WO2011046082A1 - Oxime ether derivative or salt thereof, and agricultural/horticultural germicide - Google Patents

Abstract

Provided is an oxime ether derivative represented by formula (I), or a salt thereof. (1) (In the formula, X represents a halogen atom, an alkyl group, or the like; Y represents an oxygen atom or the like; Z represents an oxygen atom or the like; R¹ represents an alkyl group or the like; R² represents a hydrogen atom or the like; R³ represents an alkyl group or the like; R⁴ or R⁵ represents a hydrogen atom or the like; m represents an integer between 0 and 2, inclusive; A or B represents an oxygen atom, CH₂, or the like; and Q represents an arylene group or a heteroarylene 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.
The present application claims priority based on Japanese Patent Application No. 2009-236427 filed in Japan on October 13, 2009, the contents of which are incorporated herein by reference.

In the cultivation of agricultural and horticultural crops, many control agents are used against crop diseases. However, its control efficacy is insufficient, its use is restricted due to the emergence of drug-resistant pathogens, phytotoxicity and contamination of plants, or the effects on human fish and the environment are large. In many cases, it is not always easy to say that they are satisfactory control agents. Therefore, there is a strong demand for the emergence of a control agent that can be safely used with few such drawbacks.

In relation to the present invention, Patent Document 1 discloses an oxyamine derivative represented by the formula (III) having a chemical structure similar to that of the compound of the present invention, and an agricultural and horticultural fungicide containing it as an active ingredient. ing.

Formula (III)

In formula (III), R ^1a represents a hydrogen atom, a C1-6 alkyl group, a C1-6 alkylcarbonyl group, or a C1-6 alkylsulfonyl group. R ^2a represents a C1-6 alkyl group or a C1-6 alkoxy group. R ^3a represents a halogen atom, a C1-6 alkyl group, or a C1-6 alkoxy group. A ^a represents a C1-6 alkylene group which may be branched or a bond. Q ^a represents a phenyl group which may be substituted with G, a group represented by the formula (IV), or a group represented by the formula (V). m ′ represents 0 or an integer of 1 to 4.

Formula (IV)

Formula (V)

In the formula (IV), R ^4a represents a hydrogen atom, a C1-6 alkyl group, a C2-6 alkenyl group, or SiR ^5a R ^6a R ^7a . R ^5a , R ^6a and R ^7a each independently represents a C1-6 alkyl group. R ^8a represents a hydrogen atom, a C1-6 alkyl group, a C1-6 haloalkyl group, or a phenyl group which may be substituted with G. Y ^a is substituted with ^a hydrogen atom, ^a C1-6 alkyl group, a C3-6 cycloalkyl group, a C3-6 cycloalkyl-C1-6 alkyl group, a C2-6 alkenyl group, a C2-6 alkynyl group, or G. And may represent a phenyl C1-6 alkyl group.
G represents a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a C1-6 haloalkyl group, or a C1-6 haloalkoxy group, and these G may be the same or different and may be substituted by 2 to 5 .

Patent Document 1 describes embodiments of several tens of compounds among oxyamine derivatives represented by the formula (III). Among them, when Q ^a is the formula (V), in Table 3 of Patent Document 1, Y ^a is a methyl group, an isopropyl group, a 2-chloro-benzyl group, a 3-chlorobenzyl group, a 4-chlorobenzyl group, Or compounds that are benzyl groups are specifically described.

Japanese Patent Laid-Open No. 2004-166863

The oxyamine derivative described in Patent Document 1 can be advantageously synthesized industrially, has a certain effect, and can be safely used as an agricultural and horticultural fungicide. However, the demand level for safety such as reduction of phytotoxicity to plants and reduction or detoxification of human and livestock fish is increasing year by year, and the emergence of new resistant bacteria, the oxyamine derivatives described in Patent Document 1 Cannot fully meet the demand for agricultural and horticultural fungicides.
In view of such a situation, the present invention is a novel oxime ether derivative and a salt thereof, and at least selected from the oxime ether derivative and a salt thereof, which can be an active ingredient of an agricultural and horticultural fungicide that is reliable and can be used safely. An object of the present invention is to provide an agricultural and horticultural fungicide containing one kind as an active ingredient.

The present inventors diligently studied to solve the above problems. As a result, an oxime ether derivative or a salt thereof, in which Q ^a in formula (III) is ^a group containing a condensed structure of an alicyclic or heteroalicyclic ring and an aromatic ring, has been obtained. And it discovered that this oxime ether derivative or its salt was useful as an active ingredient of the agricultural and horticultural fungicide which had an effect and can be used safely. The present invention has been further studied and completed based on these findings.

That is, the present invention includes the following aspects.
<1> An oxime ether derivative represented by the formula (I) or the formula (II) or a salt thereof.

Formula (I)

Formula (II)

In formula (I) and formula (II),
R ¹ is a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
R ² represents a hydrogen 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, It represents a substituted or substituted C1-8 acyl group, an unsubstituted or substituted C1-8 alkylsulfonyl group, or an unsubstituted or substituted C6-10 arylsulfonyl group.
X represents a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. n represents the number of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different. When n is 2 or more, Xs may be combined to form a ring.
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 ⁷ . R ⁷ represents a hydrogen atom or an unsubstituted or substituted C1-8 alkyl group.
In formula (I),
R ³ represents a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or an unsubstituted group. Alternatively, it represents a C1-8 alkoxy group having a substituent. R ⁴ and R ⁵ may be combined to form a ring. m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R ⁴ and / or R ⁵ may be the same or different from each other.
R ⁶ represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
A represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ R ⁹ . R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p represents the number of repetitions of A and is an integer of 1 to 3. When p is 2 or more, A's may be the same or different.
B represents an oxygen atom, a sulfur atom, or a group represented by CR ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p and q is 2 or 3.
Q represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.
In formula (II),
R ⁴ ′ and R ⁵ ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or A substituted or substituted C1-8 alkoxy group is represented. R ⁴ ′ and R ⁵ ′ may be combined to form a ring. m ′ represents the number of repeating units in parentheses, and is an integer of 0 to 2. When m ′ is 2, R ⁴ ′ and / or R ⁵ ′ may be the same or different from each other.
A ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ 'R ⁹ '. R ⁸ ′ and R ⁹ ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p ′ represents the number of repetitions of A ′ and is an integer of 1 to 3. When p ′ is 2 or more, A ′ may be the same as or different from each other.
B ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ¹⁰ 'R ¹¹ '. R ¹⁰ ′ and R ¹¹ ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q ′ represents the number of repetitions of B ′ and is an integer from 0 to 1. However, the sum of p ′ and q ′ is 2 or 3.
Q ′ represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.

<2> Q in formula (I) and Q ′ in formula (II) are each independently an unsubstituted or substituted phenylene group, an unsubstituted or substituted pyridinylene group, an unsubstituted Alternatively, a substituted pyrazinylene group, an unsubstituted or substituted pyrimidinylene group, an unsubstituted or substituted pyridazinylene group, an unsubstituted or substituted pyrrolinylene group, an unsubstituted or substituted imidazolinylene The oxime ether derivative or the salt thereof according to <1>, wherein any group selected from a group and an unsubstituted or substituted pyrazolinylene group is represented.
<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>.

The oxime ether derivatives and salts thereof of the present invention are novel compounds useful as active ingredients of agricultural and horticultural fungicides that can be advantageously produced industrially, have a certain effect, and can be used safely.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

Hereinafter, the present invention will be described in detail.
1) Oxime ether derivative The oxime ether derivative according to the present invention is a compound represented by formula (I) or formula (II).

In formula (I) and formula (II), R ¹ , R ² , R ⁷ , X, Y, and Z, and m and n are as follows.
In the formula (I), R ³ to R ⁶ , R ⁸ to R ¹¹ , Q, A and B, and p and q are as follows.
In the formula (II), R ⁴ ′ to R ⁵ ′, R ⁸ ′ to R ¹¹ ′, Q ′, A ′ and B ′, and p ′ and q ′ are as follows.

“Substituent” is a group having a structure different from that of a mother nucleus substituted with a group serving as a mother nucleus. The number of substituents may be one, or two or more. Two or more substituents may be the same or different. For example, a C1-6 alkyl group having a substituent is a group in which the parent nucleus is a C1-6 alkyl group, and any one of these hydrogen atoms is replaced with a group having a different structure ("substituent"). is there. The term “C1-6” indicates that the group serving as the mother nucleus has 1 to 6 carbon atoms. This number of carbons does not include the number of carbons present in the substituent. For example, a butyl group having an ethoxy group as a substituent is classified as a C4 alkyl group.

The “substituent” is not particularly limited as long as it is chemically acceptable and has the effects of the present invention.
As a group that can be a “substituent”,
Halogeno groups such as fluorine, chlorine, bromine and iodine;
C1-6 such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. An alkyl group;
A C3-8 cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group;
Vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-methyl-2-propenyl group, 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, 3-hexenyl group, 4 A C2-6 alkenyl group such as a hexenyl group, a 5-hexenyl group, a cinnamyl group;
A cycloalkenyl group such as a 2-cyclopropenyl group, 2-cyclopentenyl group, 3-cyclohexenyl group, 4-cyclooctenyl group, preferably a C3-8 cycloalkenyl group;
Ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-3-butynyl, 1-pentynyl 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-2-butynyl group, A C2-6 alkynyl group such as a cyclopropylethynyl group or a cyclobutylethynyl group;
C1-6 alkoxy groups such as methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, s-butoxy group, i-butoxy group, t-butoxy group;
C2-6 alkenyloxy groups such as vinyloxy group, allyloxy group, propenyloxy group, butenyloxy group;
C2-6 alkynyloxy groups such as ethynyloxy group and propargyloxy group;
C6-10 aryl groups such as phenyl group, 1-naphthyl group, 2-naphthyl group;
C6-10 aryloxy groups such as phenoxy group and 1-naphthoxy group;
A C7-11 aralkyl group such as a benzyl group or a phenethyl group;
A C7-12 aralkyloxy group such as a benzyloxy group or a phenethyloxy group;
C1-7 acyl groups such as formyl group, acetyl group, propionyl group, benzoyl group, cyclohexylcarbonyl;
C1-7 acyloxy groups such as formyloxy group, acetyloxy group, propionyloxy group, benzoyloxy group, cyclohexylcarbonyloxy group;
A C1-6 alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an i-propoxycarbonyl group, an n-butoxycarbonyl group, a t-butoxycarbonyl group;
Carboxyl group;
Hydroxyl group;

C1-6 haloalkyl groups such as chloromethyl group, chloroethyl group, 1,2-dichloro-n-propyl group, 1-fluoro-n-butyl group, perfluoro-n-pentyl group;
A C2-6 haloalkenyl group such as a 2-chloro-1-propenyl group and a 2-fluoro-1-butenyl group;
A C2-6 haloalkynyl group such as 4,4-dichloro-1-butynyl group, 4-fluoro-1-pentynyl group, 5-bromo-2-pentynyl group;
C1-6 haloalkoxy groups such as 2-chloro-n-propoxy group, 2,3-dichlorobutoxy group;
A C2-6 haloalkenyloxy group such as a 2-chloropropenyloxy group and a 3-bromobutenyloxy group;
C6-10 haloaryl group such as 4-chlorophenyl group, 4-fluorophenyl group, 2,4-dichlorophenyl group;
C6-10 haloaryloxy groups such as 4-fluorophenyloxy group, 4-chloro-1-naphthoxy group;
Halogen-substituted C1-7 acyl groups such as chloroacetyl group, trifluoroacetyl group, trichloroacetyl group, 4-chlorobenzoyl group;

Cyano group; nitro group; amino group;
A C1-6 alkylamino group such as a methylamino group, a dimethylamino group, a diethylamino group;
C6-10 arylamino groups such as anilino group, naphthylamino group, anthracenylamino group;
A C7-11 aralkylamino group such as a benzylamino group or a phenylethylamino group;
C1-6 alkylsulfonylamino groups such as methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, i-propylsulfonylamino group, n-butylsulfonylamino group, t-butylsulfonylamino group;
C1-7 acylamino groups such as formylamino group, acetylamino group, propanoylamino group, butyrylamino group, i-propylcarbonylamino group, benzoylamino group;
A C1-6 alkoxycarbonylamino group such as a methoxycarbonylamino group, ethoxycarbonylamino group, n-propoxycarbonylamino group, i-propoxycarbonylamino group;
An aminocarbonyl group having no substituent or a substituent such as an aminocarbonyl group, a dimethylaminocarbonyl group, a phenylaminocarbonyl group, an N-phenyl-N-methylaminocarbonyl group;
N unsubstituted or N substituted iminoalkyl groups such as N-methyliminomethyl group, 1-N-phenyliminoethyl group, N-hydroxyiminomethyl group, N-methoxyiminomethyl group;

A mercapto group;
C1-6 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, i-butylthio group, s-butylthio group, t-butylthio group;
C2-6 alkenylthio groups such as vinylthio group and allylthio group;
A C2-6 alkynylthio group such as an ethynylthio group or a propargylthio group;
A C6-10 arylthio group such as a phenylthio group or a naphthylthio group;
A C1-6 alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a t-butylsulfonyl group;
A C2-6 alkenylsulfonyl group such as an allylsulfonyl group;
A C2-6 alkynylsulfonyl group such as a propargylsulfonyl group;
A C6-10 arylsulfonyl group such as a phenylsulfonyl group;

Furan-2-yl group, furan-3-yl group, thiophen-2-yl group, thiophen-3-yl group, pyrrol-1-yl group, pyrrol-2-yl group, pyrrol-3-yl group, oxazole -2-yl group, oxazol-4-yl group, oxazol-5-yl group, thiazol-2-yl group, thiazol-4-yl group, thiazol-5-yl group, isoxazol-3-yl group, iso Oxazol-4-yl group, isoxazol-5-yl group, isothiazol-3-yl group, isothiazol-4-yl group, isothiazol-5-yl group, imidazol-1-yl group, imidazole-2- Yl group, imidazol-4-yl group, imidazol-5-yl group, pyrazol-1-yl group, pyrazol-3-yl group, pyrazol-4-yl group, pyrazole- -Yl group, 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 1,2,3-triazol-4-yl group, 1,2,4 -Unsaturated heterocyclic 5-membered ring groups such as triazol-3-yl group and 1,2,4-triazol-5-yl group;
Pyridin-2-yl group, Pyridin-3-yl group, Pyridin-4-yl group, Pyridazin-3-yl group, Pyridazin-4-yl group, Pyrazin-2-yl group, Pyrimidin-2-yl group, Pyrimidine Unsaturated 4-membered heterocyclic groups such as -4-yl, pyrimidin-5-yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl;
Saturated heterocyclic groups such as tetrahydrofuran-2-yl group, tetrahydrapyran-4-yl group, piperidin-3-yl group, pyrrolidin-2-yl group, morpholino group, piperidino group, N-methylpiperazinyl group;
Heterocyclic oxy groups such as 2-pyridyloxy and 3-oxazolyloxy;
A tri-C1-6 alkyl-substituted silyl group such as a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group;
A triphenylsilyl group;
Further, these “substituents” may have another “substituent” therein.

[X]
X represents a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. n represents the number of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different. When n is 2 or more, Xs may be combined to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
Examples of the C1-8 alkyl group include 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-heptyl group, n-octyl group and the like. Of these, C1-6 alkyl groups are preferred.
C1-8 alkoxy groups include 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, n-heptyloxy group, i-heptyloxy group, t-heptyloxy group, n-octyloxy group, i-octyloxy group, t-octyloxy group, 2-ethylhexyloxy group, etc. It is done. Of these, C1-6 alkoxy groups are preferred.

The C1-8 alkyl group and / or the C1-8 alkoxy group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with a C1-8 alkyl group and / or a C1-8 alkoxy group in X is a halogen atom. That is, a C1-8 haloalkyl group and / or a C1-8 haloalkoxy group.

C1-8 haloalkyl groups include fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, tribromomethyl, 2,2,2 -A trifluoroethyl group, a 2,2,2-trichloroethyl group, a pentafluoroethyl group and the like can be mentioned.

C1-8 haloalkoxy groups include chloromethoxy group, dichloromethoxy group, trichloromethoxy group, trifluoromethoxy group, 1-fluoroethoxy group, 1,1-difluoroethoxy group, 2,2,2-trifluoroethoxy group And pentafluoroethoxy group.

[Y, Z, R ^7]
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 ⁷ . R ⁷ represents a hydrogen atom or an unsubstituted or substituted C1-8 alkyl group.

Examples of the C1-8 alkyl group for R ⁷ are the same as those listed above.
The C1-8 alkyl group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with the C1-8 alkyl group in R ⁷ is a halogen atom. That is, a C1-8 haloalkyl group.

[R ^1]
R ¹ is a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
Examples of the C1-8 alkyl group for R ¹ are the same as those listed above.

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, heptenyl group, octenyl group and the like. Of these, C2-6 alkenyl groups are preferred.

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 -2-butynyl group, heptynyl group, octynyl group and the like. Of these, C2-6 alkynyl groups are preferred.

The C3-8 cycloalkyl group is a monocyclic or polycyclic alkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo [3.2.1] octyl group. Groups and the like.

The C1-8 alkyl group, C2-8 alkenyl group, C2-8 alkynyl group, and / or C3-8 cycloalkyl group in R ¹ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with a C1-8 alkyl group, a C2-8 alkenyl group, or a C2-8 alkynyl group in R ¹ is a halogen atom. That is, a C1-8 haloalkyl group, a C1-8 haloalkenyl group, or a C2-8 haloalkynyl group.
A preferred group which can be substituted with a C3-8 cycloalkyl group in R ¹ is a halogen atom or a C1-6 alkyl group.

Examples of the C1-8 haloalkyl group for R ¹ include the same as those listed above.
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, And 3-dichloro-2-propenyl group.

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 ^2]
R ² represents a hydrogen 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, It represents a substituted or substituted C1-8 acyl group, an unsubstituted or substituted C1-8 alkylsulfonyl group, or an unsubstituted or substituted C6-10 arylsulfonyl group.
Examples of the C1-8 alkyl group, C2-8 alkenyl group, and C2-8 alkynyl group in R ² are the same as those listed above.

An acyl group means a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or the like is bonded to a carbonyl group.
Examples of the C1-8 acyl group include formyl group; acetyl group, propionyl group, butyroyl group, pivaloyl group, pentanoyl group, hexanoyl group, heptanoyl group, octanoyl group and other alkylcarbonyl groups; acryloyl group, methacryloyl group, allyl Examples include alkenylcarbonyl groups such as carbonyl group and cinnamoyl group; ethynylcarbonyl group, propynylcarbonyl group; arylcarbonyl groups such as benzoyl group; heteroarylcarbonyl groups such as 2-pyridylcarbonyl group and thienylcarbonyl group. Of these, C1-7 acyl groups are preferred.

Examples of the C1-8 alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an i-propylsulfonyl group. Of these, C1-6 alkylsulfonyl groups are preferred.
Examples of the C6-10 arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.

The C1-8 alkyl group, C1-8 acyl group, C1-8 alkylsulfonyl group, or C6-10 arylsulfonyl group in R ² may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group which can be substituted with a C1-8 alkyl group in R ² is a C1-6 alkoxy group or a C1-6 acyloxy group. That is, a C1-6 alkoxy C1-8 alkyl group or a C1-6 acyloxy C1-8 alkyl group.

C1-6 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 C1-6 acyl C1-8 alkyl group include an acetyloxymethyl group, a propionyloxymethyl group, and pivaloyloxymethyl.

A preferred group that can be substituted with a C1-8 acyl group, a C1-8 alkylsulfonyl group, or a C6-10 arylsulfonyl group in R ² is a C1-6 alkyl group or a halogen atom.
Examples of the C1-8 acyl group having a substituent include a trifluoroacetyl group, a trichloroacetyl group, a 4-methylbenzoyl group, and a 2-chlorobenzoyl group.
Examples of the C6-10 arylsulfonyl group having a substituent include a 4-methylphenylsulfonyl group, a 2-chlorophenylsulfonyl group, and a 2,4-dimethylphenylsulfonyl group.

[R ^3]
R ³ represents a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
Examples of the C1-8 alkyl group, the C2-8 alkenyl group, the C2-8 alkynyl group, and the C3-8 cycloalkyl group in R ³ are the same as those listed above.
The C1-8 alkyl group, C2-8 alkenyl group, C2-8 alkynyl group, or C3-8 cycloalkyl group in R ³ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with a C1-8 alkyl group, a C2-8 alkenyl group, or a C2-8 alkynyl group in R ³ is a halogen atom. That is, a C1-8 haloalkyl group, a C1-8 haloalkenyl group, or a C2-8 haloalkynyl group.

A preferred substituent which can be substituted with a C3-8 cycloalkyl group in R ³ is a halogen atom or a C1-6 alkyl group.

^{[R 4, R 5, R} 4 ', R 5']
R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or an unsubstituted group. Alternatively, it represents a C1-8 alkoxy group having a substituent. R ⁴ and R ⁵ may be combined to form a ring. m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R ⁴ and / or R ⁵ may be the same as or different from each other.
As the halogen atom, C1-8 alkyl group, C3-8 cycloalkyl group, and C1-8 alkoxy group for R ⁴ or R ⁵ , the same as those listed above can be mentioned.

The C1-8 alkyl group, C1-8 alkoxy group, and / or C3-8 cycloalkyl group in R ⁴ or R ⁵ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ⁴ or R ⁵ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
A preferred group that can be substituted with a C3-8 cycloalkyl group in R ⁴ or R ⁵ is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a nitro group, or a cyano group.

When R ⁴ and R ⁵ are combined to form a ring, examples of the ring include C3-10 cycloalkane rings such as a cyclopropane ring, a cyclopentane ring, and a cyclohexane ring.

R ⁴ ′ and R ⁵ ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or A substituted or substituted C1-8 alkoxy group is represented. R ⁴ ′ and R ⁵ ′ may be combined to form a ring. m ′ represents the number of repeating units in parentheses, and is an integer of 0 to 2. When m ′ is 2, R ⁴ ′ and / or R ⁵ ′ may be the same as or different from each other.
As the halogen atom, C1-8 alkyl group, C3-8 cycloalkyl group, and C1-8 alkoxy group for R ⁴ ′ or R ⁵ ′, the same groups as those listed above can be mentioned.

The C1-8 alkyl group, C1-8 alkoxy group, and / or C3-8 cycloalkyl group in R ⁴ ′ or R ⁵ ′ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ⁴ ′ or R ⁵ ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
A preferred group that can be substituted with a C3-8 cycloalkyl group in R ⁴ ′ or R ⁵ ′ is a halogen atom, a C1-6 alkyl group, a C1-6 alkoxy group, a nitro group, or a cyano group.

When R ⁴ ′ and R ⁵ ′ are combined to form a ring, examples of the ring include C3-10 cycloalkane rings such as cyclopropane ring, cyclopentane ring, and cyclohexane ring.

[R ^6]
R ⁶ represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R ⁶ include the same as those listed above.
The C1-8 alkyl group or C1-8 alkoxy group in R ⁶ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ⁶ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.

^{[A, R 8, R 9} , A ', R 8', R 9 ']
A represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ R ⁹ . R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p represents the number of repetitions of A and is an integer of 1 to 3. When p is 2 or more, A's may be the same or different.
Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R ⁸ and R ⁹ include the same as those listed above.
The C1-8 alkyl group or C1-8 alkoxy group in R ⁸ and R ⁹ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ⁸ and R ⁹ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
A ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ 'R ⁹ '. R ⁸ ′ and R ⁹ ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p ′ represents the number of repetitions of A ′ and is an integer of 1 to 3. When p ′ is 2 or more, A ′ may be the same as or different from each other.
Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R ⁸ ′ and R ⁹ ′ include the same as those listed above.
The C1-8 alkyl group or C1-8 alkoxy group in R ⁸ ′ and R ⁹ ′ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group which can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ⁸ ′ and R ⁹ ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.

^{[B, R 10, R 11} , B ', R 10', R 11 ']
B represents an oxygen atom, a sulfur atom, or a group represented by CR ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p and q is 2 or 3.
Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R ¹⁰ and R ¹¹ include the same as those listed above.
The C1-8 alkyl group or C1-8 alkoxy group in R ¹⁰ and R ¹¹ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
Preferred groups at R ¹⁰ and R ^11, may be replaced by C1 ~ 8 alkyl or C1 ~ 8 alkoxy group, is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.
B ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ^{10 ′} R ^{11 ′} . R ¹⁰ ′ and R ¹¹ ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q ′ represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p ′ and q ′ is 2 or 3.
Examples of the halogen atom, C1-8 alkyl group, and C1-8 alkoxy group in R ^{10 ′} and R ¹¹ ′ include the same ones listed above.
The C1-8 alkyl group or C1-8 alkoxy group in R ¹⁰ ′ and R ¹¹ ′ may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
A preferred group that can be substituted with a C1-8 alkyl group or a C1-8 alkoxy group in R ^{10 ′} and R ¹¹ ′ is a halogen atom. That is, they are a C1-8 haloalkyl group and a C1-8 haloalkoxy group.

[Q, Q ']
Q and Q ′ each represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.
Examples of the C6-10 arylene group include a phenylene group, a biphenylene group, a naphthylene group, and an anthracenylene group.
Examples of the divalent heteroaryl group include pyridinylene group, pyrazinylene group, pyrimidinylene group, pyridazinylene group, pyrrolinylene group, imidazolinylene group, pyrazolinylene group, quinolinylene group, isoquinolinylene group, indolinylene group, isoindolinylene group, 2,2′-bipyridinylene group. And heteroarylene groups such as an oxazolidinylene group, an oxazolinylene group, and an oxazepinylene group.

Formula (VI)

Specific examples of the ring moiety (formula (VI)) formed by B, Q, A and R ⁶ in formula (I) include those represented by formula (VI-1) to formula (VI-27): Groups.

Formula (VII)

Specific examples of the ring moiety (formula (VII)) formed by B ′, Q ′, and A ′ in formula (II) are as shown in formula (VII-1) to formula (VII-20). Group.

The C6-10 arylene group or divalent heteroaryl group may have one or more substituents. When it has two or more substituents, the substituents may be the same as or different from each other.
Preferred groups that can be substituted with a C6-10 arylene group or a divalent heteroaryl group are halogen atoms, C1-6 alkyl groups, C1-6 haloalkyl groups, C1-6 alkoxy groups, C1-6 haloalkoxy groups, C2 A -6 alkynyl group or a cyano group;

2) Manufacturing method The oxime ether derivative represented by the formula (I) according to the present invention includes, for example, an oxyamine compound represented by the formula (3) (hereinafter sometimes referred to as a compound (3)) and a formula. It can be produced by reacting the compound represented by (4) (hereinafter sometimes referred to as compound (4)).

Formula (3)

Formula (4)

The amount of compound (4) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (3).

Although this reaction can be performed in the absence of a catalyst, it is preferably performed in the presence of an acid catalyst or a base catalyst, more preferably in the presence of an acid catalyst.
Examples of the acid catalyst to be used include trifluoroacetic acid, benzenesulfonic acid, p-toluenesulfonic acid, p-toluenesulfonic acid monohydrate, methanesulfonic acid, pyridinium p-toluenesulfonate, hydrochloric acid, sulfuric acid and the like. Examples of the base catalyst include pyridine, triethylamine, potassium hydroxide and the like.
The amount of the catalyst to be used is generally 0.0001-1 mol per 1 mol of compound (3).
In addition, a dehydrating agent such as anhydrous sodium sulfate or molecular sieve may be added to the reaction system.

This reaction can be carried out in a suitable solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; Halogenated hydrocarbon solvent such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane; Amide solvent such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone; Nitrile solvents such as acetonitrile and benzonitrile; alcohol solvents such as methanol, ethanol and n-propanol; and mixed solvents composed of two or more of these solvents.
The amount of the solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (3).

The reaction temperature is a temperature ranging from room temperature to the boiling point of the solvent used. The reaction time is usually several minutes to several tens of hours.

Compound (3) can be produced by a conventionally known method for producing an oxyamine compound. For example, as shown below, the compound represented by the formula (1) is reacted with carbon tetrabromide and triphenylphosphine to obtain the compound represented by the formula (2). In the presence of a base, By reacting Nt-butoxycarbonylhydroxylamine, an oxyamine compound represented by formula (9) (hereinafter sometimes referred to as compound (9)) is obtained, and an acid is allowed to act on this compound. Thus, an oxyamine compound represented by the formula (3) can be obtained.

Formula (1)

Formula (2)

Formula (9)

In the case of reacting the compound (3) and the compound (4), after mixing the compound (4) and the compound (9), an acid such as trifluoroacetic acid is added, and the compound is reacted in the reaction system. The reaction may be carried out by generating (3).

Compound (4) is, for example, a compound represented by formula (6) in the presence of a base in a fluoride compound represented by formula (5) (hereinafter sometimes referred to as compound (5)). Hereinafter, a compound represented by the formula (7) (hereinafter sometimes referred to as the compound (7)) is obtained by reacting with the compound (6). (7) is reacted with an amide compound represented by formula (8) (hereinafter sometimes referred to as compound (8)) in the presence of a base to obtain the desired compound (4). be able to.

Formula (8)

In the reaction for obtaining the compound (7), the amount of the compound (6) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of the compound (5).

Examples of the base used in the reaction for obtaining the compound (7) include metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide; sodium methoxide, sodium ethoxide, potassium methoxide. Metal alkoxides such as potassium ethoxide and potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride and calcium hydride; triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo [5.4.0] And organic bases such as undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
The amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (5).

This reaction can be carried out in a suitable organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide; ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; n-pentane, n- Aliphatic hydrocarbon solvents such as hexane and n-heptane; amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone; nitrile solvents such as acetonitrile and benzonitrile; And a mixed solvent composed of two or more thereof.
The amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (5).
The reaction to obtain compound (7) proceeds smoothly at a temperature ranging from 0 ° C. to the boiling point of the solvent used.

Specific examples of the compound (8) used in the reaction for obtaining the compound (4) include N, N-dimethylacetamide, N, N-dimethylpropionamide and the like.
The amount of compound (8) to be used is generally 0.8 to 5 mol, preferably 1 to 3 mol, per 1 mol of compound (7).

Examples of the base used in the reaction for obtaining the compound (4) include organic lithium compounds such as n-butyllithium, s-butyllithium, t-butyllithium and lithium diisopropylamide; alkali metals such as metallic sodium and metallic potassium; sodium hydride , Metal hydrides such as potassium hydride and calcium hydride;
The amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (7).

This reaction can be carried out in a suitable organic solvent. The solvent to be used is not particularly limited as long as it is inert to the reaction. For example, ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran; aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane and n-heptane Solvent; and the like.
The reaction for obtaining the compound (4) proceeds smoothly at a temperature ranging from −100 ° C. to the boiling point of the solvent used.

Among the compounds (4), the compound (4-a) in which R ¹ is a t-butyl group, R ² is a hydrogen atom and Y and Z are oxygen atoms is a halogenoformate compound (4- Compound (4-b) converted to intermediate compound (4-b) by reacting with d) and then reacted with an acid to convert R ¹ (t-butyl group) to other substituent R ^{1 ′} c) can be obtained.

The base used for the reaction of the compound (4-a) with the halogenoformate compound (4-d) includes metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. Metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, potassium t-butoxide; metal hydrides such as sodium hydride, potassium hydride, calcium hydride; triethylamine, diisopropylethylamine, pyridine, And organic bases such as 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 1,4-diazabicyclo [2.2.2] octane.
The amount of the base to be used is generally 1 to 20 mol per 1 mol of compound (4-a).

The reaction of the compound (4-a) and the halogenoformate compound (4-d) is performed in a suitable organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction. For example, halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride and 1,2-dichloroethane; sulfur-containing solvents such as dimethyl sulfoxide and diethyl sulfoxide; ether solvents such as dioxane, 1,2-dimethoxyethane and tetrahydrofuran Aromatic hydrocarbon solvents such as toluene, benzene and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-heptane; N, N-dimethylformamide, N, N-dimethylacetamide Amide solvents such as N-methylpyrrolidone; nitrile solvents such as acetonitrile and benzonitrile; and mixed solvents composed of two or more of these solvents.
The amount of the organic solvent to be used is not particularly limited, but is usually 1 to 100 ml with respect to 1 g of compound (4-a).

The reaction between the compound (4-a) and the halogenoformate compound (4-d) proceeds smoothly at a temperature ranging from −20 ° C. to the boiling point of the solvent used. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.

Acids used for the reaction for obtaining the compound (4-c) from the intermediate compound (4-b) include inorganic acids such as hydrochloric acid, sulfuric acid and nitric acid; acetic acid, trifluoroacetic acid, methanesulfonic acid, p-toluenesulfonic acid and the like. Can be mentioned.
The amount of the acid to be used is generally 1 to 20 mol per 1 mol of compound (4-b).

The reaction for obtaining the compound (4-c) from the intermediate compound (4-b) is carried out in a suitable organic solvent. The organic solvent to be used is not particularly limited as long as it is inert to the reaction, and examples thereof include those listed as solvents that can be used for the reaction with the halogenoformate compound.

The reaction for obtaining the compound (4-c) from the intermediate compound (4-b) proceeds smoothly at a temperature ranging from −20 ° C. to the boiling point of the solvent used. Although the reaction time depends on the reaction scale, it is usually from several minutes to several tens of hours.

Among the compounds (4), the compound (4-e) in which Y and Z are oxygen atoms is a compound in which the substituent R ¹ is converted to another substituent R ^{1 ″} by a known transesterification method. It can be guided to (4-f).

The oxime ether derivative represented by the formula (I) according to the present invention can also be produced by the method as shown in Example 1. Specifically, N-hydroxyphthalimide or the like is reacted with the compound represented by the formula (1) to obtain an isoindoledione derivative, which is reacted in the presence of methyl hydrazine or the like, and then the reaction product And compound (4) can also be produced.

The oxime ether derivative represented by the formula (II) according to the present invention includes, for example, an oxyamine compound represented by the formula (10) (hereinafter sometimes referred to as the compound (10)) and the formula (11). It can be produced by reacting a compound represented (hereinafter sometimes referred to as compound (11)).

Formula (10)

Formula (11)

The amount of compound (10) to be used is generally 0.5 to 2 mol, preferably 0.7 to 1.5 mol, per 1 mol of compound (11).
This reaction can be performed by the same method as the above-described reaction between the compound (3) and the compound (4).

Compound (11) can be obtained, for example, by subjecting compound (4) to hydride reduction, and obtaining the resulting alcohol compound in the same manner as in the production of compound (3) from compound (1) exemplified above. it can. Sodium borohydride and its analogs can be used for hydride reduction.

In any reaction, after completion of the reaction, the desired product can be isolated by purifying by a conventional post-treatment operation and, if desired, known and conventional purification means such as distillation, recrystallization and column chromatography.
The structure of the target product can be identified and confirmed by known analytical means such as IR spectrum, NMR spectrum, mass spectrum, and elemental analysis.

3) Salt of oxime ether derivative The salt of the oxime ether derivative according to the present invention is a salt of the compound represented by formula (I) or formula (II).
The salt is not particularly limited as long as it is an agro-horticulturally acceptable salt. Examples thereof include salts of inorganic acids such as hydrochloric acid and sulfuric acid; salts of organic acids such as acetic acid and lactic acid. These salts can be produced by a conventionally known method using an acid corresponding to the oxime ether derivative represented by the formula (I) or the formula (II).

The oxime ether derivative or a salt thereof according to the present invention includes each stereoisomer based on a carbon-nitrogen double bond and an asymmetric carbon atom, and a mixture thereof. Moreover, when a solvate and a crystal polymorph exist, they are also included.

4) Agricultural and horticultural fungicide The agricultural and horticultural fungicide of the present invention (hereinafter sometimes referred to as "the present bactericidal agent") is an oxime ether represented by the formula (I) or the formula (II) of the present invention. It contains at least one selected from a derivative or a salt thereof as an active ingredient.

The fungicide of the present invention is excellent against a wide variety of fungi, for example, bacteria belonging to algae (Oomycetes), Ascomycetes, Deuteromycetes, and Basidiomycetes. Has sterilizing power.

The fungicide of the present invention can be used by 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 flowers, turf and grass.

For example,
Sugar beet: brown spot (Cercospora beticola), black root (Aphanomyces cochlloides), root rot (Thanatephorus cucumeris), leaf rot (Thanatephorus cucumeris), etc. Cucumber: powdery mildew (Sphaerotheca fuliginea), downy mildew (Pseudoperonospora cubensis), vine blight (Mycosphaerella melonis), vine split disease (Fusarium oxysporum), mycotic disease (Sclerotinia sclerotiorum), gray mold disease (Botrytiscine , Anthracnose (Colletotrichum orbiculare), black spot (Cladosporium cucumerinum), brown spot (Corynespora cassicola), seedling blight (Pythium debaryanam, Rhizoctonia solani Kuhn), spot bacterial disease (Pseudomonas syringae pv. Lecrymans) Gray mold disease (Botrytis cinerea), leaf mold disease (Cladosporium fulvum), plague (Phytophthora infestans), etc. Eggplant: gray mold disease (Botrytis cinerea), black blight (Co rynespora melongenae), powdery mildew (Erysiphe cichoracearum), subtle mildew (Mycovellosiella nattrassii), etc. Strawberries: gray mold (Botrytis cinerea), powdery mildew (Sohaerotheca humuli), anthracnose (Colletotrichum acutatum, fragletotrichum, epilepsy) (Phytophthora cactorum) Onions: gray rot (Botrytis allii), gray mold (Botrytis cinerea), vitiligo leaf (Botrytis squamosa), downy mildew (Peronospora destructor)
Cabbage: root-knot disease (Plasmodiophora brassicae), soft rot disease (Erwinia carotovora), downy mildew (Peronospora parasitica), etc. Kidney: mycorrhizal disease (Sclerotinia sclerotiorum), gray mold disease (Botrytis cinerea), etc.

Apples: powdery mildew (Podosphaera leucotricha), black spot disease (Venturia inaequalis), monilinia disease (Monilinia mali), black spot disease (Mycosphaerella pomi), rot disease (Valsa mali), spotted leaf disease (Alternaria mali), red star disease (Gymnosporang) yamadae), ring rot (Botryosphaeria berengeriana), anthracnose (Glomerella cingulata, Colletotrichum acutatum), brown spot (Diplocarpon mali), soot spot (Zygophiala jamaicensis), soot spot (Gloeodes pomigena), etc. Peach (Phyllactinia kakicola), anthracnose (Gloeosporium kaki), keratodeciduous leaf disease (Cercospora kaki), etc. Peaches: Monilinia fructicola, black scab (Cladosporium carpophilum), homopsis rot (Phomopsis sp.), Etc. : Asperum disease (Monilinia fructicola) Grapes: Gray mold disease (Botrytis cinerea), powdery mildew (Uncinula necator), late rot (Glomerella cingulata, Colletotrichum acutatum), sticky (Plasmopara viticola), black scab (Elsinoe ampelina), brown spot (Pseudocercospora vitis), black rot (Guignardia bidwellii), etc. Pear: black scab (Venturia nashicola), red scab (Gymnosporangium asiaticum), black spot (Alternaria) kikuchiana), ring rot (Botryosphaeria berengeriana), powdery mildew (Phyllactinia mali), etc. Cha: ring spot disease (Pestalotia theae), anthracnose (Colletotrichum theae-sinensis), etc. Citrus: scab (Elsinoe fawcetti), blue mold Disease (Penicillium italicum), green mold disease (Penicillium digitatum), gray mold disease (Botrytis cinerea), sunspot disease (Diaporthe citri), scab disease (Xanthomonas campestris pv.Citri), etc.

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), eyeprint Disease (Pseudocercosporella herpotrichoides), leaf blight (Septoria tritici), blight (Leptosphaeria nodorum), snow rot microbe nuclei (Typhula incarnata), snow rot large bacilli (Myriosclerotinia borealis), blight (Gaeumanomyces graminis) ) Barley: Pyrenophora graminea, Cloudy disease (Rhynchosporium secalis), Bare smut (Ustilago tritici, U.nuda), etc. Rice: Rice blast (Pyricularia oryzae), blight (Rhizoctonia solani), idiot seedlings Diseases (Gibberella fujikuroi), sesame leaf blight (Cochliobolus niyabeanus), seedling blight (Pythium graminicolum), white leaf blight (Xanthomonas oryzae), seedling blight (Burkholderia plantarii), brown streak (Acidovorax avenae), Bacterial blight disease (B urkholderia glumae)
Tobacco: Sclerotinia sclerotiorum, powdery mildew (Erysiphe cichoracearum), etc. Tulip: Gray mold, Botrytis cinerea, etc. Bentgrass: Snow rot, Scylotinia borealis, Pythium aphanidermatum etc. Orchard Grass: Powdery mildew (Erysiphe graminis), etc. Soybean: Purpura (Cercospora kikuchii), downy mildew (Peronospora Manshurica), stem blight (Phytophthora sojae), etc. Potato: Can be used to control Phytophthora infestans, etc. .

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 fungus (Cercospora beticola), apple black rot (Venturia inaequalis), pear black star Examples include Venturia nashicola; gray mold fungus (Botrytis cinerea) that is resistant to dicarboximide fungicides (for example, vinclozolin, procymidone, iprodione).

The diseases to which the fungicide of the present invention is more preferably applied include sugar beet brown spot, wheat powdery mildew, rice blast, apple scab, cucumber gray mold, peanut brown.

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 Examples include organic and inorganic compounds such as soda, urea, and sodium sulfate.

Solvents used in 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 to plants as a solution, suspension or emulsion. Used in. 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 and the like can be mixed with the fungicides of the present invention.

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

Fungicide:
Benzimidazoles such as benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate methyl;
Dicarboximides such as clozolinate, iprodione, procymidone, vinclozolin;
Imazaril, oxpoconazole, pefazoate, prochloraz, triflumizole, triphorin, pyrifenox, fenarimol, nuarimol, azaconazole, viteltanol, bromconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, full Quinconazole, flusilazole, flutriazole, hexaconazole, imibenconazole, ipconazole, metconazole, microbutanyl, penconazole, propiconazole, prothioconazole, cimeconazole, tebuconazole, tetraconazole, triadimethone, triazimenol, triticonazole, ethaconazole , DMI-bactericides such as Ferconazole cis, ipconazole, imibenconazole;
Phenylamides such as benalaxyl, furaxyl, metalaxyl, metalaxyl-M, oxadixyl, ofulase;
Amines such as aldimorph, dodemorph, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
Phosphorothiolate systems such as EDDP, iprobenphos, pyrazophos;
Dithiolanes such as isoprothiolane;
Carboxamides such as benodanyl, boscalid, carboxin, fenfuran, flutolanil, furametopyr, mepronil, oxycarboxyl, penthiopyrad, tifluzamide;
Hydroxy- (2-amino) pyrimidines such as bupyrimeto, dimethylirimol, ethylimole;

AP fungicides (anilinopyrimidine) such as cyprodinil, mepanipyrim, pyrimethanil;
N-phenyl carbamates such as dietofencarb; azoxystrobin, picoxystrobin, pyraclostrobin, cresoxime-methyl, trifloxystrobin, dimoxystrobin, metminostrobin, orizastrobin, famoxadone, floxastrobin QoI-bactericides (Qo inhibitors) such as phenamidon, metminophen, pyribencarb;
PP fungicides (phenylpyrrole) such as fenpiconyl, fludioxonil;
Quinoline series such as quinoxyphene;
AH fungicides (aromatic hydrocarbons) such as biphenyl, chloroneb, dichlorane, kintozen, technazen, tortofos-methyl;
MBI-R such as fusalide, pyrokilone, tricyclazole;
MBI-D such as carpropamide, diclocimet, phenoxanil;
SBI agents such as fenhexamide, pyributycarb, terbinafine;
Phenylurea such as pencyclon;
QiI-bactericides (Qi inhibitors) such as cyazofamid;
Benzamides such as zoxamide;
Enopyran urones such as blasticidin, mildiomycin;
Hexopyranosyl such as kasugamycin;
Glucopyranosyl such as streptomycin, validamycin;
Cyanoacetamide such as simoxanyl;
Carbamates such as propamocarb, prothiocarb, polycarbamate;
Uncoupling agents such as vinapacryl, zinocup, ferrimzone, fluazinam;
Organotin compounds such as triphenyltin acetate, triphenyltin chloride, triphenyltin hydroxide;

Phosphoric acid esters such as phosphorous acid, tolcrofosmethyl, fosetyl;
Phthalamic acid such as teclophthalam;
Benzotriazines such as triazoxide;
Benzenesulfonamides such as fursulfamide;
Pyridazinones such as dichromedin;
CAA fungicides (carboxylic amides) such as dimethomorph, flumorph, bench avaricarb, iprovaricarb, mandipropamide;
Tetracyclines such as oxytetracycline;
Thiocarbamates such as metasulfocarb;
Etridiazole, polyoxin, oxolinic acid, hydroxyisoxazole, octinoline, sylthiophane, diflumetrim, acibenzoral S methyl, probenazole, thiazinyl, ethaboxam, cyflufenamide, proquinazide, metolaphenone, fluopicolide, cupric hydroxide, organic copper, sulfur, farbum, manzeb , Mannebu, metyram, propineb, thiuram, dineb, ziram, captan, captahol, phorpet, chlorothalonil, dicloflurane, tolylfluanid, dodin, guazatine, iminotadine, anilazine, dithianone, chloropicrin, dazomet, metam sodium salt, Other compounds such as quinomethionate, ciprofuram, silthiofam, Agrobacterium, fluorimide.

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, Tetrachlorvinphos, 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, tralomethrin , Silafluophene, brofenprox, aclinasrin and so on.
Benzoylurea and other insecticides:
Diflubenzuron, Chlorfluazuron, Hexaflumuron, Triflumuron, Tetrabenzuron, Flufenoxuron, Flucycloxuron, Buprofezin, Pyriproxyfen, Metoprene, Benzoepine, 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:
Abscisic acid, indole butyric acid, uniconazole, etiquelozate, etephone, cloxiphonac, chlormecote, chlorella extract, calcium peroxide, cyanamide, dichlorprop, gibberellin, daminozide, decyl alcohol, trinexapac ethyl, mepicoat chloride, pack Lobutrazole, paraffin, wax, piperonyl butoxide, pyraflufenethyl, flurprimidol, prohydrojasmon, prohexadione calcium salt, benzylaminopurine, pendimethalin, forchlorphenuron, potassium hydrazide maleate, 1- Naphtylacetamide, 4-CPA, MCPB, choline, oxyquinoline sulfate, ethiclozate, butorualine, 1-methylcyclopropene, abiglycine hydrochloride.

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples.

Example 1
[Production of 5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-ol]
5-Bromo-1-tetralone (2.00 g) is dissolved in N, N-dimethylformamide (18 ml), then diisopropylamine (15 ml), copper iodide (0.10 g), and dichlorobistriphenylphosphine palladium (0.19 g). And stirred at 80 ° C. for 8 hours under a propyne atmosphere. Ethyl acetate and aqueous ammonium chloride were added thereto, and the mixture was filtered through celite to separate the organic layer. Magnesium sulfate was added to the obtained organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was roughly purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 9: 1). The obtained crude product was dissolved in a mixed solvent of tetrahydrofuran (30 ml) and methanol (5 ml). To this, sodium borohydride (0.17 g) was added and stirred for 3 hours. Thereafter, aqueous ammonium chloride was added thereto, and the mixture was extracted with ethyl acetate. Magnesium sulfate was added to the organic layer, dried and filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 4: 1). The target 5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-ol (1.46 g, yield 88%) was obtained.

¹ H-NMR of the obtained compound was measured. The results are as follows.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.36 (d, 1H), 7.31 (d, 1H), 7.13 (t, 1H), 4.75 (bs, 1H), 2.99-2.90 (m, 1H ), 2.80-2.69 (m, 1H), 2.09 (s, 3H), 2.07-1.75 (m, 4H), 1.70 (d, 1H)

[Production of 2- [5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-yloxy] isoindole-1,3-dione]
5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-ol (1.46 g), N-hydroxyphthalimide (1.53 g), and triphenylphosphine (2.47 g) in tetrahydrofuran (40 ml) Dissolved. To this, diisopropyl azodicarboxylate (1.90 g) was added dropwise under ice cooling. Then, it stirred at room temperature for 3 hours. Ethyl acetate was added thereto, washed with an aqueous ammonium chloride solution, the organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; hexane: ethyl acetate = 4: 1 to 3: 1). The desired 2- [5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-yloxy] isoindole-1,3-dione (2.23 g, 86% yield) was obtained. .

¹ H-NMR of the obtained compound was measured. The results are as follows.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.87-7.73 (m, 4H), 7.65 (d, 1H), 7.38 (dd, 1H), 7.16 (t, 1H), 5.28 (t, 1H ), 3.19 to 3.11 (m, 1H), 2.75 to 2.63 (m, 1H), 2.38 to 2.28 (m, 2H), 2.10 (s, 3H), 1.91 to 1.76 (m, 2H)

[Production of methyl N- (2-methyl-5- {1- [5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-yloxyimino] ethyl} phenoxy) carbamate]
2- [5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-yloxy] isoindole-1,3-dione (0.50 g) was dissolved in methylene chloride (8 ml). Methylhydrazine (69 mg) was added thereto, and the mixture was stirred at room temperature for 2 hours. Diethyl ether was added to this and filtered, and then the solvent was distilled off under reduced pressure.
Methanol (15 ml), methyl N- (5-acetyl-2-methylphenoxy) carbamate (0.25 g), sodium acetate (0.25 g), and acetic acid (0.18 g) were added to the resulting residue and refluxed for 6 hours. did. Ethyl acetate was added thereto, washed with an aqueous ammonium chloride solution, the organic layer was dried over magnesium sulfate, filtered, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography (developing solvent; benzene: ethyl acetate = 100: 1 to 50: 1). The desired methyl N- (2-methyl-5- {1- [5- (1-propynyl) -1,2,3,4-tetrahydronaphthalen-1-yloxyimino] ethyl} phenoxy) carbamate (0.39 g, amorphous, yield 85%).

¹ H-NMR of the obtained compound (Compound No. 1-16) was measured. The results are as follows.
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.77 (s, 1H), 7.52 (d, 1H), 7.41 (d, 1H), 7.33 (d, 1H), 7.23 (dd, 1H), 7.13 (t, 2H), 5.29 (t, 1H), 3.83 (s, 3H), 3.05 to 2.97 (m, 1H), 2.79 to 2.69 (m, 1H), 2.27 (s, 3H), 2.23 to 2.21 ( m, 1H), 2.17 (s, 3H), 2.09 (s, 3H), 1.97 to 1.80 (m, 3H)

Various compounds were produced in the same manner as in the above examples. Production examples of the oxime ether derivative represented by the formula (I) are shown in Table 1, and production examples of the oxime ether derivative represented by the formula (II) are shown in Table 2, respectively. In addition, physical properties (melting point, refractive index, etc.) are also shown.
In Tables 1 and 2, Me is a methyl group, Et is an ethyl group, ⁿ Pr is an n-propyl group, ⁱ Pr is an i-propyl group, ^t Bu is a t-butyl group, Ac represents an acetyl group, and Piv represents a pivaloyl group.
Compound numbers 1-9 and 1-10 are isomers of each other.

¹ H-NMR was measured for some of the compounds obtained in the above production examples. The results are shown below.

Compound No. 1-17: viscous oil
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.71 (s, 1H), 7.53 (d, 1H), 7.50-7.47 (m, 1H), 7.23-7.11 (m, 5H), 5.33 (t , 1H), 3.83 (s, 3H), 2.90 to 2.73 (m, 2H), 2.28 (s, 3H), 2.26 to 2.21 (m, 1H), 2.18 (s, 3H), 2.02 to 1.97 (m, 2H ), 1.83 to 1.76 (m, 1H)

Compound number 1-18: viscous oil
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.51 (d, 1H), 7.47-7.12 (m, 6H), 5.71 (s, 2H), 5.33 (t, 1H), 3.87 (s, 3H ), 2.86 to 2.76 (m, 2H), 2.56 to 2.21 (m, 1H), 2.17 (s, 3H), 2.12 (s, 3H), 2.02 to 1.95 (m, 2H), 1.82 to 1.79 (m, 1H )

Compound number 1-19: viscous oil
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.49-7.45 (m, 1H), 7.38 (d, 1H), 7.26-7.09 (m, 5H), 5.69 (s, 2H), 5.32 (t , 1H), 3.85 (s, 3H), 2.85 to 2.75 (m, 2H), 2.26 (s, 3H), 2.24 to 2.17 (m, 1H), 2.16 (s, 3H), 2.10 (s, 3H), 2.01 to 1.94 (m, 2H), 1.83 to 1.76 (m, 1H)

Compound number 1-33: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.43 (d, 1H), 7.36 (d, 1H), 7.31 (d, 1H), 7.23 (dd, 1H), 7.17 to 7.12 (m, 2H ), 5.77 (dd, 1H), 5.69 (s, 2H), 3.86 (s, 3H), 3.15 (ddd, 1H), 2.93 (ddd, 1H), 2.53 to 2.41 (m, 1H), 2.30 to 2.20 ( m, 4H), 2.14 (s, 3H), 2.10 (s, 3H), 2.09 (s, 3H)

Compound number 1-44: viscous oil
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.70 (d, 1H), 7.55 (d, 1H), 7.35 to 7.21 (m, 3H), 7.15 (d, 1H), 5.78 (dd, 1H ), 5.69 (s, 2H), 3.86 (s, 3H), 3.33 to 3.23 (m, 1H), 3.11 to 3.01 (m, 1H), 2.58 to 2.46 (m, 1H), 2.38 to 2.30 (m, 1H ), 2.26 (s, 3H), 2.15 (s, 3H), 2.11 (s, 3H)

Compound number 1-46: viscous oil
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.65 (s, 1H), 7.54 (d, 1H), 7.50 (dd, 1H), 7.34-7.19 (m, 4H), 7.13 (d, 1H ), 5.79 (dd, 1H), 3.84 (s, 3H), 2.37 (dd, 1H), 2.28 (s, 3H), 2.18-2.12 (m, 4H), 1.39 (s, 3H), 1.31 (s, 3H)

Compound number 1-51: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.54 (d, 1H), 7.84 (s, 1H), 7.52 (d, 1H), 7.48 (d, 1H), 7.23-7.16 (m, 2H ), 7.10 (d, 1H), 5.40 (t, 1H), 3.84 (s, 3H), 2.91-2.73 (m, 2H), 2.47-2.41 (m, 1H), 2.27 (s, 3H), 2.17 ( s, 3H), 2.02-1.77 (m, 3H)

Compound number 1-53: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.82 (bs, 1H), 8.41 (s, 2H), 7.51 (d, 1H), 7.41 (d, 1H), 7.22 (dd, 1H), 7.11 (d, 1H), 5.28 (t, 1H), 3.82 (s, 3H), 2.90 to 2.69 (m, 3H), 2.27 (s, 3H), 2.18 (s, 3H), 2.16 to 1.78 (m, 3H)

Compound number 1-54: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.90 (s, 1H), 8.67 (s, 1H), 8.36 (d, 1H), 7.52 (d, 1H), 7.22 (dd, 1H), 7.10 (d, 1H), 7.03 (d, 1H), 5.34 (t, 1H), 3.81 (s, 3H), 2.88-2.66 (m, 2H), 2.32-2.25 (m, 4H), 2.15 (s, 3H), 2.00 to 1.77 (m, 3H)

Compound number 1-55: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.16 (s, 1H), 7.55 (s, 1H), 7.52 (d, 1H), 7.22 (dd, 1H), 7.10 (d, 1H), 5.31 (t, 1H), 3.83 (s, 3H), 3.74 (s, 3H), 2.70 to 2.41 (m, 2H), 2.25 (s, 3H), 2.21 to 1.81 (m, 4H), 2.14 (s, 3H)

Compound number 1-56: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.30 (s, 1H), 7.52 (s, 1H), 7.46 (s, 1H), 7.21 (d, 1H), 7.15 (d, 1H), 5.30 (t, 1H), 4.46 to 4.36 (m, 1H), 3.82 (s, 3H), 2.75 to 2.52 (m, 2H), 2.27 (s, 3H), 2.17 (s, 3H), 2.13 to 1.69 ( m, 4H), 1.48 (d, 6H)

Compound number 1-57: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.26 (s, 1H), 7.60 (s, 1H), 7.52 (d, 1H), 7.23 (dd, 1H), 7.11 (d, 1H), 5.31 (t, 1H), 4.42-4.29 (m, 1H), 3.82 (s, 3H), 2.75-2.39 (m, 2H), 2.27 (s, 3H), 2.17 (s, 3H), 2.13-1.77 ( m, 4H), 1.47 (dd, 6H)

Compound number 1-58: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.27 (s, 1H), 7.55 (s, 1H), 7.53 (d, 1H), 7.20 (dd, 1H), 7.11 (d, 1H), 5.29 (t, 1H), 4.64 (q, 2H), 3.81 (s, 3H), 2.79 to 2.57 (m, 2H), 2.27 (s, 3H), 2.16 (s, 3H), 2.13 to 1.74 (m, 4H)

Compound number 1-59: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 8.34 (s, 1H), 7.67 (s, 1H), 7.52 (s, 1H), 7.22 (d, 1H), 7.12 (d, 1H), 5.30 (t, 1H), 4.70 to 4.44 (m, 2H), 3.81 (s, 3H), 2.74 to 2.44 (m, 2H), 2.26 (s, 3H), 2.15 (s, 3H), 209 to 1.78 ( m, 4H)

Compound number 1-60: amorphous
¹ H-NMR (CDCl ₃ / TMS, δ (ppm)) 7.73 (s, 1H), 7.50 (dd, 1H), 7.39 (d, 1H), 7.34-7.18 (m, 4H), 5.79 (dd, 1H ), 3.83 (s, 3H), 2.35 (dd, 1H), 2.30 (s, 3H), 2.19-2.12 (m, 7H), 1.39 (s, 3H), 1.31 (s, 3H)

Next, some examples of the bactericidal agent of the present invention will be shown, but the additives and addition ratios are not limited to these 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 Compound of the present invention 40 parts Clay 48 parts Dioctyl sulfosuccinate sodium salt 4 parts Lignin sulfonic acid sodium salt 8 parts The above is uniformly mixed and finely pulverized, and a 40% active ingredient wettable powder Get.

Formulation Example 2 Emulsion Compound of the present invention 10 parts Solvesso 200 53 parts Cyclohexanone 26 parts Calcium dodecylbenzenesulfonate 1 part Polyoxyethylene alkylallyl ether 10 parts The above is mixed and dissolved to obtain an emulsion containing 10% active ingredient.

Formulation Example 3 Powder 10 parts of the present compound 90 parts of clay The above is uniformly mixed and finely pulverized to obtain a powder of 10% active ingredient.

Formulation Example 4 Granules Compound of the present invention 5 parts Clay 73 parts Bentonite 20 parts Dioctylsulfosuccinate sodium salt 1 part Potassium phosphate 1 part The above is pulverized and mixed well, water is added and kneaded and granulated and dried. As a result, granules containing 5% active ingredient are obtained.

Formulation Example 5 Suspension Compound of the present invention 10 parts Polyoxyethylene alkyl allyl ether 4 parts Polycarboxylic acid sodium salt 2 parts Glycerin 10 parts Xanthan gum 0.2 parts Water 73.8 parts Mix the above and wet until the particle size is 3 microns or less Grind to obtain a suspension of 10% active ingredient.

Formulation Example 6 Granule wettable powder Compound of the present invention 40 parts Clay 36 parts Potassium chloride 10 parts Alkylbenzenesulfonic acid sodium salt 1 part Ligninsulfonic acid sodium salt 8 parts Formaldehyde condensate of alkylbenzenesulfonic acid sodium salt 5 parts After finely pulverizing, add an appropriate amount of water and knead to make clay. The clay-like product is granulated and then dried to obtain a wettable powder with 40% active ingredient.

Test examples of the fungicide of the present invention obtained as described above are shown below.
(Test Example 1) Apple black spot disease control test The emulsion of Production Example 2 was sprayed at a concentration of 100 ppm active ingredient on apple seedlings (variety “Kokumitsu”, 3-4 leaf stage) cultivated in an unglazed pot. After naturally drying 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 darkness every 12 hours. The lesion appearance state on the leaf was compared with no treatment, and the control effect was obtained.

Compound number (compound number corresponds to the compound number in the above table. The same applies hereinafter) 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 , 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1 -27, 1-31, 1-32, 1-33, 1-34, 1-35, 1-36, 1-37, 1-38, 1-39, 1-40, 1-41, 1-42 , 1-43, 1-44, 1-45, 1-46, 1-47, 1-48, 1-49, 1-50, 1-51, 1-52, 1-53, 1-55, 1 An apple scab control trial was conducted for oxime ether derivatives of -56, 1-57, 1-59, 1-60, 1-61, 3-14, and 2-17. All the compounds showed a control value of 75% or more.

(Test Example 2) Wheat powdery mildew control test The wet seedling of Formulation Example 1 was sprayed at a concentration of 100 ppm to wheat seedlings (variety “Chihoku”, 1.0-1.2 leaf stage) cultivated in an unglazed pot. After air-drying the leaves, conidia of wheat powdery mildew (Erysiphe graminis f.sp.tritici) were shaken off and inoculated and kept 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 obtained.

Compound numbers 1-1, 1-2, 1-3, 1-7, 1-8, 1-9, 1-10, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-27, 1-31, 1-32, 1-33, 1-34, 1-35, 1-36, 1-37, 1-38, 1- 39, 1-40, 1-41, 1-42, 1-43, 1-44, 1-45, 1-46, 1-47, 1-48, 1-49, 1-50, 1-51, Wheat powdery mildew control tests were conducted on oxime ether derivatives 1-57, 1-59, 1-60, and 1-61. All the compounds showed a control value of 75% or more.

(Test Example 3) Wheat Red Rust Control Test Wheat powder of Formulation Example 1 was sprayed at a concentration of 100 ppm to wheat seedlings (variety “Noribayashi No. 61”, 1.0-1.2 leaves) grown in an unglazed pot. After the leaves were air-dried, they were inoculated with summer spores of wheat rust (Puccinia recondita) 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 obtained.

Compound Nos. 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-8, 1-9, 1-10, 1-11, 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, 1-27, 1-31, 1-32, 1-33, 1-34, 1-35, 1- 36, 1-37, 1-38, 1-39, 1-40, 1-41, 1-42, 1-43, 1-44, 1-45, 1-46, 1-47, 1-48, 1-49, 1-50, 1-51, 1-53, 1-54, 1-55, 1-56, 1-57, 1-58, 1-59, 1-60, 1-61, and 2 -17 oxime ether derivatives were tested for wheat red rust control. All the compounds showed a control value of 75% or more.

The oxime ether derivative and the salt thereof according to the present invention are novel compounds useful as active ingredients of agricultural and horticultural fungicides that can be produced industrially advantageously, have reliable effects, and can be used safely.
The agricultural and horticultural fungicide of the present invention is an agent that has an excellent control effect, does not cause phytotoxicity or contamination on the plant body, and has little toxicity to human fish and environmental impact.

Claims (3)

1. Formula (I) or Formula (II)
   

   

   Formula (I)
   
   

   

   Formula (II)
   (In Formula (I) and Formula (II),
   R ¹ is a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
   R ² represents a hydrogen 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, It represents a substituted or substituted C1-8 acyl group, an unsubstituted or substituted C1-8 alkylsulfonyl group, or an unsubstituted or substituted C6-10 arylsulfonyl group.
   X represents a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. n represents the number of X and is an integer from 0 to 4. When n is 2 or more, Xs may be the same or different. When n is 2 or more, Xs may be combined to form a ring.
   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 ⁷ . R ⁷ represents a hydrogen atom or an unsubstituted or substituted C1-8 alkyl group.
   In formula (I),
   R ³ represents a hydrogen 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, or It represents an unsubstituted or substituted C3-8 cycloalkyl group.
   R ⁴ and R ⁵ are each independently a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or an unsubstituted group. Alternatively, it represents a C1-8 alkoxy group having a substituent. R ⁴ and R ⁵ may be combined to form a ring. m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R ⁴ and / or R ⁵ may be the same or different from each other.
   R ⁶ represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group.
   A represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ R ⁹ . R ⁸ and R ⁹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p represents the number of repetitions of A and is an integer of 1 to 3. When p is 2 or more, A's may be the same or different.
   B represents an oxygen atom, a sulfur atom, or a group represented by CR ¹⁰ R ¹¹ . R ¹⁰ and R ¹¹ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q represents the number of repetitions of B and is an integer from 0 to 1. However, the sum of p and q is 2 or 3.
   Q represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group.
   In formula (II),
   R ⁴ ′ and R ⁵ ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, an unsubstituted or substituted C3-8 cycloalkyl group, or A substituted or substituted C1-8 alkoxy group is represented. R ⁴ and R ⁵ may be combined to form a ring. m represents the number of repeating units in parentheses and is an integer of 0-2. When m is 2, R ⁴ and / or R ⁵ may be the same or different from each other.
   A ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ⁸ 'R ⁹ '. R ⁸ ′ and R ⁹ ′ each independently represents a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. p ′ represents the number of repetitions of A ′ and is an integer of 1 to 3. When p ′ is 2 or more, A ′ may be the same as or different from each other.
   B ′ represents an oxygen atom, a sulfur atom, or a group represented by CR ¹⁰ ′ R ¹¹ ′. R ¹⁰ ′ and R ¹¹ ′ each independently represent a hydrogen atom, a halogen atom, an unsubstituted or substituted C1-8 alkyl group, or an unsubstituted or substituted C1-8 alkoxy group. q ′ represents the number of repetitions of B ′ and is an integer from 0 to 1. However, the sum of p ′ and q ′ is 2 or 3.
   Q ′ represents an unsubstituted or substituted C6-10 arylene group or an unsubstituted or substituted divalent heteroaryl group. Or an salt thereof.
2. Q in formula (I) and Q ′ in formula (II) are each independently an unsubstituted or substituted phenylene group, an unsubstituted or substituted pyridinylene group, an unsubstituted or substituted group. An unsubstituted or substituted pyrimidinylene group, an unsubstituted or substituted pyridazinylene group, an unsubstituted or substituted pyrrolinylene group, an unsubstituted or substituted imidazolinylene group, and The oxime ether derivative or a salt thereof according to claim 1, which represents any group selected from an unsubstituted or substituted pyrazolinylene group.
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.