WO2003006432A1 - Oxime ether compound and agricultural or horticultural bactericide - Google Patents

Abstract

An oxime ether compound represented by the general formula [I]: [I] [wherein R1 represents C1-6 alkyl, etc.; m is 0 to 3; R2 represents C1-6 haloalkyl; R3 and R4 each represents hydrogen or C1-6 alkyl; and R5 to R9 each represents hydrogen, C1-6 alkyl, C1-6 alkoxy, C1-6 alkoxy substituted by C1-6 alkoxy, C2-6 alkenyloxy, C1-6 acyloxy, (C1-6 alkyl)carbonyloxy, (C1-6 alkyl)sulfonyloxy, (C1-6 haloalkyl)sulfonyloxy, C1-6 alkylthio, C1-6 alkylamino, hydroxy, etc.] or a salt of the compound; and an agricultural or horticultural bactericide containing one or more of the compound and salt.

Description

 Specification

 Oxime ether compounds and fungicides for agricultural and horticultural use

 The present invention relates to a novel oxime ether compound and a fungicide for agricultural horticultural use containing the compound as an active ingredient.

Background art:

 In the cultivation of agricultural and horticultural crops, a number of pesticides are used against pests and diseases of crops. However, their control efficacy is insufficient, their use is limited due to the emergence of drug-resistant pathogens and pests, and their plants cause phytotoxicity and contamination, or their toxicity to humans, fishes and fish is high. Therefore, there are many that are not necessarily satisfactory control agents. Therefore, there is a strong demand for a drug that can be used safely with few such disadvantages.

 In connection with the compounds of the present invention, EP 475, EP 2,488,884, WO 93/211 157, etc., certain oxime ether compounds, insecticide, It is described as having acaricidal activity.

 Japanese Patent Application Laid-Open No. 9-30747 describes that an oximeter compound containing a compound represented by the following formula is effective as an agricultural and horticultural fungicide.

 WO 01/34568 describes that an oxime ether compound containing a compound represented by the following formula is useful as an agricultural and horticultural fungicide.

 However, these documents do not specifically describe the compound of the present invention.

Disclosure of the invention: An object of the present invention is to provide a novel oxime ether compound which can be synthesized industrially advantageously, has a certain effect, and is an excellent agricultural and horticultural fungicide with little phytotoxicity.

The present inventors have found that in the following general formula [I], the oxime ether compound in which the substituent R ^{2 at the} 4-position of the pyridine moiety is a haloalkyl group has a particularly excellent control effect on agricultural and horticultural crop diseases. And completed the present invention.

 That is,

(Wherein, R i is, C ₁ - ₆ alkyl group, C ₃ - ₈ cycloalkyl group, C ie alkoxy groups, C ₁ - ₆ alkylthio group, amino group, mono C丄_1-6 alkylamino group, di CL ^ ^ S alkylamino group, C ₁ ~ ₆ Ashiruokishi groups, C alkoxy C i ^^ s alkyl group, C ₁ ~ ₆ alkoxide aryloxycarbonyl groups, C ₂ ~ ₆ alkenyl group, tri C ₁ ~ ₆ alkyl silicate b alkoxy C _{1 1-6} § alkyl group, human Dorokishi C ₁ ~ ₆ alkyl group, arsenate Dorokishi group, Shiano group, a formyl group or a halogen atom.

m represents an integer of 0 to 3, and when m is 2 or more, R ¹ may be the same or different.

R ² represents a C i- ₆ haloalkyl group.

R ³ and R ⁴ are the same or different and represent a hydrogen atom or a C alkyl group.

R 5, R 6, _{R 7} , R 8 and R 9 are the same or different and are each a hydrogen atom; ; ^ 6 alkyl le groups, C ₃ ~ ₈ cycloalkyl groups, C ₂ ~ ₆ alkenyl groups, C ₂ ~ ₆ alkynyl groups, C i ^^ s alkoxy groups, C alkoxy C alkyl groups, C alkoxy C i ^^ s alkoxy group, C ₂ ~ ₆ Arukeniruokishi group, C ₂ ~ ₆ Arukiniruokishi group, C i ^^ e Ashiruoki shea group, C, ~ ₆ alkylcarbonyl O alkoxy group, mono-C i to ₆ alkyl force Rubamoiruokishi group di C ₁ - ₆ alkyl force Rubamoiruokishi group, C i to ₆ alkylsulfonyl O carboxymethyl group, C丄_1-6 haloalkylsulfonyl O carboxymethyl group, C ₁ - ₆ haloalkyl group, C ₁ - ₆ alkylthio O group, mono C alkylamino represents groups, di C ₁ ~ ₆ alkylamino group, C i ~ ₆ Ashiruami amino group, an amino group, a human Dorokishi group or a halogen atom. Two adjacent ones of R ⁵ , R ⁶ , R ⁷ , R ^8, and R ^{9 form} an alkylene chain containing a heteroatom, and are reduced to 5 to 7 members. A ring may be formed. The present invention provides an oxime ester compound represented by the formula:

In the present invention compounds, the R 5 is, C ₁ ~ ₆ alkoxy group, C ₁ ~ ₆ alkoxy C iota 6 alkoxy group, C ₂ ~ ₆ Arukeniruokishi group, C ₂ ~ ₆ Arukiniruokishi group, C i ^ ^ s Ashiruokishi group, C iota ~ ₆ alkylcarbonyl O alkoxy group, mono-C ₁ ~ ₆ alkyl carba mode Iruokishi group, di-C alkyl force Rubamoiruokishi group, C ₁ ~ ₆ alkylsulfonyl Okishi groups and C i ~ ₆ haloalkylsulfonyl O carboxymethyl It is preferably one group selected from the group consisting of groups.

Further, the R ⁹ is, C i S alkyl group, C ₃ ~ ₈ cycloalkyl group, C ₂ ~ ₆ alkenyl Le group, C ₂ ~ ₆ alkynyl group, C ₁ ~ ₆ alkoxy group, C ₁ ~ ₆ alkoxy C i _1-6 alkyl groups, C ₆ alkoxy C i ^^ s alkoxy groups, C ₂ - ₆ Arukeniruokishi groups, C ₂ - ₆ Al Kiniruokishi groups, C ₁ - ₆ Ashiruokishi groups, C alkylcarbonyl O alkoxy group, mono C i _1-6 alkyl force Rubamoiruokishi group, di C _i-6 alkyl force Rubamoiruokishi groups, C _1-6 alkylsulfonyl O carboxymethyl groups, C _1-6 haloalkylsulfonyl O carboxymethyl groups, C haloalkyl groups, C ₁ - ₆ alkylthio group, amino group, mono C ₁ - ₆ alkylamino group, ^di-c _〖1-6 Arukiruamino group, is preferably one group selected from the group consisting of human Dorokishi group and a halogen atom.

 Secondly, the present invention provides a fungicide for agricultural gongs comprising one or more of the oximetel compound represented by the general formula [I] or a salt thereof.

 Hereinafter, the compound of the present invention and the fungicide for agricultural and horticultural use will be described in detail.

A first aspect of the present invention is an oxime ether compound represented by the general formula [1]. In the general formula [I], R ¹ is a C i- ₆ alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-xyl, etc. Group;

Cyclohexyl cyclopropyl, cyclopentyl, 1-methylstyrene cyclopentyl, cyclohexylene, 1 - Mechirushiku port to which may have a substituent such as cyclohexyl group C ₃ ~ ₈ consequent opening alkyl group; main butoxy, ethoxy, n- Purobokishi, Isopurobokishi , N-butoxy, sec—Ci- ₆ alkoxy groups such as butoxy, isobutoxy, t-butoxy;

Ci- ₆ alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, and n-butylthio;

Amino group; Mechiruami Bruno, Echiruamino, n- Puropiruami Roh, isopropyl § Mi Bruno, mono C ₁ ~ ₆ alkylamino amino group such as n- flop Chiruamino group;

Jimechiruami Bruno, Jechiruami Bruno, di _n - Puropiruami Bruno, di one _n - butylamine Bruno, di C i ~ ₆ Arukiruami amino group such as E chill isopropyl § Mi cyano group;

C acyloxy groups such as acetoxy, propionyloxy, and piperoyloxy groups; Ci to ₆ alkoxy Cis such as methoxymethyl, 1-methoxyhexyl, 2-methoxyhexyl, ethoxymethyl, n-propoxymethyl, and n-butoxymethyl groups; ~. An alkyl group;

Ci- ₆ alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, sec-butoxycarbonyl ', isobutoxycarbonyl, t-butoxycarbonyl; ethenyl, 11 Propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-12-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, etc. C _{2 —s} alkenyl group;

Trimethylsiloxy methyl, t - heptyl dimethylsilylene Rokishimechiru, preparative Ryechirushi Li Rokishimechiru, Application Benefits n- Purobirushiri Rokishimechiru, Application Benefits C Arukirushiri proxy C丄_1-6 alkyl group such as tri-n- Puchirushiri Rokishime ethyl group;

 A hydroxy C alkyl group such as hydroxymethyl, 1-hydroxyl, 2-hydroxyl, 1-hydroxyl 2-propyl, 2-hydroxyn-propyl, 3-hydroxyn-propyl;

A hydroxy group;

Cyano group;

Represents a formyl group or a halogen atom such as fluorine, chlorine, bromine or iodine.

m represents an integer of 0 to 3, and when m is 2 or more, R ¹ may be the same or different.

R ² is fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 1,1 difluoroethyl, 2,2-difluoroethyl, 2,2,2—trufluoroethyl, penta Fluoroethyl, 2-chloroethyl, Represents a C haloalkyl group such as 22-dichloroethyl, 2-bromoethyl, and 22-dibromoethyl.

RR ⁴ is the same or different and represents a hydrogen atom; or C such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, n-hexyl, etc. Represents an alkyl group.

R ⁵ R ⁶ RR ⁸ and R ⁹ are the same or different and are each a hydrogen atom; methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isoptyl, t-butyl, n-pentyl, C ₁ ~ ₆ alkyl group such as n-hexyl group;

 Cyclopropyl, cyclopentyl, 1-methylcyclopentyl, cyclohexyl,

1 Mechirushiku port to a substituent optionally C ₃ ~ ₈ cycloalkyl group which may have a such hexyl group; Eteniru, 1 one propenyl, 2-propenyl, 1 - heptenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1 — hexenyl, to 2-hexenyl, to 3-hexenyl, 4-hexenyl, 5 - to such hexenyl group C ₂ - ₆ alkenyl group;

 Ethynyl, 1-propynyl, 2-propiel, 1-butynyl, 2-butynyl, 3-butynyl, dimethyl-2-propenyl, 2-methyl-3-butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4 —Pentynyl, 1 —methyl-2-butynyl,

2-methyl-one 3-pentynyl, 1 hexynyl, 1, C _2, such as 1-dimethyl-2-heptynyl group - ₆ alkynyl group;

C ₆ alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, t-butoxy;

 C alkoxy C alkyl groups such as methoxymethyl, methoxethyl, ethoxymethyl, n-propoxymethyl, n-butoxymethyl groups;

C alkoxy C- ₆ alkoxy groups such as methoxy methoxy, 1-methoxy ethoxy, 2-methoxy ethoxy, ethoxy methoxy, n-propoxy methoxy, n-butoxy methoxy groups;

Ariruokishi, 2 one propenyl Niruokishi, 2 Buteniruokishi, such as 2-methyl-one 3-flop port Bae Niruokishi group C ₂ - ₆ Arukeniruokishi group;

2-propynyloxy, 2-butynyloxy, 1-methyl-2-propynyloxy C ₂ such groups - ₆ Arukiniruokishi group;

C-Acyoxy groups such as acetoxy, propionyloxy, and bivaloyloxy groups; methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, isopropoxycarbonyloxy, n-butoxycarbonyloxy, t-butoxycarbonyl A C i _ ₆ alkoxycarbonyloxy group such as an alkoxy group;

Mono-Ci- _fi alkyl-functional rubamoyloxy groups such as methylcarbamoyloxy, ethylcarbamoyloxy, n-propyl carbamoyloxy, n-butyl carbamoyloxy;

Di C ₁₆ alkylcarbamoyloxy groups such as dimethylcarbamoyloxy and getylcarbamoyloxy;

C i _ ₆ alkylsulfonyloxy groups such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, n-butylsulfonyloxy;

 C haloalkylsulfonyloxy groups such as trifluoromethylsulfonyloxy, 2,2,2-trifluoroethylsulfonyloxy, and pentafluoroethylsulfonyloxy;

 Fluoromethyl, difluoromethyl, trifluoromethyl, 1—fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-tolufluoroethyl, pentafluoroethyl, 2-chloroethyl C i ~ such as, 2,2-dichloroethyl, 2-bromoethyl, and 2,2-dibromoethyl groups. Haloalkyl group;

C-alkylthio groups such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, and t-butylthio groups; methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, sec — butylamino, t — butylamino, 1-methylbutylamino, n — mono-C- ₆ alkylamino group such as pentylamino group; dimethylamino, getylamino, di-n-propylamino, di-n-butylamino, ethylisopropylamino, methyl n-diamino such as propylamino group-6 alkylamino group;

C acylamino groups such as acetylamino, propionylamino, and piperoylamino; Represents an amino group, a hydroxy group, or a halogen atom such as fluorine, chlorine, bromine, or iodine.

Among these compounds, an oxime ether compound having an oxygen functional group at the 2-position (R ⁵ ) of the benzene ring is preferred because of its excellent bactericidal activity, and the 2-position (R ⁵ ) is an oxygen functional group, and the 6-position Oximeter compounds having a substituent at (R ⁹ ) are more preferred because they have particularly good bactericidal activity.

Examples of the oxygen functional group of R ^5, C i S alkoxy groups, C alkoxy C ^^ 6 § alkoxy groups, C ₂ ~ ₆ Arukeniruokishi groups, C ₂ ~ ₆ Arukiniruokishi group, CL ^^ S Ashiru Okishi group, C alkylcarbonyl O alkoxy group, mono-C alkyl force Rubamoiruo alkoxy group, di C ₁ ~ ₆ alkyl force Rubamoiruokishi group, one selected from the group consisting of C alkylsulfonyl O carboxymethyl Moto及Pi C haloalkylsulfonyl O alkoxy group Groups are preferred.

As the 6-position substituent, C ₁ ~ ₆ alkyl group, C ₃ ~ ₈ cycloalkyl group, C ₂ ~ ₆ alkenyl group, C ₂ ~ ₆ alkynyl group, C ₁ ~ ₆ alkoxy group, C ₁ ~ ₆ Alkoxy 0 to ₆ alkyl groups, Ci to ₆ alkoxy C ₁ to ₆ alkoxy groups, C 2 to ₆ alkenyloxy groups, C ₂ to ₆ alkynyloxy groups, Ci to 6 acyloxy groups, Cι to 6 alkyl carbonylation Ruoki shea group, mono C丄_1-6 alkyl force Rubamoiruokishi group, di C ₁ to ₆ alkyl force Rubamoiruo alkoxy group, C ₁ ~ 6 alkylsulfonyl O carboxymethyl group, C ₁ ~ ₆ haloalkylsulfonyl O alkoxy group, 〇 1 ₆ Ha port alkyl group, C ₁ ~ ₆ alkylthio group, amino group, mono C i ~ ₆ alkylamino group, di-C i ^^ s alkylamino group, human Dorokishi group and the group or al one selected consisting of a halogen atom Are preferred.

 (Production of the compound of the present invention)

 The compound of the present invention can be produced as follows.

(Wherein, RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ , RR ⁸ , R ⁹ and m represent the same meaning as described above, and L represents a halogen atom such as chlorine, bromine, iodine and the like, and methanesulfonylo. Represents a leaving group such as a xy group or a para-toluenesulfonyloxy group.) The compound represented by the formula [I] is obtained by reacting a compound represented by the formula [II] with a compound represented by the formula [111] in the presence of a deacidifying agent such as a base without a solvent, preferably in a solvent. It can be obtained by stirring at a temperature of 0 to 15 (10 minutes to 24 hours at TC.

 Solvents that can be used in this reaction include ketones such as acetone, 2-butanone and cyclohexanone; ethers such as getyl ether and tetrahydrofuran; aromatics such as benzene and toluene. Hydrocarbons; alcohols such as methanol and ethanol; acetate nitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like. Further, these solvents can be used as a mixed solvent of two or more kinds.

 Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, and sodium hydride; alkali metal alkoxides such as sodium methoxide and sodium methoxide; Organic bases such as pyridine, triethylamine, 14-diazabicyclo [5,4,0] indene 7-ene (hereinafter abbreviated as DBU) can be used.

 The compound represented by the formula [Π] as a starting material of the compound of the present invention can be produced by the following method.

Addition

R ² and m have the same meaning as described above. )

 First, 2-methylpyridines represented by the formula [IV] are oxidized with an oxidizing agent such as hydrogen peroxide and m-chloroperbenzoic acid (hereinafter abbreviated as mC PBA) to obtain the formula [V Pyridine-N-oxide represented by the formula [VI] and reacting with acetic anhydride to obtain 2-acetoxymethylpyridines represented by the formula [VI]. Next, the 2-acetoxymethylpyridines represented by the formula [VI] are hydrolyzed to obtain the 2-hydroxymethylpyridines represented by the formula [VII]. Oxidized by the oxidizing agent of formula

This gives 2-pyridinecarboxyaldehydes represented by [VIII]. Furthermore, the formula [VIII] By reacting 2-pyridinecarboxyaldehyde represented by the formula with hydroxylamine, 2-pyridinecarboxyaldoxime represented by the formula [II] can be obtained.

 The 2-pyridinecarboxyaldehydes represented by the formula [VIII] can also be produced by the following method.

(In the formula, R i, R ² and m represent the same meaning as described above, Z represents a halogen atom such as chlorine, bromine, and iodine, and R represents a hydrogen atom or a CLC ₆ alkyl group.)

 That is, a pyridine having a halogen atom at the 2-position represented by the formula [IX] is reacted with an alkyllithium such as n-butyllithium to lithiate the 2-position, and then is reacted with a formylating agent such as DMF. By formylation, 2-pyridinecarboxyaldehydes represented by the formula [VIII] can be obtained.

Alternatively, a cyanogenating agent such as copper cyanide is allowed to act on a pyridine having a halogen substituted at the 2-position represented by the formula [IX], or a 2-position unsubstituted pyridine N represented by the formula [X] —Oxides are reacted with a cyanating agent such as trimethylsilyl cyanide (hereinafter abbreviated as TMSCN) to give the cyanopyridines represented by the formula [XI]. Conversion to formyl groups with a reducing agent such as diisobutylaluminum hydride (hereinafter abbreviated as DIB AH), or hydrolysis of 2-cyanopyridines represented by the formula [XI] To a 2-pyridinecarboxylic acid ester represented by the formula [XII], and by using a reducing agent such as LiAlH _{4 to} form a 2-hydroxymethylpyridine represented by the formula [VII]; Converted to formyl group by oxidizing agent such as manganese That way Can also produce 2-pyridinecarboxyaldehydes represented by the formula [VIII].

Furthermore, pyridines substituted with a halogen at the 2-position represented by the formula [IX] are reacted with carbon monoxide in alcohol in the presence of a catalyst such as a palladium complex to form an alkoxycarbonyl group at the 2-position. introduced directly after the 2-hydroxycarboxylic methyl pyridines you express by the formula [VII] by a reducing agent such as LiAlH _4, wherein by a method of converting into a ho mill base with an oxidizing agent such as manganese dioxide The 2-pyridinecarboxy aldehydes represented by [VIII] can be produced.

Among the compounds represented by the formula [III], which are starting materials of the compound of the present invention, benzyl represented by the formula [III-1] wherein R ³ and R ⁴ are hydrogen atoms and L is a halogen atom The halides are obtained by converting a heterocyclic compound having a methyl group represented by the formula [XIII] to a halogenated succinimide such as N-chlorosuccinimide, N-promosuccinimide, or N-phenylsuccinimide. It can be obtained by reacting under light irradiation.

 [XIII] [HI-1]

(In the formula, R ⁵ , R 6, RR ^8, and R ⁹ represent the same meaning as described above, and Li represents a halogen atom such as chlorine, bromine, and iodine.)

Of the compounds represented by the formula [III], which are starting materials of the compound of the present invention, R ³ and R ⁴ are hydrogen atoms, and L is a halogen atom or a sulfonyloxy group. The compound to be prepared can be produced as follows.

[XIV] ^{[ll l_2} ]

(In the formula, R 5, R ⁶ , R ⁷ , R ⁸ , R ⁹ and L have the same meanings as described above. W is a halogen atom such as chlorine, a hydroxy group, a hydrogen atom or a methoxy, ethoxy group, etc. Represents a ci- ₆ alkoxy group.)

That is, a formyl group, a carboxyl group, a halocarbonyl group represented by the formula [XIV] After obtaining a benzyl alcohol by reduction, a hydroxymethyl group is converted into a halogenomethyl group using a halogenating agent such as thionyl chloride, or a sulfonyl halide such as methanesulfonyl chloride is obtained. A compound represented by the formula [III-2] can be produced by converting a hydroxymethyl group into a sulfonyloxymethyl group by reacting the compound with a compound represented by the formula [III-2].

Among the compounds represented by the formula [III], which are the starting materials of the compound of the present invention, the compound represented by the formula [ΠΙ-3] wherein R ³ and R or R ⁴ are C i _ ₆ alkyl groups is It can be synthesized by the following method.

 [XV] (111-3)

(In the formula, R 3, R 4, R 5, R 6 R 7, R 8, R 9, and L represent the same meaning as described above, and L ² represents a halogen atom such as chlorine, bromine, and iodine.)

 That is, a ketone or an aldehyde represented by the formula [XV] is reacted with a Grignard reagent represented by the formula [XVI] to obtain a benzyl alcohol, which is then halogenated with a thionyl chloride or the like. A hydroxymethyl group is converted to a halogenomethyl group by the action of an agent, or a sulfonyl halide such as methanesulfonyl chloride is reacted to convert a hydroxymethyl group to a sulfonyloxymethyl group. Thus, the compound represented by the formula [III-3] can be produced.

 Further, the compound represented by the formula [I] can also be produced as follows.

(Wherein, RR ² , R 3, RR 5, R 6, R 7, R 8 R 9 and m represent the same meaning as described above.)

That is, the compound represented by the formula [I] can be prepared by mixing a compound represented by the formula [XVII] and a compound represented by the formula [XVIII] or a salt thereof in a solvent-free state, preferably in a solvent, at a reaction temperature of 0 to 1; 50 ° C For 10 minutes to 24 hours.

 Examples of the solvent used in the reaction include alcohols such as ethanol and methanol; ethers such as ethyl ether, tetrahydrofuran and dioxane; cellosolps such as methyl sorb and ethyl sorb; benzene and toluene. And aromatic hydrocarbons such as acetic acid, water, N, N-dimethylformamide, dimethylsulfoxide and the like. These solvents can be used alone or as a mixed solvent of two or more.

 This reaction does not necessarily require the presence of a catalyst, but the addition of an acid or base may significantly accelerate the reaction. As the acid, an inorganic acid such as sulfuric acid or hydrochloric acid, an organic acid such as p-toluenesulfonic acid, and sodium acetate or the like as a base can be used.

 The benzyloxyamines represented by the formula [XVIII] can be produced as follows.

 [III] [XIX] [XVIII]

 (In the formula, R 3, R 4, R 5, R 6, R 7, R 8 and R 9 have the same meanings as described above.) That is, a compound represented by the formula [III] is added to a base such as triethylamine. In the presence of N-hydroxyphthalimide, the compound represented by the formula [XIX] is obtained, and then hydrazine is allowed to act on the compound, whereby the benzene represented by the formula [XVIII] is obtained. Xiamins can be produced.

Among the compounds represented by the formula [I], the compound represented by the formula [1-2] wherein R ² is a CH ₂ F group can be produced as follows.

(Wherein, RR2, R3, _R4 , R5, R6, R7, R8, R9 and m represent the same meaning as described above. PG represents a protecting group such as t-butyldimethylsilyl group or the like. Represents.)

First, after protecting the hydroxyyl group of a pyridine having a hydroxymethyl group at the 4-position represented by the formula [XX] with an appropriate protecting group, use an oxidizing agent such as hydrogen peroxide, peracetic acid, or mCPBA. After obtaining pyridine N-oxides, they are reacted with acetic anhydride to obtain 2-acetoxymethyl pyridines represented by the formula [XXI]. Next, after hydrolyzing the 2-acetoxymethyl pyridines represented by the formula [XXI] to obtain 2-hydroxymethylpyridines represented by the formula [XXII], this is subjected to dioxide oxidation. Oxidation with an oxidizing agent such as manganese gives 2-pyridinecarboxyaldehydes of the formula [XXIII]. Next, 2-pyridinecarboxyaldehydes and 0-benzyloxyamide represented by the formula [XVIII] are added. The compound represented by the formula [XXIV] is obtained by condensing the compound with a compound and deprotecting the protecting group. Further, the compound represented by the formula [1-2] can be obtained by fluorination with a fluorinating agent such as getylaminosulfur trifluoride (hereinafter abbreviated as DAST).

Among the compounds represented by the formula [I], the compound represented by the formula [1-3] wherein R ² is a CHF ₂ group can be produced as follows.

(In the formula, RR ² , R 3, R 4, R 5, R 6, R 7 _s R 8, R 9 and m represent the same meaning as described above.)

 That is, a pyridine having a hydroxymethyl group at the 4-position represented by the formula [XXV] is oxidized with an oxidizing agent to convert the hydroxymethyl group into a formyl group, and then is converted to a fluorinating agent such as DAST. The compound represented by [1-3] can be obtained.

 In addition, various derivatives can be synthesized by further chemically modifying the obtained product. The chemical modification described here includes the deprotection of functional groups recognized as protecting groups in the field of organic synthesis such as t-butyldimethylsilyl group, and the conversion of primary or secondary hydroxyl groups to carbonyl groups by manganese dioxide or the like. Functional group conversion such as wittig reaction utilizing the carbonyl group, functional group conversion such as derivation of ester group by hydrolysis reaction of cyano group, halogen atom And functional group conversion using a reaction using a cyano compound recognized as a nucleophile in the field of organic chemistry from a functional group recognized as a leaving group in the field of organic synthesis.

For the salt of the compound of [1], react [I] with an inorganic or organic acid in a suitable solvent. It can be obtained by doing.

 In any case, after completion of the reaction, the desired product can be obtained by performing ordinary post-treatment. The structure of the compound of the present invention can be determined by measurement of various spectra such as NMR spectrum, IR spectrum, and mass spectrum, elemental analysis and the like. The compounds of the present invention are useful in a wide variety of filamentous fungi, such as oomycetes (Oomycetes), ascomycetes (Ascomyce t_e_s), incomplete fungi (Deuteromycetes), and basidiomycetes (Basidiomycetes). It has excellent bactericidal activity against the bacterium to which it belongs. In particular, it has an excellent bactericidal activity against gray mold as compared to the known compounds. -The composition containing the compound of the present invention as an active ingredient is used for controlling various diseases that occur in the cultivation of agricultural and horticultural crops including flowers, turf and pasture, by seed treatment, foliage application, soil application or water application. be able to.

 For example,

Sugar beet brown spot (Cerc0sP0rabetiG01a)

Rakkasei brown spot (Myc 0 s P a e r e 1 1 a a r a c h i d i s)

 Black rot (Mycos Pha ere e1 1 abereke1 eyi) Kiyuri powdery mildew (SPhaeerothec a fu1igin)

 Vine blight (My Cos Pha e re e 11 i am e 10 n i S) Sclerotia (S c 1 e ro t i i n i a s c 1 e ro t i o r u m) Gray mold (B 0 t r y t i i c i n e r e a)

 Scab (C 1 ad 0 s P 0 r i u m c u c u m e r i n m) Tomato Gray mold (Bot r y t i s c i n e r e a)

 Leaf mold (C 1 ados Por i u m f u 1 V u m) Eggplant Gray mold (B o t r y t i s c i n e Γ e a)

 Black blight (Corynes Poramae 1 ong enae)

 Powdery mildew (ErysiiPhecichhoracacearum) Strawberry gray mold (Botryttiscinerea)

Powdery mildew (S 0 haerothecahumu 1 i) Onion gray rot (Botrytisa 1 1 ii) Gray mold (Botrytiscinerea)

Kingen sclerotium disease (S c l e r o t i n i a s c 1 e r o t i o— r __ ^ jg_)

 Gray mold (Botryt i s c i n e r e a)

Apple powdery mildew (Pod os p ae a la l e u c o t r i c a) Scab (V e n t u r i a i n a e g u a 1 i s)

 Monilia's disease (Moni 1 i n i a m a 1 i)

Oysters Powdery Mildew (P h y l l a c t i n i a k a k i c o 1 a)

 Anthracnose (G 1 o e os o r i u m k a k i)

 Horn Spot Leaf Disease (Cercosporakaki)

Momo wo to rot (Mo ni 1 i ni ia f r u c t i c o l a)

Budo Gray mold (Botry tiscsininerea)

 Powdery mildew (U n c i n -a 1 a n e c a t or)

 晚 Rot (G 1 o m e r e 1 1 a c i n g u 1 a t a)

Pear Scab (V e _n t u r i n a s h i c o 1 a)

 Scab (Gymn o s p o r a n g i um a s i a t i c u m) Black spot (A 1 t e r n a r i a k i k u c i a n a)

 Anthracnose (C o 1 1 e t o t r i c h um t h e a e-s i n en s sickness, disease (E l i n o e f a w c

 Blue mold (Penic i 1 1 丄 um a 1 i c u m) Green mold (P en i c i l l i um d i g i t a t u m) Gray mold (Bot r y t i s c i n e r e a)

Ery s i p h e g r a m i n i s s p h o r d e i

 Naked smut (U s t i 1 a g o n u d a)

 Wheat rust (Gib b er β 1 1 az e a e) Wheat rust (Pu c e i n i a r e c o n d i t a)

 Leaf spot (C o c h l i o b o l u s s a t i v u s)

Eye spot disease (Ps eudocercosporella. E τ vot τ choides)

 Blight (L eptosphaerianodorum) Udon (E rysiphegr am nf. Sp. T Γ Red snow rot (M icronectriellanivalis) Rice blast (P yr—i— c— u 1— ar— i— ao _r _y z _a _e _e _ )

 Sheath blight (Riz o c t o n—i a s o 1 a n _i)

 Stupid seedling disease (Gib b e r e 1 1 a f u j i k u ro o_i) Sesame leaf blight (C o c h l i o b o l u s n i y a b e a n u s) Tanoko sclerotium (Sc 1 e _r_o t i n i a s c 1 e r o t i o r um)

 Powdery mildew (E r _y s i_ p h e c — i c o r a c e a a r u m) Tulip Gray mold (Bot r y t i s _c n e r e a)

Bentgrass Snow rot Bacterial rot (Sc1erotinborreals) Orchardgrass Powdery mildew (Erysiphipegraminis_) Soybean purpura (Cercosp_orkiikkucchii)

Potatoes' Tomato Blight (Phytophthhorainfinfestans) Kibebe disease (PseU-d—o_p_erono sjorr_acubenssies) Grapevine disease (Plasmaipara)

It can be used for pest control.

 In recent years, various pathogens have developed resistance to benzimidazole fungicides ゃ dicarboximide fungicides, etc., resulting in insufficient efficacy of these drugs, and effective drugs for resistant bacteria have been desired. . The compounds of the present invention have an excellent bactericidal effect not only on pathogenic bacteria sensitive to such drugs but also on resistant bacteria.

 For example, Botrytiscinerea and ercosporabetico 1 a), which are resistant to existing drugs such as thiophane-methyl, benomyl, and carbendazim, and the brown spot of sugar beet, Venturia _i_naequa 1 i_ss ) And pear scab (Y_enturianashico 1a), like the susceptible bacteria, the compound of the present invention has an excellent bactericidal effect.

In addition, Botrytiscinerea is resistant to dicarboximide fungicides (eg, vinclozolin, procymidone, iprodione, etc.). The compounds of the present invention also have an excellent bactericidal effect against susceptible bacteria.

 Further, the compound of the present invention can also be used as an antifouling agent for preventing aquatic organisms from adhering to aquatic organisms such as ship bottoms and fish nets.

 Diseases more preferably applied with the composition (fungicide for agricultural and horticultural use) containing the compound of the present invention as an active ingredient include sugar beet scab, wheat powdery mildew, rice blast, apple scab and apple bean scab. Gray mold and brown spot of laccasei.

 The composition containing the compound of the present invention as an active ingredient contains one or more of the compounds of the present invention as an active ingredient. When the compound of the present invention is actually applied, it can be used in a pure form without adding other components. It can be used in the form of powders, emulsions, aqueous solvents, suspensions, flowables and the like.

 Additives and carriers that can be added to the pesticide formulation include, for solid formulations, plant powders such as soybean flour and flour, diatomaceous earth, apatite, gypsum, talc, bentonite, and pyrophyllite. Organic and inorganic compounds such as mineral fine powders such as clay, clay, sodium benzoate, urea, and sodium sulfate are used.

 For liquid dosage forms, petroleum fractions such as kerosene, xylene and solvent naphtha, cyclohexane, cyclohexanone, dimethylformamide, dimethylsulfoxide, alcohol, acetone, trichloroethylene, methyl Isobutyl ketone, mineral oil, vegetable oil, water, etc. can be used as the solvent.

 Further, in order to obtain a uniform and stable form in these preparations, a surfactant can be added as required. Examples of the surfactant that can be added include, for example, alkyl phenyl ether to which polyoxyethylene is added, alkyl ether to which polyoxyethylene is added, higher fatty acid ester to which polyoxyethylene is added, and polyoxyethylene to be added. Sorbitan higher fatty acid esters, non-ionic surfactants such as tristyryl ether added with polyoxyethylene, sulfates of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonates, sulfuric acid of higher alcohols Examples thereof include an ester salt, an alkyl naphthalene sulfonate, a polycarboxylate, a lignin sulfonate, a formaldehyde condensate of an alkyl naphthalene sulfonate, and a copolymer of isobutylene-maleic anhydride.

The amount of the active ingredient of the agricultural and horticultural fungicide of the present invention is usually based on the total amount of the composition (formulation). Te, preferably 0. 0 1-9 0 weight _^0/0, more preferably 0 5-8 5% by weight 0.1.

 The obtained wettable powder, emulsion, floor pull and the like are diluted with water to a predetermined concentration, and used as a suspension or an emulsion. The formulated fungicide composition of the present invention is applied as it is or diluted with water or the like to plants, seeds, water surface or soil.

 The amount of application varies depending on the weather conditions, formulation, application time, application method, application site, target disease, target crop, etc., but usually 1 to 100 hectares of active ingredient compound. g, preferably 10 to 100 g.

 When wettable powders, emulsions, flowables, suspensions, liquids, etc. are diluted with water and applied, the application concentration is 1 to 100 ppm, preferably 10 to 250 ppm. In the case of powders, powders and the like, they can be applied as is without dilution.

 It goes without saying that the compound of the present invention is effective alone, but it can also be used in combination with one or more of various fungicides, insecticides, acaricides or synergists. Representative examples of fungicides, insecticides, acaricides, nematicides, and plant growth regulators that can be used by mixing with the compound of the present invention are shown below.

 Fungicide :

 Copper agent: Basic copper chloride, basic copper sulfate, etc.

 Sulfur agent; thiuram, zinep, maneb, mancozeb, ziram, provevineb, polycarbamate, etc.

 Polyhaloalkylthio agents; captan, phorpet, dichlorofluanid and the like. Organic chlorine agent; chlorothalonil, fusaride, etc.

 Organic phosphorus agents; IBP, EDDPP, triclofosmethyl, pyrazophos, Josetyl and the like. Benzimidazole agents; thiophanate methyl, benomyl, carbendazim, thiabendazole and the like.

 Dicarboxymid agents; iprodione, procymidone, vinclozolin, fluorimide and the like.

 Carboxamide agents; oxycarboxin, mepronil, flutranil, techopen phthalam, trichloramide, pencyclone and the like.

Asylalanine agent; metalaxyl, oxazixil, furalaxyl and the like. Methoxycrylates: kresoxime methyl, azoxystrobin, methinostrobin and the like.

 Anilinopyrimidine agents; andpurine, mepanipyrim, pyrimethanil, dibrodinyl and the like.

 SBI agent: triazimefone, triadimenol, bitertanol, microbutanil, hexaconazole, propiconazole, triflumizol, prochloraz, difrazoate, fenarimol, pyriphenox, trifolin, flusilazol, etaconazo , Diclobudrazol, fluorotriazole, flutriafen, penconazole, diniconazole, imazalil, tridemorph, fenpropimorph, petiobeto, epoxyconazole, metconazole, etc.

 Antibiotics; polyoxin, blasticidin S, kasugamycin, validamycin, dihydrostrephtomycin sulfate and the like.

 Others: propamocalp hydrochloride, quintozene, hydroxyiisoxazole, metasulfocarp, anirazine, isoprothiolane, probenazole, quinomethionate, dithianon, dinocab, diclomedine, fermzone, fluazinam, pirokilicone, tricyclizolenic acid Iminoctadine acetate, simoxanil, pyrrole ditrin, metasulfocalc, dietofencalp, pinapacryl, lecithin, baking soda, phenaminosulf, dozine, dimetmorph, fenazinoxide, carblopamide, flusulfamide, fludimoxadone, etc. .

 Insecticide · Acaricide:

 Organic phosphorus and carbamate insecticides;

Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Vamidothion, Fentate, Dimethoate, Formothione, Marathon, Trichlorfon, Thiometone, Phosmet, Dichlorvos, Acephate, EPBP, Methylparathion, Toxie Salicione, cyanophos, isoxathione, pyridafenthione, phosalon, methidathione, sulprophos, chlorfenvinphos, tetrachlorovinphos, dimethylvinphos, propaphos, isofuenphos, ethylthiometone, profenophos, pyraclophos, monocrotophos, azidinfometh Mesomyl, Chozikarp, Carbofuran, Carbosulfan, Benfracalp, Fraciocal , Purobokisuru, BPMC, MTMC, MIPC, Leveryl, Pyrimicab, Etiofencalp, Fenoxycarp, etc.

 Pyrethroid insecticides;

 Permethrin, cypermethrin, deltamethrin, fenvalerate, femp mouth patrin, pyrethrin, allesulin, tetramethrin, resmethrin, dimethrin, propasulin, phenothrin, prototrin , Fluvalinate, cyflutrin, cyhalothrin, flucitrinate, etofenprox, cycloprotoline, trolamethrin, silafluofen, profenprox, aclinasulin, etc.

 Benzoylpereas and other insecticides;

 Difluvenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, methoprene, benzepin, diafentiuron, acetamiprid , Imidacloprid, ditenviram, fipronil, cartap, thiocyclam, bensultap, nicotine sulfate, rotenone, metaaldehyde, machine oil, microbial pesticides such as BT and insect pathogenic viruses.

 Nematicides; phenamiphos, phosthiazetate, etc.

 Acaricide;

 Chlorbenzylate, phenisopromolate, dicophor, amitraz, BPPS, benzomate, hexthiazox, fenbutatin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentezine, cihexatin, pyridabene, pyridavene Tepfenvirad, pyrimidifene, fenochiocalp, dienochlor, etc.

 Plant growth regulator:

 Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA and the like. BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be described more specifically with reference to examples. Example 1 Preparation of 6-methyl-14-trifluoromethyl-12-pyridinepyridinecarboxyaldehyde 0— (2,6-dimethoxybenzyl) oxime (Compound No. 5666) i) Production of 6-methyl-4-trifluoromethyl-2-ethylpyridinecarboxylate

 1-lg (46.3 mimol) of 2-bromo-6-methyl-1-trifluoromethylpyridine was dissolved in 90 ml of DMF, and 4.55 g of cuprous cyanide (50%) was dissolved in 90 ml of DMF. 9.3 mi) and sodium iodide 7.63 g (50.9 mimol) were added, and the mixture was refluxed for 6 hours. After cooling the reaction solution to room temperature, it was poured into cold water and extracted with ethyl acetate. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (V / V)) to give 2-cyano 6-methyl-4-triethyl. 7.44 g of fluoromethylpyridine was obtained.

 7 ml of concentrated sulfuric acid was added to a solution of 4.0 g (21.5 millimoles) of 2-cyano-6-methyl-4-trifluoromethylpyridine in 7 ml of ethanol at room temperature, and the total volume was reduced. Reflux for 2 hours. After the reaction solution was cooled to room temperature, it was poured into cold water, neutralized with sodium carbonate, and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained concentrate was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (v / v)) to obtain the target compound 3 2 g were obtained.

ii) Production of 2-hydroxymethyl-6-methyl-14-trifluoromethylpyridine

To a solution of 0.52 g (13.7 mimol) of LiA1H4 in 1 ml of dry THF is stirred and stirred with ethyl 6-methyl-4-trifluoromethyl-2-pyridinepyridine 3 A solution of 2 g (13.7 mimol) in 27 ml of THF was added dropwise under ice cooling. After the addition was completed, the whole volume was further stirred at room temperature for 1 hour. To the reaction mixture was added dropwise 40 ml of ethyl ester and 3.0 ml of ethyl acetate, and the mixture was stirred at room temperature for 30 minutes. After water was added to the reaction mixture and neutralized with 1 N hydrochloric acid, insolubles were filtered through celite, and the filtrate was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered. The concentrate obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent: n-hexane: ethyl acetate = 7: 3 (v / V)) to obtain the target compound. .5 g were obtained.

iii) Production of 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldoxime

2.0 _{g of} activated manganese dioxide was added to a solution of 1.04 g (5.44 mimol) of 2-hydroxymethyl-6-methyl-4-trifluoromethylpyridine in 11 ml of benzene, and added 20 _{g of} manganese dioxide. The mixture was heated under reflux for an hour. After cooling the reaction mixture, the insolubles were filtered through celite, and the filtrate was concentrated under reduced pressure to obtain 1.03 g of crude 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldehyde.

 The whole amount of the crude 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldehyde obtained above was dissolved in 12 ml of methanol, and 0.46 g (6.7 mmol) of hydroxylaminate hydrochloride was dissolved. Was added and refluxed for 2.5 hours. After cooling, the reaction mixture was concentrated under reduced pressure. Water was added to the mixture, neutralized with a 1N aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 7: 3 (v / v)) to obtain the target compound, 1.0. 5 g were obtained.

iv) Preparation of 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldehyde 0 — (2,6-dimethoxybenzyl) oxime

27 g (remol) of 2,6-dimethoxybenzyl alcohol in 4 m 0.54 g (2.09 mimol) and 0.8 g (2.41 mimol) of carbon tetrabromide were added to this solution, and the solution was added at room temperature. Stirred for hours. The reaction solution was concentrated under reduced pressure using a single evaporator to obtain a crude product of 2,6-dimethoxybenzyl bromide.

 On the other hand, a solution of 0.3 g (1.47 mimol) of 6-methyl-4-1-trifluoromethyl-2-pyridinecarboxyaldoxime in 4 ml of N, N-dimethylformamide was added to a solution of 60-ml under ice-cooling. To the mixture was added 88 mg (2.20 mmol) of an oily sodium hydride, and the mixture was stirred at ice temperature for 30 minutes. The whole amount of the previously prepared 2,6-dimethoxybenzyl bromide crude product was added thereto under ice-cooling, and the mixture was stirred at room temperature for 40 minutes. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (V / v)) to obtain the target compound 0 25 g were obtained.

 mp. 80-83 ° C Example 2 of 6-methyl-14-trifluoromethyl-12-pyridine pyridine oxyaldehyde O— (2-fluoro-6-methoxybenzyl) oxime (Compound No. 591) Manufacture

 To a 100 ml solution of 10-Og (64.0 millimoles) of 2-fluoro-6-methoxybenzyl alcohol in 100 ml of benzene was added 8.40 g (70.6 millimoles) of thionyl chloride at room temperature. It was added and stirred at the same temperature for 1 hour. The reaction solution was concentrated under reduced pressure to obtain a crude product of 2-fluoro-1-6-methoxybenzyl chloride.

To a solution of 10.4 g (63.8 mmol) of N-hydroxyphthalimide in 100 ml of N, N-dimethylformamide was added 13.0 g (128 mg) of triethylamine. Lmol) was added. There, the previously prepared 2-fluoro-6-methoxybenzyl chloride The whole amount of the crude product was added under ice cooling, and the mixture was further stirred at 70 ° C for 2 hours. The reaction solution was cooled to room temperature, poured into ice water, and extracted with ethyl acetate. After the organic layer was washed with water, it was dried over anhydrous magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to obtain 9.37 g of a crude product of N- (2-fluoro-6-methoxybenzyl) phthalimide.

 The whole amount of the obtained crude product of N- (2-fluoro-6-methoxybenzyl) phthalimide was dissolved in 10 O ml of methanol, and 187 g of hydrazine monohydrate was added to this solution. .0 mmol) and stirred at room temperature for 1 hour. The reaction solution was concentrated under reduced pressure, dissolved in ethyl acetate, washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crystals were washed with diethyl ether to obtain 5.68 g of 2-fluoro-6-methoxybensiloxyamine.

i i) Preparation of 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldehyde 0- (2-fluoro-6-methoxybenzyl) oxime

 To a solution of 0.20 g (1.05 mimol) of 6-methyl-1-trifluoromethyl-2-pyridinecarboxyaldehyde in 3 ml of glacial acetic acid was added 2-fluoro-6-methoxybenziloxyamine 0.19 g (1.16 mmol) was added and the mixture was stirred at room temperature for 2 hours. The reaction solution was poured into ice water and extracted with ethyl acetate. The ethyl acetate layer was washed with a 5% aqueous sodium hydrogen carbonate solution and then with a saturated saline solution, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; benzene: ethyl acetate = 9: 1 (v / v)) to obtain the desired product 0.24. g was obtained.

mp. 77-80 ϋImplementation _36 Preparation of 6-Methyl-4-1-trifluoromethyl-2-pyridinepyridinecarboxyaldehyde 0- (2-Methoxy-6-methylbenzyl) oxime (Compound No. 556)

 To a solution of 5.0 g (36.8 mimol) of 2,3-dimethylanisole in 10 ml of carbon tetrachloride was added 6.55 g (36.8 mimol) of N-promosuccinimid. The mixture was refluxed for 45 minutes under light irradiation (infrared light bulb 375 WR, manufactured by Toshiba Corporation). The reaction solution was cooled to room temperature, and the precipitated succinimide was filtered off. The filtrate was concentrated under reduced pressure to obtain a crude product of 2-methoxy-6-methylbenzylbutamide.

 Then, 0.204 g (1.00 millimol) of 6-methyl-4-trifluoromethyl-2-pyridinecarboxyaldoxime and crude crude of 2-methoxy-1-6-methylbenzylbutane prepared above. 0.26 g (1.20 mimol) of the product was dissolved in 4 ml of N, N-dimethylformamide. To this solution, 0.20 g (1.79 mmol) of a 50% aqueous potassium hydroxide solution was added at room temperature, and the mixture was stirred at the same temperature for 3 hours. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (v / v)) to obtain the desired product. 0.16 g was obtained.

 mp. 8 1-8 4 "C Example 4 4-Fluorometyl-6-methyl-2-pyridinecarboxyaldehyde

Preparation of 0- (2,6-dimethoxybenzyl) oxime (Compound No. 72)

 1) Synthesis of 4-(tert-butyldimethylsilyloxy) methyl-1,6 dimethylviridine

(In the formula, it represents a t-butyldimethylsilyl group (hereinafter abbreviated as TBDMS).) To a solution of 2.06 g (15.0 mmol) of 4-hydroxymethyl-2,6-dimethylpyridine in 10 ml of dichloromethane, 2.29 g (22.6 mmol) of triethylamine and 4- Dimethylaminopyridine 0.21 g (1.7 mmol) was added at room temperature. Further, 12.27 g (15.0 mmol) of t-butyldimethylsilyl chloride was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (v / v)). 2.67 g of the desired product was obtained. ii) Preparation of 4- (tert-butyldimethyloxy) methyl-6-methyl-1-pyridinecarboxyaldehyde 0— (2,6-dimethoxybenzyl) oxime

To a solution of 2.67 g (10.6 mimol) of 4-(tert-butyldimethylsilyloxy) methyl-1,2,6-dimethylviridine in 5 ml of chloroform, add mCPBA (70% w / w). ) 2.75 g (11.1 millimoles) was added at room temperature and stirred for 10 minutes. The reaction mixture was washed with a 1N aqueous solution of sodium hydroxide, and then washed with a saturated saline solution. After drying over anhydrous magnesium sulfate, the mixture was filtered, and the filtrate was concentrated under reduced pressure to obtain 2.84 g of a crude product. The whole amount of the crude product was added to 10 ml of acetic anhydride and refluxed at 70 ° C. for 2 hours. After the reaction mixture was concentrated under reduced pressure, the resulting residue was dissolved in 30 ml of methanol, 0.6 g (10.7 mmol) of potassium hydroxide was added, and the mixture was stirred at room temperature for 2 hours. Stirred. The reaction mixture was poured into ice water and extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure to obtain 2.5 g of a crude product. The whole amount of the crude product was dissolved in 25 ml of benzene, 2.45 g (28.2 mimol) of activated manganese dioxide was added, and the mixture was refluxed for 3.5 hours. After the reaction solution was cooled to room temperature, ethyl acetate and anhydrous magnesium sulfate were added, and the insolubles were filtered off.

 The crude product obtained by concentrating the filtrate under reduced pressure was dissolved in 50 ml of acetic acid, and 2.05 g (11.2 mimol) of 2,6-dimethoxybenzyloxyamine was added. And stirred at room temperature for 1 hour. The reaction mixture was poured into ice water, neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. The ethyl acetate layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate =: 1 (v / v)) to obtain the desired product. 6 g were obtained.

i i i) 4-Fluoromethyl-6-methyl-2-pyridinecarboxyaldehyde 0—

Preparation of (2,6-dimethoxybenzyl) oxime

 4- (tert-butyldimethylsilyloxy) methyl-6-methylpyridine-12-potassium aldoxime 2,6-dimethoxybenzyl ether 1.86 g (4.3 mimol) of THF 20 The m1 solution was cooled to 0 ° C., 5.2 ml (5.2 mmol) of tetrabutylammonium fluoride (lmol / L, THF solution) was added, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was poured into ice water, and the precipitated crystals were collected by filtration to obtain 1.0 g of a crude product.

0.07 g (0.22 mimol) of the obtained crude product was dissolved in 2 ml of chloroform, and 0.04 g (0.26 mimol) of getylaminosulfur trifluorofluoride was added. The mixture was added under ice cooling, and stirred at room temperature for 2 hours. The reaction mixture was poured into ice water and extracted with black-mouthed form. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (V / v)). 0.01 g of the desired product was obtained. mp. 9 6-9 8 ° C Example 5 4-Difluoromethyl-6-methyl-2-pyridinecarboxyaldehyde

Preparation of 0— (2,6-dimethoxybenzyl) oxime (Compound No. 319)

 0.94 g (2.997 mmol) of 4-hydroxymethyl-6-methylpyridine-1-carboxyaldoxime 2,6-dimethoxybenzyl ether was dissolved in 10 ml of benzene and activated. 0.77 g (8.9 mmol) of manganese dioxide was added, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature, and ethyl acetate and magnesium sulfate were added. The filtrate was concentrated under reduced pressure to obtain 0.72 g of a crude product.

 0.3 g (0.95 mmol) of the crude product was dissolved in 2 ml of black-mouthed form, and 0.46 g (2.85 mmol) of getyl aminosulfur trifluoride was cooled on ice. In addition, the mixture was gradually heated and stirred at 60 to 70 ° C for 2 hours. The reaction mixture was poured into ice water and extracted with chloroform. The organic layer was washed with water, dried over anhydrous magnesium sulfate, and filtered. The crude product obtained by concentrating the filtrate under reduced pressure was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (v / v)) to obtain the desired product. 16 g were obtained.

mp. 86-87 ° C Example 6 Preparation of 6-bromo-14-trifluoromethyl-12-pyridinecarboxyaldehyde 0- (2,6-dimethoxybenzyl) oxime (Compound No. 748) i) 2-Promote 4-trifluoromethyl-6-methylpyridine-1-oxide

 2-Promote 4-trifluoromethyl-1-6-methylpyridine 18.5 g (77.1 mimol) in a 300 ml solution of chloroform in mC PBA (70% w / w) 20 .9 g (8.8 mmol) was added at room temperature, and the mixture was stirred at room temperature overnight. Further, 9.0 g (36.5 mmol) of mCPBA (70% / w) was added to the reaction solution, and the mixture was stirred at room temperature for one week. The reaction mixture was washed with a 1N aqueous solution of sodium hydroxide, and then washed with a saturated saline solution. After drying over anhydrous magnesium sulfate, the mixture was filtered and the filtrate was concentrated under reduced pressure to obtain 19.7 g of the desired product.

ii) Production of 2-promo-6-hydroxymethyl-1-4-trifluoromethylpyridine

 19.7 g (77.1 mimol) of 2-bromo-16-methyl-14-trifluoromethylpyridine-11-oxide was dissolved in 30 ml of acetic anhydride. The solution was gradually heated to the reflux temperature, stirred at the same temperature overnight, and concentrated under reduced pressure to give a crude product of acetic acid 6-bromo-14-trifluoromethyl-12-pyridinylmethyl ester. I got

 The crude ester product was dissolved in 60 ml of methanol, 50 ml of water and 15.0 g of potassium hydroxide were added to the solution, and the mixture was stirred at room temperature for 4 hours. The reaction mixture obtained by concentrating the reaction solution under reduced pressure was diluted with water and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; benzene: ethyl acetate = 2: 1 (vZv)) to obtain 6.8 g of the desired product. Was.

iii) Preparation of 6-bromo-1-4-trifluoromethyl-2-pyridinecarboxyaldehyde

 0.2 g (0.78 millimoles) of 2-bromo-14-trifluoromethyl-2-pyridinylmethanol was dissolved in 4 ml of benzene. 0.4 g of activated manganese dioxide was added to this solution, and the mixture was heated to reflux temperature and stirred overnight. After the reaction mixture was cooled to room temperature, insolubles were removed by filtration. The obtained filtrate was concentrated under reduced pressure to obtain 0.18 g of the desired product.

iv) Preparation of 6-bromo-1-4-trifluoromethyl-2-pyridinepyridinecarboxyaldehyde O- (2,6-dimethoxybenzyl) oxime

 0.18 g (0.71 mimol) of 2-bromo-14-trifluoromethyl-2-pyridinecarboxyaldehyde is dissolved in 3 ml of acetic acid and 0.13 g ( (0.7 mol) of 2,6-dimethoxybenzyloxyamine was added at room temperature, and the mixture was stirred overnight at the same temperature. After the reaction mixture was concentrated under reduced pressure, it was neutralized by adding an aqueous solution of sodium hydrogen carbonate. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 7: 3 (V / V)) to obtain the desired product 0.19 g was obtained.

Melting point 99-1001 ° C Example 7 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-2-pyridinepyridinecarboxaldehyde 0- (2,6-dimethoxybenzyl) oxy (compound (No. 6 94) Manufacturing i) Production of 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-2-ethyl pyridinecarboxylate

 To a solution of 2.5 g (9.0 millimoles) of 4-hydroxymethyl-2,6-dimethylviridine in 20 ml of dichloromethane was added 1.36 g (13.5 millimoles) of triethylamine and 4 —Dimethylaminopyridine (0.1 llg, 0.9 mmol) was added at room temperature. Further, t-butyldimethylsilyl chloride (1.42 g, 9.5 mmol) was added under ice-cooling, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction solution, and the mixture was extracted with chloroform. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 7: 3 (V / v)) to obtain the desired product. 2.26 g were obtained.

2-promo 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-pyridine 4.48 g (12.11 mimol), triethylamine 1.46 g (1. A mixture of 0.53 g of PdCl ₂ (PP ₃ ) ₂ 0.55 g (0.79 mimol) and ethanol 20 m 1 in a autoclave under carbon monoxide pressure (70 atm.) ) The mixture was stirred at 80 ° C for 20 hours. After the reaction, ethanol was distilled off, and the residue was dissolved in ethyl acetate, washed with water and saturated saline, and dried by adding magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 10: 1 (v / v)) to obtain 4.2 g of the desired product. Obtained.

ϋ) Production of 2- (tert-butyldimethylsilyloxy) methyl-14-trifluoromethyl-6-hydroxymethylpyridine

6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-12-pyridinepyridinecarboxylic acid ethyl ester 2.0 g (5.51 mimol) was added to 3 mL of ethanol. Was dissolved in Lumpur, NaBH ₄ 0. ₄ 5 g of (1 2.1 2 Mi Rimoru) was added under ice-cooling and stirred for 2 hours at reflux temperature. The obtained reaction mixture was cooled with ice water, neutralized with 1N hydrochloric acid under ice-cooling, insolubles were filtered through celite, and the filtrate was extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate, and filtered. The concentrate obtained by concentrating the filtrate under reduced pressure was purified by silica gel chromatography (eluent; n-hexane: ethyl acetate = 10: 1 (V / v)) to obtain the target compound. 5.5 g were obtained.

iii) Production of 6- (tert-butyldimethylsilyloxy) methyl-1-41-trifluoromethyl-2-1-pyridinecarboxyaldehyde 0— (2,6-dimethoxybenzyl) oxime

 Activated carbon dioxide was added to a solution of 1.55 g (4.82 mimol) of 2- (tert-butyldimethylsilyloxy) methyl-6-hydroxymethyl-4-trifluoromethylpyridine in 20 ml of benzene. 4.0 g of manganese was added, and the mixture was heated under reflux for 20 hours. After cooling the reaction solution, the insolubles were filtered through celite, and the filtrate was concentrated under reduced pressure to obtain crude 6- (tert-butyldimethylsilyloxy) methyl-4- (1-trifluoromethyl) -2-pyridinecarboxyaldehyde.

The total amount of the obtained crude 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-2-pyridinepyridinecarboxyaldehyde was dissolved in 10 ml of acetic acid, and 1.15 g (6.28) was added to the solution. 2,6-Dimethoxybenzyloxyamine) was added at the same temperature, and the mixture was stirred for 1.5 hours. After the reaction mixture was concentrated under reduced pressure, it was neutralized by adding an aqueous solution of sodium hydrogen carbonate. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting crude product was subjected to silica gel column chromatography (eluent: hexane: ethyl ethyl drone = 1). Purification by 0: 1 (v / v) yielded 2.0 g of the desired product.

 Viscous Oil Example 8 Preparation of 6-Hydroxymethyl-4-1-trifluoromethyl-12-pyridine Powered L-boxaldehyde (2-, 6-Dimethoxybenzyl) oxime (Compound No. 693)

 Dissolve 1.85 g (3.82 mimol) of 6- (tert-butyldimethylsilyloxy) methyl-4-trifluoromethyl-2-pyridinecarboxaldehyde 0- (2,6-dimethoxybenzyl) oxime in 8 mL of THF After cooling to 0 ° C, add 4.6 mL (4.6 mmol) of tetrabutylammonium fluoride (lmol / L, THF solution), stir at 0 ° C for 1 hour, return to room temperature, and add Stirred for hours. The reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 4: 1 (V / V)) to obtain the desired product, 1.33. g was obtained.

Melting point 1 15—1 20 ° C. Example 9 Preparation of 6—formyl 14-trifluoromethyl-2-pyridinecarboxaldehyde 0— (2,6-dimethoxybenzyl) oxime (Compound No. 717)

6-Hydroxymethyl-4 4-Trifluoromethyl-2-pyridinecarboxyal Dissolve 0.96 g (2.59 millimoles) of O- (2,6-dimethoxybenzyl) oxoxide in 10 mL of benzene, and add 1.2 g of activated manganese dioxide. The mixture was heated under reflux for 8 hours. After the reaction solution was cooled to room temperature, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain crude 6-formyl-14-methylpyridine-12-carboxyaldehyde 0— (2, 6— Dimethoxybenzyl) oxime was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 2: 1 (v / v)) to obtain 0.87 g of the desired product.

Melting point 102-105 ° C Example 1 106 1-ethenyl-4-1-trifluoromethyl-2-pyridinepyridinecarboxyaldehyde 0— (2,6-dimethoxybenzyl) Oxime (Compound No. 690) ) Manufacturing

PPh ₃ CH ₃ Br 0.43 g (1.19 mimol) was dissolved in dehydrated gel ester, and n-butyllithium (1.6 M hexane solution) 0.8 mL (1 (25 mmol) was added dropwise. 4.0 g (1.0 g) of 6-formyl-14-trifluoromethyl-2-pyridinecarboxyaldehyde 0- (2,6 dimethoxybenzyl) oxime dissolved in dehydrated ethyl acetate at room temperature in the resulting solution. (0.9 mmol) was added dropwise and the mixture was stirred for 1.5 hours. The reaction mixture was poured into ice water, filtered through celite, and the organic layer was washed with water and brine, and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 4: 1 (v / v)) to obtain 4 g of the desired product. Was.

Melting point: 80—82 2 Example 1 16—Cyanol 4-trifluoromethyl-2-pyridinecarboxyaldehyde 0— (2,6-Dimethoxybenzyl) oxime (Compound No. 724) Production i) Production of 2-cyano 6-hydroxymethyl-1-4-trifluoromethylpyridine

 2-Promo 6- (tert-butyldimethylsilyloxy) methyl-4-1.1-trifluoromethylpyridine 1.16 g (3.13 mimol) was dissolved in 10 ml of DMF, and cuprous cyanide was added. 31 g (3.44 mimol) and 0.51 g (3.44 mimol) of sodium iodide were added, and the mixture was refluxed for 4 hours. After the reaction solution was cooled to room temperature, it was poured into cold water and extracted with getyl ether. The organic layer was washed with water and saturated saline, dried over anhydrous magnesium sulfate, and filtered. The filtrate was concentrated under reduced pressure, and the concentrate was purified by silica gel column chromatography (eluent; n-hexane: ethyl acetate = 10: 1 (V / V)) to give 6- (tert- —Butylmethylsilyloxy) 0.92 g of methyl 2-cyano 4-trifluoromethylpyridine was obtained.

 The total amount of the obtained 6- (tert-butyldimethylsilyloxy) methyl-1-cyano-4-trifluoromethylpyridine was dissolved in 20 ml of THF, and the solution was cooled to 0 and cooled to 0% with tetramethylammonium fluoride (lmol / lmol). (L, THF solution) 3.5 ml (3.5 mmol) was added, and the mixture was stirred at 0 ° C for 1 hour, then returned to room temperature and stirred for 3 hours. The reaction mixture was poured into ice water, extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluent; hexane: ethyl acetate = 4: 1 (v / v)) to obtain the desired product. 48 g were obtained.

ii) Preparation of 6-cyano-1 4-trifluoromethyl-1-2-pyridinecarboxyaldehyde 0- (2,6-dimethoxybenzyl) oxime

Dissolve 0.48 g (2.37 mimol) of 2-cyano 6-hydroxymethyl-14-trifluoromethylpyridine in 5 ml of benzene, add 2.02 g of activated manganese dioxide, The mixture was refluxed for 6 hours. After the reaction solution was cooled to room temperature, insolubles were removed by filtration, and the filtrate was concentrated under reduced pressure to obtain a crude product.

 The whole amount of the obtained crude 6-cyano 4-trifluoromethyl-2-pyridinecarboxyaldehyde was dissolved in 10 ml of acetic acid, and 0.15 g (0.825 mmol) of 2,2 was dissolved at room temperature. 6-Dimethoxybenzyloxyamine was added, and the mixture was stirred overnight at the same temperature. The reaction mixture was concentrated under reduced pressure, and then neutralized by adding an aqueous solution of sodium hydrogen carbonate. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate. This was concentrated under reduced pressure, and the obtained crude product was purified by silica gel column chromatography (eluate; hexane: ethyl acetate = 7: 3 (v / v)) to obtain the desired product. 17 g were obtained.

Melting point: 122-126 ° C. Table 1 shows typical examples of the compounds of the present invention including the above Examples.

Table 1

d ΟΟ / εθ OAV

 * 2 NMR data of compound No. 6 94

 1 H-NMR (CDC 13, TM SS ppm) Data: 0.12 (s, 6 H), 0.97 (s, 9 H), 3.87 (s, 6 H), 4 .88 (s2H), 5.42 (s2H), 6.60 (d, 2H), 7.30 (t, 1H), 7.77 (bs, 1H) ), 7.97 (bs 1 H), 8.15 (s 1 H)

〔Fungicide〕

Next, examples of the fungicide of the present invention will be described. The additives and the addition ratio are not limited to these examples, and can be changed in a wide range. Parts in Examples of preparations indicate parts by weight. Example 1 2 wettable powder

 Compound of the present invention 40 parts

 Clay 4 8 parts

 Dioctyl sulfosuccinate sodium salt 4 parts

 Lignin sulfonic acid sodium salt 8 parts

 If the above are uniformly mixed and finely pulverized, a wettable powder with an active ingredient of 40% is obtained.

Example 13 Emulsion

 Compound of the present invention 10 parts

 Solbesso 2 0 0 5 3 parts

 Cyclohexanone 2 6 parts

 Dodecylbenzenesulfonic acid calcium salt 1 part

 Polyoxyethylene alkylaryl ether 10 parts

 By mixing and dissolving the above, an emulsion containing 10% of the active ingredient is obtained.

Example 14 Dust

 Compound of the present invention 10 parts

 Clay 90 parts

 If the above are uniformly mixed and finely ground, a powder containing 10% of the active ingredient is obtained.

Example 15 Granules

 5 parts of the compound of the present invention

 Clay 7 3 parts

 Bentonite 20 parts

 Dioctyl sulfosuccinate sodium salt 1 part

 Potassium phosphate 1 part

 The above is pulverized and mixed well, water is added and kneaded well, and the mixture is granulated and dried to obtain granules having an active ingredient of 5%.

Example 16 Suspension

 Compound of the present invention 0 parts

 Polyoxetylene alkylarylether 4 parts

 Sodium polycarboxylate 2 parts

Glycerin 0 parts Xanthan gum 0.2 parts

 Water 73.8 parts

 The above ingredients are mixed and wet-pulverized to a particle size of 3 microns or less to obtain a 10% active ingredient suspension.

Example 17 wettable powder for granules

 Compound of the present invention 40 parts

 Clay 3 6 parts

 Lithium chloride 10 parts

 Sodium alkylbenzene sulfonate 1 part

 Lignin sulfonic acid sodium salt 8 parts

 Formaldehyde condensate of sodium alkyl benzene sulfonate

 5 copies

 After mixing the above uniformly and finely pulverizing, add an appropriate amount of water and knead it into a clay. If the clay is granulated and dried, a wettable powder with an active ingredient of 40% is obtained.

Industrial applicability:

 Next, Test Examples show that the compound of the present invention is useful as an active ingredient of various plant disease controlling agents. The control effect was determined by visually observing the diseased state of the test plant at the time of the survey, that is, the degree of the growth of the fungal spots appearing on the leaves, stems, etc., and comparing it with the untreated one to determine the control effect. Test example 1 Green bean blight control test

Flowers green beans were grown in nursery pad bets (cultivar "Naka quail") was excised and immersed in a chemical solution prepared to a concentration of the active ingredient 5 0 pp _m milk agent of Example. After immersion, it was air-dried at room temperature and spray-inoculated with kidney bean fungus (Botrytiscinerea). The inoculated flowers were placed on untreated leaf leaves and kept in a high-humidity constant temperature room (20 ° C) where light and darkness were repeated for 12 hours 繰 り 返 す for 7 days. The lesion diameter on the leaves was compared with that of untreated leaves, and the control value was determined. As a result, the following compounds exhibited excellent control values of 75% or more. The compound numbers correspond to the compound numbers (No.) in Table 1.

 Compound number (N o ·): 62, 72, 96, 31 19, 56, 56 66, 591, 63 53, 69 0, 72, 4, 74, 70 4 8

Claims

 The scope of the claims

 General formula [I]

(Wherein, R i is, CS alkyl group, C ₃ ~ ₈ cycloalkyl group, C ie alkoxy groups, C ₁ ~ ₆ alkylthio group, amino group, mono C alkylamino group, di-C ₁ ~ ₆ alkyl group, C ₁ ~ ₆ Ashiruokishi group, C alkoxy C ₁ ~ ₆ alkyl group, C IS alkoxides aryloxycarbonyl group, C ₂ ~ ₆ alkenyl group, tri C ₁ ~ ₆ alkyl silicate b alkoxy C ₁ ~ ₆ § alkyl group, human Dorokishi C _1-6 alkyl group, arsenate Dorokishi group, Shiano group, a formyl group or a halogen atom.

m represents an integer of 0 to 3, and when ia is 2 or more, R ¹ may be the same or different c

R ² represents a C haloalkyl group.

R ³ and R ⁴ are the same or different and represent a hydrogen atom or a C i- ₆ alkyl group.

R 5, R 6, R 7 R 8 and R 9 are the same or different, a hydrogen atom, C ₁ ~ ₆ alkyl le group, C ₃ ~ ₈ cycloalkyl group, C ₂ ~ ₆ alkenyl group, C ₂ ~ ₆ alkynyl, C i ~ ₆ alkoxy group, C alkoxy C i ^^ s alkyl group, C i ^^ e alkoxy C alkoxy group, C 2 ~ ₆ Arukeniruokishi group, C ₂ ~ ₆ Arukiniruokishi group, C ₁ - 6 Ashiruoki shea group, C, ~ ₆ alkylcarbonyl O alkoxy group, mono-C alkyl force Rubamoiruokishi group, di C丄_1-6 alkyl force Rubamoiruokishi group, C iota _1-6 alkylsulfonyl O carboxymethyl group, C ₁ - ₆ haloalkyl Suruhoniruokishi group, C ₁ - ₆ haloalkyl group, C ₁ - ₆ alkylthio O group, mono C丄_1-6 alkylamino group, di C ₁ - ₆ alkylamino group, C ₁ - ₆ Ashiruami amino group, an amino group, human Represents a droxy group or a halogen atom. Two adjacent ones of R ⁵ , RR ⁷ , R 8, and R ^g may be an alkylene chain containing a hetero atom to form a 5- to 7-membered condensed ring. )

An oxime ether compound represented by the formula:

2. The R ⁵ is, C i S alkoxy groups, C丄_1-6 alkoxy C alkoxy groups, C ₂ - 6 Arukeniruokishi groups, C ₂ - ₆ Arukiniruokishi groups, C ₁ - 6 Ashiruokishi groups, ^c i ~ 6 One kind selected from the group consisting of an alkylcarbonyloxy group, a mono-C- ₆ alkyl power rubamoyloxy group, a di-C ₆ alkyl power rubamoyloxy group, a C- ₆ alkyl sulfonyloxy group and a C haloalkylsulfonyloxy group. 2. The oxymester compound according to 1, which is a group.

3. The R ^g is, C ₁ ~ ₆ alkyl group, C ₃ ~ ₈ cycloalkyl group, C ₂ ~ ₆ alkenyl group,

C ₂ ~ ₆ alkynyl groups, C ₁ ~ 6 alkoxy groups, C alkoxy C 1 ~ 6 alkyl groups, C E 6 alkoxy C alkoxy groups, C ₂ ~ ₆ Arukeniruokishi groups, C ₂ ~ ₆ alkynyl Okishi groups, C ie Ashiruokishi group, C ₁ ~ ₆ alkylcarbonyl O alkoxy group, mono-C i ~ ₆ alkyl force Rubamoiruokishi group, di C ₁ ~ ₆ alkyl force Rubamoiruokishi group, C ₁ ~ ₆ § Le kills sulfonyl O carboxymethyl group, C i ^^ e haloalkyl Selected from the group consisting of sulfonyloxy groups, Ci ^ s haloalkyl groups, C ^ e alkylthio groups, amino groups, mono C- ₆ alkylamino groups, di Ci- ₆ alkylamino groups, hydroxy groups and halogen atoms 3. The oxime ether compound according to 1 or 2, which is one kind of a group.

 4. A fungicide for agricultural and horticultural use comprising one or more of the oxime ether compounds or salts thereof according to any one of 1 to 3 above.