temperature for 1 hour, 5.8 g of 2-chloro-4,5-ditrifluoromethylpyridine was added dropwise. The mixture was stirred at room temperature for 3 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure to obtain 7.2 g of an oily target product.

Reference Example 1-b Production of 2- (4,5-ditrifluoromethylpyridin-2-yloxy) propionic acid In 50 ml of dioxane was added methyl 2- (4,5-ditrifluoromethylpyridin-2-yloxy) 7.2 g of propionate were dissolved. A solution prepared by dissolving 1.2 g of sodium hydroxide in 20 ml of water was added dropwise to this solution. The mixture was stirred at room temperature for 10 hours, poured into water, acidified with citric acid and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was washed with hexane to obtain 4.9 g of the desired product. 106-109 ° C

<Production Example 2> 2- (3-chloro-5-trifluoromethylpyridin-2-yloxy) -N-
Preparation of (1,1-diethyl-2-oxopropyl) propionamide (Compound No. A-3) 2- (3-chloro-5-trifluoromethylpyridin-2-yloxy) -N- was added to 40 ml of acetonitrile.
0.7 g of (1,1-diethyl-2-propynyl) propionamide and 10 ml of 10% hydrochloric acid were added. The mixture was stirred at room temperature for 3 hours, poured into water, neutralized with sodium bicarbonate and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was washed with hexane to obtain 0.6 g of the desired product. 132-135 ° C

<Production Example 3> 2- (3-chloro-5-trifluoromethylpyridin-2-yloxy) -N-
Production of (1,1-diethyl-2-propynyl) propionamide (Compound No. A-2) 2- (3-chloro-5-
1.0 g of trifluoromethylpyridin-2-yloxy) propionic acid was dissolved, and 1.1 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved.
Was added. After stirring at room temperature for 30 minutes, 1,1-diethyl-
0.4 g of 2-propynylamine was added. The mixture was stirred at room temperature for 3 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.0 g of the desired product.
105-106 ° C

<Production Example 4> 2- (3-chloro-5-trifluoromethylpyridin-2-ylthio) -N- (1-
Preparation of Isopropyl-1-methyl-2-oxopropyl) propionamide (Compound No. A-16) 0.3 g of 60% sodium hydride was washed with hexane,
It was suspended in 20 ml of dimethylformamide. 1.5 g of 3-chloro-5-trifluoromethyl-2-mercaptopyridine was added dropwise to this suspension. After stirring at room temperature for 1 hour,
1.7 g of N- (1-isopropyl-1-methyl-2-oxopropyl) -2-bromopropionamide was added dropwise. The mixture was stirred at room temperature for 2 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.3 g of the desired product. 114-117 ° C

<Production Example 5> 2- (3,5-dichloropyridin-2-yloxy) -N- (1-isopropyl-1)
Production of -methyl-2-oxopropyl) propionamide (Compound No. A-8) 0.7 g of N- (1-isopropyl-1-methyl-2-oxopropyl) -2-hydroxypropionamide was dissolved in 30 ml of tetrahydrofuran. . 60
0.15 g of sodium hydride was added. After stirring at room temperature for 30 minutes, 0.7 g of 2,3,5-trichloropyridine was added. The mixture was stirred at room temperature for 6 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.0 g of the desired product. 123-125 ° C

<Production Example 6> Preparation of 2- (2-iodo-6-methylpyridin-3-yloxy) -N- (1-isopropyl-1-methyl-2-propynyl) propionamide (Compound No. B-1) Production Wash 0.2% of 60% sodium hydride with hexane,
It was suspended in 20 ml of dimethylformamide. 1.0 g of 2-iodo-6-methyl-3-pyridinol was added to this suspension.
Was added dropwise. After stirring at room temperature for 1 hour, 1.1 g of N- (1-isopropyl-1-methyl-2-propynyl) -2-bromopropionamide was added dropwise. The mixture was stirred at room temperature for 4 hours, poured into water and extracted with diethyl ether. The diethyl ether layer was dried over anhydrous magnesium sulfate, and diethyl ether was distilled off under reduced pressure. The residue was washed with hexane to obtain 0.8 g of the desired product. 133-1
36 ° C

<Production Example 7> 2- (2,6-Ditrifluoromethylpyridin-4-yloxy) -N- (1-isopropyl-1-methyl-2-oxopropyl) propionamide (Compound No. C-2) To 40 ml of acetonitrile, 0.4 g of 2- (2,6-ditrifluoromethylpyridin-4-yloxy) -N- (1-isopropyl-1-methyl-2-propynyl) propionamide and 10 ml of 10% hydrochloric acid were added. . The mixture was stirred under reflux for 3 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate,
Ethyl acetate was distilled off under reduced pressure. The residue was washed with hexane to obtain 0.4 g of the desired product. 130-132 ° C

<Production Example 8> 2- (3,5-dichloropyridin-2-yloxy) -N- (2-hydroxy-1-
Preparation of isopropyl-1-methylpropyl) propionamide (Compound No. A-37) 2- (3,5-dichloropyridin-2-yloxy) -N- (1-isopropyl-1-methyl-2-oxo) in 20 ml of methanol. Propyl) propionamide 0.35
g was dissolved. To this solution was added sodium borohydride 0.1 mL.
04 g was added under ice cooling. After stirring at room temperature for 1 hour, the mixture was poured into water and extracted with ethyl acetate. After the ethyl acetate layer was dried over anhydrous magnesium sulfate, the ethyl acetate was distilled off under reduced pressure to obtain 0.6 g of the desired product. Refractive index 1.5304 (2
(0 ° C.) Examples of the compounds of the present invention produced according to the methods shown in Production Examples 1 to 8 are shown in Tables 13 to 18 together with the compounds shown in the above Production Examples.

The isomer A is diastereomer A,
Isomer B represents diastereomer B, and isomer M represents a diastereomer mixture. Diastereomer A indicates a low-polarity diastereomer separated by silica gel column chromatography or high-performance liquid chromatography, and diastereomer B indicates a high-polarity diastereomer similarly separated.

[0079]

[Table 13]

[0080]

[Table 14]

[0081]

[Table 15]

[0082]

[Table 16]

[0083]

[Table 17]

[0084]

[Table 18]

The fungicide for agricultural and horticultural use of the present invention contains a pyridyloxy (thio) alkanoic acid amide derivative represented by the general formula [I] as an active ingredient. When the compound of the present invention is used as an agricultural and horticultural fungicide, the active ingredient can be used in an appropriate dosage form according to the purpose. Usually, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, a surfactant and the like can be added to the active ingredient to be used in the form of powders, wettable powders, emulsions, granules and the like.

Suitable carriers include, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; 2-propyl alcohol; xylene; cyclohexanone; And liquid carriers. As the surfactant and dispersant, for example, dinaphthyl methanesulfonate, alcohol sulfate, alkylaryl sulfonate, lignin sulfonate,
Polyoxyethylene glycol ether, polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan monoalkylate and the like can be mentioned. Examples of the auxiliary include carboxymethyl cellulose. These preparations are diluted to an appropriate concentration and sprayed or applied directly.

The fungicide for agricultural and horticultural use of the present invention can be used by foliage application, nursery box application, soil application or water surface application. The compounding ratio of the active ingredient is appropriately selected according to need, but is 0.1 to 20% (by weight) in the case of powder and granules, and 5 to 80% (by weight) in the case of emulsion and wettable powder. Appropriate.

The application rate of the fungicide for agricultural and horticultural use of the present invention varies depending on the kind of the compound to be used, the target disease, the tendency of occurrence, the degree of damage, the environmental conditions, the dosage form to be used, and the like. For example, when used as is, such as powders and granules,
The active ingredient may be appropriately selected from the range of 0.1 g to 5 kg, preferably 1 g to 1 kg per 10 ares. When used in liquid form such as emulsions and wettable powders, 0.1
ppm to 10,000 ppm, preferably 1 to 3000 ppm
It is preferable to appropriately select from the range of 0 ppm.

The compounds according to the invention can be used according to the above-mentioned application forms, for example, algal fungi (Omycetes), ascomycetes (Asc)
omycetes), deuteromycetes (Deuteromy)
cetes), and Basidiomycete
tes) can be controlled. Next, specific bacterial names are given as non-limiting examples. Genus Pseudoperonospora (Pseudoperonospora),
For example, downy mildew (Pseudoperonospora)
cubensis), sphaeroteca (Sphaero)
theca), such as powdery mildew (Sphaero)
theca fuliginea), Venturia (V
enturia), such as the scab fungus (Venturi)
a inaequalis), Pyricularia (Pyr)
icularia), such as blast fungus (Pyric)
ularia oryzae), Gibberella (Gibbe)
rella), for example, Gibberel
la fujikuroi, Botrytis (Botry)
tis) genus, for example, Botrytis
cinerea), Alternari (Alternari)
a) Genus, for example, Komatsuna black spot fungus (Alternar)
ia brassicicola), Rhizoctonia (R
genus hizoctonia, for example, Rhizobium (Rhiz)
octonia solani), pacnia (Puc)
cinia) genus, for example, rust fungus (Puccinia)
recondita).

Further, the compound of the present invention may be mixed with an insecticide, other fungicides, herbicides, plant growth regulators, fertilizers and the like, if necessary. Next, the formulation method will be specifically described with reference to typical formulation examples of the agricultural and horticultural fungicides of the present invention. In the following description, “%” indicates weight percentage.

Formulation Example 1 Powder 2% of the compound (A-1), 5% of diatomaceous earth and 93% of clay were uniformly mixed and pulverized to obtain a powder.

Formulation Example 2 Wettable powder 50% of the compound (A-1), 45% of diatomaceous earth, 2% of sodium dinaphthylmethanedisulfonate and 3% of sodium ligninsulfonate were uniformly mixed and pulverized to obtain a wettable powder.

Formulation Example 3 Emulsion 30% of compound (A-1), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene were uniformly dissolved to form an emulsion.

Formulation Example 4 Granules Compound (A-1) 5%, sodium salt of lauryl alcohol sulfate 2%, sodium ligninsulfonate 5%, carboxymethyl cellulose 2% and clay 86
% Is uniformly mixed and pulverized. 20% of water was added to the mixture, and the mixture was kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and then dried to obtain granules.

Next, the effect of the fungicide for agricultural and horticultural use of the present invention will be specifically described with reference to test examples.

Test Example 1 Rice Blast Prevention Effect Test Rice seeds (variety: Asahi Aichi) about 15 in a clay pot with a diameter of 7 cm
Each seed was sown and grown in a greenhouse for 2 to 3 weeks. A wettable powder prepared according to Formulation Example 2 was diluted with water so that the active ingredient concentration became 500 ppm, and the rice seedling having the fourth leaf completely developed was sprayed with 10 ml per pot. After air-drying, a conidia suspension of rice blast fungus (Pyricularia oryzae) was spray-inoculated and immediately placed in a 25 ° C moist chamber for 24 hours. Thereafter, they were transferred to a greenhouse, and the number of lesions on the fourth leaf was examined 5 days after the inoculation. The control value was determined by Equation 1, and the results of evaluation based on the criteria in Table 19 are shown in Tables 20 to 23.

[0097]

(Equation 1)

[0098]

[Table 19]

[0099]

[Table 20]

[0100]

[Table 21]

[0101]

[Table 22]

[0102]

[Table 23]

Test Example 2 Rice Blast Water Surface Application Test Three 1.5-leaf stage paddy rice (variety: Asahi Aichi) seedlings were transplanted to four places at four places each in a white porcelain bowl having a diameter of 9 cm and grown in a greenhouse. The wettable powder prepared according to Formulation Example 2 at the 2.5 leaf stage was subjected to water application to a pot such that the active ingredient concentration was 300 g per 10 ares. Ten days after the treatment, a conidia suspension of rice blast fungus (Pyricularia oryzae) was spray-inoculated and immediately placed in a 25 ° C moist chamber for 24 hours. Then, they were transferred to a greenhouse, and five days after the inoculation, the number of lesions on the highest leaf at the time of the inoculation was examined. The control value was determined by Equation 1, and the results evaluated according to the criteria in Table 19 are shown in Tables 24 to 25.
It was shown to.

[0104]

[Table 24]

[0105]

[Table 25]

[0106]

The compound of the present invention has a high control effect against rice blast and the like, and also has characteristics that it does not cause phytotoxicity to crops and has excellent residual effect and rain resistance. It is useful as an agricultural and horticultural fungicide.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI C07D 213/85 C07D 213/85 (72) Inventor Katsunori Matsumoto 408-1, Shioda, Fukuda-cho, Iwata-gun, Shizuoka Prefecture Inside the Eye Research Institute (72) Inventor Norihisa Yonekura 408-1, Shioda, Fukuda-machi, Iwata-gun, Shizuoka Prefecture Inside the K-I Research Institute Inc. Person Kazuo Kumakura 532-1, Morishita, Toyota-machi, Iwata-gun, Shizuoka Prefecture (72) Inventor Kenichi Muramatsu 3-15-15, Kuzugaoka, Kakegawa-shi, Shizuoka Prefecture

Claims (4)

[Claims] 1. A compound of the general formula [I] [Wherein, X is a hydrogen atom, a C ₁ -C ₆ alkyl group, a C _1-
C ₄ haloalkyl group, C ₁ -C ₆ alkoxy group, C _1-
A C ₄ haloalkoxy group, a C ₂ -C ₆ alkenyloxy group, a C ₂ -C ₆ alkynyloxy group, a C ₁ -C ₆ alkylthio group, a C ₁ -C ₄ haloalkylthio group, a halogen atom, an amino group, a nitro group, A cyano group, a phenyl group (the group is a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ haloalkyl group,
It may be substituted by a C ₁ -C ₆ alkoxy group or a halogen atom. ) Or a phenoxy group, which is a C ₁ -C
C ₆ alkyl group, C ₁ -C ₄ haloalkyl group, C ₁ -C
_It may be substituted by a ₆ alkoxy group or a halogen atom. N represents an integer of 1 to 4, R ¹ represents a hydrogen atom, a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group or a C ₁ -C ₄ haloalkyl group, and R ² and R
³ each independently represent a C ₁ -C ₆ alkyl group, C _2-
A C ₆ alkenyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group), a C ₃ -C ₆ cycloalkyl C ₁
Represents a C ₆ -alkyl group or a C ₁ -C ₄ haloalkyl group, or R ² and R ³ together with the carbon atom to which they are attached are a 5- to 7-membered cycloalkyl group (the C ₁
It may be substituted by -C ₆ alkyl group. ) To form, Q is _C 2 -C ₆ alkyl group, ethynyl group, group -
COR ⁴ (R ⁴ is a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group) or C ₁ -C ₄ Represents a haloalkyl group) or a group —CH (OH) R ⁵ (R
⁵ represents a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted with a halogen atom or a C ₁ -C ₆ alkyl group) or a C ₁ -C ₄ haloalkyl group. . A represents an oxygen atom or a sulfur atom. ] The pyridyloxy (thio) alkanoic acid amide derivative represented by these. 2. A compound of the general formula [I] [Wherein X is a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₆ alkoxy group, a C ₁ -C ₄ haloalkoxy group, a C ₁ -C ₄ haloalkylthio group, a halogen atom , An amino group, a nitro group, a cyano group, a phenyl group (the group may be substituted by a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₆ alkoxy group or a halogen atom. ) Or a phenoxy group, wherein the group is C
₁ -C ₆ alkyl _group, C 1 -C ₄ haloalkyl groups, _{C 1}
It may be replaced by -C ₆ alkoxy group or a halogen atom. N represents an integer of 1 to 4, R ¹ represents a hydrogen atom or a C ₁ -C ₆ alkyl group, and R ² and R
³ each independently represent a C ₁ -C ₆ alkyl group, C _2-
Represents a C ₆ alkenyl group, a C ₃ -C ₆ cycloalkyl group (which may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group) or a C ₁ -C ₄ haloalkyl group, or R ² and R ³ together with the carbon atom to which they are attached form a 5- to 7-membered cycloalkyl group, which may be substituted by a C ₁ -C ₆ alkyl group, and Q is C ₂ -C ₆ alkyl group, ethynyl group, group —COR ⁴ (R ⁴ is a C ₁ -C ₆ alkyl group, C ₃
-C ₆ cycloalkyl group (the group is a halogen atom, C _1-
It may be substituted by a C ₆ alkyl group. ) Or C ₁
~C represents a ₄ haloalkyl group. ) Or the group -CH (OH)
R ⁵ (R ⁵ is a C ₁ -C ₆ alkyl group, a C ₃ -C ₆ cycloalkyl group (the group may be substituted by a halogen atom or a C ₁ -C ₆ alkyl group) or C ₁ -C ₄ A represents an oxygen atom or a sulfur atom. ] The pyridyloxy (thio) alkanoic acid amide derivative represented by these. 3. A compound of the general formula [I] [Wherein, X represents a C ₁ -C ₆ alkyl group, a C ₁ -C ₄ haloalkyl group, a C ₁ -C ₄ haloalkoxy group, a halogen atom, a C ₁ -C ₆ alkoxy group, a nitro group or a cyano group, n represents an integer of 1 to 4, and R ¹ is a hydrogen atom or C
Represents a ₁ to ₆ alkyl group, and R ² and R ³ are each independently a C _{1 to} C ₆ alkyl group, a C _{3 to} C ₆ cycloalkyl group (the group is a halogen atom or a C _{1 to} C ₆ alkyl group). Or a C ₁ -C ₄ haloalkyl group, or R ² and R ³ together with the carbon atom to which they are attached are a 5- to 7-membered cycloalkyl group (the group may be substituted by _C 1 -C ₆ alkyl group.) to form, Q is group -COR ^{4 (R 4} is C
_1- C ₆ alkyl group) or CH (OH) R ⁵ (R
⁵ represents a C ₁ -C ₆ alkyl group), and A represents an oxygen atom or a sulfur atom. ] The pyridyloxy (thio) alkanoic acid amide derivative represented by these. 4. A fungicide for agricultural and horticultural use containing the pyridyloxy (thio) alkanoic acid amide derivative according to claim 1, 2 or 3 as an active ingredient.