KR20000075703A - Oxime ether compounds, their use and intermediates for preparations of the same - Google Patents

Abstract

According to the present invention there is provided an oxime ether compound represented by the formula:

These compounds not only have good antibacterial effects in agriculture and / or horticulture, but also have excellent pesticidal and / or acaricide effects.

Description

Oxime ether compounds, their uses and intermediates for their manufacture {OXIME ETHER COMPOUNDS, THEIR USE AND INTERMEDIATES FOR PREPARATIONS OF THE SAME}

The present inventors have found that the oxime ether compound of formula 4 has excellent agricultural and / or horticultural antimicrobial effect, and insecticidal and / or mite effect, and thus the present invention has been completed.

That is, the present invention provides an oxime ether compound of formula 4 (hereinafter referred to as the present compound), and an agricultural and / or horticultural antifungal agent containing the same as an active ingredient, and an insecticide and / or acaricide.

(Wherein R ¹ is a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyalkyl group, a haloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group,

One of T, U and V is a CR ² group, the other represents a CH group or a nitrogen atom, the other represents a CR ³ group or a nitrogen atom,

W represents a CR ³³ group or a nitrogen atom,

R ² , R ³ and R ³³ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a cyano group, a nitro group, an alkoxycarbonyl group, an alkylthio group or a haloalkylthio group ,

R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, wherein an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group or hetero Cyclic groups may have one or more substituents,

R ⁵ and R ⁶ are the same or different and represent an alkyl group,

X represents an NR ⁷ group, an oxygen atom or a sulfur atom,

R ⁷ represents an alkyl group optionally substituted with one or more substituents,

Y represents a CH group or a nitrogen atom,

Z represents an oxygen atom or an NH group, provided that when Y is a CH group, Z is an oxygen atom.

The present invention also provides compounds of the formulas 5 to 8 which are useful as intermediates for the preparation of the compounds.

(Wherein R ¹ , R ⁴ , R ⁶ , T, U, V, W, X and Y are as defined above),

(Wherein R ¹ , R ⁴ , R ⁶ , T, U, V, W and X are as defined above),

(Wherein R ¹ , R ⁵ , R ⁶ , T, U, V, W, X and Z are as defined above),

Wherein R ⁵ and R ⁶ are as defined above.

The present invention relates to oxime ether compounds, their use and their preparation intermediates. More specifically, the present invention provides compounds having excellent agricultural and / or horticultural antibacterial effects, and excellent pesticidal and / or acaricide effects.

In the present invention, examples of the alkyl group represented by R ¹ include a C1-C10 alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, decyl group and the like. .

Examples of the cycloalkyl group represented by R ¹ include a C3-C10 cycloalkyl group such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclodecyl group and the like.

Examples of the alkoxyalkyl group represented by R ¹ include a C 2 -C 10 alkoxyalkyl group such as a methoxymethyl group, 2-ethoxyethyl group, 4-methoxybutyl group, 5-pentyloxypentyl group and the like.

Examples of the haloalkyl group represented by R ¹ include a C1-C5 haloalkyl group, such as a trifluoromethyl group, a chloromethyl group, a 2-fluoroethyl group, and the like.

Examples of the alkoxycarbonyl group represented by R ¹ are C2-C5 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group, i-propoxycarbonyl group, i-butoxycarbonyl group, t- Butoxycarbonyl group, and the like.

Examples of the halogen atom represented by R ² , R ³ or R ³³ include a chlorine atom, bromine atom, fluorine atom and the like.

Examples of the alkyl group represented by R ² , R ³ or R ³³ include a C1-C5 alkyl group such as a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group and the like.

Examples of the alkoxy group represented by R ² , R ³ or R ³³ are C 1 -C 5 alkoxy groups such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, pentyloxy group And the like.

Examples of haloalkyl groups represented by R ² , R ³ or R ³³ include C 1 -C 5 haloalkyl groups such as trifluoromethyl groups and the like.

Examples of haloalkoxy groups represented by R ² , R ³ or R ³³ include C 1 -C 5 haloalkoxy groups such as trifluoromethoxy group, difluoromethoxy group, bromodifluoromethoxy group, chlorodifluoromethoxy group, 1,1,2,2-tetrafluoroethoxy group, 2,2,2-trifluoroethoxy group, and the like.

Examples of the alkoxycarbonyl group represented by R ² , R ³ or R ³³ include C 2 -C 5 alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group, i-propoxycarbonyl group, i- Butoxycarbonyl group, t-butoxycarbonyl group, and the like.

Examples of the alkylthio group represented by R ² , R ^3, or R ³³ include C 1 -C 5 alkylthio groups such as methylthio group, ethylthio group, n-propylthio group, n-butylthio group, n-pentylthio group, i-propylthio group, i-butylthio group, t-butylthio group, etc. are included.

Examples of haloalkylthio groups represented by R ² , R ³ or R ³³ include C 1 -C 5 haloalkylthio groups such as trifluoromethylthio group, difluoromethylthio group, bromodifluoromethylthio group, chlorodi Fluoromethylthio group, 1,1,2,2-tetrafluoroethylthio group, 2,2,2-trifluoroethylthio group, and the like.

Examples of the alkyl group represented by R ⁴ include C1-C10 alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1-methylpropyl group, pentyl group, 1-methylbutyl group, 1-ethyl Butyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropyl group, hexyl group, 1-methylpentyl group, 1- Ethylpentyl group, 3,3-dimethylbutyl group, heptyl group, 3,7-dimethyloctyl group and the like.

Examples of the alkenyl group represented by R ⁴ include a C3-C10 alkenyl group such as an allyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 3-methyl-2-propenyl group, 2-butenyl group , 2-pentenyl group, 3-methyl-2-butenyl group, geranyl group and the like.

Examples of the alkynyl group represented by R ⁴ include a C3-C10 alkynyl group such as propargyl group, 1-methyl-2-propynyl group, 3-methyl-2-propynyl group and the like.

Examples of the cycloalkyl group represented by R ⁴ include a C5-C10 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and the like.

Examples of the cycloalkenyl group represented by R ⁴ include a C5-C10 cycloalkenyl group such as a cyclopentenyl group, a cyclohexenyl group, and the like.

Examples of the aryl group represented by R ⁴ include a phenyl group, α-naphthyl group, β-naphthyl group and the like.

Examples of the heterocyclic group represented by R ⁴ are 2-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 3-pyrazolyl group, 2-thiazolyl group, 2-imidazolyl Group, 3- (1,2,4-triazolyl group), and the like.

Examples of substituents for an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group and heterocyclic group in R ⁴ include:

(1) halogen atoms (chlorine atom, bromine atom, fluorine atom, etc.);

(2) OR ⁸ group {wherein R ⁸ is a hydrogen atom, a C1-C10 alkyl group [eg, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, pentyl group, hexyl group Etc.], C1-C5 haloalkyl group [for example, trifluoromethyl group, difluoromethyl group, bromodifluoromethyl group, 1,1,2,2-tetrafluoroethyl group, 2,2,2-trifluoroethyl group Etc.], C3-C6 cycloalkyl group [e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, etc.], C2-C10 alkoxyalkyl group [e.g. 2-methoxyethyl group, etc.], C1-C10 acyl group [e.g. C1-C10 alkanoyl groups optionally substituted with a wheat group, an acetyl group, a propanoyl group, a pivaloyl group, and a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, etc.), such as a chloroacetyl group and a benzoyl group], C2- C11 alkoxycarbonyl group [for example, methoxycarbonyl group, ethoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group ], N- (C1-C10 alkyl) carbamoyl group [eg, N-methylcarbamoyl group, N-ethylcarbamoyl group, etc.], N, N-di- (C1-C10 alkyl) carbamoyl group [eg, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, etc.] or phenyl group [Phenyl group is a halogen atom (e.g., chlorine atom, bromine atom, fluorine atom, etc.), C1-C5 alkyl group (e.g., methyl group , Ethyl group, tert-butyl group and the like) or trifluoromethyl group; For example, 4-chlorophenyl group, 4- (trifluoromethyl) phenyl group, 3,4-dichlorophenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2-chloro-4- (trifluoromethyl) phenyl group, 4-fluorophenyl group, 3,5-dichlorophenyl group, 4-tert-butyl phenyl group, 2-chloro-6-fluorophenyl group, etc.];

(3) a group represented by N (R ⁹ ) R ¹⁰ {wherein R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, a C1-C10 alkyl group [eg, a methyl group, an ethyl group, a butyl group, etc.], C5-C6 cyclo Alkyl group [e.g., cyclopentyl group or cyclohexyl group], C1-C10 acyl group [e.g., acetyl group, propanoyl group, butanoyl group, halogen atom (chlorine atom, bromine atom, fluorine atom, etc.) optionally substituted C10 alkanoyl groups such as trifluoroacetyl group and the like, benzoyl group and the like], C2-C11 alkoxycarbonyl group, N- (C1-C10 alkyl) carbamoyl group [eg N-methylcarbamoyl group, N-ethylcarbamo Diary, etc.], N, N-di (C1-C10 alkyl) carbamoyl group [for example, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group, etc.], C1-C5 alkylsulfonyl group [for example , Methylsulfonyl group, etc.], C6-C10 aryl (eg, phenyl, α-naphthyl or β-naphthyl) sulfonyl group [eg, p-toluenesulfonyl group, etc.], C1-C5 haloalkylsulfonyl group And the like [eg, trifluoromethanesulfonyl group, trichloromethanesulfonyl group, 2,2,2-trifluoroethanesulfonyl group and the like], C1-C5 alkylsulfinyl group [eg, methylsulfinyl group and the like], or C1- C5 haloalkylsulfinyl group [e.g., trifluoromethanesulfinyl group, etc.], or phenyl group [phenyl group is a halogen atom (chlorine atom, bromine atom, fluorine atom, etc.), C1-C5 alkyl group (e.g., methyl group, ethyl group, tert-butyl Groups, etc.) or trifluoromethyl groups; For example, 4-chlorophenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-chloro-6-fluorophenyl group, 4-fluorophenyl group, etc. Or R ⁹ and R ¹⁰ together represent a tetramethylene group, a pentamethylene group or a 3-oxapentamethylene group};

(4) a group represented by C (R ¹³ ) = NOR ¹⁴ {wherein R ¹³ and R ¹⁴ are the same or different and are a hydrogen atom, a C1-C10 alkyl group [eg, methyl group, ethyl group, propyl group, isopropyl group, butyl Group, isobutyl group, tert-butyl group, pentyl group, hexyl group and the like], C3-C6 cycloalkyl group [e.g. cyclopropyl group, cyclopentyl group and cyclohexyl group] or phenyl group [phenyl group is a halogen atom (chlorine atom, Bromine atom, fluorine atom, etc.), C1-C5 alkyl group (eg, methyl group, ethyl group, tert-butyl group, etc.), trifluoromethyl group, cyano group or nitro group; For example, 4-chlorophenyl group, 4-trifluoromethylphenyl group, 4-ethylphenyl group, 3,4-dichlorophenyl group, 3,5-dichlorophenyl group, 2-chloro-6-fluorophenyl group, 4-fluorophenyl group, 4-cyanophenyl group, 4-nitrophenyl group, etc.];

(5) C1-C5 alkylthio groups (eg, methylthio group, ethylthio group, propylthio group, isopropylthio group, pentylthio group, etc.);

(6) C1-C5 haloalkylthio groups [eg, 2,2,2-trifluoroethylthio groups, 4-chlorobutylthio groups, and the like];

(7) C1-C10 acyl groups [e.g., C1-C10 alkanoyl groups optionally substituted with halogen atoms (chlorine atoms, bromine atoms, fluoro atoms, etc.) (e.g., formyl groups, acetyl groups, propanoyl groups, butanoyl groups) , Pentanoyl group, isobutanoyl group and the like), benzoyl group and the like];

(8) C2-C11 alkoxycarbonyl groups [eg, methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, octyloxycarbonyl group, etc.];

(9) N- (C1-C10 alkyl) carbamoyl group [eg, N-methylcarbamoyl group, N-ethylcarbamoyl group, etc.];

(10) N, N-di (C1-C10 alkyl) carbamoyl groups [eg, N, N-dimethylcarbamoyl groups, N, N-diethylcarbamoyl groups and the like];

(11) cyano groups;

(12) nitro groups;

(13) aryl groups such as phenyl group, α-naphthyl group, β-naphthyl group and the like; Aryl groups are halogen atoms [e.g., chlorine atoms, bromine atoms, fluorine atoms, etc.], C1-C10 alkyl groups [e.g., methyl groups, ethyl groups, tert-butyl groups, etc.], C3-C10 cycloalkyl groups [e.g., cyclopropyl groups, cyclophenes Methyl group, cyclohexyl group, etc.], C1-C5 haloalkyl group [eg, trifluoromethyl group, etc.], hydroxy group, C1-C10 alkoxy group [eg, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, etc.], C1-C5 haloalkoxy group [e.g., trifluoromethoxy group, difluoromethoxy group, etc.], amino group, cyano group, nitro group, C2-C6 alkoxycarbonyl group [e.g., methoxycarbonyl group, ethoxycarbonyl group, etc.], C3 -C8 cycloalkoxy group [eg, cyclopentyloxy group, cyclohexyloxy group, etc.], N- (C1-C5 alkyl) carbamoyl group [eg, N-methylcarbamoyl group, N-ethylcarbamoyl group, etc.], N, N-di (C1-C5 alkyl) carbamoyl groups [eg, N, N-dimethylcarbamo Group, N, N-diethylcarbamoyl group, etc.], C1-C10 acyl group [e.g., C1-C10 alkanoyl group (e.g., acetyl group, etc.), benzoyl group, etc.], one or more halogen atoms, C1-C3 alkyl group , A phenoxy group optionally substituted with a C1-C3 haloalkyl group or a C1-C3 alkylthio group [eg, phenoxy group, 4-chlorophenoxy group], a phenyl group optionally substituted with one or more cyano groups, 2-pyridyloxy group [2-pyrid A diloxy group may be substituted with one or more trifluoromethyl groups or halogen atoms; 5-trifluoromethylpyridin-2-yloxy group, 3-chloro-5-trifluoromethylpyridin-2-yloxy group, etc.], morpholin-4-yl group, benzyloxy group, benzoyloxy group, C1- C5 alkylsulfonyloxy group [eg, methylsulfonyloxy group, etc.], C1-C5 haloalkylsulfonyloxy group [eg, trifluoromethylsulfonyloxy group, etc.], trifluoromethanesulfonylamino group, R ¹¹ OC (O) O group, R ¹¹ (R ¹² ) NC (O) O group, R ¹¹ C (O) N (R ¹² ) group, R ¹¹ OC (O) NH group, R ¹¹ (R ¹² ) NC (O) NH group Wherein R ¹¹ and R ¹² are the same or different and represent a C 1 -C 5 alkyl group such as a methyl group, an ethyl group, etc. or a C 1 -C 10 alkylthio group [eg, methylthio group, ethylthio group, etc.] have}; And

(14) heterocyclic groups {eg, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 1-pyrazolyl group, 3 -Pyrazolyl group, 4-pyrazolyl group, 5-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 4-isoxazolyl group, 1- (1,2,4 -Triazolyl) group, 3- (1,2,4-triazolyl) group, 3-oxolanyl, succinimide-1-yl group, maleimide-1-yl group, phthalimide-1-yl group Etc; Heterocyclic groups include one or more halogen atoms [eg, chlorine atoms, bromine atoms, fluorine atoms, etc.], C1-C10 alkyl groups [eg, methyl groups, ethyl groups, tert-butyl groups, etc.], C3-C10 cycloalkyl groups [eg, cyclopropyl Groups, cyclopentyl groups, cyclohexyl groups, etc.], C1-C5 haloalkyl groups [eg, trifluoromethyl groups, etc.], hydroxy groups, C1-C10 alkoxy groups [eg, methoxy groups, ethoxy groups, etc.], amino groups or C1-C10 Alkylthio group (eg, methylthio group, ethylthio group, etc.).

Examples of the alkyl group of R ⁵ and R ⁶ include a C1-C5 alkyl group such as a methyl group, an ethyl group, a propyl group and the like. Among these, a methyl group is preferable from an agricultural and horticultural antimicrobial effect.

Examples of the alkyl group of R ⁷ include a C1-C5 alkyl group such as a methyl group, an ethyl group, a propyl group and the like. Examples of the substituent of R ⁷ include halogen atom [eg, chlorine atom, bromine atom, fluorine atom, etc.], C1-C5 alkoxy group [eg, methoxy group, ethoxy group, etc.], C2-C5 alkoxycarbonyl group [eg, methoxycarbonyl group , Ethoxycarbonyl group, etc.], N- (C1-C5 alkyl) carbamoyl group [eg, N-methylcarbamoyl group, N-ethylcarbamoyl group, etc.], N, N-di (C1-C5 alkyl) carbamo Diary (for example, N, N-dimethylcarbamoyl group, N, N-diethylcarbamoyl group and the like), cyano group and the like.

Examples of 6-membered cyclic aromatic rings containing T, U, V, and W include benzene rings, pyridine rings, pyrimidine rings, and the like.

In terms of agricultural and / or horticultural antibacterial effects, R ¹ is a methyl group, T is C-CH ₃ , U is CH, V is CH, W is CH, R ⁵ is methyl group, R ⁶ is methyl group, X is oxygen atom And the present compound wherein Y is CH and Z is an oxygen atom is preferable. Examples of preferred compounds include methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate, methyl 3- [5- {1- (2,4-dichloro Benzyloxyimino) ethyl} -2-methylphenoxy] -3-methoxyacrylate, methyl 2- {5- (1-propargyloxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylic Latex, methyl 2- {5- (1-n-propyloxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate, and the like. In the present compound, that is, the compound represented by the formula (5) and the compound represented by the formula (6), (E) and (Z) isomers due to C = N bond and / or C = C bond may be present, and any of the above isomers, and these Mixtures of are included in the present invention (the terms (E) and (Z) used here are according to the Cahn-Ingold-Prelog method which is used extensively in the designation of geometric isomers).

The present compound can be prepared according to the synthetic schemes shown in Scheme 7, Scheme 8, Scheme 9 or Scheme 10 below.

Wherein R ⁴⁴ is R ⁴ excluding hydrogen, R ¹ , R ⁵ , R ⁶ , T, U, V, W, X, Y and Z are as defined above and L ¹ is a halogen atom (e.g., Leaving groups such as chlorine atoms, bromine atoms, iodine atoms, etc.), sulfonate ester groups (e.g., mesyloxy groups, tosyloxy groups, etc.), sulfate ester groups (methoxysulfonyloxy groups, ethoxysulfonyloxy groups, etc.) Indicates).

(Wherein R ¹ , R ⁴ , R ⁵ , R ⁶ , T, U, V, W, X, Y and L ¹ are as defined above and when Y is a CH group, L ² is an alkoxy group (e.g., C1-C5 alkoxy group such as methoxy group, ethoxy group, etc.), aryloxy group (such as phenoxy group) or acyloxy group (e.g., C1-C5 acyloxy group such as acetoxy group), and when Y is nitrogen, L ² is an alkoxy group (e.g., a C1-C5 alkoxy group such as methoxy group, ethoxy group, isoamyloxy group, butoxy group, tert-butoxy group, etc.) or a chlorine atom).

Wherein R ¹ , R ⁴⁴ , R ⁵ , R ⁶ , T, U, V, W, X and L ¹ are as defined above.

Wherein R ¹ , R ⁴ , R ⁵ , R ⁶ , T, U, V, W and X are as defined above.

Starting compound [I] in Scheme 7 may be prepared, for example, according to Scheme 11 below.

Wherein R ¹ , R ⁵ , R ⁶ , T, U, V, W, X, Y, L ¹ and L ² are as defined above and R ¹¹ is an alkyl group (e.g., methyl, ethyl, propyl, C1-C5 alkyl group such as butyl group), or two R ¹¹ together represent an alkylene group (e.g., C2-C5 alkylene group such as ethylene group, 1,2-dimethylethylene group, propylene group and the like).

Starting compound 6 of scheme 8 and starting compound [VII] of scheme 11 can be prepared according to Scheme 12, for example.

Wherein R ¹ , R ⁴ , R ⁶ , X, T, U, V and W are as defined above and L ¹ is a halogen atom (eg chlorine atom, bromine atom, iodine atom, etc.) or sulfonate ester Group (for example, a mesyloxy group, a tosyloxy group, etc.)).

When R ¹ is a cyano group, an alkoxycarbonyl group or a nitro group, the intermediate compound [XIII] of Scheme 12 may also be prepared by the following Scheme 13.

Wherein R ¹¹ represents a cyano group, an alkoxycarbonyl group or a nitro group, R ⁴⁴ , L ¹ , L ² , X, T, U, V and W are as defined above and X ′ is synthesized as an XH group in step 13c. Chemically derived groups).

When X represents an oxygen atom, X 'represents an oxygen ether group such as benzyloxy group, methoxymethyloxy group, methylthiomethyloxy group, benzyloxymethyloxy group, tetrahydropyran-2-yloxy group and the like.

When X represents a sulfur atom, X 'represents a sulfur ether group such as methoxymethylthio group, isobutoxymethylthio group, tetrahydropyran-2-ylmethylthio group and the like.

When X represents an NR ⁷ group (wherein R ⁷ is as defined above), X 'is a nitro group or N (R ⁷ ) R ²⁰ group (wherein R ⁷ is as defined above and R ²⁰ is t -Acyl groups such as butoxycarbonyl group, formyl group, acetyl group and the like).

Step 7a and step 7c of Scheme 7, step 9c of step 9c, step 9d, step 9f and step 9i, and carbonyl compounds of steps 12a and 12d of Scheme 12 {[I], [IV], [II] or [VII]} in the reaction of the hydroxylamine derivative {HONH ₂ , R ⁴ ONH ₂ or R ⁴⁴ ONH ₂ }, the reaction temperature is usually 0 to 150 ℃, the reaction time is usually 1 to 24 hours, hydroxylamine The molar ratio of derivative to carbonyl compound is usually from 1 to 5. The hydroxylamine derivatives can be used as salts with acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like.

If desired, acid catalysts or base catalysts may be used in the reaction. The molar ratio of catalyst to hydroxylamine derivative is usually from 0.01 to 100. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like, carboxylic acids such as acetic acid, trifluoroacetic acid, oxalic acid, benzoic acid and the like, sulfonic acids such as p-toluenesulfonic acid, camm Formic acid, methanesulfonic acid, trifluoromethanesulfonic acid and the like, Lewis acids such as zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride and the like, and mixtures thereof. The acid catalyst may form salts with alkali metals such as sodium, potassium and the like, organic bases such as pyridine, triethylamine, N, N-dimethylaniline and the like. Examples of these are pyridinium p-toluenesulfonate and the like. Examples of basic catalysts include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, potassium carbonate and the like, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and the like, Alkaline earth metal alkoxides such as magnesium ethoxide and the like, organic bases such as pyridine, 2-picolin, 4-picolin, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N, N-dimethyl Aniline, N, N-diethylaniline, and the like, and mixtures thereof. The basic catalyst can form salts with inorganic acids such as hydrochloric acid, sulfuric acid, and the like, carboxylic acids such as acetic acid, benzoic acid, and Lewis acids such as zinc chloride and the like. Examples of these include sodium acetate and the like.

If desired, a solvent may be used for the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert- Aliphatic hydrocarbon solvents such as butyl methyl ether, such as hexane, heptane, ligroin, petroleum ether, etc., aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, etc. Organic base solvents such as pyridine, triethylamine, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline and the like, organic acid solvents such as acetic acid and the like, ester solvents such as ethyl formate, butyl acetate Nitro compound solvents such as ethyl acetate, diethyl carbonate, such as nitroethane, nitrobenzene, nitrile Mediums such as acetonitrile, isobutyronitrile and the like, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane, water and the like, and mixtures thereof .

After completion of the reaction, the reaction solution may be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, may be further purified by recrystallization, distillation, chromatography, and the like to separate the target compound.

Step 7b of Scheme 7, Step 8b of Scheme 8, Step 9b of Scheme 9, Step 9e, Step 9h and Step 9j, Step 11c of Scheme 11, Step 12b and Step 12c of Scheme 12, and Step 13b of Scheme 13 In the nuclear substitution reaction, the reaction temperature is from 0 to 150 ° C., the reaction time is usually from 1 to 24 hours, and the electrophilic agent {R ⁴⁴ -L ¹ , R ⁵ -L ¹ or L ¹¹ -CH ₂ CO ₂ R ⁶ } vs. The molar ratio of the nucleophile {compound 4 (R ⁴ = H), compound 5, [III], [VI], [IX], [VII], [XII], [XIII] or [II]} is usually 1 To 10;

The reaction can usually be carried out in the presence of a base and the molar ratio of base to electrophilizing agent is usually in the range of 1 to 10. Examples of bases include inorganic salts such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, potassium carbonate, sodium hydride, potassium hydride, silver oxide and the like, alkali metal alkoxides such as potassium-tert- Butoxide, sodium methoxide, sodium ethoxide and the like, alkaline earth metal alkoxide such as magnesium ethoxide, organic base such as pyridine, 2-picoline, 4-picolin, 4-dimethylaminopyridine, quinoline, triethylamine , Ethyldiisopropylamine, N, N-dimethylaniline, N, N-diethylaniline, and the like, and mixtures thereof.

If desired, a solvent may be used for the reaction. Examples of solvents are alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, etc. aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene and the like, organic base solvents such as Nitro compounds such as pyridine, triethylamine, N-methylaniline, N, N-dimethylaniline, N, N-diethylaniline and the like, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate and the like Solvents such as nitroethane, nitrobenzene and the like, nitrile solvents such as acetonitrile, isobutyro Trill et al., Include N, N- dimethylformamide, dimethyl sulfoxide, N, N- dimethyl-2-imidazolidinone, such as money, sulfolane, water, and mixtures thereof.

After completion of the reaction, the reaction solution may be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, may be further purified by recrystallization, distillation, chromatography, and the like to separate the target compound.

In the acetalization reaction of step 11a of Scheme 11, the reaction temperature is usually 0 to 150 ° C, and the reaction time is usually 1 to 24 hours.

When a compound is prepared in which R ¹¹ of compound [XI] is an alkyl group (eg, a C1-C5 alkyl group such as methyl group, ethyl group, propyl group, butyl group, etc.), the reaction reagent used to acetalize carbonyl compound [VIII] Is an alcohol compound represented by R ¹¹ 0H, and is used in an excess of 2 mol or more with respect to the carbonyl compound [VII].

When a compound in which two R ^{11 s} of the compound [XI] together represent an alkylene group (eg, a C2-C5 alkylene group such as an ethylene group, a 1,2-dimethylethylene group, a propylene group, or the like) is produced, a carbonyl compound [ The reaction reagent used for the acetalization of iii] is an alkylenediol compound corresponding to the acetal moiety and is used in excess of 1 mol relative to the carbonyl compound [iii].

The reaction is usually carried out in the presence of an acid catalyst and the molar ratio of acid catalyst to carbonyl compound [VII] is usually from 0.01 to 100. Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid and the like, carboxylic acids such as acetic acid, trifluoroacetic acid, oxalic acid, benzoic acid and the like, sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid , Lewis acids such as zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride, and the like, and mixtures thereof, such as methanesulfonic acid, trifluoromethanesulfonic acid, and the like. The acid catalyst may form salts with alkali metals such as sodium, potassium and the like, organic bases such as pyridine, triethylamine, N, N-dimethylaniline and the like. Examples are pyridinium p-toluenesulfonate and the like.

As reaction reagents orthoesters can be added in addition to the reactions to promote the reaction, the molar ratio of orthoesters to carbonyl compounds [XIII] used is from 1 to solvent as the solvent. Examples of orthoesters include methyl orthoformate, ethyl orthoformate and the like.

If desired, a solvent may be used for the reaction. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, and aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, Aromatic hydrocarbon solvents such as petroleum ether, such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, etc., organic acid solvents such as acetic acid, ester solvents such as ethyl formate, butyl acetate, Nitro compound solvents such as ethyl acetate, diethyl carbonate and the like, nitroethane, nitrobenzene and the like, nitrile solvents such as acetonitrile, isobutyronitrile and the like, N, N-dimethylformamide, dimethyl sulfoxide, N, N -Dimethyl-2-imidazolidon, sulfolane and the like, and mixtures thereof.

After completion of the reaction, the reaction solution may be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, may be further purified by recrystallization, distillation, chromatography, and the like to separate the target compound.

In step 8a of Scheme 8, step 11b of Scheme 11, and step 13a of Scheme 13, the reaction temperature is usually 0 to 150 ° C, the reaction time is usually 1 to 24 hours, and the reagent {O = YL ² used in the reaction. } The molar ratio of reagent {Compound 6, [XI] or [XIV]} is usually in the range from 1 to 100.

The reaction is carried out in the presence of a base. Examples of bases include inorganic bases such as sodium hydride, potassium hydride and the like, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium tert-butoxide and the like, alkaline earth metal alkoxides such as magnesium ethoxide and the like, and alkali metals Amides such as sodium amide, lithium amide, lithium diisopropylamide, sodium hexamethyldisilazide, lithium hexamethyldisilazide and the like, and mixtures thereof.

If desired, a solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride, monochlorobenzene, pyridine, triethylamine, N-methylaniline, N Organic base solvents such as N-dimethylaniline, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate, nitro compound solvents such as nitroethane, nitrobenzene, acetonitrile, isobutyronitrile and the like Such as nitrile solvent, N, N-dimethylformamide, dimeth Tilsulfoxide, N, N-dimethyl-2-imidazolidon, sulfolane and the like, and mixtures thereof.

After completion of the reaction, the reaction solution was treated with an aqueous acid solution such as dilute hydrochloric acid, subjected to usual post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, further purified by recrystallization, chromatography or the like to separate the target compound. Can be.

In the reaction of Step 10 of Scheme 10 and Step 11d of Scheme 11, the reaction temperature is usually 0 to 150 ° C, the reaction time is usually 1 to 24 hours, and alkylamine to alkyl ester represented by R ⁶ -NH ₂ {Compound 4 , (Y = N, Z = O) or [I] (Y = N, Z = O)} is usually 1 to 100.

If desired, a solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as dichloroethane, carbon tetrachloride, monochlorobenzene, nitro compound solvents such as nitroethane, nitrobenzene, aceto Nitrile solvents such as nitrile, isobutyronitrile, and the like, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane and the like, and mixtures thereof.

After completion of the reaction, the reaction solution is subjected to usual post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, further purified by recrystallization, chromatography or the like to separate the target compound.

In the reaction of Step 9a and Step 9g of Scheme 9, the reaction temperature is usually 0 to 150 ° C, and the reaction time is usually 1 to 24 hours. The molar ratio of 2-chloro-2- (hydroxyimino) acetate ester to Compound [II] or [VII] used in the reaction is from 1 to 10. Methods of preparing 2-chloro-2- (hydroxyimino) acetate esters are described, for example, in US Pat. No. 3584032.

The reaction is usually carried out in the presence of a base, and the molar ratio of base to compound [II] or [VII] is usually from 1 to 100. Inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, pyridine, 2-picoline, 4-picoline, 4-dimethylaminopyridine, Organic bases such as quinoline, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline, N, N-diethylaniline, and the like, and mixtures thereof.

If desired, a solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, pyridine, triethylamine, N-methylaniline Organic base solvents such as N, N-dimethylaniline, N, N-diethylaniline, etc., organic acid solvents such as acetic acid, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate, nitroethane, Nitro compound solvents such as nitrobenzene, acetonitrile, iso It comprises a nitrile solvent, N, N- dimethylformamide, dimethyl sulfoxide, N, N- dimethyl-2-imidazoline money, sulfolane, water and the like, and mixtures thereof, such as a tee nitrile.

After completion of the reaction, the reaction solution is subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, further purified by recrystallization, chromatography or the like to separate the target compound.

In step 13c of Scheme 13, when X represents an oxygen atom and X 'represents an oxygen ether group, when X represents a sulfur atom and X' represents a sulfur ether group, Or X is NR⁷(Where R⁷Group is as defined above and X 'is N (R⁷R²⁰Group, R²⁰When the group represents an acyl group such as t-butoxycarbonyl group, formyl group or acetyl group, the reaction is usually carried out in the presence of an acid. The reaction temperature is usually from 0 to 150 ° C, the reaction time is usually from 1 to 100 hours, and the molar ratio of acid to compound [XVI] is usually 0.001 to solvent as the capacity. Examples of acids to be used for the reaction include carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid, benzoic acid, sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid and the like. Inorganic acids such as sulfuric acid, nitric acid, hydrochloric acid, hydrobromic acid, perchloric acid, and the like, Lewis acids such as zinc chloride, aluminum chloride, boron trifluoride diethyl ether complex, trimethylsilyl chloride, trimethylsilyl iodide and the like, and mixtures thereof do.

If desired, a solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, etc., aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, ethyl formate, butyl acetate, ethyl acetate, Ester solvents such as diethyl carbonate, nitro compound solvents such as nitroethane, nitrobenzene, nitrile solvents such as acetonitrile, isobutyronitrile, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl 2-imidazolinedone, sulfolane, water and the like, and mixtures thereof It includes water.

After completion of the reaction, the reaction solution may be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent, and, if necessary, further purified by recrystallization, chromatography or the like to separate the target compound.

When X is an NR ⁷ group (wherein the R ⁷ group is defined above) and X 'represents a nitro group, step 13c includes the step represented by Scheme 14 below:

Wherein R ¹¹ , R ⁴⁴ , R ⁷ , T, U, V, W and L ¹ are as defined above and R ²¹ represents a hydrogen atom, an alkyl group such as a methyl group, a chloromethyl group, a trichloromethyl group and a trifluoro Haloalkyl groups such as the methyl group).

Process 14a is usually carried out in the presence of an acid using zinc, iron, tin or tin chloride. The reaction temperature is 0 to 150 ° C, and the reaction time is 1 to 100 hours. The molar ratio of acid to compound [VII] is 1 to solvent as provisional capacity. Examples of acids to be used for the reaction include carboxylic acids such as acetic acid, propionic acid, butyric acid, trifluoroacetic acid, pentafluoropropionic acid, sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, camphorsulfonic acid, sulfuric acid, nitric acid, hydrochloric acid, Inorganic acids such as hydrobromic acid and the like, and mixtures thereof.

If desired, a solvent may be used in the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, etc., aromatic hydrocarbon solvents such as toluene, xylene, etc., organic acid solvents such as acetic acid, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate, etc. And mixtures thereof.

After completion of the reaction, the reaction solution may be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent and, if necessary, separated into the target compound by additional purification such as recrystallization, chromatography and the like.

The acylation reaction of step 14b is carried out using an acylating agent such as R ²¹ COOH itself or its esters, acid halides or anhydrides. The molar ratio of acylating agent to compound [VII] is a potent capacity from 1 to solvent. The reaction temperature is usually in the range of 0 to 200 ° C, and the reaction time is usually 1 to 200 hours. The reaction can be carried out in the presence of an acid or base catalyst as necessary. The molar ratio of catalyst to starting compound [VII] is usually from 0.0001 to 100.

Examples of acid catalysts include inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid, sulfonic acids such as p-toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, zinc chloride, boron trifluoride diethyl ether complex, trimethylsilyl Lewis acids such as chlorides and the like, and mixtures thereof. The acid catalyst may form salts with alkali metals such as sodium, potassium, and the like, or organic bases such as pyridine, triethylamine, N, N-dimethylaniline, and the like. Examples thereof are pyridinium p-toluenesulfonate and the like.

Examples of base catalysts include inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, potassium hydroxide, barium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, sodium methoxide, sodium ethoxide, potassium tert-butoxide Alkali metal alkoxides such as seeds, alkaline earth metal alkoxides such as magnesium ethoxide, etc., sodium amides, lithium amides, lithium diisopropylamides, alkali metal amides such as sodium hexamethyldisilazide, lithium hexamethyldisilazide, pyridine , Organic bases such as 2-picolin, 4-picolin, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline, N, N-diethylaniline, and the like, and Mixtures. The base catalyst can form salts with inorganic acids such as hydrochloric acid, sulfuric acid and the like, carboxylic acids such as acetic acid, benzoic acid and the like, Lewis acids such as zinc chloride and the like. One example is sodium acetate.

If desired, a solvent may be used in the reaction. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether, aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, etc. Aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, etc., ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate, nitroethane, nitro Nitro compound solvents such as benzene, nitrile solvents such as acetonitrile, isobutyronitrile and the like, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane, water and the like, And mixtures thereof.

After completion of the reaction, the reaction solution can be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent and, if necessary, separated into the target compound by addition purification such as recrystallization, chromatography and the like.

In step 14c, the reaction temperature is usually in the range of 0 to 150 ° C, and the reaction time is usually 1 to 24 hours. The molar ratio of compound R ⁷ -L ¹ to compound [ ^VII ] is usually 1 to 10.

The reaction is usually carried out in the presence of a base and the molar ratio of base to compound R ⁷ -L ¹ is 1 to 10. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate, sodium hydride, potassium hydride, silver oxide and the like, potassium-tert-butoxide, sodium methoxide Alkali metal alkoxides such as sodium ethoxide, alkaline earth metal alkoxides such as magnesium ethoxide, pyridine, 2-picoline, 4-picoline, 4-dimethylaminopyridine, quinoline, triethylamine, ethyldiisopropylamine Organic bases such as N, N-dimethylaniline, N, N-diethylaniline, and the like, and mixtures thereof.

If desired, a solvent may be used for the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, pyridine, triethylamine, N-methylaniline Organic base solvents, such as N, N-dimethylaniline, N, N-diethylaniline, ester solvents such as ethyl formate, butyl acetate, ethyl acetate, diethyl carbonate, nitro compounds such as nitroethane, nitrobenzene and the like For nitrile such as solvent, acetonitrile, isobutyronitrile, etc. Medium, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane, water, and the like, and mixtures thereof.

After completion of the reaction, the reaction solution can be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent and, if necessary, separated into the target compound by addition purification such as recrystallization, chromatography and the like.

In process 14d which is a hydrolysis reaction, the reaction temperature is usually in the range of 0 to 150 ° C, and the reaction time is usually 1 to 24 hours. The reaction is usually carried out in the presence of a base or acid, and the molar ratio of base or acid to compound [VII] is usually from 0.001 to 1000. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, barium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium carbonate, calcium carbonate and the like, alkali metal alkoxy such as potassium-t-butoxide, sodium methoxide, sodium ethoxide and the like. , Alkaline earth metal alkoxides such as magnesium ethoxide and the like, and mixtures thereof.

Examples of acids include inorganic acids such as hydrochloric acid, perchloric acid, hydrobromic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, polyphosphoric acid, and the like, sulfonic acid such as p-toluenesulfonic acid, camphorsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, Lewis acids such as boron trifluoride diethyl ether complex, trimethylsilyl chloride, and the like, and mixtures thereof. Acids can form salts with alkali metals such as sodium, potassium, and the like, organic bases such as pyridine, triethylamine, N, N-dimethylaniline, and the like. Examples are pyridinium p-toluenesulfonate and the like.

If desired, a solvent may be used for the reaction. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, isopropanol and the like, ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tert-butyl methyl ether and the like, Aliphatic hydrocarbon solvents such as hexane, heptane, ligroin, petroleum ether, aromatic hydrocarbon solvents such as toluene, xylene, halogenated hydrocarbon solvents such as chloroform, dichloroethane, carbon tetrachloride, monochlorobenzene, pyridine, triethylamine, N-methylaniline Organic base solvents such as N, N-dimethylaniline, N, N-diethylaniline, nitro compound solvents such as nitroethane, nitrobenzene, nitrile solvents such as acetonitrile, isobutyronitrile, N, N-dimethylform Amide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane, water and the like, and mixtures thereof It includes.

After completion of the reaction, the reaction solution can be subjected to conventional post-treatment such as extraction, concentration, etc. with an organic solvent and, if necessary, separated into the target compound by addition purification such as recrystallization, chromatography and the like.

In the scheme 11, when X represents a sulfur atom, the compound [VII] can also be prepared according to Scheme 15, for example, by reacting the diazonium compound [XII] with a thiolate salt [XIII]. Diazonium salt [XII] can be manufactured by a well-known method.

Wherein R ¹ , R ⁶ , T. U, V, and W are as defined above, and L ⁻ represents a monoanion of a strong acid such as chlorine ion, bromine ion, or sulfate ion, nitrate ion, or the like. ).

When the present compounds are used as active ingredients for agricultural and / or horticultural antimicrobials, emulsifiable thickeners, water dispersible powders, suspensions, powders or powders are usually mixed with adjuvants for solid carriers, liquid carriers, surfactants or other formulations. It may be formulated into granules or used without the addition of other ingredients. These formulations contain, as active ingredient, the compound in a weight ratio of usually 0.1 to 99.9%, preferably 1 to 90%.

Examples of solid carriers used in the formulation include kaolin clay, attapulgite, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, corn cob powder, rhodium skin powder, urea, ammonium sulfate, synthetic hydrated silicon oxide, and the like. And fine powders or granules thereof; examples of liquid carriers include aromatic hydrocarbons such as xylene, methylnaphthalene, alcohols such as isopropanol, ethylene glycol, cellosolve, ketones such as acetone, cyclohexanone, isophorone, soybean oil and cottonseed oil. Vegetable oils such as dimethyl sulfoxide, acetonitrile, water and the like.

Examples of surfactants include anionic surfactants such as alkylsulfate salts, alkyl (aryl) sulfonate salts, dialkylsulfosuccinate salts, polyoxyethylene alkyl aryl ether phosphate salts, naphthalenesulfonate formalin condensates, and the like. Warm surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl polyoxypropylene block copolymers, sorbitan fatty acid esters and the like.

Examples of adjuvants for formulation include lignin sulfonate salts, alginate salts, polyvinyl alcohols, gum arabic, CMC (carboxymethyl cellulose), PAP (isopropyl acid phosphate) and the like.

The compounds can be used by any method of application known to those skilled in the art, for example by leaf application, soil treatment, seed infection.

When the compound is used as an active ingredient for agricultural and / or horticultural antimicrobials, the amount of the compound applied depends on the type of plant to be tested (crops, etc.), the type of the disease, the extent of the disease, the formulation, the method of application, the application time and the climatic conditions. And usually 0.01 to 50 g / ar, preferably 0.05 to 10 g / ar.

When emulsifiable thickeners, water-dispersible powders, suspending agents and the like are applied after dilution with water, the application concentration of the compound is usually 0.0001 to 0.5%, preferably 0.0005 to 0.2%, and powders, granules and the like are themselves Is applied without dilution.

The compounds can be used as agricultural and / or horticultural fungicides for farmland, fields, orchards, tea plantations, grasslands, grasses, and potential antimicrobial effects can be expected by use in combination with other agricultural and / or horticultural antimicrobials. have. Examples of other agricultural and horticultural antimicrobials include azole antibacterial compounds such as propiconazole, triadimenol, prochloraz, fenconazole, tebuconazole, flusilazole, diconiconazole, bromoconazole, epoxyconazole, dipe Noconazole, cyproconazole, metconazole, triflumiazole, tetraconazole, michaelrobutanyl, fenbuconazole, hexaconazole, fluquinconazole, triticonazole (RPA 400727), bitteranol, forehead Cyclic amine antimicrobial compounds, such as zulil, flutriafol, such as phenpropimorph, tridemorph, fenpropidine, and benzimidazole antimicrobial compounds, such as carbendazim, benomil, thibendazole, thiophanate Methyl etc., procymidone, cyprodinyl, pyrimethanyl, dietofencarb, thiuram, fluazinam, mancozeb, ifprodione, vinclozoline, chlorothalonil, captan, mepanipyrim, fenpiclo Neil, Fludiozonyl, Decle Fluanide, polpet, cresoxime-methyl (or methyl methoxyimino-α- (o-tolyloxy) -o-tolylacetate or BAS490F), azoxystrobin (or methyl (E)-{2- [6 -(2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3-methoxyacrylate, or ICIA5504), N-methyl-α-methoxyimino-2-[(2,5-dimethyl Phenoxy) methyl] phenylacetamide and the like. In addition, the present compound can be used in combination or mixed with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers and the like.

Examples of plant diseases that can be inhibited by the present compounds are as follows:

Rice blast (Pyricularia oryzae), sesame seed disease (Cochliobolus miyabeanus) and leaf blight (Rhizoctonia solani),

Cereal powdery mildew (Erysiphe graminis), red fungal disease (Gibberella zeae), rust disease (Puccinia striiformis, P. graminis, P. recondita, P. hordei), eye rot (Typhula sp., Micronectriella nivalis) Ustilago tritici (U. nuda), Tilletia caries, icespots (eyespot, Pseudocercosporella herpotrichoides), cloud disease (Rhynchosporium secalis), spot disease (Septoria tritici) and bark (Leptosphaeria nodorum),

Resin (Diaporthe citri), tangerine (Elsinoe fawcetti) and green mold disease (Penicillium digitatum, P. italicum) of tangerine,

Apple rot (Sclerotinia mali), ovule (Valsa mali), powdery mildew (Podosphaera leucotricha), spotted deciduous disease (Alternaria mali) and black star (Venturia inaequalis),

Black star disease (Venturia nashicola, V. pirina), black pattern disease (Alternaria kikuchiana) and red star disease (Gymnosporandium haraeanum)

Peach brown rot (Sclerotinia cinerea), beetle disease (scab, Cladosporium carpophilum) and stem blight (phomopsis rot, Phomopsis sp.),

Grape Eyelid Disease (Elsinoe ampelina), Anthrax (Glomerella cingulata), Powdery mildew (Uncinula necator), Rust (Phakopsora amelopsidis), Black rot (Guignardia biwellii), and Plasmopara viticola,

Anthrax (Gloeosporium kaki) and deciduous diseases (Cercospora kaki, Mycosphaerelle nawae),

Park's anthrax (Colletotrichum lagenarium), powdery mildew (Sphaerotheca fuliginea), gummy stem blight, Mycosphaerella melonis, Fusarium oxysporum, Pseudoperonospora cubensis, late blight (Phytoththora sp. ),

Tomato leaf blight (Alternaria solani), leaf fungus (Cladosporium fulvum) and late blight (Phytophthora infestans),

Brown pattern disease (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum),

Cruciferous Black Pattern Disease (Alternaria japonica) and White Pattern Disease (Cercosporella brassicae),

Rust of green onions (Puccinia allii),

Cercospora kikuchii, soybean disease (Elsinoe glycines) and mummies (Diaporthe phaseolorum var. Sajae.),

Anthrax (Collectotrichum lindemthianum) of kidney beans,

Peanut black pattern disease (Cercospora personata) and spot leaf spot (Cercospora arachidocola),

Powdery mildew (Erysiphe pisi),

Potato plaque (Alternaria solani) and late blight (Phytophthora infestans),

Powdery mildew (Sphaerotheca humuli),

Tea's net blister blight (Exobasidium reticulatum) and white scab (Elsinoe leucospila),

Tobacco red star disease (Alternaria longipes), powdery mildew (Erysiphe cichoracearum), anthrax (Collectotrichum tabacum), fungal disease (Peronospora tabacina) and late blight (Phytophthora nicotianae),

Beet spots (leaf spot, Cercospora beticola),

Rose spot (Dipolocarpon rosae) and powdery mildew (Sphaerotheca pannosa),

Chrysanthemum spots (Sepotoria chrysanthemiindici) and white rust (Puccinia horiana), and

Asy mildew disease (Botrytis cinerea) and Sclerotinia sclerotiorum of various crops.

If the present compounds are used as active ingredients for insecticides and / or pesticides, they can be used without the addition of any other ingredients. However, they are usually formulated into oil solutions, emulsifying concentrates, water dispersible powders, flow agents, granules, powders, aerosols, fumigants (such as aerosols), toxic baits, or the like, or by solid carriers, liquid carriers, gas carriers, By mixing with bait or the like and, if desired, by adding a surfactant or other formulation aid.

These formulations contain, as active ingredients, the compound in a proportion of usually 0.01 to 95% by weight.

Examples of solid carriers used for the formulation include clay (e.g. kaolin clay, diatomaceous earth, synthetic hydrated silicon oxide, bentonite, fubasami clay, acid clay, etc.), talc, ceramic or other inorganic minerals (e.g., sericite, Fine powders or granules of quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), chemical fertilizers (such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride, etc.). Examples of liquid carriers include water, alcohols (e.g., methanol, ethanol, etc.), ketones (e.g., acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, methylnaphthalene, etc.), Aliphatic hydrocarbons (e.g. hexane, cyclohexane, kerosine, light oil, etc.), esters (e.g. ethyl acetate, butyl acetate, etc.), nitriles (e.g. acetonitrile, isobutyronitrile, etc.), ethers (e.g. diisopropyl Ethers, dioxanes, and the like), acid amides (e.g., N, N-dimethylformamide, N, N-dimethylacetamide, etc.), halogenated hydrocarbons (e.g., dichloromethane, trichloroethane, carbon tetrachloride, etc.), dimethyl sulfoxide , Vegetable oils such as soybean oil, cottonseed oil and the like. Examples of gas carriers, ie propellants, are flan gas, butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbonic acid gas and the like.

Examples of surfactants are alkylsulfate salts, alkylsulfonate salts, alkylarylsulfonate salts, alkyl aryl ethers and polyoxyethylene compounds thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives and the like.

Examples of formulation aids such as adhesives and dispersants include casein, gelatin, polysaccharides (eg, starch powder, gum arabic, cellulose derivatives, alginic acid, etc.), lignin derivatives, bentonides, sugars, synthetic water soluble polymers (eg, polyvinyl alcohol , Polyvinyl pyrrolidone, polyacrylic acid, and the like). Examples of stabilizers include PAP (acid isopropyl phosphate), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tert-butyl Mixtures of 4-methoxyphenol), vegetable oils, mineral oils, surfactants, and fatty acids or esters thereof.

Examples of toxic bait base materials include bait components such as cereal powders, vegetable oils, sugars, crystalline celluloses and the like, antioxidants such as dibutylhydroxytoluene, nordihydroguaiaretic acid, etc. And misuse-preventing substances such as dehydroacetic acid, such as red pepper powder, aggressive flavoring agents such as cheese flavor, onion flavor and the like.

The preparation thus prepared is used on its own or after dilution with water or the like. Alternatively, the formulation may be used in combination or in combination with other pesticides, nematicides, mites, antibacterials, herbicides, plant growth regulators, synergists, fertilizers, soil conditioners, animal feeds and the like.

Pesticides and / or nematicides and / or mites are for example organophosphorus compounds such as phenythrothione [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphothioate], Pention [O, O-dimethyl O- (3-methyl-4- (methylthio) phenyl) phosphothioate], diazinone [O, O-diethyl-0-2-isopropyl-6-methylpyridine Midin-4-ylphosphothioate], chlorpyriphos [O, O-diethyl-0-3,5,6-trichloro-2-pyridylphosphothioate], acetate [0, S- Dimethylacetylphosphoroamidothioate], methidathione [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-ylmethyl 0,0- Dimethylphosphorodithioate], disulfotone [O, O-diethyl S-2-ethylthioethylphosphorothioate], DDVP [2,2-dichlorovinyldimethylphosphate], sulfpropos [0-ethyl 0 -4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophosph [0-4-cyanophenyl O, O-dimethylfo Sporothioate], Dioxabenzo phosphate [2-methoxy-4H-1,3,2-benzodioxaphosphinine-2-sulfide], Dimethoate [O, O-dimethyl-S- (N -Methylcarbamoylmethyl) dithiophosphate], pentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], tri Chlorone [dimethyl 2,2,2-trichloro-1-hydroxyethylphosphonate], azine force-methyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazine -3-ylmethyl 0,0-dimethylphosphorodithioate], monocrotophosph [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinylphosphate], ethion [0,0,0 ', 0'-tetraethyl S, S'-methylenebis (phosphorodithioate)], and phosphothiazate [N- (0-methyl-S-sec-butyl) phosphorylthiazolidine-2- On); Carbamate compounds such as BPMC (2-sec-butylphenylmethylcarbamate), benfuracarb [ethyl N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbo Nyl (methyl) aminothio] -N-isopropyl-β-alanineate], propoxur [2-isopropoxyphenyl N-methylcarbamate], carbosulfan [2,3-dihydro-2 , 2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamate], carbaryl [1-naphthyl-N-methylcarbamate], methyl [S-methyl -N-[(methylcarbamoyl) oxy] thioacetimidae], thiophencarb [2- (ethylthiomethyl) phenylmethylcarbamate], aldicarb [2-methyl-2- (methylthio ) Propionaldehyde O-methylcarbamoyloxime], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], and phenothiocarb [S-4 Phenoxybutyl-N, N-dimethylthiocarbamate; Pyrethroid compounds such as etofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzylether], penvalerate [(RS) -α-cyano-3-phenoxy Benzyl (RS) -2- (4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl ) -3-methylbutyrate], phenpropatrine [(RS) -α-cyano-3-phenoxybenzyl 2,2,3,3-tetramethylcyclopropanecarboxylate], cypermethrin [(RS) -α-cyano-3-phenoxybenzyl (1RS, 3RS)-3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzyl ( 1RS, 3RS) -3- (2,2-dichlorovinyl) -2,2-dimethylcyclopropanecarboxylate], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z) -(1RS, 3RS) -3- (2-chloro-3,3,3-prefluoropropenyl) -2,2-dimethylcyclopropanecarboxylate], deltamethrin [(S) -α-sia No-m-phenoxybenzyl (1R, 3R) -3- (2,2-di Lomovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprotrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-e) Methoxyphenyl) cyclopropanecarboxylate], fluvalinate [α-cyano-3-phenoxybenzyl N- (2-chloro-α, α, α-trifluoro-p-tolyl) -D-valinate ], Bifenthrin [2-methylbiphenyl-3-ylmethyl (Z)-(1RS) -cis-3- (2-chloro-3,3,3-trifluoroprop-1-enyl) -2 , 2-dimethylcyclopropanecarboxylate], acrinatrin [cyano- (3-phenoxyphenyl) methyl [1R- {1α (S ^* ), 3α (Z)}]-2,2-dimethyl-3 -[3-oxo-3- (2,2,2-trifluoro-1- (trifluoromethyl) ethoxy-1-propenyl) cyclopropanecarboxylate], 2-methyl-2- (4 -Bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin [(S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (1,2,2 , 2-tetrabromoethyl) -2,2-dimethylcyclopropanecarboxylate, And silafluorophene [4-ethoxylphenyl [3- (4-fluoro-3-phenoxyphenyl) propyl] dimethylsilane]; Thiadiazine derivatives such as bupropezin (2-tert-butylimino-3-isopropyl-5-phenyl-1,3,5-triazinazin-4-one; nitroimidazolidine derivatives such as Imidacloprid [1- (6-chloro-3-pyridylmethyl) -N-nitroimidazolidine-2-ylideneamine]; neracetoxin derivatives such as cartopes [S, S '-(2- Dimethylaminotrimethylene) bis (thiocarbamate)], thiocyclam [N, N-dimethyl-1,2,3-tritian-5-ylamine], and bensultap [S, S'-2- Dimethylaminotrimethylene di (benzenethiosulfonate)] N-cyanoamidine derivatives such as N-cyano-N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine; Chlorinated hydrocarbon compounds, such as endosulfan [6,7,8,9,10,10-hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,4 , 3-benzodioxathiepine oxide], gamma-BHC [1,2,3,4,5,6-hexachlorocyclohexane], and 1,1-bis (chlorophenyl) -2,2,2- Trichloroethanol; Benzoylphenylurea compounds such as chlorfluazuron [1- (3,5-dichloro-4- (3-chloro-5-trifluoromethylpyridin-2-yloxy) phenyl) -3- (2,6 -Difluorobenzoyl) urea], teflubenzuron [1- (3,5-dichloro-2,4-difluorophenyl) -3- (2,6-difluorobenzoyl) urea], and fulfe Noxrone [1- (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl) -3- (2,6-difluorobenzoyl) urea]; formamidine derivatives, For example, amitraz [N, N '-[(methylimino) dimethylidene] -di-2,4-xylidene], and chlordimeform [N'-(4-chloro-2-methylphenyl) -N Thiourea derivatives, such as diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N'-tert-butylcarbodiimide], phenyl Pyrazole Compound, Tevfenozide [N-tert-butyl-N '-(4-ethylbenzoyl) -3,5-dimethylbenzohydrazide], 4-bromo-2- (4-chlorophenyl) -1 -Ethoxymethyl-5-tree Fluoromethylpyrrole-3-carbonitrile, bromopropylate [isopropyl 4,4'-dibromobenzylate], tetradipon [4-chlorophenyl 2,4,5-trichlorophenylsulphone], quinome Thionate [S, S-6-methylquinoxaline-2,3-diyldithiocarbonate], propargate [2- (4-tert-butylphenoxy) cyclohexyl prop-2-yl sulfite] , Fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] oxide], hexythiaxose [(4RS, 5RS) -5- (4-chlorophenyl) -N-chlorohexyl -4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], clofentezin [3,6-bis (2-chlorophenyl) -1,2,4,5-tetrazine ], Pyridathiobene [2-tert-butyl-5- (4-tert-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], penpyoxymate [tert-butyl (E)- 4-[(1,3-dimethyl-5-phenoxypyrazol-4-yl) methyleneaminooxymethyl] -benzoate], tevfenpyrad [N-4-tert-butylbenzyl] -4-chloro-3 -Ethyl-1-methyl-5-pyrazolecarboxami ], Polynactin complexes [eg, tetranactin, dinactin, trinectin], milbectin, avermectin, ivermectin, azadillactin [AZAD], pyrimidipene [5-chloro-N- [2- { 4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidin-4-amine], pymetrozine [2,3,4,5-tetrahydro-3-oxo 4-[(pyridin-3-yl) methyleneamino] -6-methyl-1,2,4-triazine.

When the present compounds are used as agricultural pesticides and / or mites, the application amount is usually 0.1 to 100 g / 10. When emulsifiable thickeners, water dispersible powders, flow agents and the like are used after dilution with water, the application concentration is usually from 0.1 to 5000 ppm. Granules, powders and the like are not diluted but are used as a preparation in themselves. When the present compounds are used as epidemic pesticides and / or mites, emulsifying thickeners, water dispersible powders, flow agents and the like are usually applied after dilution with 0.1 to 5000 ppm with water, oil solutions, aerosols , Fumigants, toxic baits, etc., apply by themselves.

These doses and concentrations may vary depending on the type of preparation, the time of application, the place of application, the method of application, the type of pest, the degree of damage, etc., and may increase or decrease outside the above ranges.

Pests and harmful mites, and mites, for which the present compounds exhibit control activity, may include, for example:

Hemiptera:

Delphacidae such as Laodelphax striatellus, Nilaparvata lugens, Sogatella furcifera; Deltocephalidae such as Nephotettix cincticeps and Nephotettix virescense; Aphididae, Pentatomidae, Aleyrodidae, Coccidae, Tingidae, Psyllidae

Lepidoptera:

Pyralidae such as Chilo suppressalis, Cnaphalocrocis medinalis and Plodia interpunctella; Chestnut moth (Noctuidae), for example, Spodoptera litura, moss (Pseudaletia separata) and moth (Mamestra brassicae); For example, Adoxophyes spp .; Carnivorous moth (Carposinidae); Oyster moth (Lyonetiidae); Poison moth (Lymantriidae); Plusiae; Agrothis spp. Such as Agrothis segetum and Agrothis ipsilon; Heliothis spp .; Chinese cabbage moth (Plutella xylostella); Clothespin moth (Tinea pellionella); Webbing clothes moth, Tineola bisselliella

Diptera:

Mosquitos (Calicidae) such as common mosquito, Culex pipiens pallens and Culex tritaeniorhynchus; Aedes spp. Such as Aedes aegypti and Aedes albopictus; Anopheles spp. Such as Anopheles sinensis; Mosquito (Chironomidae); Muscidae such as Musca domestica and false stablefly (Muscina stabulans); Calliphoridae; Sarcophagidae; Anthomyiidae such as lesser housefly, Fannia canicularis, Hylemya platura and Delia antigue; Fruit Fly (Tephritidae); Drosophilidae; Moths (Psychodidiae); Hornbill (Simuliidae); Tabanidae; Chimpanzee (Stomoxyidae)

Coleoptera:

Corn rootworms such as Cornflower rootworm (Diabrotica virgifora) and Twelve pointed pumpkin leaf worms (Diabrotica undecimipunctata); Scarabaeidae such as the copper beetle (Anomala cuprea) and the beetle (Anomala rufocuprea); Cureulionidae such as corn weevil (Sitophilus zeamalis), rice weevil (Lissorhoptrus oryzophilus) and red bean weevil (Callosobruchys chineneis); Tenebrionidae such as the brownie (Tenebrio moliter) and the Night Rice Thief (Tribolium castaneum); Chrysomelidae such as the flea leaf beetle (Phyllotrata stroilata) and the cucumber leaf beetle (Aulacophora femoralis); Comb, Anobiidae; Ladybug (Epilachna spp.) Such as ladybug (Epilachna vigintioctopunctata); Lycotidae (Lyctidae); Dogwood (Bostrychidae); Ceramysidae, Paederus fuscipes

Dictyoptera:

Wheels (Blattella germanica), wheels (Periplaneta fuliginosa), wheels (Perilplaneta americana), brown wheels (brown cockroach, Periplaneta brunnea), and wings (Blatta orientalis)

Thysanoptera:

Thrips palmi and Hawaiian shepherd (Thrips hawaiiensis)

Logging (Hymenoptera):

Formicidae; Wasps (Vespidae); Bethylidae; Tenthredinidae, for example, Athalia rosae japonensis

Grasshopper (Orthoptera):

Ground dog (Gryllotalpidae); Grasshopper (Acrididae)

Aphaniptera:

Purex irritans

Anoplura:

Tooth (Pediculus humanus capitis), quadrilateral (Phthirus pubis)

Termite (Isoptera):

Termites (Reticulitermes speratus), Formosan subterranean termite (Coptotermes formosanus)

Acarina:

Phytoparasitic mites such as Tetranychus urticae, Panonychus citri, Tetranychus cinnabarinus and Panonychus ulmi, animal parasitic mite (Ixodes) such as Boophilus microphus, and house dust mites.

The compounds are also effective in controlling pests that are resistant to conventional insecticides or acaricides.

The following preparations, formulations and test examples describe the invention in detail, but do not limit the scope of the invention.

Preparation Example 1 [Example of Step 7c of Scheme 7]

Methyl 2- (N-methyl-3-acetylanilino) -3-methoxyacrylate (prepared according to Reference Example 1 below) 0.2 g (0.76 mmol), methoxylamine hydrochloride 0.07 g (0.84 mmol), pyridine 0.1 ml (1.2 mmol) and 2 ml of methanol were mixed at room temperature and the mixture was stirred for 3 hours. The reaction mixture was concentrated under reduced pressure and the resulting residue was partitioned between 10 mL ethyl acetate and 10 mL dilute hydrochloric acid. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and the residue obtained by concentration under reduced pressure was subjected to silica gel column chromatography to obtain the desired methyl 2- {N-methyl-3- (1- 0.2 g (0.68 mmol) of methoxyiminoethyl) anilino} -3-methoxyacrylate (this compound 2) were obtained.

Preparation Example 2 [Example of Step 7a of Scheme 7]

Methyl 2- (N-methyl-3-acetylanilino) -3-methoxyacrylate (prepared according to Reference Example 1 below) 0.4 g (1.5 mmol), hydroxylamine hydrochloride 0.12 g (1.7 mmol), pyridine 0.15 mL (1.9 mmol) and 5 mL of methanol were mixed at room temperature and the mixture was stirred overnight. The reaction mixture was concentrated under reduced pressure and the resulting residue was partitioned between 30 ml of ethyl acetate and 30 ml of dilute hydrochloric acid. The organic layer was washed once with dilute hydrochloric acid and once with water, concentrated under reduced pressure, and the desired methyl 2- {N-methyl-3- (1-hydroxyiminoethyl) anilino} -3-methoxyacrylate ( 0.4 g (1.4 mmol) of the present compound 3 was obtained.

Preparation Example 3 [Example of Step 7b of Scheme 7]

A mixture of 24 mg (1.0 mmol) sodium hydride and 2 ml of N, N-dimethylformamide was added to methyl 2- {N-methyl-3- (1-hydroxyiminoethyl) anilino} -3-methoxyacrylate ( Compound 3: Prepared in Preparation Example 2) 0.2 g (0.72 mmol) of a 0.5 ml solution of N, N-dimethylformamide was added at a time with stirring at room temperature, followed by stirring at room temperature for 1 hour. Subsequently, 0.1 ml (0.84 mmol) of benzyl bromide was added at one time at room temperature and then stirred at room temperature for 3 hours. The reaction mixture was poured into 10 ml of a mixture of ice and dilute hydrochloric acid, and extracted with 10 ml of ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to give 0.2 g (0.54) of the desired methyl 2- {N-methyl-3- (1-benzyloxyiminoethyl) anilino} -3-methoxyacrylate (Compound 4). mmol) was obtained.

Preparation Example 4 [Example of Step 7c of Scheme 7]

N-methyl-2- (N-methyl-3-acetylanilino) -2-methoxyiminoacetamide (prepared in Reference Example 2 below) 0.10 g (0.39 mmol), 40 mg (0.48) methoxylamine hydrochloride mmol), pyridine 0.063 mL (0.78 mmol) and 2.0 mL methanol were stirred overnight at room temperature. The resulting mixture was concentrated and the residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated to give the desired N-methyl-2- {N-methyl-3- (1-methoxyiminoethyl) anilino} -2-methion. 0.11 g (0.38 mmol) of oxyiminoacetamide (this compound 31) was obtained.

Preparation Example 5 [Example of Step 7c of Scheme 7]

Methyl 2- (3-acetylphenoxy) -3-methoxyacrylate (prepared in Reference Example 3 below) 0.20 g (0.80 mmol), 0.20 g (1.3 mmol) 0-benzylhydroxyamine hydrochloride, 0.080 mL pyridine (1.0 mmol) and 1 ml of methanol were stirred overnight at room temperature. The resulting reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {3- (1-benzyloxyiminoethyl) phenoxy} -3-methoxyacrylate (this compound 12 ) 0.25 g (0.70 mmol) was obtained.

Preparation Example 6 (Example of Step 12d of Scheme 12 and Example of Step 8a and Step 8b of Scheme 8)

(i) [Example of Step 12d of Scheme 12]

Methyl 2- (N-methyl-3-formylanilino) acetate (prepared in Reference Example 4 below) 0.50 g (2.4 mmol), 0-benzylhydroxylamine hydrochloride 0.40 g (2.5 mmol), pyridine 0.20 mL ( 2.5 mmol) and 5 ml of methanol were stirred overnight at room temperature and concentrated. The residue was partitioned between ethyl acetate and dilute hydrochloric acid, and the organic layer was washed with aqueous sodium bicarbonate solution and dried over magnesium sulfate. Concentration gave 0.74 g (2.4 mmol) of the desired methyl 2- {N-methyl-3- (benzyloxyiminomethyl) anilino} acetate (example of the intermediate represented by compound 6).

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 8.09 (1H, s), 7.1-7.5 (7H), 6.9-7.0 (2H), 6.69 (1H, br.d), 5.21 (2H, s), 4.08 (2H, s), 3.71 (3H, s), 3.07 (3H, s)

(Ii) [Example of Step 8a of Scheme 8]

Methyl 2- {N-methyl-3- (benzyloxyiminomethyl) anilino} acetate 0.74 g (2.4 mmol), methyl formate 1.0 mL (16 mmol), sodium hydride 0.10 g (4.2 mmol) and N, N- 8 ml of dimethylformamide was stirred at room temperature for 2 hours. The resulting mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid and extracted twice with aqueous sodium carbonate solution. The resulting basic aqueous solution was adjusted to pH 6 with concentrated hydrochloric acid. The precipitated organics were extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated to give the desired methyl 3-hydroxy-2- {N-methyl-3- (benzyloxyiminomethyl) anilino} acrylate (example of intermediate represented by compound 5) 50 mg (0.13 mmol) was obtained.

(Iii) [Example of Step 8b of Scheme 8]

1.0 ml (16 mmol) of methyl iodide, 1.0 g (7.2 mmol) of potassium carbonate and 4 ml of N, N-dimethylformamide were added to methyl 3-hydroxy-2- {N-methyl-3- (benzyloxyiminomethyl ) Anilino} acrylate was added to 50 mg (0.13 mmol) and stirred overnight at room temperature. The resulting mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated to obtain a residue obtained by silica gel column chromatography, and the desired methyl 2- {N-methyl-3- (benzyloxyiminomethyl ) 50 mg (0.13 mmol) of anilino)}-3-methoxyacrylate (this compound 1) were obtained.

Preparation Example 7 [Example of Step 7c of Scheme 7 (Step 9c of Scheme 9)]

Methyl 2- (N-methyl-3-acetylanilino) -2-methoxyiminoacetate [prepared in Reference Example 2 (ii) below] 0.18 g (0.67 mmol), hydroxylamine-O-benzyl ether hydrochloride 0.13 g (0.81 mmol), 0.11 mL (1.4 mmol) of pyridine and 2.0 mL of methanol were stirred overnight at room temperature. The resulting mixture was concentrated and the residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {N-methyl-3- (1-benzyloxyiminoethyl) anilino} -2 0.24 g (0.65 mmol) of -methoxyiminoacetate (this compound 199) were obtained.

Preparation Example 8 [Example of Step 7c of Scheme 7]

Methyl 2- (3-acetylphenylthio) -3-methoxyacrylate [prepared in Reference Example 5] 0.20 g (0.75 mmol), 0-benzylhydroxylamine hydrochloride 0.13 g (0.81 mmol), pyridine 0.073 mL (0.9 mmol) and 2.0 ml of methanol were stirred overnight at room temperature. The resulting reaction mixture was concentrated and the resulting residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to the desired methyl 2- {3- (1-benzyloxyiminoethyl) phenylthio} -3-methoxyacrylate (this compound 209 ) 0.23 g (0.65 mmol) was obtained.

Preparation Example 9 [Examples of Step 8a and Step 8b of Scheme 8]

Methyl 2- {3- (1-benzyloxyiminoethyl) -6-chlorophenoxy} acetate instead of methyl 2- {N-methyl-3- (benzyloxyiminomethyl) anilino} acetate as starting material [see below] Preparation Example 6], except that in the same manner as in Preparation Example 6 (ii) and (iii) to the target methyl 2- {3- (1-benzyloxyiminoethyl) -6-chlorophenoxy} -3 -Methoxyacrylate (This Compound 132) was obtained.

Preparation Example 10 [Example of Step 8b of Scheme 8]

2- [3- {N-methyl-N- (methyl 3-hydroxyacrylate-2-yl) amino} phenyl] -2-methoxyiminoacetonitrile (prepared in Reference Example 7 below) 119 mg (0.412) mmol), potassium carbonate 100 mg (0.724 mmol), 0.05 mL (0.8 mmol) methyl iodide and 1 mL dimethylformamide were stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid, extracted with ethyl acetate, and the organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to the desired 2- [3- {N-methyl-N- ( 120 mg (0.396 mmol) of methyl 3-methoxylacrylate-2-yl) amino} phenyl] -2-methoxyiminoacetonitrile (this compound 272) were obtained.

Preparation Example 11 [Example of Step 7b of Scheme 7]

Methyl 2- {3- (1-hydroxyiminoethyl) phenoxy} -3-methoxyacrylate [prepared in Reference Example 8] 500 mg (1.89 mmol), 2,3-dichloro-5-trifluoro 408 mg (1.89 mmol) of methylpyridine, 300 mg (2.17 mmol) of potassium carbonate and 3 ml of N, N-dimethylformamide were stirred for 2 hours with heating to 100 ° C. and the resulting mixture was poured into diluted hydrochloric acid, and diluted with ethyl acetate. Extracted. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, and the residue obtained by concentration was purified by silica gel column chromatography to give the desired methyl 2- [3- {1- (3-chloro-5-trifluoromethylpyridine 800 mg (1.80 mmol) of 2-yl) oxyiminoethyl} phenoxy] -3-methoxyacrylate (this compound 116) were obtained.

Preparation Example 12 [Example of Step 7b of Scheme 7]

Methyl 2- {N-methyl-3- (1-hydroxyiminoethyl) anilino} -3-methoxyacrylate [Prepared in Preparation Example 2 (This Compound 3)] 500 mg (1.80 mmol), 2,3 A mixture obtained by stirring 389 mg (1.80 mmol) of dichloro-5-trifluoromethylpyridine, 300 mg (2.17 mmol) of potassium carbonate and 3 ml of N, N-dimethylformamide for 2 hours while heating to 100 ° C. Poured into diluted hydrochloric acid and extracted with ethyl acetate. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, and the residue obtained by concentration was purified by silica gel column chromatography, and the desired methyl 2- [N-methyl-3- {l- (3-chloro-5-tri 800 mg (1.75 mmol) of fluoromethylpyridin-2-yl) oxyiminoethyl} anilino] -3-methoxyacrylate (this compound 252) were obtained.

Preparation Example 13 [Example of Step 8b of Scheme 8]

15 g (about 41 mmol) of crude product of methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -3-hydroxyacrylate [prepared in Reference Example 9], methyl iodide A mixture of 8.8 g (62 mmol), 9.7 g (70 mmol) of potassium carbonate and 100 mL of N, N-dimethylformamide was stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated crude crystals were washed with hexane, filtered and dried to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate (this compound 215) 9.8 g (27 mmol) was obtained.

Preparation Example 14 [Example of Step 7c of Scheme 7]

Methyl 2- (5-acetyl-2-methylphenoxy) -3-methoxyacrylate [Prepared in Reference Example 10] 0.12 g (0.47 mmol), 0.12 g (0.76 mmol) 0-benzylhydroxyamine hydrochloride , 0.046 mL (0.58 mmol) of pyridine and 0.6 mL of methanol were stirred at room temperature for 5 hours. The resulting reaction mixture was concentrated and the resulting residue was partitioned between ethyl acetate and water. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy}- 0.15 g (0.41 mmol) of 3-methoxyacrylate (this compound 215) were obtained.

Preparation Example 15

1.0 g (about 2.7 mmol) of crude product of methyl 2- {5- (1-benzyloxyiminoethyl) -2-ethylphenoxy} -3-hydroxyacrylate [prepared in Reference Example 11] below, methyl iodide 0.59 g (4.1 mmol) of potassium, 0.64 g (4.6 mmol) of potassium carbonate and 6 mL of N, N-dimethylformamide were stirred at room temperature for 1 hour. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to obtain 0.36 g of target methyl 2- {5- (1-benzyloxyiminoethyl) -2-ethylphenoxy} -3-methoxyacrylate (this compound 216) ( 1.0 mmol) was obtained.

Preparation Example 16

Methyl 2- (5-acetyl-2-methyl-phenylthio) -3-methoxyacrylate [prepared in Reference Example 12] 0.28 g (1.0 mmol), 0.17 g (1.1 mmol) 0-benzylhydroxyamine hydrochloride ), Pyridine 0.10 g (1.2 mmol) and 6 mL of methanol were stirred overnight at room temperature. The resulting reaction mixture was concentrated and the residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methyl-phenylthio} -3-methoxyacrylic. 0.35 g (0.91 mmol) of the rate (this compound 217) were obtained.

Preparation Example 17

Methyl 2- (5-acetyl-2-methyl-phenylthio) -2- (methoxyimino) acetate [prepared in Reference Example 13] 0.70 g (2.5 mmol), 0.65 g of 0-benzylhydroxyamine hydrochloride ( 4.0 mmol), pyridine 0.25 g (3.1 mmol) and 4 ml of methanol were stirred at room temperature for 1 hour. The resulting reaction mixture was concentrated and the resulting residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methyl-phenylthio} -2- (methoxy 0.88 g (2.3 mmol) of mino) acetate (this compound 232) were obtained.

Preparation Example 18

0.40 g (1.0 mmol) of methyl 2- {5- (1-benzyloxyiminoethyl) -2-methyl-phenylthio} -2- (methoxyimino) acetate [Prepared in Preparation 17 (this compound 232)], A mixture of 3 ml of methanol and 2.3 g (29 mmol) of a 40% solution of methylamine in methanol was stirred at room temperature for 1 hour. The resulting reaction mixture was filtered and the filtrate was concentrated to give the desired N-methyl-2- {5- (1-benzyloxyiminoethyl) -2-methyl-phenylthio} -2- (methoxyimino) acetamide Compound 233) 0.40 g (1.0 mmol) was obtained.

Preparation Example 19

Methyl 2- (5-acetyl-2-methylphenoxy) -2- (methoxyimino) acetate [prepared in Reference Example 14] 24 mg (0.091 mmol), 0 mg of benzylhydroxyamine hydrochloride 16 mg (0.10 mmol), 9 mg (0.11 mmol) of pyridine and 2 mL of methanol were stirred at room temperature for 3 hours. The resulting reaction mixture was concentrated and the resulting residue was partitioned between ethyl acetate and dilute hydrochloric acid. The organic layer was washed sequentially with dilute hydrochloric acid, aqueous sodium bicarbonate solution and water, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -2- (methoxy 29 mg (0.078 mmol) of mino) acetate (the present compound 256) were obtained.

Preparation Example 20

29 mg (0.078 mmol) of methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -2- (methoxyimino) acetate [prepared in Preparation Example 19 (this compound 256)], A solution of 2 ml of methanol and 100 mg (1.3 mmol) of a methylamine 40% solution in methanol was left overnight at room temperature, to which 100 mg (1.3 mmol) of a methylamine 40% solution in methanol was added, followed by stirring for 3 hours. It was. The resulting reaction solution was subjected to silica gel thin layer chromatography to obtain the desired N-methyl-2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -2- (methoxyimino) acetamide (this compound 257) 23 mg (0.062 mmol) were obtained.

Preparation Example 21

Methyl 2- {5- (1-hydroxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate [prepared in Reference Example 16] 200 mg (0.717 mmol), 20 mg (0.83 mmol) sodium hydride ) And 2 ml of N, N-dimethylformamide were stirred at room temperature for 20 minutes, and 105 mg of 1-chloro-2-methoxyiminopropane was added thereto. The addition was mixed for 1 hour, and the resulting reaction mixture was poured into diluted hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated oil was purified by silica gel column chromatography, and the desired methyl 2- {5- (1- (2-methoxyiminopropoxy) iminoethyl) -2-methylphenoxy} -3-methoxyacrylic 150 mg (0.412 mmol) of late (this compound 446) were obtained.

Reference Example 1

(Iii) [Example of Step 12c of Scheme 12]

A mixture of 25 g (0.17 mol) N-methyl-3-acetylaniline, 24 g (0.17 mol) potassium carbonate, 16 ml (0.17 mol) methyl bromoacetate and 300 ml N, N-dimethylformamide was stirred overnight The mixture was poured into 500 ml of a mixture of ice and dilute hydrochloric acid, and extracted with 500 ml of ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give 24 g (0.11 mmol) of the desired methyl 2- (N-methyl-3-acetylanilino) acetate. It was.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.2-7.4 (3H), 6.89 (1H, m), 4.14 (2H, s), 3.73 (3H, s), 3.12 (3H, s), 2.59 (3H, s)

(Ii) [Example of Step 11a of Scheme 11]

23.8 g (0.10 mmol) of methyl 2- (N-methyl-3-acetylanilino) acetate, 1.0 g (5.3 mmol) of p-toluenesulfonic acid monohydrate, 20 mL of trimethyl orthoformate (0.18 mmol) and 300 mL of methanol The mixture was heated to reflux for 3 hours with stirring. After standing at room temperature, 1 mL (7.2 mmol) of triethylamine was added and the residue concentrated under reduced pressure was partitioned between ethyl acetate and water. The organic layer was dried over magnesium sulfate and concentrated to give 28 g (0.10 mol) of the desired methyl 2- {N-methyl-3- (1,1-dimethoxyethyl) anilino} acetate.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.21 (1H, t), 6.8-7.0 (2H), 6.60 (1H, br.d), 4.09 (2H, s), 3.72 (3H, s), 3.18 (6H, s), 3.07 (3H, s), 1.52 (3H, s)

(Iii) [Example of Step 11b of Scheme 11]

A mixture of 10 g (37 mmol) of methyl 2- {N-methyl-3- (1,1-dimethoxyethyl) anilino} acetate and 20 ml (0.32 mol) of methyl formate was dissolved in 2.5 g (0.10 mol) of sodium hydride. And to a mixture of 200 ml of N, N-dimethylformamide at once and stirred at room temperature. After addition stirring at room temperature for 3 hours, the mixture was poured into 300 ml of a mixture of ice and dilute hydrochloric acid and extracted with 500 ml of ethyl acetate. The organic layer was washed once with dilute hydrochloric acid, and extracted twice with 300 ml of an aqueous sodium carbonate solution. The resulting sodium carbonate solution was made slightly acidic with concentrated hydrochloric acid and the desired material precipitated out as crystals. The mixture was extracted twice with 500 ml of ethyl acetate. The organic layer was washed once with water, dried over magnesium sulfate and concentrated to give the desired methyl 3-hydroxy-2- (N-methyl-3-acetylanilino). 1.1 g (3.7 mmol) of acrylate were obtained.

¹ H-NMR (CDCl ₃ , TMS) (2: 1 mixture of isomers)

δ (ppm): 7.23 (1H × 1/3, s), 7.1-7.4 (3H + 1H × 2/3), 6.36 (1H, m), 3.69 (3H × 1/3, s), 3.64 (3H × 2/3, s), 3.12 (3H × 1/3, s), 3.09 (3H × 2/3, s), 2.53 (3H × 1/3, s), 2.40 (3H × 2/3, s )

(Iii) [Example of Step 11c of Scheme 11]

1.1 g (4.4 mmol) of methyl 3-hydroxy-2- (N-methyl-3-acetylanilino) acrylate, 1 g (7.2 mmol) of potassium carbonate, 0.5 mL (8.02 mmol) of methyl iodide and N, A mixture of 15 ml of N-dimethylformamide was stirred overnight at room temperature, poured into 30 ml of a mixture of ice and dilute hydrochloric acid, and extracted with 30 ml of ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated to obtain a residue obtained by silica gel column chromatography, and the desired methyl 3-methoxy-2- (N 1.0 g (3.2 mmol) of -methyl-3-acetylanilino) acrylate was obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.43 (1H, s), 7.2-7.4 (3H), 6.83 (1H, br.d), 3.88 (3H, s), 3.67 (3H, s), 3.10 (3H, s), 2.53 (3H, s)

Reference Example 2

(Iii) [Example of Step 9a of Scheme 9]

A solution of 1.9 g (13 mmol) of methyl 2-chloro-2-hydroxyiminoacetate in 2 ml of toluene was dissolved in 2.0 g (13 mmol) of N-methyl-3-acetylaniline, 1.9 ml (13 mmol) of triethylamine and toluene. After addition to 15 ml of the mixture under stirring with ice cooling, stirring was continued for 12 hours while gradually raising the temperature to room temperature. The resulting reaction mixture was partitioned between ethyl acetate and water, and the organic layer was washed once with water and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to obtain 1.0 g (4.0 mmol) of the desired methyl 2- (N-methyl-3-acetylanilino) -2-hydroxyiminoacetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.53 (1H, d), 7.41 (1H, br.s), 7.35 (1H, t), 6.94 (1H, br.d), 3.77 (3H, s), 3.31 (3H, s) , 2.57 (3H, s)

(Ii) [Example of Step 9b of Scheme 9]

A mixture of 0.84 g (3.4 mmol) of methyl 2- (N-methyl-3-acetylanilino) -2-hydroxyiminoacetate, 0.10 g (4.2 mmol) of sodium hydride and 10 ml of tetrahydrofuran was added at room temperature for 20 minutes. After stirring, the mixture was ice-cooled, and 0.46 mL (3.4 mmol) of dimethylsulfate was added dropwise thereto, and stirring was continued for 2 hours while the temperature was raised to room temperature. The resulting mixture was poured into ice and aqueous sodium chloride solution and extracted with ethyl acetate. The organic layer was dried over magnesium sulfate, and the obtained residue was subjected to silica gel column chromatography to give 0.36 g (1.4 mmol) of the desired methyl 2- (N-methyl-3-acetylanilino) -2-methoxyiminoacetate. Obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.52 (1H, d), 7.3-7.4 (2H), 6.93 (1H, br.d), 4.04 (3H, s), 3.80 (3H, s), 3.27 (3H, s), 2.58 (3H, s)

(Iii) [Example of Step 11d of Scheme 11]

A mixture of 0.25 g (0.95 mmol) of methyl 2- (N-methyl-3-acetylanilino) -2-methoxyiminoacetate, 3 ml of methanol and 3 g (27 mmol) of a 28% solution of methylamine in methanol Stir at 50 ° C for hours. The concentrated residue was dissolved in ethyl acetate and washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution. The organic layer was dried over magnesium sulfate and concentrated to give 0.20 g (0.76 mmol) of the desired N-methyl-2- (N-methyl-3-acetylanilino) -2-methoxyiminoacetamide.

¹ H-NMR (CDCl ₃ , TMS) (2: 1 mixture of isomers)

δ (ppm): 7.3-7.8 (3H), 6.6-7.1 (2H), {3.83 (3H × 2/3), 3.40 (3H × 1/3), angle s}, {3.27 (3H × 2/3) ), 3.24 (3H × 1/3), angle s}, {2.89 (3H × 2/3), 2.75 (3H × 1/3), angle d}, {2.58 (3H × 2/3), 2.56 ( 3H × 1/3) each s}

Reference Example 3

(Iii) [Example of Step 12c of Scheme 12]

A mixture of 4.4 g (32 mmol) of 3-hydroxyacetophenone, 3.3 ml (35 mmol) of methyl bromoacetate, 5.3 g (38 mmol) of potassium carbonate and 60 ml of N, N-dimethylformamide was stirred at room temperature overnight. . The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to give 6.2 g (30 mmol) of the desired methyl 2- (3-acetylphenoxy) acetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.60 (1H, d), 7.49 (1H, br.s), 7.40 (1H, t), 7.14 (1H, br.d), 4.71 (2H, s), 3.83 (3H, s) , 2.58 (3H, s)

(Ii) [Example of Step 11a of Scheme 11]

A mixture of 6.2 g (30 mmol) of methyl 2- (3-acetylphenoxy) acetate, 0.60 g (3.1 mmol) of p-toluenesulfonic acid monohydrate, 30 ml (270 mmol) of trimethyl orthoformate and 20 ml of methanol was added. Heated to reflux for hours. The resulting solution was cooled to room temperature, to which 1 mL (7.2 mmol) of triethylamine was added, followed by stirring for 15 minutes. The concentrated residue was partitioned between ethyl acetate and water, the organic layer was dried over magnesium sulfate and concentrated to give 7.4 g (29 mmol) of the desired methyl 2- {3- (1,1-dimethoxyethyl) phenoxy) acetate. ) Was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.27 (1H, t), 7.13 (1H, br.d), 7.08 (1H, br.s) 6.83 (1H, br.d), 4.65 (2H, s), 3.81 (3H, s ), 3.18 (6H, s), 1.52 (3H, s)

(Iii) [Example of Step 11b of Scheme 11]

7.4 g (29 mmol) methyl 2- {3- (1,1-dimethoxyethyl) phenoxy} acetate, 10 mL (170 mmol) methyl formate, 1.5 g (63 mmol) sodium hydride and N, N-dimethyl 100 ml of formamide was stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and extracted twice with aqueous sodium carbonate solution. The resulting aqueous alkaline layer was adjusted to about pH 6 with concentrated hydrochloric acid and the precipitate was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated to give 5.0 g (21 mmol) of the crude product of the desired methyl 2- (3-acetylphenoxy) -3-hydroxyacrylate.

(Iii) [Example of Step 11c of Scheme 11]

Crude product of methyl 2- (3-acetylphenoxy) -3-hydroxyacrylate 5.0 g (21 mmol), 2 mL (32 mmol) methyl iodide, 5 g (36 mmol) potassium carbonate and N, N A mixture of 50 ml of dimethylformamide was stirred at rt overnight. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and sequentially with an aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to give 2.7 g (11 mmol) of the desired methyl 2- (3-acetylphenoxy) -3-methoxyacrylate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.59 (1H, d), 7.51 (1H, br.s), 7.37 (1H, t), 7.35 (1H, s), 7.18 (1H, br.d), 3.87 (3H, s) , 3.71 (3H, s), 2.58 (3H, s)

Reference Example 4

(Iii) A mixture of 10 g (66 mmol) of 3-nitrobenzaldehyde, 0.30 g (1.6 mmol) of p-toluenesulfonic acid monohydrate and 0.20 L of methanol was heated to reflux for 3 hours and then cooled to room temperature. 1.0 mL (7.2 mmol) of triethylamine was added to the resulting mixture, and the residue obtained by concentration was partitioned between 200 mL of ethyl acetate and water. The organic layer was dried over magnesium sulfate and filtered to give an ethyl acetate solution, to which 0.50 g (2.2 mmol) of platinum dioxide was added and shaken for 3 hours under a hydrogen gas atmosphere at room temperature. The filtered solution was concentrated to give 11 g (66 mmol) of the desired 3- (dimethoxymethyl) aniline.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.14 (1H, t), 6.7-6.9 (2H), 6.64 (1H, br.d), 5.29 (1H, s), 3.67 (2H, br), 3.32 (6H, s)

(Ii) 12 mL (85 mmol) of trifluoroacetic anhydride, 11 g (66 mmol) of 3- (dimethoxymethyl) aniline, 14 mL (100 mmol) of triethylamine and 0.20 L of methylene chloride, with stirring under ice cooling Was added dropwise for 30 minutes and allowed to warm to room temperature over 1 hour. The resulting mixture was concentrated and 14 g (100 mmol) of potassium carbonate, 6.4 mL (100 mmol) of methyl iodide and 100 mL of N, N-dimethylformamide were added to the residue and stirred overnight at room temperature. The resulting mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution and dried over magnesium sulfate. To the residue obtained by concentration was added 8.3 g (60 mmol) of potassium carbonate, 100 ml of methanol and 10 ml of water, heated to reflux for 1 hour, and cooled to room temperature. The resulting reaction mixture was concentrated and the residue was partitioned between ethyl acetate and water. The organic layer was dried over magnesium sulfate, and concentrated to a residue obtained by adding 0.20 L of methanol and 0.30 g (1.6 mmol) of p-toluenesulfonic acid monohydrate, followed by heating to reflux for 3 hours. The mixture was cooled to rt and 1 mL (7.2 mmol) of triethylamine was added and then concentrated. The residue was partitioned between ethyl acetate and water and the organic layer was dried over magnesium sulfate and concentrated to give 3.5 g (19 mmol) of the desired N-methyl-3- (dimethoxymethyl) aniline.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.19 (1H, t), 6.78 (1H, d), 6.72 (1H, br.s), 6.59 (1H, br.d), 5.32 (1H, s), 3.33 (6H, s) , 2.84 (3H, s)

(Iii) 3.5 g (19 mmol) of N-methyl-3- (dimethoxymethyl) aniline, 2.0 ml (21 mmol) of methyl bromoacetate, 3.0 g (22 mmol) of potassium carbonate and N, N-dimethylformamide 40 Ml of the mixture was stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to obtain 3.5 g (17 mmol) of the desired methyl 2- (N-methyl-3-formylanilino) acetate.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 9.96 (1H, s), 7.39 (1H, t), 7.24 (1H, d), 7.17 (1H, br.s), 6.94 (1H, br.d), 4.15 (2H.s) , 3.73 (3H, s), 3.12 (3H, s)

Reference Example 5

(i) [Example of Step 12c of Scheme 12]

2.84 g (19 mmol) of 3-acetylbenzenethiol, 2.0 mL (21 mmol) of methyl bromoacetate, 4.0 g (29 mmol) of potassium carbonate and 40 mL of N, N-dimethylformamide were stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to give 2.7 g (12 mmol) of the desired methyl 2- (3-acetylphenylthio) acetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.00 (1H, s), 7.81 (1H, d), 7.61 (1H, d), 7.41 (1H, t), 3.73 (3H, s), 3.70 (2H, s), 2.59 (3H , s)

(Ii) [Example of Step 11a of Scheme 11]

A mixture of 2.7 g (12 mmol) of methyl 2- (3-acetylphenylthio) acetate, 0.11 g (0.53 mmol) of p-toluenesulfonic acid monohydrate, 10 mL (92 mmol) of trimethylorthoformate and 30 mL of methanol was added. Heated to reflux for hours. The reaction solution was cooled to room temperature, to which 0.50 ml (3.6 mmol) of triethylamine was added, followed by stirring for 15 minutes. The concentrated residue was partitioned between ethyl acetate and water, the organic layer was washed with water, dried over anhydrous magnesium sulfate and concentrated to give the desired methyl 2- {3- (1,1-dimethoxyethyl) phenylthio} acetate 2.6 g (9.6 mmol) was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.54 (1H, s), 7.3-7.4 (3H), 3.72 (3H, s), 3.66 (2H, s), 3.17 (6H, s), 1.51 (3H, s)

(Iii) [Example of Step 11b of Scheme 11]

A solution of 2.1 g (7.7 mmol) of methyl 2- {3- (1,1-dimethoxyethyl) phenylthio} acetate in 10 ml (170 mmol) of methyl formate was added 1.0 g (17 mmol) of potassium hydride and 1,2- To a mixture of 30 ml of dimethoxyethane was added with stirring under an argon atmosphere, followed by addition stirring at room temperature for 2 hours. The resulting reaction mixture was poured into iced water and the aqueous layer was washed twice with diethyl ether. Concentrated hydrochloric acid was added to make the aqueous layer acidic and the precipitate was extracted twice with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated to give 1.8 g (7.2 mmol) of the desired methyl 2- (3-acetylphenylthio) -3-hydroxyacrylate.

¹ H-NMR (TMS, CDCl ₃ ) (2: 1 mixture of isomers)

δ (ppm): 7.7-8.3 (3H), 7.3-7.5 (2H), 3.77 (2/3 × 3H, s), 3.76 (1/3 × 3H, s), 2.57 (3H, s)

(Iii) [Example of Step 11c of Scheme 11]

1.8 g (7.2 mmol) of methyl 2- (3-acetylphenylthio) -3-hydroxyacrylate, 0.5 mL (8.0 mmol) of methyl iodide, 1.0 g (7.2 mmol) of potassium carbonate and N, N-dimethylform The mixture of 14 ml of amide was stirred overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and sequentially with an aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to obtain 1.8 g (6.8 mmol) of the desired methyl 2- (3-acetylphenylthio) -3-methoxyacrylate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.02 (1H, s), 7.79 (1H, s), 7.70 (1H, d), 7.3-7.5 (2H), 4.01 (3H, s), 3.73 (3H, s), 2.56 (3H , s)

Reference Example 6: Preparation of Intermediate of Compound No. 132

(i) [Example of Step 12c of Scheme 12]

Methyl-2- (3-acetyl in the same manner as in Reference Example 3 (iii), except that 200 mg (1.17 mmol) of 3-hydroxy-4-chloroacetophenone is used instead of 3-hydroxyacetophenone. 192 mg (0.79 mmol) of -6-chlorophenoxy) acetate were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.4-7.6 (3H), 4.79 (2H, s), 3.81 (3H, s), 2.57 (3H, s)

(Ii) [Example of Step 12d of Scheme 12]

Preparation Example, except that 192 mg (0.792 mmol) of methyl-2- (3-acetyl-6-chlorophenoxy) acetate was used instead of methyl 2- (N-methyl-3-formylanilino) acetate 182 mg (0.751 mmol) of methyl 2- {3- (1-benzyloxyiminoethyl) -6-chlorophenoxy} acetate (intermediate of the present compound) were obtained in the same manner as in 6 (iii).

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.1-7.4 (8H), 5.22 (2H, s), 4.74 (2H, s), 3.80 (3H, s), 2.32 (3H, s)

Reference Example 7 (Example of Preparation of Intermediate of Present Compound 272)

(Iii) [Example of Step 13a of Scheme 13]

2.34 g (14.4 mmol) of 2- (3-nitrophenyl) acetonitrile were added to a mixture of 380 mg (15.8 mmol) of sodium hydride and 25 ml of dimethylformamide at room temperature with stirring. After stopping the vigorous release of the hydrogen gas, 2.23 g (21.6 mmol) of tert-butyl nitrite were added at room temperature and then stirring continued overnight. The reaction solution was poured into 100 ml of diluted hydrochloric acid, and extracted with 100 ml of ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The concentrated residue was subjected to silica gel column chromatography to give 647 mg (2.29 mmol) of the desired 2- (3-nitrophenyl) -2-hydroxyiminoacetonitrile.

(Ii) [Example of Step 13b of Scheme 13]

647 mg (2.29 mmol) of 2- (3-nitrophenyl) -2-hydroxyiminoacetonitrile were added to a mixture of 8 ml of tetrahydrofuran and 70 mg (2.9 mmol) of sodium hydride at room temperature with stirring. . After the vigorous discharge of hydrogen gas was stopped, 0.3 ml (3.17 mmol) of dimethyl sulfate was added while cooling the reaction solution, and stirring was continued for 1 hour while the temperature was raised to room temperature. The resulting reaction solution was diluted with 30 mL of diethyl ether, washed with saturated aqueous sodium chloride solution, dried over magnesium sulfate and concentrated to give a residue obtained by silica gel column chromatography to give the title 2- (3-nitrophenyl) -2-. 527 mg (2.57 mmol) of methoxyiminoacetonitrile were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 8.68 (1H, br.s), 8.33 (1H, br.d), 8.11 (1H, br.d), 7.68 (1H, t), 4.28 (3H, s)

(Iii) [Example of Step 14a of Scheme 14]

A mixture of 0.87 g (16 mmol) of iron powder and 1.5 ml of a 10% aqueous solution of acetic acid was stirred at 100 ° C. for 1 hour. 527 mg (2.57 mmol) of 2- (3-nitrophenyl) -2-methoxyiminoacetonitrile, 2.5 ml of acetic acid and 2.5 ml of ethyl acetate were added to the reaction solution, heated to reflux for 20 minutes, and then cooled. The reaction solution was poured into 25 ml of aqueous sodium bicarbonate solution, extracted twice with ethyl acetate, the combined organic layers were further washed twice with aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired 2- (3-aminophenyl)- 438 mg (2.50 mmol) of 2-methoxyiminoacetonitrile were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.1-7.3 (2H), 7.10 (1H, br.s), 6.78 (1H, br.d), 4.20 (3H, s), 3.81 (2H, br.)

(Iii) [Example of Step 14b of Scheme 14]

Under ice-cooling, trifluoroacetic anhydride was added to a mixture of 438 mg (2.50 mmol) of 2- (3-aminophenyl) -2-methoxyiminoacetonitrile and ethyl acetate with stirring. After the ice bath was removed, stirring was continued for 1 hour, and the reaction solution was concentrated under reduced pressure to obtain 664 mg (2.45 mmol) of the desired 2- (3-trifluoroacetoaminophenyl) -2-methoxyiminoacetonitrile. .

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.97 (1H, br.s), 7.94 (1H, br.), 7.81 (1H, br.d), 7.67 (1H, br.d), 7.52 (1H, t), 4.24 (3H , s)

(Iii) [Example of Step 14c of Scheme 14]

The total amount of 2- (3-trifluoroacetoaminophenyl) -2-methoxyiminoacetonitrile obtained in (iii) above in suspension of 1 mg of dimethylformamide in 70 mg (2.9 mmol) of sodium hydride, methyl urine To a mixture of 0.3 ml (4.82 mmol) and 5 ml of dimethylformamide was added with stirring the mixture under ice cooling. The ice bath was removed and stirring continued for 1 hour at room temperature. The reaction solution was poured into dilute hydrochloric acid, extracted with 20 mL of ethyl acetate, the organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to the desired 2- {3- (N-methyltrifluoro 593 mg (2.08 mmol) of acetoamino) phenyl} -2-methoxyiminoacetonitrile were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.83 (1H, br.d), 7.73 (1H, br.s), 7.54 (1H, t), 7.38 (1H, br.d), 4.24 (3H, s), 3.41 (3H, s)

(Iii) [Example of Step 14d of Scheme 14]

Whole amount of 2- {3- (N-methyltrifluoroacetamino) phenyl} -2-methoxyiminoacetonitrile obtained in (iii), 1.0 g (7.2 mmol) of potassium carbonate, 5 ml of methanol, and water 3 The ml mixture was heated to reflux for 30 minutes, cooled to room temperature, the methanol is distilled off under reduced pressure, the resulting mixture is partitioned between 20 ml of water and 20 ml of ethyl acetate, the organic layer is dried over magnesium sulfate and concentrated to 316 mg (1.67 mmol) of 2- {3- (N-methylamino) phenyl} -2-methoxyiminoacetonitrile were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.24 (1H, t), 7.12 (1H, br.d), 7.00 (1H, br.s), 6.72 (1H, br.d), 4.20 (3H, s), 2.88 (3H, s)

(Iii) [Example of Step 12b of Scheme 12]

Whole amount of 2- {3- (N-methylamino) phenyl} -2-methoxyiminoacetonitrile obtained in (iii), 400 mg (2.89 mmol) of potassium carbonate, 0.24 ml (2.53 mmol) of methyl bromoacetate And a mixture of 5 ml of dimethylformamide was stirred overnight at room temperature. The resulting reaction solution was poured into dilute hydrochloric acid, extracted with 20 mL of ethyl acetate, the organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and the residue was concentrated by silica gel column chromatography, to obtain a target. 192 mg (0.736 mmol) of-{3- (N-methyl-N-methoxycarbonylmethylamino) phenyl} -2-methoxyiminoacetonitrile (intermediate of the present compound) were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.29 (1H, t), 7.18 (1H, br.d), 7.07 (1H, br.s), 6.78 (1H, br.d), 4.20 (3H, s), 4.13 (2H, s), 3.74 (3H, s), 3.12 (3H, s)

(Iii) [Example of Step 8a of Scheme 8]

Hydrogenation of a solution in 1 mL (16 mmol) of methyl formate of 192 mg (0.736 mmol) of 2- {3- (N-methyl-N-methoxycarbonylmethylamino) phenyl} -2-methoxyiminoacetonitrile To a mixture of 35 mg (1.5 mmol) sodium and 4 ml of dimethylformamide was added dropwise with stirring the mixture at room temperature. After continuing stirring for 3 hours, the reaction solution was poured into diluted hydrochloric acid and extracted with 20 ml of ethyl acetate. The organic layer was washed once with diluted hydrochloric acid, extracted twice with aqueous sodium carbonate solution, the combined aqueous sodium carbonate layers were weakly acidic using concentrated hydrochloric acid, the precipitate was extracted with 20 ml of ethyl acetate, and the organic layer was washed once with water, Dried over magnesium sulfate and concentrated to the desired 2- [3- {N-methyl-N- (methyl 3-hydroxyacrylate-2-yl) amino} phenyl] -2-methoxyiminoacetonitrile (prepared of this compound) Intermediate) 119 mg (0.412 mmol) were obtained.

¹ H-NMR (CDCl ₃ , TMS) (3: 1 mixture of isomers)

δ (ppm): 7.70 (1H, br.s), 7.0-7.4 (3H), 6.80 (1H), 4.20 (3H × 3/4, s), 4.19 (3H × 1/4, s), 3.72 ( 3H × 1/4, s), 3.67 (3H × 3/4, s), 3.12 (3H × 1/4, s), 3.09 (3H × 3/4, s)

Reference Example 8 [Example of Step 7a of Scheme 7] (Intermediate of Compound 116)

Methyl 2- (3-acetylphenoxy) -3-methoxyacrylate [prepared in Reference Example 3] 3.0 g (12 mmol), hydroxyaminehydrochloride 1.0 g (14 mmol), pyridine 1.2 mL (15 mmol) And 30 ml of methanol was stirred at room temperature for 5 hours, and the residue obtained by concentration was partitioned between ethyl acetate and water. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {3- (1-hydroxyiminoethyl) phenoxy} -3-methoxyacrylate (this compound 351). ) 3.2 g (12 mmol) were obtained.

¹ H-NMR (CDCl ₃ , TMS)

δ (ppm): 7.35 (1H, s), 7.2-7.3 (3H), 6.97 (1H, m), 3.87 (3H, s), 3.73 (3H, s), 2.25 (3H, s)

Reference Example 9 [Preparation of Intermediate of Present Compound 215 (1)]

(i) [Example of Step 12c of Scheme 12]

21.88 g (0.136 mol) of methyl bromoacetate was added to a mixture of 19.58 g (0.130 mol) of 3-hydroxy-4-methylacetophenone, 21.53 g (0.156 mol) of potassium carbonate and 20 ml of N, N-dimethylformamide. Dropwise at 25 ° C. and then stirred at room temperature for 5 hours. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with aqueous sodium bicarbonate solution and once with water, dried over magnesium sulfate and concentrated to give 27.87 g (0.125 mol) of the desired methyl 2- (5-acetyl-2-methylphenoxy) acetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.48 (1H, dd), 7.33 (1H, d), 7.23 (1H, d), 4.72 (2H, s), 3.80 (3H, s), 2.55 (3H, s), 2.34 (3H , s)

(Ii) [Example of Step 12d of Scheme 12]

11 g (50 mmol) of methyl 2- (5-acetyl-2-methylphenoxy) acetate, 13 g (81 mmol) of 0-benzylhydroxyamine hydrochloride, 4.9 g (63 mmol) of pyridine and 60 ml of methanol Stirred for 3 h. The resulting reaction mixture was concentrated and the resulting residue was partitioned between ethyl acetate and water. The organic layer was washed sequentially with dilute hydrochloric acid and aqueous sodium bicarbonate solution, dried over magnesium sulfate, and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} acetate (intermediate for preparing the compound) 16 g (49 mmol) was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.1-7.45 (8H, m), 5.22 (2H, s), 4.68 (2H, s), 3.79 (3H, s), 2.29 (3H, s), 2.22 (3H, s)

(Iii) [Example of Step 8a of Scheme 8]

Hydrogenation of 16 g (49 mmol) of methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} acetate, 29 g (490 mmol) of methylformate and 10 ml of 1,2-dimethoxyethane To a mixture of 12 g (108 mmol) of potassium (35% oil dispersion) and 160 mL of 1,2-dimethoxyethane was added dropwise under argon gas with stirring under ice cooling, and stirring was continued for 3 hours while gradually warming to room temperature. The resulting reaction mixture was poured into water, washed twice with diethyl ether, and the aqueous layer was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -3-hydroxyacrylate (intermediate for preparing the compound) 15 g (about 41 mmol) of crude product) were obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.01 (1H × 1/2, s), 7.55 (1H × 1/3, s), 7.28-7.5 (m), 7.1-7.2 (2H, m), 5.23 (2H × 1/2 , s), 5.20 (2H × 1/2, s), 4.72 (3H × 1/3, s), 3.68 (3H × 1/2, s), 3.55 (3H × 1/2, s), 3.40 ( 3H × 2/3, s), 2.35 (3H × 1/2, s), 2.29 (3H × 1/2, s), 2.23 (3H × 1/2), 2.16 (3H × 1/2, s)

Reference Example 10 (Preparation Example (2) of Present Compound 215)

(i) (Example of Step 11a of Scheme 11)

5.0 g (22 mmol) of methyl 2- (5-acetyl-2-methylphenoxy) acetate, 0.43 g (2.2 mmol) of p-toluenesulfonic acid monohydrate, 21.5 g (200 mmol) of trimethyl orthoformate and 15 ml of methanol Was heated to reflux for 7 hours. The reaction solution was left to cool to room temperature, to which 0.55 g (5.4 mmol) of triethylamine was added and stirred for 15 minutes. The residue obtained by concentration was partitioned between ethyl acetate and water, the organic layer was dried over magnesium sulfate and concentrated to the desired methyl 2- {5- (1,1-dimethoxyethyl) -2-methylphenoxy} 2.7 g (about 10 mmol) of crude product of acetate were obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 6.8-7.2 (3H, m), 4.68 (2H, s), 3.79 (3H, s), 3.18 (6H, s), 2.28 (3H, s), 1.50 (3H, s)

(Ii) [Example of Step 11b of Scheme 11]

1.0 g (about 3.7 mmol) of crude product of methyl 2- {5- (1,1-dimethoxyethyl) -2-methylphenoxy} acetate, 1.3 g (22 mmol) methyl formate, sodium hydride (60% oil) Dispersion) 0.32 g (8.1 mmol) and 13 ml of N, N-dimethylformamide were stirred at room temperature for 2 hours. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with dilute hydrochloric acid and extracted twice with aqueous sodium carbonate solution. The resulting alkaline aqueous layer was adjusted to pH 6 with concentrated hydrochloric acid and the precipitate was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate and concentrated to give 0.40 g (about 1.6 mol) of the crude product of the desired methyl 2- (5-acetyl-2-methylphenoxy) -3-hydroxyacrylate.

(Iii) [Example of Step 11c of Scheme 11]

0.4 g (about 1.6 mmol) of crude product of methyl 2- (5-acetyl-2-methylphenoxy) -3-hydroxyacrylate, 0.35 g (2.4 mmol) methyl iodide, 0.38 g (2.7 mmol) potassium carbonate ) And 40 ml of N, N-dimethylformamide were stirred at room temperature for 4 hours. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The residue obtained by concentration was subjected to silica gel column chromatography to give 0.12 g (0.65 mmol) of the desired methyl 2- (5-acetyl-2-methylphenoxy) -3-methoxyacrylate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.2-7.5 (4H, m), 3.90 (3H, s), 3.71 (3H, s), 2.54 (3H, s), 2.41 (3H, s)

Reference Example 11 (Example of Preparation of Intermediate of Present Compound 216)

(Iii) [Example of Step 12c of Scheme 12]

5.0 g (30 mmol) of 3-hydroxy-4-ethylacetophenone, 5.1 g (33 mmol) of methyl bromoacetate, 5.1 g (37 mmol) of potassium carbonate and 60 ml of N, N-dimethylformamide at room temperature overnight Stirred. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution and dried over magnesium sulfate to give 6.6 g (28 mmol) of the desired methyl 2- (5-acetyl-2-ethylphenoxy) acetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.53 (1H, dd), 7.35 (1H, d), 7.27 (1H, d), 4.74 (2H, s), 3.81 (3H, s), 2.78 (2H, q), 2.58 (3H , s), 1.25 (3H, t)

(Ii) [Example of Step 12d of Scheme 12]

6.6 g (28 mmol) of methyl 2- (5-acetyl-2-ethylphenoxy) acetate, 7.2 g (45 mmol) of 0-benzylhydroxyamine hydrochloride, 2.7 g (35 mmol) of pyridine and 35 ml of methanol Stir overnight at. The resulting reaction mixture was concentrated to partition the residue between ethyl acetate and water. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-ethylphenoxy} acetate ( 9.2 g (27 mmol) of this compound preparing intermediate) were obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.1-7.45 (8H, m), 5.22 (2H, s), 4.68 (2H, s), 3.79 (3H, s), 2.71 (2H, q), 2.22 (3H, s), 1.21 (3H, t)

(Iii) [Example of Step 8b of Scheme 8]

5.3 g (88 mmol) of methyl formate are added to a mixture of 0.78 g (19 mmol) of potassium hydride and 30 ml of 1,2-dimethoxyethane under argon atmosphere, followed by methyl 2- {5- (1-benzyloxyimino 3.00 g (8.8 mmol) of ethyl) -2-ethylphenoxy} acetate were added and stirred at room temperature for 3 hours. The resulting reaction mixture was poured into iced water, washed twice with diethyl ether, the aqueous layer was poured into dilute hydrochloric acid and extracted with ethyl acetate. The ethyl acetate layer was washed with water, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1-benzyloxyiminoethyl) -2-ethylphenoxy} -3-hydroxyacrylate (intermediate for preparing the compound) 1.0 g (about 2.8 mol) of crude product were obtained.

Reference Example 12 (Preparation of Intermediate of Present Compound 217)

(i) [Example of Step 15 of Scheme 15]

1.49 g (10 mmol) of 3-amino-4-methylacetophenone was suspended in 8 ml of 10% sulfuric acid, and the solution obtained by dissolving 0.71 g (10 mmol) of sodium nitrite in 4 ml of water was added dropwise at about 5 deg. It was. Copper salt prepared by separating the yellow precipitate obtained by dropwise addition of 1.07 ml of methyl thioglycolate to a solution obtained by dissolving copper salt of methyl thioglycolate (1.49 g of copper sulfate pentahydrate in 10 ml of water). ) Was added in portions at the same temperature. After stirring for 3 hours at room temperature, diethyl ether was added to the reaction mixture and then filtered. The filtrate was separated and the organic layer was washed sequentially with dilute hydrochloric acid and dilute aqueous sodium hydroxide solution (twice), and water, and dried over magnesium sulfate. The residue obtained by concentration was subjected to silica gel column chromatography to give 0.53 g (2.22 mmol) of the desired methyl 2- (5-acetyl-2-methyl-phenylthio) acetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.95 (1H, d), 7.71 (1H, dd), 7.27 (1H, d), 3.73 (3H, s), 3.70 (2H, s), 2.58 (3H, s), 2.45 (3H , s)

(Ii) [Example of Step 11a of Scheme 11]

0.52 g (2.18 mmol) of methyl 2- (5-acetyl-2-methyl-phenylthio) acetate, 40 mg (0.21 mmol) of p-toluenesulfonic acid monohydrate, 2.36 g (21.8 mmol) of trimethylorthoformate and methanol 10 ML of the mixture was heated to reflux for 4 h. To the reaction mixture was also added 40 mg (0.21 mmol) of p-toluenesulfonic acid monohydrate, 2.36 g (21.8 mmol) of trimethyl orthoformate and 10 mL of methanol, followed by addition heating to reflux for 5 hours. The reaction solution was cooled to room temperature and 0.36 g (3.53 mmol) of triethylamine were added and stirred for 15 minutes. The residue obtained by concentration was partitioned between ethyl acetate and water, the organic layer was washed with water, dried over magnesium sulfate and concentrated to give the desired methyl 2- {5- (1,1-dimethoxyethyl) -2-methyl 0.61 g (2.14 mmol) of -phenylthio} acetate was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.47 (1H, d), 7.25 (1H, dd), 7.17 (1H, d), 3.71 (3H, s), 3.65 (2H, s), 3.17 (6H, s), 2.41 (3H , s), 1.51 (3H, s)

(Iii) [Example of Step 11b of Scheme 11]

A solution of 600 mg (2.11 mmol) of methyl formate in 3.07 g (46 mmol) of methyl 2- {5- (1,1-dimethoxyethyl) -2-methyl-phenylthio} acetate was added to 274 mg (6.86 mmol) of potassium hydride. ) And 7 ml of 1,2-dimethoxyethane were added dropwise under argon atmosphere with stirring at room temperature, followed by stirring at room temperature for 2 hours 30 minutes. The resulting reaction mixture was poured into iced water and the aqueous layer was extracted twice with diethyl ether. The aqueous layer was made acidic by addition of concentrated hydrochloric acid and the precipitate was extracted twice with ethyl acetate. The ethyl acetate layers were combined, washed with water, dried over magnesium sulfate and concentrated to give 450 mg (1.69 mmol) of the desired methyl 2- (5-acetyl-2-methyl-phenylthio) -3-hydroxyacrylate. .

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.73 (1H, br.d), 7.63 (1H, dd), 7.60 (1H, s), 7.22 (1H, d), 3.77 (3H, s), 2.53 (3H, s), 2.44 (3H, s)

(Iii) [Example of Step 11c of Scheme 11]

0.44 g (1.65 mmol) methyl 2- (5-acetyl-2-methyl-phenylthio) -3-hydroxyacrylate, 0.26 g (1.82 mmol) methyl iodide, 0.25 g (1.82 mmol) potassium N 6 ml of, N-dimethylformamide was stirred at room temperature for 3 hours. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted with ethyl acetate. The organic layer was washed once with diluted hydrochloric acid and once with aqueous sodium bicarbonate solution, and dried over magnesium sulfate. The residue obtained by concentration was subjected to silica gel thin layer chromatography to give 0.28 g (1.0 mmol) of the desired methyl 2- (5-acetyl-2-methyl-phenylthio) -3-methoxyacrylate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.05 (1H, s), 7.55-7.7 (2H, m), 7.19 (1H, d), 3.99 (3H, s), 3.71 (3H, s), 2.51 (3H, s), 2.45 (3H, s)

Reference Example 13 (Example of Preparation of Intermediates of the Present Compounds 232 and 233)

(i) [Starting materials (II) of Schemes 9 and 12]

11.19 g (75 mmol) of 3-amino-4-methylacetophenone is suspended in 15 ml of concentrated hydrochloric acid and 15 g of ice, and the solution obtained by dissolving 5.52 g (80 mmol) of sodium nitrate in 12.5 ml of water is dissolved in about It was added dropwise at 5 ° C. This was added dropwise to a solution obtained by dissolving 14.00 g (87 mmol) of potassium xanthate (potassium O-ethyl dithiocarbonate) in 18 ml of water while maintaining the solution temperature at 40 to 45 ° C, and then at the same temperature The addition was stirred for 30 minutes. Diethyl ether was added to the reaction solution, the layers were separated, and the aqueous layer was extracted twice with diethyl ether. The organic layers were combined, washed sequentially with dilute aqueous solution of sodium hydroxide and water, and dried over magnesium sulfate.

The residue (17.90 g) obtained by concentration was dissolved in 50 mL of 95% ethanol, and 17.5 g of potassium hydroxide was added dropwise at a bath temperature of 100 DEG C, followed by heating to reflux for 5 hours 30 minutes. After ethanol was distilled off from the reaction mixture, water and diethyl ether were added to the residue, the layers were separated, and the aqueous layer was washed three times with diethyl ether. 65 ml of 6N sulfuric acid and 0.2 g of zinc were added to the aqueous layer, extracted with diethyl ether, the diethyl ether layer was dried over magnesium sulfate and concentrated to give 9.33 g of a crude product of 5-acetyl-2-methyl-thiophenol. Obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.86 (1H, d), 7.64 (1H, dd), 7.24 (1H, d), 3.42 (1H, s), 2.56 (3H, s), 2.38 (3H, s)

(Ii) [Example of Step 9a of Scheme 9]

A solution obtained by dissolving 1.01 g (10 mmol) of triethylamine in 10 ml of tetrahydrofuran was obtained from 1.66 g (about 10 mmol) of a crude product of 5-acetyl-2-methyl-thiophenol and methyl 2-chloro-2. To the solution obtained by dissolving 1.38 g (10 mmol) of-(hydroxyimino) acetate, the solution was added dropwise with stirring, and stirring was continued at room temperature for 4 hours. The resulting reaction mixture was filtered, the filtrate was concentrated, and the obtained residue was subjected to silica gel column chromatography to obtain the desired methyl 2- (5-acetyl-2-methyl-phenylthio) -2- (hydroxyimino) acetate. 1.91 g (7.1 mmol) was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.04 (1H, d), 7.87 (1H, dd), 7.36 (1H, d), 3.53 (3H, s), 2.58 (3H, s), 2.54 (3H, s)

(Iii) [Example of Step 9b of Scheme 9]

1.90 g (7.1 mmol) of methyl 2- (5-acetyl-2-methyl-phenylthio) -2-hydroxyiminoacetate, 1.18 g (1.2 mmol) of potassium carbonate, 1.07 g (1.2 mmol) of dimethyl sulfate and tetrahydro A mixture of 22 mL of furan was stirred overnight at room temperature. The resulting reaction mixture was filtered and the residue obtained by concentrating the filtrate was subjected to silica gel column chromatography to obtain 1.42 g of desired methyl 2- (5-acetyl-2-methyl-phenylthio) -2-methoxyiminoacetate. 5.1 mmol) was obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 8.02 (1H, d), 7.86 (1H, dd), 7.36 (1H, d), 4.12 (3H, s), 3.50 (3H, s), 2.57 (3H, s), 2.53 (3H , s)

Reference Example 14 (Example of Preparation of Intermediates of the Present Compounds 256 and 257)

(i) -1 [Example of Step 9b of Scheme 9]

90 mg (2.25 mmol) of sodium hydride (60% oil dispersion) are suspended in 3 ml of tetrahydrofuran, and 300 mg (2.0 mmol of 3-hydroxy-4-methylacetophenone at 5 to 10 ° C. under nitrogen atmosphere. ) Was added dropwise. After stopping the release of hydrogen gas, at the same temperature, a solution of 275 mg (2.0 mmol) of methyl 2-chloro-2-hydroxyiminoacetate was added dropwise thereto. To this, 408 mg (4.0 mmol) of triethylamine were added dropwise, and stirring was continued overnight at room temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted twice with diethyl ether. The combined organic layers were washed three times with water, dried over magnesium sulfate and concentrated, and the resulting residue was subjected to silica gel thin layer chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to give the desired methyl 2- (5- 27 mg (ca. 0.11 mmol) of crude product of acetyl-2-methylphenoxy) -2-hydroxyiminoacetate were obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.62 (1H, dd), 7.32 (1H, d), 7.31 (1H, d), 3.82 (3H, s), 2.55 (3H, s), 2.43 (3H, s)

(Iii) -2 [Example of Step 9a of Scheme 9]

148 mg (2.55 mmol) of powdered potassium hydroxide are suspended in 3 ml of N, N-dimethylformamide, and at about 5 ° C., 300 mg (2.0 mmol) of 3-hydroxy-4-methylacetophenone are added, To this was added dropwise a solution obtained by dissolving 275 mg (2.0 mmol) of methyl 2-chloro-2-hydroxyiminoacetate in 2 ml of N, N-dimethylformamide at 5 to 10 ° C. After stirring at room temperature for 1 hour, 408 mg (4.0 mmol) of triethylamine were added dropwise at the same temperature, and stirring was continued overnight at the same temperature. The resulting reaction mixture was poured into dilute hydrochloric acid and extracted twice with diethyl ether. The organic layers were combined, washed with water, dried over magnesium sulfate and concentrated to give a residue obtained by silica gel thin layer chromatography (developing solvent; hexane: ethyl acetate = 1: 1) to obtain the desired methyl 2- (5-acetyl- 17 mg (ca. 0.068 mmol) of crude product of 2-methylphenoxy) -2-hydroxyiminoacetate were obtained.

(Ii) [Example of Step 9b of Scheme 9]

Crude product of methyl 2- (5-acetyl-2-methylphenoxy) -2-hydroxyiminoacetate {synthesized from (i) -1 and (i) -2}} 44 mg (about 0.18 mmol), potassium carbonate A mixture of 28 mg (0.20 mmol), 26 mg (0.20 mmol) of dimethyl sulfate, and 3 mL of tetrahydrofuran was stirred at room temperature for 6 hours. The resulting reaction mixture was subjected to silica gel thin layer chromatography to give 24 mg (0.091 mmol) of the desired methyl 2- (5-acetyl-2-methylphenoxy) -2-methoxyiminoacetate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.61 (1H, dd), 7.25-7.35 (2H, m), 4.04 (3H, s), 3.83 (3H, s), 2.54 (3H, s), 2.41 (3H, s)

Reference Example 15

133.27 mL (133.26 mmol) of 1N dilute sulfuric acid was added 273.51 g (740.38 mmol) of methyl 2- {5- (1-benzyloxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate, 82.25 g of paraformaldehyde (2.379 mol) and 2.7 L of acetonitrile were added with stirring at room temperature, followed by stirring at 25 ° C. for 15 hours and 30 ° C. for 3 hours. The resulting reaction mixture was stirred at room temperature with 7.54 mL (54.1 mmol) of triethylamine added, and then concentrated under reduced pressure. The resulting residue was dissolved in 8 liters of ethyl acetate, washed twice with 8 liters of 2N dilute hydrochloric acid and once with 8 liters of 5% aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated to give the resulting residue on silica gel column chromatography. Purification by chromatography gave 154.83 g (633.10 mmol) of the desired methyl 2- (5-acetyl-2-methylphenoxy) -3-methoxyacrylate.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.2-7.5 (4H, m), 3.90 (3H, s), 3.71 (3H, s), 2.54 (3H, s), 2.41 (3H, s)

Reference Example 16

15.0 g (56.8 mmol) of methyl 2- (5-acetyl-2-methylphenoxy) -3-methoxyacrylate, 6.00 g (86.3 mmol) of hydroxylamine hydrochloride, 5.00 mL (61.8 mmol) of pyridine and 200 methanol Ml was stirred at room temperature for 1 hour. The resulting reaction mixture was concentrated and partitioned between ethyl acetate and water, the organic layer was washed once with dilute hydrochloric acid and once with aqueous sodium bicarbonate solution, dried over anhydrous magnesium sulfate and concentrated to give the desired methyl 2 14.5 g (52.0 mmol) of-{5- (1-hydroxyiminoethyl) -2-methylphenoxy} -3-methoxyacrylate (this compound 463) were obtained.

¹ H-NMR (TMS, CDCl ₃ )

δ (ppm): 7.35 (1H, s), 7.17 (1H, d), 7.12 (1H, d), 7.03 (1H, s), 3.87 (3H, s), 3.71 (3H, s), 2.36 (3H , s), 2.23 (3H, s)

Examples of the compound together with the compound number are shown in Tables 1 and 2 below.

Compound represented by:

Compound represented by the following formula

In Tables 1 and 2, Me is a methyl group, Et is an ethyl group, n-Pr is a propyl group, i-Pr is isopropyl group, n-Bu is a butyl group, t-Bu is a tert-butyl group, Am is an amyl group, Bz is a benzyl group, F ₅ Bz is a 2,3,4,5,6-pentafluorobenzyl group, Ph is a phenyl group, and 4-CF ₃ -PhCH (CH ₃ ) is a 1- (4-trifluoromethylphenyl) ethyl group , Py is a pyridyl group, c is a cyclo, sec is a secondary, SUIM is a succinimide-1-yl group, (A) is a 3-Cl-5-CF ₃ -Py-2-yl group, and (B) is 5 Each -CF ₃ -Py-2-yl group is represented.

The physical properties [ ¹ H-NMR (CDCl ₃ , TMS, δ (ppm)) data of some embodiments of the present compound are then shown below. This compound is shown by the compound number shown in Table 1 and Table 2.

Present compound 1:

8.07 (1H, s), 7.2-7.5 (6H), 7.17 (1H, dd), 6.94 (1H, br.d), 6.87 (1H, br.s), 6.65 (1H, br.d), 5.20 ( 2H, s), 3.84 (3H, s), 3.67 (3H, s), 3.08 (3H, s)

Present compound 2:

7.40 (1H, s), 7.16 (1H, t), 6.98 (1H, d), 6.91 (1H, br.s), 6.64 (1H, br.d), 3.99 (3H, s), 3.87 (3H, s), 3.66 (3H, s), 3.10 (3H, s), 2.18 (3H, s)

Present compound 3:

7.41 (1H, s), 7.19 (1H, t), 6.9-7.0 (2H), 6.66 (1H, br.d), 3.84 (3H, s), 3.67 (3H, s), 3.08 (3H, s) , 2.23 (3H, s)

Present Compound 4:

7.2-7.5 (6H), 7.16 (1H, t), 6.97 (1H, d), 6.93 (1H, br.s), 6.63 (1H, br.d), 5.23 (2H, s), 3.83 (3H, s), 3.67 (3H, s), 3.09 (3H, s), 2.23 (3H, s)

Present compound 5:

7.40 (1H, s), 7.17 (1H, t), 6.99 (1H, br.d), 6.93 (1H, br.s), 6.64 (1H, br.d), 4.22 (2H, q), 3.86 ( 3H, s), 3.67 (3H, s), 3.09 (3H, s), 2.19 (3H, s), 1.31 (3H, t)

Present compound 6:

7.39 (1H, s), 7.16 (1H, t), 6.99 (1H, br.d), 6.93 (1H, br.s), 6.63 (1H, br.d), 4.13 (2H, t), 3.86 ( 3H, s), 3.67 (3H, s), 3.09 (3H, s), 2.20 (3H, s), 1.73 (2H, sex.), 0.97 (3H, t)

Present Compound 7:

7.40 (1H, s), 7.18 (1H, dd), 6.9-7.1 (2H), 6.62 (1H, br.d), 3.86 (3H, s), 3.67 (3H, s), 3.09 (3H, s) , 2.16 (3H, s), 1.34 (9H, s)

Present compound 8:

7.40 (1H, s), 7.17 (1H, t), 6.99 (1H, br.d), 6.93 (1H, br.s), 6.64 (1H, br.d), 6.07 (1H, ddt), 5.34 ( 1H, br.d), 5.23 (1H, br.d), 4.69 (2H, br.d), 3.86 (3H, s), 3.67 (3H, s), 3.09 (3H, s), 2.05 (3H, s)

Present compound 9:

7.42 (1H, s), 7.17 (1H, t), 6.9-7.0 (2H), 6.65 (1H, br.d), 5.26 (2H, s), 3.87 (3H, s), 3.67 (3H, s) , 3.08 (3H, s), 2.15 (3H, s)

Present Compound 10:

7.41 (1H, s), 7.18 (1H, t), 6.9-7.0 (2H), 6.67 (1H, br.d), 6.20 (1H, t), 4.76 (2H, d), 3.87 (3H, s) , 3.68 (3H, s), 3.09 (3H, s), 2.19 (3H, s)

Present Compound 11:

7.33 (1H, s), 7.2-7.3 (3H), 6.93 (1H, br.d), 3.98 (3H, s), 3.87 (3H, s), 3.72 (3H, s), 2.19 (3H, s)

Present Compound 12:

7.2-7.5 (9H), 6.93 (1H, br.d), 5.23 (2H, s), 3.85 (3H, s), 3.72 (3H, s), 2.23 (3H, s)

Present Compound 13:

7.60 (2H, d), 7.46 (2H, d), 7.1-7.6 (4H), 6.89 (1H, m), 5.39 (1H, q), 3.82 (3H, s), 3.70 (3H, s), 2.69 (3H, s), 1.60 (3H, d)

Present Compound 14:

7.60 (2H, d), 7.48 (2H, d), 7.36 (1H, s), 7.14 (1H, t), 6.91 (1H, br.d), 6.83 (1H, br.d), 6.62 (1H, br.d), 5.40 (1H, q), 3.82 (3H, s), 3.65 (3H, s), 3.04 (3H, s), 2.26 (3H, s), 1.60 (3H, d)

Present Compound 30:

7.4-7.5 (2H), 7.31 (1H, t), 7.17 (1H, br.d), 4.00 (3H, s), 3.80 (3H, s), 3.63 (3H, s), 3.26 (3H, s) , 2.19 (3H, s)

Present Compound 31:

7.13-7.25 (2H), 7.06 (1H, br.s), 6.75 (1H, br.d), 6.68 (1H, br), 3.97 (3H, s), 3.89 (3H, s), 3.27 (3H, s), 2.88 (3H, d), 2.18 (3H, s)

Present Compound 55:

8.00 (1H, s), 7.52 (1H, s), 7.43 (1H, d), 7.1-7.3 (2H), 3.99 (3H, s), 3.98 (3H, s), 3.73 (3H, s), 2.17 (3H, s)

Present Compound 115:

8.56 (1H, s), 7.95 (1H, dd), 7.52 (1H, d), 7.3-7.5 (4H), 7.02 (1H, dd), 3.90 (3H, s), 3.74 (3H, s), 2.52 (3H, s)

Present Compound 116:

8.46 (1H, br.s), 7.95 (1H, br.s), 7.44 (1H, br.d), 7.3-7.4 (3H), 7.02 (1H, br.d), 3.88 (3H, s), 3.73 (3H, s), 2.54 (3H, s)

Present Compound 122:

7.33 (1H, s), 7.2-7.3 (3H), 6.95 (1H, m), 4.74 (2H, s), 3.86 (3H, s), 3.77 (3H, s), 3.72 (3H, s), 2.28 (3H, s)

Compound 132:

7.0-7.5 (9H), 5.21 (2H, s), 3.86 (3H, s), 3.72 (3H, s), 2.18 (3H, s)

Compound 163:

8.55 (1H, br.s), 7.94 (1H, br.d), 7.52 (1H, d), 7.43 (1H, s), 7.27 (1H, m), 7.10 (1H, br.d), 7.02 ( 1H, br.s), 6.74 (1H, br.d), 3.89 (3H, s), 3.70 (3H, s), 3.13 (3H, s), 2.51 (3H, s)

Present Compound 174:

7.41 (1H, s), 7.19 (1H, t), 6.9-7.0 (2H), 6.67 (1H, t), 4.81 (2H, s), 3.88 (3H, s), 3.68 (3H, s), 3.06 (3H, s), 2.23 (3H, s)

Present Compound 199:

7.1-7.5 (7H), 7.06 (1H, br.s), 6.77 (1H, br.d), 5.23 (2H, s), 4.02 (3H, s), 3.74 (3H, s), 3.26 (3H, s), 2.23 (3H, s)

Present Compound 200:

7.1-7.5 (7H), 7.05 (1H, br.s), 6.75 (1H, br.d), 6.66 (1H, br), 5.22 (2H, s), 3.87 (3H, s), 3.25 (3H, s), 2.86 (3H, d), 2.21 (3H, s)

Present Compound 201:

6.9-7.5 (10H), 3.88 (3H, s), 3.73 (3H, s), 2.42 (3H, s)

Present Compound 202:

8.43 (1H, s), 7.72 (1H, d), 7.2-7.4 (5H), 6.94 (1H, m), 5.19 (2H, s), 3.87 (3H, s), 3.72 (3H, s), 2.21 (3H, s)

Compound 203:

7.1-7.4 (8H), 6.93 (1H, d), 4.86 (2H, t), 3.88 (3H, s), 3.73 (3H, s), 3.01 (2H, t), 2.17 (3H, s)

Compound 204:

7.2-7.4 (6H), 6.9-7.0 (4H), 4.53 (2H, t), 4.28 (2H, t), 3.86 (3H, s), 3.72 (3H, s), 2.21 (3H, s)

Present Compound 205:

7.2-7.4 (6H), 6.9-7.0 (4H), 4.38 (2H, t), 4.11 (2H, t), 3.87 (3H, s), 3.72 (3H, s), 2.20 (3H, s), 2.1 -2.3 (2H, m)

Present Compound 206:

7.33 (1H, s), 7.2-7.3 (3H), 6.95 (1H, m), 4.95 (2H, s), 3.87 (3H, s), 3.73 (3H, s), 2.44 (3H, s), 2.32 (3H, s), 2.15 (3H, s)

Compound 207:

7.33 (1H, s), 7.2-7.3 (3H), 6.93 (1H, d), 3.7-4.4 (6H), 3.86 (3H, s), 3.72 (3H, s), 2.22 (3H, s), 1.6 -2.1 (3H)

Present Compound 208:

7.2-7.4 (6H), 6.8-7.0 (3H), 5.16 (2H, s), 3.87 (3H, s), 3.83 (3H, s), 3.73 (3H, s), 2.20 (3H, s)

Compound 209:

7.99 (1H, s), 7.51 (1H, s), 7.1-7.5 (8H), 5.23 (2H, s), 3.97 (3H, s), 3.73 (3H, s), 2.23 (3H, s)

Present Compound 210:

7.2-7.5 (8H), 6.93 (1H, m), 5.34 (2H, s), 3.85 (3H, s), 3.71 (3H, s), 2.27 (3H, s)

Present Compound 211:

7.2-7.4 (8H), 6.94 (1H, m), 5.19 (2H, s), 3.85 (3H, s), 3.72 (3H, s), 2.24 (3H, s)

Present Compound 212:

7.2-7.4 (8H), 6.94 (1H, m), 5.17 (2H, s), 3.85 (3H, s), 3.72 (3H, s), 2.22 (3H, s)

Present Compound 213:

7.2-7.4 (6H), 7.02 (1H, m), 6.94 (1H, m), 5.37 (2H, s), 3.86 (3H, s), 3.72 (3H, s), 2.17 (3H, s)

Present Compound 214:

8.59 (2H, d), 7.2-7.4 (6H), 6.94 (1H, m), 5.24 (2H, s), 3.86 (3H, s), 3.73 (3H, s), 2.29 (3H, s)

Present Compound 215:

7.0-7.45 (9H, m), 5.20 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.19 (3H, s)

Present Compound 216:

7.0-7.45 (9H, m), 5.20 (2H, s), 3.83 (3H, s), 3.70 (3H, s), 2.76 (2H, q), 2.19 (3H, s), 1.26 (3H, t)

Present Compound 217:

7.98 (1H, s), 7.25-7.45 (7H, m), 7.10 (1H, s), 5.20 (2H, s), 3.93 (3H, s), 3.70 (3H, s), 2.41 (3H, s) , 2.19 (3H, s)

Present Compound 220:

6.85-7.5 (9H), 5.19 (2H, s), 3.91 (3H, s), 3.83 (3H, s), 3.71 (3H, s), 2.18 (3H, s)

Compound 232: (14: 1 mixture of isomers)

7.71 (1H, d), 7.58 (1H, dd), 7.2-7.45 (6H, m), {5.22 (2H × 14/15), 5.10 (2H × 1/15), each s}, 4.10 (3H, s), (3.43 (3H × 14/15), 3.35 (3H × 1/15), angle s}, 2.46 (3H, s), {2.21 (3H × 14/15), 2.15 (3H × 1/15 ), Each s}

Present Compound 233:

7.69 (1H, d), 7.52 (1H, dd), 7.2-7.45 (6H, m), 6.25 (1H, br), 5.21 (2H, s), 3.99 (3H, s), 2.66 (3H, d) , 2.47 (3H, s), 2.21 (3H, s)

Present Compound 237:

7.0-7.5 (9H), 5.37 (2H, s), 3.85 (3H, s), 3.71 (3H, s), 2.37 (3H, s)

Present Compound 247:

7.2-7.5 (6H), 7.17 (1H, t), 6.96 (1H, d), 6.91 (1H, br.s), 6.63 (1H, dd), 5.21 (2H, s), 3.85 (3H, s) , 3.67 (3H, s), 3.08 (3H, s), 2.74 (2H, q), 1.11 (3H, t)

Compound 250:

7.2-7.4 (4H), 6.93 (1H, m), 3.96 (3H, s), 3.87 (3H, s), 3.72 (3H, s), 2.70 (2H, dd), 1.2-1.7 (4H), 0.91 (3H, t)

Present Compound 251:

7.47 (1H, s), 7.15 (1H, t), 6.9-7.0 (2H), 6.64 (1H, br.d), 3.97 (3H, s), 3.85 (3H, s), 3.67 (3H, s) , 3.49 (2H, q), 2.18 (3H, s), 1.19 (3H, t)

Present Compound 252:

8.46 (1H, br.s), 7.93 (1H, br.s), 7.41 (1H, s), 7.22 (1H, t), 7.09 (1H, br.d), 6.99 (1H, br.d), 6.71 (1H, br.d), 3.88 (3 H, s), 3.68 (3H, s), 3.11 (3H, s), 2.52 (3H, s)

Present Compound 253:

7.33 (1H, s), 7.15 (2H, dd (AB)), 7.02 (1H, s), 3.96 (3H, s), 3.88 (3H, s), 3.70 (3H, s), 2.35 (3H, s ), 2.15 (3H, s)

Present Compound 254:

8.63 (2H, d), 7.41 (1H, s), 7.18 (1H, t), 7.10 (1H, br.d), 7.07 (1H, t), 6.99 (1H, br.s), 6.69 (br. s), 3.87 (3H, s), 3.68 (3H, s), 3.11 (3H, s), 2.51 (3H, s)

Compound 256: (8: 1 mixture of isomers)

7.0-7.45 (8H, m), {5.20 (2H × 8/9), 5.08 (2H × 1/9), each s}, {4.03 (3H × 8/9), 3.97 (3H × 1/9) , Angle s}, {3.79 (3H × 8/9), 3.73 (3H × 1/9), angle s}, {2.34 (3H × 8/9), 2.22 (3H × 1/9), angle s} , {2.18 (3H × 8/9), 2.14 (3H × 1/9), each s}

Compound 257: (10: 1 mixture of isomers)

7.0-7.45 (8H, m), {6.63 and 6.33, combined 1H, each br}, {5.20 (2H × 10/11), 5.08 (2H × 1/11), each s}, {3.92 (3H × 10/11), 3.88 (3H × 1/11), angle s}, {2.84 (3H × 10/11), 2.73 (3H × 1/11), angle s}, {2.35 and 2.36, combined 3H, Angle s}, {2.18 (3H × 10/11), 2.15 (3H × 1/11), angle s}

Present Compound 272:

7.44 (1H, s), 7.23 (1H, dd), 7.14 (1H, br.d), 7.03 (1H, br.s), 6.73 (1H, br.d), 4.17 (3H, s), 3.89 ( 3H, s), 3.69 (3H, s), 3.10 (3H, s)

Present Compound 301:

8.67 (1H, s), 7.39 (1H, s), 7.38 (1H, s), 7.1-7.3 (3H), 3.92 (3H, s), 3.74 (3H, s), 2.47 (3H, s), 2.41 (3H, s)

Present Compound 302:

8.56 (1H, br.s), 7.94 (1H, br.d), 7.46 (1H, d), 7.0-7.4 (4H), 3.90 (3H, s), 3.73 (3H, s), 2.48 (3H, s), 2.40 (3H, s)

Present Compound 321:

7.0-7.4 (8H), 5.14 (2H, s), 3.81 (3H, s), 3.68 (3H, s), 2.34 (3H, s), 2.16 (3H, s)

Present Compound 322:

7.61 (2H, d), 7.50 (2H, d), 7.31 (1H, s), 7.14 (2H, s), 6.99 (1H, s), 5.24 (2H, s), 3.83 (3H, s), 3.69 (3H, s), 2.34 (3H, s), 2.20 (3H, s)

Present Compound 324:

7.64 (2H, d), 7.48 (2H, d), 7.31 (1H, s), 7.14 (2H, s), 6.97 (1H, s), 5.24 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.21 (3H, s)

Compound 326:

7.0-7.4 (8H), 5.15 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (6H, s), 2.17 (3H, s)

Present Compound 329:

7.34 (2H, d), 7.33 (1H, s), 7.15 (1H, d), 7.13 (1H, d), 7.03 (1H, s), 6.89 (2H, s), 5.12 (2H, s), 3.86 (3H, s), 3.81 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.16 (3H, s)

Present Compound 332:

7.48 (2H, d), 7.32 (1H, s), 7.27 (2H, d), 7.13 (2H, s), 6.99 (1H, s), 5.13 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.34 (3H, s), 2.18 (3H, s)

Compound 333:

7.0-7.4 (8H), 5.18 (2H, s), 3.83 (3H, s), 3.69 (3H, s), 2.35 (3H, s), 2.19 (3H, s)

Compound 336:

7.0-7.6 (8H), 5.15 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.20 (3H, s)

Present Compound 351:

7.2-7.4 (5H), 6.97 (1H, m), 3.87 (3H, s), 3.73 (3H, s), 2.25 (3H, s)

Present Compound 353:

7.0-7.4 (9H), 4.19 (2H, t), 3.84 (3H, s), 3.70 (3H, s), 2.74 (2H, dd), 2.35 (3H, s), 2.16 (3H, s), 2.03 (2H, m)

Present Compound 356:

7.0-7.5 (8H), 5.26 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.34 (3H, s), 2.18 (3H, s)

Present Compound 357:

7.0-7.5 (8H), 5.32 (2H, s), 3.86 (3H, s), 3.71 (3H, s), 2.36 (3H, s), 2.24 (3H, s)

Present Compound 359:

7.0-7.5 (8H), 5.21 (2H, s), 3.86 (3H, s), 3.70 (3H, s), 2.40 (3H, s), 2.35 (3H, s), 2.17 (3H, s)

Compound 360:

7.33 (1H, s), 7.0-7.2 (6H), 5.18 (2H, s), 3.86 (3H, s), 3.70 (3H, s), 2.36 (3H, s), 2.35 (3H, s), 2.32 (3H, s), 2.17 (3H, s)

Present Compound 362:

7.65 (1H, br.s), 7.57 (2H, br.t), 7.48 (1H, br.d), 7.31 (1H, s), 7.14 (2H, s), 7.00 (1H, s), 5.24 ( 2H, s), 3.84 (3H, s), 3.69 (3H, s), 2.35 (3H, s), 2.20 (3H, s)

Present Compound 366:

7.68 (1H, s), 7.60 (2H, t), 7.46 (1H, dd), 7.34 (1H, s), 7.14 (2H, s), 6.99 (1H, s), 5.21 (2H, s), 3.86 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.21 (3H, s)

Present Compound 371:

7.0-7.4 (8H), 5.17 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.18 (3H, s), 1.30 (9H, s)

Present Compound 373:

6.9-7.4 (7H), 5.34 (2H, s), 3.87 (3H, s), 3.70 (3H, s), 2.34 (3H, s), 2.13 (3H, s)

Present Compound 374:

7.1-7.4 (7H), 5.46 (2H, s), 3.87 (3H, s), 3.70 (3H, s), 2.34 (3H, s), 2.14 (3H, s)

Present Compound 377:

6.9-7.4 (7H), 5.12 (2H, s), 3.86 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.18 (3H, s)

Compound 383: (2: 1 mixture of isomers)

7.0-7.4 (7H), {5.23 (2H × 1/3), 5.13 (2H × 2/3), each s}, {3.86 (3H × 1/3), 3.86 (3H × 2/3), each s}, 3.70 (3H, s), 2.35 (3H, s), {2.31 (3H × 1/3), 2.60 (3H × 2/3), each s}, {2.30 (3H × l / 3), 2.70 (3H × 2/3), each s}, 2.17 (3H, s)

Present Compound 393:

8.17 (1H, d), 7.85 (2H, dd), 7.4-7.6 (4H, m), 7.32 (1H, s), 7.18 (1H, d), 7.13 (1H, d), 7.04 (1H, s) , 5.66 (2H, s), 3.84 (3H, s), 3.71 (3H, s), 2.35 (3H, s), 2.16 (3H, s)

Compound 414:

8.66 (1H, s), 7.39 (1H, s), 7.38 (1H, s), 7.29 (1H, d), 7.24 (1H, d), 7.13 (1H, s), 3.92 (3H, s), 3.74 (3H, s), 2.47 (3H, s), 2.41 (3H, s)

Present Compound 417:

7.33 (1H, s), 7.18 (1H, dd), 7.12 (1H, d), 7.02 (1H, d), 4.21 (2H, q), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.15 (3H, s), 1.30 (3H, t)

Present Compound 418:

7.32 (1H, s), 7.18 (1H, dd), 7.13 (1H, d), 7.02 (1H, d), 4.12 (2H, t), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.16 (3H, s), 1.65-1.8 (2H, m), 0.97 (3H, t)

Present Compound 419:

7.32 (1H, s), 7.18 (1H, dd), 7.13 (1H, d), 7.03 (1H, d), 4.35-4.5 (1H, m), 3.87 (3H, s), 3.70 (3H, s) , 2.35 (3H, s), 2.14 (3H, s), 1.28 (6H, d)

Present Compound 421:

7.32 (1H, s), 7.18 (1H, dd), 7.12 (1H, d), 7.03 (1H, d), 4.15-4.3 (1H, m), 3.87 (3H, s), 3.70 (3H, s) , 2.35 (3H, s), 2.14 (3H, s), 1.5-1.8 (2H, m), 1.25 (3H, d), 0.94 (3H, t)

Present Compound 422:

7.32 (1H, s), 7.0-7.2 (3H, m), 3.93 (2H, d), 3.87 (3H, s), 3.70 (3H, s), 2.33 (3H, s), 2.16 (3H, s) , 1.95-2.1 (1H, m), 0.95 (6H, d)

Present Compound 423:

7.33 (1H, s), 7.20 (1H, dd), 7.12 (1H, d), 7.08 (1H, d), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.13 (3H, s), 1.33 (9H, s)

Present Compound 430:

7.32 (1H, s), 7.16 (1H, d), 7.13 (1H, d), 6.99 (1H, s), 4.70 (2H, s), 4.23 (2H, q), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.24 (3H, s), 1.28 (3H, t)

Present Compound 433:

7.33 (1H, s), 7.19 (1H, d), 7.14 (1H, d), 7.03 (1H, s), 4.76 (2H, d), 3.88 (3H, s), 3.71 (3H, s), 2.46 (1H, t), 2.41 (3H, s), 2.19 (3H, s)

Present Compound 434:

7.32 (1H, s), 7.15 (1H, d), 7.13 (1H, d), 7.02 (1H, s), 6.06 (1H, m), 5.32 (1H, d), 5.21 (1H, d), 4.67 (2H, d), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.18 (3H, s)

Present Compound 435:

7.34 (1H, d), 7.15 (2H, s), 7.06 (1H, s), 6.18 (1H, s), 4.74 (2H, d), 3.88 (3H, s), 3.71 (3H, s), 2.36 (3H, s), 2.15 (3H, s)

Present Compound 436:

7.31 (1H, s), 7.14 (2H, s), 7.00 (1H, s), 4.60 (2H, s), 3.86 (3H, s), 3.70 (3H, s), 2.53 (3H, s), 2.23 (3H, s), 1.48 (9H, s)

Compound 438:

6.6-7.5 (13H), 5.17 (2H, s), 3.85 (3H, s), 3.67 (3H, s), 3.09 (3H, s), 2.21 (3H, s)

Present Compound 439:

6.4-7.5 (14H), 5.14 (2H, s), 5.06 (2H, s), 3.83 (3H, s), 3.66 (3H, s), 3.08 (3H, s), 2.19 (3H, s)

Present Compound 440:

8.19 (1H, d), 7.8-7.9 (2H), 7.4-7.6 (4H), 7.40 (1H, s), 7.18 (1H, t), 7.00 (1H, br.d), 6.96 (1H, br. s), 6.65 (1H, br.d), 5.69 (2H, s), 3.85 (3H, s), 3.68 (3H, s), 3.10 (3H, s), 2.22 (3H, s)

Present Compound 441:

6.6-7.4 (13H), 5.16 (2H, s), 3.84 (3H, s), 3.66 (3H, s), 3.08 (3H, s), 2.24 (3H, s), 2.21 (3H, s)

Present Compound 442:

6.6-7.7 (14H), 5.26 (2H, s), 3.84 (3H, s), 3.66 (3H, s), 3.09 (3H, s), 2.24 (3H, s)

Present Compound 443:

7.76 (1H, d), 7.64 (1H, dd), 7.5-7.6 (5H), 7.43 (1H, t), 7.40 (1H, s), 7.17 (1H, t), 6.99 (1H, d), 6.95 (1H, s), 6.64 (1H, d), 5.29 (2H, s), 3.85 (3H, s), 3.66 (3H, s), 3.09 (3H, s), 2.26 (3H, s)

Compound 444:

7.32 (1H, s), 7.17 (1H, d), 7.13 (1H, d), 7.03 (1H, s), 4.99 (1H, s), 4.91 (1H, s), 4.59 (2H, s), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.19 (3H, s), 1.79 (3H, s)

Compound 445: (5: 1 mixture of isomers)

7.32 (1H, s), 7.2-7.3 (3H), 6.94 (1H, m), {5.00 (2H × 1/6), 4.68 (2H × 5/6), each s}, {3.98 (3H × 1 / 6), 3.85 (3H × 5/6), angle s}, {3.89 (3H × 5/6), 3.84 (3H × 1/6), angle s}, 3.71 (3H, s), {2.21 ( 3H × 5/6), 2.18 (3H × 1/6), each s}, {2.23 (3H × 1/6), 1.92 (3H × 5/6), each s}

Compound 446: (5: 1 mixture of isomers)

7.33 (1H, s), 7.17 (1H, d), 7.14 (1H, d), 7.03 (1H, s), {4.98 (2H × 1/6), 4.66 (2H × 5/6), each s} , (3.89 (3H × 5/6), 3.84 (3H × 1/6), angle s}, 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), {2.19 (3H × 1/6), 2.17 (3H × 5/6), each s}, 1.91 (3H, s)

Compound 447: (5: 1 mixture of isomers)

7.40 (1H, s), 7.17 (1H, t), 6.97 (1H, d), 6.92 (1H, br.s), 6.66 (1H, br.d), (5.00 (2H × 1/6), 4.68 (2H × 5/6), angle s}, {3.89 (3H × 5/6), 3.83 (3H × 1/6), angle s}, 3.87 (3H, s), 3.67 (3H, s), 3.09 (3H, s), {2.22 (3H × 1/6), 2.21 (3H × 5/6), each s}, 1.93 (3H, s)

Compound 448: (5: 1 mixture of isomers)

7.2-7.3 (2H), 7.05 (1H, m), 6.78 (1H, m), {5.00 (2H × 1/6), 4.68 (2H × 5/6), each s}, 4.02 (3H, s) , (3.89 (3H × 5/6), 3.84 (3H × 1/6), angle s}, 3.76 (3H, s), 3.25 (3H, s), (2.22 (3H × l / 6), 2.21 ( 3H × 5/6), each s}, 1.92 (3H, s)

Compound 449: (5: 1 mixture of isomers)

7.1-7.4 (2H), 7.05 (1H, m), 6.80 (1H, m), 6.70 (1H, br.), (5.00 (2H × 1/6), 4.67 (2H × 5/6), each s }, 3.90 (3H, s), {3.89 (3H × 5/6), 3.84 (3H × 1/6), each s}, 3.27 (3H, s), 2.88 (3H, d), {2.22 (3H × 1/6), 2.20 (3H × 5/6), each s}, 1.91 (3H, s)

Compound 450:

7.32 (1H, s), 7.18 (1H, d), 7.15 (1H, d), 7.02 (1H, s), 5.42 (1H, s), 5.36 (1H, s), 4.70 (2H, s), 3.85 (3H, s), 3.69 (3H, s), 2.35 (3H, s), 2.21 (3H, s)

Present Compound 451:

7.33 (1H, s), 7.0-7.3 (3H), 5.11 (1H, d), 4.65 (2H, d), 3.87 (3H, s), 3.71 (3H, s), 2.35 (3H, s), 2.17 (3H, s), 1.25 (9H, s)

Present Compound 452:

7.0-7.4 (8H), 5.17 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.36 (3H, s), 2.34 (3H, s), 2.19 (3H, s)

Present Compound 453:

6.9-7.4 (9H), 5.34 (1H, q), 3.81 (3H, s), 3.68 (3H, s), 2.33 (3H, s), 2.20 (3H, s), 1.59 (3H, d)

Present Compound 454:

7.39 (1H, s), 7.38 (1H, d), 7.32 (1H, s), 7.24 (1H, dd), 7.14 (2H, s), 7.01 (1H, s), 3.85 (3H, s), 3.70 (3H, s), 2.34 (3H, s), 2.21 (3H, s)

Present Compound 455:

7.0-7.5 (7H), 5.26 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.24 (3H, s)

Present Compound 456:

7.75 (1H, s), 7.63 (1H, d), 7.37 (1H, d), 7.33 (1H, s), 7.15 (1H, d), 7.14 (1H, d), 7.09 (1H, t), 7.01 (1H, s), 5.13 (2H, s), 3.85 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.19 (3H, s)

Present Compound 457:

7.34 (1H, s), 7.16 (1H, d), 7.12 (1H, d), 7.04 (1H, s), 6.92 (1H, s), 6.84 (1H, s), 5.97 (2H, s), 5.20 (2H, s), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.20 (3H, s)

Present Compound 458:

7.0-7.5 (9H), 6.66 (1H, d), 6.42 (1H, dt), 4.83 (2H, d), 3.81 (3H, s), 3.69 (3H, s), 2.35 (3H, s), 2.20 (3H, s)

Present Compound 459:

7.31 (1H, s), 7.16 (1H, d), 7.14 (1H, d), 6.98 (1H, s), 5.92 (1H, m), 5.33 (1H, d), 5.24 (1H, d), 4.74 (2H, s), 4.62 (2H, d), 3.87 (3H, s), 3.70 (3H, s), 2.35 (3H, s), 2.24 (3H, s)

Present Compound 460:

6.95-7.4 (9H, m), 3.89 (3H, s), 3.72 (3H, s), 2.39 (3H, s), 2.38 (3H, s)

Present Compound 461:

8.19 (2H, d), 7.52 (2H, d), 7.31 (1H, s), 7.13 (2H, s), 6.98 (1H, s), 5.27 (2H, s), 3.83 (3H, s), 3.68 (3H, s), 2.34 (3H, s), 2.22 (3H, s)

Present compound 462:

7.36 (1H, s), 7.05-7.2 (3H, m), 5.23 (2H, s), 3.89 (3H, s), 3.71 (3H, s), 2.35 (3H, s), 2.12 (3H, s)

Compound 463:

7.35 (1H, s), 7.17 (1H, d), 7.12 (1H, d), 7.03 (1H, s), 3.87 (3H, s), 3.71 (3H, s), 2.36 (3H, s), 2.23 (3H, s)

Next, a formulation example is described. Part means parts by weight, and the compound is indicated by the compound number shown in Table 1 and Table 2.

Formulation Example 1

50 parts of the present compounds 1-493 and 1001-1078, 3 parts of calcium lignin sulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrated silicon oxide are sufficiently ground and mixed to obtain a water-dispersible powder, respectively.

Formulation Example 2

25 parts of the present compounds 1-493 and 1001-1078 each, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water were mixed and wet-pulverized until the particle size of the active ingredient was 5 microns or less. Obtain a flow agent, respectively.

Formulation Example 3

2 parts each of the present compounds 1-493 and 1001-1078, 88 parts of kaolin clay and 10 parts of talc are sufficiently ground and mixed to obtain a powder.

Formulation Example 4

20 parts each of the present compounds 1-493 and 1001-1078, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecyl benzenesulfonate and 60 parts of xylene were sufficiently mixed to obtain an emulsifying thickener, respectively.

Formulation Example 5

2 parts of each of the compounds 1-493 and 1001-1078, 1 part of synthetic hydrated silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay were sufficiently ground and mixed, kneaded well by adding water, Granulation and drying give granules respectively.

Formulation Example 6

20 parts each of the present compounds 1-493 and 1001-1078 and 1.5 parts of sorbitan trioleate are mixed with 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol, and the mixture is finely ground (particle size 3 µm or less) with a sand grinder. 40 parts of aqueous solution containing 0.1 parts of aluminum magnesium silicate and 0.05 parts of xanthan gum are added, and 10 parts of propylene glycol is also added, followed by stirring and mixing to obtain a 20% suspension concentrate, respectively.

Formulation Example 7

0.1 parts each of the present compounds 1-493 and 1001-1078 are dissolved in 5 parts trichloroethane and 5 parts xylene, and the solution is mixed with 89.9 parts deodorized kerosene to obtain 0.1% oil solution, respectively.

Formulation Example 8

0.1 parts of each of the compounds 1-493 and 1001-1078, 0.2 parts of tetramethrin, 0.1 parts of d-phenotrine, 10 parts of trichloroethane and 59.6 parts of deodorized kerosene were mixed and dissolved, and the solution was filled into an aerosol container. The valve portion is attached and 30 parts of propellant (liquefied petroleum gas) are charged under pressure through the valve portion to obtain an oily aerosol, respectively.

Formulation Example 9

0.2 parts each of the present compounds 1-493 and 1001-1078, 0.2 parts d-allethrin, 0.2 parts d-phenotrine, 5 parts xylene, 3.4 parts deodorized kerosine and an emulsifier {ATMOS 300 (trade name of Atlas Chemical Company)} One part is mixed and dissolved, and 50 parts of this solution and pure water are filled into an aerosol container, and a valve portion is attached thereto, and 40 parts of a propellant (liquefied petroleum gas) are charged under pressure through the valve portion to obtain an aqueous aerosol, respectively.

Formulation Example 10

To 0.3 g of the present compound 1-493 and 1001-1078, 0.3 g of d-allerine was added, the mixture was dissolved in 20 ml of acetone, and the carrier for mosquito coils (tabu powder, pyrethrum mark powder and wood flour 4 :) was added. The mixture was mixed uniformly by stirring with 99.4 g), 120 ml of water was added, kneaded sufficiently, and then molded and dried to obtain a mosquito coil, respectively.

Formulation Example 11

Acetone is added to 0.4 g of the compounds 1-493 and 1001-1078, 0.4 g of d-alletrin and 0.4 g of piperonyl butoxide, and dissolved to make a total volume of 10 ml. 0.5 ml of this solution was uniformly impregnated with the base material for electric mosquito mat (2.5 cm x 1.5 cm, thickness 0.3 cm) (made by molding a fiberized mixture of cotton wool and pulp into a sheet form), and the electric mosquito mat was respectively To obtain.

Formulation Example 12

100 mg of each of Compounds 1-493 and 1001-1078 were dissolved in an appropriate amount of acetone, and the solution was impregnated into a porous ceramic plate (4.0 cm × 4.0 cm, thickness 1.2 cm) to obtain a thermal fumigant, respectively.

Formulation Example 13

10 mg of each of the present compounds 1-493 and 1001-1078 was dissolved in 0.5 ml of acetone, and this solution was added to 5 g of an animal solid bait powder (Breeding Solid Feed CE-2; do. Acetone is then removed by air drying to yield 0.5% toxic bait, respectively.

The following test examples then show that the compounds are useful as agricultural and / or horticultural microbial fungicides and as insecticides and / or mites. The compound is shown by the compound number shown in Table 1 and Table 2.

The effect of the compounds is assayed by calculating the percentage of diseased area on the tested plant for agricultural and / or horticultural antimicrobial use, or the mortality of test worms for pesticidal or mite use.

Test Example 1 Efficacy of the present compound on febrile disease (preventive effect)

Sand loam was filled into plastic pots, rice (breed: Nihonbare) was planted and grown in greenhouses for 20 days. Then, compound numbers 1, 2, 4-14, 30, 31, 115, 116, 163, 174, 199, 200, 215, 216, 217, 220, 231, 232, 233, 237, 247, 250, 251 , 252, 253, 255, 257, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374 , 377, 383, 393, 414, 417, 418, 419, 421, 422, 423, 430, 433-436, 438-462 were prepared in accordance with the method of Formulation Example 1 as a water-dispersible powder, Diluted to a predetermined concentration (500 or 200 ppm) and sprayed on rice seedlings. After the treatment, the seedlings were air dried, and the spores of the thermal jar were inoculated into the rice seedlings. After inoculation, the seedlings were left for 6 days at 28 ° C. under high humidity and the efficacy of the test compounds was assayed. As a result, all the compounds inhibited the development of the blast disease. The disease area ratio on the treated seedlings was less than 30%.

Experimental Example 2: Efficacy of the present compound on leaf blot (preventive effect)

Sand loam was filled into plastic pots, rice (breed: Nihonbare) was planted and grown in greenhouses for 20 days. Compounds 1, 2, 4-14, 31, 116, 199, 200, 216, 220, 231, 237, 255, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333 , 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 414, 417, 418, 419, 421, 422, 423, 430, 433-436, 438 Each compound of -462 was prepared as a water-dispersible powder according to the method of Formulation Example 1, diluted with water to a predetermined concentration (500-200 ppm), and sprayed sufficiently on the leaves of rice seedlings. After treatment, the seedlings were air dried and inoculated with rice seedlings with mycelia of leaf blot. After inoculation, the seedlings were left for 6 days at 28 ° C. under high humidity and the efficacy of the test compounds was assayed. As a result, all compounds inhibited the development of leaf blot. The pest area on the treated seedlings was 3/10 times that on the untreated seedlings.

Test Example 3: Effect of the present compound on wheat powdery mildew (therapeutic effect)

Sand loam was filled into plastic pots, wheat (variety: Norin 73) was planted and grown in a greenhouse for 10 days. Powdery mildew spores of wheat were inoculated on wheat. After inoculation, the seedlings were left for 2 days in a 23 ° C greenhouse. Compound number 1, 2, 4-14, 30, 31, 115, 116, 163, 174, 199, 200, 215, 216, 217, 220, 232, 237, 247, 251, 252, 253, 255, 256, 257, 272, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 417, 418, 419, Each compound of 421, 422, 423, 430, 433-436, 438-462 is prepared as a suspending agent according to the method of Formulation Example 2, diluted to a predetermined concentration (500 or 200 ppm) with water, and inoculated on inoculated wheat Sprayed. After treatment, the seedlings were left for 7 days under illumination and the efficacy of the test compound was assayed. As a result, all compounds inhibited the development of powdery mildew in wheat. The proportion of pest area on the treated seedlings was less than 30%.

Test Example 4: Efficacy of the present compound against brown leaf rust of wheat (prevention effect)

Sand loam was filled into plastic pots, wheat (variety: Norin 73) was planted and grown in a greenhouse for 10 days. Compound number 1, 2, 3, 4, 30, 31, 115, 116, 163, 174, 199, 200, 215, 216, 217, 220, 231, 237, 247, 251, 252, 253, 255, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 417, 418, The compound of 419, 421, 422, 423, 430, 433-436, 438-462 was prepared as an emulsifying thickener according to the method of Formulation Example 4, diluted with water to a predetermined concentration (500 or 200 ppm), and the leaves of wheat. Sprayed onto the bed sufficiently. After treatment, the seedlings were air dried and inoculated with wheat brown leaf rust spores. After inoculation, the seedlings were kept at 23 ° C. in the dark for 1 day under high humidity and further 6 days under illumination, after which the efficacy of the test compound was assayed. As a result, all the compounds suppressed brown leaf rust of wheat. The disease area ratio on the treated seedlings was less than 30%.

Test Example 5 Efficacy of the present compound on wheat spot disease (preventive effect)

Sand loam was filled into plastic pots, wheat (variety: Norin 73) was planted there and grown in a greenhouse for 10 days. Each compound of Compound Nos. 1, 2, 4, 6-9, 12, 115, 116, 163, 215, 252, 255 and 272 was prepared as an emulsifying thickener according to the method of Formulation Example 4, 500 ppm) and sprayed to the leaves of wheat sufficiently. After the treatment, the seedlings were air dried and the wheat spotted spores were inoculated into the wheat. After inoculation, the seedlings were left for 3 days in high humidity 15 ° C. darkness and also for 18 days under illumination to assay the efficacy of the test compounds. The compound and all the compounds suppressed wheat spot disease. The disease area ratio on the treated seedlings was less than 10%.

Experimental Example 6: Efficacy of the present compound on the bark of wheat (prevention effect)

Sand loam was filled into plastic pots, wheat (variety: Norin 73) was planted there and grown in a greenhouse for 10 days. Compound number 1, 2, 4, 6-9, 12, 115, 116, 163, 215, 220, 233, 237, 252, 255, 257, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 374, 377, 383, 393, 414, 417, 418, 419, 421, 422, 423, 430, 433-436, Each compound of 438-440, 442-448, 450-462 was prepared as an emulsifying thickener according to the method of Formulation Example 4, diluted with water to a predetermined concentration (500 or 200 ppm), and sprayed to the leaves of the wheat sufficiently. After treatment, the seedlings were air dried and seeded with wheat blight spores. After inoculation, the seedlings were left for 4 days in high humidity 15 ° C. darkness and also for 7 days under illumination to assay the efficacy of the test compounds. As a result, all compounds inhibited the development of bark of wheat. The disease area ratio on the treated seedlings was less than 30%.

Experimental Example 7: Efficacy of the present compound on the eyespot of wheat (preventive effect)

Sand loam was filled into plastic pots, wheat (variety: Norin 73) was planted and grown in a greenhouse for 10 days. Compound number 1-12, 116, 163, 174, 215, 220, 233, 237, 247, 252, 255, 272, 301, 322, 324, 326, 329, 336, 353, 357, 359, 360, 366, Each compound of 371, 373, 374, 377, 383, 393, 414, 422, 430, 433, 434, 436, 438-443, 445, 446, 477, 449-456, 458 and 459 was prepared according to Formulation Example 4. Prepared with an emulsifying thickener, diluted with water to a predetermined concentration (500 ppm) and sprayed sufficiently on the leaves of wheat. After treatment, the seedlings were air dried and the PDA medium containing the icepot spores of the wheat was placed on the bottom of the wheat. After inoculation, the seedlings were left for 7 days at 15 ° C. darkness under high humidity and also for 4 days under illumination to assay the efficacy of the test compounds. As a result, all compounds inhibited the development of wheat ice pots. The diseased area on the treated seedlings was 3/10 times the untreated area.

Test Example 8: Efficacy of the present compound against cucumber disease of cucumber (prevention effect)

Sand loam was filled into plastic pots, cucumbers (variety: Sagamihanpaku) were planted and grown in greenhouses for 20 days. Each compound of Compound No. 1, 2, 4, 115, 116, 163, 174, 215, 216, 217, 252, 272 was prepared as a water dispersible powder according to the method of Formulation Example 1, and prescribed concentration (500 ppm) as water. ) And sprayed sufficiently on cucumber leaves. After the treatment, the seedlings were air dried and cucumbers were inoculated with cucumber fungal spores. After inoculation, the seedlings were kept at 23 ° C. for 1 day under high humidity and also for 10 days in the greenhouse, and the efficacy of the test compound was assayed. As a result, all the compounds suppressed the development of cucumber cucumber disease. The disease area ratio on the treated seedlings was less than 10%.

Test Example 9: Efficacy of the present compound on cucumber mold disease of cucumber (prevention effect)

Sand roms were placed in plastic pots, cucumbers (variety: Sagamihanpaku) were planted and grown in greenhouses for 12 days. Compound number 1, 2, 4-13, 30, 31, 116, 163, 174, 199, 200, 215, 220, 237, 247, 252, 255, 257, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 414, 417, 418, 419, 421, 422, 423, Each compound of 430, 433-436, 439, 440, 442-447, and 450-462 was prepared as a water dispersible powder according to the method of Formulation Example 1, diluted with water to a predetermined concentration (500-200 ppm), Cucumber leaves were thoroughly sprayed. After treatment, the seedlings were air dried and PDA medium containing cucumber gray mold mycelium was left at the bottom of the cucumber leaf. After inoculation, the seedlings were left at 10 ° C. for 4 days under high humidity and the efficacy of the test compounds was assayed. As a result, all compounds inhibited the development of cucumber fungal disease in cucumber. The proportion of seedlings treated was less than 30%.

Test Example 10: Efficacy of the present compound on cucumber powdery mildew (preventive effect)

Sand loam was filled into plastic pots, cucumbers (variety: Sagamihanpaku) were planted and grown in a greenhouse for 12 days. Compound number 1, 2, 4-8, 11, 12, 14, 116, 215, 216, 217, 220, 257, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 414, 417, 418, 419, 421, 422, 423, 430, 433-436, 438, 440, Each compound of 442, 444, 446, 447 and 450-462 was prepared as a suspension according to Formulation Example 2, diluted to a predetermined concentration (500 or 200 ppm) with water and sprayed sufficiently on the cucumber leaves. After treatment, the seedlings were air dried and cucumber powdered spores were inoculated. After inoculation, the seedlings were left at 23 ° C. for 12 days and the efficacy of the test compound was assayed. As a result, all compounds inhibited the development of cucumber powdery mildew. The disease area ratio on the treated seedlings was less than 30%.

Test Example 11: Efficacy of the present compound against grape fungal disease (prevention effect)

The sandy loam was filled in a plastic pot, grapes (variety: Berry A) was planted and grown in a greenhouse for 40 days. Compound number 1, 2, 4, 115, 116, 163, 174, 215, 216, 217, 220, 230, 232, 233, 237, 252, 272, 301, 302, 321, 322, 324, 326, 329, 332, 333, 336, 353, 356, 357, 359, 360, 362, 366, 371, 373, 374, 377, 383, 393, 417, 418, 419, 421, 422, 423, 430, 433-436, Each compound of 438, 440, 442-448 and 450-462 was prepared as a suspension according to the method of Formulation Example 2, diluted with water to a predetermined concentration (500 or 200 ppm) and sprayed sufficiently onto grape leaves. After treatment, the seedlings were air dried and inoculated with grape neutrophil dwellers. After inoculation, the seedlings were allowed to stand for 1 day at 23 ° C. under high humidity and also for 6 days in the greenhouse, and the efficacy of the test compound was assayed. As a result, all the compounds inhibited the development of powdery mildew in grapes. The proportion of pest area on the treated seedlings was less than 30%.

Test Example 12 Insecticidal Test on Tobacco Spider Moth (Spodoptera litura)

2 ml of the dilution obtained by preparing the compounds of the compound Nos. 4, 9 and 13 as an emulsifying thickener according to the method of Formulation Example 4 and diluting to a predetermined concentration (500 ppm) with water in a 11 cm diameter polyethylene cup, It was immersed in 13 g of the artificial food of the prepared Spodoptera litura. Four weeks old Spodoptera litura was released in a cup, and after 6 days, the survival rate was examined to determine the mortality rate. As a result, the test compound showed 80% mortality.

Test Example 13: Insecticidal test on Nilaparvata lugens

Sand loam was charged into a plastic pot, rice (variety: Nihonbare) was planted and grown in a greenhouse. Each compound of Compound Nos. 2, 4-6, 8-10, and 14 was prepared as a water dispersible powder by the method according to Formulation Example 1, diluted with water to a predetermined concentration (500 ppm), and adhered to the leaves so as to sufficiently adhere to the rice leaves. Sprayed. After spraying, the seedlings were air dried and loosened about 30 larvae of Nilaparvata lugens. After release of the larvae, the seedlings were left in the greenhouse for 6 days, and their survival was examined to determine the lethality. As a result, all compounds showed a mortality of at least 80%.

Test Example 14 Insecticidal Test against Twelve Spotted Pumpkin Beetles (Diabrotica undecimpunctata)

The bottom of a 5.5 cm diameter polyethylene cup was covered with filter paper of the same diameter as the bottom. Compounds 2 and 4-10 were each prepared as an emulsifiable thickener according to the method of Formulation Example 4, diluted with water to a predetermined concentration (50 ppm) to obtain 1 ml of the diluent, and added dropwise onto the filter paper. About 30 eggs of twelve zucchini leaves were placed on filter paper and one corn seed was placed thereon as food. After 8 days, the survival rate of the hatched larvae was examined to determine the mortality rate. As a result, all compounds showed a mortality of at least 80%.

Test Example 15 Insecticidal Test on Aphid gossypii

Five test worm adults were released on true leaf seedlings (first lobe generator) of cucumbers planted in polyethylene cups. After 1 day of release, the present compounds 5, 6, 8 and 10 were each prepared as an emulsifiable thickener according to the method of Formulation Example 4, and the dilution obtained by diluting to a predetermined concentration (500 ppm) with water was 20 ml / pot. Sprayed in amounts. After 6 days of spraying the drug solution, a control value was obtained according to the following formula. As a result, the compounds each exhibited a control effect of 90% or more.

Control = {1- (CbTai) / (TbCai)} × 100

Cb: Number of worms in untreated compartments prior to treatment

Cai: Number of Bugs in Untreated Compartments Observed

Tb: Number of worms in the treatment compartment before treatment

Tai: Number of worms in the treatment compartment during observation

Test Example 16: Spray Test on Spotted Mite (Tetranychus urticae)

Phaeseolus vulgaris L.var.humilis Alef. (Raw leaf stage) planted in a polyethylene cup was allowed to parasite 20 female adults of Tetranychus urticae per leaf and left at constant room temperature. After 6 days, the present compounds 5, 6, 7, 8, 9, 10 and 13 were prepared as an emulsifying thickener by the method according to Formulation Example 4, and the dilution obtained by diluting to a predetermined concentration (500 ppm) with water was 20 The pot was sprayed in an amount of ml / pot. After 8 days of spraying, the degree of damage of Tetranychus urticae was examined. As a result, almost no damage was observed in the compartments treated with this test compound.

Test Example 17: Insecticidal test for Musca domestica

The bottom of a 5.5 cm diameter polyethylene cup was covered with filter paper of the same diameter as the bottom. 0.7 ml of the dilution obtained by diluting the present compound 1, 2, 4, 5, 7, 8, 9, 10 and 13 with an emulsifying thickener and diluting with water to a predetermined concentration (500 ppm) was added dropwise onto a filter paper. , 30 mg of sucrose was uniformly fed into the cup as food. Ten adult females of the housefly (Musca domestica) were released into the cup, and the mortality was determined by examining their survival for 24 hours after closing the cup. As a result, the test compounds each exhibited a mortality of 80% or more.

Test Example 18: Insecticidal test for common mosquitoes (Culex pipens pallens)

Compounds 1, 4, 6, 8, 10, 12, and 13 were each prepared as an emulsifiable thickener according to the method of Formulation Example 4, diluted with water to a predetermined concentration (500 ppm), and 0.7 ml of the dilution obtained was ionized. To 100 ml of exchanged water (active ingredient concentration: 3.5 ppm) was added. Twenty larvae of 1 week old Culex pipens pallens were released there, and after 8 days of treatment, adult hatching inhibition rate was examined. As a result, the test compounds each exhibited an adult hatching inhibition rate of 80% or more.

The compounds have excellent agricultural and / or horticultural antimicrobial effects, as well as excellent pesticidal and / or acaricide effects.

Claims (30)

Oxime ether compounds represented by the formula: In the formula, R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxyalkyl group, a haloalkyl group, a cyano group, a nitro group or an alkoxycarbonyl group, One of T, U and V represents a CR ² group, the other represents a CH group or a nitrogen atom, the other represents a CR ³ group or a nitrogen atom, W represents a CR ³³ group or a nitrogen atom, R ² , R ³ and R ³³ are the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a haloalkyl group, a haloalkoxy group, a cyano group, a nitro group, an alkoxycarbonyl group, an alkylthio group or a haloalkylthio group , R ⁴ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group, wherein an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and Heterocyclic groups may have one or more substituents, R ⁵ and R ⁶ are the same or different and represent an alkyl group, X represents an NR ⁷ group, an oxygen atom or a sulfur atom, R ⁷ represents an alkyl group optionally substituted with one or more substituents, Y represents a CH group or a nitrogen group, Z represents an oxygen atom or an NH group, provided that when Y is a CH group, Z is an oxygen atom. The compound of claim 1, wherein the substituent in the definition of R ⁴ is a halogen atom; An OR ⁸ group; N (R ⁹ ) R ¹⁰ groups; C (R ¹³ ) = NOR ¹⁴ group; C ₁ -C ₅ alkylthio group; C ₁ -C ₅ haloalkylthio group; C ₁ -C ₁₀ acyl group; C ₂ -C ₁₁ alkoxycarbonyl group; N- (C ₁ -C ₁₀ alkyl) carbamoyl group; N, N-di (C ₁ -C ₁₀ alkyl) carbamoyl group; Cyano group; Nitro group; Aryl groups optionally substituted with one or more substituents; Or a heterocyclic group optionally substituted with one or more substituents, Wherein, R ⁸ is a hydrogen atom, C ₁ -C ₁₀ alkyl group; C ₁ -C ₅ haloalkyl group; C ₃ -C ₆ cycloalkyl group; C ₂ -C ₁₀ alkoxyalkyl group; C ₁ -C ₁₀ acyl group; C ₂ -C ₁₁ alkoxycarbonyl group; N- (C ₁ -C ₁₀ alkyl) carbamoyl group; N, N- di - (C ₁ -C ₁₀ alkyl) carbamoyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group and a trifluoromethyl group; R ⁹ and R ¹⁰ are the same or different and each is a hydrogen atom; C ₁ -C ₁₀ alkyl group; C ₅ -C ₆ cycloalkyl group; C ₁ -C ₁₀ acyl group; C ₂ -C ₁₁ alkoxycarbonyl group; N- (C ₁ -C ₁₀ alkyl) carbamoyl group; N, N- di - (C ₁ -C ₁₀ alkyl) carbamoyl group; C ₁ -C ₅ alkylsulfonyl group; C ₆ -C ₁₀ arylsulfonyl group; C ₁ -C ₅ haloalkylsulfonyl group, C ₁ -C ₅ alkylsulfinyl group; C ₁ -C ₅ haloalkylsulfinyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group and a trifluoromethyl group; Or R ⁹ and R ¹⁰ together form a tetramethylene group, a pentamethylene group or a CH ₂ CH ₂ OCH ₂ CH ₂ group; R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₆ cycloalkyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group, a trifluoromethyl group, a cyano group and a nitro group; Substituents for an aryl group as R ⁴ are a halogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₁₀ cycloalkyl group; C ₁ -C ₅ haloalkyl group; Hydroxyl group; C ₁ -C ₁₀ alkoxy group; C ₁ -C ₅ haloalkoxy group; Amino group; Cyano group; Nitro group; C ₂ -C ₆ alkoxycarbonyl group; C ₃ -C ₈ cycloalkoxy group; N- (C ₁ -C ₅ alkyl) carbamoyl group; N, N- di - (C ₁ -C ₅ alkyl) carbamoyl group; C ₁ -C ₁₀ acyl group; Phenoxy groups optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ haloalkyl group and a C ₁ -C ₃ alkylthio group; Phenyl groups optionally substituted with one or more cyano groups; 2-pyridyloxy group optionally substituted with one or more substituents selected from the group consisting of a trifluoromethyl group and a halogen atom; Morpholin-1 -yl group; Benzyloxy group; Benzoyloxy group; C ₁ -C ₅ alkylsulfonyloxy group; C ₁ -C ₅ haloalkylsulfonyloxy group; Trifluoromethanesulfonylamino group; R ¹¹ OC (O) O group; R ¹¹ (R ¹² ) NC (O) O groups; R ¹¹ C (O) N (R ¹² ) groups; R ¹¹ OC (O) NH group; R ¹¹ (R ¹² ) NC (O) NH groups; Or a C ₁ -C ₁₀ alkylthio group; Wherein R ¹¹ and R ¹² are the same or different and each is a C ₁ -C ₅ alkyl group; The substituent of the heterocyclic group as R ⁴ is a halogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₁₀ cycloalkyl group; C ₁ -C ₅ haloalkyl group; Hydroxyl group; C ₁ -C ₁₀ alkoxy group; Amino group; Or a C ₁ -C ₁₀ alkylthio group; Substituents for alkyl groups in R ⁷ are halogen atom; C ₁ -C ₅ alkoxy group; C ₂ -C ₅ alkoxycarbonyl group; N- (C ₁ -C ₅ alkyl) carbamoyl group; N, N- di - (C ₁ -C ₅ alkyl) oxime ether compounds represent a carbamoyl group or a cyano group. The method according to claim 1 or 2, R ¹ is a hydrogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₁₀ cycloalkyl group; C ₂ -C ₁₀ alkoxyalkyl group; C ₁ -C ₅ haloalkyl group; Cyano group; Nitro group; Or a C ₂ -C ₅ alkoxycarbonyl group; R ² , R ³ and R ³³ are the same or different and each is a hydrogen atom; Halogen atom; C ₁ -C ₅ alkyl group; C ₁ -C ₅ alkoxy group; C ₁ -C ₅ haloalkyl group; C ₁ -C ₅ haloalkoxy group; Cyano group; Nitro group; C ₂ -C ₅ alkoxycarbonyl group; C ₁ -C ₅ alkylthio group; Or a C ₁ -C ₅ haloalkylthio group; R ⁴ is a hydrogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₁₀ alkenyl group; C ₃ -C ₁₀ alkynyl group; C ₃ -C ₁₀ cycloalkyl group; C ₅ -C ₁₀ cycloalkenyl group; Aryl group; Or a heterocyclic group; Wherein a C ₁ -C ₁₀ alkyl group; C ₃ -C ₁₀ alkenyl group; C ₃ -C ₁₀ alkynyl group; C ₃ -C ₁₀ cycloalkyl group; C ₅ -C ₁₀ cycloalkenyl group; Aryl group; Or the heterocyclic group may have one or more substituents; R ⁵ and R ⁶ are the same or different and each is a C ₁ -C ₅ alkyl group; R ⁷ is an oxime ether compound which is a C ₁ -C ₅ alkyl group optionally substituted with one or more substituents. The method according to any one of claims 1 to 3, R ⁴ is an OR ⁸ group; N (R ⁹ ) R ¹⁰ groups; C (R ¹³ ) = NOR ¹⁴ group; C ₁ -C ₅ alkylthio group; C ₁ -C ₅ acyl group; C ₂ -C ₅ alkoxycarbonyl group; N- (C ₁ -C ₅ alkyl) carbamoyl group; N, N-di (C ₁ -C ₅ alkyl) carbamoyl group; Cyano group; Nitro group; Aryl groups optionally substituted with one or more substituents; And a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents selected from the group consisting of heterocyclic groups optionally substituted with one or more substituents, Wherein R ⁸ is a hydrogen atom; C ₁ -C ₅ alkyl group; C ₂ -C ₅ alkoxyalkyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group and a trifluoromethyl group; R ⁹ and R ¹⁰ are the same or different and each is a hydrogen atom; C ₁ -C ₅ alkyl group; C ₁ -C ₅ acyl group; C ₂ -C ₅ alkoxycarbonyl group; N- (C ₁ -C ₅ alkyl) carbamoyl group; N, N- di - (C ₁ -C ₅ alkyl) carbamoyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group and a trifluoromethyl group; Or R ⁹ and R ¹⁰ together form a tetramethylene group, a pentamethylene group or a CH ₂ CH ₂ OCH ₂ CH ₂ group; R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom; C ₁ -C ₁₀ alkyl group; C ₃ -C ₆ cycloalkyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group, a trifluoromethyl group, a cyano group and a nitro group; Substituents for an aryl group as R ⁴ are a halogen atom; C ₁ -C ₅ alkyl group; C ₃ -C ₆ cycloalkyl group; C ₁ -C ₅ haloalkyl group; Hydroxyl group; C ₁ -C ₅ alkoxy group; Amino group; Or a C ₁ -C ₅ alkylthio group; The substituent of the heterocyclic group as R ⁴ is a halogen atom; C ₁ -C ₅ alkyl group; C ₃ -C ₆ cycloalkyl group; C ₁ -C ₅ haloalkyl group; Hydroxyl group; C ₁ -C ₅ alkoxy group; Amino group; Or an oxime ether compound that is a C ₁ -C ₅ alkylthio group. The method according to any one of claims 1 to 4, Aryl group; α-naphthyl group; Or β-naphthyl group; As R ⁴ , a heterocyclic group is 2-pyridyl group; 4-pyridyl group; 2-pyrimidinyl group; 4-pyrimidinyl group; 3-pyrazolyl group; 2-thiazolyl group; 2-imidazolyl group; Or 3- (1,2,4-triazolyl) group; In the definition of R ⁴ , a heterocyclic group as a substituent of an alkyl group, alkenyl group, alkynyl group, cycloalkyl group, cycloalkenyl group, aryl group or heterocyclic group is 2-pyridyl group; 3-pyridyl group; 4-pyridyl group; 2-pyrimidinyl group; 4-pyrimidinyl group; 5-pyrimidinyl group; 1-pyrazolyl group; 3-pyrazolyl group; 4-pyrazolyl group; 5-pyrazolyl group; 2-thiazolyl group; 4-thiazolyl group; 5-thiazolyl group; 1- (1,2,4-triazolyl) group; 3- (1,2,4-triazolyl) group; Succinimido-1-yl group; Maleimido-1-yl group; Or an oxime ether compound that is a phthalimido-1-yl group. The method according to any one of claims 1 to 3 and 5, T, U, V and W are not nitrogen atoms; R ⁴ is a C ₁ -C ₁₀ alkyl group optionally substituted with one or more substituents; Wherein the substituent is a C (R ¹³ ) = NOR ¹⁴ group; C ₂ -C ₅ alkoxycarbonyl group; Or one or more substituents selected from the group consisting of halogen atoms, C ₁ -C ₁₀ alkyl groups, C ₁ -C ₅ haloalkyl groups, C ₁ -C ₁₀ alkoxy groups, cyano groups, nitro groups and C ₂ -C ₆ alkoxycarbonyl groups Substituted phenyl group; R ¹³ and R ¹⁴ are the same or different and each is a hydrogen atom, a C ₁ -C ₁₀ alkyl group; C ₃ -C ₆ cycloalkyl group; Or a phenyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₁ -C ₅ alkyl group, a trifluoromethyl group, a cyano group or a nitro group. The method according to any one of claims 1 to 3 and 5, T, U, V and W are not nitrogen atoms; R ⁴ is an allyl group optionally substituted with one or more substituents selected from the group consisting of a halogen atom, a C ₂ -C ₅ alkoxycarbonyl group, a cyano group and a nitro group; 1-methyl-2-propenyl group; 2-methyl-2-propenyl group; 3-methyl-2-propenyl group; Or 3-methyl-2-butenyl group. The method according to any one of claims 1 to 3 and 5, T, U, V and W are not nitrogen atoms; R ⁴ is a propargyl group optionally substituted with one or more substituents selected from halogen atoms and C ₂ -C ₅ alkoxycarbonyl groups; 1-methyl-2-propynyl group; An oxime ether compound which is a 2-butynyl group. The method according to any one of claims 1 to 4, Aryl group is phenyl; As R ⁴ , a heterocyclic group is 2-pyridyl group; Or a 4-pyridyl group; In the definition of R ₄ , a heterocyclic group as a substituent of an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group or a heterocyclic group is 2-pyridyl group; 3-pyridyl group; Or 4-pyridyl group. The compound according to any one of claims 1 to 5, wherein one of T, U and V represents a CH group, the other represents a CH group or a nitrogen atom, the other represents a CH group or a nitrogen atom, and W is Oxime ether compounds which represent a CH group or a nitrogen atom. The oxime ether compound according to any one of claims 1 to 10, wherein R ⁵ , R ⁶ and R ⁷ are methyl groups. The oxime ether compound according to any one of claims 1 to 11, wherein T, U, V and W are nitrogen. The oxime ether compound according to any one of claims 1 to 12, wherein X is an NR ⁷ group, wherein R ⁷ is as defined above. The oxime ether compound according to any one of claims 1 to 12, wherein X is an oxygen atom. The oxime ether compound according to any one of claims 1 to 12, wherein X is a sulfur atom. 15. The oxime ether compound of claim 14, wherein T represents a CCH ₃ group and U, V, W and Y represent a CH group. The oxime ether compound according to any one of claims 1 to 15, wherein Y is a CH group. The oxime ether compound according to any one of claims 1 to 15, wherein Y is a nitrogen atom and Z is an oxygen atom. The oxime ether compound according to any one of claims 1 to 15, wherein Y is a nitrogen atom and Z is a NH group. The oxime ether compound according to any one of claims 1 to 19, wherein R ¹ is a methyl group. An agricultural and / or horticultural antimicrobial agent comprising the oxime ether compound according to any one of claims 1 to 20 as an active ingredient. A pesticide and / or acaricide comprising the oxime ether compound according to any one of claims 1 to 20 as an active ingredient. 21. A method for controlling plant diseases comprising applying an effective amount of an oxime ether compound according to any one of claims 1 to 20 to a leaf, soil or seed of a plant. A pest or tick control method comprising applying an effective amount of an oxime ether compound according to any one of claims 1 to 20 to a leaf, soil or seed of a plant. Use of the oxime ether compound according to any one of claims 1 to 20 as an agricultural and / or horticultural antimicrobial agent. Use of an oxime ether compound according to any one of claims 1 to 20 as an insecticide and / or acaricide. Compound represented by the following formula: In formula, R <^1> , R <^4> , R <^6> , T, U, V, W, X, and Y are as having defined in any one of Claims 1-20. Compound represented by the following formula: In formula, R <^1> , R <^4> , R <^6> , T, U, V, W, and X are as having defined in any one of Claims 1-20. Compound represented by the following formula: Wherein R ¹ , R ⁵ , R ⁶ , T, U, V, W, X and Z are any one of claims 1, 3, 10-16 and 18-20. As defined in paragraph Compound represented by the following formula: Wherein R ⁵ and R ⁶ are as defined in any one of claims 1, 3, and 11.