JP2001064237A - Acrylic acid derivatives, their uses and intermediates for their production - Google Patents

Abstract

(57) [Problem] To provide a compound having an excellent plant disease controlling effect. SOLUTION: General formula 1 Wherein W represents an oxygen atom or a CH ₂ group, and X represents C
Represents R ⁴ group or a nitrogen atom, Y represents CR ⁵ group or a nitrogen atom, R ^1, R ² and R ³ are the same or different, represent a hydrogen atom, a halogen atom, R ^4, R ^5, R
⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom or the like. And a fungicide for agricultural and horticultural use containing the same as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an acrylic acid derivative and its use.

[0002]

SUMMARY OF THE INVENTION An object of the present invention is to provide a compound having an excellent plant disease controlling effect.

[0003]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an acrylic acid derivative represented by the following general formula 3 has an excellent plant disease controlling effect, and have accomplished the present invention. That is, the present invention provides a compound represented by the following general formula:

Embedded image In the formula, W represents an oxygen atom or a CH ₂ group, and X represents C
Represents R ⁴ group or a nitrogen atom, Y represents CR ⁵ group or a nitrogen atom, R ^1, R ² and R ³ are the same or different, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group An optionally substituted C1-C10 alkyl group, an optionally substituted C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, an optionally substituted C3-C10 cycloalkyl group, An optionally substituted C5-C10 cycloalkenyl group, an optionally substituted C6-C10 aryl group,
Optionally substituted C1-C9 heteroaryl group, optionally substituted C1-C6 alkoxy group, optionally substituted phenoxy group, optionally substituted C1
To C9 heteroaryloxy group, an optionally substituted C2 to C6 alkoxycarbonyl group, an optionally substituted C1 to C6 alkylthio group or an optionally substituted C3 to C30 trialkylsilyl group,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different,
Hydrogen atom, halogen atom, C1-C4 alkyl group, C1
Represents a -C4 haloalkyl group or a C1-C4 alkoxy group. The present invention provides an acrylic acid derivative represented by｝ (hereinafter, referred to as the present compound) and a fungicide for agricultural and horticultural use containing the same as an active ingredient.

The present invention further provides a compound of the general formula 4 useful as an intermediate for producing the compound of the present invention.

Embedded image[Where A¹Is B (OH)_TwoGroup, B (OR⁹)_TwoGroup or S
nR^Ten _ThreeR represents a group⁹ Represents a C1 to C10 alkyl group.
Just two Rs⁹In -CH_TwoCH_Two-Group or -C (C
H_Three)_TwoC (CH_Three)_Two-Represents a group, R^TenAre C1 to C10
W represents an oxygen atom or CH_TwoRepresents a group
And X is CR^FourY represents CR or a nitrogen atom^FiveBase
Or a nitrogen atom;⁶, R⁷And R⁸Is the same
Or differently, a hydrogen atom, a halogen atom, C1-C4
Alkyl group, C1-C4 haloalkyl group or C1-C4
Represents an alkoxy group. And a compound represented by the formula:
You.

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, examples of the halogen atom represented by R ¹ , R ² and R ³ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and R ¹ , R ² and R ^{3 represent} The optionally substituted C1 to C10 shown
As the C1 to C10 alkyl group in the alkyl group,
For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, 1-methylpropyl group,
Pentyl group, 1-methylbutyl group, 1-ethylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 2,2
-Dimethylpropyl group, 1,2-dimethylpropyl group,
1,1-dimethylpropyl group, a hexyl group, 1-methylpentyl group, 1-ethylpentyl group, 3,3-dimethylbutyl group, heptyl group, 3,7-dimethyl octyl group and the like, R ^1, R C2~C in optionally substituted C2~C10 alkenyl group represented by ² and R ³
Examples of 10 alkenyl groups include vinyl, allyl, 1-methyl-2-propenyl, and 2-methyl-2-
Propenyl group, 2-butenyl group, 2-pentenyl group, 3
-Methyl-2-butenyl group and the like. Examples of the C2-C10 alkynyl group in the optionally substituted C2-C10 alkynyl group represented by R ¹ , R ² and R ³ include, for example, an ethynyl group, a propargyl group, 1-methyl-
2-propynyl group, 2-butynyl group and the like,
Optionally substituted C represented by R ¹ , R ² and R ³⁵
The C3~C10 cycloalkyl group in 3~C10 cycloalkyl groups such as cyclopropyl group, a cyclopentyl group, a cyclohexyl group and the like, R ^1,
Optionally substituted represented by R ² and R ³ C5~C
The 10 cycloalkenyl C5~C10 cycloalkenyl group in group, for example, cyclopentenyl group, cyclohexenyl group and the like, R ^1, R ² and C6~C10 may be substituted represented by R ³ ant - Le As the C6-C10 aryl group in the group, a phenyl group,
α-naphthyl group, β-naphthyl group and the like, R ¹ ,
Optionally substituted represented by R ² and R ³ C1~C
Examples of the C1 to C9 heteroaryl group in the 9 heteroaryl group include a 2-pyridyl group, a 3-pyridyl group,
4-pyridyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 2-thienyl group, 3-thienyl group, 2-furyl group, 3-furyl group, pyrrol-1-yl group, 1-pyrazolyl group, 3-pyrazolyl Group, 4-pyrazolyl group, 2-thiazolyl group, 4-thiazolyl group, 5-thiazolyl group, 2
-Oxazolyl group, 5-oxazolyl group, 2-imidazolyl group, 3- (1,2,4-triazolyl) group, 2-benzothienyl group, 3-benzothienyl group, benzothiazol-2-yl group, 2-quinolinyl And the like.
Optionally substituted C1 represented by ¹ , R ² and R ³
The C1~C6 alkoxy group in ~C6 alkoxy group, such as methoxy, ethoxy, t-butoxy group and the like, R ^1, R ² and may be substituted represented by R ³ C1 to C9 heteroaryl The C1-C9 heteroaryloxy group in the aryloxy group includes 2-
Pyridyloxy group, 2- (5-trifluoromethyl) pyridyloxy group, 3-pyridyloxy group, 4-pyridyloxy, 2-pyrimidyloxy group, 4-pyrimidyloxy group, 5-pyrimidyloxy, 3-thienyloxy group and the like. is, as a C2~C6 alkoxycarbonyl group in R ^1, R ² and optionally substituted by C2~C6 alkoxycarbonyl group represented by R ^3, for example, a methoxycarbonyl group, an ethoxycarbonyl group and the like, R ¹ as the C1~C6 alkylthio group in optionally substituted C1~C6 alkylthio group represented by R ² and R ^3, for example, methylthio group, ethylthio group and the like, represented by R ^1, R ² and R ³ C3 to C30 in the optionally substituted C3 to C30 trialkylsilyl group The trialkyl silyl groups, such as trimethylsilyl group, triethylsilyl group, t- butyl dimethyl silyl group and the like,

[0005] represented by R ^1, R ² and R ^3, which may be substituted C1~C10 alkyl group, optionally substituted C2~C10 alkenyl group, may be substituted C2~C10 Alkynyl group, optionally substituted C3-C10 cycloalkyl group, optionally substituted C5-C10 cycloalkenyl group, optionally substituted C6-C10 aryl group, optionally substituted C1-C9 Heteroaryl group, optionally substituted C
A 1-C6 alkoxy group, an optionally substituted phenoxy group, an optionally substituted C1-C9 heteroaryloxy group, a C2-C6 alkoxycarbonyl group, an optionally substituted C1-C6 alkylthio group and a substituted Examples of the substituent in the optionally substituted C3 to C30 trialkylsilyl group include a halogen atom [a chlorine atom, a bromine atom, a fluorine atom and an iodine atom], a C1 to C10 atom.
Alkyl group (for example, methyl group, ethyl group, propyl group,
Isopropyl, butyl, isobutyl, 1-methylpropyl, pentyl, 1-methylbutyl, 1-ethylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 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, etc.), C3-C20 trialkylsilyl group [for example, trimethylsilyl group, triethylsilyl group, etc.] C1-C10 haloalkyl group [for example, trifluoromethyl group, 2,3 2,2-trifluoroethyl group, 1,1,
2,2-tetrafluoroethyl group etc.], C3-C10 cycloalkyl group [eg cyclopropyl group, cyclopentyl group, cyclohexyl group etc.], C1-C10 alkoxy group [eg methoxy group, ethoxy group, n-propoxy group, iso- Propoxy group, n-butoxy group, sec-butoxy group, isobutoxy group, n-pentyloxy group, etc.),
C1-C10 haloalkoxy groups [for example, trifluoromethoxy group, difluoromethoxy group, bromodifluoromethoxy group, chlorodifluoromethoxy group, fluoromethoxy group, 2,2,2-trifluoroethoxy group,
1,2,2-tetrafluoroethoxy group etc.], C1-C
10 alkylthio groups [e.g., methylthio group, ethylthio group, n-propylthio group, n-butylthio group, isobutylthio group, sec-butylthio group, n-pentylthio group, n-hexylthio group, etc.], C1-C10 haloalkylthio groups [e.g. Trifluoromethylthio group, difluoromethylthio group, bromodifluoromethylthio group, chlorodifluoromethylthio group, fluoromethylthio group,
2,2,2-trifluoroethylthio group, 1,1,2,2
2-tetrafluoroethylthio group etc.], C2-C10 alkoxycarbonyl group [methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxy Carbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc.), phenyl group, pyridyl group, pyrimidyl group, phenoxy group, benzyloxy group, pyridin-2-yloxy group wherein the phenyl group, pyridyl Group, pyrimidyl group, phenoxy group, benzyloxy group and pyridin-2-yloxy group are each a halogen atom (for example, chlorine atom), a C1-C6 alkyl group (for example, methyl group, ethyl group, etc.), C1-C6 Alkoxy groups (eg, methoxy Group, ethoxy group, etc.), may be substituted with one or more groups selected from the group consisting of a trifluoromethyl group and a cyano group. ｝, Hydroxyl group, cyano group,
A nitro group, etc., which may be substituted;
10 aryl groups and optionally substituted C1 to C9
Examples of the substituent in the heteroaryl group further include a methylenedioxy group and a difluoromethylenedioxy group, wherein each of the methylenedioxy group and the difluoromethylenedioxy group substitutes for two adjacent carbon atoms on the aryl group. I do. ｝ Can also be given.

Examples of the halogen atom represented by R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom, and R ⁴ , R ⁵ , R ⁶ , R ⁷ and the C1~C4 alkyl group represented by R ^8, for example a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group and the like, R ^4, R ^5, R ^6, C1 to represented by R ⁷ and R ⁸
Examples of the C4 haloalkyl group include a fluoromethyl group, a trifluoromethyl group, a trichloromethyl group, a chlorodifluoromethyl group, and the like, and R ⁴ , R ⁵ , R ⁶ , and R ⁷
And The C1~C4 alkoxy group represented by R ^8, for example, methoxy, ethoxy, and the like. R
Examples of the C1-C10 alkyl group represented by ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group, and the like. The C1~C10 alkyl group represented by R ^10, for example a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group.

The compounds of the present invention have (E) and (Z) isomers based on the C ＝ C bond of the dioxypropenoic acid moiety, and each of these isomers and mixtures thereof are included in the present invention.
Above all, from the viewpoint of agricultural fungicide efficacy, the compound of the present invention in which W in Formula 3 is an oxygen atom has the C =
Based on C bonds (Z) compound isomer or (Z) geometric isomer mixture containing a large amount of isomers it is preferred, W in the general formula of 3 the C = C bond is the compound of the present invention is a CH ₂ group The compound of the (E) isomer based on or a mixture of geometric isomers containing a large amount of the (E) isomer is preferred. (The terms (E) and (Z) as used herein are defined by the Cahn-Ingold-Prelog rule, which is widely used to indicate geometric isomers.)

[0008] Among the compounds of the present invention, examples of a more preferable compound in terms of the efficacy of controlling plant diseases include methyl 3-methoxy-2- (2-methyl-5-phenylphenoxy)-.
2-propenoate.

The compound of the present invention is described, for example, in the following [Production method A],
It can be produced according to [Production method B] or [Production method C]. Depending on the content of X or Y, for example, it can be produced according to [Production Method D]. In these production methods, a protecting group can be used if necessary to protect the functional group from the reaction.

[Production Method A] A compound represented by the general formula [I] is reacted with a compound represented by the general formula CH ₃ -L ¹ in the presence of a base, or a compound represented by the general formula N ₂ CH-L ³ A process for producing the compound of the present invention, which comprises reacting the compound with the compound shown.

Embedded image In the formula, L ¹ represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, and L ³ represents a trialkyl such as a trimethylsilyl group. Represents a silyl group, and represents W, X, Y, R ¹ , R ² , R ³ , R ⁶ , R ⁷
And R ⁸ have the same meaning as described above. ｝ In the reaction of step 5 in the chemical formula 5, the reaction temperature is usually 0 to 100.
° C, the reaction time is usually in the range of 1 to 24 hours, and the molar ratio of the compound represented by the general formula CH ₃ -L ¹ is as follows:
It is usually in the range of 1 to 10 with respect to the compound represented by the general formula [I]. The molar ratio of the base used in the reaction is usually in the range of 1 to 10 with respect to the compound represented by the general formula [I]. As the base, for example, inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate calcium carbonate, sodium hydride and the like, potassium-t
-Alkali metal alkoxides such as butoxide, sodium methoxide and sodium ethoxide; organic bases such as pyridine, triethylamine, ethyldiisopropylamine and aniline, and mixtures thereof. The reaction is usually performed in a solvent. Examples of the solvent include 1,4-dioxane, tetrahydrofuran,
Ether solvents such as ethylene glycol dimethyl ether and t-butyl methyl ether, aliphatic hydrocarbon solvents such as n-hexane and n-heptane, aromatic hydrocarbon solvents such as toluene, and halogenated carbon such as monochlorobenzene Hydrogen solvents, organic base solvents such as pyridine, triethylamine and N, N-dimethylaniline, ester solvents such as butyl acetate and ethyl acetate, nitrile solvents such as acetonitrile,
N, N-dimethylformamide, dimethylsulfoxide, water and the like or a mixture thereof are mentioned. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the reaction of the step 5 ′ in the chemical formula 5, the compound represented by the general formula [I] and the compound represented by the general formula N ₂ CH-
The reaction temperature when reacting with the compound represented by L ³ is usually in the range of -20 to 50 ° C., and the reaction time is usually 0.1 to 0.5.
It is in the range of 1 to 24 hours, and the molar ratio of the compound represented by the general formula N ₂ CH-L ³ is usually in the range of 1 to 10 with respect to the compound represented by the general formula [I]. The reaction is usually performed in a solvent. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether, aliphatic hydrocarbon solvents such as n-hexane and n-heptane, and toluene. Aromatic hydrocarbon solvents, halogenated hydrocarbon solvents such as monochlorobenzene, organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline, ester solvents such as butyl acetate and ethyl acetate, nitrile solvents such as acetonitrile; Examples thereof include N-dimethylformamide, dimethylsulfoxide and the like, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

[Production method B] A method for producing the compound of the present invention, wherein the compound represented by the general formula [II] is reacted with the compound represented by the general formula [III] in the presence of a catalyst.

Embedded image中 where A^TwoIs B (OH)_TwoGroup, B (OR⁹)_TwoGroup or S
nR^Ten _ThreeL represents a group^Two Is chlorine, bromine, iodine
And leaving groups such as trifluoromethanesulfonyloxy group
W, X, Y, R¹, R^Two, R^Three, R^Four, R^Five, R⁶,
R⁷, R⁸, R⁹And R^TenMeans the same as above
You.に お い て In the reaction of Step 6 in Scheme 6, the reaction temperature is
The temperature is usually in the range of 20 to 120 ° C, and the reaction time is usually 1 to 2
4 hours, the compound represented by the general formula [III]
The molar ratio of the compound to the compound represented by the general formula [II] is
Usually in the range of 1 to 5. Of the catalyst used in the reaction
The molar ratio with respect to the compound represented by the general formula [II] is
It is always in the range of 0.001 to 0.1. Examples of catalysts
For example, palladium (II) acetate, tetrakis (triphenyl)
Ruphosphine) palladium (0), '1,1'-bis
(Diphenylphosphino) ferrocene dichloropara
Di (II) methylene chloride complex, bis- (triphenyi)
Ruphosphine) palladium (II) dichloride
Palladium catalysts can be mentioned. The reaction is carried out if necessary
Groups (eg, sodium acetate, potassium acetate, potassium carbonate
, Potassium tribasic phosphate, inorganic bases such as sodium bicarbonate) and correlation transfer
Catalyst (eg, tetrabutylammonium bromide,
Quaternary amines such as benzyltriethylammonium bromide
Ammonium salt). Also general
In the compound represented by the formula [III], A^TwoIs SnR^Ten _Three
If necessary, copper (II) oxide, silver oxide
It may be performed in the presence of (II). The reaction is usually
It is performed in a medium. As the solvent, for example, methanol,
Ethanol, propanol, butanol, isopropano
Alcohol solvents such as 1,4-dioxane, tetra
Hydrofuran, ethylene glycol dimethyl ether,
ether solvents such as t-butyl methyl ether; n-hexyl;
Aliphatic hydrocarbon solvents such as sun and n-heptane, toluene
Aromatic hydrocarbon solvents such as acetonitrile, etc.
Solvent, N, N-dimethylformamide, dimethylsulfo
Oxide, water and the like, or a mixture thereof are mentioned. The
The reaction is more specifically described, for example, in J. Am. Org, Che
m. , 1997, 62, 7170-7173.
Law, J.A. Org. Chem. , 1995, 60, 750
8-7510 or Angew. Che
m. Int. Ed. Engl. , 1986, 25, 50
This is performed according to the method described in 8-524 and the like. After the reaction
The reaction mixture is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration.
Thus, the desired compound can be obtained. Rejoin if necessary
Purification by crystallization, distillation, chromatography, etc.
The compound can be isolated.

In the general formulas [I] and [II], the compound wherein W is an oxygen atom can be obtained by, for example, the following scheme.
Alternatively, it can be produced according to the method shown in Scheme 8.

Embedded image 中 wherein L ¹ , L ² , X, Y, R ¹ , R ² , R ³ , R ⁶ , R ⁷
And R ⁸ have the same meaning as described above. ｝

Embedded image 中 wherein L ¹ , L ² , X, Y, R ¹ , R ² , R ³ , R ⁶ , R ⁷
And R ⁸ have the same meaning as described above. Ｗ In the general formulas [I] and [II], W is CH
_The compound having _two groups can be produced, for example, according to the method shown in Scheme 9 below.

Embedded image Where L ¹ , L ² , L ³ , X, Y, R ¹ , R ² , R ³ ,
R ⁶ , R ⁷ and R ⁸ have the same meaning as described above. ｝

In the reaction of Step 71 of Scheme 7 and Step 9e of Scheme 9, a compound represented by the general formula [XVI] or a compound represented by the general formula [XXX] and a compound represented by the general formula CH ₃ -L ¹ When the compound is reacted in the presence of a base, the reaction temperature is usually 0 to 100 ° C.
The reaction time is usually in the range of 1 to 24 hours, and the molar ratio of the compound represented by the general formula CH ₃ -L ¹ is the compound represented by the general formula [XVI] or
X] is usually in the range of 1 to 10. The reaction is carried out in the presence of a base, the molar ratio of the base being:
The compound represented by the general formula [XVI] or the general formula [XX
X] is usually in the range of 1 to 10. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate calcium carbonate, and sodium hydride; alkali metal alkoxides such as potassium-t-butoxide, sodium methoxide, and sodium ethoxide; and pyridine. And organic bases such as triethylamine, ethyldiisopropylamine and aniline, and mixtures thereof. The reaction is usually performed in a solvent. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether, n-hexane, and n-heptane. Such as an aliphatic hydrocarbon solvent, an aromatic hydrocarbon solvent such as toluene,
Halogenated hydrocarbon solvents such as monochlorobenzene; organic base solvents such as pyridine, triethylamine and N, N-dimethylaniline; ester solvents such as butyl acetate and ethyl acetate; nitrile solvents such as acetonitrile; N, N-dimethylformamide; Sulfoxide, water and the like or a mixture thereof are mentioned. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the reaction of Step 71 of Scheme 7 and Step 9e of Scheme 9, the compound represented by the general formula [XVI] or the compound represented by the general formula [XXX] and the compound represented by the general formula N ₂ CH-L ³ When the compound is reacted with the compound, the reaction temperature is usually in the range of -20 to 50 ° C, the reaction time is usually in the range of 0.1 to 24 hours, and the compound represented by the general formula N
The molar ratio of the compound represented by ₂ CH-L ³ is represented by the general formula [XV
It is usually in the range of 1 to 10 with respect to the compound represented by I] or the compound represented by the general formula [XXX]. The reaction is usually performed in a solvent. As the solvent, for example, 1,
Ether solvents such as 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butylmethyl ether; aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene; Halogenated hydrocarbon solvents such as chlorobenzene, organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline, ester solvents such as butyl acetate and ethyl acetate, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide Etc. or a mixture thereof. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the reaction of Step 7j of Scheme 7, Step 8f of Scheme 8 and Step 9c of Scheme 9, the reaction temperature is usually in the range of 0 to 80 ° C., and the reaction time is usually in the range of 1 to 24 hours. The molar ratio of HCOOCH ₃ to be subjected to the reaction is usually 1 to 1 with respect to the compound represented by the general formula [XV], the compound represented by the general formula [IX] or the compound represented by the general formula [XXIX]. 100
Range. The reaction is usually carried out in the presence of a base. Examples of the base include inorganic bases such as sodium hydride and potassium hydride, alkali metal alkoxides such as sodium methoxide, sodium ethoxide and potassium-t-butoxide, and sodium amide. And alkali metal amides such as lithium amide, lithium diisopropylamide, sodium hexamethyldisilazide, and lithium hexamethyldisilazide, and mixtures thereof. The reaction is carried out in a solvent, if necessary, and examples of the solvent include 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and t-butyl methyl ether.
Ether solvents such as ter, aliphatic hydrocarbon solvents such as n-hexane and n-heptane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as monochlorobenzene,
Organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline and the like, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethyl-2-imidazolidone, sulfolane and the like and mixtures thereof. Can be After completion of the reaction, the reaction solution is treated with an acidic aqueous solution such as dilute hydrochloric acid, and then subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the desired compound can be isolated by purification by recrystallization, chromatography or the like.

In the reaction of Step 7g of Scheme 7 and 8d of Scheme 8, the reaction temperature is usually from 0 to 80.
° C, the reaction time is usually in the range of 1 to 24 hours, and the molar ratio of the compound represented by the general formula L ¹ CH ₂ COOCH ₃ is the compound represented by the general formula [XII] or the compound represented by the general formula [VIII 1 to 5
Range. The reaction is usually carried out in the presence of a base, and the molar ratio of the base is usually in the range of 1 to 10 with respect to the compound represented by the general formula L ¹ CH ₂ COOCH ₃ . As the base, for example, an inorganic base such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, potassium hydride, potassium-t-butoxide, sodium methoxide,
Alkali metal alkoxides such as sodium ethoxide,
Organic bases such as pyridine, triethylamine, ethyldiisopropylamine, and N, N-dimethylaniline, and mixtures thereof. The reaction is carried out in a solvent as necessary. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether, n-hexane, n-hexane and the like. Aliphatic hydrocarbon solvents such as heptane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as monochlorobenzene, organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline, butyl acetate, ethyl acetate, etc. Ester solvents, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the reaction of Step 7k of Scheme 7, Step 8a, Step 8c, Step 8e of Scheme 8 and Step 9d of Scheme 9, the reaction temperature is usually 20 to 1
The reaction time is usually in the range of 1 to 24 hours, and the molar ratio of the compound represented by the general formula [III] is the same as that of the compound represented by the general formula [XVI],
It is usually in the range of 1 to 5 with respect to the compound represented by I], the compound represented by the general formula [XII], the compound represented by the general formula [XV] or the compound represented by the general formula [XXX]. The reaction is carried out using a catalyst such as palladium acetate (I
I), tetrakis (triphenylphosphine) palladium (0), {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex, bis- (triphenylphosphine) palladium (II) The reaction is carried out in the presence of a palladium catalyst such as dichloride or the like, and the molar ratio of the catalyst is usually in the range of 0.001 to 0.1 with respect to the compound represented by the general formula [III]. The reaction may be carried out, if necessary, with a base (eg, an inorganic base such as sodium acetate, potassium acetate, potassium carbonate, tripotassium phosphate, baking soda) or a phase transfer catalyst (eg, a quaternary such as tetrabutylammonium bromide, benzyltriethylammonium bromide). (Ammonium salt). When A ² is a SnR ¹⁰ ₃ group in the compound represented by the general formula [III], the reaction may be carried out in the presence of copper (II) oxide or silver (II) oxide as necessary. . The reaction is usually performed in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; Examples thereof include aliphatic hydrocarbon solvents such as n-hexane and n-heptane, aromatic hydrocarbon solvents such as toluene, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, water, and the like, and mixtures thereof. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the reaction of Step 9a in Scheme 9, the reaction temperature is usually in the range of 20 to 120 ° C., the reaction time is usually in the range of 1 to 24 hours, and the molar ratio of dimethyl malonate is represented by the general formula [XXVII]. Is usually in the range of 1 to 3. The reaction is usually performed in the presence of a base, and the molar ratio of the base is represented by the general formula [XXVII].
Is usually in the range of 1 to 10.
Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride and potassium hydride, alkali metal alkoxides such as potassium-t-butoxide, sodium methoxide and sodium ethoxide, pyridine and triethylamine. , Ethyl diisopropylamine, organic bases such as N, N-dimethylaniline, and mixtures thereof. The reaction is carried out in a solvent as necessary, and as the solvent, for example, 1,
Ether solvents such as 4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butylmethyl ether; aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene; Halogenated hydrocarbon solvents such as chlorobenzene, organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline, alcoholic solvents such as methanol and ethanol, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide; Water and the like or a mixture thereof are mentioned. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like. The compound represented by the general formula [XXVII] can be produced, for example, according to the production method described in JP-A-11-217579.

In the reaction of Step 9b in Scheme 9, the reaction temperature is in the range of 80 to 250 ° C., and the reaction time is usually in the range of 1 to 24 hours. The reaction may be performed in the presence of an inorganic salt such as lithium chloride and lithium bromide, if necessary. The reaction is optionally performed in a solvent,
Examples of the solvent include ether solvents such as 1,4-dioxane, triglyme and tetraglyme, aliphatic hydrocarbon solvents such as n-octane, aromatic hydrocarbon solvents such as toluene and xylene, monochlorobenzene, dichlorobenzene and the like. Organic solvents such as pyridine, N, N-dimethylaniline, N, N-dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone or a mixture thereof Mixtures. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

The compound represented by the general formula [III] can be produced, for example, by the method shown in the following Scheme 10.

Embedded image In the formula, A ² , L ¹ , X, Y, R ¹ , R ² and R ³ represent the same meaning as described above. In the reaction of step 10 of the chemical formula 10, for example, an organic compound obtained by reacting a compound represented by the general formula [XVII] with a metal (eg, magnesium, lithium, etc.) in a solvent (eg, diethyl ether, tetrahydrofuran, etc.) A method of reacting a metal compound with a borate ester (for example, trimethyl borate, triethyl borate, etc.) (more specifically, for example, J. Am. Chem. Soc., 1
958, 80, 4291-4293. ) Or a solvent (dimethyl sulfoxide, N, N
Base (for example, an inorganic base such as potassium acetate) and a catalyst (for example, ｛1, dimethylformamide).
A method of reacting a compound represented by the general formula [XVII] with bis (pinacolato) diboron in the presence of 1'-bis (diphenylphosphino) ferrocene {dichloropalladium (II) methylene chloride complex (more specifically, Is described, for example, in J. Org.
The method is carried out according to the method described in U.S. Pat. ) And a compound represented by the general formula [XVII] in the presence of a catalyst (eg, tetrakis (triphenylphosphine) palladium (0) or the like) in a solvent (eg, toluene) with R ¹⁰ ₃ SnSnR ¹⁰ ₃ (eg, , Bu ₃ SnSnB
u ₃ or the like (more specifically, for example, Chem. Letters, 1981, 829-8).
Performed according to the method described in No. 30. ) And the like. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

Among the compounds represented by the general formula [VIII], those in which X and Y are nitrogen atoms can be produced, for example, according to the method shown in the following Scheme 11.

Embedded image In the formula, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ have the same meaning as described above. ｝

[Production Method C] A method for producing the compound of the present invention, wherein the compound represented by the general formula [XX] is reacted with the compound represented by the general formula [XXI] in the presence of a catalyst.

Embedded image Wherein A ¹ , L ¹ , W, X, Y, R ¹ , R ² , R ³ , R ⁶ ,
R ^7, R ^8, R ⁹ and R ^{1 0} are as defined above.に お い て In the reaction of the step 12 in the chemical formula 12, the reaction temperature is usually in the range of 20 to 120 ° C., and the reaction time is usually 1
２４24 hours, and the molar ratio of [XXI] to [XX] is usually in the range of 1-5. The molar ratio of the catalyst used in the reaction is usually in the range of 0.001 to 0.1 with respect to the compound represented by the general formula [XX]. Examples of the catalyst include palladium (II) acetate, tetrakis (triphenylphosphine) palladium (0), {1,
Palladium catalysts such as 1'-bis (diphenylphosphino) ferrocene @ dichloropalladium (II) methylene chloride complex and bis- (triphenylphosphine) palladium (II) dichloride. The reaction may be carried out, if necessary, with a base (for example, an inorganic base such as sodium acetate, potassium acetate, potassium carbonate, tripotassium phosphate and sodium bicarbonate) or a phase transfer catalyst (for example, quaternary such as tetrabutylammonium bromide and benzyltriethylammonium bromide). (Ammonium salt). In the general formula [XX] The compound represented by, if A ¹ is SnR ¹⁰ ₃ groups are optionally oxidized copper (II), also be carried out in the presence of silver oxide (II). The reaction is usually performed in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol and isopropanol; ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and t-butyl methyl ether; n-
The presence of a catalyst in an aliphatic hydrocarbon solvent such as hexane or n-heptane, an aromatic hydrocarbon solvent such as toluene, a nitrile solvent such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, water, or a mixture thereof. Do it below. The reaction is more specifically, for example,
J. Org, Chem. , 1997, 62, 7170-
7173; Org. Chem. , 19
95, 60, 7508-7510 or A.
ngew. Chem. Int. Ed. Engl. , 19
86, 25, 508-524. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound.
If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

The compound represented by the general formula [XX] can be produced, for example, by the method shown in the following Scheme 13.

Embedded image 中 In the formula, A ¹ , L ¹ , W, X, Y, R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above.に お い て In the reaction of the step 13 of the scheme 13, the reaction temperature is usually in the range of 20 to 100 ° C., and the reaction time is usually 1
２４24 hours, and the molar ratio of A ¹ -A ¹ to [XXII] is usually 1-5. The reaction is carried out, for example, in a solvent (dimethylsulfoxide, N, N-dimethylformamide, etc.) in a base (for example, an inorganic base such as potassium acetate) and a catalyst (for example, 1,1, '-bis (diphenylphosphino)). In the presence of ferrocene (dichloropalladium (II) methylene chloride complex or the like), the compound represented by the general formula [XX
II] with bis (pinacolato) diboron or the like (more specifically, for example, the method described in J. Am.
Org. Chem. , 1995, 60, 7508-75.
Performed according to the method described in No. 10. ) And the solvent (catalyst (e.g. with toluene, etc.) in, tetrakis (triphenylphosphine) compound represented by the general formula [XXII] in the presence of a palladium (0) etc.) and R ¹⁰ ₃ SnSnR ¹⁰ ₃ (e.g. , Bu ₃ SnSnBu _3, etc. (more specifically, for example, Chem. Letters, 1
981, 829-830. ) And the like. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain a target compound. If necessary, recrystallization, distillation,
The target compound can be isolated by purification by chromatography or the like.

[Production Method D] Among the compounds of the present invention, a compound in which X and Y in the general formula 3 are nitrogen atoms can also be produced, for example, by the method shown in the following scheme 14.

Embedded image [Wherein, W, X, Y, R ¹ , R ² , R ³ , R ⁶ , R ⁷ and R ⁸ represent the same meaning as described above. ]

The compound of the formula [XXIII] wherein W is an oxygen atom can also be produced, for example, according to the method shown in the following Scheme 15.

Embedded image In the formula, L ¹ , R ⁶ , R ⁷ and R ⁸ have the same meaning as described above. ｝

When the compound of the present invention is used as an active ingredient in a fungicide for agricultural and horticultural use, it may be used as it is without adding any other components. Mix with adjuvants, emulsions, wettable powders,
It is used by being formulated into water dispersible granules, emulsion preparations, flowable preparations, powders, granules and the like. These preparations usually contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 90.
%contains. Examples of the solid carrier used in the preparation include, for example, kaolin clay, attapargite clay, bentonite, montmorillonite, acid clay,
Mineral substances such as pyrophyllite, talc, diatomaceous earth, calcite, natural organic substances such as corn cob powder, walnut husk powder,
Fine powders or granules made of synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, and synthetic inorganic substances such as synthetic hydrated silicon oxide, and the like, and liquid carriers include, for example, aromatic substances such as xylene, alkylbenzene, and methylnaphthalene. Aromatic hydrocarbons, alcohols such as isopropanol, ethylene glycol, propylene glycol and cellosolve, ketones such as acetone, cyclohexanone and isophorone, soybean oil, vegetable oils such as cottonseed oil, petroleum aliphatic hydrocarbons, Esters, dimethyl sulfoxide,
Acetonitrile, water and the like. Examples of the surfactant include alkyl sulfates, alkyl (ally
B) anionic surfactants such as sulfonate, dialkyl sulfosuccinate, polyoxyethylene alkyl aryl ether phosphate, lignin sulfonate, and naphthalenesulfonic acid formalin condensate; polyoxyethylene alkyl aryl ether; Non-ionic surfactants such as polyoxyethylene alkyl polyoxypropylene block copolymers and sorbitan fatty acid esters are included. Pharmaceutical adjuvants include, for example, water-soluble polymers such as polyvinyl alcohol and polyvinyl pyrrolidone, gum arabic, alginic acid and its salts, polysaccharides such as CMC (carboxymethylcellulose) and xanthan gum;
Examples include inorganic substances such as aluminum magnesium silicate and alumina sol, preservatives, coloring agents, stabilizers such as PAP (acidic isopropyl phosphate), and BHT. Specific examples of the application method of the compound of the present invention include foliage application, soil treatment, seed disinfection, and the like, and can be used in any application method usually used by those skilled in the art.

When the compound of the present invention is used as an active ingredient in an agricultural and horticultural fungicide, the application rate of the active ingredient depends on the type of target plant (crop, etc.), the type of target disease, the degree of occurrence of disease,
Although it may vary depending on the form of formulation, application method, application time, weather conditions, etc., it is usually 0.01 to 50 g, preferably 0.05 to 10 g per arc. When the emulsion, wettable powder, suspending agent, etc. are diluted with water and applied, the application concentration is
0.0001 to 3%, preferably 0.0005 to 1%, and dusts, granules and the like are applied without any dilution.

The compound of the present invention can be used as a fungicide for agricultural and horticultural use in fields, paddy fields, orchards, tea fields, pastures, lawns, and the like. It can also be expected to increase the bactericidal efficacy. Other agricultural and horticultural fungicides that can be mixed include, for example, propiconazo-
, Triadimenol, prochloraz, penconazo
, Tebuconazole, flusilazole, diniconazole
, Bromconazole, epoxyconazole, difenoconazole, cyproconazole, metconazole, triflumizole, tetraconazole, microbutanyl,
Azol-based germicidal compounds such as fenbuconazole, hexaconazole, fluquinconazole, triticonazole, bitertanol, imazalil, and flutriaphor;
Cyclic amine fungicides such as fenpropimorph, tridemorph and fenpropidine, benzimidazole fungicides such as carbendazim, benomyl, thiabendazole and thiophanate-methyl, procymidone, cyprodinil, pyrimethanil, dietofencarb, thiuram, fluazinam , Mancozeb, iprodione, vinclozolin, chlorothalonil, captan, mepanipyrim, fenpiclonil, fludioxonil, diclofluanid, folpet, kresoxim-methyl, azoxystrobin, trifloxystrobin, picoxystrobin, N-methyl-α-methoxyimino- 2-[(2,
5-dimethylphenoxy) methyl] phenylacetamide, spiroxamine, quinoxyfen, fenhexamide, famoxadone, phenamidone (RP-40721
3), iprovaricarb and the like.

The compound of the present invention can be mixed with or used in combination with other agricultural and horticultural insecticides, acaricides, nematicides, herbicides, plant growth regulators, and fertilizers. Examples of such insecticides and / or miticides and / or nematicides include fenitrothion [O, O-dimethyl O- (3-methyl-4-nitrophenyl) phosphorothioate] and phenythion [O, O- Dimethyl O- (3-methyl-4-
(Methylthio) phenyl) phosphorothioate], diazinone [O, O-diethyl O-2-isopropyl-
6-methylpyrimidin-4-yl phosphorothioe-
G), chlorpyrifos [O, O-diethyl O-3,
5,6-trichloro-2-pyridyl phosphorothioe-
Acetoate [O, S-dimethylacetylphosphoramide thioate], methidathion [S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3] -Ylmethyl O, O-dimethyl phosphorodithioate], disulfotone [O, O-diethyl S
-2-ethylthioethyl phosphorothioate], DDV
P [2,2-dichlorovinyldimethylphosphate],
Sulfophophos [O-ethyl O-4- (methylthio) phenyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophenyl O, O-dimethyl phosphorothioate], dioxabenzophos [2 -Methoxy-4H-1,3,2-benzodioxaphosphinin-2
-Sulfide], dimethoate [O, O-dimethyl S
-(N-methylcarbamoylmethyl) dithiophospho-
G), phentoate [ethyl 2-dimethoxyphosphinothioylthio (phenyl) acetate], malathion [diethyl (dimethoxyphosphinothioylthio) succinate], trichlorfon [dimethyl 2,2,2
-Trichloro-1-hydroxyethylphosphonate],
Azinphosmethyl [S-3,4-dihydro-4-oxo-1,2,3-benzotriazin-3-ylmethyl
O, O-dimethyl phosphorodithioate], monocrotophos [dimethyl (E) -1-methyl-2- (methylcarbamoyl) vinyl phosphate], ethion [O, O,
O ', O'-tetraethyl S, S'-methylenebis (phosphorodithioate)], phosthiazetate [N-
Organic phosphorus compounds such as (O-methyl-S-sec-butyl) phosphorylthiazolidine-2-one], BPMC [2
-Sec-butylphenylmethylcarbamate], benfracarb [ethyl N- (2,3-dihydro-2,2-
Dimethylbenzofuran-7-yloxycarbonyl (methyl) aminothio] -N-isopropyl-β-alaninate], propoxur [2-isopropoxyphenyl
N-methyl carbamate], carbosulfan [2, 3
-Dihydro-2,2-dimethyl-7-benzo [b] furanyl N-dibutylaminothio-N-methylcarbamoyl
), Carbaryl [1-naphthyl N-methylcarbamate], mesomyl [S-methyl-N-[(methylcarbamoyl) oxy] thioacetimidate], ethiophenecarb [2- (ethylthiomethyl) phenylmethylcarbamate Bamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime], oxamyl [N, N-dimethyl-2-methylcarbamoyloxyimino-2- (methylthio) acetamide], phenothiocarb [ Carbamate-based compounds such as S-4-phenoxybutyl-N, N-dimethylthiocarbamate and ethofenprox [2- (4-ethoxyphenyl) -2-methylpropyl-3-phenoxybenzyl ether- Ter], fenvalerate [(RS) -α
-Cyano-3-phenoxybenzyl (RS) -2-
(4-chlorophenyl) -3-methylbutyrate], esfenvalerate [(S) -α-cyano-3-phenoxybenzyl (S) -2- (4-chlorophenyl)-
3-methylbutyrate], fenpropatrin [(R
S) -α-Cyano-3-phenoxybenzyl 2,2
3,3-tetramethylcyclopropanecarboxyle
G), 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-methylcyclopropanecarboxylate −
G], cyhalothrin [(RS) -α-cyano-3-phenoxybenzyl (Z)-(1RS, 3RS) -3-
(2-chloro-3,3,3-trifluoropropenyl)
-2,2-dimethylcyclopropanecarboxyle-
G), deltamethrin [(S) -α-cyano-m-phenoxybenzyl (1R, 3R) -3- (2,2-dibromovinyl) -2,2-dimethylcyclopropanecarboxylate], cycloprothrin [(RS) -α-cyano-3-phenoxybenzyl (RS) -2,2-dichloro-1- (4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate [α-cyano-3-
Phenoxybenzyl N- (2-chloro-α, α, α-
Trifluoro-p-tolyl) -D-barynate], bifensulin [2-methylbiphenyl-3-ylmethyl]
(Z)-(1RS) -cis-3- (2-chloro-3,
3,3-trifluoroprop-1-enyl) -2,2-
Dimethylcyclopropanecarboxylate], acrinasulin [(1R- {1α (S *), 3α (Z)}]-
2,2-dimethyl-3- [3-oxo-3- (2,2,
2-trifluoro-1- (trifluoromethyl) ethoxy-1-propenyl] cyclopropanecarboxylic acid cyano (3-phenoxyphenol) methyl ester)], 2-
Methyl-2- (4-bromodifluoromethoxyphenyl) propyl (3-phenoxybenzyl) ether, tralomethrin [(S) -α-cyano-3-phenoxybenzyl (1R) -cis-3- (1,2, Pyrethroid compounds such as 2,2-tetrabromoethyl) -2,2-dimethylcyclopropanecarboxylate and silafluorene [[4-ethoxyphenyl (3- (4-fluoro-3-phenoxyphenyl) propyl) dimethylsilane]; Thiadiazine derivatives such as buprofezin (2-t-butylimino-3-isopropyl-5-phenyl-1,3,5-triadiadinan-4-one), nitroimidazolidine derivatives, cartap (S, S '-(2-dimethylamino) Trimethylene) bis (thiocarbamate)],
Thiocyclam [N, N-dimethyl-1,2,3-trithian-5-ylamine], bensultap [S, S'-
2-dimethylaminotrimethylene di (benzenethiosulfonate)], N-cyano-N'-methyl-N '-(6-chloro-3-pyridylmethyl) acetamidine and the like. N-cyanoamidine derivative, endosulfan [6,7,8,9,10,10-
Hexachloro-1,5,5a, 6,9,9a-hexahydro-6,9-methano-2,4,3-benzodioxathiepin oxide], gamma-BHC (1,2,
3,4,5,6-hexachlorocyclohexane], 1,
Chlorinated hydrocarbon compounds such as 1-bis (chlorophenyl) -2,2,2-trichloroethanol and chlorofluazurone [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], flufenoxuron [1-
Benzoylphenylurea-based compounds such as (4- (2-chloro-4-trifluoromethylphenoxy) -2-fluorophenyl) -3- (2,6-difluorobenzoyl) urea], amitraz [N, N '[( Methylimino)
Dimethylidin] di-2,4-xylysine], chlordimeform [N '-(4-chloro-2-methylphenyl)-
N, N-dimethylmetanimidamide], thiourea derivatives such as diafenthiuron [N- (2,6-diisopropyl-4-phenoxyphenyl) -N′-t-butylcarbodiimide], phenylpyrazones -Based compound, tebufenozide [Nt-butyl-N '
-(4-ethylbenzoyl) -3,5-dimethylbenzohydrazide], 4-bromo-2- (4-chlorophenyl) -1-ethoxymethyl-5-trifluoromethylpyrrol-3-carbonitrile, bromopropyl [Isopropyl 4,4'-dibromobenzylate], tetradiphone [4-chlorophenyl 2,4,5-trichlorophenyl sulfone], quinomethionate [S, S-6
-Methylquinoxaline-2,3-diyldithiocarbonate], propargate [2- (4-t-butylphenoxy) cyclohexylprop-2-ylsulfite], fenbutatin oxide [bis [tris (2
-Methyl-2-phenylpropyl) tin] oxide], hexthiazox [(4RS, 5RS) -5-
(4-chlorophenyl) -N-chlorohexyl-4-methyl-2-oxo-1,3-thiazolidine-3-carboxamide], clofentezine [3,6-bis (2-chlorophenyl) -1,2,4 , 5-tetrazine, pyridathioben [2-t-butyl-5- (4-t-butylbenzylthio) -4-chloropyridazin-3 (2H) -one], fenpyroximate [t-butyl (E) -4-
[(1,3-dimethyl-5-phenoxypyrazole-4)
-Yl) methyleneaminooxymethyl] benzoe-
G), tebufenpyrad [N-4-t-butylbenzyl) -4-chloro-3-ethyl-1-methyl-5-pyrazolcarboxamide], polynactin complex [tetranactin, dinactin, trinactin], milbemectin, avermectin , Iva-mectin, azadirachtin [AZAD], pyrimidifen [5-chloro-
N- [2- {4- (2-ethoxyethyl) -2,3-dimethylphenoxy} ethyl] -6-ethylpyrimidine-
4-amine, pymetrozine [2,3,4,5-tetrahydro-3-oxo-4-[(pyridin-3-yl) -methyleneamino] -6-methyl-1,2,4-triazine and the like. .

Examples of plant diseases which can be controlled by the compound of the present invention include the following diseases. Rice blast (Pyricularia oryzae), sesame leaf blight (Cochliobolus miyabeanus), sheath blight (Rhizoc)
tonia solani, wheat powdery mildew (Erysiphe grami)
nis), Fusarium head blight (Gibberella zeae), Rust (Puccinia
striiformis, P. graminis, P. recondita, P. horde
i), snow rot (Typhula sp., Micronectriella nivalis),
Naked smut (Ustilago tritici, U.nuda), black smut (Tilletia caries), eye spot disease (Pseudocercosporella)
herpotrichoides), scald (Rhynchosporium secalis)
, Leaf blight (Septoria tritici), Fusarium wilt (Leptosphaer)
ia nodorum), citrus black spot (Diaporthe citr)
i), scab (Elsinoe fawcetti), fruit rot (Peni
cillium digitatum, P. italicum), Monilia disease of apples (Sclerotinia mali), Rot rot (Valsa mali), Powdery mildew (Podosphaera leucotricha), Spot leaf rot (Al
ternaria mali), scab (Venturia inaequalis), pear scab (Venturia nashicola, V. pirina), black spot (Alternaria kikuchiana), red scab (Gymnosporangium)
haraeanum), peach scab (Sclerotinia cinerea), scab (Cladosporium carpophilum), phomopsis rot (Phomopsis sp.), grape scab (Elsinoe ampe)
lina), late rot (Glomerella cingulata), powdery mildew (Uncinula necator), rust (Phakopsora ampelopsi)
dis), black lot disease (Guignardia bidwellii), downy mildew (Plasmopara viticola), oyster anthracnose (Gloeospo
rium kaki), deciduous disease (Cercospora kaki, Mycosphaerell
a nawae), Anthracnose of cucumber (Colletotrichum lagenariu)
m), powdery mildew (Sphaerotheca fuliginea), vine wilt
(Mycosphaerella melonis), vine disease (Fusarium oxy
sporum), downy mildew (Pseudoperonospora cubensis), plague (Phytophthora sp.), seedling blight (Pythium sp.), tomato ring spot (Alternaria solani), leaf mold (Clados)
porium fulvum), plague (Phytophthora infestans), eggplant brown spot (Phomopsis vexans), powdery mildew (Erysip)
he cichoracearum), black spot of cruciferous vegetables (Alterna
ria japonica), vitiligo (Cercosporella brassicae),
Leek rust (Puccinia allii), soybean purpura (Ce)
rcospora kikuchii), black rot (Elsinoe glycines),
Black spot disease (Diaporthe phaseolorum var. Sojae), kidney anthracnose (Colletotrichum lindemthianum), peanut black spot (Cercospora personata), brown spot (Cerco
spora arachidicola), pea powdery mildew (Erysiph)
e pisi), potato summer blight (Alternaria solani),
Plague (Phytophthora infestans), strawberry powdery mildew (Sphaerotheca humuli), tea net blast (Exobasidiu)
m reticulatum), white scab (Elsinoe leucospila), tobacco scab (Alternaria longipes), powdery mildew (Erys)
iphe cichoracearum), anthracnose (Colletotrichum tabac)
um), downy mildew (Peronospora tabacina), plague (Phytop
hthora nicotianae), brown spot of sugar beet (Cercospora b
eticola), rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), chrysanthemum spot on chrysanthemum (Septor
ia chrysanthemi-indici), white rust (Puccinia hori)
ana), gray mold on various crops (Botrytis cinerea)
, Sclerotinia sclerotiorum, etc.

[0032]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Preparation Examples, Test Examples, etc., but the present invention is not limited to these Examples. First, Production Examples of the compound of the present invention and Production Examples of intermediates for producing the compound of the present invention are shown in Production Examples and Reference Production Examples. The numbers of the compounds of the present invention are the compound numbers described in Tables 1 and 12 below.

Production Example 1 Methyl 2- (5-iodo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.8
62 mmol), 126 mg of phenylboronic acid (1.0
3 mmol), tetra-n-butylammonium bromide 2
78 mg (0.862 mmol), potassium carbonate 276
mg (2.15 mmol), palladium (II) acetate 1
9.3 mg (0.086 mmol) and 3 ml of water were mixed and stirred at 70 ° C. for 1 hour. The mixture was cooled to room temperature, diluted with t-butyl methyl ether, washed with water, dried (sodium sulfate), and then concentrated under reduced pressure.
The precipitated crystals were washed with n-hexane and treated with methyl 3-methoxy-2- (2-methyl-5-phenylphenoxy).
-2-propenoate (Compound 1-1 of the present invention) 350 m
g was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 6.92-7.52 (9H, m), 3.88
(3H, s), 3.71 (3H, s), 2.39 (3
H, s)

Production Example 2 Methyl 2- (5-iodo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.8
62 mmol), 3-phenylphenylboronic acid 205
mg (1.03 mmol), 278 mg (0.862 mmol) of tetra-n-butylammonium bromide, 276 mg (2.15 mmol) of potassium carbonate, 19.3 mg (0.086 mmol) of palladium (II) acetate and 3 ml of water At 70 ° C. for 1 hour. The mixture was cooled to room temperature, diluted with ethyl acetate, washed with water, dried (sodium sulfate), and concentrated under reduced pressure. The precipitated crystals were washed with n-hexane, and methyl 3-methoxy-2- {2-methyl-5- (3-phenylphenyl) was used.
Phenoxy I-2-propenoate (Compound 1- of the present invention)
23) 234 mg were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 6.50-7.49 (13H, m), 3.88
(3H, s), 3.71 (3H, s), 2.40 (3
H, s)

Production Example 3 Methyl 2- (5-iodo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.8
62 mmol), 4-fluorophenylboronic acid 180
mg (1.29 mmol), 416 mg (1.29 mmol) of tetra-n-butylammonium bromide, 298 mg (2.15 mmol) of potassium carbonate, 38.7 mg (0.172 mmol) of palladium (II) acetate and 3 ml of water And stirred at 70 ° C. for 30 minutes. The mixture was cooled to room temperature, diluted with t-butyl methyl ether, washed with water, dried (sodium sulfate), and then concentrated under reduced pressure. The precipitated crystals were washed with n-hexane to obtain 187 mg of methyl 3-methoxy-2- {2-methyl-5- (4-fluorophenyl) phenoxy} -2-propenoate (the present compound 1-36). ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.42-7.47 (2H, m), 7.31
(1H, s), 7.19 (1H, m), 7.05 to 7.
11 (3H, m), 6.86 (1H, d, J = 1.7H)
z), 3.88 (3H, s), 3.71 (3H, s),
2.38 (3H, s)

Production Example 4 Methyl 2- (5-iodo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.8
62 mmol), 177 m of 4-methylphenylboronic acid
g (1.30 mmol), tetra-n-butylammonium bromide 416 mg (1.29 mmol), potassium carbonate 298 mg (2.15 mmol), palladium (II) acetate 38.7 mg (0.17 mmol) and water 3
After mixing, the mixture was stirred at 70 ° C. for 1 hour. The mixture was cooled to room temperature, diluted with ethyl acetate, washed with water, dried (sodium sulfate), and concentrated under reduced pressure. The precipitated crystals were washed with n-hexane, and methyl 3-methoxy-
2- {2-methyl-5- (4-methylphenyl) phenoxy} -2-propenoate (Compound 1-40 of the present invention)
206 mg were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.40 (2H, d, J = 1.7 Hz),
7.33 (1H, s), 7.19-7.22 (3H,
m), 7.12 (1H, m), 6.91 (1H, d, J
= 1.42 Hz), 3.87 (3H, s), 3.71
(3H, s), 2.38 (6H, s)

Production Example 5 Methyl 2- (5-bromo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.9
46 mmol), 194 mg (1.23 mmol) of 3,5-difluorophenylboronic acid, 360 mg (1.12 mmol) of tetra-n-butylammonium bromide, 327 mg (2.37 mmol) of potassium carbonate, 21 mg of palladium (II) acetate (0 mg). 0.094 mmol) and 3 ml of water. The mixture was stirred at 80 ° C for 5 hours, cooled to room temperature, added with ethyl acetate and celite, and filtered. The filtrate was washed with water, dried (sodium sulfate), and then concentrated under reduced pressure. The residue was subjected to silica gel preparative thin-layer chromatography (n-hexane: ethyl acetate =
2: 1)) and methyl 2- {2-methyl-5
-(3,5-difluorophenyl) phenoxy} -3-
Methoxy-2-propenoate (Compound 1-1 of the present invention)
1) 141 mg was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.36 (1H, s), 7.22 to 7.33
(1H, m), 7.09 (1H, dd, J = 7.8,
1.9 Hz), 6.99 to 7.02 (2H, m), 6.
86 (1H, d, J = 1.5 Hz), 6.72 to 6.7
5 (1H, m), 3.90 (3H, s), 3.72 (3
H, s), 2.39 (3H, s)

Production Example 6 Methyl 2- (5-bromo-2-methylphenoxy)-
300 mg of 3-methoxy-2-propenoate (0.9
46 mmol), 224 mg (1.18 mmol) of 3-trifluoromethylphenylboronic acid, tetra-n bromide
-Butylammonium 360mg (1.12mmo
l), potassium carbonate 327 mg (2.37 mmol),
21 mg of palladium (II) acetate (0.094 mmol
After mixing 1) and 3 ml of water, the mixture was stirred at 80 ° C. for 6 hours. After cooling the mixture to room temperature, ethyl acetate and celite were added, and the mixture was filtered. The filtrate was washed with water, dried (sodium sulfate), and then concentrated under reduced pressure. The precipitated crystals were washed with n-hexane, and methyl 2- {2-methyl-5
-(3-trifluoromethylphenyl) phenoxy}-
3-methoxy-2-propenoate (Compound 1- of the present invention)
13) 182 mg were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.51-7.73 (4H, m), 7.36
(1H, s), 7.24 to 7.26 (1H, m), 7.
13 (1H, dd, J = 7.6, 1.8 Hz), 6.9
0 (1H, d, J = 1.8 Hz), 3.90 (3H,
s), 3.72 (3H, s), 2.40 (3H, s)

Production Example 7 The following product was obtained in the same manner as in Production Example 6. Methyl 2- {2-methyl-5- (3-fluorophenyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-2 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 6 0.8-7.4 (8H, m), 3.89 (3
H, s), 3.72 (3H, s), 2.39 (3H,
s)

Production Example 8 421 mg (1.42 mmol) of methyl 3-methoxy-2- (2-methyl-5-bromo-benzyl) acrylic acid
l), 225 mg of phenylboronic acid (1.85 mmol)
l), 1.5 g of tripotassium phosphate hydrate (7.1 mmol
l), {1,1'-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride 58 mg (0.071 mmol), palladium (II) acetate 16 mg (0.071 mmol) and ethylene glycol dimethyl ether After mixing 6ml, 83 ℃
For 1 hour. The mixture was cooled to room temperature, ethyl acetate and celite were added and filtered. The solvent was distilled off from the filtrate under reduced pressure, and the residue was subjected to preparative thin-layer chromatography on silica gel (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 3-methoxy-2- (2- 410 mg of methyl-5-phenylbenzyl) acrylic acid (Compound 2-1 of the present invention) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.2-7.6 (9H, m), 3.85 (3
H, s), 3.67 (3H, s), 3.61 (2H,
s), 2.39 (3H, s)

Production Example 9 Methyl 2- (5-iodo-2-methylphenoxy)-
200 mg of 3-methoxy-2-propenoate (0.5 mg
74 mmol), 4,4,5,5-tetramethyl-2-
{3- (4-pyrimidyl)} phenyl-1,3,2-dioxoborolane 162 mg (0.574 mmol), tripotassium phosphate hydrate 610 mg (2.87 mmol),
{1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 23
mg (0.03 mmol), palladium (II) acetate 6
mg (0.03 mmol) and 3 ml of ethylene glycol dimethyl ether, followed by stirring at 83 ° C. for 1.5 hours. After the mixture was cooled to room temperature, saturated saline was added, and the mixture was extracted with ethyl acetate. The organic layer was dried (sodium sulfate) and concentrated under reduced pressure. The residue was purified by silica gel preparative thin-layer chromatography (n-hexane:
Ethyl acetate = 1: 1) to give methyl 3-methoxy-2- [2-methyl-5- {3- (4-pyrimidinyl) phenyl} phenoxy] -2-propenoate (Compound 1-32 of the present invention). ) 128 mg were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 9.28 (1H, s), 8.78 (1H,
d, J = 5.1 Hz), 8.23 (1H, t, J = 1.
9 Hz), 8.2 (1H, m), 7.74 (1H, dd,
J = 5.0 Hz, J = 1.3 Hz), 7.62 (1H,
m), 7.54 (1H, t, J = 7.7 Hz), 7.34
(1H, s), 7.21-7.25 (2H, m), 6.
97 (1H, d, J = 1.7 Hz), 3.89 (3H,
s), 3.72 (3H, s), 2.41 (3H, s)

Production Example 10 Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) phenoxy} -3-methoxy-2-propenoate 200 mg (0.574 mmol), 128 mg (0.805 mmol) of 2-bromopyrimidine, 855 mg (4.03 mmol) of tripotassium phosphate hydrate, {1,1 ′
-Bis (diphenylphosphino) ferrocene @ dichloropalladium (II) methylene chloride complex 33 mg (0.
040 mmol), 9 mg of palladium (II) acetate
(0.04 mmol) and 3 ml of ethylene glycol dimethyl ether, followed by stirring at 83 ° C. for 4 hours. After cooling the mixture to room temperature, the solvent was distilled off under reduced pressure. The residue was subjected to silica gel column chromatography (eluted with n-hexane: ethyl acetate = 2: 8 to 0:10) to give methyl 3-methoxy-2- {2-methyl-5- (2-pyrimidinyl) phenoxy}-. 102 mg of 2-propenoate (Compound 1-51 of the present invention) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.74 (2H, d, J = 4.5 Hz),
8.02 (1H, dd, J = 7.8 Hz, 1.6H
z), 7.83 (1H, d, J = 1.7 Hz), 7.3
8 (1H, s), 7.28 (1H, s), 7.12 (1
H, t, J = 1.5), 3.88 (3H, s), 3.7
0 (3H, s), 2.42 (3H, s)

Production Example 11 Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) phenoxy} -3-methoxy-2-propenoate 200 mg (0.574 mmol), 2-chloro-5-
156 mg of trifluoromethylpyridine (0.859 m
mol), tripotassium phosphate hydrate 610 mg (2.87)
mmol), {1,1'-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 23.5 mg (0.029 mmol), palladium (II) acetate 6.4 mg (0.029 mmol) and ethylene glycol After mixing 3 ml of dimethyl ether, the mixture was stirred at 83 ° C. for 6 hours. The mixture was cooled to room temperature, ethyl acetate and celite were added and filtered. The solvent was distilled off from the filtrate under reduced pressure, and the residue was subjected to silica gel preparative thin-layer chromatography (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 2- [2-methyl-
213 mg of 5- {5- (trifluoromethyl) -2-pyridyl} phenoxy] -3-methoxy-2-propenoate (Compound 1-92 of the present invention) were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.9 (1H, s), 7.9 (1H, d)
d), 7.7 (1H, d), 7.6 (1H, dd), 7.
46 (1H, d, J = 1.7 Hz), 7.37 (1H, d, J = 1.7 Hz)
s), 7.28 (1H, s), 3.89 (3H, s),
3.71 (3H, s), 2.42 (3H, s)

Production Example 12 Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) phenoxy} -3-methoxy-2-propenoate 200 mg (0.574 mmol), 2-chloro-6-
156 mg of trifluoromethylpyridine (0.859 m
mol), tripotassium phosphate hydrate 610 mg (2.87)
mmol), {1,1'-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 23.5 mg (0.029 mmol), palladium (II) acetate 6.4 mg (0.029 mmol) and ethylene glycol After mixing 3 ml of dimethyl ether, the mixture was stirred at 83 ° C. for 4 hours. After cooling the mixture, ethyl acetate and celite were added and filtered. The filtrate was evaporated under reduced pressure to remove the solvent, and the residue was subjected to silica gel preparative thin-layer chromatography (n-hexane: ethyl acetate = 2: 1).
) And methyl 2- [2-methyl-5- {6}
This gave 136 mg of-(trifluoromethyl) -2-pyridyl {phenoxy] -3-methoxy-2-propenoate (Compound 1-91 of the present invention). ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.87 to 7.82 (2H, m), 7.56
(2H, dt), 7.48 (1H, d, J = 2.1H)
z), 7.39 (1H, s), 7.28-7.25 (1
H, m), 3.91 (3H, s), 3.72 (3H,
s), 2.42 (3H, s)

Production Example 13 Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) phenoxy} -3-methoxy-2-propenoate 200 mg (0.574 mmol), 3-bromo-1-
153 mg of (4-pyrimidinylmethoxy) benzene
(0.577 mmol), tripotassium phosphate hydrate 610
mg (2.87 mmol), {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride 23.5 mg (0.029 m
mol), 6.4 mg of palladium (II) acetate (0.0
29 mmol) and ethylene glycol dimethyl ether
3 ml of ter were mixed and stirred at 83 ° C. for 5 hours. After cooling the mixture to room temperature, ethyl acetate and celite were added, and the mixture was filtered. The solvent was distilled off from the filtrate under reduced pressure,
The residue was subjected to silica gel preparative thin-layer chromatography (developed with n-hexane: ethyl acetate = 1: 1) to give methyl
140 mg of 2- [2-methyl-5- {3- (4-pyrimidinylmethoxy) phenoxy} -3-methoxy-2-propenoate (Compound 1-27 of the present invention) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 9.2 (1H, s), 8.7 (1H, d),
7.6 (1H, d), 7.1-7.4 (6H, m), 6.
9 (2H, m), 5.2 (2H, s), 3.89 (3
H, s), 3.72 (3H, s), 2.4 (3H, s)

Production Examples 14 to 26 The following objects were obtained in the same manner as in Production Example 13. Methyl 2- {2-methyl-5- (3-benzyloxyphenyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-25) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 6.9-7.5 (13H, m), 5.1 (2
H, s), 3.9 (3H, s), 3.7 (3H, s),
2.4 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (3-methylphenyl) phenoxy} -2-propenoate (Compound 1-6 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm ): 7.34 (1H, s), 7.26-7.30
(3H, m), 7.21 (1H, d, J = 7.7 Hz),
7.11-7.14 (m, 2H), 6.91 (d, 1
H, J = 1.1 Hz) 3.88 (3H, s), 3.71
(3H, s), 2.40 (3H, s), 2.38 (3
H, s)

Methyl 3-methoxy-2- {2-methyl-5- (3-methoxyphenyl) phenoxy} -2-propenoate (Compound 1-16) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm ): 7.04-7.36 (6H, m), 6.85
-6.92 (2H, m), 3.88 (3H, s), 3.
85 (3H, s), 3.58 (3H, s), 2.14 (3
H, s)

Methyl 3-methoxy-2- {2-methyl-5- (2,3,4,5,6-pentafluorophenyl) phenoxy} -2-propenoate (Compound 1-45) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.26-7.33 (2H, m), 7.0
(1H, m), 6.75 (1H, m), 3.87 (3
H, s), 3.71 (3H, s), 2.41 (3H, s)

Methyl 2- {2-methyl-5- (4-methyl-2-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-59) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.59 (1H, d, J = 5.0 Hz),
8.02 (1H, dd, J = 7.8, 1.5 Hz),
7.82 (1H, d, J = 1.4 Hz), 7.38 (1
H, s), 7.26 (1H, d, J = 7.7 Hz),
7.00 (1H, d, J = 5.0 Hz), 3.88 (3
H, s), 3.70 (3H, s), 2.55 (3H,
s), 2.42 (3H, s)

Methyl 2- {2-methyl-5- (4-n
-Butyl-2-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-111) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.59 (1H, d, J = 5.1Hz),
8.0 (1H, dd), 7.9 (1H, d), 7.3
(2H, m), 6.96 (1H, d, J = 5.1H)
z), 3.89 (3H, s), 3.70 (3H, s),
2.78 (3H, t, J = 7.8 Hz), 2.42 (3
H, s), 1.7-1.8 (2H, m), 1.3-1.
5 (2H, m), 0.96 (3H, t, J = 7.3H
z)

Methyl 2- {2-methyl-5- (4-s
ec-butyl-2-pyrimidinyl) phenoxy {-3-
Methoxy-2-propenoate (Compound 1-11 of the present invention)
2) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.61 (1 H, d, J = 5.0 Hz),
8.06 (1H, dd, J = 7.8 Hz), 7.86
(1H, d, J = 1.3 Hz), 7.38 (1H, d, J = 1.3 Hz)
s), 7.26 (1H, d, J = 7.7 Hz), 6.
96 (1H, d, J = 5.1 Hz), 3.89 (3H,
s), 3.71 (3H, s), 2.7-2.9 (1H,
m), 2.42 (3H, s), 1.6-1.9 (3H,
m), 1.3 (3H, d, J = 1.3 Hz), 0.88
(3H, t, J = 7.5Hz)

Methyl 2- {2-methyl-5- (4-trifluoromethyl-2-pyrimidinyl) phenoxy}-
3-methoxy-2-propenoate (Compound 1- of the present invention)
68) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.98 (1 H, d, J = 5.0 Hz),
8.09 (1H, dd, J = 7.8, 1.7 Hz),
7.85 (1H, d, J = 1.4 Hz), 7.44 (1
H, d, J = 5.0 Hz), 7.40 (1H, s),
7.29 (1H, d, J = 7.9 Hz), 3.90
(3H, s), 3.72 (3H, s), 2.44 (3H, s)
s)

Methyl 2- {2-methyl-5- (4-methoxy-2-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-69) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.45 (1H, d, J = 5.7 Hz),
8.02 (1H, dd, J = 7.8, 1.4 Hz),
7.82 (1H, d, J = 1.6 Hz), 7.37 (1
H, s), 7.31 (1H, d, J = 7.8 Hz),
6.58 (1H, d, J = 5.8 Hz), 4.05 (3
H, s), 3.88 (3H, s), 3.70 (3H,
s), 2.42 (3H, s)

Methyl 2- {2-methyl-5- (4,6
-Dimethyl-2-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-62 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.0 (1H, d), 7 .8 (1H, d),
7.38 (1H, s), 7.2 (1H, d), 6.87
(1H, s), 3.89 (3H, s), 3.70 (3
H, s), 2.50 (6H, s) 2.41 (3H, s)

Methyl 2- {2-methyl-5- (6-phenoxy-2-pyridyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-73 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.69 (1H, t, J = 7.7 Hz),
7.16-7.46 (10H, m), 6.77 (1H,
dd, J = 8.0, 0.5 Hz), 3.75 (3H,
s), 3.69 (3H, s), 2.36 (3H, s)

Methyl 2- {2-methyl-5- (6-benzyloxy-2-pyridyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-72 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.24-7.63 (11H, m), 6.7
0 (1H, d, J = 8.0 Hz), 3.84 (3H,
s), 3.70 (3H, s), 2.40 (3H, s)

Methyl 2- {2-methyl-5- (6-methyl-2-pyridyl) phenoxy} -3-methoxy-2
-Propenoate (Compound 1-86 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.52-7.61 (2H, m), 7.34
−7.42 (3H, m), 7.23 (1H, d, J =
7.9 Hz), 7.05 (1H, d, J = 7.5 Hz)
), 3.89 (3H, s), 3.70 (3H, s),
2.39 (3H, s), 2.04 (3H, s)

Production Example 27 Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) phenoxy} -3-methoxy-2-propenoate 200 mg (0.574 mmol), 2-chloro-4-
82 mg (0.575 mmol) of ethylpyrimidine, 610 mg (2.87 mmol) of tripotassium phosphate hydrate,
{1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 23
mg (0.029 mmol) and 3 ml of ethylene glycol dimethyl ether, and the mixture was stirred at 83 ° C for 3 hours. After cooling the mixture to room temperature, ethyl acetate and celite were added, and the mixture was filtered. The solvent was distilled off from the filtrate under reduced pressure, and the residue was subjected to silica gel preparative thin-layer chromatography (developed with n-hexane: ethyl acetate = 1: 1) to give methyl 2- {2-methyl-5- (4-ethyl-2
159 mg of (-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-64 of the present invention) were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.4 (1H, d,), 8.0 (1H, d)
d), 7.8 (1H, d), 7.4 (1H, s), 7.
3 (1H, d), 7.0 (1H, d), 3.89 (3
H, s), 3.70 (3H, s), 2.8 (2H, q),
2.42 (3H, t), 1.35 (3H, t)

Production Examples 28 to 33 The following objects were obtained in the same manner as in Production Example 27. Methyl 2- {2-methyl-5- (4-n-propyl-
2-pyrimidinyl) phenoxy {-3-methoxy-2-
Propenoate (Compound 1-66 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.60 (1 H, d, J = 5.3 Hz),
8.04 (1H, dd, J = 7.8, 1.4 Hz),
7.84 (1H, d, J = 1.3 Hz), 7.37 (1
H, s), 7.26 (1H, d, J = 7.4 Hz),
6.97 (1H, d, J = 5.0 Hz), 3.88
(3H, s), 3.70 (3H, s), 2.76 (2H,
t, J = 7.2 Hz), 2.42 (3H, s), 1.7
8-1.86 (2H, m), 1.01 (3H, t, J =
7.2Hz)

Methyl 2- {2-methyl-5- (4-n
-Propyloxy-2-pyrimidinyl) phenoxy｝-
3-methoxy-2-propenoate (Compound 1- of the present invention)
113) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.44 (1 H, d, J = 5.7 Hz),
7.99 (1H, dd, J = 7.8, 1.4 Hz),
7.81 (1H, d, J = 1.3 Hz), 7.36 (1
H, s), 7.2 (1H, d), 6.55 (1H, d,
J = 5.7 Hz), 4.42 (3H, t, 6.5H)
z), 3.88 (3H, s), 3.70 (3H, s),
2.42 (3H, s), 1.81-1.88 (2H,
m), 1.05 (3H, t, J = 7.6 Hz)

Methyl 2- {2-methyl-5- (4-cyano-2-pyrimidinyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-115) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.93 (1H, d, J = 4.9 Hz),
8.05 (1H, dd, J = 7.8 Hz), 7.81
(1H, d, J = 1.7 Hz), 7.40-7.43
(2H, m), 7.85 (1H, d, J = 7.8 Hz)
), 3.91 (3H, s), 3.72 (3H, s),
2.43 (3H, s)

Methyl 2- {2-methyl-5- (6-chloro-2-pyridyl) phenoxy} -3-methoxy-2
-Propenoate (the present compound 1-82) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.64 (1 H, t, J = 7.8 Hz),
7.54 (2H, d, J = 7.7 Hz), 7.36 (2
H, m), 7.22-2.26 (2H, m), 3.90
(3H, s), 3.71 (3H, s), 2.40 (3H,
s)

Methyl 2- {2-methyl-5- (6-methoxy-2-pyridyl) phenoxy} -3-methoxy-
2-propenoate (Compound 1-94 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.10-7.61 (6H, m), 6.64
(1H, dd, J = 8.6, 0.6 Hz), 4.00
(3H, s), 3.88 (3H, s), 3.71 (3H, s)
s), 2.40 (3H, s)

Methyl 2- {2-methyl-5- (6-methylthio-2-pyridyl) phenoxy} -3-methoxy-2-propenoate (Compound 1-114 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.46-7.56 (3H, m), 7.12
−7.36 (3Hm), 7.08 (1H, d, J = 7.
8 Hz), 3.88 (3H, s), 3.71 (3H,
s), 2.62 (3H, s), 2.40 (3H, s)

Production Example 34 Methyl 3-methoxy-2- {2-methyl-5- (4
(4,5,5-tetramethyl-1,3,2-dioxoborolan-2-yl) -benzyl} acrylic acid 200 mg
(0.578 mmol), 2-bromochlorobenzene 1
44 mg (0.752 mmol), tripotassium phosphate hydrate 613 mg (2.9 mmol), {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 24 mg (0.029 mmol)
mmol) and 3 ml of ethylene glycol dimethyl ether, and the mixture was stirred at 83 ° C for 3 hours. The mixture was cooled to room temperature, ethyl acetate was added and filtered. The filtrate was evaporated under reduced pressure to remove the solvent, and the residue was subjected to silica gel preparative thin-layer chromatography (n-hexane: ethyl acetate =
2: 1), methyl 3-methoxy-2-
{2-methyl-5- (3-chlorophenyl) benzyl}
126 mg of acrylic acid (the present compound 2-3) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.5 (2H, m), 7.2-7.5 (5
H, m), 3.87 (3H, s), 2-68 (3H,
s), 3.61 (2H, s), 2.39 (3H, s)

Production Examples 35 to 41 The following objects were obtained in the same manner as in Production Example 27. Methyl 3-methoxy-2- {2-methyl-5- (4-
(Chlorophenyl) benzyl} acrylic acid (Compound 2-37 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.16-7.49 (8H, m), 3.85
(3H, s), 3.67 (3H, s), 3.60 (2H,
s), 2.39 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (4-trifluoromethyl-2-pyrimidinyl)
Benzyl @ acrylic acid (Compound 2-68) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.98 (1 H, d, J = 4.9 Hz),
8.31 (1H, d, J = 1.1 Hz), 8.19 (1
H, dd, J = 7.9 Hz), 7.52 (1H, s),
7.43 (1H, d, J = 4.9 Hz), 7.2 (1
H, s), 3.89 (3H, s), 2-68 (3H,
s), 3.64 (2H, s), 2.44 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (6-methyl-2-pyridyl) benzyl} acrylic acid (Compound 2-86 of the present invention) ¹ H-NMR (CDCl ₃ , TMS) δ ( ppm): 7.70-7.72 (2H, m), 7.58
(1H, t, J = 7.7 Hz), 7.48 (1H,
s), 7.43 (1H, d, J = 7.9 Hz), 7.2
0 (1H, d, J = 8.3 Hz), 7.03 (1H,
d, J = 7.5 Hz), 3.86 (3H, s), 3.6
6 (3H, s), 3.62 (2H, s), 2.59 (3
H, s), 2.39 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (6-trifluoromethyl-2-pyridyl) benzyl} acrylic acid (Compound 2-91) ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.82-7.87 (3H, m), 7.76
(1H, dd, J = 7.8, 1.8 Hz), 7.53
-7.55 (1H, m), 7.50 (1H, s), 7.
23 (1H, d, J = 7.9 Hz), 3.89 (3H,
s), 2-68 (3H, s), 3.63 (2H, s),
2.42 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (6-chloro-2-pyridyl) benzyl} acrylic acid (Compound 2-82) ¹ H-NMR (CDCl ₃ , TMS) δ ( ppm): 7.67-7.74 (2H, m), 7.65
(1H, t, J = 7.7), 7.56 (1H, d, J
= 7.6 Hz), 7.50 (1H, s), 7.18-
7.22 (2H, m), 3.88 (3H, s), 3.6
7 (3H, s), 3.62 (2H, s), 2.40 (3
H, s)

Methyl 3-methoxy-2- {2-methyl-5- (6-methoxy-2-pyridyl) benzyl} acrylic acid (Compound 2-94) ¹ H-NMR (CDCl ₃ , TMS) δ ( ppm): 7.74-7.80 (2H, m), 7.58
(1H, t, J = 8.0), 7.50 (1H, s),
7.18-7.27 (2H, m), 6.63 (1H,
d, J = 8.2 Hz), 4.02 (3H, s), 3.8
5 (3H, s), 6.67 (2H, s), 3.62 (3
H, s), 2.40 (3H, s)

Methyl 3-methoxy-2- {2-methyl-5- (5-chloro-2-pyridyl) benzyl} acrylic acid (Compound 2-83) ¹ H-NMR (CDCl ₃ , TMS) δ ( ppm): 8.6 (1H, m), 7.58-7.71 (
4H, m), 7.49 (1H, s), 7.18-7.2
7 (2H, m), 7.21 (1H, d, J = 8.4H
z), 3.86 (3H, s), 3.66 (3H, s),
6.62 (2H, s), 2.40 (3H, s)

Production Example 42 Methyl 2- (5-bromo-2-methylphenoxy)-
200 mg of 3-methoxy-2-propenoate (0.6
31 mmol), 2- (trimethyltin) pyridine 229
mg (0.947 mmol), bis- (triphenylphosphine) palladium (II) dichloride 22 mg
(0.031 mmol), copper (II) oxide 50 mg
(0.629 mmol) and 3 ml of ethylene glycol dimethyl ether, followed by stirring at 80 ° C. for 6 hours. The mixture was cooled to room temperature, diluted with ethyl acetate, washed with water, dried (sodium sulfate), and concentrated under reduced pressure. The residue was subjected to silica gel preparative thin layer chromatography (developed with n-hexane: ethyl acetate = 2: 1),
141 mg of methyl 2- {2-methyl-5- (2-pyridyl) phenoxy] -3-methoxy-2-propenoate (the present compound 1-78) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 8.64 to 8.65 (1H, m), 7.64 to
7.71 (2H, m), 7.52 (1H, dd, J =
7.8 Hz, 1.7 Hz), 7.36 to 7.40 (2
H, m), 7.16-7.26 (2H, m), 3.88
(3H, s), 3.70 (3H, s), 2.40 (3
H, s)

Intermediate Production Example 1 Methyl 2- (5-bromo-2-methylphenoxy)-
2.00 g of 3-methoxy-2-propenoate (6.3
1 mmol), bis (pinacolato) diboron 1.92
g (7.56 mmol), {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (I
I) 0.26 g of methylene chloride complex (0.318 mmol
l), 1.86 g (19.0 mmol) of potassium acetate and dimethylsulfoxide (50 ml), and then mixed.
Stirred at 0 ° C. for 8 hours. The mixture was cooled to room temperature, water was added, and extracted with ethyl acetate. The organic layer was washed with water, saturated brine, dried (anhydrous sodium sulfate) and concentrated under reduced pressure. The precipitated crystals were washed with n-hexane and treated with methyl 2- {2-methyl-5- (4,4,5,5).
-Tetramethyl-1,3,2-dioxoborolan-2-
Il) phenoxy} -3-methoxy-2-propenoate (2.00 g) was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.4 (1H, d), 7.3 (1H, s),
7.2 (1H, d), 7.1 (1H, s), 3.86
(3H, s), 3.69 (3H, s), 2.38 (3
H, s), 1.31 (12H, s) Intermediate Production Example 2 2.00 g of methyl 3-methoxy-2- {2-methyl-5-bromo-benzyl} acrylic acid (6.31 mmol)
l), 2.22 g of bis (pinacolato) diboron (8.
74 mmol), {1,1′-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride complex 0.27 g (0.331 mmol), potassium acetate 1.96 g (20.0 mmol) and dimethyl sulfoxide ( 40 ml) and mixed at 80 ° C for 8 hours.
Stirred for hours. The mixture was cooled to room temperature, filtered through celite, added water and extracted with ethyl acetate. The organic layer was washed with water, saturated brine, dried (anhydrous sodium sulfate) and concentrated under reduced pressure. Residue is t-butyl methyl ether
Crystallized from ter, methyl 3-methoxy-2- {2-
Methyl-5- (4,4,5,5-tetramethyl-1,
790 mg of 3,2-dioxoborolan-2-yl) benzyl @ acrylic acid were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.50-7.54 (2H, m), 7.46
(1H, s), 7.11 (1H, d, J = 7.4H
z), 3.84 (3H, s), 3.65 (3H, s),
3.56 (2H, s), 2.35 (3H, s) 1.31
(12H, s)

Reference Production Example 1 20.39 g of 5-amino-2-methylphenol (0.
A mixture of 166 mol), 48% hydrobromic acid (127 ml) and water 157 ml was cooled to 0 ° C., and sodium nitrite 11.42 g (0.166 mol) / water 35
ml was added dropwise so that the liquid temperature was kept at 5 ° C. or lower. The reaction solution of the resulting diazonium salt was added dropwise to a mixture of 98 ml of 48% hydrobromic acid at 0 ° C. with copper (I) bromide. The temperature of the mixture was gradually raised to 100 ° C., and the mixture was stirred at 100 ° C. for 30 minutes.
Cooled and extracted with ethyl acetate. The organic layer was washed with water, washed with saturated saline, dried (anhydrous sodium sulfate), concentrated, and the residue was subjected to silica gel column chromatography (n-
Eluting with hexane: ethyl acetate = 95: 5 to 75:15) to give 5-bromo-2-methylphenol.
98 g were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 6.97 (2H, s), 6.94 (1H,
s), 4.97 (1H, s), 2.19 (3H, s)

Reference Production Example 2 12.98 g of 5-bromo-2-methylphenol (6
9.4 mmol), 11.68 g of methyl bromoacetate (7
6.3 mmol), 12.47 g of potassium carbonate (90.
2 mol) and N, N-dimethylformamide 150
After stirring the ml mixture at room temperature for 3 hours, water was added and extracted with ethyl acetate. The organic layer is washed successively with water, saturated aqueous sodium bicarbonate and saturated saline, and dried (anhydrous sodium sulfate).
Thereafter, the mixture was concentrated to obtain 18.77 g of methyl 2- (5-bromo-2-methylphenoxy) acetate. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.02 (2H, s), 6.83 (1H, d,
J = 0.8 Hz), 4.63 (2H, s), 3.81
(3H, s), 2.23 (3H, s)

Reference Production Example 3 A mixture of 18.4 g (71.0 mmol) of methyl 2- (5-bromo-2-methylphenoxy) acetate, 42.64 g (710 mmol) of methyl formate, and 36 ml of ethylene glycol dimethyl ether was prepared. 30% potassium hydride (20.89) cooled to 0 ° C. over 40 minutes
g, 156 mmol) and 185 ml of ethylene glycol dimethyl ether. The resulting mixture was heated to room temperature, stirred for 3 hours, poured into a saturated aqueous ammonium chloride solution, adjusted to pH 4 with a 5% hydrochloric acid aqueous solution, and extracted with ethyl acetate. The organic layer was washed successively with water and saturated saline, dried (anhydrous sodium sulfate),
Concentration gave crude methyl 2- (5-bromo-2-methylphenoxy) -3-hydroxy-2-propenoate. Crude methyl 2- (5-bromo-2-methylphenoxy) -3-hydroxy-2-propenoate obtained in the above reaction, 15.12 g of methyl iodide (107 mmol)
l), a mixture of 16.68 g (121 mol) of potassium carbonate and 200 ml of N, N-dimethylformamide was stirred at room temperature for 6 hours, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with a 2% aqueous hydrochloric acid solution, water, saturated aqueous sodium hydrogen carbonate and saturated brine, dried (anhydrous sodium sulfate) and concentrated, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 100: 0-5
0:50) and methyl 2- (5-bromo-
10.08 g of 2-methylphenoxy) -3-methoxy-2-propenoate were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.31 (1H, s), 7.0 (2H, m),
3.88 (3H, s), 3.72 (3H, s), 2.2
8 (3H, s)

Reference Production Example 4-1 10.0 g of 5-iodo-2-methylaniline (42.9)
mol), concentrated sulfuric acid (5 ml) and water (15 ml) was cooled to -10 ° C and sodium nitrite was added to the mixture.
0 g (43.5 mol) / 4 ml of water and 15 ml of water were added dropwise so that the liquid temperature was kept at −3 ° C. or lower. 8.0 g of copper (II) sulfate pentahydrate was added to the obtained reaction solution of the diazonium salt.
(32.0 ml) was added dropwise at 75 ° C. to a mixture of 55 ml of 10% sulfuric acid and 37 ml of toluene. 75 mixture
After stirring at 2 ° C. for 2 hours, the mixture was cooled and extracted with t-butyl methyl ether. The organic layer was concentrated, and the residue was subjected to silica gel column chromatography to obtain 5.33 g of 5-iodo-2-methylphenol. Reference Production Example 4-2 20.48 g of 5-iodo-2-methylphenol (8
7.5 mmol), 9.1 ml of methyl bromoacetate (9
6.1 mmol), potassium carbonate 14.5 g (105 m
ol) and 175 ml of N, N-dimethylformamide
Was stirred at room temperature overnight, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, dried (anhydrous sodium sulfate) and concentrated.
The residue was subjected to silica gel column chromatography to obtain 15.76 g of methyl 2- (5-iodo-2-methylphenoxy) acetate. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.23 (1H, dd, J = 7.8, 1.6H)
z), 6.98 (1H, d, J = 1.3 Hz), 6.8
8 (1H, d, J = 7.5 Hz), 4.62 (2H,
s), 3.81 (3H, s), 2.23 (3H, s)

Reference Production Example 5 Methyl 2- (5-iodo-2-methylphenoxy) was obtained from methyl 2- (5-iodo-2-methylphenoxy) acetate in the same manner as in Reference Production Example 2 and Reference Production Example 3. ) -3-Methoxy-2-propenoate was obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.32 (1H, s), 7.23 (1H, dd,
J = 7.8, 1.6 Hz), 6.99 (1H, d, J =
1.6 Hz), 6.88 (1H, dd, J = 7.7,
0.6 Hz), 3.88 (3H, s), 3.72 (3
H, s), 2.29 (3H, s)

Reference Production Example 6 9.0 g (59.9 mmol) of 3-bromoacetophenone
1), 17.1 g (118 mmol) of N, N ′, N ″ -methylidenetrisformamide, 0.57 g (3.0 mmol) of p-toluenesulfonic acid and formamide 2
After stirring 7 g of the mixture at 160 ° C. for 2 hours,
% Aqueous solution of caustic soda and 5% hydrochloric acid solution to pH
After adjusting to 4, the mixture was extracted with ethyl acetate. The organic layer was washed successively with a saturated aqueous ammonium chloride solution and a saturated saline solution,
After drying (anhydrous sodium sulfate), the mixture was concentrated, and the obtained solid was recrystallized (from ethanol: water = 1: 2) to give 4- (3
2.49 g of -bromophenoxy) pyrimidine were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 9.29 (1 H, d, J = 0.9 Hz),
8.81 (1H, d, J = 5.4 Hz), 8.28 (1
H, t, J = 1.7 Hz), 8.01 (1H, d, J =
7.8 Hz), 7.71 (1H, dd, J = 5.1,
1.2 Hz), 7.7 (1H, dd), 7.40 (1
H, t, J = 7.8 Hz) 4- (3-bromophenoxy) pyrimidine 0.70 g
(6.31 mmol), bis (pinacolato) diboron 0.91 g (3.9 mmol), {1,1'-bis (diphenylphosphino) ferrocene} dichloropalladium (II) methylene chloride 0.121 g (0.149 g)
mmol), potassium acetate 0.88 g (9.0 mmol)
l) and dimethyl sulfoxide (2 ml),
The mixture was stirred at 80 ° C for 4 hours. After cooling the mixture to room temperature,
Water was added and extracted with ethyl acetate. The organic layer was washed with water, washed with saturated saline, dried (anhydrous sodium sulfate), and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 4,4,5,5-tetramethyl-2- {3- (4-pyrimidyl) phenyl} -1,3,3.
520 mg of 2-dioxoborolane were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 9.3 (1H, s), 8.8 (1H, d),
8.5 (1H, s), 8.2 (1H, d), 8.0 (1
H, d), 7.8 (1H, d), 7.5 (1H, t),
1.37 (12H, s)

Reference Production Example 7 5.0 g (53.1 mmol) of 4-methylpyrimidine,
11.34 g of N-bromosuccinimide (63.7 mm
ol), 0.65 g (2.7 mmol) of 1,1′-azobis (cyclohexanecarbonitrile) and 100 ml of carbon tetrachloride were stirred at 76 ° C. for 8 hours. After cooling the mixture, insolubles were filtered off. After concentrating the filtrate, the residue and ethyl acetate were mixed, washed sequentially with water and saturated saline, dried (anhydrous sodium sulfate), and concentrated. The obtained residue, 1.24 g of 3-bromophenol (7.17 m
mol), 1.5 g (10.9 mmol) of potassium carbonate
And N, N-dimethylformamide (30 ml) were mixed and stirred at 60 ° C. for 8 hours. After cooling the mixture to room temperature, water was added, extracted with t-butyl methyl ether, washed with water, washed with saturated saline, dried (anhydrous sodium sulfate), and concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to obtain 268 mg of 3-bromo-1- (4-pyrimidinyl) methoxybenzene. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 9.20 (1H, s), 8.76 (1H,
d, J = 5.1 Hz), 7.54 (1H, d, J = 4.
8 Hz), 7.13 to 7.18 (3H, m), 6.88
-6.92 (1H, m, J = 4.8 Hz), 5.15
(2H, s)

Reference Production Example 8 (1) 30.0 g (0.114 mol) of 2-methyl-5-bromobenzylbromide prepared according to the method described in JP-A-11-217579, dimethylmalonic acid 1
A mixture of 5.77 g (0.119 mol), 6.45 g (0.113 mol) of 95% sodium methoxide and 300 ml of methanol was stirred at 65 ° C. for 4 hours, cooled, and the solvent was distilled off. The obtained residue was extracted with methyl t-butyl ether. The obtained aqueous layer was adjusted to pH 4 with a 5% aqueous hydrochloric acid solution, and then extracted with ethyl acetate. The organic layer was sequentially washed with 5% aqueous hydrochloric acid, water and saturated saline, dried (anhydrous sodium sulfate), concentrated, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 100: 0 to 0: 0). 100 eluted) and dimethyl 2
-(2-methyl-5-bromo-benzyl) malonic acid 1
7.21 g were obtained. (2) 17.21 g (54.6 mmol) of the obtained dimethyl 2- (2-methyl-5-bromo-benzyl) malonic acid
l), a mixture of 4.63 g (103 mmol) of lithium chloride, 2.2 ml of water and 150 ml of dimethyl sulfoxide were stirred at 165 ° C. for 3 hours, acetic acid and water were added, the mixture was concentrated, and the residue was subjected to silica gel column chromatography (n). -Hexane: ethyl acetate = 100: 0-0:
Elution with 100) to give 6.68 g of methyl 3- {2-methyl-5-bromo-phenyl} propionate. (3) 6.89 g of the obtained methyl 3- {2-methyl-5-bromo-phenyl} propionate (26.0 mmol)
l), a mixture of 15.6 g (260 mmol) of methyl formate and 15 ml of ethylene glycol dimethyl ether were cooled to -8 ° C or lower over 30 minutes with 30% potassium hydride (7.64 g, 57.1 mmol) and ethylene. It was added dropwise to a mixture of 67 ml of glycol dimethyl ether. The resulting mixture was heated to room temperature, stirred for 3 hours, poured into water, and extracted with methyl t-butyl ether. The obtained aqueous layer was adjusted to pH 4 with a 5% aqueous hydrochloric acid solution, and then extracted with ethyl acetate. The organic layer was washed successively with water and saturated saline, dried (anhydrous sodium sulfate), concentrated, and crude methyl 3-hydroxy-2- {2-methyl-
6.1 g of 5-bromo-benzyl-acrylic acid was obtained. (4) The obtained crude methyl 3-hydroxy-2- {2-
6.1 g of methyl-5-bromo-benzyl diacrylic acid
(21 mmol), 2M trimethylsilyldiazomethane
After a mixture of 21 ml (42 mmol) of a hexane solution and 40 ml of dimethoxyethane was stirred at room temperature overnight, acetic acid and water were added, the mixture was concentrated, and the residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate =
100: 0 to 0: 100).
Methoxy-2- {2-methyl-5-bromo-benzyl}
5.36 g of acrylic acid were obtained. ¹ H-NMR (CDCl ₃ , TMS) δ (ppm): 7.49 (1H, s), 7.2 (2H, m),
6.97 (1H, d, J = 8.6 Hz), 3.86 (3
H, s), 2-68 (3H, s), 3.50 (2H,
m), 2.28 (3H, s)

Next, examples of the compounds of the present invention are shown in Tables 1 to 12 together with the compound numbers. General formula 16

Embedded image A compound represented by the formula:

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[Table 5]

[0088]

[Table 6]

Formula 17

Embedded image A compound represented by the formula:

[Table 7]

[0090]

[Table 8]

[0091]

[Table 9]

[0092]

[Table 10]

[Table 11]

[0093]

[Table 12]

In the above table, Me is a methyl group, Et is an ethyl group, Pr is a propyl group, Bu is a butyl group, Ph is a phenyl group, Py is a pyridyl group,
Bn means a benzyl group. Also, n- is normal-
, I- is iso-, sec- is secondary, t-
Represents the meaning of tertiary.

Next, formulation examples are shown. Parts represent parts by weight, and the compounds of the present invention are indicated by the numbers described in Tables 1 to 12. Formulation Example 1 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 parts each, calcium lignin sulfonate 3
Parts, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 of each of 28 and 1.5 parts of sorbitan trioleate, 28.5 parts of an aqueous solution containing 2 parts of polyvinyl alcohol
And finely pulverized by a wet pulverization method. Then, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate are added thereto, and 10 parts of propylene glycol are further added. In addition, the mixture is stirred and mixed to obtain each flowable preparation. Formulation Example 3 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 parts of each, 88 parts of kaolin clay and 10 parts of talc are thoroughly pulverized and mixed to obtain each powder. Formulation Example 4 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 parts, 14 parts of polyoxyethylene styryl phenyl ether, 6 parts of calcium dodecylbenzenesulfonate and 75 parts of xylene,
Each emulsion is obtained. Formulation Example 5 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 parts each, 1 part of synthetic hydrous silicon oxide, 2 parts of calcium lignin sulfonate, 30 parts of bentonite and 65 parts of kaolin clay, well mixed with water, kneaded well, and granulated and dried. , To obtain each granule. Formulation Example 6 Compounds 1-1 to 1-131 and 2-1 to 2-1 of the present invention
28 parts, 35 parts of white carbon containing 50 parts of polyoxyethylene alkyl ether sulfate ammonium salt, and 55 parts of water are mixed and pulverized by a wet pulverization method to obtain each flowable preparation.

Next, Test Examples show that the compounds of the present invention are useful as fungicides for agricultural and horticultural use. In addition, this invention compound is shown by the number of Table 1-2. The control effect of the compound of the present invention was evaluated by visually observing the area of the lesion on the test plant at the time of the investigation, and comparing the area of the lesion in the untreated section with the area of the lesion in the section treated with the compound of the present invention. did.

Test Example 1: Rice Blast Control Test (Preventive Effect) A plastic pot was filled with sandy loam, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Then, the present compound 1-1, 1-23, 1-36, 1-40, 1-
11, 1-13, 1-2, 2-1, 1-32, 1-5
1, 1-92, 1-91, 1-27, 1-25, 1-
6, 1-16, 1-45, 1-59, 1-111, 1-
112, 1-68, 1-69, 1-62, 1-73, 1
-72, 1-86, 1-64, 1-66, 1-113,
1-115, 1-82, 1-94, 1-114, 2-8
6, 2-91, 2-82, 2-94, 2-83 and 1
Each of -78 was made into a flowable formulation according to Formulation Example 6, and then given a predetermined concentration of water (500 ppm; however, Compound 1-4 of the present invention).
5, 2-86, 2-82, 2-94 and 2-83 are 200p
pm), and it was foliage-sprayed so as to sufficiently adhere to the rice leaf surface. After spraying, the plants were air-dried and sprayed with a suspension of the blast fungus. After inoculation, the plants were placed in a humid atmosphere at 28 ° C. for 6 days, and the control effect was examined. As a result, the compounds 1-1, 1-23, 1-36, 1-40 and 1-1 of the present invention were obtained.
1, 1-13, 1-2, 2-1, 1-32, 1-51,
1-92, 1-91, 1-27, 1-25, 1-6, 1
-16, 1-45, 1-59, 1-111, 1-11
2, 1-68, 1-69, 1-62, 1-73, 1-7
2, 1-86, 1-64, 1-66, 1-113, 1-
115, 1-82, 1-94, 1-114, 2-86,
2-91, 2-82, 2-94, 2-83 and 1-7
The lesion area on the plants in the 8 treatments was 10% or less of the lesion area in the non-treatment.

Test Example 2: Wheat powdery mildew control test (therapeutic effect) A plastic pot was filled with sandy loam, and wheat (Agriculture and Forestry 73)
No. 2) and sown in a greenhouse for 10 days. The wheat seedlings with the second leaves developed were sprinkled with wheat powdery mildew spores and inoculated. After inoculation, they were placed in a greenhouse at 23 ° C. for 2 days.
After each of the present compounds 1-1, 1-23, 1-36, 1-40 and 1-32 was made into a flowable formulation according to Formulation Example 6, it was diluted to a predetermined concentration (500 ppm) with water, and then diluted. ,
The foliage was sprayed so that the powdery mildew fungus was sufficiently attached to the leaves of the wheat inoculated. After spraying, it was further placed under lighting for 7 days, and then the control effect was investigated. As a result, the compounds of the present invention 1-1, 1-23, 1-36, 1-40 and 1-32
The lesion area on the plant in the treated area is 1% of the lesion area in the untreated area.
0% or less.

Test Example 3: Wheat powdery mildew control test (preventive effect) A plastic pot was filled with sandy loam,
No.) and sowed in a greenhouse for 10 days. Compounds of the present invention 1-11, 1-13, 1-2, 2-1, 1-51,
1-92, 1-91, 1-27, 1-25, 1-6, 1
-16, 1-59, 1-111, 1-112, 1-6
8, 1-69, 1-62, 1-73, 1-72, 1-8
6, 1-64, 1-66, 1-113, 1-115, 1
-82, 1-94, 1-114, 2-3, 2-37, 2
-68, 2-86, 2-91, 2-82, 2-94, 2
-83 and 1-78 were made into flowable agents according to Formulation Example 6, and then given a predetermined concentration with water (500 ppm; however, compounds of the present invention 2-86, 2-82, 2-94 and 2-83 were 200 ppm).
And sprayed it so that the second leaf was sufficiently adhered to the wheat leaf surface of the developed wheat seedling. After spraying, the plants were air-dried, and one day later, wheat powdery mildew spores were sprinkled and inoculated. After inoculation, the plants were placed under 23 ° C. illumination for 7 days, and the control effect was examined. As a result, the compound of the present invention 1-
11, 1-13, 1-2, 2-1, 1-51, 1-9
2, 1-91, 1-27, 1-25, 1-6, 1-1
6, 1-59, 1-111, 1-112, 1-68, 1
-69, 1-62, 1-73, 1-72, 1-86, 1
-64, 1-66, 1-113, 1-115, 1-8
2, 1-94, 1-114, 2-3, 2-37, 2-6
8, 2-86, 2-91, 2-82, 2-94, 2-8
3 and 1-78, the lesion area on the plant in the treated section was 10% or less of the lesion area in the untreated section.

Test Example 4: Wheat rust control test (preventive effect) A plastic pot was filled with sandy loam, and wheat (Agriculture and Forestry 73)
No.) and sowed in a greenhouse for 10 days. Compounds of the present invention 1-1, 1-23, 1-36, 1-40, 1-1
1, 1-13, 1-2, 2-1, 1-32, 1-51,
1-92, 1-91, 1-27, 1-25, 1-6, 1
-16, 1-45, 1-59, 1-111, 1-11
2, 1-68, 1-69, 1-62, 1-73, 1-7
2, 1-86, 1-64, 1-66, 1-113, 1-
115, 1-82, 1-94, 1-114, 2-3, 2
-37, 2-68, 2-86, 2-91, 2-82, 2
After each of -94, 2-83 and 1-78 was made into a flowable formulation according to Formulation Example 6, it was given a predetermined concentration (500 ppm;
However, the present compounds 1-45, 2-86, 2-82,
-94 and 2-83 were diluted to 200 ppm) and sprayed with foliage so as to adhere well to the wheat leaf surface. After spraying, the plants were air-dried and inoculated with spores of wheat rust. After the inoculation, they were first placed in a dark and humid environment at 23 ° C. for 1 day, and further placed in a light for 6 days, and then examined for their controlling effect. as a result,
Present compound 1-1, 1-23, 1-36, 1-40,
1-11, 1-13, 1-2, 2-1, 1-32, 1-
51, 1-92, 1-91, 1-27, 1-25, 1-
6, 1-16, 1-45, 1-59, 1-111, 1-
112, 1-68, 1-69, 1-62, 1-73, 1
-72, 1-86, 1-64, 1-66, 1-113,
1-115, 1-82, 1-94, 1-114, 2-
3, 2-37, 2-68, 2-86, 2-91, 2-8
The lesion area on the plants in the 2, 2-94, 2-83 and 1-78 treatments was 10% or less of the lesion area in the untreated treatment.

Test Example 5 Wheat Blight Control Test (Preventive Effect) A plastic pot was filled with sandy loam, and wheat (Agriculture and Forestry 73)
No. 2) and sown in a greenhouse for 10 days. Present compound 1-1, 1-23, 1-36, 1-40, 1-32,
1-51, 1-92, 1-91, 1-27, 1-45,
1-66, 1-113, 1-94, 1-114, 2-9
Each of 1, 2-82, 2-94, 2-83 and 1-78 was made into a flowable formulation according to Formulation Example 6, and was then given a predetermined concentration of water (500 ppm; however, the present compound 1-45, 2- 8
2, 2-94 and 2-83 were diluted to 200 ppm) and sprayed so that they adhered well to the wheat leaves. After spraying, the plants were air-dried and spray-inoculated with a spore suspension of wheat wilt. After the inoculation, they were first placed in a dark and humid environment at 15 ° C. for 4 days, and then placed under illumination for 7 days. As a result, the compounds 1-1 and 1-2 of the present invention were obtained.
3, 1-36, 1-40, 1-32, 1-51, 1-9
2, 1-91, 1-27, 1-45, 1-66, 1-1
13, 1-94, 1-114, 2-91, 2-82, 2
The lesion area on the plants in the -94, 2-83 and 1-78 treatments was 10% or less of the lesion area in the untreated treatment.

Test Example 6: Control Test for Wheat Eye Spot Disease (Preventive Effect) A plastic pot was filled with sandy loam,
No.) and sowed in a greenhouse for 10 days. Compounds of the present invention 1-1, 1-23, 1-11, 1-13, 1-2,
1-32, 1-6, 1-59, 1-11, 1-11
2, 1-68, 1-69, 1-62, 1-86, 1-6
4, 1-113, 2-68 and 2-91 were made into flowable formulations according to Formulation Example 6, and then each was diluted with water to a predetermined concentration (500 ppm), which was sufficiently adhered to the wheat leaf surface. Foliage was sprayed as follows. After spraying, the plants were air-dried and inoculated with a mashed potato medium containing spores of wheat eye spot disease fungus. At first after inoculation, put in dark and humid for 15 days at 15 ℃,
After being put under the light for further 4 days, the control effect was investigated.
As a result, the compounds of the present invention 1-1, 1-23, 1-11,
1-13, 1-2, 1-32, 1-6, 1-59, 1-
111, 1-112, 1-68, 1-69, 1-62,
1-86, 1-64, 1-113, 2-68 and 2-
The lesion area on the plant in the 91 treated section was 10% or less of the lesion area in the untreated section.

Test Example 7 Test for Control of Grape Downy Mildew (Preventive Effect) A plastic pot was filled with sandy loam, and grape (berry) was added.
A) were sown and grown in a greenhouse for 40 days. Compound of the present invention 1-1, 1-23, 1-36, 1-40, 1-1
3, 2-1, 1-32, 1-51, 1-92, 1-9
1, 1-27, 1-25, 1-6, 1-16, 1-4
5, 1-59, 1-111, 1-112, 1-68, 1
-69, 1-62, 1-73, 1-72, 1-86, 1
-64, 1-66, 1-113, 1-115, 1-8
2, 1-94, 1-114, 2-3, 2-37, 2-6
8, 2-86, 2-91, 2-82, 2-94, 2-8
After each of 3 and 1-78 was made into a flowable formulation according to Formulation Example 6, it was diluted with water to a predetermined concentration (200 ppm) and sprayed with foliage so as to sufficiently adhere to the vine leaf surface. After spraying, the plants were air-dried and spray-inoculated with a zoosporangial suspension of grape downy mildew. Initially after inoculation, 23 ° C, 1
After standing for 6 days in a greenhouse, the control effect was investigated. As a result, the compounds of the present invention 1-1, 1-23, 1
-36, 1-40, 1-13, 2-1, 1-32, 1-
51, 1-92, 1-91, 1-27, 1-25, 1-
6, 1-16, 1-45, 1-59, 1-111, 1-
112, 1-68, 1-69, 1-62, 1-73, 1
-72, 1-86, 1-64, 1-66, 1-113,
1-115, 1-82, 1-94, 1-114, 2-
3, 2-37, 2-68, 2-86, 2-91, 2-8
The lesion area on the plants in the 2, 2-94, 2-83 and 1-78 treatments was 10% or less of the lesion area in the untreated treatment.

Test Example 8 Test for Controlling Effect of Cucumber Powdery Mildew (Preventive Effect) A plastic pot was filled with sandy loam, cucumber (Sagami Hanjiro) was sowed, and grown in a greenhouse for 12 days. Compounds of the present invention 1-1, 1-23, 1-36, 1-40, 1-1
1, 1-13, 1-2, 2-1, 1-32, 1-51,
1-92, 1-91, 1-25, 1-6, 1-16, 1
-59, 1-111, 1-112, 1-68, 1-6
After each of 9, 1-62, 1-73, 1-72 and 1-86 was made into a flowable formulation according to Formulation Example 6, it was diluted with water to a predetermined concentration (500 ppm) and the cucumber leaf surface Foliage was sprayed so as to sufficiently adhere to the leaves. After spraying, the plants were air-dried and inoculated with spores of cucumber powdery mildew. After 12 days at 23 ° C. after the inoculation, the control effect was investigated. As a result, the compounds of the present invention 1-1, 1-23, 1-36, 1-
40, 1-11, 1-13, 1-2, 2-1, 1-3
2, 1-51, 1-92, 1-91, 1-25, 1-
6, 1-16, 1-59, 1-111, 1-112, 1
The lesion area on the plants in the -68, 1-69, 1-62, 1-73, 1-72 and 1-86 treatment sections was 10% or less of the lesion area in the non-treatment section.

[0105]

INDUSTRIAL APPLICABILITY The compound of the present invention has excellent plant disease controlling effect.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) A01N 43/54 A01N 43/54 B C07D 213/24 C07D 213/24 213/26 213/26 213/30 213 / 30 213/32 213/32 213/55 213/55 213/61 213/61 213/64 213/64 213/84 213/84 Z 239/26 239/26 239/28 239/28 239/30 239 / 30 239/34 239/34 239/38 239/38 239/46 239/46 239/52 239/52 F term (reference) 4C055 AA01 BA01 BA02 BA03 BA06 BA13 BA16 BA39 BA42 BA47 BA59 BB02 BB04 BB11 CA01 CA02 CA06 CA13 CA16 CA39 CB11 DA01 DA06 DA13 DA16 DA39 DB11 4H006 AA01 AA03 AB03 BJ50 BM30 BN30 4H011 AA01 BA01 BB06 BB09 BC01 BC07 BC18 BC19 BC20 DA02 DA15 DA16 DD03 DH02 DH14

Claims (14)

[Claims] 1. A compound represented by the general formula: Wherein W represents an oxygen atom or a CH ₂ group, and X represents C
Represents R ⁴ group or a nitrogen atom, Y represents CR ⁵ group or a nitrogen atom, R ^1, R ² and R ³ are the same or different, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxyl group An optionally substituted C1-C10 alkyl group, an optionally substituted C2-C10 alkenyl group, an optionally substituted C2-C10 alkynyl group, an optionally substituted C3-C10 cycloalkyl group, An optionally substituted C5-C10 cycloalkenyl group, an optionally substituted C6-C10 aryl group,
Optionally substituted C1-C9 heteroaryl group, optionally substituted C1-C6 alkoxy group, optionally substituted phenoxy group, optionally substituted C1
To C9 heteroaryloxy group, an optionally substituted C2 to C6 alkoxycarbonyl group, an optionally substituted C1 to C6 alkylthio group or an optionally substituted C3 to C30 trialkylsilyl group,
R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different,
Hydrogen atom, halogen atom, C1-C4 alkyl group, C1
Represents a -C4 haloalkyl group or a C1-C4 alkoxy group. ] The acrylic acid derivative shown by these. 2. The acrylic acid derivative according to claim 1, wherein W in the acrylic acid derivative represented by the general formula 1 is an oxygen atom. 3. The acrylic acid derivative according to claim 1, wherein W in the acrylic acid derivative represented by the general formula 1 is a CH ₂ group. 4. An optionally substituted C1 to C10 alkyl group or an optionally substituted C2 to C10 alkenyl group for R ¹ , R ² and R ³ in the acrylic acid derivative represented by the above general formula 1. An optionally substituted C2-C10 alkynyl group, an optionally substituted C3
To C10 cycloalkyl group, optionally substituted C5
~ C10 cycloalkenyl group, optionally substituted C
A 1-C6 alkoxy group, an optionally substituted phenoxy group, an optionally substituted C1-C9 heteroaryloxy group, a C2-C6 alkoxycarbonyl group, an optionally substituted C1-C6 alkylthio group, Each of the optionally substituted C3-C30 trialkylsilyl groups is the same or different and is at least one group selected from Group A below, and optionally substituted C6-C3 groups.
10 aryl groups or optionally substituted C1 to C9
The acrylic acid derivative according to any one of claims 1 to 3, wherein each substituent in the heteroaryl group is the same or different and is at least one group selected from the group consisting of the following groups A and B. Group A: halogen atom, C1-C10 alkyl group, C3-
C20 trialkylsilyl group, C1-C10 haloalkyl group, C3-C10 cycloalkyl group, C3-C10 cycloalkenyl group, C1-C10 alkoxy group, C1-C10
C10 haloalkoxy group, C1-C10 alkylthio group, C1-C10 haloalkylthio group, C2-C10 alkoxycarbonyl group, phenyl group, pyridyl group, pyrimidyl group, phenoxy group, benzyloxy group, pyridin-2-yloxy group (here, Each of the phenyl group, pyridyl group, pyrimidyl group, phenoxy group, benzyloxy group and pyridin-2-yloxy group is a halogen atom, a C1-C6 alkyl group, a C1-C6 alkoxy group,
It may be substituted with one or more groups selected from the group consisting of a trifluoromethyl group and a cyano group. ), An amino group, a hydroxyl group, a cyano group, and a nitro group. Group B: methylenedioxy group and difluoromethylenedioxy group (each of the methylenedioxy group and difluoromethylenedioxy group is two carbon atoms adjacent to the aryl moiety) Bonds to an atom.)｝ 5. The acrylic acid according to claim 1, wherein at least one of R ¹ , R ² and R ³ in the acrylic acid derivative represented by the general formula 1 is a hydrogen atom. Derivatives. 6. The acrylic acid according to claim 1, wherein at least any two of R ¹ , R ² and R ³ in the acrylic acid derivative represented by the general formula 1 are hydrogen atoms. Derivatives. 7. The acrylic acid derivative according to claim 1, wherein R ⁶ , R ⁷ and R ⁸ in the acrylic acid derivative represented by the general formula 1 are hydrogen atoms. 8. The acrylic acid derivative according to claim 1, wherein in the general formula 1, X and Y are CH groups. 9. The acrylic acid derivative according to claim 1, wherein in the general formula 1, X and Y are nitrogen atoms. 10. The acrylic acid derivative according to claim 1, wherein X is a nitrogen atom and Y is a CH group. 11. A fungicide for agricultural and horticultural use comprising the acrylic acid derivative according to any one of claims 1 to 10 as an active ingredient. 12. A compound represented by the general formula:[Where A¹Is B (OH)_TwoGroup, B (OR⁹)_TwoGroup or S
nR^Ten _ThreeR represents a group⁹ Represents a C1 to C10 alkyl group.
Just two Rs⁹In -CH_TwoCH_Two-Group or -C (C
H_Three)_TwoC (CH_Three)_Two-Represents a group, R^TenAre C1 to C10
W represents an oxygen atom or CH_TwoRepresents a group
And X is CR^FourY represents CR or a nitrogen atom^FiveBase
Or a nitrogen atom;⁶, R⁷And R⁸Is the same
Or differently, a hydrogen atom, a halogen atom, C1-C4
Alkyl group, C1-C4 haloalkyl group or C1-C4
Represents an alkoxy group. ] The compound shown by these. 13. The compound according to claim 12, wherein W in the compound represented by formula 2 is an oxygen atom. 14. The compound according to claim 12, wherein W in the compound represented by Formula 2 is a CH ₂ group.