WO2011108396A1 - Oxime ether derivatives or salts thereof, and germicides for agricultural or horticultural use - Google Patents

Abstract

Novel oxime ether derivatives represented by general formula (I) or salts thereof; and germicides for agricultural or horticultural use, which each contain at least one compound selected from among these compounds as an active ingredient. In general formula (I), X is C1-8 alkyl or the like; n represents the number of substituents X and is an integer of 0 to 4; R1 and R2 are each independently hydrogen or the like; m represents the number of repeats of a unit in parentheses and is an integer of 0 to 8; R3 is C1-8 alkyl or the like; R4 is C1-8 alkyl or the like; R5 is hydrogen or the like; Y is oxygen or sulfur; Z is oxygen or the like; and Q is a substituted or unsubstituted pyrazole-ring group.

Description

Oxime ether derivatives or salts thereof, and agricultural and horticultural fungicides

The present invention relates to an oxime ether derivative or a salt thereof, and an agricultural and horticultural fungicide. More specifically, the present invention relates to a novel oxime ether derivative or a salt thereof, and an agricultural and horticultural fungicide containing as an active ingredient at least one selected from the oxime ether derivative or a salt thereof.
This application claims priority on March 1, 2010 based on Japanese Patent Application No. 2010-044194 filed in Japan, the contents of which are incorporated herein by reference.

In the cultivation of agricultural and horticultural crops, various control agents are used against crop diseases. However, many of these control agents have insufficient control efficacy, their use is limited by the emergence of drug-resistant pathogens, cause phytotoxicity and pollution to plants, or are toxic to human fish and have an impact on the environment. It is difficult to say that it is a satisfactory control agent because of the problems such as large For this reason, there is a strong demand for the emergence of a control agent that has few such problems, has a high control effect, and can be used safely.

In connection with the present invention, oxyamine derivatives (Patent Document 1), oxime derivatives (Patent Document 2), oxime ether derivatives (Patent Document 3), and the like have been proposed.

Japanese Patent Laid-Open No. 2004-166863 Japanese Patent Laid-Open No. 2003-231672 WO2009 / 075112

The oxyamine derivatives, oxime derivatives, or oxime ether derivatives or salts thereof described in Patent Documents 1 to 3 can be easily synthesized industrially, have a high control effect, and can be used as safe control agents. It was. However, the compounds described in Patent Documents 1 to 3 require a relatively large application amount (g / ha) of the compound required for use as a control agent depending on the target disease. Due to the low permeability of the compound to crops, there was a case where a sufficient control effect was not obtained in practical use.
In view of such circumstances, the present invention can be easily manufactured industrially, has a large control effect even at a low concentration and a small application amount, and has high penetrability and residual effect on many agricultural and horticultural crops. It is an object of the present invention to provide a novel oxime ether derivative or a salt thereof, and an agricultural and horticultural fungicide, which can be an active ingredient of an agricultural and horticultural fungicide that has a reliable disease control effect and can be used safely. .

The present inventors diligently studied to solve the above problems. As a result, a novel oxime ether derivative having a pyrazole ring group represented by the formula (I) or a salt thereof was obtained. These oxime ether derivatives or salts thereof can be easily produced industrially, and agricultural and horticultural fungicides containing at least one selected from these compounds as an active ingredient have a low concentration and an application rate. At least, the control effect is large, the penetration and retentivity to many agricultural and horticultural crops is high, and the control effect against diseases is certain, and there is little phytotoxicity and pollution to plants, We found that it has excellent safety because it has little impact on the environment. The present invention has been completed by further studies based on these findings.

That is, the present invention includes the following aspects.

[1] An oxime ether derivative represented by the formula (I) or a salt thereof (hereinafter sometimes referred to as the present compound).

[In the formula (I), X represents a halogen atom, a C1-8 alkyl group, a C1-8 alkoxy group, a C1-8 haloalkyl group, or a C1-8 haloalkoxy group. n represents the number of substitutions of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different.
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a C1-8 alkyl group, a C1-8 haloalkyl group, or an unsubstituted or substituted C3-8 cycloalkyl group. R ¹ and R ² may be bonded together to form a ring. m represents the number of repeating units in parentheses and is an integer from 0 to 8. When m is 2 or more, R ¹ and R ² may be the same or different.
R ³ is a hydrogen atom, a C1-8 alkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 haloalkenyl group, a C2-8 haloalkynyl group, or an unsubstituted or Represents a C3-8 cycloalkyl group having a substituent.
R ⁴ represents a hydrogen atom, a C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 halo. It represents an alkenyl group or a C2-8 haloalkynyl group.
R ⁵ is a hydrogen atom, C1-8 alkyl group, acyl group, formyl group, C1-8 alkoxy C1-8 alkyl group, C2-8 acyloxy C1-8 alkyl group, C1-8 alkoxycarbonyl group, C1-8 alkyl A sulfonyl group or an unsubstituted or substituted phenylsulfonyl group is represented.
Y represents an oxygen atom or a sulfur atom.
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ . R ⁶ represents a hydrogen atom or a C1-8 alkyl group.
Q represents an unsubstituted or substituted pyrazole ring group. ]

[2] X is a C1-8 alkyl group, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-8 alkyl group, and Y and Z are oxygen atoms , Q is unsubstituted or substituted 1H-pyrazol-3-yl group, unsubstituted or substituted 2H-pyrazol-3-yl group, or unsubstituted or substituted 1H-pyrazol- The oxime ether derivative or the salt thereof according to [1] above, which is a 4-yl group, m is 1, and n is 0 to 1.

[3] An agricultural and horticultural fungicide containing as an active ingredient at least one selected from the oxime ether derivatives or salts thereof according to [1] or [2] (hereinafter sometimes referred to as the present invention fungicide) .)

The compound of the present invention can be easily produced industrially, has a large control effect at a small application rate for many agricultural and horticultural crops, and has an excellent osmotic migration and residual effect, and therefore has a control effect against diseases. It is a novel compound useful as an active ingredient of an agricultural and horticultural fungicide that is reliable and can be used safely.

The fungicide of the present invention has an excellent control effect even when the concentration of the compound of the present invention is low and the application amount is small, does not cause phytotoxicity or contamination on the plant body, and is toxic to human and livestock and has an impact on the environment. It is a drug with excellent safety.

Such an effect of the present invention is difficult to predict from the knowledge of Patent Documents 1 to 3, and has a large control effect even at a low concentration and a small application amount, and is effective for many agricultural and horticultural crops. From the patent document 3, it is impossible to predict the effect that the effect of controlling the disease is certain due to the high permeability and residual effect.

(1) Oxime ether derivative or salt thereof The compound of the present invention is an oxime ether derivative represented by the formula (I) or a salt thereof.

[X]
In the formula (I), X represents a halogen atom, a C1-8 alkyl group, a C1-8 alkoxy group, a C1-8 haloalkyl group, or a C1-8 haloalkoxy group. n represents the number of substitutions of X and is an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1. When n is 2 or more, Xs may be the same or different.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
The C1-8 alkyl group may be linear or branched. For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n- A heptyl group, n-octyl group, etc. are mentioned.
The C1-8 alkoxy group may be linear or branched. For example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, etc. Is mentioned.
The C1-8 haloalkyl group is not particularly limited as long as it is an alkyl group substituted with a halogen atom. For example, fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, dibromomethyl group, trifluoromethyl group, trichloromethyl group, tribromomethyl group, 2,2,2-trifluoroethyl group, Examples include 2,2,2-trichloroethyl group, pentafluoroethyl group and the like.
The C1-8 haloalkoxy group is not particularly limited as long as it is an alkoxy group substituted with a halogen atom. For example, chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group, pentafluoroethoxy group, etc. Can be mentioned.
Of these, X is preferably a C1-8 alkyl group.

[R ^1, R ^2]
R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a C1-8 alkyl group, a C1-8 haloalkyl group, or an unsubstituted or substituted C3-8 cycloalkyl group. m represents the number of repeating units in parentheses and is an integer from 0 to 8, preferably an integer from 0 to 3, more preferably an integer from 0 to 1. When m is 2 or more, R ¹ and R ² may be the same or different.

The halogen atom, C1-8 alkyl group, and C1-8 haloalkyl group in R ¹ and R ² are the same as those described as the halogen atom, C1-8 alkyl group, and C1-8 haloalkyl group in X above. Is mentioned.
Examples of the unsubstituted C3-8 cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.
Substituents for C3-8 cycloalkyl groups include: halogen atoms such as fluorine, chlorine and bromine; C1-6 alkyl groups such as methyl and ethyl groups; C1-6 alkoxy groups such as methoxy and ethoxy groups Nitro group; cyano group; and the like.
R ¹ and R ² may be bonded together to form a ring. The ring may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom. Examples of such a ring include a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, and a tetrahydropyran ring.

[R ^3]
R ³ is a hydrogen atom, a C1-8 alkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 haloalkenyl group, a C2-8 haloalkynyl group, or an unsubstituted or Represents a C3-8 cycloalkyl group having a substituent.

C1 ~ 8 alkyl group for R ^3, examples of C3 ~ 8 cycloalkyl group having C1 ~ 8 haloalkyl group, and an unsubstituted or substituted group, such as in the X or R ^1, C1 ~ 8 alkyl, C1 ~ 8 Examples include the same haloalkyl groups and those described as unsubstituted or substituted C3-8 cycloalkyl groups.

C2-8 alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2 -Propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4-pentenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group Group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group and the like.
C2-8 alkynyl groups include ethynyl, 1-propynyl, propargyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl Group, 1-pentynyl group, 2-pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-2-butynyl group, 2-methyl-3-pentynyl group, 1-hexynyl group, 1,1-dimethyl Examples include a -2-butynyl group.
The C2-8 haloalkenyl group includes a 3-chloro-2-propenyl group, a 4-chloro-2-butenyl group, a 4,4-dichloro-3-butenyl group, a 4,4-difluoro-3-butenyl group, 3 , 3-dichloro-2-propenyl group and the like.
C2-8 haloalkynyl groups include 3-chloro-1-propynyl group, 3-chloro-1-butynyl group, 3-bromo-1-butynyl group, 3-bromo-2-propynyl group, 3-iodo-2 -Propynyl group and the like.

[R ^4]
R ⁴ represents a hydrogen atom, a C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 halo. It represents an alkenyl group or a C2-8 haloalkynyl group.

Examples of the C1-8 alkyl group in R ⁴ include the same as those described as the C1-8 alkyl group in X.
Examples of the unsubstituted or substituted C3-8 cycloalkyl group in R ⁴ include the same as those described as the unsubstituted or substituted C3-8 cycloalkyl group in R ^{1 and the} like. It is done.
In R ⁴ , the C2-8 alkenyl group, C2-8 alkynyl group, C1-8 haloalkyl group, C2-8 haloalkenyl group, and C2-8 haloalkynyl group include the C2-8 alkenyl group in R ³ , Examples thereof include those described as C2-8 alkynyl groups, C1-8 haloalkyl groups, C2-8 haloalkenyl groups, and C2-8 haloalkynyl groups.

[R ^5]
R ⁵ is a hydrogen atom, C1-8 alkyl group, acyl group, formyl group, C1-8 alkoxy C1-8 alkyl group, C2-8 acyloxy C1-8 alkyl group, C1-8 alkoxycarbonyl group, C1-8 alkyl A sulfonyl group or an unsubstituted or substituted phenylsulfonyl group is represented.
Examples of the C1-8 alkyl group for R ⁵ include the same as those described as the C1-8 alkyl group for X.
Examples of the acyl group include an acetyl group, a propionyl group, a pivaloyl group, a trifluoroacetyl group, a trichloroacetyl group, a benzoyl group, a 4-methylbenzoyl group, and a 2-chlorobenzoyl group.
C1-8 alkoxy C1-8 alkyl group includes methoxymethyl group, ethoxymethyl group, i-propoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, 2-ethoxyethyl group, Examples include 1-methoxy-n-propyl group, 2-methoxy-n-propyl group, 3-methoxy-n-propyl group and the like.
Examples of the C2-8 acyloxy C1-8 alkyl group include an acetoxymethyl group, an acetoxyethyl group, a propenyloxymethyl group, a pivaloyloxymethyl group, a 1-acetoxyethyl group, a 2-acetoxyethyl group, and a 1-acetoxy-n. -Propyl group and the like.
Examples of the C1-8 alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group and the like.
Examples of the C1-8 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an i-propylsulfonyl group.
Examples of the unsubstituted or substituted phenylsulfonyl group include a phenylsulfonyl group, a 4-methylphenylsulfonyl group, a 2-chlorophenylsulfonyl group, and a 2,4-dimethylphenylsulfonyl group.

In the present invention, it is preferable that R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-8 alkyl group.

[Y, Z]
Y represents an oxygen atom or a sulfur atom.
Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ .
R ⁶ represents a hydrogen atom or a C1-8 alkyl group. Examples of the C1-8 alkyl group for R ⁶ include the same as those described as the C1-8 alkyl group for X.
In the present invention, Y and Z are preferably oxygen atoms.

[Q]
Q represents an unsubstituted or substituted pyrazole ring group. The bonding position of the pyrazole ring group and the carbon having R ¹ and R ² is not particularly limited. Q is an unsubstituted or substituted 1H-pyrazol-3-yl group, an unsubstituted or substituted 2H-pyrazol-3-yl group, or an unsubstituted or substituted 1H-pyrazol- A 4-yl group is preferred.

Examples of the substituent of the pyrazole ring group include a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C2-8 alkenyl group, an unsubstituted or substituted C2 -8 alkynyl group, unsubstituted or substituted C1-8 alkoxy group, unsubstituted or substituted C1-8 alkylthio group, unsubstituted or substituted C1-8 alkylsulfonyl group, or unsubstituted Examples thereof include a substituted or substituted C1-8 alkylsulfonyloxy group.

The halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in the substituent of the pyrazole ring group are described as the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in the above X or R ¹ etc. The same as

Examples of the C1-8 alkyl group having a substituent include a chloromethyl group, a fluoromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, and a 2,2,2-trifluoro-1-methylethyl group. C1-8 haloalkyl groups such as: C3-8 cycloalkyl C1-8 alkyl groups such as cyclopropylmethyl, cyclobutylmethyl, and cyclopropylethyl groups; C1-8 such as methoxymethyl, ethoxymethyl, and ethoxyethyl groups 8 alkoxy C1-8 alkyl group; cyano C1-8 alkyl group such as cyanomethyl group; nitro C1-8 alkyl group such as nitromethyl group; C1-8 alkylthio C1-8 alkyl group such as methylthiomethyl group, ethylthiomethyl group; C6-10 aryl such as benzyl group and phenethyl group Kill group; acetyloxymethyl group, C1 ~ 7 acyloxy C1 ~ 8 alkyl group such as propionyloxymethyl group; and the like.

Examples of the C2-8 alkenyl group and C2-8 alkynyl group in the substituent of the pyrazole ring group include the same as those described as the C2-8 alkenyl group and C2-8 alkynyl group in R ³ .

Examples of the C1-8 alkylthio group include methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group and the like.

Examples of the C1-8 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an i-propylsulfonyl group, and an n-butylsulfonyl group.

Examples of the C1-8 alkylsulfonyloxy group include a methylsulfonyloxy group, an ethylsulfonyloxy group, an i-propylsulfonyloxy group, and an n-butylsulfonyloxy group.

Among the compounds of the present invention, particularly preferred compounds are those in which the oxime ether derivative represented by the formula (I) or a salt thereof, wherein X is a C1-8 alkyl group, R ¹ , R ² , R ³ , R ⁴ and R ⁵ is independently a hydrogen atom or a C1-8 alkyl group, Y and Z are oxygen atoms, Q is unsubstituted or substituted 1H-pyrazol-3-yl group, unsubstituted or substituted A 2H-pyrazol-3-yl group having a group or an 1H-pyrazol-4-yl group having no substituent or a substituent, wherein m is 1 and n is 0 to 1.

In the oxime ether derivative of the present invention, geometric isomers based on carbon-nitrogen double bonds (cis-trans isomers) may exist, and all of these isomers are included in the present invention.

The salt of the oxime ether derivative that is the compound of the present invention is not particularly limited as long as it is a chemically acceptable salt. For example, salts of alkali metals such as lithium, sodium and potassium; salts of alkaline earth metals such as calcium and magnesium; salts of transition metals such as iron and copper; organic bases such as ammonia, triethylamine, tributylamine, pyridine and hydrazine And the like.

The compound of the present invention has an excellent bactericidal activity against a wide variety of filamentous fungi, for example, bacteria belonging to algae fungi (Oomycetes), ascomycetes (Ascomycetes), imperfect fungi (Deuteromycetes), basidiomycetes (Basidiomycetes) Therefore, it is useful as an active ingredient of agricultural and horticultural fungicides.

The compound of the present invention can be easily produced industrially in accordance with a known method, for example, the method described in Patent Document 3. The structure of the produced compound can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.

Specific examples of the compound of the present invention include compounds shown in Tables (1) to (3). However, the compounds in Tables (1) to (3) are for illustrative purposes, and the compounds of the present invention are not limited thereto.
In the table, Et represents an ethyl group, ⁱ Pr represents an isopropyl group, ⁿ Bu represents an n-butyl group, ^s Bu represents a s-butyl group, ^t Bu represents a t-butyl group, and ^c Pr represents a cyclo A propyl group and Ac represents an acetyl group, respectively.

(2) Agricultural and horticultural fungicide The fungicide of the present invention contains at least one selected from the compounds of the present invention as an active ingredient.

The fungicides of the present invention, like the compounds of the present invention, are bacteria belonging to a wide variety of fungi, for example, algae fungi (Oomycetes), ascomycetes (Ascomycetes), incomplete fungi (Deuteromycetes), basidiomycetes (Basidiomycetes) Excellent sterilizing power.

The fungicide of the present invention can be used by using means such as seed treatment, foliage spraying, soil application or water surface application for the control of various diseases that occur during cultivation of agricultural and horticultural crops including flower buds, turf and grass. it can.

For example, “sugar beet” brown spot (Cercospora beticola); “peanut” brown spot (Mycosphaerella arachidis); black astringency (Mycosphaerella berkeleyi); “cucumber” powdery mildew (Sphaerotheca fuliginea), vine blight ( Mycosphaerella melonis), Mycorrhizal disease (Sclerotiniainsclerotiorum), Gray mold disease (Botrytis cinerea), Black spot disease (Cladosporium cucumerinum), Brown spot disease (Corynespora cassicola), Seedling disease (Pythium debaryanam, Rhizoctonia solani Kuhn) Disease (Pseudomonas syringae pv.Lecrymans); “Tomato” gray mold (Botrytis cinerea), leaf mold (Cladosporium fulvum); “Nasal” gray mold (Botrytis cinerea), black blight (Corynespora melongenae), powdery mildew Mildew (Erysiphe cichoracearum), mildew (Mycovellosiella nattrassii); “strawberry” gray mold (Botrytis cinerea), powdery mildew (Sohaerotheca humuli) , Anthracnose (Colletotrichum acutatum, Colletotrichumariafragariae); gray rot of onion (Botrytis allii), gray mold (Botrytis cinerea), leafy blight (Botrytis squamosa); brassicae), soft rot (Erwinia carotovora); ”carrot nuclei (Sclerotinia sclerotiorum)”, gray mold (Botrytis cinerea); “apple” powdery mildew (Podosphaera leucotricha), black scab (Venturia inaequalis), monilia Disease (Monilinia mali), rot disease (Valsa mali), spotted leaf disease (Alternaria mali), red star disease (Gymnosporangium yamadae), ring rot (Botryosphaeria berengeriana), anthracnose disease (Colletotrichum gloeosprioides), brown spot disease (Diplocarpon) ); “Oyster” powdery mildew (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), keratodeciduous leaf disease (Cercospora kaki); “peach sweet cherry” ash Disease (Monilinia fructicola); “Grape” gray mold disease (Botrytis cinerea), powdery mildew (Uncinula necator), late rot (Glomerella cingulata); “pear” black star disease (Venturia nashicola), red star disease (Gymnosporangium asiaticum) ), Black spot disease (Alternaria kikuchiana); “cha” ring spot disease (Pestalotia theae), anthracnose disease (Colletotrichum theae-sinensis); “citrus” scab (Elsinoe fawcetti), blue mold disease (Penicillium italicum) , Green mold disease (Penicillium digitatum), gray mold disease (Botrytis cinerea), black spot disease (Diaporthe citri), scab (Xanthomonas campestris pv. Citri); “wheat” powdery mildew (Erysiphe graminis f. Sp. Tritici) , Red mold (Gibberella zeae), red rust (Puccinia recondita), brown snow rot (Pythium iwayamai), red snow rot (Monographella nivalis), eye spot disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), dry blight (Leptosphaeria nodorum), snowy rot micronucleus nuclear disease (Typhula incarnata), snow rot large mycobacterial disease (Myriosclerotinia borealis), blight (Gaeumanomyces graminis); (Pyrenophora graminea), cloud disease (Rhynchosporium secalis), naked scab (Ustilago tritici, U.nuda); rice blast (Pyricularia oryzae), blight (Rhizoctonia solani), idiotic seedling (Gibberella fujikuroi) , Sesame leaf blight (Cochliobolus niyabeanus); “Tobacco” sclerotia (Sclerotinia sclerotiorum), powdery mildew (Erysiphe cichoracearum); “Tulip” gray mold (Botrytis cinerea); Nuclear disease (Sclerotinia borealis); “Orchardgrass” powdery mildew (Erysiphe graminis); “Soybean” purpura (Cercospora kikuchii); “Potato tomato” plague (Ph ytophthora infestans); “cucumber” downy mildew (Pseudoperonospora cubensis); “grape” downy mildew (Plasmopara viticola), etc. to control various diseases that occur in the cultivation of agro-horticultural crops including flowers, turf and grass Can be used for

In addition, the bactericidal agent of the present invention has an excellent bactericidal effect against bacteria that have become resistant to conventional bactericides such as benzimidazole bactericides and dicarboximide fungicides. As such resistant bacteria, gray mold fungus (Botrytis cinerea), sugar beet brown fungus (Cercospora beticola), apple black rot fungus (Venturia inaequalis), pear black star that show resistance to benzimidazole fungicides such as thiophanate methyl, benomyl, and carbendazim Examples include Venturia nashicola; gray mold fungus (Botrytis cinerea) that is resistant to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione).

Favorable diseases to which the fungicide of the present invention is applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple black spot, cucumber gray mold, peanut brown spot and the like. The fungicide of the present invention is a highly safe drug with little phytotoxicity, low toxicity to fish and warm-blooded animals.

The fungicide of the present invention is used in a form that can be taken by general agricultural chemicals, that is, in the form of agrochemical preparations such as wettable powders, granules, powders, emulsions, aqueous solvents, suspensions, and wettable granules. May be.

Additives and carriers used for solid preparations include vegetable powders such as soybean flour and wheat flour, mineral fine powders such as diatomaceous earth, apatite, gypsum, talc, bentonite, pyrophyllite and clay, benzoic acid Organic and inorganic compounds such as soda, urea and mirabilite can be mentioned.

Solvents used for liquid formulations include kerosene, xylene and petroleum aromatic hydrocarbons, cyclohexane, cyclohexanone, dimethylformamide, dimethyl sulfoxide, alcohol, acetone, trichloroethylene, methyl isobutyl ketone, mineral oil, vegetable oil, Water etc. are mentioned.

In these preparations, a surfactant can be added as necessary in order to take a uniform and stable form.
The surfactant that can be added is not particularly limited. For example, alkylphenyl ether added with polyoxyethylene, alkyl ether added with polyoxyethylene, higher fatty acid ester added with polyoxyethylene, polyoxyethylene Sorbitan higher fatty acid ester added with polyoxyethylene, nonionic surfactant such as tristyryl phenyl ether added with polyoxyethylene, sulfate ester salt of alkylphenyl ether added with polyoxyethylene, alkylbenzene sulfonate, sulfuric acid of higher alcohol Examples include ester salts, alkyl naphthalene sulfonates, polycarboxylates, lignin sulfonates, formaldehyde condensates of alkyl naphthalene sulfonates, and isobutylene-maleic anhydride copolymers.

The wettable powder, emulsion, flowable powder, aqueous solvent and granular wettable powder thus obtained are diluted with water to a predetermined concentration and sprayed on plants in the form of a solution, suspension or emulsion. Used in the way. Powders and granules are used as they are sprayed on plants.

The amount of the active ingredient in the fungicide of the present invention is usually preferably 0.01 to 90% by weight, more preferably 0.05 to 85% by weight, based on the whole preparation.

The application amount of the fungicide of the present invention varies depending on weather conditions, formulation form, application magnetism, application method, application place, disease to be controlled, target crop, etc., but usually 1 to 1,000 g of active ingredient compound per hectare, 10 to 100 g is preferred.

When a wettable powder, emulsion, suspension, aqueous solvent, granular wettable powder or the like is diluted with water and applied, the applied concentration is 1 to 1000 ppm, preferably 10 to 250 ppm.

In addition to the compounds of the present invention, other fungicides, insecticides / acaricides, synergists and the like can also be mixed with the fungicides of the present invention.

Typical examples of other fungicides, insecticides, acaricides, and plant growth regulators that can be used in combination are shown below.

Fungicide:
Captan, phorpet, thiuram, ziram, dineb, manneb, mancozeb, propineb, polycarbamate, chlorothalonil, quintosen, captaphor, iprodione, prosaimidin, vinclozolin, fluoroimide, thymoxanyl, mepronil, flutolanil, pencyclon, oxycarboxyl, fosetyl aluminum, Propamocurve, triadimephone, triadimenol, propiconazole, diclobutrazole, viteltanol, hexaconazole, microbutanyl, flusilazole, metconazole, etaconazole, fluotrimazole, cyproconazole, epoxyconazole, flutriaphene, beconazole , Diniconazole, cyproconazole, phenalimol, triflumizole, prochlor , Imazalyl, pefrazoate, tridemorph, fenpropimorph, triphorin, butiobate, pyrifenox, anilazine, polyoxin, metalaxyl, oxadixyl, furalaxyl, isoprothiolane, probenazole, pyrrolnitrin, blasticidin S, kasugamycin, validamycin, dihydrostreptomycin sulfate , Benomyl, carbendazim, thiophanate methyl, hymexazole, basic copper chloride, basic copper sulfate, fentin acetate, triphenyltin hydroxide, dietofencarb, metasulfocarb, quinomethionate, binapacryl, lecithin, baking soda, dithianon, dinocup, phenaminosulfur, Dichromemedin, guazatine, dodin, IBP, edifenphos, mepanipyrim, fermzone, Rikuramido, methasulfocarb, fluazinam, Etokinorakku, dimethomorph, pyroquilon, tecloftalam, fthalide, phenazine oxide, thiabendazole, tricyclazole, vinclozolin, cymoxanil, cyclobutanyl, guazatine, propamocarb hydrochloride, oxolinic acid, hydroxy isoxazole, etc. iminoctadine acetate.

Insecticides and acaricides:
Organophosphorus and carbamate insecticides:
Fenthion, Fenitrothion, Diazinon, Chlorpyrifos, ESP, Bamidthione, Fentoate, Dimethoate, Formothion, Marathon, Trichlorfone, Thiomethone, Phosmet, Dichlorvos, Acephate, EPBP, Methyl parathion, Oxydimethone methyl, Ethion, Salicione, Cyanophos, Fenthion, Salon Methidathione, Sulprophos, Chlorfenvinphos, Tetrachlorbinphos, Dimethylvinphos, Propafos, Isophenphos, Ethylthiomethone, Profenofos, Piracrofos, Monocrotophos, Adinfosmethyl, Aldicarb, Mesomil, Thiodicarb, Carbofuran, Carbosulfan, Benhracarb, Furatiocarb Propoxyl, BPMC, MTMC, MIPC, Kalbarri Le, Pirimi curve, Ethiophene carb, Phenoxy carb, EDDP.

Pyrethroid insecticides:
Permethrin, cypermethrin, deltamethrin, fenvalerate, fenpropatoline, pyrethrin, allethrin, tetramethrin, resmethrin, dimethrin, propraslin, phenothrin, protorin, fulvalinate, cyfluthrin, cyhalothrin, flucitrinate, etofenprox, cycloprotorin, thoramethrin , Silafluophene, brofenprox, aclinasrin, etc.

Benzoylurea and other insecticides:
Diflubenzuron, chlorfluazuron, hexaflumuron, triflumuron, tetrabenzuron, flufenoxuron, flucycloxuron, buprofezin, pyriproxyfen, metoprene, benzoepin, diafenthiuron, acetamiprid, imidacloprid, nitenpyram, fipronil, cartap , Thiocyclam, bensultap, nicotine sulfate, rotenone, metaldehyde, machine oil, microbial pesticides such as BT and entomopathogenic viruses.

Nematicides:
Phenamifos, phostiazates, etc.

Acaricide:
Chlorbenzilate, phenisobromolate, dicophore, amitraz, BPPS, benzomate, hexithazox, fenbutazin oxide, polynactin, quinomethionate, CPCBS, tetradiphone, avermectin, milbemectin, clofentedin, cihexatin, pyridaben, fenpyroximate, tebufenpyrad, thiomidibene Dienochlor etc.

Plant growth regulator:
Gibberellins (eg, gibberellin A3, gibberellin A4, gibberellin A7), IAA, NAA and the like.

Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples.

The compound of the present invention was produced according to the method described in Patent Document 3. Some of the produced compounds of the present invention are shown in Tables (4) to (6) together with physical property values. The NMR data is shown in Table (7).

Next, formulation examples of the fungicide of the present invention are shown below, but the additives and addition ratios are not limited to these formulation examples, and can be varied in a wide range. Moreover, the part in a formulation Example shows a weight part.

Formulation Example 1 Wetting agent Oxime ether derivative compound of the present invention 40 parts Clay 48 parts Dioctyl sulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts or more uniformly mixed and finely pulverized, active ingredient 40% Get a wettable powder.

Formulation Example 2 Emulsion Oxime ether derivative compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts Mixing and dissolving the above, an emulsion containing 10% active ingredient obtain.

Formulation Example 3 Powder A oxime ether derivative compound of the present invention 10 parts Clay 90 parts The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granule Oxime ether derivative compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctyl sulfosuccinate sodium salt 1 part Potassium phosphate 1 part After the above is well ground and mixed, water is added and kneaded well Granulation and drying to obtain granules with 5% active ingredient.

Formulation Example 5 Suspension agent Oxime ether derivative compound of the present invention 10 parts Polyoxyethylene alkylallyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts Is pulverized wet until it becomes 3 microns or less to obtain a suspension with 10% active ingredient.

Formulation Example 6 Granule wettable powder Oxime ether derivative compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Lignin sulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts or more After mixing the mixture uniformly and finely pulverizing, add an appropriate amount of water and knead to make a clay. The clay-like product is granulated and then dried to obtain a wettable powder containing 40% of the active ingredient.

A test for confirming the activity of the fungicide of the present invention was performed as follows.
The control effect was calculated as a control value from the following Abbot formula.
Control value (%) = (1−α / β) × 100
α corresponds to the amount of fungal infection in the treated plant,
β corresponds to the amount of fungal infection in untreated (control) plants.
A control value of 0% means that the level of infection of the treated plants is consistent with that of the untreated control plants, and an effect of 100% means that the treated plants were not infected at all.

(Test Example 1) Apple scab control test The emulsion produced according to the formulation of Formulation Example 2 was diluted with water to adjust the active ingredient concentration to 100 ppm. The diluent was sprayed on apple seedlings grown in an unglazed pot (variety “Kokumi”, 3-4 leaf stage). Next, it was naturally dried at room temperature. Conidia spores of Venturia inaequalis were inoculated and kept in a room at 20 ° C. and high humidity for 2 weeks, repeating light and dark every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was examined.
The apple scab control test was conducted using compound numbers 1, 2, 3, 4, 5, 6, 7, 9, 10, 11, 12, 13, 14, 15, 16, 17, in Tables (4) to (6). The oxime ether derivative compounds of 18, 19, 20, 21, 22, 23, 24, 25, 26, and 27 were used. As a result, all the compounds showed an excellent control value of 75% or more.

(Test Example 2) Wheat powdery mildew control test A wettable powder prepared according to the formulation of Formulation Example 1 was diluted with water to adjust the active ingredient concentration to 100 ppm. The diluent was sprayed on wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) grown in an unglazed pot. The leaves were then air dried. The conidia of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were shaken off and inoculated in a greenhouse at 22-25 ° C. for 7 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was examined.
The wheat powdery mildew prevention test was conducted using compound numbers 1, 3, 4, 5, 7, 11, 12, 13, 16, 17, 18, 19, 20, 21, 22, 23, Tables (4) to (6). 24, 25, 26, and 27 oxime ether derivative compounds were carried out. As a result, all the compounds showed an excellent control value of 75% or more.

(Test Example 3) Wheat red rust control test A wettable powder produced according to the formulation of Preparation Example 1 was diluted with water to adjust the active ingredient concentration to 100 ppm. The diluent was sprayed on wheat seedlings grown in an unglazed pot (variety “Noribayashi No. 61”, 1.0-1.2 leaf stage). The leaves were then air dried. The wheat spores (Puccinia recondita) summer spores were shaken and inoculated, and kept in a greenhouse at 22-25 ° C. for 10 days. The lesion appearance state on the leaf was compared with no treatment, and the control effect was examined.
Wheat red rust control test was conducted using compound numbers 1, 3, 4, 5, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 in Tables (4) to (6). , 20, 21, 22, 23, 24, 25, 26, and 27 oxime ether derivative compounds. As a result, all the compounds showed an excellent control value of 75% or more.

The compound of the present invention can be easily produced industrially, has a large control effect at a small application rate for many agricultural and horticultural crops, and has an excellent osmotic migration and residual effect, and therefore has a control effect against diseases. It is a novel compound useful as an active ingredient of an agricultural and horticultural fungicide that is reliable and can be used safely.

In addition, the fungicide of the present invention has an excellent control effect even when the concentration of the compound of the present invention is low and the application amount is small, and does not cause phytotoxicity or pollution to the plant body. It is a drug with excellent safety and less influence.

Claims (3)

1. An oxime ether derivative represented by the formula (I) or a salt thereof.
   

   

   [In the formula (I), X represents a halogen atom, a C1-8 alkyl group, a C1-8 alkoxy group, a C1-8 haloalkyl group, or a C1-8 haloalkoxy group. n represents the number of substitutions of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different.
   R ¹ and R ² each independently represents a hydrogen atom, a halogen atom, a C1-8 alkyl group, a C1-8 haloalkyl group, or an unsubstituted or substituted C3-8 cycloalkyl group. R ¹ and R ² may be bonded together to form a ring. m represents the number of repeating units in parentheses and is an integer from 0 to 8. When m is 2 or more, R ¹ and R ² may be the same or different.
   R ³ is a hydrogen atom, a C1-8 alkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 haloalkenyl group, a C2-8 haloalkynyl group, or an unsubstituted or Represents a C3-8 cycloalkyl group having a substituent.
   R ⁴ represents a hydrogen atom, a C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, a C2-8 alkenyl group, a C2-8 alkynyl group, a C1-8 haloalkyl group, a C2-8 halo. It represents an alkenyl group or a C2-8 haloalkynyl group.
   R ⁵ is a hydrogen atom, C1-8 alkyl group, acyl group, formyl group, C1-8 alkoxy C1-8 alkyl group, C2-8 acyloxy C1-8 alkyl group, C1-8 alkoxycarbonyl group, C1-8 alkyl A sulfonyl group or an unsubstituted or substituted phenylsulfonyl group is represented.
   Y represents an oxygen atom or a sulfur atom.
   Z represents a single bond, an oxygen atom, a sulfur atom, or a group represented by NR ⁶ . R ⁶ represents a hydrogen atom or a C1-8 alkyl group.
   Q represents an unsubstituted or substituted pyrazole ring group. ]
2. X is a C1-8 alkyl group, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a hydrogen atom or a C1-8 alkyl group, Y and Z are oxygen atoms, and Q is An unsubstituted or substituted 1H-pyrazol-3-yl group, an unsubstituted or substituted 2H-pyrazol-3-yl group, or an unsubstituted or substituted 1H-pyrazol-4- The oxime ether derivative or a salt thereof according to claim 1, which is an yl group, m is 1, and n is 0 to 1.
3. An agricultural and horticultural fungicide containing as an active ingredient at least one selected from the oxime ether derivatives or salts thereof according to claim 1 or 2.