WO2001000562A1

WO2001000562A1 - Acrylic acid derivatives, use of the same and intermediates for the preparation thereof

Info

Publication number: WO2001000562A1
Application number: PCT/JP2000/004080
Authority: WO
Inventors: Hiroshi Sakaguchi
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 1999-06-25
Filing date: 2000-06-22
Publication date: 2001-01-04
Also published as: AU5428700A

Abstract

Acrylic acid derivatives represented by general formula (1); plant disease controllers containing the same as the active ingredient; and a method for controlling plant diseases with the derivatives, wherein W is oxygen or CH2; X is CR4 or nitrogen; Y is CR5 or nitrogen; R?1, R2 and R3¿ are each independently hydrogen, halogeno, cyano, nitro, amino, hydroxyl, optionally substituted C¿1?-C10 alkyl, or the like; and R?4, R5, R6, R7 and R8¿ are each independently hydrogen, halogeno, C¿1?-C4 alkyl, or the like.

Description

Description Acrylic acid derivatives, their uses and intermediates for their production

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

Disclosure of the invention

An object of the present invention is to provide a compound having an excellent plant disease controlling effect. 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 formula (1) has an excellent plant disease controlling effect, and have accomplished the present invention.

That is, the present invention provides the following formula (1):

{Wherein W represents an oxygen atom or a CH ₂ group,

X represents a CR ⁴ group or a nitrogen atom,

Y represents CR ⁵ or a nitrogen atom,

RR ² and R ³ are the same or different,

Hydrogen atom, halogen atom, cyano group, nitro group, amino group, 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,

An optionally substituted C 1 -C 9 heteroaryl group,

An optionally substituted C1-C6 alkoxy group,

A phenoxy group which may be substituted, An optionally substituted C1-C9 heteroaryloxy group, an optionally substituted C2-C6 alkoxycarbonyl group,

An optionally substituted C1-C6 alkylthio group or

Represents an optionally substituted C3-C30 trialkylsilyl group,

R ⁴ , R ⁵ , R ⁶ R ⁷ and R ⁸ are the same or different and are a hydrogen atom, a halogen atom,

Represents a C1-C4 alkyl group, a C1-C4 haloalkyl group or a C1-C4 alkoxy group. The present invention provides an acrylic acid derivative represented by the formula (hereinafter, referred to as the present compound), a plant disease controlling agent containing the same as an active ingredient, and a plant disease controlling method using the active ingredient.

The present invention provides a compound of formula [XX '] useful as an intermediate for producing the compound of the present invention:

{Wherein W, RR ⁷ and R ⁸ represent the same meaning as described above,

A ¹ is B (OH) ₂ group, B (OR ⁹⁾ represents ₂ group or R ^lfl ₃ Sn group,

R ⁹ , R ¹ . Is a force representing a C 1 -C 10 alkyl group, with two R ⁹ —CH. CH represents one group or one C (CH ₃ ) ₂ C (CH ₃ ) ₂ . } Is provided. Further, the present invention provides a compound of the formula [Γ]:

{Wherein, W, X, Y, RR 2, R; RR 7 and R ⁸ to Table Wa as defined above. } And a compound represented by the formula

CH, L

{Wherein L ¹ is a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a methanesulfonyloxy group, a trifluoromethanesulfonyloxy group, etc. Represents a leaving group. } In the presence of a base, or a compound of the formula [1] and a compound of the formula

N ₂ CHL ³

{Wherein L ³ represents a trialkylsilyl group such as a trimethylsilyl group. }, A method for producing the acrylic acid derivative of the above formula (1),

And the formula [IΓ]:

{Wherein L ² 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, W, RR ⁷ and R ⁸ has the same meaning as described above. } With the following formula [III]:

Cm]

{Where, X, Y, RR ² and R ³ represent the same meaning as described above,

A ² represents B (OH) ₂ group, B (OR ⁹⁾ ₂ group or S n R ^1Q ₃ group,

R ⁹ and R ¹ . Represents an alkyl group of C1～C 10, one of two R ⁹ CH ₂ CH ₂ - group or a _{_{C (CH 3) 2 C (}} CH 3) may represent a ₂ _ group. A method for producing an atalylic acid derivative of the above formula (1), characterized by reacting a compound of formula (1) with a compound of formula [XX ']:

{Wherein Α ¹ represents the same as A ^2, and WR ⁶ R ⁷ and R ⁸ have the same meaning as described above. } And a compound of formula [XXI]:

[XXI]

{Wherein L ¹ , XYR \ R ² and R ³ represent the same meaning as described above. And a method for producing an acrylic acid derivative of the formula (1), characterized by reacting with a compound represented by the formula (I):

First, the substituents RR ² and R ³ shown in the compound of the present invention of the formula (1) and other chemical formulas shown in the present specification will be described.

Examples of the halogen atom represented by R and R ³ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

Examples of the C 1 C 10 alkyl group in the optionally substituted C 1 C 10 alkyl group represented by R \ R ² and R ³ include, 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, 12-dimethylpropyl group, 1, 1 —Dimethylpropyl group, hexyl group, 1-methylpentyl group, 1-ethylpentyl group, 33-dimethylbutyl group, heptyl group, 37-dimethyloctyl group, nonyl group, decyl group and the like.

Examples of the C 2 C 10 alkenyl group in the optionally substituted C 2 C 10 alkenyl group represented by R \ R ² and R ³ include, for example, a vinyl group, an aryl group, Examples thereof include a methyl-2-propenyl group, a 2-methyl-2-propenyl group, a 2-butul group, a 2-pentyl group, and a 3-methyl-2-butul group.

The C 2 to C 1 0 alkynyl group in R \ R ² and optionally substituted C 2 to C 1 0 alkynyl group represented by R ^3, for example Echuru group, propargyl group, 1-methyl-2-propynyl group , 2-butul group and the like.

The C 3 to C 1 0 cycloalkyl group in the optionally substituted C 3 to C 1 be the 0 cycloalkyl Le group represented by R \ R ² and R ^3, for example, cyclopropyl group, consequent opening pentyl group, consequent opening Hexyl group and the like.

The C 5~C 1 0 cycloalkenyl group in the substituted C 5~C 1 optionally 0 Shikuroaruke alkenyl group represented by RR ² and R ^3, e.g. cyclopent group, hexenyl group, etc. cyclohexylene.

The C 6 -C 10 aryl group in the optionally substituted C 6 -C 10 aryl group represented by R \ R ² and R ³ includes a phenyl group, an α-naphthyl group, a β- And a naphthyl group.

Examples of the C 1 -C 9 heteroaryl group in the optionally substituted C 1 -C 9 heteroaryl group represented by RR ² and R ³ include, for example, a 2 pyridyl group, a 3 pyridyl group, a 4 pyridyl group, and a 2-pyridyl group. Pyrimidinyl group, 4-pyrimidinyl group, 2-thenyl group, 3-thenyl group, 2-furyl group, 3-furyl group, pyrrole-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-benzobenzoyl A 3-benzobenzoyl group, a benzothiazole-2-yl group, a 2-quinolinyl group and the like.

The definitive good C 1 through C 6 alkoxy group optionally substituted C 1 through C 6 alkoxy group represented by R \ R ² and R ^3, for example, main butoxy group, an ethoxy group, t _ butoxy group, Penchiruokishi group And a hexyloxy group.

The C 1 through C 9 heteroaryl § reel O alkoxy group in the substituted C 1 through C 9 optionally Heteroariru Okishi group represented by R \ R ² and R ^3, 2- Pirijiruo alkoxy group, 2- (5- Trifluoromethyl) pyridyloxy group, 3-pyridyloxy And a 4-pyridyloxy group, a 2-pyrimidyloxy group, a 4-pyrimidyloxy group, a 5-pyrimidyloxy group, and a 3-cheeroxy group.

The C 2 to C 6 alkoxycarbonyl group in R ^1, R ² and optionally substituted C 2 to C 6 Arukokishikaru Boniru group represented by R ^3, for example, main butoxy carbo - group, an ethoxycarbonyl group, And a propoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group and the like.

The C 1 through C 6 alkylthio group in R \ R ² and R ³ optionally substituted C 1 through C 6 alkylthio group represented by, for example, methylthio group, Echiruchio group, propylthio group, butylthio group, pentylthio group, Hexylthio group and the like.

Examples of the C 3 -C 30 trialkylsilyl group in the optionally substituted C 3 -C 30 trialkylsilyl group represented by RR ² and R ³ include, for example, a trimethylensilyl group, a triethylsilyl group, and a t-butyldimethyl group. Examples thereof include a silyl group, tripentinolesilyl group, trihexylsilyl group, triheptylsilyl group, trioctylsilyl group, trinoersilyl group, and tridecylsilyl group.

Also shown in RR ² and R ^3, optionally substituted C 1 through C 1 0 aralkyl kill group, an optionally substituted C 2 to C 1 0 alkenyl group, it may also be substituted Rere C 2-C10 alkynyl group, optionally substituted C3-C10 cycloalkyl group, optionally substituted C5-C10 cycloalkenyl group, optionally substituted C6-C 10 aryl group, optionally substituted C1-C9 heteroaryl group, optionally substituted C1-C6 alkoxy group, optionally substituted phenoxy group, optionally substituted C1-C9 heteroaryloxy group, C2-C6 alkoxycarbonyl group, optionally substituted C1-C6 alkylthio group and optionally substituted C3-C30 trialkylsilyl Examples of the group include a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom ,

C1-C10 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-methylbutyl group, 2 —Methylbutyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,2-dimethylpropyl group, 1,1-dimethyl Propyl, hexyl, 1-methylpentyl, 1-ethylpentyl, 3,3-dimethylbutyl, heptyl, 3,7-dimethyloctyl, etc., nonyl, decyl),

C3-C20 trialkylsilyl group [e.g., trimethylsilinole group,

A C1-C10 haloalkyl group [for example, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 1,1,2,2-tetrafuronoethyl group, etc.],

C3-C10 cycloalkyl group (e.g., cyclopropyl group, pen-pentyl group, hexa-hexyl group, etc.),

A C 1 -C 10 alkoxy group (for example, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxy group, an n_pentyloxy group, etc.),

C1-C10 haloalkoxy group [for example, trifluoromethoxy group, difluoromethoxy group, bromodifluoromethoxy group, chlorodifluoromethoxy group, fluoromethoxy group, 2,2,2-trifluoroethoxy group , 1, 1, 2, 2-tetrafluoroethoxy group etc.),

C 1 -C 10 alkylthio group (for example, 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 group [for example, trifluoromethylthio group, difluoromethylthio group, bromodifluoromethylthio group, chlorodifluoromethylthio group, fluoromethylthio group, 2,2,2-trifluoro Oloethylthio group, 1, 1, 2, 2-tetrafluoroethylthio group, etc.),

C2-C10 alkoxy carbonyl group [methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, isopropoxycarbonyl group, n-butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, n —Pentyloxycarbonyl group, n-hexyloxycarbonyl group, etc.), phenyl group, pyridyl group, pyrimidyl group, phenoxy group, benzyloxy group, pyridine-1T oxy group {where the phenyl group, pyridyl group, Pyrimidyl Group, a phenoxy group, a benzyloxy group and a pyridine-1-yloxy group each represent a halogen atom (eg, a chlorine atom), a C 1 -C 6 alkyl group (eg, a methyl group, an ethyl group, etc.), a C 1 -C 6 It may be substituted with one or more groups selected from the group consisting of an alkoxy group (for example, a methoxy group, an ethoxy group, etc.), a trifluoromethyl group and a cyano group. },

Examples include those which may be substituted with at least one same or different substituent selected from the group including amino acids, hydroxyl groups, cyano groups, nitro groups and the like.

As the optionally substituted C 6 -C 10 aryl group and the optionally substituted C 1 -C 9 heteroaryl group, in addition to the above substituent groups, a methylenedioxy group, difluoromethylenediol Xy group {wherein each of the methylenedioxy and difluoromethylenedioxy groups replaces two adjacent carbon atoms on the aryl group. }, Which may be substituted with at least one same or different substituent selected from the group containing.

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.

The C 1 through C 4 alkyl group represented by R \ R ^5, RR ⁷ and R ^8, methyl group For example, Echiru group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a 1-methylpropyl group can give.

R ^4, R ^5, as the C 1 through C 4 haloalkyl group represented by R ^6, R ⁷ and R ^8, eg if Furuoromechiru groups, trifluoperazine Ruo Lome Chino les group, trichloromethyl group, Kuronoreji Furuoromechiru, black hole propyl And a chlorobutyl group.

The C 1 through C 4 alkoxy group represented by ^{^{^{R 4, R 5, R 6}}} , R 7 and R ^8, examples Ebame butoxy group, an ethoxy group, n- propoxy group, n- butoxy group, and the like.

The C 1 through C 1 0 alkyl group represented by R ^9, for example, a methyl group, E ethyl group, a propyl group, an isopropyl group, butyl group, isobutyl group, 1 Mechirupu port propyl group and the like.

The compound of the present invention of the formula (1) has geometric isomers of (E) and (Z) based on the C = C bond of the dioxypropenoic acid moiety. It represents either one. Among them, C = C in terms of agricultural fungicide efficacy A compound of the (Z) isomer or a mixture of geometric isomers containing a large amount of the (Z) isomer based on the bond is preferred. (The terms (E) and (Z) as used herein are defined by the Kahn-Ingold-Prelog rule, which is widely used to refer to geometric isomers.) Is the following formula ():

(Wherein, W, X, Y, RR ² , R ³ , R ⁶ , R ⁷ and R ⁸ have the same meanings as described above.).

Among the compounds of the present invention, examples of more preferred compounds in terms of the efficacy of controlling plant diseases include methyl 3-methoxy-2- (2-methyl-15-fueurphenoxy) -12-propanoate (described below). Compounds represented by numbers 11 in Table 1). The compound of the present invention can be produced, for example, according to the following [Production method A], [Production method B] or [Production method C]. Depending on the content of X or Y, for example, it can be manufactured according to [Manufacturing method D]. Hereinafter, these production methods and the like will be described with reference to Schemes 1 to 11, but the compounds of the present invention and the compounds shown in the schemes will be described below. In the following scheme, the preferred embodiment is exemplified using the (Z) -form. For example, for the reaction using the compounds of the formulas [XX'L [1 '] and [Π'], the compounds of the formulas [XX], [I] and [Π] are exemplified in the following scheme. . The reaction shown in the scheme can be carried out without any problem using any of the isomers Ε and Ζ. Of course, the reaction can be similarly carried out using a mixture of both isomers. In these production methods, a protecting group can be used if necessary.

[Production method Α] A compound of the present invention in which a compound of the formula [I] is reacted with a compound of the formula CH ₃ —L ¹ in the presence of a base or with a compound of the formula N ₂ CH—L ³ The production method A of (1) will be described below.

N ₂ CH-L ³

Scheme 1 In the chemical formula of the above scheme 1, 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, L ³ represents a Tutorials Kirushiriru group such as trimethylsilyl ^{^{^{group, WXYR 1, R 2 RR 6}}} R 7 and R ⁸ represent the a same meaning.

In the reaction of Scheme 1, step a, the reaction temperature is generally Ri range der of 0 1 0 0 ° C, the formula CH ₃ - amount of the compound represented by L ^1, the compound 1 mode represented by the formula [I] It is usually in the range of 110 moles per mole.

The amount of the base used in the reaction is usually in the range of 1 to 10 mol per 1 mol of the compound represented by the formula [I]. Examples of the base include inorganic bases such as sodium hydroxide, sodium hydroxide, sodium carbonate, sodium carbonate, calcium carbonate, sodium hydride, and alkalis such as potassium methoxide, sodium methoxide, sodium methoxide. Examples thereof include metal alkoxides, organic bases such as pyridine, triethylamine, ethyldiisopropylamine, and aniline, and mixtures thereof.

The reaction is usually performed in a solvent. Solvents include, for example, 1,4-dioxane, tetrahydrofuran, ethyleneglycol-no-resin-methino-leno-tenol, t-butynoleme Chirue - an ether solvent such as ether, _n - hexane, _n - aliphatic hydrocarbons solvents such as heptane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents monochrome port benzene, pyridine, Toryechiruamin, N Organic base solvents such as N, N-dimethylaniline, etc., ester solvents such as butyl acetate and ethyl acetate, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethyl sulfoxide, water, etc. or a mixture thereof Is raised.

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 step a ′ of scheme 1, the compound represented by the formula [I] and the compound represented by the formula N ₂ CH—L ³ are usually reacted at a temperature in the range of 120 to 50 ° C. The amount of the compound represented by the formula N ₂ CH—L ^{: s} is usually in the range of 1 to 10 mol per 1 mol of the compound represented by the formula [I].

The reaction is usually carried out in a solvent, and for example, the same solvent as exemplified in the above step a can be used.

[Production method B]

The production method B of the compound of the present invention in which the compound represented by the formula [II] and the compound represented by the formula [III] shown in Scheme 2 are reacted in the presence of a catalyst will be described below.

In the chemical formula shown in the above scheme 2, A ² , L ² , W, X, Y, RR ² , R ³ , RR ⁷ and R ⁸ represent the same meaning as described above.

The reaction of Scheme 2 is usually performed in the range of 20 to 120 ° C. The amount of the compound represented by the formula [III] to be used is generally in the range of 1 to 5 mol per 1 mol of the compound represented by the formula [II].

The amount of the catalyst used in the reaction is usually in the range of 0.001 to 0.1 mol per 1 mol of the compound represented by the formula [II]. Examples of the catalyst include palladium acetate (11), tetrakis (triphenylphosphine) palladium (0), {1,1'-bis (diphenylphosphine) phenoctene) dichloropalladium (II) methylene chloride Complex, bis- (triphenylphosphine) palladium

(II) Palladium catalysts such as dichloride.

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, sodium bicarbonate) or a phase transfer catalyst (eg, tetrabutylammonium bromide, benzyltriethyl) It may be performed in the presence of a quaternary ammonium salt such as ammonium bromide. Moreover, A ² is S nR ¹⁰ ₃ group (wherein R ^1G is, the R ⁹ and. Representing the same C1~C10 alkyl group) in the compound represented by the formula [III] when it is, the necessary In some cases, it is carried out in the presence of copper oxide (11) and silver oxide (II).

The reaction is usually performed in a solvent. Examples of the solvent include alcohol solvents such as methanol, ethanol, propanol, butanol, and isopropanol;

Ether solvents such as 4-dioxane, tetrahydrofuran, ethylene glycolone resin methinolate ether, t-butyl methyl ether; aliphatic hydrocarbon solvents such as n-hexane and n-heptane; aromatic hydrocarbon solvents such as toluene; Examples include nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like, or mixtures thereof.

The reaction is more specifically carried out, for example, by the method described in J. Org, Chem., 1999, 62, 7170-7173, J. Org. Chem., 1995, 60, 7508—75 10 or according to the method described in Ange w. Chem. Int. Ed. Engl., 1986, 25, 508—524. Do it. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent, concentration, and the like, to obtain a target compound. If necessary, the target compound can be isolated by purification by recrystallization, distillation, chromatography or the like.

In the formulas [I] and [II], the compound wherein W is an oxygen atom can also be produced, for example, according to the method shown in the following scheme 3 or scheme 4.

Scheme 3

In the chemical formula of the above scheme 3, Ι L ² L ³ XYR \ R ² R ³ R R ⁷ and R ⁸ have the same meaning as described above.

Step 31 of Scheme 3 is the same as described in Step a of Scheme 1 except that Formula [I] is

It can be implemented under the conditions read as [XVI].

The reaction in Step 3j of Scheme 3 is usually performed in the range of 0 to 80 ° C. The amount of HCOOCH ₃ to be used in the reaction is usually in a range of 1-100 moles per mole of the compound of the formula [XV].

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 teroxide, and sodium amide. And alkali metal amides such as lithium amide, lithium diisopropyl amide, sodium hexamethyldisilazide and lithium hexamethyldisilazide, and mixtures thereof.

The reaction is carried out in a solvent, if necessary. Examples of the solvent include ether solvents such as 1,4-dioxane, tetrahydrofuran, ethyleneglycol-1-dimethinoleate, and t-butylmethyl ether; Aliphatic hydrocarbon solvents such as xane and n-heptane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as monochrome benzene; organic bases such as pyridine, triethylamine, N, N-dimethylaniline Solvents, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, N, N-dimethinole-2-imidazolidone, sulfolane and the like, and mixtures thereof.

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. The reaction of Steps 3f and 3g in Scheme 3 is usually performed in the range of 0 to 80 ° C, and the amount of the compound represented by the formula I ^ CH ₂ COOCH ₃ is determined by the formula [XII] or the formula [X]. It is usually in the range of 1 to 5 mol per 1 mol of the compound shown.

The reaction is usually performed in the presence of a base, and the amount of the base to be used is generally in the range of 1 to 10 mol per 1 mol of the compound represented by the formula L CHsCOOCHs. As the base, for example, sodium hydroxide, hydroxylated room, carbonic acid room, hydrogenated sodium, Inorganic bases such as potassium hydride; alkali metal alkoxides such as potassium-t-butoxide, sodium methoxide and sodium ethoxide; organic bases such as pyridine, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline; Alternatively, a mixture thereof may be mentioned.

The reaction is carried out in a solvent as necessary, and examples of the solvent include the solvents exemplified in Step a of Scheme 1.

After completion of the reaction, the target compound can be obtained by performing the same treatment as described in step a.

The reaction of Step 3k in Scheme 3 is performed under the reaction conditions of Scheme 2 by using the compound

The same can be done by replacing [Π] with [XVI].

Steps 3b, 3d, and 3h are performed by a reduction reaction of a nitro group.In step 3a, a substituent is appropriately introduced by, for example, a halogenation method, and in steps 3c, 3e, and 3i, It may be performed by a Sandmeyer reaction or the like.

HCOOCH3 J process 4 f

[la] Scheme 4 In the chemical formula of the above scheme 4, 1ΛL ² , X, Y, R \ R ² , R ³ , R ⁶ , ^RT, and R ⁸ represent the same meaning as described above.

The reaction of step 4f of scheme 4 can be carried out under the same conditions as the reaction of step 3j of scheme 3, and the base to be used and the solvent to be used if necessary are described in step 3j. And the same as those exemplified in the above. The amount of HCOOCH ₃ to be used in the reaction is in the range of usually 1-100 moles per mole of the compound represented by the formula [IX].

After completion of the reaction, the reaction mixture is treated in the same manner as described in step 3j to isolate the target compound can do.

The 4d reaction in Scheme 4 is described in the description of Step 3g in Scheme 3 by the formula

[XII] can be carried out under the same conditions as in Formula [VIII].

In the reaction of Step 4a, Step 4c, and Step 4e in Scheme 4, the compound [Π] in the description of the step in Scheme 2 is a compound represented by the formula [VI], a compound represented by the formula [XII] or a compound represented by the formula [XII] [XV].

In the formulas [I] and [II], the compound in which W is a CH ₂ group can be produced, for example, according to the method shown in Scheme 5 below.

[lb] [lib] scheme 5

In the chemical formula of the above scheme 5, 1ΛL ² , L ³ , X, Y, R \ R ² , RR ⁶ , and R ⁸ have the same meanings as described above.

The reaction of step 5e of scheme 5 is performed under the same conditions except that the compound of formula [XXX] is used instead of the compound of formula [I] in steps a and a 'of scheme 1. Can be implemented.

The reaction of Step 5c of Scheme 5 is carried out under the same conditions as in Step 3j of Scheme 3 except that the compound of Formula [XXIX] is used instead of the compound of Formula [XV], and the target compound is obtained. Obtainable.

The reaction of Step 5d in Scheme 5 can be carried out under the same conditions as in Step 3k of Scheme 3 except that a compound represented by the formula [XXX] is used, and the desired product can be obtained. The reaction of Step 5a in Scheme 5 is usually performed in the range of 20 to 120 ° C. The amount of dimethyl malonate to be used is generally in the range of 1 to 3 moles per mole of the compound represented by the formula [XXVII].

The reaction is usually carried out in the presence of a base, and the amount of the base to be used is generally in the range of 1 to 10 mol per 1 mol of the compound represented by the formula [XXVII]. Examples of the base include inorganic bases such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium hydride, potassium hydride, and alkali metal alkoxides such as potassium t-butoxide, sodium methoxide, and sodium ethoxide. And organic bases such as pyridine, triethylamine, ethyldiisopropylamine, N, N-dimethylaniline, and mixtures thereof.

The reaction is carried out in a solvent as necessary. Examples of the solvent include 1,4-dioxane, tetrahydrofuran, ether solvents such as ethylene glycol dimethyl ether and t-butyl methyl ether, _n- hexane, n-heptane and the like. Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as monochrome benzene, organic base solvents such as pyridine, triethylamine, N, N-dimethylaniline, methanol, ethanol, etc. Alcohol solvents, nitrile solvents such as acetonitrile, N, N-dimethylformamide, dimethylsulfoxide, water and the like, and mixtures thereof.

The compound represented by the formula [XXVII] can be produced, for example, according to the production method described in JP-A-11-219579. The reaction of step 5b of Scheme 5 is usually performed in the range of 80 to 250 ° C.

The reaction may be carried out in the presence of an inorganic salt such as lithium chloride and lithium bromide, if necessary.

The reaction is carried out in a solvent, if necessary. Examples of the solvent include ether solvents such as 1,4-dioxane, triglyme, and tetraglyme; aliphatic hydrocarbon solvents such as n-octane; and toluene and xylene. Aromatic hydrocarbon solvents, monochlorobenzenes, halogenated hydrocarbon solvents such as dichlorobenzene, organic base solvents such as pyridine, N, N-dimethylaniline, N, N-dimethylformamide, dimethyl sulfoxide, Examples include N-methylpyrrolidone, 1,3-dimethyl-12-imidazolidinone, or a mixture thereof.

The compound represented by the formula (III) can be produced, for example, by the method shown in the following scheme 6.

[XVII]

Scheme 6 In the chemical formulas in Scheme 6, A ² , L \ X, Y, RR ² and R ³ have the same meaning as described above.

The reaction of scheme 6 can be carried out, for example, by reacting a compound represented by the formula [XVII] with a metal (eg, magnesium, lithium, etc.) in a solvent (eg, diethyl ether, tetrahydrofuran, etc.). The reaction can also be performed by reacting a metal compound with a borate ester (eg, trimethyl borate, triethyl borate, etc.). (More specifically, it is carried out according to the method described in, for example, J. Am. Chem. Soc., 1958, 80, 4291-4293.) In a solvent (dimethylsulfoxide, N, N-dimethylformamide, etc.), a base (eg, an inorganic base such as potassium acetate, etc.) and a catalyst (eg, {1, 1′-bis (diphenylphosphino)) The compound represented by the formula [XVII] and bis (pinacolato) diboron may be reacted in the presence of a benzophenone dichloropalladium (II) methylene chloride complex). (More specifically, for example, it is carried out according to the method described in J. Org. Chem., 1995, 60, 7508-7510.)

Furthermore, the solvent catalyst (e.g., tetrakis (bird whistle two Rufosufin) palladium (0) etc.) at (toluene) in the presence in the formula [XV II] are of compounds of represented by the and R ^ie ₃ S n S nR It may be performed by a method of reacting with ^1Q ₃ (for example, Bu ₃ Sn SnBu ₃ etc.). (More specifically, for example, it is carried out according to the method described in Chem. Letters, 1981, 829-830.)

The compound [VIII ′] in which X and Y represented by the formula [VIII] in Scheme 4 are nitrogen atoms can also be produced, for example, according to the method shown in the following Scheme 7.

[VII ΙΊ

Scheme 7

In the chemical formula of Scheme 7, RR ² , R ³ , RR ⁷ and R ⁸ have the same meaning as described above.

[Production method C]

The production method C of the compound of the present invention, in which the compound represented by the formula [XX] and the compound represented by the formula [XXI] are reacted in the presence of a catalyst, will be described below.

[XX] [XXI] Scheme 8

In the chemical formula of Scheme 8, A ¹ represents B (OH) ₂ group, B (OR ⁹⁾ ₂ group or S nR ^{1 ()} ₃ group, LW, X, Y, RR 2, R 3, R 6, R ^7, R ^8, R ⁹ and R ^1. Has the same meaning as described above.

In the reaction of Scheme 8, in the description of the steps of Scheme 2, the formula [II] is replaced with [XX] The procedure can be carried out under the same conditions by replacing [III] with [XX] for [I].

The compound represented by the formula [XX] can be produced, for example, by the method shown in the following scheme 9.

[XXII] [XX] Scheme 9

In the chemical formula of Scheme 9, ALW, R ⁶ , R ⁷ and R ⁸ have the same meaning as described above.

The reaction of Scheme 9 is usually performed in the range of 20 to 100 ° C. A ¹ - amount of A ¹ is usually in the range of 1 to 5 moles relative to the compound [XXII] 1 mol.

The reaction is carried out, for example, in a solvent (dimethyl sulfoxide, N, N-dimethylformamide, etc.) in a base (eg, an inorganic base such as potassium acetate, etc.) and a catalyst (eg, {1,1′-bis (diphene) / Refosufuino) fuekisen} dichloropalladium (II) methylene chloride complex) in the presence of a compound of formula [XXII] and bis

(Pinacholate) It can also be produced by a method of reacting with diboron or the like. (More specifically, for example, J. Org. Chem., 1995, 60, 750

Perform according to the method described in 8-7510. ) Or a compound represented by the formula [XXII] in the presence of a catalyst (eg, tetrakis (triphenylphosphine) palladium (0), etc.) in a solvent (eg, toluene) and R ^1G ₃ Sn SnR ^ie ₃ ( (For example, Bu ₃ Sn SnBu ₃ etc.). (More specifically, for example, the method is described in Chem. Letters, 1981, 829-830.)

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, chromatography, etc. Purification allows isolation of the target compound. [Production method D]

Among the compounds of the present invention, a compound in which X and Y in the formula (1) are nitrogen atoms is, for example, a condensation reaction of the compound [XXIII] with a 1,3-dioxo compound in the following scheme 10. May be produced by the production method D.

[XXIII] Scheme 10 In the chemical formula of the above scheme 10, W, R ¹ , R ² , RRR ⁷ and R ⁸ represent the same meaning as described above.

In the formula [XXIII], the compound wherein W is an oxygen atom may be produced, for example, according to the method shown by the following scheme 11.

[XX I] [XX I I I]

Scheme 1 in 1 above scheme 1 1 formula, the teeth ^1, RR ⁷ and R ⁸ Wath table as defined above. The reaction in each step of Scheme 11 can be carried out according to the method of the corresponding step described in Schemes 1 to 10.

When the compound of the present invention is used as an active ingredient in an agricultural and horticultural fungicide, it may be used as it is without adding any other components, but it is usually a solid carrier, a liquid carrier, a surfactant, and other pharmaceutical auxiliaries. And used in emulsions, wettable powders, wettable powders for granules, emulsions, flowable preparations, powders, granules and the like. These preparations usually contain 0.1 to 90% by weight of the compound of the present invention as an active ingredient.

Examples of the solid carrier used in the case of vigorous formulation include minerals such as kaolin clay, atta-palgia clay, bentonite, montmorillonite, acid clay, pyrophyllite, tanolek, diatomaceous earth, calcite, corn cob powder, Fine powders or granules composed of natural organic substances such as walnut shell powder, synthetic organic substances such as urea, salts such as calcium carbonate and ammonium sulfate, and synthetic inorganic substances such as synthetic hydrous silicon oxide are examples of the liquid carrier. For example, aromatic hydrocarbons such as xylene, alkylbenzene, and methyl naphthalene, alcohols such as isopropanol, ethylene glycol, propylene glycol, and cellosolve, acetone, and cyclohexano And ketones such as isophorone, vegetable oils such as soybean oil and cottonseed oil, petroleum aliphatic hydrocarbons, esters, dimethyl sulfoxide, acetonitrile, water and the like. Examples of the surfactant include an alkyl ester sulfate, an alkyl (aryl) sulfonate, a dialkyl sulfosuccinate, a polyoxyethylene alkyl aryl-phosphate ester salt, a lignin sulfonate, and a formalin condensate of naphthalene sulfonic acid. And the like, nonionic surfactants such as polyoxyethylene alkyl aryl ether, polyoxyethylene alkyl polyoxypropylene block copolymer, and sorbitan fatty acid ester.

Pharmaceutical adjuvants include, for example, water-soluble polymers such as polyvinyl alcohol, polyvinylinolepyrrolidone, etc., polysaccharides such as gum arabic, alginic acid and salts thereof, CMC (carboxymethylcellulose), xanthan gum, etc., and aluminum magnesium silique. Examples include inorganic substances such as alumina sol, preservatives, coloring agents, and stabilizers such as PAP (acid 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 further, it 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 the target plant (crop, etc.), the type of the target disease, the degree of occurrence of the disease, the formulation, the application method, the application time may vary depending weather conditions, etc., per 1 are normally 0. 0 1 to 5 0 g, preferably 0. 0 5 to 1 0 ₈ Dearu.

When the emulsion, wettable powder, suspending agent and the like are diluted with water and applied, the application concentration is 0.0001 to 3%, preferably 0.0005 to 1%. The granules, etc. are applied without dilution.

The compound of the present invention can be used as a fungicide for agricultural and horticultural use in fields, paddy fields, orchards, tea gardens, meadows, turf, and the like. Can be expected to increase. Other agricultural and horticultural fungicides that can be mixed are, for example, propiconazole, triadimenol, prochloraz, penconazol, tebuconazo monole, funoresilazonole, giniconazo monole, bromconazo monole, epokishikonazo. Ichinore, Difuenoconazonore, Ciproconazonore, Metoconazoru, Tri Fusolemizole, tetraconazo, microbutaninole, fenbuconazo, hexaconazole, fluquinconazole, triconazole, azole-based germicidal compounds such as bitenoletanol, imazalil, and furtriahole, fenpropimorph , Fungicidal compounds such as tridemorph and fenprovidin, benzimidazole fungicides such as carbendazim, benomyl, thiabendazoline, thiophanate methyl, procymidone, cyprodiel, pyrimethanil, jetfencap, thiuram, fluazinam, prozinam, prozinam. , Vinclozolin, chlorothalonil, captan, mepanipyrim, fenpiclonil, fluoxodinore, diclofenoleanid, phonorepet, Taresoxime methinole, azoxystrobin, trifloxystrobin, picoxistrobin, N-methyl_α-methoximino-1-([2,5-dimethylphenoxy) methyl] phenylacetamide, spiroxamine, quinoxyphene, Examples include fenhexamide, famoxadone, phenamidone (RP—407213), iplovalicarb. 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 the insecticide and / or acaricide and / or nematicide which may be used include, for example, fenitrothion [θ, Ο-dimethylΟ- (3-methynole-14-nitrophenyl) phosphorothioate], phenylion [0 ,， —Dimethyl Ο— (3-Methyl-14- (methylthio) phenyl) phosphorothioate], diazinon [0, Ο—Jetyl Ο—2-isopropyl-16-methylpyrimidine-14-yl phosphorothioate], chlorpyrifos [0, Ο —Jetinole 0—3,5,6—Trichloro-1-2-pyridinole phosphorothioate], acephate (0, S—dimethylacetylphosphoramidothioate), methidathion (S—2,3-dihydro draw 5—medium) Toxic-2-oxo-1,3-, 3-thiadiazoyl-3-ylmethyl O, O-dimethylphosphorodithioate], disis Leuton [O, 0 _Jetinole S--2-ethynolethioethyl phosphorothioate], DDVP [2,2-dichlorovinyl dimethylinolephosphate], Sulfophos [0-ethinole O-4- (methylinolethio) phen Nyl S-propyl phosphorodithioate], cyanophos [O-4-cyanophen 0, O-dimethyl phosphorothioate], dioxabenzophos [2-meth Xy-4H-1,3,2-benzodioxaphosphinin_2-2-sulfide), dimethoate [O, O-dimethyl S- (N-methylcarbamoylmethyl) dithiophosphate], Fentate [Ethyl 2-dimethoxyphosphinothioyl thio (phenyl) acetate], Malathion [Jetyl (dimethoxyphosphinothioylthio) succinate], Trichloronefon [Dimethyl 2,2,2-trichloro-l-oxyl) Phosphonate], azinphosmethyl [S-3,4—dihydro 4-oxo-1,2,3-benzotriazine_3-—T-methyl O, O-dimethylphosphorodithioate], monochlorotophos [dimethyl (E ) — 1— Methyl-2— (Methinorecanolevamoyl) vinyl phosphate), ethion [〇, O, 〇 ', 〇' Organic phosphorus compounds such as ethyl S, S'-methylenebis (phosphorodithioate)], phosphatiazate [N- (O-methyl-S-sec-butyl) phosphorylthiazolidine-1-one], BPMC [2-sec-butylphenylmethyl] Carbamate), benfracarb [ethinole N- (2,3-dihydro 2,2-dimethynolebenzofuran 7-yloxycarbonyl (methyl) amino] 1-Nf-sopropyl-13-arananinate], propoxur [2f N-Methylenol N-methinole N-methinole N-methinole carbamate), N-methinole carbamine, 2,3-dihydro-1,2,2-dimethinole 7-Venzo [b] Furaninole N-dibuty Mate), canolevalyl [1-naphthyl N-methylcarbamate], mesomil [S-methyl-N- [ Rucarbamoyl) oxy] thioacetimidate], ethiofencalp [2- (ethylthiomethyl) phenyl methylcarbamate], aldicarb [2-methyl-2- (methylthio) propionaldehyde O-methylcarbamoyloxime], oxaxamyl [N, N- Dimethyl-2-methylcarbamoyloxyimino 2_ (methylthio) acetamide], phenothanolone [S-4-phenoxybutyl-N, N_dimethinoretica-a carbamate compound such as bamate, etfenprox [2- (4-ethoxyphenyl) 1-2-methylpropinole-3-phenoxybenzyl-1-enole], phenvalerate [(RS) -α-cyano-3-phenoxybenzyl (RS)-2-(4-chloro Mouth Fenino) 1-3-methinolebutyrate], esfenba Rate [(S)-.alpha.-Shiano 3- phenoxyethanol benzyl (S) - 2 - (4- chlorophyll Phenyl) -13-methylbutyrate], fenpropatrin [(RS) _a-si-no-1-3-phenoxybenzinole 2,2,3-tetramethylcyclopropane power ruboxylate], sinolemethrin [ (RS) —α-cyano-3-phenoxybenzyl (1 RS 3 RS) — 3- (2,2-dichlorobutyl) 122-dimethylcyclopropanecarboxylate], permethrin [3-phenoxybenzylene (1 RS 3 RS)-3-(2,2-Dichroic vinyl) 1,2,2-methylcyclopropanecarboxylate], cyhalothrin [(RS) Cyanol 3-phenoxybenzyl (Z)-(1 RS, 3 RS) — 3— (2-chloro33 3 3-trifluoropropinyl) -122-dimethylcyclopropanecarboxylate], denoletamethrin [(S) —α-cyano-1: m-phenoxybenzyl (1

R, 3 R) — 3— (22-dibromobiel) 122-dimethinolecyclopronecarboxylate], cycloprothrine [(RS) —α-cyano 3-phenoxybenzyl (RS) -2,2 —Dichloro 1— (4-ethoxyphenyl) cyclopropanecarboxylate], fluvalinate [α_cyano-3-phenoxibendinole Ν— (2-chloroαα, α-trifnoreo ρ-trinore) 1D

—Valinate, Bifenthrin [2-Mechinorebihueniru 3 -Inoremechinore]

(Ζ) — (IRS) -cis-3- (2-chloro 3,33-triphenylenopropane-1-yl) -1,2,2-dimethylcyclopropanecarboxylate] acrinasulin [(1R— {1 a (S *) 3 a (Z)}] 1 2 2-dimethyl-3- 1 [3-oxo-3- (2,2,2-trinoleolol 1- (trifluoromethyl) ethoxy-1 1-propionyl] cyclopropane Carboxylic acid cyano (3-phenoxyphenol) methyl ester)], 2-methyl-1- (4-bromodifluoromethoxyphenyl) propynole (3-phenoxybenzyl) ether, tramethrin methulin [(S) -α-cyano 3-phenoxybenzyl (1 R) —cis-3 _ (1 2,2,2-tetrabromoethyl) 1-22 dimethylcyclopropane ruboxylate], silaf / leophene [[4-ethoxyphenyl ( 3— (4—Fnoreolow 3— Pyrethroid compounds such as phenoxyphenyl) propynole) dimethylsilane], and thiadiazine derivatives such as buprofezin (2_t-butylimino 3-isopropyl-1-5-phenyl_135-triadiadinane-141-one); Nitroimidazolidine derivatives, cartap (S, S '-(2-dimethylaminotrimethylene) bis (thiocarbamate)), thiocyclam [N, N_dimethyl-1,2,3-trithiane-5-ylamine], bensultap [S, S' —2—Dimethylamino trimethylene di (benzenethiosulfonate)] and other N-cyanoamidines such as N-cyano-1N′—methyl-1-N ′ — (6-chloro-1-3-pyridylmethyl) acetamidine Derivatives, endosulfan [6,7,8,9,10,10-Hexachloro-1,5,5a, 6,9,9a-Hexahydro 6,9-methano-1,2,4,3-benzodi Gamma-BHC (1,2,3,4,5,6-hexachlorocyclohexane), 1,1-bis (chloro-phenine) 1-2, 2, 2—Triclo Chlorinated hydrocarbon compounds such as ethanol monochloride, chlorfluazuron [11 (3,5-dichloro-4- (3-chloro-5 _trifluoromethylpyridine-12-yloxy) phenyl) 13 — (2,6-difluorobenzoyl) ゥ rea], tefluvensuron [11 (3,5-dichloro-2,4-difluorophenyl) 13- (2,6-difluorobenzobenzole) ゥ rea ], Funolefenoxuron [1- (4- (2-chloro-4)

—Trifluoromethinolephenoxy) 1-2-fluorophenyl) -13- (2,6-difluorobenzoyl) ゥ rea] and other benzoylphenyl ゥ rea compounds, amitraz [N, N '[( Formamidine derivatives such as methylimino) dimethylidin] di 2,4-xylidine], chronoresimeform [ム '-((4-chloro-2-2-methinolephenyl)] Ν, Ν-dimethylmethanimidamide], diafenthiuron [ Ν_

Thiourea derivatives such as (2,6-diisopropynole-1-4-phenoxyphenyl) -N'-t-butynole compound, phenylhydrazole compounds, tebufenozide [N-t-butyl-N'- (4-Ethylbenzoyl) -1,5-dimethylbenzene hydrazide], 4-bromo-12- (4-chlorophenoxy) 1-1-ethoxymethylone 5-trifluorotrifluoromethylpyrrole-3-carbone Tolyl, bromopropylate [isopropyl 4, 4'-dibromobenzylate], tetradiphone [4-chloropheninole 2,4,5-trichloromouth phenylsnolephone], quinomethionate [S, S-6-methylquinoxaline] 2,3-diyldicarbonate], pulp pargite [2- (4-t-butylphenoxy) cyclohexynoleprop- 1 Sulfite), fenbutatin oxide [bis [tris (2-methyl-2-phenylpropyl) tin] oxide], hexthiazox [(4 RS, 5 RS)-5-(4-clos feninole) ) 1-N-chlorohexynole-1- 4-methynole — 2-oxo-1,3-thiazolidine-13-carboxamide], clofuentezine [3,6-bis (2-chlorophenyl) 1-1,2,4, 5-tetrazine, pyridatiobene (2-t-butynoleic 5- (4-t-butynolebenzinorethio) -14-cloth pyridazine-1-3 (2H) -one), fenpyroximeto [t-butyl (E) -4- [(1,3-dimethyl-5-phenoxypyrazole-41-yl) methyleneaminooxymethyl] benzoate], tebufenpyrado [N-4-t-butylbenzyl] -14-chloro-3-ethino -1-Mechinore one 5-pyrazole one Norekarubokisa Mi de], poly Na Kuching complex [Tetoranakuchin, Jinakuchin, Torinaku Chin], Minore base Mekuchin, avermectin, I bar one Mekuchin, Azajirakuchin

[AZAD], pyrimidifene [5-chloro-N- [2- {4- (2-ethoxyethyl) -1,2,3-dimethynolephenoxy} ethyl] 16-ethylpyrimidine-14-amine, pimetrozine 2, 3, 4, 5—tetrahydro-1-3-oxo-4

[(Pyridine-3-yl) -methyleneamino] 16-methyl-11,2,4-triazine and the like.

Plant diseases that can be controlled by the compound of the present invention include, for example, the following diseases.

Rice blast (Pyricularia oryzae), Sesame leaf blight (Cochliobolus miyabeanus 紋紋紋 3 內 (Rhizoctonia solani) ヽ

Erysiphe graminis (Erysiphe graminis), red force, bi;) Hei (Gibberella zeae), Pabinia (Puccinia strni'ormis, P. graminis, P. recondita, P. hordei), Snow rot (Typhula) sp., Micronectriella nivalis), Bark smut (Ustilago tritici, U. nuda), Black smut (Tilletia caries), Eye spot (Pseudocercosporella herpotrichoides), Cloud-shaped (Rhynchosporium secalis), Leaf blight (Septoria tricillium) Disease (Leptosphaeria nodorum),

Black spot of citrus (Diaporthe citri), soybean sickness (Elsinoe fawcetti), fruit rot 3 內 (Penicil 丄 ium digitatum, P. itali cum), Apple model two rear disease (Sclerotinia mal i), canker (Valsa mal i), powdery mildew (Podosphaera leucotricha), leaf spot disease (Alternaria mai l Li, scab _(Venturis inaequal is) Λ

Pear scab (Venturis nashicola, V. pirina), Ping kuro (Alternaria kikuchiana) Akaboshi (Gymnosporangium haraeanum)

Peach scab (Sclerotinia cinerea), scab (Cladosporium carpophi lum), phomopsis rot (Phoitiops is sp.),

Grape scab (El sinoe ampelina), 晚 rot (Glomerel la cingulata), powdery mildew (Uncinula necator), sabi bun (Phakopsora ampelopsidis) Buch crot (Guignardia bi dwel lii), downy mildew (Plasmopara vi ticola) ^ Oyster anthracnose (Gloeosporium kaki), defoliation;) hei (Cercospora kaki,

Mycosphaerel la nawae),

^ (Pseudoperonospora cubensis), と and 炳 (Pseudoperonospora cubensis), 、炭投投炭炭炭炭 (Pseudoperonospora cubensis) Phytophthora sp.), Phytutth sp.

Ring rot (Alternaria solani), Leaf blight (Cladosporium fulvum), Phytophthora infestans ヽ

Eggplant brown spot (Phomopsis vexans), tsutonko bing (Erysiphe cichoracearum), cruciferous vegetables black spot (Alternaria japonica) _N white spot (Cercosporel la brassicae),

Green onion rust (Puccinia al li i), soybean purpura (Cercospora kikuchi i) Black spot (Elsinoe glycines), Black spot (Diaporthe phaseolorum var. Sojae), Green bean anthracnose (Colletotrichum l indemthianum), Black sickness of Lackasey

(Cercospora personata) _Ν ¾¾Ε 3 (Cercospora arachidicola) _xゥゥ (Erysiphe pisi), Potato summer blight (Alternaria solani), Plague

(Phytophthora infestans), strawberry blight (Sphaerotheca humuli), chaff net (Exobasidium reticulatum) ヽ white scab (Elsinoe leucospi la), tabaco scab (Alternaria longipes) Blight (Erysiphe cichoa) , Anthracnose (Colletotrichum tabacum), Downy mildew (Peronospora tabacina), Plague

(Phytophthora nicotianae) ^ Leaf spot of Anzai (Cercospora beticola) Black rot (Diplocarpon rosae) of Nofu, Powdery mildew (Sphaerotheca pannosa), Brown spot of yak (Septoria chrysanthemi— indici), White scab horiana), gray rot of various crops (Botrytis cinerea), sclerotium disease (Sclerotinia sclerotiorum), etc.

Example

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, Test Examples, and the like, but the present invention is not limited to only 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 to 12 below. Production Example 1

Methyl 2- (5-odo-1-2-methinolephenoxy) 1-3-methoxy-12-propanoate 300 mg (0.862 mmo 1), feninoleboronic acid 126 mg (1.03 mmo 1 ), Tetra-n-butylammonium bromide 278 mg (0.862 mmo 1), potassium carbonate 276 mg (2.15 mmo 1), palladium acetate (II) 19.3 mg (0 .08 6 mm 0 1) 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 concentrated under reduced pressure. The precipitated crystals were washed with n-hexane to obtain 50 mg of methyl 3-methoxy-2- (2-methyl-15-phenylphenoxy) -12-propanoate (Compound 1-1 of the present invention). .

_{! H-NMR (CDC 1 3} , TMS)

δ (pm): 6.92-7.5 2 (9 H, m), 3.88 (3 H, s), 3.71 (3 H, s), 2.39 (3H, s) Example 2 Methyl 2- (5-iodo-2-methylphenoxy) -3-methoxy-2-propylamine 300 mg (0.862 mmo 1) 3-phenylphenylboronic acid 205 mg (1.03 mmo 1), tetrabromide n-Butyl ammonium 278 mg (0.862 mmo 1), potassium carbonate 276 mg (2.15 mmo 1), palladium (II) acetate 19.3 mg (0.086 mmo 1) and water 3 After mixing m1, 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-15- (3-phenylphenyl) phenoxy} -12-propanoate (the present compound 1-23) 234m g was obtained.

8 (ppm): 6.50-7.49 (13H, m), 3.88 (3H, s), 3.71 (3H, s), 2.40 (3H, s) Production Example 3

Methyl 2- (5-method-2-methylphenoxy) 1-3-Methoxy-1 2-propenoate 300 mg (0.862 mmo 1), 4-Funoleolopheninoleboronate 18 Omg (1.29 mm o 1) , Tetra-n-butylammonium bromide 416 mg (1.29 mmo 1), potassium carbonate 298 mg (2.15 mmo 1), palladium oxalate (II) 38.7 mg (0.172 mmo 1) After mixing water and 3 ml of water, the mixture was 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 concentrated under reduced pressure. The precipitated crystals were washed with n-hexane, and methyl 3-methoxy-2- (2-methynole-5- (4-phenololenophenol) phenoxy} -2-propanoate (compound 1 of the present invention) 36) 187 mg were obtained.

δ (ppm): 7.42-7.47 (2H, m), 7.31 (1H, s), 7.19 (lH, m), 7.05 to 7.11 (3H, m) , 6.86 (1H, d, J = 1.7Hz), 3.88 (3H, s), 3.71 (3H, s), 2.38 (3H, s) Production example 4

Methyl 2- (5-Ed _2-Methylphenoxy) 1 3-Methoxy 2-Prodenoate 300mg (0.86 2mmo 1), 4-Methylphenylboronic acid 1

77 mg (1.3 Ommo 1), tetra-n-butylammonium bromide 4 16 mg (1.29 mmol), potassium carbonate 298 mg (2.15 mmol), palladium acetate (II 38.7 mg (0.17 mmo 1) and 3 ml of water were mixed, and 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) fuunoxy} —2-provenoet (compound of the present invention 1-40) 206 mg I got

^{_{L H-NMR (CDC 1 3}} , TMS)

δ (ppm): 7.40 (2H, d, J = 1.7 Hz), 7.33 (1 H, s), 7.

19-7.22 (3H, m), 7.12 (1H, m), 6.91 (1H, d, J = 1.42Hz), 3.87 (3H, s ), 3.71 (3H, s), 2.38 (6

H, s) Production example 5

Methyl 2- (5-bromo-l-methylphenoxy) -l-3-methoxyl-l-propionate 300mg (0.946mmo 1) 3,5-difluorophenylboronic acid 194mg (1.23mmo) 1), tetra-n-butylammonium bromide 36 Omg (1.12 mmo 1), potassium carbonate 327 mg (2.37 mmo 1), palladium acetate (II) 21 mg (0. 094 mmo 1) and 3 m 1 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 concentrated under reduced pressure. The residue was subjected to preparative thin-layer chromatography on silica gel (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 2- {2-methyl-5- (3,5-Difluorophenyl) phenoxy} —3-methoxy-1-2-provenoate (Compound 1-44 of the present invention) was obtained in an amount of 14 lmg.

δ (ppm): 7.36 (1 H, s), 7.22 to 7.33 (1H, m), 7.09 (1H, dd, J = 7.8, 1.9 Hz), 6. 99 ~ 7.02 (2H, m),

6.86 (1H, d, J = 1.5Hz), 6.72 to 6.75 (1H, m), 3.90 (3H, s), 3.72 (3H, s), 2.39 (3 H, s) Production example 6

Methyl 2- (5-brom-2-methylphenoxy) 1-3-methoxy-12-propenoate 300 mg (0.946 mm o 1), 3-trifnoroleolomethylphenylboronic acid 224 mg (1.18 mm o 1), tetra-n-butylammonium bromide 360 mg (1.12 mmo 1), potassium carbonate 327 mg (2.37 mm o 1), palladium acetate (II) 21 mg (0.094 mm o 1) and After mixing 3 ml of water, the mixture was stirred at 80 ° C for 6 hours. After the mixture was cooled to room temperature, ethyl acetate and celite were extracted and filtered. The filtrate was washed with water, dried (sodium sulfate), and concentrated under reduced pressure. The precipitated crystals are washed with n-hexane, and methyl 2- {2-methyl-1- (3-trifluoromethylphenyl) phenoxy} —3-methoxy-2-propinoate (Compound 1 of the present invention) — 1 3) 182 mg was obtained.

δ (ppm): 7.5 1 to 7.73 (4 H, m), 7.36 (1 H, s), 7.24 to

7.26 (1H, m), 7.13 (1H, dd, J = 7.6, 1.8Hz), 6.90 (1H, d, J = 1.8Hz), 3.90 (3H, s), 3.72 (3H, s), 2.40 (3H, s) Production Example 7

The following objects were obtained in the same manner as in Production Example 6.

Methyl 2- {2-methyl-5- (3-fluorophenyl) phenoxy} -13-methoxy-2_propanoate (Compound 1-2 of the present invention) _{^ I-NMR (CDC 1 3} , TMS)

δ (ppm): 6.8—7.4 (8 H, m), 3.89 (3 H, s), 3.72 (3H, s), 2.39 (3H, s) Production Example 8

Methyl 3-methoxy-2- (2-methyl-5-bromo-benzyl) Acrylic acid 421 mg (1.42 mm o 1), Phenylenoboronic acid 225 mg (1.85 mm o 1), Triphosphate hydrate 1.5 g (7.1 mm o 1), {1,1'-bis (diphenylphosphino) phenoctene} dichloropalladium (II) methylene chloride complex 58 mg (0.071 mm o 1), Palladium (II) acetate 16 mg

(0.071 mmo 1) and 6 ml of ethylene glycol dimethyl ether, and then stirred at 83 ° C 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 silica gel preparative thin-layer chromatography (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 3-methoxyethoxy. 2- (2-Methyl-5-phenylbenzinole) atalilic acid (Compound 2-1) 41 Omg was obtained.

δ (ppm): 7.2-7.6 (9H, m), 3.85 (3H, s), 3.67 (3H, s), 3.61 (2H, s), 2.39 ( 3H, s)

Production Example 9

Methyl 2- (5-iodo-2-methylphenoxy) 1-3-Methoxy-1 2-propinoate 20 Omg (0.5574mmo 1), 4, 4, 5, 5-tetramethynole —2— {3-(4-pyrimidyl 1) Phenyl-1,3,2-dioxoborolane (162 mg, 0.574 mmo 1), triphosphate phosphate hydrate 61 Omg (2.87 mmo 1), {1,1'-bis (diphenylphosphine) G) Dichloro mouth palladium (II) methylene chloride complex 23 mg (0.03 mmo 1), palladium acetate (II) 6 mg (0.03 mmo 1) and ethylene glycol dimethyl ether 3 m 1 are mixed and then mixed at 83 ° C. For 1.5 hours. Mix to room temperature After cooling, 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 subjected to preparative thin-layer chromatography on silica gel (developed with n-hexane: ethyl acetate = 1: 1) to give methyl 3

—Methoxy 2— [2-Methyl-5- {3- (4-pyrimidinyl) phenyl} phenoxy] —2-Probenoet (Compound of the present invention 1-32) 128 mg Obtained.

6 (ppm): 9.28 (1H, s), 8.78 (1H, d, J = 5.1Hz), 8.23 (1H, t, J = 1.9) Hz), 8.2 (lH, m), 7.74 (1H, dd, J = 5.0Hz, J = 1.3Hz), 7.62 (1H, m) , 7.54 (1H, t, J = 7.7Hz), 7.34 (1H, s), 7.21-7.25 (2H, m), 6.97 (1H, d, J = 1.7Hz), 3.89 (3H, s), 3.72 (3H, s), 2.41 (3H, s)

Production Example 10

Methyl 2— {2 _methyl-1 5— (4,4,5,5-tetramethyl-1,3,2

—Dioxoborolan-1-yl) phenoxy} —3-Methoxy-2-propionate 200 mg (0.574 mmo 1), 2-bromopyrimidine 128 mg (0.805 mmo 1), phosphoric acid 85% (3.5 mmo)), {1,1'_bis (dipheninolefosfuino) phenoctene} dichloropalladium (II) methylene complex 33 mg (0.404) mm o 1), palladium acetate

After 9 mg (0.04 mmo 1) of (II) and 3 ml of ethylene glycol dimethyl ether were mixed, the mixture was stirred 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-1-5- (2-pyrimigel) Phenoxy} -2-propanolite (Compound 1-51) of the present invention (102 mg) was obtained.

δ (ppm): 8.74 (2H, d, J = 4.5 Hz), 8.02 (1H, dd, J = 7.8 Hz, 1.6 Hz), 7.83 (1 H, d, J = l. 7 Hz), 7.3 8 (1H, s), 7.28 (1H, s), 7.12 (1H, t, J = 1.5), 3.88 (3H, s), 3.70 (3 H, s), 2.42 (3 H, s) Production Example 1 1

Methyl 2— {2-Methyl-1 5— (4, 4, 5, 5-Tetramethyl-1 1, 3, 2

—Dioxoborolan-1-yl) phenoxy} — 3-Methoxy-1-probenoate 200 mg (0.5 74 mmo 1), 2-chloro-5-triphnorelomethinole pyridine 1 56 mg (0. 859 mmo1), triphosphate hydrate 610 mg (2.87 mmo)), {1,1'-bis (diphenylphosphino) fuerosene} dichloropalladium (II ) methylene chloride complex 23. 5mg (0. 02 9m mo]), palladium (II) 6. 4 mg (0. 029 mm o 1) and E Ji render recall dimethyl E - after mixing the ether 3 _m〗, 83 The mixture was stirred at ° 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 preparative thin-layer chromatography on silica gel (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 2- [2-methyl 5- (5- (trifluoromethyl) 1-2-pyridyl} phenoxy] -3-methoxy-2-propinoate (Compound 1-92 of the present invention) (213 mg) was obtained.

NMR— NMR (CDC 1 TMS)

5 (ppm): 8.9 (1 H, s), 7.9 (1 H, dd), 7.7 (1 H, d), 7.6 (1 H, dd), 7.46 (1 H, d, J = 1.7 Hz), 7.37 (1H, s), 7.28 (1H, s), 3.89 (3H, s), 3.71 ( 3 H, s), 2.4 2 (3 H, s) Production example 1 2

Methyl 2— {2-methyl-5 _ (4,4,5,5-tetramethyl-1,3,2

—Dioxoborolan-1-yl) phenoxy} —3-Methoxy-2-probenoate 200 mg (0.5 74 mmo 1), 2-chloro-1-methyl 6-triphnoleolomethinole pyridine 1 56 mg (0. 8 5 9 mm o 1), triphosphate hydrate 610 mg (2.87 mmo l), {1, 1 '-bis (diphenylphosphine) ferrose Dichloropalladium (II) methylene chloride complex 23.5 mg (0.029 mmol), palladium (II) acetate 6.4 mg (0.029 mmo1) and ethylendicol dimethyl ether ₃ ml were mixed together. The mixture was stirred at 83 ° C for 4 hours. After cooling the mixture, ethyl acetate and celite were found 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 (developed with n-hexane: ethyl acetate = 2: 1) to give methyl 2- [2-methyl-5 - {6 - (triphenylmethyl Ruo ii methyl) one 2-pyridyl} phenoxy] - 3-main butoxy one ₂ - propenyl Noeto (present compound 1-9 1) to give the 1 36m g.

_{Ή-NMR (CDC 1 3,} TMS)

5 (ppm): 7.87 to 7.82 (2H, m), 7.56 (2H, dt), 7.48 (1H, d, J = 2.1Η Η), 7. 39 (1H, s), 7.28 to 7.25 (1H, m), 3.91 (3H, s), 3.72 (3H, s), 2.42 (3H, s)

Production example 1 3

Methyl 2- {2-methinolay 5— (4,4,5,5-tetramethinolate 1,3,2-dioxoborolan-1-yl) phenoxy} -13-methoxy-1-2-probenoeet 200mg (0 5 74 mm o 1), 3-bromo-1- (4-pyrimidinolemethoxy) benzene153 mg (0.557 mmo 1), tripotassium phosphate hydrate 61 Omg (2.87 mm o 1) , {1, 1'-bis (diphenylphosphino) phenoctene} dichloropalladium (II) methylene chloride complex 23.5 mg (0.029 mmo 1), palladium acetate (II) 6.4 mg (0.0 29 mmo 1) and 3 ml of ethylenedaricol dimethyl ether 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, 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 140 mg of 5-({3- (4-pyrimidylmethoxy) phenoxy} phenoxy] —3-methoxy-2-propinoate (Compound 1-27 of the present invention) was obtained. ^{_{X H-NMR (CDC 1 3}} , TMS)

δ (ppm): 9.2 (1H, s), 8.7 (lH, d), 7.6 (1H, d), 7.1 to 7.4 (6H, m), 6 .9 (2H, m), 5.2 (2H, s), 3.89 (3H, 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 respectively.

Methyl 2- {2-methyl-5- (3-benzyloxyphenyl) phenoxy} ― 3-methoxy-1-2-propanoate (Compound 1-25 of the present invention)

δ (ppm): 6.9-7.5 (13H, m), 5.1 (2H, s), 3.9 (3H, s), 3.7 (3H, s), 2. 4 (3H, s) methyl 3-methoxy-1- 2- {2-methynole-5- (3-methylphenyl) phenoxy} 12-probenoet (Compound 116 of the present invention)

_{Ή-NMR (CDC 1 3,} TMS)

δ (ppm): 7.34 (lH, s), 7.26—7.30 (3H, m), 7.21 (1H, d, J = 7.7 Hz), 7.1 1—7 14 (m, 2H), 6.91 (d, 1H, J = 1.1 Hz) 3.88 (3H, s), 3.71 (3H, s), 2.40 (3H, s), 2.38 (3H, s) methyl 3-methoxy 2- {2-methyl-1- (3-methoxyphenyl) phenoxy} 12-propanoate (Compound 1-16 of the present invention)

I NMR (CDC 13, T S)

δ (ppm): 7.04-7.36 (6 H, m), 6.85-6.92 (2H, m),

3.88 (3H, s), 3.85 (3H, s), 3.58 (3H, s), 2.14 (3H, s) Methyl 3-Methoxy 2— {2-Methyl-5_ (2 , 3, 4, 5, 6—penta Fluorophenyl) phenoxy} —2-propanoate (compounds of the present invention 114)

^ -NMR (CDC 1 J, TMS)

δ (ppm): 7.26-7.33 (2H, m), 7.0 (1H, m), 6.75 (1H, m), 3.87 (3H, s), 3.7 1 (3H, s), 2.41 (3H, s) methyl 2- {2-methyl_5— (4-methyl-12-pyrimidinyl) phenoxy} 1-3-methoxy-2-probenoate (book Invention compound 1-59)

δ (ppm): 8.59 (1H, d, J = 5.0 Hz), 8.02 (1 H, dd, J = 7.8, 1.5 Hz), 7.82 (1H, d, J = 1.4 Hz), 7.38 (1H, s), 7.26 (1H, d, J = 7.7Hz), 7.00 (1H, d, J = 5.0Hz), 3.88 (3H, s), 3.70 (3H, s), 2.55 (3H, s), 2.42 (3H, s) methyl 2- (2-methyl-5- (4-n-butyl) 1-Pyrimidinyl) phenoxy} —3-Methoxy-1-2-propionate (Compound of the present invention 1 1 1 1 1)

LH-NMR (CDC 1 a, TMS)

δ (ppm): 8.59 (1Η, d, J = 5.1Ηζ), 8.0 (1H, dd), 7.9 (1H, d), 7.3 (2H, m ), 6.96 (1H, d, J = 5.1Hz), 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 = 7.3 Hz) Methyl 2- (2-methyl-5- (4-sec-butyl-12-pyrimidinyl) phenoxy} —3-methoxy-12-propinoate (Compound 1— 1 12)

δ (ppm): 8.61 (1 H, d, J = 5.0 Hz) _N 8.06 (1 H, dd, J = 7.8Hz), 7.86 (1H, d, J = 1.3Hz), 7.38 (1H, s), 7.26 (1H, d, J = 7.7Hz), 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) fuunoxy} -13-methoxy-2-propinoate (Compounds of the present invention 1-168)

δ (ppm): 8.98 (1 H, d, J = 5.0 Hz), 8.09 (1 H, dd, J = 7.8, 1.7 Hz), 7.85 (1H, d , J = 1.4 Hz), 7.44

(1H, d, J = 5.OHz), 7.40 (1H, s), 7.29 (1H, d, J = 7.9Hz), 3.90 (3H, s) ), 3.72 (3H, s), 2.44

(3H, s) methyl 2- {2-methyl-5- (4-methoxy-12-pyrimidinyl) phenoxy} -13-methoxy-12-propinoate (Compound 1-69)

δ (ppm): 8.45 (1H, d, J = 5.7Hz), 8.02 (1H, dd, J = 7.8, 1.4Hz), 7.82 (1H) , d, J = 1.6 Hz), 7.37 (1H, s), 7.31 (1 H, d, J = 7.8 Hz), 6.58 (1H, d, J = 5.8 Hz) _Λ 4.05 (3 H, s), 3.88 (3 H, s), 3.70 (3 H, s), 2.42 (3H, s) Methyl 2— {2-methyl- 5- (4,6-Dimethyl-2-pyrimidinyl) phenoxy} —3-Methoxy-1-2-propinoate (Compound 1-62 of the present invention)

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 (3H, s), 2.50 (6H, s) 2. 41 (3H, s) methyl 2- {2-methyl-5- (6-phenoxy-12-pyridyl) phenoxy} -13-methoxy-2-propinoate (Compound 1-73 of the present invention)

Ή-NMR (CDC 1 a, TMS)

δ (ppm): 7.69 (1H, t, J = 7.7Hz), 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-12 pyridyl) ) Fenoxy} —3-Methoxy 2-propanoate (Compound 1-72)

δ (ppm): 7.24-7.63 (ll H, m), 6.70 (1 H, d, J = 8.0 Hz), 3.84 (3 H, s), 3.70 (3H , s), 2.40 (3H, s) methyl 2- {2_methyl_5 -— (6-methyl-1-pyridyl) phenoxy} —3-methoxy-12-propinoate (Compound 1— 86)

5 (ppm): 7.52-7.61 (2H, m), 7.34-7.42 (3H, m), 7.23 (1H, d, J = 7.9Hz), 7. 05 (1 H, d, J = 7.5 Hz), 3.89 (3 H, s), 3.70 (3H, s), 2.39 (3H, s), 2.04 (3 H , s)

Production Example 27

Methyl 2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2dioxoborolan-1-2-yl) phenoxy} — 3-Methoxy-2_probenoe 200 mg (0.574 mm o 1), 2-methyl 4-ethylpyrimidine 82 2 mg (0.575 mm o 1), triphosphate hydrate 61 Omg (2.87 m mo 1), {1, 1 '-bis (dipheninolefosfuino) phenoctene} dichloropalladium (II) methylene chloride complex 23 mg (0.029 mmo 1) and ethylendicol dimethyl ether _{3 m} 1 It mixed and stirred at 83 ° C for 3 hours. After 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 = 1: 1) to give methyl 2- {2-methyl 5- (4-ethyl-12-pyrimidinyl) phenoxy} -13-methoxy-12-propinoate (the present compound 1-64) (159 mg) was obtained.

_{Ή-NMR (CDC 1 3,} TMS)

δ (ppm): 8.4 (1H, d,), 8.0 (1H, dd), 7.8 (1H, d),

7.4 (1H, s), 7.3 (1H, d), 7.0 (1H, d), 3.89 (3H, 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-methynole-5- (4-n-propynole-1-pyrimidinyl) phenoxy} —3-methoxy-12-propinoate (Compound 1-66 of the present invention)

! H-NMR (CDC 1 TMS)

δ (ppm): 8.60 (1 H, d, J = 5.3 H z), 8.04 (1H, d d, J

= 7.8, 1.4Hz), 7.84 (1H, d, J = 1.3Hz), 7.37 (1H, s), 7.26 (1H, d, J = 7. 4H z), 6.97 (1 H, d, J = 5.0 Hz), 3.88 (3H, s), 3.70 (3H, s), 2.76 (2 H, t, J = 7 2Hz), 2.42 (3H, s), 1.78—1.86 (2H, m), 1.01 (3H, t, J = 7.2Hz) Methyl 2-—2-methyl 15- (4_n-Propoxy-12-pyrimidyl) phenoxy} _3-Methoxy 2_propanoate (Compound 1-1-1 13) ^X H-NMR (CDC 13 ₎ TMS)

δ (ppm): 8.44 (1H, d, J = 5.7Hz), 7.99 (1H, dd, J = 7.8, 1.4Hz), 7.81 (1H , d, J = 1.3 Hz, 7.36 (1 H, s), 7.2 (1 H, d), 6.55 (1 H, d, J = 5.7 Hz) , 4.42 (3H, t, 6.5 Hz), 3.88 (3H, s), 3.70 (3H, s), 2.42 (3H, s), 1.8 1—1. 8 8 (2 H, m), 1.05 (3 H, t, J = 7.6 Hz) Methyl 2— {2-Methyl-5— (4-Cyanol 2-pyrimidinyl) phenoxy} —3— Methoxy 2-probenoate (compound of the present invention)

^L H-NMR (CDC 1 TMS)

δ (ppm): 8.93 (1H, d, J = 4.9Hz), 8.05 (1H, dd, J = 7.8Hz), 7.81 (1H, d, J = 1.7Hz, 7.40-7.43 (2H, m), 7.85 (1H, d, J = 7.8Hz), 3.91 (3H, s), 3. 72 (3H, s), 2.43 (3H, s) methyl 2- {2-methyl-1-5- (6-chloro-1--2-pyridyl) phenoxy} -3-methoxy-2-propanoate (The present invention Compound 1-82)

_{Ή-NMR (CDC 1 3,} TMS)

δ (ppm): 7.64 (1H, t, J = 7.8Hz), 7.54 (2H, d, J =-

7.7Hz), 7.36 (2H, m), 7.22-2.26 (2H, m), 3.90 (3H, s), 3.71 (3H, s), 2. 40 (3 H, s) methyl 2- {2-methyl-1-5_ (6-methoxy-2-pyridyl) phenoxy} -13-methoxy-12-propinoate (Compound 1-94 of the present invention)

^ -NMR (CDC 1 TMS)

δ (ppm): 7.10—7.61 (6H, m), 6.64 (1H, dd, J = 8.6, 0.6Hz), 4.00 (3H, s), 3.88 (3H, s), 3.71 (3H, s), 2.4◦ (3H, s) Methyl 2- {2-methyl-1- (6-methylthio-1-pyridyl) phenoxy} —3-methoxy-12-propinoate (Compound 1-1-14)

NMR— NMR (CDC 1 TMS)

δ (ppm): 7.46-7.56 (3H, m), 7.12-7.36 (3Hm), 7.08 (1H, d, J = 7.8Hz), 3.88 (3H, s), 3.71 (3H, s), 2.62 (3H, s), 2.40 (3H, s)

Methyl 3-Methoxy-1-2- (2-Methyl-1-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-1-2 f) -benzyl) Atalinoleic acid 200 mg (0.578 mm o 1), 2-bromocopene benzene 144 mg (0.752 mmo 1), triphosphate hydrate 61 3 mg (2.9 mmo 1), {1,1'-bis (diphenylphosphino) The mixture was mixed with 24 mg (0.029 mmo 1) of dichloropalladium (II) salt dimethylene complex and 3 ml of ethylene glycol dimethyl ether, and stirred at 83 ° C. for 3 hours. The mixture was cooled to room temperature, ethyl acetate was 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-1- 2- {2- 126 mg of methyl-5- (3-chlorophenyl) benzyl} acrylic acid (Compound 2-3 of the present invention) was obtained.

NMR (CDC 1 TMS)

δ (ppm): 7.5 (2 H, m), 7.2—7.5 (5 H, m), 3.87 (3 H, s), 2-68 (3H, s), 3. 6 1 (2H, s), 2.39 (3H, s) Production example 35 41

Methyl 3-methoxy-2- {2-methyl-5- (4-chlorophenyl) benzyl} atalilic acid (Compound 2-37 of the present invention) ^{_{X H-NMR (CDC 1 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-1 2— {2-Methyl-1 5— (4-Trifluoromethyl-1 2)

—Pyrimidinyl) benzyl} acrylic acid (Compound 2 _ 68)

LH-NMR (CDC 1 J, TMS)

δ (ppm): 8.98 (1H, d, J = 4.9 Hz), 8.31 (1H, d, J = 1.1 Hz), 8.19 (1H, dd, J = 7.99Hz), 7.52 (1H, s), 7.43 (1H, d, J = 4.9Hz), 7.2 (1H, s), 3.8

9 (3H, s), 2-68 (3H, s), 3.64 (2H, s), 2.44 (3H, s) Methyl 3-Methoxy 1 2— {2-Methyl 5— (6 —Methyl-1-pyridyl) benzyl} acrylic acid (Compound 2-86 of the present invention)

δ (ppm): 7.70-7.72 (2H, m), 7.58 (1H, t, J = 7.7 Hz), 7.48 (1H, s), 7.43 (1 H, d, J = 7.9Hz), 7.20 (1H, d, J = 8.3Hz), 7.03 (1H, d, J = 7.5Hz), 3.86 ( 3H, s), 3.66 (3H, s), 3.62 (2H, s), 2.59

(3H, s), 2.39 (3H, s) methyl 3-methoxy-2-{2-methyl-5- (6-trifluoromethyl-12-pyridyl) benzyl} acrylic acid (Compound 2 of the present invention) — 91)

One NMR (CDC 1 _3, TMS)

δ (ppm): 7.82—7.87 (3H, m), 7.76 (1H, dd, J = 7.8, 1.8Hz), 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-1- (2-methyl-1-5- (6-chloro-2-pyridyl) benzyl) acrylic acid (Compound 2-82 of the present invention)

^ -NMR (CDC 1 TMS)

δ (ppm): 7.67-7.74 (2H, m), 7.65 (1H, t, J = 7.7), 7.56 (1H, d, J = 7.6Hz) , 7.50 (1H, s), 7.18-7.22 (2H, m), 3.88 (3H, s), 3.67 (3H, s), 3.62 (2H , s), 2.40 (3H, s) methyl 3-methoxy-2- {2-methyl-15- (6-methoxy-2-pyridyl) benzyl} acrylic acid (Compound 2-94 of the present invention)

^ I-NMR (CDC 1 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 = 8.2Hz), 4.02 (3H, s), 3.85 (3H, s), 6.67 (2H, s), 3.62 (3H, s), 2.40 (3H, s) Methyl 3-Methoxy-1-2- {2-methyl-5- (5-chloro-1--2-pyridyl) benzyl} acrylic acid (the compound of the present invention) 2—83)

: H-NMR (CDC 1 TMS)

δ (ppm): 8.6 (lH, m), 7.58—7.71 (4H, m), 7.49 (1H, s), 7.18-7.27 (2H, m) , 7.21 (1H, d, J = 8.4Hz), 3.86 (3H, s), 3.66 (3H, s), 6.62 (2H, s), 2.40 ( 3H, s) Production example 42

Methyl 2- (5-bromo-1-2-methylphenoxy) _3-methoxy-1_2_propanoate 200 mg (0.631 mmo 1), 2- (trimethyltin) pyridine 229 mg (0.947 mmo 1), bis-1 ( Trienninophosphine para After mixing 22 mg (0.031 mmo 1) of di (II) dichloride, 5 Omg (0.629 mmo 1) of copper oxide (II) and 3 ml of ethylene glycol dimethyl ether, the mixture was stirred 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 (n-hexane: ethyl acetate = 2:

(Developed in step 1)) and give 14 lmg of methyl 2- {2-methyl-15- (2-pyridyl) phenoxy] -3--3-methoxy-2-propionate (Compound 1-78 of the present invention). Obtained.

δ (ppm): 8.64 to 8.65 (1H, m), 7.64 to 7.71 (2H, m),

7.52 (1H, dd, J = 7.8Hz, 1.7Hz), 7.36 to 7.40 (2H, m), 7.16 to 7.26 (2H, m), 3. 88 (3H, s), 3.70 (3H, s), 2.40 (3H, s) Intermediate Production Example 1

Methyl 2- (5-bromo-1-2-methylphenoxy) 1-3-Methoxy-2-prodenoate 2.00 g (6.3 1 mm o 1), bis (pinacolato) diboron 1.92 g (7.56 mm o 1), {1,1'-bis (dipheninolefosfuino) erocene} dichloropalladium (II) chloride methylene complex 0.26 g (0.318mmo1), 1.86 g of potassium acetate After mixing 19.0 mm0 1) and dimethyl sulfoxide (50 ml), the mixture was stirred at 80 ° 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, washed with saturated saline, dried (anhydrous sodium sulfate), and concentrated under reduced pressure. The precipitated crystals are washed with n-hexane, and methyl 2- {2-methyl-1-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-1-2-yl) phenoxy} 1-3 —Methoxy_2-2-propanoate (2.00 g) was obtained.

δ (ppm): 7.4 (1 H, d), 7.3 (1 H, s), 7.2 (1 H, d), 7.1 (1 H, s), 3.86 (3H , s), 3.69 (3H, s), 2.38 (3 H, s), 1.3 1 (1 2 H, s)

Intermediate Production Example 2

Methyl 3-methoxy-2- (2-methyl-5-bromo-benzyl) Acrylic acid

2.00 g (6.31 mmo 1), bis (pinacolato) diboron 2.22 g (8.74 mmo l), {1, 1 '—bis (diphenylphosphino) fuerosen} (II) After mixing 0.27 g (0.331 mm ₀ 1) of methylene chloride complex, 1.96 g (20.0 mmo 1) of potassium acetate and dimethyl sulfoxide (40 ml), The mixture was stirred at C for 8 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, washed with a saturated saline solution, dried (anhydrous sodium sulfate), and then concentrated under reduced pressure. The residue was crystallized from t-butyl methyl ether to give methyl 3-methoxy-2- {2-methyl-5- (4,4,5,5-tetramethyl-1,3,2-dioxoborolan-2-ii). Benzyl) acrylic acid 79 Omg was obtained.

6 (ppm): 7.50—7.54 (2H, m), 7.46 (1H, s), 7.11

(1 H, d, J = 7.4 Hz), 3.84 (3 H, s), 3.65 (3 H, s),

3.56 (2H, s), 2.35 (3 H, s) 1.31 (12H, s) Reference Production Example 1

Cool a mixture of 20.39 g (0.166 mol), 48% hydrobromic acid (127 ml) and water 157 ml 1 to 5- ° -amino-2-methylphenolone to 0 ° C. To this was added 35 ml of sodium nitrite (1.14 g, 0.166 mol) in water 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 mixture was gradually heated to 100 ° C., stirred at 100 ° C. for 30 minutes, cooled, and extracted with ethyl acetate. The organic layer is washed with water, washed with saturated saline, dried (anhydrous sodium sulfate), concentrated, and the residue is subjected to silica gel column chromatography (eluted with n-hexane: ethyl acetate = 95: 5 to 75:15). Then, 12.98 g of 5-bromo-1-methylphenol was obtained. _{^ -NMR (CDC 1 3, TMS} )

8 (ppm): 6.97 (2H, s), 6.94 (1H, 4.97 (1H, s)

2.19 (3H, s) Reference Production Example 2

5-bromo-1-2-methinolephenol 1 2.98 g (69.4 mmol), methyl bromoacetate 1 1.68 g (76.3 mmol), lium carbonate 12.47 g (90.2mo 1) After a mixture of and N, N-dimethylformamide 15 Om1 was stirred at room temperature for 3 hours, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium bicarbonate and saturated saline, dried (anhydrous sodium sulfate) and concentrated to give 18.77 g of methyl 2- (5-bromo-12-methylphenoxy) acetate. .

Ή-NMR (CDC 1 TMS)

δ (ppm): 7.02 (2H, s), 6.83 (1H, d, J-0.8Hz), 4.63 (2H, s), 3.81 (3H, s), 2.23 (3H, s) Reference Production Example 3

A mixture of methyl 2- (5-brom-2-methylphenoxy) acetate 18.4 g (7 1. Ommo 1), methyl formate 42.64 g (71 Ommo 1) and ethylene glycol dimethyl ether 36 m 1 was taken for 40 minutes. It was added dropwise to a mixture of 30% potassium hydride (20.89 g, 156 mmol) and 185 ml of ethylene glycol dimethyl ether cooled to 0 ° C. The resulting mixture was heated to room temperature, stirred for 3 hours, poured into a saturated aqueous solution of ammonium chloride, adjusted to pH 4 with a 5% aqueous solution of hydrochloric acid, and extracted with ethyl acetate. The organic layer was washed successively with water and a saturated saline solution, dried (anhydrous sodium sulfate), and concentrated to obtain crude methyl 2- (5-bromo-1-methylphenoxy) -13-hydroxy-2-propanoate. Was.

Crude methyl 2- (5-bromo-12-methylphenoxy) -13-hydroxy-12-propanoate, methyl iodide obtained in the above reaction, methyl iodide 15.12 g (107mmo 1), a mixture of 16.68 g (12 lmo 1) of potassium carbonate and 20 Om1 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 is washed successively with a 2% aqueous hydrochloric acid solution, water, saturated aqueous sodium hydrogen carbonate and saturated saline, dried (anhydrous sodium sulfate) and concentrated, and the residue is subjected to silica gel column chromatography (n-hexane: ethyl acetate). = 100: 0 to 50:50) to give methyl 2- (5-bromo-12-methylphenoxy) -13-methoxy-12-propinoate (10.08 g).

_{Ή-NMR (CDC 1 3,} TMS)

δ (ppm): 7.3 1 (1 H, s) ヽ 7.0 (2 H, m), 3.88 (3 H, s), 3.72 (3 H, s), 2.28 ( 3 H, s) Reference production example 4-1

5-Anode 2-Methylaniline 10.0 g (42.9 mol), concentrated sulfuric acid (5 ml) and water (15 ml) were cooled to 110 ° C and mixed with sodium nitrite. 3. Og (43.5mo 1) 4 ml of Z water and 15 ml of water were added dropwise so that the liquid temperature was kept at -3 ° C or less. The resulting diazonium salt reaction solution was added to a mixture of copper (II) sulfate 5 hydrate 8.Og (32.Omml), 10% sulfuric acid 55 ml and toluene 37 ml at 75 ° C. It was dropped. The mixture was stirred at 75 ° C for 2 hours, 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 7.33 g of 5-node-12-methylphenol.

Reference Production Example 4 1 2

5 ョ一 2 2-Methynolephenole 20.48 g (87.5 mmol), bromomethyl acetate 9.1 ml (96.1 mmo 1), potassium carbonate 14.5 g (105 mo 1) A mixture of N, N-dimethylformamide and 175 ml of N, N-dimethylformamide was stirred at room temperature at room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed successively with water, saturated aqueous sodium bicarbonate and saturated saline, dried (anhydrous sodium sulfate), concentrated, and the residue was subjected to silica gel column chromatography to give methyl 2- (5-phosphate). Methylphenoxy) acetate 1 5.76 g was obtained. _{'H-NMR (CDC 1 3} , TMS)

5 (ppm): 7.23 (1 H, dd, J = 7.8, 1.6 Hz), 698 (1 H, d, J = 1.3 Hz), 6.88 (1 H, d , J = 7.5 Hz), 4.62 (2 H, s), 3.81 (3 H, s), 2.23 (3 H, s) Reference Production Example 5

From methyl 2- (5-iodo-2-methylphenoxy) acetate, use the same method as in Reference Production Example 2 and Reference Production Example 3 to obtain methyl 2- (5-odo-1-2-methylphenoxy) -13-methoxy-2-pro Obtained benoate.

6 (ppm): 7.32 (1 H, s), 7.23 (1 H, dd, J = 7.8, 1.6 Hz), 6.99 (1 H, d, J = 1. 6 Hz) _x 6.88 (1 H, dd, J = 7.7, 0.6 Hz), 3.88 (3H, s), 3.72 (3 H, s), 2.29 (3H, s ) Reference Production Example 6

3 1-bromoacetophenone 9. Og (59.9 mmo 1), N, N ', N "-methylidenetrisformamide 1 7.1 g (118 mmo 1), p-toluenesulfonate 0 A mixture of 57 g (3.Ommo 1) and formamide 27 g was stirred at 160 ° C for 2 hours, cooled, poured into 5% aqueous sodium hydroxide solution, and adjusted to pH 4 with 5% aqueous hydrochloric acid solution. The organic layer was washed successively with saturated aqueous ammonium chloride and saturated brine, dried (anhydrous sodium sulfate) and concentrated, and the obtained solid was recrystallized (ethanol: water). = 1: 2) to give 2.49 g of 4_ (3-promophenoxy) pyrimidine.

_{^ -NMR (CDC 1 3, TMS} )

6 (ppm): 9.29 (1H, d, J = 0.9 Hz), 8.81 (1H, d, J = 5.4Hz), 8.28 (1H, t, J = 1) 7Hz) ゝ 8.01 (1H, d, J = 7.8Hz), 7.7 1 (1H, dd, J = 5.1, 1.2Hz) 7.7 (1H, dd), 7.40 (1 H, t, J = 7.8 Hz) 4- (3-bromophenoxy) pyrimidine 0.70 g (6.31 mmo 1), bis (pinacolato) diboron 0.91 g (3.9 mmo 1), {1,1'_bis

(Diphenylphosphino) phenoctene} dichloropalladium (II) methylene chloride complex 0.121 g (0.149 mmo 1), potassium drunkate 0.88 g (9.0 mmo 1) and dimethyl sulfoxide (2 ml) and stirred at 80 ° C for 4 hours. After the mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, washed with a saturated saline solution, dried (anhydrous sodium sulfate), and then 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} -1,3,2-dioxoborolane 52 Omg.

Ή-NMR (CDC 1 TMS)

5 (ppm): 9.3 (1 H, s), 8.8 (1 H, d), 8.5 (1 H, s), 8.2 (1 H, d), 8.0 (1 H, d), 7.8 (1H, d), 7.5 (1H, t), 1.37 (12H, s) Reference production example 7

4-Methylpyrimidine 5. Og (53.1 mmo 1), N-bromosuccinimide 1.1.34 g (63.7 mmo 1), 1,1'-azobis (cyclohexane power rubonitrile A mixture of 0.65 g (2.7 mmo 1) and 100 ml of carbon tetrachloride was stirred at 76 ° C. for 8 hours. After cooling the mixture, insolubles were filtered off. After concentrating the filtrate, the residue and ethyl acetate are mixed, washed successively with water and saturated saline, and dried.

After (anhydrous sodium sulfate), the mixture was concentrated.

The residue obtained, 1.24 g (7.17 mmo 1) of 3-bromophenol, 1.5 g (10.9 mmo 1) of potassium carbonate and N, N-dimethylformamide (3 Oml) And stirred at 60 ° C. for 8 hours. After the mixture was cooled to room temperature, water was added, extracted with t-butyl methyl ether, washed with water, washed with saturated saline, dried (anhydrous sodium sulfate), and then concentrated under reduced pressure. The residue was subjected to silica gel column chromatography to give 3-bromo-1- (4-pyrimidinyl) methoxybenzene 2

68 mg were obtained.

δ (ppm): 9.20 (1 H, s), 8.76 (1 H, d, J = 5.1 Hz) 754 (1 H, d, J = 4.8 Hz), 7. 13-7.18 (3H, m), 688-6.92 (1H, m, J = 4.8 Hz), 5.15 (2H, s) Reference Production Example 8

(1) 2-Methinole-5-bromopenzinolebromide 30.Og (0.114mo1), dimethinolemalonic acid produced according to the method described in JP-A-111-217579 A mixture of 15.77 g (0.119 mol), 95% sodium methoxide 6.45 g (0.113mo1) and methanol 300 ml was stirred at 65 ° C for 4 hours, It was cooled and the solvent was distilled off. The obtained residue was extracted with methyl t-butyl ether. The resulting 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 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).溶出 0: 100) to give 17.21 g of dimethyl 2- (2-methyl-15-bromo-benzyl) malonic acid.

(2) The obtained dimethyl 2- (2-methinolate 5-bromo-benzyl) malonic acid 17.21 g (54.6 mmo 1), lithium chloride 4.63 g (103 mmo 1), water 2. A mixture of 2 ml and 150 ml of dimethyl sulfoxide was 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 = Elution at 100: 0 to 0:10:00) to give 6.68 g of methyl 3_ {2-methyl-5-bromo-phenyl} propionate.

(3) The resulting 3- {2-methyl-5-bromo-phenyl} methyl propionate 6.89 g (26.0 mm o 1), methyl formate 15.6 g (260 mm o 1) And a mixture of ethylenedalicol dimethyl ether 15 ml in 30% potassium hydride (7.64 g, 57.1 mm o 1) cooled to below 8 ° C over a period of 00 min. It was added dropwise to a mixture of 67 ml of dimethyl ether. The resulting mixture was heated to room temperature, stirred for 3 hours, poured into water, and methyl t-butyl was added. Extracted with 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-12- {2-methinolay 5-bromo-1-benzyl} acrylic acid 6.lg I got

(4) Obtained crude methyl 3-hydroxy-2- {2-methyl-5-bromobenzyl} acrylic acid 6.lg (2 lmmo 1) _N trimethylsilyldiazomethane 2M hexane solution 2 lm l (42 mm o 1) and 40 ml of dimethoxetane were stirred at room temperature overnight, then acetic acid and water were added, and the mixture was concentrated. The residue was subjected to silica gel column chromatography (n-hexane: ethyl acetate = 100: 0). To 0: 100 elution) to give 5.36 g of methyl 3-methoxy-2- (2-methyl-5-bromo-benzyl) acrylic acid.

_{'H-NMR (CDC 1 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 compound of the present invention are shown in Tables 1 to 12 together with the compound numbers.

Formula (1 1 1)

Compound represented by

[Table 2]

v A Y 1

K K K 3 Κ Κ K 丄ー t) Shi H Shi H hsnU Π Η Η H

11 ||, J Lu

S i s H 4 ~ L Linolem n n Η Η H

1 o

-28 shi H shi H l- \ ^J y HH Η Η H

1 29 Shi H Shi-H o-Py H H Η Η H

1-30 CH then H 4-ry H H Η Η H

1-31 CH CH 2—Elbow; H H Η Η H c

1-32 CH H H 4 ヒ Η H H H Η Η H l-33 CH H H 5 ヒ 5 H H H Η Η H

,

l-34 CH CH Nano HH Η Η H l-35 CH CH N0 ₂ HH Η Η H

1-36 CH CH H r H Η Η H

1-37 CH CH H L 丄 H Η Η H l-38 CH then H H Br H Η Η H n,

1 39 39 H H H 丄 H Η Η H

1-40 CH CH H Me H Η Η H A u

1-41 CH H H CF ₃ H Η Η H

> \

1-42 H H ₃ H H ₃ Η Η H υ

1-43 H H H Η Π H υ

1 44 LH then H b r Η H cr υ υ

1 1 45 Γ Γ Γ Η Π H 丄 4b ii ii M M Π Π π π Me u n

1-47 CH CH BnO H Η Η Me H

1-48 CH CH H F Η Η Me H

1-49 CH CH H H Η Η OMe H

1-50 CH CH HF Η Η OMe H 1 1 1 I 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Lin

--a -J> σ> Oi σ¾ cn cn cn on n cn cn CD CO cn o O CO-] n co:

X: No.

Cd m n m cn.

a CD> 1 1 CD CD

〇 o 〇 o CD

C

3: = n

S: n e ΓΠ: o

O CD CD CD

O =,: e re en: rn r re:: rn::: a:: r

[Table 6]

Equation (1-2)

Compound.

[Table 8]

XYR ¹ R ² R ³ R ⁶ R ⁷ R ⁸

2-26 CH CH BnO H H H H H

2-27 CH CH 4-PyCH ₂ 0 HHHHH

2-28 CH CH 2-Py H H H H H H

2-29 CH CH 3-Py H H H H H

2-30 CH CH 4-Py H H H H H

2-31 CH CH 2-pyrimidinyl H H H H H

2-32 CH CH 4 -pyrimidinyl H H H H H

2-33 CH CH 5 -pyrimidinyl H H H H H

2-34 CH CH Ciano H H H H H

2-35 CH CH NO, H H H H H

2-36 CH CH H F H H H H

2-37 CH CH H CI H H H H

2-38 CH CH H Br H H H H

2-39 CH CH H I H H H H

2-40 CH CH H Me H H H H

2-41 CH CH H CF ₃ HHHH

2-42 CH CH CF ₃ H CF ₃ HHH

2-43 CF CH H H H H H H H

2-44 CH CH F H F H H H

2-45 CF CF F F F H H H

2-46 CH CH H H H H Me H

2-47 CH CH BnO H H H Me H

2-48 CH CH H F H H Me H

2-49 CH CH H H H H OMe H

2-50 CH CH HFHH OMe H HHHH Hd NN

H H H H H Hd N N L-Z

H H H H H OMd N N L-Z

H H H H H 0 "0 N N ZL-Z

H H H H H 013 N N IL-Z

H H H o H N N OL-Z

H H H H H N N 69-2

H H H H H N N 89-2

H H H H H N N 19-Z

H H H H H N N 99-Z

H H H H N N 99-Z

H H H H H N N f9-Z

H H H N N £ 9-Z

H H H H N N Z9-Z

H H H H N N 19-2

H H H H H N N 09-2

H H H H H N N 69-2

H H H 13 H 13 N N 89-2

H H H H 13 H N N L -Z

H H H H H 13 N N 99-Z

H H H d d d N N 92-Z

H H H d H d N N -Z

H H H H d H N N £ 2-Z

H H H H H d N N Z2-Z

H H H H H H N N

₈ H ₉ H _ε Η _Z H with X

[6 挲]

99

080tO / 00df / XDd S00 / 10 OM [Table 10]

XYRRRRR 'R ⁸

2-76 N N H H H H Me H

2-77 N N H H H H O e H

2-78 N CH H H H H H H

2-79 N CH F H H H H H

2-80 N CH H F H H H H

2-81 N CH H H F H H H

2-82 N CH C1 H H H H H

2-83 N CH H CI H H H H

2-84 N CH H H CI H H H

2-85 N CH C1 H CI H H H

2-86 N CH Me H H H H H

2-87 N CH H Me H H H H

2-88 N CH H H Me H H H

2-89 N CH Me H Me H H H

2-90 N CH Et H H H H H

2-91 N CH CF ₃ HHHHH

2-92 N CH H CF ₃ HHHH

2-93 N CH HH CF ₃ HHH

2-94 N CH MeO H H H H H

2-95 N CH EtO H H H H H

2-96 N CH BnO H H H H H

2-97 N CH H H H H Me H

2-98 N CH CF ₃ HHH Me H

2-99 N CH H H H H OMe H

2-100 N CH CF ₃ HHH OMe H

[Table 12]

In the above table, Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, Ph represents a phenyl group, Py represents a pyridyl group, and B represents a pyridyl group. n means a benzyl group. Also, n- is normal, i- is iso-, sec- is secondary, and t- is tertiary. Next, formulation examples are shown. The parts represent parts by weight, and the compounds of the present invention are indicated by the numbers shown in Tables 1 to 12 above.

Formulation Example 1

Compound of the Present Invention 11 :! Approximately 50 parts of each of 128 and 2-1 to 2-128, 3 parts of calcium ligninsulfonate, 2 parts of sodium diallyl sulfate, and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed. Obtain each wettable powder.

Formulation Example 2

Compounds 1-1 of the present invention: 1-128 and 2-1-2-28, each containing 20 parts of sonolebitan trioleate, and 1.5 parts of polybutyl alcohol, Aqueous solution

After mixing with 28.5 parts and finely pulverizing by a wet grinding method, 40 parts of an aqueous solution containing 0.05 part of xanthan gum and 0.1 part of aluminum magnesium silicate was added thereto, Further, 10 parts of propylene glycol is added and mixed with stirring to obtain each flowable preparation.

Formulation Example 3

The compound of the present invention 1-1-1 to 1-28 and 2-1 to 2-128 each 2 parts, force ink 188 and talc 10 parts are thoroughly ground and mixed to give each powder. obtain.

Formulation Example 4

Compounds of the Present Invention 1-1—I: I — 128 and 2— :! ~ 2-1 2 8 5 parts each, Polio Each of the emulsions is obtained by thoroughly mixing 14 parts of xylethylenestyrylphenyl ether, 6 parts of dodecylbenzenesulfonic acid and 7 parts of xylene. Formulation Example 5

Compound of the Present Invention 11 :! ~ 1— 1 28 and 2— :! 2 parts each of 2 to 128, synthetic 1 part hydrous silicon oxide, 2 parts calcium ligninsulfonate, 30 parts bentonite and 65 parts kaolin clay, pulverize and mix well, add water and knead well. Each granule is obtained by drying the granules.

Formulation Example 6

Compound of the Present Invention 11 :! 11-128 and 2-1-2-128, 10 parts of each, 35 parts of white carbon containing 50 parts of a poly (ethylene glycol) ether ammonium salt, and 55 parts of water are mixed and wet-processed. Each flowable preparation is obtained by finely pulverizing by a pulverization method. Next, Test Examples show that the compounds of the present invention are useful as agricultural and horticultural fungicides. The compounds of the present invention are indicated by the numbers shown in Tables 1 to 12.

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 survey 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)

Plastic pots were filled with sandy loam, and rice (Nipponbare) was sown and grown in a greenhouse for 20 days. Thereafter, the compounds of the present invention 1-1, 1-23, 1-36, 1-40, 1-11, 1-13, 1-2, 2-1, 1-32, 1_51, 1-192, 1 1 9 1, 1—27, 1 1 25, 1 -6, 1 1 16, 1—45, 1 1 59, 1—1 1 1, 1—1 1 2, 1—68, 1—69, 1 1 62, 1—73, 1—72, 1—

86, 1-64, 1-66, 1- 1 1 3, 1-115, 1-82, 1-94, 1-114, 2-86, 2-91, 2-82, 2-94, Each of 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, compounds 1-45, 2-86, 2-82, 2-94 of the present invention). And 2_83 (200 ppm) and sprayed so that it adheres well 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 environment at 28 ° C for 6 days, and the control effect was investigated. As a result, the compound of the present invention 1-1, 1-23, 1-136, 1-40, 1-11,1-113, 1-2, 2-1, 1-32, 1-151, 1-- 92, 1—91, 1—27, 1—25, 1—6, 1—16,

1—45, 1—59, 1—1 1 1, 1—1 12, 1—68, 1—69, 1—62, 1—73, 1—72, 1—86, 1—64, 1—66 , 1—1 13, 1—1 15,

1-182, 1-94, 1-114, 2-86, 2-91, 2-82, 2-94,

The lesion area on the plants in the 2-83 and 1-78 treated areas was less than 10% of the lesion area in the untreated area. Test example 2: Wheat powdery mildew control test (Therapeutic effect)

A plastic pot was filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. The wheat seedlings that had developed the second leaf were sprinkled with wheat powdery mildew spores and inoculated. After inoculation, they were placed in a greenhouse at 23 ° C for 2 days. Compound 11 of the present invention Each of 1, 1, 23, 1-36, 1-40 and 1-32 was made into a flowable preparation according to Preparation Example 6, and then diluted with water to a predetermined concentration (500 ppm). Was sprayed on the leaves of wheat inoculated with the powdery mildew fungus so as to sufficiently adhere to the leaves. After spraying, and after 7 days under lighting, the control effect was investigated. As a result, the area of the lesion on the plant of the compound of the present invention 11-1, 1-23, 1-36, 1-40 and 1-32 treatment area was 10% or less of the lesion area of the non-treatment area. . Test example 3: Wheat powdery mildew control test (preventive effect)

Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. Compounds of the present invention 1 1 1 1 1 1 1 1 2 1 2 1 2 1 1 51 1 92 1 1 91 1 27 1 25 1 6 1 1 16 1 5 9, 1—111, 1—1 12, 1—68, l-69 1—62, 1—73, 1—72, 1—86, 1—64, 1—66, 1—113, 1—1 15, 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 (500 ppm; water) of the compound of the present invention 2-86, 2-82, 2-9 with water. 4 and 2_83 were diluted to 200PPII1) and sprayed so that the second leaf was sufficiently attached 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 lighting for 7 days, and the control effect was examined. As a result, the compounds of the present invention 1 1 1 1 1 1 1 1 3 1 2 1 2 1 2 1 2 1 1 1 1 2 1 2 1 2 1 2 1 2 1 2 1 2 1 — 59, 1— 1 1 1, 1— 1 12, 1—68, 1—69, 1—62, 1—73, 1—72, 1—86, 1—64, 1—66, 1—1 13 , 1—115, 1—82, 1—94, 1—1 14, 2—3, 2—37, 2—68, 2—86, 2

— The areas of lesions on plants in the treated plots of 91, 2-82, 2-94, 2-83, and 1-78 were less than 10% of the lesion area in the untreated plot. Test example 4: Wheat rust control test (preventive effect)

Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. Compound of the present invention 1-1, 1-23, 1-36, 1-40, 1-11-1, 1-11, 1-12-2-1, 1-132, 1-151, 1-192, 1-1 91,

1 1 27, 1 1 25, 1-6, 1 1 16, 1 1 45, 1 1 59, 1—1 1 1, 1

— 1 12, 1 1 68, 1 -69, 1-62, 1 1 73, 1 1 72, 1 -86, 1 1 64, 1-66, 1-1 13, 1-1 15, 1-82, 1—94, 1—114,

Each of 2-3, 2-37, 2-68, 2-86, 2_91, 2-82, 2-94, 2-83 and 1-78 was made into a floor veneer formulation according to Formulation Example 6, and then water was added. Dilute to the specified concentration (500 ppm; however, the compounds of the present invention 1-45, 2-86, 2-82, 2-94 and 2-83 are 200PPII1), and dilute it so that it adheres well to the wheat leaf surface. Foliage was sprayed. After spraying, the plants were air-dried and inoculated with spores of wheat leaf rust. After the seeding, they were first placed in a dark and humid environment at 23 ° C for 1 day, and then put in illumination for 6 days. As a result, the compounds of the present invention 1_1, 1-23, 1-136, 1-140, 1_1 1, 1-13, 1-1-2, 2-1, 1-132, 1_51, 1-192, 1-91, 1 — 27, 1-25, 1-6, 1-16, 1-45, 1_59, 1- 1 1 1, 1—1 1 2, 1—68, 1—69, 1—6 2, 1—73, 1—7 2, 1—8 6, 1—64, 1—6 6, 1—1 1 3, 1—1 1 5, 1—8 2, 1—94, 1—1 1, 4, 2, 3, 2, 37, 2—68, 2—86, 2-91, 2—82, 2 — The lesion area on plants in the 94, 2-83 and 1-78 treatment areas was less than 10% of the lesion area in the untreated area. Test Example 5: Wheat blight control test (preventive effect)

Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. Compound of the present invention 1-1, 1-123, 1-136, 1-40, 1-32, 1-151, 1-192, 1-91, 1-127, 1-145, 1-1 66, 1 1 1 1

3, 1-94, 1-114, 2-91, 2-91, 2-94, 2-83, and 1-78 were converted into flowable preparations according to Preparation Example 6, and then water At the specified concentration

(200 ppm for the compounds of the present invention 1-45, 2-82, 2-94 and 2-83) and sprayed on the foliage so as to sufficiently adhere to the wheat leaf surface. After spraying, the plants were air-dried and sprayed with a spore suspension of wheat wilt. After inoculation, they were first placed in dark and humid at 15 ° C for 40 days, and then put under lighting for 7 days. As a result, the compounds of the present invention 1-1, 1-23, 1-36, 1-40, 1-132, 1-151, 1-192, 1-29-1, 1-27, 1-45, 1-66, 1--11, 1-94, 1-114, 2-91, 2-82, 2-94, 2-83 and 1-78 Is 10 of the lesion area in the untreated plot. /. It was as follows. Test Example 6: Wheat eye spot control test (preventive effect)

Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown 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, 1-1 1 1, 1-1 1 2, 1-1 68, 1-69, 1-62, 1 -86, 1-64, 1-1 After making 1, 3, 68 and 2-91 as flowable preparations according to Preparation Example 6, each was diluted with water to a predetermined concentration (500 _PPm ) and adhered sufficiently to the wheat leaf surface. Foliage was sprayed as if to do. Plants after spraying Was air-dried, and a mashed potato medium containing spores of wheat eye spot fungus was inoculated into the strain. After the seeding, the plants were placed at 15 ° C, in a dark and humid environment for 7 days, and then placed under illumination for 4 days. As a result, the compound of the present invention 1-1, 1_23, 1-11-1, 1-113, 1-2, 1-132, 1-6, 1_59, 1-111, 1-11, 1- 68, 1—69, 1—62, 1—86, 1—64, 1—1 1 3, 2, —68 and

The lesion area on the plants in the 2-91 treatment plot was less than 10% of the lesion area in the untreated plot. Test example 7: Grape downy mildew control effect test (preventive effect)

Fill plastic pots with sandy loam, sow grapes (berry A), and in a greenhouse

Grow for 40 days. Compound of the present invention 1-1, 1-23, 1-36, 1-140, 1-13, 2-1, 1-132, 1-151, 1-192, 1-91, 1-27, 1-1 2 5, 1 -6, 1 1 16, 1 -45, 1 1 59, 1-1 1 1, 1-1 12, 1-6 8, 1 -69, 1 -62, 1-73, 1-72 , 1—86, 1—64, 1—66, 1—1 1 3, 1—1 1 5, 1, 1—82, 1—94, 1—1 14, 2—3, 2—37,

2 68, 2 86, 2-91, 2-82, 2 94, after the flowable formulation of each of the 2-83 and 1-78 according to Formulation Example 6, water at a predetermined concentration (200 ppm _m) And sprayed it so that it adheres well to the vine leaf surface. After spraying, the plants were air-dried and spray-inoculated with a zoosporangial suspension of grape downy mildew. After the inoculation, the plants were placed at 23 ° C and a high humidity for one day, and then placed in a greenhouse for 6 hours. As a result, the compounds of the present invention 1_1, 1_23, 1-36, 1-40, 1-11, 2-11, 1-132, 1-151, 1-192, 1-91, 1-127, 1 1 25, 1 1 6, 1 1 16, 1 1 45, 1 -59, 1-1 1 1, 1-1 12, 1-1 68, 1-69, 1 -62 1-73, 1-72, 1 One 86, One One 64, One 66, One 113, One 115, One 82, One 94, One 114, Two Three, Two 37, Two 68,

The lesion area on the plants in the 2-86, 2-91, 2-82, 2-94, 2-83 and 1-78 treatment plots was less than 10% of the lesion area in the untreated plot. Test example 8: Test for controlling the effect of cucumber powdery mildew (preventive effect) The pots were filled with sandy loam, sown with Kiuri (Sagami Hanjiro), 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—1 91, 1-125, 1-6, 1-16-1, 1-159, 1-11-1, 1-112, 1-68, 1-69, 1-62, 1-73, 1-72 and Each of 1-86 was made into a flowable formulation according to Formulation Example 6, diluted with water to a predetermined concentration (500 ppm), and sprayed with foliage so as to sufficiently adhere to the leaves of the cucumber. After spraying, the plants were air-dried and inoculated with the spores of Cucumber powdery mildew. After 12 days at 23 ° C after 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, 1-1-3, 1-2, 2-1, 1-132, 1-51, 1-1 92, 1-19-1, 1-125, 1-6, 1-16-1, 1-59, 1-11-1, 1-11-12, 1-6, 1-169, 1-162, 1-- The lesion area on the plants in the 73, 1-72 and 1-86 treatment areas was less than 10% of the lesion area in the untreated area.

Effect of the Invention The compound of the present invention has excellent plant disease controlling effect.

Claims

The scope of the claims

1. Equation (1)

Wherein W represents an oxygen atom or a CH ₂ group,

X represents ^one C R ′ group or a nitrogen atom,

Y represents CR ⁵ or a nitrogen atom,

R ^l , R ² and R ³ are the same or different,

An optionally substituted C1-C1 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,

An optionally substituted C 1 -C 9 heteroaryl group,

An optionally substituted C1-C6 alkoxy group,

A phenoxy group which may be substituted,

An optionally substituted C 1 -C 9 heteroaryloxy group,

An optionally substituted C2-C6 alkoxycarbonyl group,

An optionally substituted C1-C6 alkylthio group or

Represents an optionally substituted C3-C30 trialkylsilyl group,

R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are the same or different and are a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group or a C;! -C 4 alkoxy group Represents ]

An atrial acid derivative represented by the formula:

2. The acrylic acid derivative of the formula (1) according to claim 1, wherein W is an oxygen atom.

3. The acrylic acid derivative of the formula (1) according to claim 1, wherein W is a CH ₂ group.

4. In RR ² and R ³ ,

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 C1-C6 alkoxy group,

A phenoxy group which may be substituted,

An optionally substituted C1-C9 heteroaryloxy group,

An optionally substituted C2-C6 alkoxycarbonyl group,

An optionally substituted C1-C6 alkylthio group, and

An optionally substituted C3-C30 trialkylsilyl group is

A group which may be substituted with one or more same or different groups selected from the following group A,

The optionally substituted C 6 -C 10 aryl group or the optionally substituted C 1 -C 9 heteroaryl group is the same or different one or more selected from the group consisting of the following groups A and B The acrylic acid derivative of the formula (1) according to any one of claims 1 to 3, wherein the acrylic acid derivative is a group which may be substituted with a group of the formula (1).

Group A

(Halogen atom, C1-C10 alkyl group, C3-C20 trialkylsilyl group,

C1-C10 haloalkynole group, C3-C10 cycloazoalkyl group, C3-C10 cycloalkenyl group, C1-C10 alkoxy group, C1-C10 haloalkoxy group, C1-C10 alkynolethio group , C1-C10 haloalkylthio, C2-C10 alkoxycarbonyl, phenyl, pyridyl, pyrimidyl, phenoxy Group, benzyloxy group, pyridine-12-yloxy group (wherein each of the phenyl group, pyridyl group, pyrimidyl group, phenoxy group, benzyloxy group and pyridine-12-yloxy group is a halogen atom, C 1 -C It may be substituted with one or more groups selected from the group consisting of 6 alkyl groups, C 1 -C 6 alkoxy groups, trifluoromethyl groups and cyano groups.), Amino groups, hydroxyl groups, cyano groups and nitro groups Base}

Group B

{Methylenedioxy group and difluoromethylenedioxy group (each of the methylenedioxy group and difluoromethylenedioxy group binds to two adjacent carbon atoms in the aryl moiety)}

5. Acrylic acid derivatives of the formula (1) according to any one of claims i~4 at least any one of hydrogen atoms of the RR ² and R ^3. 6. At least ^two of RR ² and R ³ are hydrogen atoms.

An acrylic acid derivative of the formula (1) according to any one of 1 to 4.

7. Akuriru acid derivatives of the formula (1) according to any one of claims 1~4 R ^6, R ⁷ and R ⁸ are hydrogen atoms.

8. The acrylic acid derivative of the formula (1) according to any one of claims 1 to 7, wherein X and Y are CH groups.

9. The acrylic acid derivative of the formula (1) according to any one of claims 1 to 7, wherein X and Y are nitrogen atoms.

10. The acrylic acid derivative of formula (1) according to any one of claims 1 to 7, wherein X is a nitrogen atom and Y is a CH group.

1 1. A plant disease controlling agent comprising the atalylic acid derivative of the formula (1) according to any one of claims 1 to 10 as an active ingredient.

2. Expression [XX,]

Wherein, A ¹ is B (OH) ₂ group, B (OR ⁹⁾ represents ₂ group or R ^ie ₃ Sn group, the force R ⁹ represents a C 1 through C 1 0 alkyl group ,, two R ⁹ Represents a CH ₂ CH ₂ _ group or a C (CH ₃ ) ₂ C (CH ₃ ) ₂ — group,

W represents an oxygen atom or a CH ₂ group,

X represents a CR ⁴ group or a nitrogen atom,

Y represents CR ⁵ or a nitrogen atom,

RR ^5, RR ⁷ and R ⁸ are the same or different, represent a hydrogen atom, a halogen atom, C 1 through C 4 alkyl groups, C 1 through C 4 haloalkyl group or a C 1 through C 4 alkoxy groups. ] The intermediate compound shown by these.

13. The compound of the formula [XX '] according to claim 12, wherein W is an oxygen atom.

14. The compound of the formula [XX ′] according to claim 12, wherein W is a CH ₂ group.

5. Equation [I,]

{Wherein, W, X, Y, R \ R 2, R 3, R 6, R 7 and R ⁸ are as defined in claim 1 Far Means the meaning of } And a compound represented by the formula

CH ₃ — Yes

{Wherein, L ¹ represents a leaving group. } In the presence of a base or a compound represented by the formula

N ₂ CHL ³

{Wherein L ³ represents a trialkylsilyl group. The method for producing an acrylic acid derivative of the formula (1) according to claim 1, wherein the compound is reacted with a compound represented by formula (1).

16. L ¹ represents a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a methanesolephoninoleoxy group, a trifrenoleolomethaneszolephonyloxy group,

16. The production method according to claim 15, wherein L ³ represents a trimethylsilyl group.

17. Expression [XX,]

(Wherein W represents an oxygen atom or a CH ₂ group,

R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group or a C 1 -C 4 alkoxy group, and A ¹ is B ( OH) ₂ group, B (oR ⁹⁾ represents a ₂ group or R ^w ₃ Sn group.

Here, R ⁹ and R ¹⁰ represent a C ¹ to C 10 alkyl group, and two R ⁹ may represent one CH ₂ CH ₂ — group or one C (CH ₃ ) ₂ C (CH ₃ ) ₂ — group Good. } And the following formula [XXI]:

[XX I]

{In the formula, X represents a CR ⁴ group or a nitrogen atom,

Y represents CR ⁵ or a nitrogen atom,

R \ R ² and R ³ are the same or different,

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,

An optionally substituted C 1 -C 9 heteroaryl group,

An optionally substituted C1-C6 alkoxy group,

A phenoxy group which may be substituted,

An optionally substituted C1-C9 heteroaryloxy group,

An optionally substituted C2-C6 alkoxycarbonyl group,

An optionally substituted C1-C6 alkylthio group or

Represents an optionally substituted C3-C30 trialkylsilyl group,

R ⁴ is the same or different and represents a hydrogen atom, a halogen atom, a C1-C4 alkyl group, a C1-C4 haloalkyl group or a C1-C4 alkoxy group,

L ¹ represents a leaving group. } In the presence of a palladium catalyst. A process for producing an acrylic acid derivative of the formula (1).

1 8. Formula [II ']:

{Wherein, L ² represents a leaving group, W represents an oxygen atom or a CH ₂ group,

R ⁶ , R ⁷ and R ⁸ are the same or different and represent a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 haloalkyl group or a C 1 -C 4 alkoxy group. } And a compound of the following formula [III]:

cm]

{In the formula, X represents a CR ⁴ group or a nitrogen atom,

Y represents CR ⁵ or a nitrogen atom,

RR ² and R ³ are the same or different,

An optionally substituted C1-C10 alkyl group,

An optionally substituted C2-C10 alkenyl group,

An optionally substituted C 2 -C 10 alkynyl group,

An optionally substituted C3-C10 cycloalkyl group,

An optionally substituted C5-C10 cycloalkenyl group,

An optionally substituted C6-C10 aryl group,

An optionally substituted C 1 -C 9 heteroaryl group,

An optionally substituted C1-C6 alkoxy group,

A phenoxy group which may be substituted,

An optionally substituted C1-C9 heteroaryloxy group,

An optionally substituted C2-C6 alkoxycarbonyl group,

An optionally substituted C1-C6 alkylthio group or Represents an optionally substituted C3-C30 trialkylsilyl group,

A ² represents B (OH) ₂ groups, B (OR ⁹ ) ₂ groups or S n R ^w ₃ groups,

R ⁹ and R ¹⁰ represent a C1-C10 alkyl group, and two R ⁹ may represent one CH ₂ CH ₂ — group or one C (CH ₃ ) ₂ C (CH ₃ ) ₂ — group . 2. The method for producing an acrylic acid derivative of the formula (1) according to claim 1, wherein the compound represented by the formula (1) is reacted in the presence of a palladium catalyst.

19. A method for controlling plant diseases using the acrylic acid derivative of the formula (1) according to claim 1 as an active ingredient.

20. Use of the atalylic acid derivative of the formula (1) according to claim 1 as a plant disease controlling agent.