JP2002053560A - Uracil compound and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound having high herbicidal activity. SOLUTION: This compound is an uracil compound of the general formula [I] (wherein, W is an oxygen atom or the like; Y is an oxygen atom or the like; R1 is a 1-3C alkyl or 1-3C haloalkyl; R2 is a 1-3C alkyl; R4 is H or methyl; R5 is 1-6C alkyl or the like; X1 is a halogen atom or the like; X2 is H or the like; and X3 and X4 are each H or the like). Herbicides each comprising the above compound as the active ingredient are provided.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to uracil compounds and uses thereof.

[0002]

An object of the present invention is to provide a compound having an excellent herbicidal activity.

[0003]

At present, a large number of herbicides are commercially available and used. However, the weeds to be controlled are of many types and their outbreaks are long-term, so that they have a higher herbicidal effect and a wide range of killing. There is a need for a herbicide that has a grass spectrum and does not cause phytotoxicity problems for crops. JP-A-63-
Japanese Patent No. 41466 discloses that certain phenyluracil compounds have herbicidal activity, but these phenyluracil compounds do not have sufficient performance as herbicides. Also, PCT application published specification WO 97-01541, PCT application published specification WO 9
No. 8-41093 discloses that certain substituted phenoxyphenyluracil compounds have herbicidal activity, but these substituted phenoxyphenyluracil compounds do not have sufficient performance as herbicides. The present inventors have conducted intensive studies to find a compound having an excellent herbicidal activity. As a result, they have found that a uracil compound represented by the following general formula [I] has an excellent herbicidal activity, and reached the present invention. That is, the present invention provides a compound represented by the general formula [I]:

Embedded image Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Y represents an oxygen atom, a sulfur atom, an imino group or a C1-C3 alkylimino group, R ¹ represents a C1-C3 alkyl group or a C1-C3 haloalkyl group, and R ² represents a C1-C1 alkylimino group. R ⁴ represents a hydrogen atom or a methyl group; R ⁵ represents a hydrogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-alkyl group; X ¹ represents a halogen atom, a cyano group, or a nitro group; X ² represents a hydrogen atom or a halogen atom;
X ³ and X ⁴ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3- C6 haloalkynyl group, C1-C6 alkoxy C1-C6 alkyl group,
Represents a C1-C6 alkoxy group, a C1-C6 haloalkoxy group, a C1-C6 alkoxycarbonyl C1-C6 alkoxy group or a cyano group. (Hereinafter referred to as the compound of the present invention) and a herbicide containing the same as an active ingredient.

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

Embedded image Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, X ¹ represents a halogen atom, a cyano group, a nitro group, X ² represents a hydrogen atom or a halogen atom, X ³ And X ⁴ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3-C6 halo. Alkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkyl group Carboxylate a carbonyl C1-C6 alkoxy group or a cyano group. An aniline compound represented by the general formula [XXXIV]

Embedded image Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, R ¹⁸ represents a C1-C6 alkyl group or a phenyl group, X ¹ represents a halogen atom, a cyano group, a nitro group , X ² represents a hydrogen atom or a halogen atom, and X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 Haloalkenyl group, C3-C6 alkynyl group, C3-C6 haloalkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alcohol Shi group, a C1-C6 haloalkoxy group, C1-C6 alkoxycarbonyl C1-C6 alkoxy group or a cyano group. A compound represented by the formula:
And the general formula [XXXIII]

Embedded image Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, X ¹ represents a halogen atom, a cyano group, a nitro group, X ² represents a hydrogen atom or a halogen atom, X ³ And X ⁴ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3-C6 halo. Alkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkyl group Alkoxy represents a carbonyl C1-C6 alkoxy group or a cyano group. ] Is also provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, C represented by W
Examples of the 1-C3 alkylimino group include a methylimino group,
And C1-C3 represented by Y, such as an ethylimino group.
Examples of the alkylimino group include a methylimino group and an ethylimino group. The C1-C3 alkyl group represented by R ¹ means a methyl group, an ethyl group, a propyl group, or an isopropyl group, and a C1-C3 haloalkyl group. Is
Bromomethyl group, chloromethyl group, fluoromethyl group,
Dichloromethyl group, trichloromethyl group, difluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 1,1-difluoroethyl group, 3,3,3-trifluoropropyl group and the like, and represented by R ² C1-
The C3 alkyl group, a methyl group, an ethyl group, a propyl group, means an isopropyl group, C1-C represented by R ⁵
Examples of the 6 alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an s-butyl group, and a t-butyl group. As the C1-C6 haloalkyl group, a bromomethyl group, a chloromethyl group, Fluoromethyl group, dichloromethyl group, trichloromethyl group, difluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,2,2-trichloroethyl group, 3,3
3-trifluoropropyl group, 3,3,3-trichloropropyl group and the like. Examples of the C3-C6 alkenyl group include an allyl group, a 1-methylallyl group, a 1,1-dimethylallyl group, a 2-methylallyl group, 1-butenyl group, 2
-Butenyl group, 3-butenyl group and the like, and C3-C
6 haloalkenyl groups include 1-chloroallyl group, 1
-Bromoallyl group, 2-chloroallyl group, 3,3-dichloroallyl group and the like. Examples of the C3-C6 alkynyl group include a 2-propynyl group, a 1-methyl-2-propynyl group and a 1,1-dimethyl-2 group. -Propynyl group, 2-butynyl group, 3-butynyl group, 1-methyl-2-butynyl group and the like, and as the C3-C6 haloalkynyl group,
3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 1-fluoro-2-propynyl group, 1-chloro-2-propynyl group, 1-bromo-2-propynyl group, 1-chloro-2 -Butynyl group and the like;

[0006] The C1-C6 alkyl group represented by R ^18, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, s- butyl group, a t- butyl group and the like are exemplified,

The halogen atom represented by X ¹ means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and X ²
The halogen atom represented by is a fluorine atom, a chlorine atom,
A halogen atom represented by X ³ or X ⁴ means a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and a C1-C6 alkyl group includes a methyl group and an ethyl group. Propyl group, isopropyl group, butyl group, s-butyl group, t-butyl group and the like. Examples of the C1-C6 haloalkyl group include a bromomethyl group, a chloromethyl group, a fluoromethyl group, a dichloromethyl group, and a trichloromethyl group. , Difluoromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, trifluoromethyl group, pentafluoroethyl group, 2-fluoroethyl group, 1,1-difluoroethyl group, 2,
Examples thereof include a 2,2-trichloroethyl group, a 3,3,3-trifluoropropyl group, a 3,3,3-trichloropropyl group, and the C3-C6 alkenyl group includes an allyl group, a 1-methylallyl group, , 1-dimethylallyl group,
Examples thereof include a 2-methylallyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group. Examples of the C3-C6 haloalkenyl group include a 1-chloroallyl group, a 1-bromoallyl group, a 2-chloroallyl group, 3-dichloroallyl group and the like, and C3-C6 alkynyl group includes 2
-Propynyl group, 1-methyl-2-propynyl group, 1,
1-dimethyl-2-propynyl group, 2-butynyl group, 3
-Butynyl group, 1-methyl-2-butynyl group and the like. Examples of the C3-C6 haloalkynyl group include a 3-chloro-2-propynyl group, a 3-bromo-2-propynyl group,
A 1-fluoro-2-propynyl group, a 1-chloro-2-propynyl group, a 1-bromo-2-propynyl group, a 1-chloro-2-butynyl group, and the like, and a C1-C6 alkoxy C1-C6 alkyl group. Is a methoxymethyl group,
2-methoxyethyl group, 1-methoxyethyl group, 3-methoxypropyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxypropyl group, isopropoxymethyl group, 2-isopropoxyethyl group, and the like, C1
-C6 alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, s
-Butoxy group, t-butoxy group and the like, and C1-C
Examples of the 6 haloalkoxy group include a chloromethoxy group, a bromomethoxy group, a dichloromethoxy group, a trichloromethoxy group, a trifluoromethoxy group, a 2-fluoroethoxy group, and a 2,2,2-trichloroethoxy group.
The C1-C6 alkoxycarbonyl C1-C6 alkoxy group includes a methoxycarbonylmethoxy group, an ethoxycarbonylmethoxy group, a 1-methoxycarbonylethoxy group, a 1-ethoxycarbonylethoxy group, a 2-methoxycarbonylethoxy group, a 2-ethoxycarbonylethoxy group. And the like.

In the compounds of the present invention, from the viewpoint of herbicidal activity, R ¹ is a methyl group substituted with a fluorine atom (for example, trifluoromethyl group, chlorodifluoromethyl group, difluoromethyl group, etc.) or a fluorine atom. Ethyl group (for example, pentafluoroethyl group, 1,
1-difluoroethyl group, etc.), more preferably a trifluoromethyl group. Among them, preferably a methyl group or an ethyl group for R ^2, and more preferably a methyl group. Among them, for R ⁵ is C1-C3 alkyl group ( For example, a methyl group, an ethyl group, and a propyl group are preferable, and among them, a methyl group and an ethyl group are more preferable.
¹ is preferably a halogen atom, among which a chlorine atom is more preferable, X ² is preferably a halogen atom, and among them, a fluorine atom is more preferable, X ³ is preferably a hydrogen atom, and X ⁴ is preferably a hydrogen atom. , W is preferably an oxygen atom, and /
Or, for Y, an oxygen atom is preferable. Further, the substitution position of W on the benzene ring is preferably an ortho position of Y, and at this time, R ⁴ is preferably a hydrogen atom or a methyl group, and among them, a hydrogen atom is more preferable. Particularly preferred compounds are those wherein R ¹ is a trifluoromethyl group, R ² is a methyl group, R ⁴ is a hydrogen atom, R ⁵ is a methyl group, X ¹ is a chlorine atom, X ² Is a fluorine atom, and X
³ is a hydrogen atom, X ⁴ is a hydrogen atom, W is an oxygen atom, Y is an oxygen atom, compounds substitution position of W on the benzene ring is ortho position of Y; R ¹ is tri X is a fluoromethyl group, R ² is a methyl group, R ⁴ is a hydrogen atom, R ⁵ is an ethyl group, X ¹ is a chlorine atom, X ² is a fluorine atom, and X ³ is a hydrogen atom. Atom, X
Compounds in which ⁴ is a hydrogen atom, W is an oxygen atom, Y is an oxygen atom, and the substitution position of W on the benzene ring is the ortho position of Y. The compound of the present invention may have some isomers derived from a double bond, optical isomers derived from an asymmetric carbon, and diastereomers.
The compounds of the present invention also include these isomers and mixtures thereof.

Next, a method for producing the compound of the present invention will be described. The compound of the present invention can be produced, for example, by the following production methods (Production Method 1) to (Production Method 6). (Production Method 1) The compound of the present invention has the general formula [III]

Embedded image [Wherein, R ¹ , R ² , W, Y, X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. And a general formula [IV]

Embedded image Wherein, R ⁴ and R ⁵ have the same meanings as defined above, R ⁶
Represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group. To a compound of the formula (1) in the presence of a base. The reaction is usually performed in a solvent, and the reaction temperature is usually in the range of 0 to 200.
° C, preferably 20 to 100 ° C, and the reaction time is usually from instant to 72 hours. The amount of the reagent used for the reaction is such that the compound represented by the general formula [IV] is 1 mol per 1 mol of the compound represented by the general formula [III];
The theoretical amount of the base is 1 mol, but can be arbitrarily changed depending on the reaction situation. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2]
Organic bases such as octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, and lithium carbonate And inorganic bases such as sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, potassium hydride and lithium hydroxide. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene, aromatic halogenated hydrocarbons such as benzotrifluoride, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, etc. Ketones such as ethers, acetone, 2-butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile , Acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide,
Examples thereof include a sulfur compound such as sulfolane or a mixture thereof. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

(Production method 2) Among the compounds of the present invention, the compound of the formula [I] wherein W is an oxygen atom is represented by the formula [V]

Embedded image [Wherein, R ¹ , R ² , Y, X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. And a compound of the general formula [V
I]

Embedded image [Wherein, R ⁴ and R ⁵ represent the same meaning as described above. With the alcohol compound of the formula (1) in the presence of a dehydrating reagent. The reaction is usually performed in a solvent, and the reaction temperature is usually in the range of -20 to 15
The reaction temperature is 0 ° C, preferably 0 to 100 ° C, and the reaction time is usually from an instant to 48 hours. Examples of the dehydrating reagent include a combination of a triarylphosphine such as triphenylphosphine or a trialkylphosphine such as triethylphosphine, and a di (lower alkyl) azodicarboxylate such as diethylazodicarboxylate and diisopropylazodicarboxylate. No. The amount of the reagent used in the reaction is 1 to 3 mol, preferably 1 to 1.2 mol, of the alcohol compound represented by the general formula [VI] per mol of the compound represented by the general formula [V]. The triarylphosphine or trialkylphosphine is 1-3 mol, preferably 1-1.5 mol, and the di (lower alkyl) azodicarboxylate is 1-3 mol, preferably 1-1.5 mol. The ratio of these reagents can be arbitrarily changed according to the reaction situation. Examples of the solvent used in the reaction include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, benzotrifluorene. Halogenated aromatic hydrocarbons such as lido, diethyl ether, diisopropyl ether, dioxane,
Examples thereof include ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, and diglyme, and mixtures thereof. After completion of the reaction, for example, the following 1)
Alternatively, the desired compound of the present invention can be obtained by the operation shown in 2). 1) The reaction solution is poured into water, extracted with an organic solvent, the organic layer is dried and concentrated, and the residue is subjected to chromatography. 2) The reaction solution is concentrated as it is, and the residue is subjected to chromatography. The obtained compound of the present invention can be purified by an operation such as recrystallization.

(Production method 3) The compound of the present invention has the general formula [V
II]

Embedded image [Wherein, R ¹ , R ² , R ⁴ , W, Y, X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. And a carboxylic acid compound represented by the general formula [VIII]:

Embedded image [Wherein, R ⁵ has the same meaning as described above. And an alcohol compound represented by the formula: In the reaction, for example, a carboxylic acid compound represented by the general formula [VII] is reacted with a chlorinating agent to obtain an acid chloride (hereinafter, referred to as <Step 3-1>), and then the general formula [VII]
The reaction is performed by reacting the alcohol compound represented by I] with a base (hereinafter, referred to as <Step 3-2>).

<Step 3-1> The reaction is carried out without solvent or in a solvent, and the reaction temperature is usually from 0 to 150 ° C., and the reaction time is usually from instant to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mol of the chlorinating agent per 1 mol of the carboxylic acid compound represented by the general formula [VII], but may be arbitrarily changed depending on the reaction conditions. be able to. Examples of the chlorinating agent to be used include thionyl chloride, sulfuryl chloride, phosgene, oxalyl chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus oxychloride and the like. As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methylene chloride , Chloroform, carbon tetrachloride,
Aliphatic halogenated hydrocarbons such as 1,2-dichloroethane and 1,2,3-trichloropropane, aliphatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, diethyl ether, diisopropyl ether, methyl- t-butyl ether, 1,4
-Ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diglyme, and mixtures thereof. After the completion of the reaction, for example, the reaction solution is concentrated, and the concentrated residue is used as it is in <Step 3-2>
Used for

<Step 3-2> The reaction is carried out without solvent or in a solvent, and the reaction temperature is usually in the range of -20 to 100 ° C.
And the range of the reaction time is usually from instant to 24 hours.
The amount of the reagent used for the reaction is such that the alcohol compound and the base represented by the general formula [VIII] are each based on 1 mol of the carboxylic acid compound represented by the general formula [VII] used in <Step 3-1>. The ratio of 1 mole is the theoretical amount,
It can be arbitrarily changed according to the reaction situation. As the base to be used, for example, inorganic bases such as sodium hydrogen carbonate, potassium hydrogen carbonate, lithium carbonate, sodium carbonate, potassium carbonate, pyridine, quinoline, 4-dimethylaminopyridine, 2-picoline, 3-picoline, 4-picoline, 2,3-lutidine, 2,4-lutidine, 2,5
-Lutidine, 2,6-lutidine, 3,4-lutidine,
3,5-lutidine, 3-chloropyridine, 2-ethyl-
Nitrogen-containing aromatic compounds such as 3-methylpyridine, 5-ethyl-2-methylpyridine, triethylamine, diisopropylethylamine, tri-n-propylamine, tri-n-butylamine, benzyldimethylamine, phenethyldimethylamine, N-methyl Morpholine, 1,8-
Diazabicyclo [5.4.0] undec-7-ene,
Tertiary amines such as 1,5-diazabicyclo [4.3.0] non-5-ene or 1,4-diazabicyclo [2.2.2] octane are exemplified. As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, nonane, decane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, methylene chloride , Chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,
Aliphatic halogenated hydrocarbons such as 2,3-trichloropropane, aliphatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, diethyl ether, diisopropyl ether, methyl-t-butyl ether, 1,4- Examples thereof include ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and diglyme, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization. In addition, the reaction is not limited to the above method, and may be performed by a method of reacting in the presence of a condensing agent such as carbonyldiimidazole or dicyclohexylcarbodiimide, a method of reacting in the presence of an acid catalyst, and other known methods. It is possible.

(Production Method 4) Among the compounds of the present invention, the compound wherein X ¹ in the general formula [I] is a nitro group or a cyano group is a compound of the general formula [IX]

Embedded image [Wherein, R ¹ , R ² and X ² represent the same meaning as described above,
R ⁷ represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and X ¹¹ represents a nitro group or a cyano group. And a uracil compound represented by the general formula [X]:

Embedded image [Wherein, R ⁴ , R ⁵ , W, Y, X ³ and X ⁴ represent the same meaning as described above. To a compound of the formula (1) in the presence of a base. The reaction is usually carried out without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 2 hours.
4 hours. The amount of the reagent used for the reaction is determined by the general formula [I
The theoretical amount of the compound represented by the general formula [X] is 1 mole, and the ratio of the base is 1 mole, based on 1 mole of the uracil compound represented by the formula [X]. Can be. As the base used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5
-Diazabicyclo [4.3.0] non-5-ene, 1,
4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N,
N-diethylaniline, triethylamine, tri-n-
Propylamine, triisopropylamine, tri-n-
Organic bases such as butylamine and diisopropylethylamine, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride,
Lithium hydroxide, sodium hydroxide, potassium hydroxide,
Examples include inorganic bases such as calcium hydroxide and barium hydroxide. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene, aromatic halogenated hydrocarbons such as benzotrifluoride, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, etc. Ketones such as ethers, acetone, 2-butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile , Acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide,
Examples thereof include a sulfur compound such as sulfolane or a mixture thereof. The reaction may be accelerated by using a catalyst. Examples of the catalyst include copper iodide, copper bromide, copper chloride, copper powder, and the like. The amount of the catalyst used for the reaction is determined by the amount of the uracil compound 1 represented by the general formula [IX].
The ratio is from 0.0001 to 0.1 mol per mol, but can be arbitrarily changed depending on the reaction situation.
After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

(Production Method 5) Among the compounds of the present invention, the compound wherein X ¹ in the general formula [I] is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be produced by the method shown in the following scheme. Can be.

Embedded image [Wherein R ¹ , R ² , R ⁴ , R ⁵ , W, X ² , X ³ and X ⁴
Represents the same meaning as described above, X ¹² represents a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and Y ¹ represents an oxygen atom, a sulfur atom or a C1-C3 alkylimino group. ]

<Step 5-1>: Step of producing a compound represented by the general formula [XII] from a compound represented by the general formula [XI] The compound represented by the general formula [XII] is, for example, a compound represented by the general formula [XI] A compound represented by the formula:
It can be produced by reduction in a solvent. The reaction is usually performed without a solvent or in a solvent, and the reaction temperature is in the range of 0 to 200 ° C, preferably room temperature to heating to reflux. The range of the reaction time is usually from instant to 24 hours.
The amount of the reagent used for the reaction was 3 mol per 1 mol of the compound represented by the general formula [XI].
The ratio of the mole to excess amount is 1 to 10 moles of the acid, but can be arbitrarily changed depending on the reaction situation.
As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is filtered and then poured into water, and the resulting crystals are collected by filtration or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization and concentration to obtain the desired product. be able to. The object is
Purification can also be performed by operations such as chromatography and recrystallization. <Step 5-2>: Step of producing a compound represented by the general formula [XIII] from a compound represented by the general formula [XII] The compound represented by the general formula [XIII] is i) a compound represented by the general formula [XII] After diazotizing the indicated compound in a solvent, ii) subsequently potassium iodide, copper [I] bromide, copper chloride [I] or a mixture of hydrofluoric acid and boric acid (depending on the desired compound) (Hereinafter referred to as borofluoric acid) in a solvent.
In the first stage diazotization reaction, the reaction temperature range is usually -2.
The reaction time is usually from instantaneous to 5 hours. The amount of the reagent used for the reaction is determined by the general formula [XII]
The amount of the diazotizing agent is theoretically 1 mole per 1 mole of the compound represented by the formula, but can be arbitrarily changed depending on the reaction conditions. Examples of the diazotizing agent used include nitrite compounds such as sodium nitrite, potassium nitrite, isoamyl nitrite and t-butyl nitrite. Examples of the solvent include acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like, and a mixture thereof. The reaction solution after completion of the reaction is used for the next reaction as it is. The reaction of the second stage has a reaction temperature range of 0 to 80 ° C. and a reaction time range of usually instantaneous to 24 hours.
Time. The amount of the reagent used for the reaction is represented by the general formula [XI
The amount of potassium iodide, copper [I] bromide, copper [I] chloride or borofluoric acid is 1 to 3 mol per 1 mol of the compound represented by I]. ,
It can be arbitrarily changed depending on the reaction situation. still,
When copper [I] bromide is used, the reaction can be performed in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be performed in the presence of copper [II] chloride. You can also. Examples of the solvent used include acetonitrile, diethyl ether, t-butyl methyl ether, hydrogen bromide, hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention is obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.
(Org. Syn. Coll. Vol. 2, 604 (1943), Vol.
1,136 (1932)) The reaction is not limited to the above-mentioned method, but may include potassium iodide, copper [I] bromide, copper chloride in a solvent depending on the target compound.
In the presence of [I] or borofluoric acid, the compound represented by the general formula [XI
It can also be produced by reacting the compound of the formula (I) with a diazotizing agent (Heterocycles., 38, 1).
581 (1994)). When copper [I] bromide is used, the reaction can be carried out in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be carried out in the presence of copper [II] chloride. Can also be performed.

(Production Method 6) The compound of the present invention has the general formula [X
XXI]

Embedded image [Wherein, R ¹ , R ⁴ , R ⁵ , W, Y, X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. A uracil compound represented by the general formula [XXXX]

Embedded image [In the formula, R ¹⁸ represents a leaving group such as a chlorine atom, a bromine atom, an iodine atom, a methanesulfonyloxy group, a p-toluenesulfonyloxy group, and R ² has the same meaning as described above. ]
Can be produced by reacting with a compound represented by the formula in the presence of a base. The reaction is usually carried out without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, preferably 20 to 100 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used for the reaction is determined by the amount of the uracil compound 1 represented by the general formula [XXXI].
The theoretical amount of the compound represented by the general formula [XXXX] is 1 mol, and the molar ratio of the base is 1 mol.
It can be arbitrarily changed depending on the reaction situation. As the base used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.
3.0] Non-5-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n- Propylamine,
Organic bases such as triisopropylamine, tri-n-butylamine and diisopropylethylamine, metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate,
Inorganic bases such as sodium bicarbonate, potassium bicarbonate, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like can be mentioned. As the solvent used, for example, n-hexane, n-heptane, ligroin,
Aliphatic hydrocarbons such as cyclohexane and petroleum ether,
Aromatic hydrocarbons such as benzene, toluene and xylene,
Chlorobenzene, dichlorobenzene, aromatic halogenated hydrocarbons such as benzotrifluoride, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme,
Ketones such as acetone, 2-butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; , N-dimethylformamide,
Examples thereof include acid amides such as N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol, ethylene glycol, isopropanol, and t-butanol, and mixtures thereof. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

The compound represented by the general formula [IV], the alcohol compound represented by the general formula [VI], the alcohol compound represented by the general formula [VIII] and the compound represented by the general formula [X] used in the production method of the compound of the present invention. The compound shown is
A commercially available product can be used or can be produced by a known method. The carboxylic acid compound represented by the general formula [VII] can be produced by acid-hydrolyzing the compound of the present invention represented by the general formula [I].

Some of the production intermediates used in the production method of the compound of the present invention include, for example, the following (intermediate production method 1)
(Intermediate Production Method 19). (Intermediate Production Method 1) Among the compounds represented by the general formula [III], compounds in which W and Y are oxygen atoms or sulfur atoms (compounds represented by the general formula [XIX]), and compounds represented by the general formula [XIV] The compounds shown can be prepared by the methods described in the following schemes.

Embedded image [Wherein, R ¹ , R ² , R ⁷ , X ² , X ³ , X ⁴ and X ¹² represent the same meaning as described above, and R ¹⁵ and R ¹⁷ each independently represent an oxygen atom or a sulfur atom, R ¹⁶ is a trialkylsilyl group such as a t-butyldimethylsilyl group; a C1-C6 alkyl group which may be substituted such as a t-butyl group or a methyl group; a benzyl group which may be substituted such as a benzyl group;
Represents a protecting group such as a methoxymethyl group, an acetyl group, a methoxycarbonyl group, and an ethoxycarbonyl group. ]

<Step A1-1>: General formula [XXXXI]
For preparing a compound represented by the general formula [XIV] from a compound represented by the general formula [XIV]
XI] and a compound represented by the general formula [XXXXXXII] in the presence of a base. The reaction is usually performed without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mol of the compound represented by the general formula [XXXXXXII] and 1 mol of the base represented by 1 mol of the compound represented by the general formula [XXXXXX]. However, it can be arbitrarily changed depending on the reaction situation. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propyl Organic bases such as amine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydride, potassium hydride, etc. Inorganic base. As the solvent used, for example, n-
Aliphatic hydrocarbons such as hexane, n-heptane, ligroin, cyclohexane and petroleum ether; aromatic hydrocarbons such as benzene, toluene and xylene; aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and benzotrifluoride , Diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, acetone,
Ketones such as butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; Examples thereof include acid amides such as dimethylformamide and N, N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof. After completion of the reaction, for example, the following 1),
An object can be obtained by the operation shown in 2) or 3). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) The reaction solution is poured into water, and the precipitated crystals are collected by filtration. 3) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. In addition, the target substance can be purified by an operation such as chromatography and recrystallization.

<Step A1-2>: Step of producing a compound represented by the general formula [XVI] from a compound represented by the general formula [XIV] The compound represented by the general formula [XVI]
V] and a compound represented by the general formula [XV] in the presence of a base. The reaction is usually carried out without a solvent or in a solvent, and the reaction temperature is in the range of -20 to 200 ° C, preferably -5 to 80 ° C, and the reaction time is usually instantaneous to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mole of the compound represented by the general formula [XV] and 1 mole of the base relative to 1 mole of the compound represented by the general formula [XIV]. However, it can be arbitrarily changed depending on the reaction situation. As the base used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,
5-diazabicyclo [4.3.0] non-5-ene,
1,4-diazabicyclo [2.2.2] octane, 4-
Dimethylaminopyridine, N, N-dimethylaniline,
N, N-diethylaniline, triethylamine, tri-
n-propylamine, triisopropylamine, tri-
Organic bases such as n-butylamine and diisopropylethylamine, and inorganic bases of lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, and lithium hydroxide. Can be As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene,
Aromatic halogenated hydrocarbons such as benzotrifluoride, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, acetone, 2-butanone, methyl isobutyl ketone, etc. Ketones, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, nitro compounds such as nitromethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, N, N-dimethylformamide, N, N-dimethyl Examples include acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof. After the completion of the reaction, the desired product can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is sequentially washed with hydrochloric acid and saturated saline, dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. In addition, the target substance can be purified by an operation such as chromatography and recrystallization.

<Step A1-3>: Step of producing a compound represented by the general formula [XVII] from a compound represented by the general formula [XVI] The compound represented by the general formula [XVII] is, for example, a compound represented by the general formula [XVI] Can be produced by reducing the compound represented by the formula (I) with iron powder in a solvent in the presence of an acid. The reaction temperature ranges from 0 to 200 ° C., preferably from room temperature to heating to reflux. The reaction time range is usually from instant to 2
4 hours. The amount of the reagent used for the reaction is represented by the general formula [X
VI], the amount of iron powder is 3
The ratio of the mole to excess amount is 1 to 10 moles of the acid, but can be arbitrarily changed depending on the reaction situation.
As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is filtered and poured into water, and the resulting crystals are collected by filtration or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization and concentration to obtain the desired product. be able to. The target substance can be purified by an operation such as chromatography, recrystallization and the like. <Step A1-4>: Step of producing compound represented by general formula [XVIII] from compound represented by general formula [XVII] The compound represented by general formula [XVIII] is i) represented by general formula [XVII] After diazotizing the indicated compound in a solvent, ii) followed by potassium iodide, copper (I) bromide,
It can be produced by reacting with copper (I) chloride or borofluoric acid in a solvent. In the diazotization reaction of the first stage, the reaction temperature is usually from -20 to 20 ° C, and the reaction time is usually from instant to 5 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mol per 1 mol of the compound represented by the general formula [XVII], but may be arbitrarily changed according to the reaction situation. be able to. Examples of the diazotizing agent used include nitrite compounds such as sodium nitrite, potassium nitrite, isoamyl nitrite and t-butyl nitrite. Examples of the solvent include acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like, and a mixture thereof. The reaction solution after completion of the reaction is used for the next reaction as it is. In the reaction of the second stage, the reaction temperature range is 0 to 80 ° C., and the reaction time range is usually instantaneous to 24 hours. The amount of the reagent to be subjected to the reaction is such that the amount of potassium iodide, copper (I) bromide, copper (I) chloride or borofluoric acid is 1 mol of the compound represented by the general formula [XVII]. The ratio is 1 to 3 mol, but can be arbitrarily changed depending on the reaction situation. When copper bromide [I] is used, copper bromide [I]
The reaction can be carried out in the presence of copper chloride [I], and when copper chloride [I] is used, the reaction can be carried out in the presence of copper chloride [II]. Examples of the solvent include acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid,
Examples include hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration to obtain the desired product. . The target product can be purified by an operation such as chromatography, recrystallization and the like. In addition, the reaction is not limited to the above method, but may be carried out in a solvent (for example, acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, or a mixture thereof), potassium iodide, bromide, or the like. It can also be produced by reacting a compound represented by the general formula [XVII] with a diazotizing agent in the presence of copper (I), copper (I) chloride or borofluoric acid. (Heterocycles., 38, 1581 (1994)
Etc.)

<Step A1-5>: General formula [XVIII]
For producing a compound represented by the general formula [XIX] from a compound represented by the general formula [XIX]:
ups in Organic Synthesis (A Wiley-Interscience pub
lication company) according to the general formula [XVI
II] with boron tribromide, HB
r / acetic acid, concentrated hydrochloric acid, concentrated sulfuric acid, or the like for deprotection. The general formula [XV
Among the compounds represented by III], when R ¹⁶ is a benzyl group, the compound can also be produced by deprotection by hydrogenation in the presence of a catalyst. The reaction is usually performed in a solvent. The reaction temperature range is usually -2.
It is 0-150 degreeC, Preferably it is 0-50 degreeC. The range of the reaction time is usually from instant to 48 hours. The reaction can be carried out under a pressurized condition, and is usually carried out under a condition of 1 to 5 atm. The amount of the catalyst used for the reaction is represented by the general formula [X
VIII] to 0.001 to 100% by weight. Examples of the catalyst used for the reaction include anhydrous palladium / carbon, hydrated palladium / carbon, platinum oxide and the like. Examples of the solvent include carboxylic acids such as formic acid, acetic acid and propionic acid, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, and ethers such as 1,4-dioxane, tetrahydrofuran and ethylene glycol dimethyl ether. , Methanol, ethanol, alcohols such as isopropanol, water or a mixture thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water and crystals formed are collected, or the reaction solution is poured into water and then extracted with an organic solvent and concentrated. To give the desired product. The target product can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 2) Among the compounds represented by the general formula [III], the compound wherein W is NH (the compound represented by the general formula [XXIII]) can be prepared by the method described in the following scheme. Can be manufactured.

Embedded image [Wherein R ¹ , R ² , R ⁷ , Y, X ¹ , X ² , X ³ and X ⁴
Represents the same meaning as described above. <Step A2-1>: Step of producing a compound represented by the general formula [XXII] from a compound represented by the general formula [XX] is performed by converting the compound represented by the general formula [XXII] into a compound represented by the general formula [X
X] and a compound represented by the general formula [XXI] in the presence of a base. The reaction is usually performed without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mole of the compound represented by the general formula [XXI] and 1 mole of the base relative to 1 mole of the compound represented by the general formula [XX]. However, it can be arbitrarily changed depending on the reaction situation. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2]
Organic bases such as octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, and lithium carbonate And inorganic bases such as sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, potassium hydride and lithium hydroxide. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene, aromatic halogenated hydrocarbons such as benzotrifluoride, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, etc. Ketones such as ethers, acetone, 2-butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile , Acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide,
Examples thereof include a sulfur compound such as sulfolane or a mixture thereof. The reaction may be accelerated by the addition of a catalyst. The amount of the catalyst used for the reaction is 0.000 to 1 mol of the compound represented by the general formula [XX].
The ratio is preferably 1 to 0.1 mol, but can be arbitrarily changed depending on the situation of the reaction. Examples of the catalyst include copper iodide, copper bromide, copper chloride, copper powder and the like. After the completion of the reaction, the desired product can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The target substance can be purified by operations such as chromatography and recrystallization. <Step A2-2>: Step of producing compound represented by general formula [XXIII] from compound represented by general formula [XXII] The compound represented by general formula [XXIII] is represented by, for example, general formula [XXII] By reducing the compound to be prepared with iron powder in a solvent in the presence of an acid. The reaction temperature ranges from 0 to 200 ° C, preferably from room temperature to
Heat reflux. The range of the reaction time is usually from instant to 24 hours. The amount of the reagent used for the reaction is determined by the general formula [XXI
With respect to 1 mol of the compound represented by I], the amount of the iron powder is 3 mol to an excess amount, and the acid is 1 to 10 mol.
It can be arbitrarily changed depending on the reaction situation. As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is filtered, and the resulting crystals (by adding water as needed) are collected by filtration, or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization and concentration, The desired product can be obtained. The object is
It is also possible to purify by operations such as chromatography and recrystallization.

(Intermediate Production Method 3) Among the compounds represented by the general formula [III], compounds in which W is an oxygen atom (compounds represented by the general formula [V]) are prepared by the method described in the following scheme. , Can also be manufactured.

Embedded image [Wherein, R ¹ , R ² , Y, X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. The compound represented by the general formula [V] is a compound represented by the general formula [XXI]
After the compound of the formula [II] is reacted with a diazotizing agent in a solvent, ii) the compound is then heated in an acidic solvent or reacted with a copper salt in the presence of a copper catalyst. . In the reaction of the first stage, the reaction temperature is usually from -20 to 10 ° C, and the reaction time is usually from instant to 5 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mol per 1 mol of the compound represented by the general formula [XXIII], but may be arbitrarily changed according to the reaction situation. be able to. Examples of the diazotizing agent used include nitrite compounds such as sodium nitrite, potassium nitrite, isoamyl nitrite and t-butyl nitrite. Examples of the solvent include acetonitrile, hydrochloric acid, hydrobromic acid, sulfuric acid, water, and the like, and mixtures thereof. The reaction solution after completion of the reaction is used for the next reaction as it is. The reaction in the second step of heating in an acidic solvent is performed at a reaction temperature ranging from 60 ° C. to heating under reflux, and a reaction time generally ranging from an instant to 48 hours. Examples of the acidic solvent include hydrochloric acid, hydrobromic acid, aqueous sulfuric acid and the like. After completion of the reaction, the reaction solution can be obtained by collecting the generated crystals (by adding water as necessary) or by performing a usual post-treatment such as extraction with an organic solvent and concentration.
The target product can be purified by operations such as chromatography and recrystallization. The reaction of reacting the copper salt in the presence of the copper catalyst in the second stage is carried out in a solvent, and the reaction temperature ranges from 0 ° C. to the reflux temperature, and the reaction time generally ranges from instant to 24 hours. The amount of reagent used for the reaction is
The amount of the copper catalyst is 0.001 to 5 mol, and the amount of the copper salt is 1 to 100 mol, based on 1 mol of the compound represented by the general formula [XXIII]. Can be changed. The copper catalyst used includes copper (I) oxide and the like, and the copper salt includes copper sulfate (II), copper nitrate (II) and the like. As the solvent,
For example, water, hydrochloric acid, sulfuric acid and the like or a mixture thereof can be mentioned. After completion of the reaction, the reaction solution is subjected to ordinary post-treatments such as extraction with an organic solvent and concentration to obtain the desired product. The target product can be purified by operations such as chromatography and recrystallization.

(Intermediate Production Method 4) The compound represented by the general formula [IX] can be produced by the method described in the following scheme.

Embedded image [Wherein, R ¹ , R ² , R ⁷ , X ² and X ¹¹ represent the same meaning as described above. The compound represented by the general formula [IX] has the general formula [XXI
V] can be produced by diazotizing a compound represented by the formula [V] in a solvent and subsequently reacting the compound with a halogenating agent. <First Step (Diazotization Reaction)> Reaction temperature: -20 to 20 ° C. Reaction time: Instantaneous to 5 hours Amount of diazotizing agent: 1 mol to excess amount per 1 mol of compound represented by general formula [XXIV] Diazotizing agent: nitrite compounds such as sodium nitrite, potassium nitrite, isoamyl nitrite, t-butyl nitrite, etc. Solvent: acetonitrile, hydrochloric acid, etc. <Second step> Reaction temperature: 0 to 80 ° C. Reaction time: instantaneous to 24 Time Amount of halogenating agent: 1 to 3 mol per 1 mol of compound represented by general formula [XXIV] Halogenating agent: potassium iodide, copper (I) bromide, copper (I) chloride or borofluoric acid Solvent: acetonitrile, hydrochloric acid, etc. The reaction is carried out in a solvent in the presence of a halogenating agent by the general formula [X
XIV] and a diazotizing agent. Reaction temperature: 0 to 80 ° C Reaction time: instantaneous to 48 hours Amount of diazotizing agent: 1 mol to excess amount per 1 mol of compound represented by formula [XXIV] Diazonizing agent: isoamyl nitrite, t nitrite -Nitrite compound such as butyl, etc. Amount of halogenating agent: 1 to 3 mol per 1 mol of compound represented by general formula [XXIV] Halogenating agent: potassium iodide, copper (I) bromide, copper chloride ( I) or borofluoric acid, etc. Solvent: acetonitrile, etc. When copper [I] is used, the reaction can be carried out in the presence of copper [II], and when copper [I] is used. Is
The reaction can be carried out in the presence of copper [II] chloride.

(Intermediate Production Method 5) Among the compounds represented by the general formula [X], compounds in which W is an oxygen atom or a sulfur atom (compounds represented by the general formula [XXVI]) are described in the following scheme. It can be manufactured by the method described above.

Embedded image [Wherein, R ⁴ , R ⁵ , R ⁶ , R ¹⁵ , Y, X ³ and X ⁴ represent the same meaning as described above. The compound represented by the general formula [XXVI] has the general formula [XXVI]
V] and a compound represented by the general formula [IV] in a solvent in the presence of a base. Reaction temperature: 0 to 200 ° C Reaction time: instantaneous to 72 hours Amount of compound represented by general formula [IV]: general formula [XX
V] 1 to 3 mol per 1 mol of the compound represented by the formula: The amount of the base: 1 to 3 mol per 1 mol of the compound represented by the general formula [XXV] Base: triethylamine, potassium carbonate, sodium hydride, etc. Solvent: Tetrahydrofuran, acetonitrile, N, N-
Dimethylformamide, dimethylsulfoxide, methanol, water, etc. or a mixture thereof

(Intermediate Production Method 6) Among the compounds represented by the general formula [X], compounds in which Y is an oxygen atom or a sulfur atom (compounds represented by the general formula [XXX]) are described in the following scheme. It can be manufactured by the method described above.

Embedded image [Wherein R ⁴ , R ⁵ , R ⁶ , R ¹⁶ , R ¹⁷ , W, X ³ and X
⁴ has the same meaning as described above. ]

<Step A6-1>: General formula [XXVII]
For producing a compound represented by the general formula [XXVIII] from a compound represented by the general formula [XXVIII], a compound represented by the general formula [XXVIII] and a compound represented by the general formula [XXVII] It can be produced by reacting with benzyl, benzyl bromide or the like. (Protective
Groups in Organic Synthesis (A Wiley-Interscience
<publishing company publication)) <Step A6-2>: Step of producing compound represented by general formula [XXIX] from compound represented by general formula [XXVIII] [XX
The compound represented by the formula [VIII] and the compound represented by the general formula [IV] can be produced by reacting the compound in a solvent in the presence of a base. Reaction temperature: 0 to 200 ° C Reaction time: instantaneous to 72 hours Amount of compound represented by general formula [IV]: general formula [XXV]
III] 1 to 3 mol per 1 mol of the compound represented by the formula: The amount of the base: the compound 1 represented by the general formula [XXVIII]
1 to 3 mol based on mol Base: triethylamine, potassium carbonate, sodium hydride, etc. Solvent: tetrahydrofuran, acetonitrile, N, N-
Dimethylformamide, dimethylsulfoxide, methanol, water, etc. or a mixture thereof <Step A6-3>: a step of producing a compound represented by the general formula [XXX] from a compound represented by the general formula [XXIX], general formula [XXX] The compounds shown in "Protective Groups", Vol. 4 (Guidance on Organic Chemistry Experiments) (published by Kagaku Dojin)
in Organic Synthesis (A Wiley-Intersciencepublicat
ion, published by Ion Co., Ltd.) according to the general formula [XXIX]
Can be produced by deprotecting the compound represented by Among the compounds represented by the general formula [XXIX], compounds in which R ¹⁸ is a silyl group such as a t-butyldimethylsilyl group include trifluoroacetic acid or tetrabutylammonium fluoride, methylene chloride, ethyl acetate or water. By reacting in a solvent of Among the compounds represented by the general formula [XXIX], the compound in which R ¹⁸ is an optionally substituted benzyl group such as a benzyl group is obtained by reacting with hydrogen in the presence of a catalyst. Reaction temperature: -20 to 150 ° C, preferably 0 to 50 ° C Reaction time: instantaneous to 48 hours Catalyst amount: 0.001 to 100% by weight based on 1 mol of the compound represented by the general formula [XXIX] Catalyst: Anhydrous palladium / carbon, hydrous palladium / carbon,
Solvent: acetic acid, ethyl acetate, methanol, etc.

(Intermediate Production Method 7) Among the compounds represented by the general formula [XXXI], compounds wherein Y is an oxygen atom or a sulfur atom can be produced by the method described in the following scheme.

Embedded image [Wherein R ¹ , R ⁴ , R ⁵ , R ⁷ , R ¹⁷ , W, X ¹ , X ² , X
³ and X ⁴ represent the same meaning as described above, and R ¹⁸ represents C1 to C6
R ¹⁹ represents a C1-C6 alkyl group (eg, a methyl group, an ethyl group, etc.); <Step A7-1>: Step of producing a compound represented by the general formula [XXXII] from a compound represented by the general formula [XXXVI]
XXXVI] is represented by the general formula [XXXVI]
After converting into the compound represented by the formula [I], the compound represented by the general formula [XXX]
VIII],
Can be manufactured. (Bio-Organic and
Medicinal Chemistry Letters Volume 5, 1035
Page, (1995)) <Step A7-2>: Step of producing compound represented by general formula [XXXIII] from compound represented by general formula [XXXII] The compound represented by general formula [XXXIII] is a compound represented by the general formula From the compound represented by the formula [XXXII]
It can be produced by a method according to a known method described in JP-A-466-466 or the like. Specifically, the general formula [XXXI
The compound represented by the general formula [XXXIII] can be obtained by isocyanating the compound of the formula [I] in a solvent or without solvent.
Can be produced. Isocyanating agent: phosgene, trichloromethyl chloroformate, oxalyl chloride, etc. Amount of isocyanating agent: 1 mole to excess amount per mole of compound represented by general formula [XXXII] Solvent: benzene, toluene, etc. Aromatic hydrocarbons, halogenated aromatic hydrocarbons such as chlorobenzene, esters such as ethyl acetate, etc. Reaction temperature: room temperature to reflux temperature Reaction time: instantaneous to 48 hours After completion of the reaction, the reaction solution is directly concentrated, etc. By performing the post-processing operation, the target product can be obtained. The compound can be purified by an operation such as recrystallization. <Step A7-3>: Step of producing compound represented by general formula [XXXIV] from compound represented by general formula [XXXII]
XXII] to JP-A-63-4146.
It can be produced by a method according to a known method described in, for example, Japanese Unexamined Patent Publication No. 6-64. Specifically, the general formula [XXXII]
And a compound represented by the general formula [b-4]

Embedded image [Wherein, R ¹⁸ and X ¹² represent the same meaning as described above. The compound represented by the general formula [XXXIV] can be produced by reacting the compound represented by the general formula [XXXIV] with the compound represented by the general formula [XXXIV]. The reaction is usually performed in a solvent, but also without a solvent. The reaction temperature range is -20 to 200 ° C
Range. The reaction temperature range is from instant to 48 hours. The amount of the compound represented by the general formula [b-4] to be subjected to the reaction is from 0.5 mol to an excess amount per 1 mol of the compound represented by the general formula [XXXII], preferably 1 0.0 to 1.2 moles. The amount of the base to be subjected to the reaction is determined by the amount of the compound 1 represented by the general formula [XXXII].
The ratio is from 0.5 mol to an excess amount, preferably from 1.0 to 1.2 mol, per mol. As the base,
Examples include inorganic bases such as sodium carbonate and sodium hydroxide, and organic bases such as pyridine, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine. Examples of the solvent include aliphatic halogenated hydrocarbons such as chloroform, ethers such as tetrahydrofuran and 1,4-dioxane, nitriles such as acetonitrile, esters such as ethyl acetate, water, and mixtures thereof. Can be After completion of the reaction, the reaction solution is filtered and concentrated as it is, or the reaction solution is poured into water and the resulting crystals are collected by filtration, or the reaction solution is poured into water and then subjected to organic solvent extraction and concentration. The target product can be obtained by performing ordinary post-processing operations. The compound can be purified by an operation such as chromatography and recrystallization.

<Step A7-4>: General formula [XXXII]
Step of producing a compound represented by the general formula [XXXIX] from a compound represented by the general formula [XXXIX]
XXIII] and a compound represented by the general formula [XXXV] by a method according to a known method described in JP-A-63-41466 and the like. Specifically, by reacting a compound represented by the general formula [XXXIII] with a compound represented by the general formula [XXXV] in a solvent in the presence of a base,
XXIX] can be produced. Amount of compound represented by general formula [XXXV]: general formula [X
XXIII], relative to 1 mole of the compound
10 mol ratio Type of base: Inorganic base such as sodium hydride, metal alkoxide such as sodium methoxide, sodium ethoxide, etc. Amount of base: Compound 1 represented by general formula [XXXIII]
Solvent: aromatic hydrocarbons such as benzene and toluene, halogenated aromatic hydrocarbons such as chlorobenzene, N, N-
Amides such as dimethylformamide, ethers such as tetrahydrofuran, halogenated aliphatic hydrocarbons such as chloroform, sulfur compounds such as dimethylsulfoxide, and mixtures thereof. Reaction temperature: -40 ° C to solvent reflux temperature Reaction time: instantaneous to 72 Time After the reaction, the reaction solution is filtered and concentrated as it is, or the reaction solution is poured into an acid to collect crystals, or the reaction solution is poured into an acid and then extracted with an organic solvent and concentrated. And the like to obtain the desired product. Examples of the acid to be added include hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and an aqueous solution thereof. The obtained compound represented by the general formula [XXXIX] is reacted with the compound represented by the general formula [XXXXXX] according to the method described in (Production method 6) without performing post-treatment such as isolation. The compound of the present invention can also be produced.

<Step A7-5>: General formula [XXXIV]
For preparing a compound represented by the general formula [XXXIX] from a compound represented by the general formula [XXXIX]
XXIV] and a compound represented by the general formula [XXXV] can be produced by a method according to a known method described in JP-A-63-41466 and the like. Specifically, it is possible to produce a compound represented by the general formula [XXXIX] by reacting a compound represented by the general formula [XXXIV] and a compound represented by the general formula [XXXV] in the presence of a base. it can. The reaction is usually performed in a solvent, and the reaction temperature is in a range of −20 to 200 ° C.
And preferably 0 to 130 ° C. The range of the reaction time is usually from instant to 72 hours. The amount of the compound represented by the general formula [XXXV] to be subjected to the reaction is determined according to the general formula [XX]
XIV], relative to 1 mole of the compound represented by the formula
It is a ratio of an excess amount, preferably a ratio of 0.8 to 1.2 mol. The amount of the base subjected to the reaction is represented by the general formula [X
XXIV], in a ratio of 0.5 equivalent to an excess amount, preferably 0.8 to 1.2 equivalent. As the base, 4-dimethylaminopyridine,
Organic bases such as diisopropylethylamine; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride, and potassium hydride; and metal alkoxides such as sodium methoxide, sodium ethoxide, and potassium t-butoxide. As the solvent, acetone, ketones such as methyl isobutyl ketone, hexane, heptane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene,
Aromatic hydrocarbons such as ethylbenzene, xylene and mesitylene, diethyl ether, diisopropyl ether,
Ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, methyl tert-butyl ether, N, N-dimethylformamide,
Acid amides such as N, N-dimethylacetamide, tertiary amines such as pyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine; sulfur compounds such as dimethylsulfoxide and sulfolane; And the like. After completion of the reaction, the reaction solution is filtered and concentrated as it is, a crystal formed by pouring an acid into the reaction solution is collected by filtration, or an organic solvent is extracted and concentrated after pouring the acid into the reaction solution. After that, the desired product can be obtained. Examples of the acid to be added include hydrochloric acid, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and an aqueous solution thereof. The compound was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization. The obtained compound represented by the general formula [XXXIX] is reacted with the compound represented by the general formula [XXXXXX] according to the method described in (Production method 6) without performing post-treatment such as isolation. The compound of the present invention can also be produced.

(Intermediate Production Method 8) Among the compounds represented by the general formula [III], those in which Y and W are an oxygen atom or a sulfur atom can also be produced by the method described in the following scheme.

Embedded image [Wherein R ¹ , R ² , R ¹⁵ , R ¹⁶ , R ¹⁷ , X ² , X ³ and X ⁴ have the same meanings as described above, and R ²⁰ represents a methyl group, an ethyl group, a trifluoromethyl group, a trichloro group. It represents optionally substituted C1~C6 alkyl group such as a methyl group, R ²⁶
Is a C1-C6 which may be substituted such as a methyl group or an ethyl group.
An optionally substituted phenyl group such as an alkyl group or a phenyl group or an optionally substituted phenyl group such as a benzyl group
X ¹³ represents a nitro group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. ]

<Step A8-1>: Step of producing a compound represented by the general formula [a-2] from a compound represented by the general formula [a-1] For example, "Guide to Organic Chemistry Experiments" Vol. 4 (published by Kagaku Dojinsha), Protective G
roups in Organic Synthesis (A Wiley-Interscience p
ublication) according to the general formula [a-
It can be produced by deprotecting the compound represented by 1) or by the method described below. The reaction is usually carried out without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 2 hours.
4 hours. The amount of the reagent used for the reaction is represented by the general formula [a
The theoretical amount of the reagent is 1 mole with respect to 1 mole of the compound represented by the formula [-1], but can be arbitrarily changed depending on the reaction situation. Examples of the reagent used include boron trifluoride diethyl ether complex, boron trifluoride methanol complex, and triethyloxonium tetrafluoroborate. As the solvent used, hexane, heptane, octane, aliphatic hydrocarbons such as ligroin, benzene, toluene, ethylbenzene, xylene, aromatic hydrocarbons such as mesitylene, methylene chloride,
Chloroform, carbon tetrachloride, 1,2-dichloroethane,
Aliphatic halogenated hydrocarbons such as 1,2,3-trichloropropane, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and benzotrifluoride;
Ethers such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, and methyl tert-butyl ether; alcohols such as methanol and ethanol; and mixtures thereof. After completion of the reaction, the reaction solution is poured into water, and the precipitated crystals are collected by filtration and dried, or extracted with an organic solvent and the organic layer is dried and concentrated, or the reaction solution is directly concentrated. By performing the treatment operation, the desired compound can be obtained. The compound can be purified by an operation such as recrystallization or chromatography.

<Step A8-2>: Step of producing a compound represented by the general formula [a-3] from a compound represented by the general formula [a-2] The compound represented by the general formula [a-3] The general formula [a-
2] and a general formula [b-1]

Embedded image [Wherein, R ²⁶ and X ¹² represent the same meaning as described above. ]
Can be produced by reacting with a compound represented by the formula in the presence of a base. The reaction is usually performed in a solvent, but can be performed without a solvent. The reaction temperature ranges from -20 to 200C. The reaction temperature range is from instant to 48 hours. The general formula [b-
The amount of the compound represented by the formula [1] is from 0.5 mol to an excess amount, preferably from 1.0 to 1.2 mol, per 1 mol of the compound represented by the general formula [a-2]. Percentage.
The amount of the base used in the reaction is a ratio of 0.5 equivalent to an excess amount of the compound represented by the general formula [a-2],
Preferably, the ratio is 1.0 to 1.2 equivalents. Examples of the base include inorganic bases such as sodium carbonate and sodium hydroxide, pyridine, 4-dimethylaminopyridine, N, N-
Organic bases such as dimethylaniline, N, N-diethylaniline, triethylamine, diisopropylethylamine and the like can be mentioned. As the solvent, aliphatic halogenated hydrocarbons such as chloroform, tetrahydrofuran, 1,4-
Examples include ethers such as dioxane, nitriles such as acetonitrile, esters such as ethyl acetate, water, and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water to collect crystals, or the reaction solution is poured into water and then extracted with an organic solvent and concentrated. To give the desired compound. The target compound can be purified by an operation such as chromatography and recrystallization.

<Step A8-3>: Step of producing a compound represented by the general formula [a-5] from a compound represented by the general formula [a-3] The compound represented by the general formula [a-5] The general formula [a-
3] and a compound represented by the general formula [XXXV] in the presence of a base. The reaction is usually performed in a solvent, and the reaction temperature is in a range of -20 to 200 ° C, preferably 0 to 200 ° C.
~ 130 ° C. The range of the reaction time is usually from instant to 72 hours. The amount of the compound represented by the general formula [XXXV] to be subjected to the reaction is 0.5 mol to an excess amount, preferably 0 mol, per 1 mol of the compound represented by the general formula [a-3]. 0.8 to 1.2 moles. The amount of the base to be subjected to the reaction is in a ratio of 0.5 equivalent to an excess amount, preferably 0.8 to 1.2 equivalent, relative to the compound represented by the general formula [a-3]. is there. As the base, 4-
Organic bases such as dimethylaminopyridine and diisopropylethylamine; inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride and potassium hydride; and metal alkoxides such as sodium methoxide, sodium ethoxide and potassium t-butoxide. As the solvent, acetone, ketones such as methyl isobutyl ketone,
Hexane, heptane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, ethylbenzene, xylene,
Aromatic hydrocarbons such as mesitylene, diethyl ether,
Diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether,
Ethers such as methyl-t-butyl ether; nitro compounds such as nitromethane and nitrobenzene; acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; pyridine; N, N-dimethylaniline;
Examples include tertiary amines such as N, N-diethylaniline, triethylamine and diisopropylethylamine, sulfur compounds such as dimethylsulfoxide and sulfolane, and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, a crystal formed by pouring an acid into the reaction solution is collected by filtration, or an organic solvent is extracted and concentrated after pouring the acid into the reaction solution. After that, the desired product can be obtained. Examples of the acid used at this time include hydrogen chloride, acetic acid, trifluoroacetic acid, p-toluenesulfonic acid, and an aqueous solution thereof. The compound can be purified by an operation such as chromatography and recrystallization. The compound represented by the general formula [a-5] can be directly used in the next step without isolation.

<Step A8-4>: Step of producing a compound represented by the general formula [a-4] from a compound represented by the general formula [a-2] The compound represented by the general formula [a-4] The general formula [a-
It can be produced by reacting a compound represented by 2) with an isocyanate agent in a solvent or in the absence of a solvent to form isocyanate. Isocyanating agent: phosgene, trichloromethylchloroformate, oxalyl chloride, etc. Amount of isocyanating agent: 1 mol to excess amount per 1 mol of compound represented by general formula [a-2] Solvent: benzene, toluene Aromatic hydrocarbons such as chlorobenzene, halogenated aromatic hydrocarbons such as chlorobenzene, esters such as ethyl acetate, etc. Reaction temperature: room temperature to reflux temperature Reaction time: instantaneous to 48 hours The desired product can be obtained by performing post-treatment operations such as concentration of the compound as it is. The compound can be purified by an operation such as recrystallization.

<Step A8-5>: Step of producing compound represented by general formula [a-5] from compound represented by general formula [a-4] The compound represented by general formula [a-5] The general formula [a-
4] and a compound represented by the general formula [XXXV] in a solvent in the presence of a base. Amount of compound represented by general formula [XXXV]: general formula [a
-4] in a ratio of 0.9 to 10 moles per mole of the compound represented by the formula: Kinds of bases: inorganic bases such as sodium hydride, potassium hydride, sodium hydroxide, sodium methoxide;
Metal alkoxides such as sodium ethoxide, etc. Amount of base: 0.1 to 10 mol based on 1 mol of compound represented by general formula [a-4] Solvent: aromatic hydrocarbons such as benzene and toluene; Halogenated aromatic hydrocarbons such as chlorobenzene, N, N-
Amides such as dimethylformamide; ethers such as tetrahydrofuran; halogenated aliphatic hydrocarbons such as chloroform; sulfur compounds such as dimethylsulfoxide; and mixtures thereof. Time The reaction solution after completion of the reaction is neutralized and poured into water, and the precipitated crystals are collected by filtration and dried, or extracted with an organic solvent, and the organic layer is dried and concentrated. The target compound can be obtained by performing post-treatment operations such as concentration of the compound as it is. The compound is recrystallized, chromatographic
Purification can also be performed by such operations. The compound represented by the general formula [a-5] can be directly used in the next step without isolation.

<Step A8-6>: Step of producing compound represented by general formula [a-6] from compound represented by general formula [a-5] The compound represented by general formula [a-6] is The general formula [a-
5] and a compound represented by the general formula [XXXX] in the presence of a base. The reaction is usually performed in a solvent, and the reaction temperature is in a range of -20 to 200 ° C, preferably 0 to 200 ° C.
１００100 ° C. The range of the reaction time is usually from instant to 48 hours. The amount of the compound [XXXX] to be subjected to the reaction is from 0.5 mol to an excess amount, preferably from 0.8 mol to 1 mol of the compound represented by the general formula [a-5].
1.2 moles. The amount of the base used in the reaction is from 0.5 mol to an excess amount, preferably from 0.8 mol to 1 mol of the compound represented by the general formula [a-5].
1.2 moles. Pyridine, 4
Organic bases such as -dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine, sodium carbonate, potassium carbonate, sodium hydride, potassium hydride and the like. Hexane, heptane,
Aliphatic hydrocarbons such as octane, ligroin and cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene and mesitylene, diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether , Ethers such as methyl-t-butyl ether, nitro compounds such as nitromethane and nitrobenzene, N, N-
Acid amides such as dimethylformamide and N, N-dimethylacetamide; tertiary amines such as pyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine; sulfur compounds such as dimethylsulfoxide and sulfolane And alcohols such as methanol, ethanol, ethylene glycol, isopropanol and t-butanol, and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water and crystals formed are collected, or the reaction solution is poured into water and then extracted with an organic solvent and concentrated. To give the desired product. The compound can be purified by an operation such as chromatography and recrystallization.

<Step A8-7>: Step of producing compound represented by general formula [a-7] from compound represented by general formula [a-6] The compound represented by general formula [a-7] is as follows: , Protective Gro
ups in Organic Synthesis (A Wiley-Interscience pub
lication company) according to the general formula [a-
6] with boron tribromide, HBr
/ Can be produced by deprotection using acetic acid, concentrated hydrochloric acid or concentrated sulfuric acid. The general formula [a-
In the case where R ¹⁶ is a benzyl group among the compounds represented by 6], the compound can also be produced by deprotection by hydrogenation in the presence of a catalyst. The reaction is
It is usually performed in a solvent. The reaction temperature range is usually -20 to
The temperature is 150 ° C, preferably 0 to 50 ° C. The range of the reaction time is usually from instant to 48 hours. The reaction can be carried out under a pressurized condition, and is usually carried out under a condition of 1 to 5 atm. The amount of the catalyst used for the reaction is represented by the general formula [a-
6] in the range of 0.001 to 100% by weight. Examples of the catalyst used for the reaction include anhydrous palladium / carbon, hydrated palladium / carbon, platinum oxide and the like.
Examples of the solvent include carboxylic acids such as formic acid, acetic acid and propionic acid, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, and ethers such as 1,4-dioxane, tetrahydrofuran and ethylene glycol dimethyl ether.
Examples thereof include ters, alcohols such as methanol, ethanol, and isopropanol, water, and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water and crystals formed are collected, or the reaction solution is poured into water and then extracted with an organic solvent and concentrated. To give the desired product. The target product can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 9) The compound represented by the general formula [a-1] can also be produced by the method described in the following scheme.

Embedded image [Wherein, R ⁷ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ²⁰ , X ² , X ³ , X ⁴
And X ¹² have the same meaning as described above. ]

<Step A9-1>: Step of producing a compound represented by the general formula [a-9] from a compound represented by the general formula [a-8] The compound represented by the general formula [a-9] The general formula [a-
8] and a compound represented by the general formula [XV] in the presence of a base. The reaction is usually performed without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used in the reaction is based on 1 mol of the compound represented by the general formula [a-8] and 1 mol of the compound represented by the general formula [XV] and 1 mol of the base are theoretically. The amount can be arbitrarily changed depending on the reaction situation. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2]
Organic bases such as octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine and diisopropylethylamine, sodium methoxy Metal alkoxides such as sodium ethoxide, potassium t-butoxide, lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydride, potassium hydride, lithium hydroxide, Inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide and the like can be mentioned. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane,
Aliphatic hydrocarbons such as petroleum ether, aromatic hydrocarbons such as benzene, toluene and xylene, chlorobenzene,
Aromatic halogenated hydrocarbons such as dichlorobenzene and benzotrifluoride, diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, ethers such as tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, acetone, 2-
Ketones such as butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitro compounds such as nitromethane and nitrobenzene; nitriles such as acetonitrile and isobutyronitrile; N, N-dimethyl Examples thereof include acid amides such as formamide and N, N-dimethylacetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, alcohols such as methanol, ethanol, ethylene glycol, isopropanol and t-butanol, and mixtures thereof. After the completion of the reaction, the desired product can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. In addition, the target substance can be purified by an operation such as chromatography and recrystallization.

<Step A9-2>: Step of producing a compound represented by the general formula [a-10] from a compound represented by the general formula [a-9] The compound represented by the general formula [a-10] For example, it can be produced by reducing a compound represented by the general formula [a-9] with iron powder in a solvent in the presence of an acid. The reaction temperature of the reaction is from 0 to 200 ° C., preferably from room temperature to heating to reflux. The reaction time range is usually from instant to 2
4 hours. The amount of the reagent used for the reaction is represented by the general formula [a
-9], the amount of the iron powder is 3
The ratio of the mole to excess amount is 1 to 10 moles of the acid, but can be arbitrarily changed depending on the reaction situation.
As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is directly or after filtration, poured into water, and the resulting crystals are collected by filtration or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization and concentration to give the desired product. Can be obtained. The target substance can be purified by an operation such as chromatography, recrystallization and the like.

<Step A9-3>: Step of producing compound represented by general formula [a-11] from compound represented by general formula [a-10] The compound represented by general formula [a-11] , I) diazotizing the compound represented by the general formula [a-10] in a solvent, and ii) subsequently, potassium iodide, copper (I) bromide,
It can be produced by reacting with copper (I) chloride or borofluoric acid in a solvent. The first stage diazotization reaction has a reaction temperature range of -20 to 20 ° C,
The range of the reaction time is usually from instant to 5 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mol per 1 mol of the compound represented by the general formula [a-10]. Can be changed. As the diazotizing agent used, sodium nitrite, potassium nitrite, isoamyl nitrite, t-nitrite
Nitrite compounds such as butyl and the like can be mentioned. As the solvent, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid,
Water and the like or a mixture thereof are mentioned. The reaction solution after completion of the reaction is used for the next reaction as it is. In the reaction of the second stage, the reaction temperature range is 0 to 80 ° C., and the reaction time range is usually instantaneous to 24 hours. The amount of the reagent used in the reaction is determined based on 1 mol of the compound represented by the general formula [a-10], based on potassium iodide, copper (I) bromide, and copper (I) chloride.
Alternatively, the amount of borofluoric acid is 1 to 3 moles each, but can be arbitrarily changed depending on the reaction situation. When copper [I] bromide is used, the reaction can be carried out in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be carried out in the presence of copper [II] chloride. Can also be performed.
Examples of the solvent include acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration to obtain the desired product. . The target product can be purified by an operation such as chromatography, recrystallization and the like. In addition, the reaction is not limited to the above method, and a solvent (for example, acetonitrile, diethyl ether, t-butylmethyl Ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, etc. or a mixture thereof) to react the compound represented by the general formula [a-10] with a diazotizing agent.

(Intermediate Production Method 10) Of the compounds represented by the general formula [III], X ¹ is a nitro group, a fluorine atom,
Compounds which are a chlorine atom, a bromine atom or an iodine atom and Y and W are an oxygen atom or a sulfur atom can also be produced by the method described in the following scheme.

Embedded image [Wherein R ¹ , R ² , R ⁷ , R ¹⁷ , X ² , X ³ , X ⁴ and X
¹² has the same meaning as described above. ]

<Step A10-1>: Step of producing a compound represented by the general formula [a-12] from a compound represented by the general formula [XIV] The compound represented by the general formula [a-12] is a compound represented by the general formula The formula [XI
V] and a general formula [b-2]

Embedded image [Wherein, R ¹⁷ , X ³ and X ⁴ represent the same meaning as described above. To a compound of the formula (1) in the presence of a base. The reaction is usually carried out without a solvent or in a solvent, and the reaction temperature range is from 0 to 20.
0 ° C., and the reaction time is usually from instant to 24 hours. The amount of the reagent used for the reaction is theoretically 1 mol of the compound represented by the general formula [b-2] and 1 mol of the base relative to 1 mol of the compound represented by the general formula [XIV]. The amount can be arbitrarily changed depending on the reaction situation. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propyl Organic bases such as amine, triisopropylamine, tri-n-butylamine, and diisopropylethylamine; and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, and barium carbonate. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene,
Aromatic halogenated hydrocarbons such as benzotrifluoride, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, acetone, 2-butanone, methyl isobutyl ketone, etc. Ketones, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, nitro compounds such as nitromethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, N, N-dimethylformamide, N, N-dimethyl Examples include acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof. After the completion of the reaction, the desired product can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. In addition, the target substance can be purified by an operation such as chromatography and recrystallization.

<Step A10-2>: General formula [a-12]
A step of producing a compound represented by the general formula [a-13] from a compound represented by the general formula [a-13]. For example, a compound represented by the general formula [a-12] It can be produced by reduction with iron powder in the presence of an acid. The reaction temperature of the reaction is from 0 to 200 ° C., preferably from room temperature to heating to reflux. The reaction time range is usually instantaneous ~
24 hours. The amount of the reagent used for the reaction is such that the amount of the iron powder is 3 mol to an excess amount, and the amount of the acid is 1 to 10 mol, relative to 1 mol of the compound represented by the general formula [a-12]. Can be arbitrarily changed depending on the reaction conditions. As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is directly or after filtration, poured into water, and the resulting crystals are collected by filtration, or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization, drying, and concentration, The desired product can be obtained. The target substance can be purified by an operation such as chromatography, recrystallization and the like.

<Step A10-3>: General formula [a-13]
A step of producing a compound represented by the general formula [a-14] from a compound represented by the general formula [a-14]: i) a compound represented by the general formula [a-13] in a solvent Ii) followed by potassium iodide, copper (I) bromide,
It can be produced by reacting with copper (I) chloride or borofluoric acid in a solvent. In the first stage diazotization reaction, the reaction temperature range is -20 to 20.
20 ° C., and the reaction time is usually from instant to 5 hours. The amount of the reagent used in the reaction is theoretically 1 mole of the diazotizing agent per 1 mole of the compound represented by the general formula [a-13]. Can be changed. Examples of the diazotizing agent used include nitrite compounds such as sodium nitrite, potassium nitrite, isoamyl nitrite and t-butyl nitrite. Examples of the solvent include acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid, water and the like, and a mixture thereof. The reaction solution after completion of the reaction is used for the next reaction as it is. In the reaction of the second stage, the reaction temperature range is 0 to 80 ° C., and the reaction time range is usually instantaneous to 24 hours. The amount of the reagent used in the reaction is determined based on the amount of potassium iodide, copper (I) bromide, copper (I) chloride or borofluoric acid per mole of the compound represented by the general formula [a-13]. Is a ratio of 1 to 3 mol, respectively, but can be arbitrarily changed depending on the reaction situation. When copper [I] bromide is used, the reaction can be carried out in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be carried out in the presence of copper [II] chloride. Can also be performed. As the solvent, for example, acetonitrile, diethyl ether, t-butyl methyl ether,
Examples include hydrobromic acid, hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration to obtain the desired product. . The target product can be purified by an operation such as chromatography, recrystallization and the like. In addition, the reaction is not limited to the above method, and a solvent (for example, acetonitrile, diethyl ether, diethyl ether,
t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid,
Water or a mixture thereof) in the general formula [a-13]
Can be produced by reacting a compound represented by the formula (1) with a diazotizing agent.

(Intermediate Production Method 11) Among the compounds represented by the general formula [III], those in which Y and W are oxygen atoms can also be produced by the method described in the following scheme. [Wherein, R ¹ , R ² , R ²⁰ , X ¹ , X ² , X ³ and X ⁴ represent the same meaning as described above. ]

<Step A11-1>: General formula [a-15]
Step for producing a compound represented by the general formula [a-16] from a compound represented by the general formula [a-16] The compound represented by the general formula [a-16] can be produced, for example, in "Handbook of Organic Chemistry Experiments" Vol. , Protective
Groups in Organic Synthesis (A Wiley-Interscience
publication [publishing company], the general formula [a
-15] by deprotecting the compound
Alternatively, it can be produced by the method described below.
The reaction is usually carried out without solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mole of the reagent to 1 mole of the compound represented by the general formula [a-15], but can be arbitrarily changed depending on the reaction situation. it can. As the reagent used,
Examples include a boron trifluoride methanol complex, and triethyloxonium tetrafluoroborate. Examples of the solvent used include aliphatic hydrocarbons such as hexane, heptane, octane, and ligroin; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and mesitylene; methylene chloride, chloroform;
Aliphatic halogenated hydrocarbons such as dichloroethane, 1,2,3-trichloropropane, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, 1,4-dioxane, tetrahydrofuran, ethyleneglycol Dimethyl ether, methyl-
Ethers such as t-butyl ether; alcohols such as methanol and ethanol; and mixtures thereof. After completion of the reaction, the reaction solution is poured into water, and the precipitated crystals are collected by filtration and dried, or extracted with an organic solvent and the organic layer is dried and concentrated, or the reaction solution is directly concentrated. By performing the treatment operation, the desired compound can be obtained. The compound is recrystallized, chromatographic
Purification can also be performed by such operations.

<Step A11-2>: General formula [a-16]
A process for producing a compound represented by the general formula [a-17] from a compound represented by the general formula [a-17]
16] in a solvent or in the absence of a solvent with an isocyanating agent to produce an isocyanate. Isocyanating agent: phosgene, trichloromethyl chloroformate, oxalyl chloride, etc. Amount of isocyanating agent: 1 mole to excess amount per mole of compound represented by general formula [a-16] Solvent: benzene, toluene Aromatic hydrocarbons such as chlorobenzene, halogenated aromatic hydrocarbons such as chlorobenzene, esters such as ethyl acetate, etc. Reaction temperature: room temperature to reflux temperature Reaction time: instantaneous to 48 hours By performing a post-treatment operation such as concentration, the desired product can be obtained. The compound can be purified by an operation such as recrystallization.

<Step A11-3>: General formula [a-17]
A process for producing a compound represented by the general formula [a-18] from a compound represented by the general formula [a-18]
17] and a compound represented by the general formula [XXXV] in a solvent in the presence of a base. Amount of compound represented by general formula [XXXV]: general formula [a
-17] to 0.9 to 10 with respect to 1 mole of the compound represented by the formula:
Molar ratio Type of base: inorganic bases such as sodium hydride, potassium hydroxide, sodium hydroxide, sodium methoxide,
Metal alkoxides such as sodium ethoxide and the like Amount of base: 0.1 to 10 mol based on 1 mol of the compound represented by the general formula [a-17] Solvent: aromatic hydrocarbons such as benzene and toluene; Halogenated aromatic hydrocarbons such as chlorobenzene, N, N-
Amides such as dimethylformamide, ethers such as tetrahydrofuran, halogenated aliphatic hydrocarbons such as chloroform, and mixtures thereof. Reaction temperature: −40 ° C. to solvent reflux temperature. Reaction time: instantaneous to 72 hours. Neutralize, pour the reaction solution into water, filter the precipitated crystals by filtration, or dry, or extract with an organic solvent and dry and concentrate the organic layer, or post-treat the reaction solution as it is By performing the operation, the desired compound can be obtained. The compound can be purified by an operation such as recrystallization or chromatography. The compound represented by the general formula [a-18] can be directly used for the next step reaction without isolation.

<Step A11-4>: General formula [a-18]
A process for producing a compound represented by the general formula [a-29] from a compound represented by the general formula [a-29]
18] and a compound represented by the general formula [XXXX] in the presence of a base. The reaction is usually performed in a solvent,
The range of the reaction temperature is -20 to 200C, preferably 0 to 100C. Reaction time range is usually from instant to 48
Time. The amount of the compound [XXXX] to be subjected to the reaction is from 0.5 mol to an excess amount, preferably 0.8 mol, per 1 mol of the compound represented by the general formula [a-18].
１．２1.2 mol. The amount of the base to be subjected to the reaction is from 0.5 mol to an excess amount per 1 mol of the compound represented by the general formula [a-18], and preferably 0.8 mol.
１．２1.2 mol. As the base, pyridine,
Organic bases such as 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine, and inorganic bases such as sodium carbonate, potassium carbonate, sodium hydride and potassium hydride. Hexane,
Aliphatic hydrocarbons such as heptane, octane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, mesitylene, diethyl ether, diisopropyl ether, 1,4-dioxane, tetrahydrofuran, ethylene Ethers such as glycol dimethyl ether and methyl tert-butyl ether; nitro compounds such as nitromethane and nitrobenzene; N, N-dimethylformamide;
Acid amides such as N, N-dimethylacetamide, tertiary amines such as pyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine and diisopropylethylamine; sulfur compounds such as dimethylsulfoxide and sulfolane; And the like. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water and crystals formed are collected, or the reaction solution is poured into water and then extracted with an organic solvent and concentrated. To give the desired product. The compound can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 12)
Among the compounds represented by I], those wherein X ¹ is a nitro group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, can also be produced by the method described in the following scheme. [Wherein, R ⁴ , R ⁵ , R ⁷ , R ¹⁷ , R ²⁰ , W, X ² , X ³ ,
X ⁴ , X ¹² and X ¹³ represent the same meaning as described above. ]

<Step A12-1>: General formula [a-19]
A process for producing a compound represented by the general formula [a-20] from a compound represented by the general formula [a-20]
19] and a compound of the general formula [b-3] [Wherein, R ⁴ , R ⁵ , R ¹⁷ , W, Y, X ³ , X ⁴ and n
Represents the same meaning as described above. And a compound represented by the formula:
It can be produced by reacting in the presence of a base. The reaction is usually performed without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used for the reaction is such that the compound represented by the general formula [b-3] is 1 mol and the base is 1 mol per 1 mol of the compound represented by the general formula [a-19]. Is a stoichiometric amount, but can be arbitrarily changed depending on the situation of the reaction. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .0] non-5-ene, 1,4-diazabicyclo [2.2.2]
Organic bases such as octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, and lithium carbonate And inorganic bases such as sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride and potassium hydride. As the solvent used, for example, n-hexane, n-heptane, ligroin, cyclohexane, aliphatic hydrocarbons such as petroleum ether, benzene, toluene, aromatic hydrocarbons such as xylene, chlorobenzene, dichlorobenzene,
Aromatic halogenated hydrocarbons such as benzotrifluoride, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, acetone, 2-butanone, methyl isobutyl ketone, etc. Ketones, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, nitro compounds such as nitromethane and nitrobenzene, nitriles such as acetonitrile and isobutyronitrile, N, N-dimethylformamide, N, N-dimethyl Examples include acid amides such as acetamide, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof. The reaction may be accelerated by using a catalyst. Catalysts include copper iodide, copper bromide, copper chloride,
Copper powder and the like are mentioned, and the amount of the catalyst used for the reaction is 0.1 to 1 mol of the compound represented by the general formula [a-19].
The ratio is from 0001 to 0.1 mol, but can be arbitrarily changed according to the situation of the reaction. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

<Step A12-2>: General formula [a-20]
A step of producing a compound represented by the general formula [a-21] from a compound represented by the general formula [a-21]. It can be produced by reduction with iron powder in the presence of an acid. The reaction temperature of the reaction is from 0 to 200 ° C., preferably from room temperature to heating to reflux. The reaction time range is usually instantaneous ~
24 hours. The amount of the reagent used for the reaction is such that the amount of the iron powder is 3 mol to an excess amount, and the amount of the acid is 1 to 10 mol, relative to 1 mol of the compound represented by the general formula [a-20]. Can be arbitrarily changed depending on the reaction conditions. As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is directly or after filtration, poured into water, and the resulting crystals are collected by filtration, or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization, drying, and concentration, The desired product can be obtained. The target substance can be purified by an operation such as chromatography, recrystallization and the like.

<Step A12-3>: General formula [a-21]
For producing a compound represented by the general formula [a-22] from a compound represented by the general formula [a-22]: i) a compound represented by the general formula [a-21] in a solvent Ii) followed by potassium iodide, copper (I) bromide,
It can be produced by reacting with copper (I) chloride or borofluoric acid in a solvent. The first stage diazotization reaction has a reaction temperature range of -20 to 20 ° C,
The range of the reaction time is usually from instant to 5 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mole of the diazotizing agent to 1 mole of the compound represented by the general formula [a-21]. Can be changed. As the diazotizing agent used, sodium nitrite, potassium nitrite, isoamyl nitrite, t-nitrite
Nitrite compounds such as butyl and the like can be mentioned. As the solvent, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid,
Water and the like or a mixture thereof are mentioned. The reaction solution after completion of the reaction is used for the next reaction as it is. In the reaction of the second stage, the reaction temperature range is 0 to 80 ° C., and the reaction time range is usually instantaneous to 24 hours. The amount of the reagent used in the reaction is determined based on 1 mol of the compound represented by the general formula [a-21], potassium iodide, copper (I) bromide, and copper (I) chloride.
Alternatively, the amount of borofluoric acid is 1 to 3 moles each, but can be arbitrarily changed depending on the reaction situation. When copper [I] bromide is used, the reaction can be carried out in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be carried out in the presence of copper [II] chloride. Can also be performed.
Examples of the solvent include acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration to obtain the desired product. . The target product can be purified by an operation such as chromatography, recrystallization and the like. The reaction is not limited to the above-mentioned method, but includes potassium iodide, copper (I) bromide (or a mixture with copper (II) bromide), copper (I) chloride (or a mixture with copper (II) chloride) ) Or borofluoric acid in the presence of a solvent (eg, acetonitrile, diethyl ether,
t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid,
Water or a mixture thereof) in the general formula [a-21]
Can be produced by reacting a compound represented by the formula (1) with a diazotizing agent.

<Step A12-4>: General formula [a-22]
Step for producing a compound represented by the general formula [a-23] from a compound represented by the general formula [a-23] The compound represented by the general formula [a-23] can be produced, for example, in "Handbook of Organic Chemistry Experiments" Vol. , Protective
Groups in Organic Synthesis (A Wiley-Interscience
publication [publishing company], the general formula [a
-22], the compound represented by
Alternatively, it can be produced by the method described below.
The reaction is usually carried out without solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used in the reaction is a theoretical amount of 1 mole of the reagent to 1 mole of the compound represented by the general formula [a-22], but may be arbitrarily changed depending on the reaction situation. it can. As the reagent used,
Examples include a boron trifluoride methanol complex, and triethyloxonium tetrafluoroborate. Examples of the solvent used include aliphatic hydrocarbons such as hexane, heptane, octane, and ligroin; aromatic hydrocarbons such as benzene, toluene, ethylbenzene, xylene, and mesitylene; methylene chloride, chloroform;
Aliphatic halogenated hydrocarbons such as dichloroethane, 1,2,3-trichloropropane, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene, benzotrifluoride, 1,4-dioxane, tetrahydrofuran, ethyleneglycol Dimethyl ether, methyl-
Ethers such as t-butyl ether; alcohols such as methanol and ethanol; and mixtures thereof. After completion of the reaction, the reaction solution is poured into water, and the precipitated crystals are collected by filtration and dried, or extracted with an organic solvent and the organic layer is dried and concentrated, or the reaction solution is directly concentrated. By performing the treatment operation, the desired compound can be obtained. The compound is recrystallized, chromatographic
Purification can also be performed by such operations.

<Step A12-5>: General formula [a-20]
Of producing a compound represented by the general formula [a-23] from a compound represented by the general formula [a-23] Among the compounds represented by the general formula [a-23], a compound in which X ¹³ is a nitro group is, for example, a compound represented by the general formula [a] -20] can be produced according to the method described in <Step A12-4>.

(Intermediate Production Method 13)
V] and the compound represented by the general formula [a-15], wherein X ¹ is a nitro group, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and the compound represented by the general formula [a-20] And a compound represented by the general formula [a-
22] can also be produced by the method described in the following scheme. [Wherein, R ⁴ , R ⁵ , R ⁷ , R ¹⁷ , X ² , X ³ , X ⁴ , X ¹² and X ¹³ represent the same meaning as described above, and R ²⁵ represents a methyl group, an ethyl group, a trifluoromethyl A C1-C6 alkyl group which may be substituted such as a group or a trichloromethyl group; a C1-C6 alkoxy group such as a methoxy group or an ethoxy group; or a phenoxy group which may be substituted such as a phenoxy group. ]

<Step A13-1>: General formula [a-24]
A process for producing a compound represented by the general formula [a-25] from a compound represented by the general formula [a-25]
24] and a compound represented by the general formula [b-2] in the presence of a base. The reaction is usually performed without a solvent or in a solvent, the reaction temperature is in the range of 0 to 200 ° C, and the reaction time is usually in the range of instant to 24 hours. The amount of the reagent used for the reaction is determined by the amount of the compound 1 represented by the general formula [a-24].
The compound represented by the general formula [b-2] is 1 mol
The theoretical ratio of the mole ratio and the base ratio is 1 mole, but can be arbitrarily changed depending on the reaction conditions. As the base to be used, pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-diazabicyclo [5.4.0] undec-7-ene, 1,5-diazabicyclo [4.3 .
0] non-5-ene, 1,4-diazabicyclo [2.
2.2] octane, 4-dimethylaminopyridine, N,
Organic bases such as N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, sodium methoxide, sodium ethoxide, potassium t-butoxide Such as metal alkoxides, lithium carbonate, sodium carbonate,
Potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride,
Potassium hydride, lithium hydroxide, sodium hydroxide,
Inorganic bases such as potassium hydroxide, calcium hydroxide, barium hydroxide and the like can be mentioned. As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, benzotrifluoride Aromatic halogenated hydrocarbons such as, diethyl ether, diisopropyl ether, methyl-t-butyl ether,
Ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diglyme; ketones such as acetone, 2-butanone and methyl isobutyl ketone; esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; and nitro such as nitromethane and nitrobenzene Compounds, nitriles such as acetonitrile, isobutyronitrile, N, N-dimethylformamide, N, N
Acid amides such as dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof. The reaction may be accelerated by using a catalyst. Examples of the catalyst include copper iodide, copper bromide, copper chloride, copper powder, and the like. The ratio is from 0.0001 to 0.1 mol, but can be arbitrarily changed depending on the situation of the reaction. After completion of the reaction, the target compound of the present invention can be obtained by, for example, the following operation 1) or 2). 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

<Step A13-2>: General formula [a-25]
A step of producing a compound represented by the general formula [a-26] from a compound represented by the general formula [a-26]. It can be produced by reduction with iron powder in the presence of an acid. The reaction temperature of the reaction is from 0 to 200 ° C., preferably from room temperature to heating to reflux. The reaction time range is usually instantaneous ~
24 hours. The amount of the reagent used for the reaction is such that the amount of the iron powder is 3 mol to an excess amount, and the amount of the acid is 1 to 10 mol, relative to 1 mol of the compound represented by the general formula [a-25]. Can be arbitrarily changed depending on the situation of the reaction. As the acid to be used, acetic acid and the like can be mentioned. Examples of the solvent to be used include water, acetic acid, ethyl acetate and the like or a mixture thereof. After completion of the reaction, the reaction solution is directly or after filtration, poured into water, and the resulting crystals are collected by filtration, or subjected to ordinary post-treatments such as extraction with an organic solvent, neutralization, drying, and concentration, The desired product can be obtained. The target substance can be purified by an operation such as chromatography, recrystallization and the like.

<Step A13-3>: General formula [a-26]
Step of producing a compound represented by the general formula [a-27] from a compound represented by the general formula [a-27]: i) a compound represented by the general formula [a-26] in a solvent Ii) followed by potassium iodide, copper (I) bromide,
It can be produced by reacting with copper (I) chloride or borofluoric acid in a solvent. The first stage diazotization reaction has a reaction temperature range of -20 to 20 ° C,
The range of the reaction time is usually from instant to 5 hours. The amount of the reagent to be subjected to the reaction is a theoretical amount of 1 mol of the diazotizing agent per 1 mol of the compound represented by the general formula [a-26]. Can be changed. As the diazotizing agent used, sodium nitrite, potassium nitrite, isoamyl nitrite, t-nitrite
Nitrite compounds such as butyl and the like can be mentioned. As the solvent, for example, acetonitrile, hydrobromic acid, hydrochloric acid, sulfuric acid,
Water and the like or a mixture thereof are mentioned. The reaction solution after completion of the reaction is used for the next reaction as it is. In the reaction of the second stage, the reaction temperature range is 0 to 80 ° C., and the reaction time range is usually instantaneous to 24 hours. The amount of the reagent used for the reaction is determined based on 1 mol of the compound represented by the general formula [a-26], potassium iodide, copper (I) bromide, and copper (I) chloride.
Alternatively, the amount of borofluoric acid is 1 to 3 moles each, but can be arbitrarily changed depending on the reaction situation. When copper [I] bromide is used, the reaction can be carried out in the presence of copper [II] bromide. When copper [I] chloride is used, the reaction can be carried out in the presence of copper [II] chloride. Can also be performed.
Examples of the solvent include acetonitrile, diethyl ether, t-butyl methyl ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, and the like, and mixtures thereof. After completion of the reaction, the reaction mixture is subjected to ordinary post-treatment such as filtration of the generated crystals (by adding water as necessary) or extraction with an organic solvent and concentration to obtain the desired product. . The target product can be purified by an operation such as chromatography, recrystallization and the like. In addition, the reaction is not limited to the above method, and a solvent (for example, acetonitrile, diethyl ether, t-butylmethyl Ether, hydrobromic acid, hydrochloric acid, sulfuric acid, water, and the like or a mixture thereof) to react the compound represented by the general formula [a-26] with a diazotizing agent. When copper bromide [I] is used, copper bromide [II]
The reaction can be carried out in the presence of copper chloride [I], and when copper chloride [I] is used, the reaction can also be carried out in the presence of copper chloride [II].

<Step A13-4>: General formula [a-27]
A process for producing a compound represented by the general formula [a-28] from a compound represented by the general formula [a-28]
27] and a compound represented by the general formula [IV] in the presence of a base. The reaction is usually performed in a solvent, and the reaction temperature is usually from 0 to 200 ° C, and the reaction time is usually from an instant to 72 hours. The amount of reagent used for the reaction is
For 1 mol of the compound represented by the general formula [a-27],
The theoretical amount of the compound represented by the general formula [IV] is 1 mole and the amount of the base is 1 mole, but can be arbitrarily changed depending on the reaction conditions. As the base used, pyridine, quinoline, benzyldimethylamine,
Phenethyldimethylamine, N-methylmorpholine,
1,8-diazabicyclo [5.4.0] undec-7
-Ene, 1,5-diazabicyclo [4.3.0] non-
5-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine And organic bases such as tri-n-butylamine and diisopropylethylamine; and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, calcium carbonate, barium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium hydride and potassium hydride. Can be As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, benzotrifluoride Aromatic halogenated hydrocarbons such as, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, ketones such as acetone, 2-butanone, methyl isobutyl ketone; Esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate; nitriles such as acetonitrile and isobutyronitrile; acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide Dimethyl sulfoxide, sulfur compounds such as sulfolane, or mixtures thereof. After completion of the reaction, for example, by the operation shown in 1) or 2) below,
The desired compound of the present invention can be obtained. 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

<Step A13-5>: General formula [a-25]
For producing a compound represented by the general formula [a-28] from a compound represented by the general formula [a-28] Among the compounds represented by the general formula [a-28], a compound in which X ¹³ is a nitro group is, for example, a compound represented by the general formula [a-28] -25] and a compound represented by the general formula [IV] in the presence of a base. The reaction is usually performed in a solvent, and the reaction temperature is usually from 0 to 200 ° C, and the reaction time is usually from an instant to 72 hours. The amount of the reagent used in the reaction is 1 mole of the compound represented by the general formula [a-25] and 1 mole of the compound represented by the general formula [IV], and the amount of the base is 1 mole relative to 1 mole of the compound represented by the general formula [a-25]. Is a stoichiometric amount, but can be arbitrarily changed according to the reaction situation. As the base used,
Pyridine, quinoline, benzyldimethylamine, phenethyldimethylamine, N-methylmorpholine, 1,8-
Diazabicyclo [5.4.0] undec-7-ene,
1,5-diazabicyclo [4.3.0] non-5-ene, 1,4-diazabicyclo [2.2.2] octane,
Organic bases such as 4-dimethylaminopyridine, N, N-dimethylaniline, N, N-diethylaniline, triethylamine, tri-n-propylamine, triisopropylamine, tri-n-butylamine, diisopropylethylamine, lithium carbonate, and carbonic acid Inorganic bases such as sodium, potassium carbonate, calcium carbonate, barium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, potassium hydride and the like can be mentioned. As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, petroleum ether, aromatic hydrocarbons such as benzene, toluene, xylene, chlorobenzene, dichlorobenzene, benzotrifluoride Aromatic halogenated hydrocarbons such as, ethers such as diethyl ether, diisopropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, diglyme, ketones such as acetone, 2-butanone, methyl isobutyl ketone; Ethyl formate, ethyl acetate, butyl acetate,
Esters such as diethyl carbonate; nitriles such as acetonitrile and isobutyronitrile; acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; sulfur compounds such as dimethyl sulfoxide and sulfolane; or mixtures thereof. Is mentioned. After completion of the reaction, for example, by the operation shown in 1) or 2) below,
The desired compound of the present invention can be obtained. 1) The reaction solution is poured into water, extracted with an organic solvent, and the organic layer is dried and concentrated. 2) Concentrate the reaction solution as it is or, if necessary, filter and concentrate the filtrate. The obtained compound of the present invention was obtained by chromatography,
Purification can also be performed by an operation such as recrystallization.

(Intermediate Production Method 14) Among the compounds represented by the general formula [III], the compound wherein W is an oxygen atom is
It can also be produced by the method described in the following scheme.

Embedded image [Wherein R ¹ , R ² , R ⁶ , X ¹ , X ² , X ³ , X ⁴ and Y
Represents the same meaning as described above, R ²³ represents an optionally substituted alkylcarbonyl group such as a formyl group or an acetyl group, or an optionally substituted alkoxycarbonyl group such as a methoxycarbonyl group; R ²⁴ represents a hydrogen atom; It represents an optionally substituted alkyl group such as a methyl group or an optionally substituted alkoxy group such as a methoxy group. ]

(Intermediate Production Method 15) Among the compounds represented by the general formula [III], those in which X ⁴ is a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom can be prepared by the method described in the following scheme. Can also be manufactured. [Wherein, R ¹ , R ² , R ⁶ , R ¹⁶ , W, X ¹ , X ² , X ³ , X
¹² and Y have the same meaning as described above. ]

(Intermediate Production Method 16) General Formula [a-25]
And among the compounds represented by [a-27], R ²⁵ is R
^The compound having ²⁰ groups can also be produced by the method described in the following scheme.

Embedded image Wherein R ¹⁶ , R ¹⁷ , R ²⁰ , X ² , X ³ , X ⁴ and X ¹³
Represents the same meaning as described above. The compound represented by the general formula [a-42] is Protective G
roups in Organic Synthesis (A Wiley-Interscience p
ublication) according to the general formula [a-
41] with boron tribromide, HB
r / acetic acid, concentrated hydrochloric acid, concentrated sulfuric acid, or the like for deprotection. Amount of reagent: 1 equivalent to 1 mol of compound [a-41]
Ratio of excess amount Solvent: aromatic hydrocarbons such as benzene and toluene, halogenated aliphatic hydrocarbons such as methylene chloride and chloroform, halogenated aromatic hydrocarbons such as chlorobenzene and the like, and mixtures thereof. . Reaction temperature: −20 ° C. to reflux temperature Reaction time: instantaneous to 48 hours After completion of the reaction, the reaction solution is poured into water or an acid such as concentrated hydrochloric acid is poured into the reaction solution, and the precipitated crystals are collected by filtration. After drying, or extraction with an organic solvent and drying and concentration of the organic layer, or a post-treatment operation such as concentration of the reaction solution as it is, the desired compound can be obtained. The compound can be purified by an operation such as recrystallization or chromatography. In addition, among the compounds represented by the general formula [a-41], when R ¹⁶ is a benzyl group which may be substituted, the compound can be produced by hydrogenation in the presence of a catalyst. The reaction is usually performed in a solvent. The range of the reaction temperature is usually -20 to 150 ° C, preferably 0 to 50 ° C. The range of the reaction time is usually from instant to 48 hours. The reaction can be carried out under a pressurized condition, and it is preferable to carry out the reaction under a condition of 1 to 5 atm. The amount of the catalyst used for the reaction is determined by the amount of the compound [a-4]
1] of 0.001 to 100% by weight. Examples of the catalyst used for the reaction include anhydrous palladium / carbon, hydrated palladium / carbon, platinum oxide and the like. Examples of the solvent include carboxylic acids such as formic acid, acetic acid and propionic acid, esters such as ethyl formate, ethyl acetate, butyl acetate and diethyl carbonate, and ethers such as 1,4-dioxane, tetrahydrofuran and ethylene glycol dimethyl ether. , Methanol, ethanol, propanol, isopropanol, butanol, t-butanol, amyl alcohol,
Examples thereof include alcohols such as isoamyl alcohol and t-amyl alcohol, water, and mixtures thereof.
After completion of the reaction, the reaction solution can be subjected to ordinary post-treatment operations such as filtration and concentration as it is to obtain the desired product. The compound can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 17) General Formula [XXXI]
Among the compounds represented by, compounds wherein Y is an oxygen atom or a sulfur atom can be produced by the method described in the following scheme. Wherein R ⁴ , R ⁵ , R ¹⁷ , W, X ² , X ³ , X ⁴ and X
¹³ represents the same meaning as described above, and R ¹¹ represents a C1-C3 perfluoroalkyl group. ]

<Step A17-1>: General formula [a-43]
From a compound represented by the general formula [a-44] (depending on conditions, a hydrate represented by the general formula [a-45] in which water is bonded to the compound represented by the general formula [a-44]) The compound represented by the general formula [a-44] can be obtained by a process represented by the general formula [a-44].
43] and a compound of the general formula [a-49]

Embedded image [Wherein, R ¹¹ and R ²⁶ represent the same meaning as described above. Can be produced by reacting the compound of the formula (1) with or without a solvent. The reaction temperature is usually from room temperature to 150 ° C. or the boiling point of the solvent used.
Further, the reaction rate can be increased by removing by-product alcohol (methanol, ethanol, etc.) from the reaction system. The general formula [a-
The amount of the compound represented by the formula [49] is usually 1 to 5 mol per 1 mol of the compound represented by the general formula [a-43]. As the solvent used, for example, aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane, 1,2-dichloroethane, 1,2,2
Aliphatic halogenated hydrocarbons such as 3-trichloropropane, aromatic hydrocarbons such as benzene, toluene and xylene, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and benzotrifluoride, or a mixture thereof. No. After completion of the reaction, the reaction solution is filtered and concentrated as it is, the reaction solution is poured into water and the resulting crystals are collected by filtration, or the reaction solution is poured into an acid such as concentrated hydrochloric acid or water, and then The target compound can be obtained by ordinary post-treatment operations such as extraction with an organic solvent, washing with water, drying and concentration. The target compound can be purified by an operation such as chromatography and recrystallization.

<Step A17-2>: General formula [a-44]
A process for producing a compound represented by the general formula [a-48] from a compound represented by the general formula [a-48]
44] and a cyanate salt at 55 ° C. to 150 ° C. in the presence of a protonic acid. Examples of the cyanate to be subjected to the reaction include potassium cyanate and sodium cyanate. Examples of the acid to be subjected to the reaction include aliphatic carboxylic acids such as acetic acid, propionic acid, and butyric acid, and benzoic acid. Aromatic carboxylic acids, sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid, inorganic acids such as hydrochloric acid and sulfuric acid, and boric acid such as phenylboric acid. The amount of the cyanate to be subjected to the reaction is 1 to 10 mol, preferably 1 to 2 mol, per 1 mol of the compound represented by the general formula [a-44]. . The amount of the acid used for the reaction is determined by the amount of the compound 1 represented by the general formula [a-44].
The ratio is from 1.1 mol to a large excess with respect to the mol. The reaction may be carried out using a solvent. Examples of the solvent include aliphatic hydrocarbons such as n-hexane, n-heptane, ligroin, cyclohexane and petroleum ether;
Aliphatic halogenated hydrocarbons such as dichloroethane, 1,2,3-trichloropropane, benzene, toluene,
Aromatic hydrocarbons such as xylene, aromatic halogenated hydrocarbons such as chlorobenzene, dichlorobenzene and benzotrifluoride; ethers such as dioxane, tetrahydrofuran, ethylene glycol dimethyl ether and diglyme; ketones such as methyl isobutyl ketone; nitromethane , Nitro compounds such as nitrobenzene, nitriles such as acetonitrile, isobutyronitrile, N, N-
Examples thereof include acid amides such as dimethylformamide and N, N-dimethylacetamide; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof.
The reaction is usually completed in 30 minutes to 100 hours. The reaction is preferably carried out by first bringing the reaction mixture from -20 ° C to 5 ° C.
After aging at 0 ° C, aging is performed at 55 ° C to 150 ° C until most of the compound represented by the general formula [a-44] in the reaction mixture disappears. After completion of the reaction, the reaction solution is filtered and concentrated as it is, or the reaction solution is poured into water and the resulting crystals are collected by filtration, or the reaction solution is poured into water and then subjected to organic solvent extraction and concentration. The target product can be obtained by performing ordinary post-processing operations. The compound can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 18) [Wherein, R ¹ , R ¹⁵ and R ¹⁷ represent the same meaning as described above,
R ²⁷ is a trialkylsilyl group such as a t-butyldimethylsilyl group; a C1-C6 alkyl group which may be substituted such as a t-butyl group, an isopropyl group or a methyl group; a benzyl group which may be substituted such as a benzyl group A protecting group such as a methoxymethyl group, an acetyl group, a methoxycarbonyl group or an ethoxycarbonyl group; R ²⁸ represents a hydrogen atom or a C1-C3 alkyl group such as a methyl group or an ethyl group; X ²¹ represents a bromine atom or iodine; X22 represents a hydrogen atom or a fluorine atom, and M represents a monovalent metal such as copper (I). The compound represented by the general formula [a-51] has the general formula [a-51]
50] and a metal cyanide salt represented by the general formula [XXXXXXIV]. The reaction is usually performed in a solvent, and the reaction temperature is usually from 140 ° C to 250 ° C. The range of the reaction time is usually from instant to 24 hours. Examples of the metal cyanide salt represented by the general formula [XXXXXXIV] to be subjected to the reaction include copper cyanide. The amount of the reagent to be subjected to the reaction is such that the amount of the metal cyanide salt represented by the general formula [XXXXXXIV] is 1 mol to excess per mol of the compound represented by the general formula [a-50]. Is the proportion of the quantity,
Preferably it is 1-2 mol, but it can be arbitrarily changed according to the reaction situation. Solvents that can be used in the reaction include, for example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-
Examples thereof include acid amides such as 2-pyrrolidone, sulfur compounds such as dimethyl sulfoxide and sulfolane, and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, or the reaction solution is poured into water and then subjected to ordinary post-treatment operations such as extraction with an organic solvent, washing with water, drying and concentration to obtain the target compound. Obtainable. The target compound can be purified by an operation such as chromatography and recrystallization.

(Intermediate Production Method 19) Wherein R ¹⁵ , R ¹⁷ , R ²⁵ , R ²⁷ , X ²¹ , X ²² and M
Represents the same meaning as described above. The compound represented by the general formula [a-53] includes, for example, a compound represented by the general formula [a-52] and a compound represented by the general formula [XXXXXXI]
V] and a metal cyanide salt thereof. The reaction is usually performed in a solvent, and the reaction temperature is usually from 140 ° C to 250 ° C.
The range of the reaction time is usually from instant to 24 hours. Examples of the metal cyanide salt represented by the general formula [XXXXXXIV] to be subjected to the reaction include copper cyanide. The amount of the reagent to be subjected to the reaction is based on 1 mol of the compound represented by the general formula [a-52] and 1 mol of the compound represented by the general formula [XXXXXXI]
The amount of the cyan compound represented by the formula [V] is from 1 mol to an excess amount, preferably from 1 to 2 mol, but can be arbitrarily changed depending on the reaction conditions. Examples of the solvent that can be used in the reaction include N, N-dimethylformamide, N, N-dimethylacetamide, N
Acid amides such as -methyl-2-pyrrolidone; sulfur compounds such as dimethylsulfoxide and sulfolane; and mixtures thereof. After completion of the reaction, the reaction solution is filtered and concentrated as it is, or the reaction solution is poured into water and then subjected to ordinary post-treatment operations such as extraction with an organic solvent, washing with water, drying and concentration to obtain the target compound. Obtainable.
The target compound can be purified by an operation such as chromatography and recrystallization.

The compound represented by the general formula [XXXXXXII] is described, for example, in International Patent Application Publication No. WO 98/088.
No. 24 or can be produced according to the method described in the publication, and can be represented by a compound represented by the general formula [XXXXI], a compound represented by the general formula [XXI], or a compound represented by the general formula [XXIV] The compound represented by the general formula [XX] and the compound represented by the general formula [XXV] can be commercially available or can be produced by a known method.

The compound of the present invention has excellent herbicidal activity,
Some show excellent selectivity between crops and weeds. That is, the compound of the present invention has a herbicidal effect on various weeds, which are the following problems, in foliage treatment and soil treatment in the field. Red-bellied weed: Oenother
a erythrosepala), Oenothera laciniata Ranunculaceae weeds: Togemino foxne button (Ranu)
nculus muricatus, Ibomi buttercup (Ranunculus sardous) Polygonaceae Weed: Polygonum con
volvulus), Polygonum (Polygonum)
lapathifolium), Polygonum pensylvanicu
m), Hartade (Polygonum persica)
ria), Rumex crisp
s), Rumex obtusifo (Rumex obtusifo)
lius) and knotweed (Polygonum csp)
idatum) Purslaneaceae Weed: Purslane (Portulaca)
oleracea) Weeds of the family Coleoptera: Chickweed (Stellaria med)
ia), Dutch Cerastium g
lomeratum) Acalyaceae Weed: Shiroza (Chenopodial al)
bum), Butterfly (Kochia scopari)
a) Amaranthaceae weed: Amaranthus r
etroflexus)
lanthus hybridus Brassicaceae Weed: Wild Radish (Raphan)
us raphanistrum)
inapis arvensis, Capsicum (Caps)
bur bursa-pastoris) and Mamegunbainazu (Lepidium virginicu)
m)

Legume weeds: American hornflower (Se
sbania exaltata), lobster (Ca
ssia obtusifolia), Florida Vega
Weed (Desmodium torutuosu)
m), white clover (Trifomium repen)
s), Vicia sativ (Vicia sativ)
a), Clickago palm (Medicago lup)
ulina) Malvaceae Weed: Abutilon theop
hrusti), American deer (Sida sp.)
inosa) Violet weeds: Field panji (Viola ar)
vensis), Wild Panji- (Viola tr)
icor) Rubiaceae Weed: Gallium apari
ne) Convolvulaceae weed: American morning glory (Ipomoea)
hederacea), Malva Asagao (Ipomoe)
a purpura), Malva American morning glory (I
pomoea hederacea var integ
riuscula) and bean sagao (Ipomoea)
lacunosa), Convolvulus convolvulus (Convol)
vulus arvensis)

Lamiaceae Weeds: Larvae (Lami)
um purpurum), Photohenosa (Lamiu)
amampicule) Solanaceae Weed: White Datura (Datur)
a Stramonium), Dog Physalis (Sola)
num nigrum Scrophulariaceae Weed: Veronica
ca persica), Tachiinoufuguri (Vero)
nica arvensis)
onica hederaefolia Asteraceae Weed: Xanthium pensy
lvanicum), wild sunflower (Helianth)
us annuus), chamomile (Matricari)
a chamomilla), dog chamomile (Matr)
icaria performata or inodor
a), Common Mary Gold (Chrysanthem)
um segetum), savory ostrich (Matrica)
ria matricarioides, Ragweed (Ambrosia artemisiifoli)
a), Ambrosia trifid
a), Artemisia cana
densis), mugwort (Artemisia pri)
nceps), Solidago (Solidag)
o altissima), Dandelion (Tar)
axacum officinale Weaselaceae Weed: Forget-me-nots (Myosotis a)
Ravensis (Coleoptera: Chrysomelidae): Asclepias
syriaca spurges weed: Euphorbi
a helioscopia), Onishikisou (Eu)
phorbia maculata Anthracidae Weed: Geranium
carolinianum)

Oxalis weeds: Purple oxalis (Ox
aris corymbosa Cucurbitaceae Weeds: Arechiuri (Sicyos angula)
tus) Grass weed: Echinochloa cr
us-galli), Enokorogosa (Setaria)
viridis), Aquinoe nokorogosa (Setari)
a faberi), Meishishiba (Digitalias)
anguinalis), Hawkgrass (Eleusine)
indica), Poa annua (Poa annu)
a), Blackgrass (Alopecurus myo)
suloides), oats (Avena fat)
ua), Sorghum sorghum (Sorghum hale)
pense), barley (Agropyron rep)
ens), Umanohashiki (Bromus tecto)
rum), Cynodone dact (Cynodone dact)
ylon), cane millet (Panicum dich)
otomiflorum), Texas honeycomb (Pan)
icum texanum), Shata cane (Sor
ghum vulgare)
opecurus geniculatus Cyperaceae Weed: Commelina co
mmunis) Rhododendron weeds: horsetail (Equisetum arve)
nse) Cyperaceae Weeds: Cygous cyperus (Cyperus)
iria), nectarine (Cyperus rotund)
us), yellowtail sedge (Cyperus esculen)
tus)

Some of the compounds of the present invention include corn (Zea mays) and wheat (Tritic).
um aestivum), barley (Hordeum)
vulgare), rice (Orysa sativ)
a), Sorghumcolor, soybean (Glycine max), cotton (Gossip)
ium spp. ), Sugar beet (Beta vulgar)
is), peanuts (Arachis hypogae)
a) Sunflower (Helianthus annuu)
s), and does not show any phytotoxicity which would be a problem for main crops such as rapeseed (Brassica napus) and horticultural crops such as flowers and vegetables. Further, the compound of the present invention, soybean,
Various weeds that are problematic in non-tillage cultivation of corn, wheat, etc. can be effectively eliminated. Moreover, some of the compounds of the present invention do not exhibit any harmful effects on crops.

Further, the compound of the present invention has a herbicidal effect on various weeds which are the following problems in flooding treatment of paddy fields. Grass weeds: Echinochloa o
ryzicola) Scrophulariaceae Weed: Azena (Lindernia p.
rocumbens) Loxodontaceae Weeds: Rota indi
ca), hamemisohagi (Ammannaia multi)
flora) Dipterocarpaceae Weeds: Dictyostelium (Elatine tr)
iandra) Cyperaceae Weeds: Cyperus
diffirmis), fireflies (Sirpus j)
uncoides, pine trees (Eleocharis)
Acicularis) and Cyperus (Cyper)
us serotinus, Krogwai (Eleoc)
haris kuroguwai Watermelonaceae Weed: Monochoria v
aginalis) Weeds: Urikawa (Sagittaria p.
ygmaea), Omodaka (Sagittariat)
rifolia), Spiderfish (Alismacan)
aliculatum Weevil: Weevil (Potamogeto)
N distinctus Apiaceae Weeds: Api (Oenanthe Javanic)
a) Moreover, some of the compounds of the present invention do not show any phytotoxicity that would cause a problem for transplanted rice.

Furthermore, the compound of the present invention can be used, for example, on slopes of embankments, riverbeds, road shoulders and slopes, railroads, parks, parks, grounds, parking lots, airports, lands for industrial facilities such as factories and storage facilities, and rest areas. Arable land, or non-agricultural land where weed growth needs to be controlled, such as in urban land, or
A wide range of weeds that occur in orchards, pastures, lawns, and forests can be removed. The compound of the present invention can be used in rivers, waterways,
Water hyacinth (Eichh) which occurs in canals and reservoirs
herbicides on aquatic weeds such as Ornia crassipes. The compound of the present invention has properties similar to those of the herbicidal compound described in International Patent Application Publication No. WO95 / 34659, and the herbicide resistance gene and the like described in the specification are introduced. In the case of cultivating crops imparted with herbicide tolerance, it becomes possible to use the compound of the present invention at a higher dose than that used in cultivation of normal crops without tolerance, which is undesirable. Weeds can be effectively removed.

When the compound of the present invention is used as an active ingredient of a herbicide, a solid carrier, a liquid carrier, a surfactant,
It is mixed with other formulation auxiliaries to form emulsions, wettable powders, suspensions, granules, concentrated emulsions, wettable granules and the like. These preparations contain the compound of the present invention as an active ingredient in a weight ratio of 0.001 to 80%, preferably 0.005 to 80%.
７０70%. As a solid carrier, mineral powder such as kaolin clay, attapulgite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, organic fine powder such as walnut shell powder, and water-soluble organic fine powder such as urea Examples thereof include fine powders of inorganic salts such as ammonium sulfate and fine powders of synthetic hydrous silicon oxide. As the liquid carrier, methylnaphthalene, phenylxylylethane,
Aromatic hydrocarbons such as alkylbenzene such as xylene,
Alcohols such as isopropanol, ethylene glycol and 2-ethoxyethanol, esters such as dialkyl phthalate, ketones such as acetone, cyclohexanone and isophorone, mineral oil such as machine oil, soybean oil ,
Vegetable oils such as cottonseed oil, dimethyl sulfoxide, N, N-
Examples include dimethylformamide, acetonitrile, N-methylpyrrolidone, water and the like. Surfactants used for emulsification, dispersion, wet spreading, etc. include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, dialkyl sulfosuccinates, polyoxyethylene alkyl aryl ether phosphates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ethers;
Ter, polyoxyethylene alkyl aryl ether,
Examples include nonionic surfactants such as polyoxyethylene polyoxypropylene block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbitan fatty acid ester. Other auxiliaries for preparations include ligninsulfonate, alginate, polyvinyl alcohol-
, Gum arabic, CMC (carboxymethylcellulo-
And PAP (acidic isopropyl phosphate).

The compound of the present invention is usually formulated and subjected to soil treatment, foliage treatment or flooding treatment before or after emergence of weeds. Soil treatment includes soil surface treatment and soil admixture treatment.
There is a local treatment for treating only weeds so as not to adhere to crops. In addition, by using it by mixing with other herbicides,
Increased herbicidal efficacy may be observed. Furthermore, it can be mixed or used in combination with an insecticide, an acaricide, a nematicide, a fungicide, a plant growth regulator, a fertilizer, a soil conditioner, and the like.
Examples of such herbicides are shown below. Atrazine, cyanazine (cya)
nazine), dimethamethrin (dimethameme)
trin), metribuzin,
Promethrin, simazine (si
mazine), simetryn (symmetryn), chlortoluron, diuron, fluometuron (fluomet)
uron), isoproturon (isoproturon)
n), linuron, metabenzthiazuron, propanil, bentazone (bent)
azone), bromoxynil
l), ioxynil, pyridate butamifos, dithiopyr (d
ithiopyr), etalfluralin (ethalf)
luralin), pendimesalin (pendime)
thalin), thiazopyr,
Trifluralin, acetochlor, arachlor (al
achlor, butachlor
r), diethatyl-ethyl
yl), dimethenamide (dimethenamide)
d), fluthiamide, mefenacet, metrachlor, pretilachlor (pr)
etilachlor), propachlor (propa)
chlor), cinmethililine (cinmethyli)
n) Acifluorfen, acifluorfen-Na salt (acifluorfen-so)
dim), benzfendizone
zone), bifenox, butafenacil, chlomethoxynil, fomesafen, lactofen
fen), oxadiazon, oxadiargyl, oxyfluorfen, carfentrazone-ethyl
l), fluazolate, fullmicrolacpentyl (flumiclorac-pe)
ntyl), flumioxazin (flumioxazi)
ne), fluthiacet methyl
-Methyl), isopropazole (isoprop)
azol), sulfentrazone (sulfentra)
zone), thidiazimine
n), azafenidin, pyraflufen-ethyl
l), sinidone-ethyl difenzoquat, diquat, paraquat
t)

2,4-D, 2,4-DB, clopyralid, dicamba
a), fluroxypyr, MC
PA, MCPB, mecoprop,
Quinclorac, triclopyr azimsulfuron, bensulfuron-meth
yl), chlorimuron ethyl
-Ethyl), chlorsulfuron (chlorsul)
furon), cloranslam methyl (clorans)
ulam-methyl), cyclosulfamuron (c
iclosulfamuron, dicloslam (di)
Closlam), ethoxysulfuron (ethox)
ysulfuron), flazasulfuron (flaza)
sulfuron), flucarbazone (flucarb)
azone), flumetsura (flumetsula)
m), flupyrsulfur (flupyrsulfur)
on), halosulfuron methyl (halosulfur)
on-methyl), imazosulfuron (imazo)
sulfuron), iodosulfuron (iodos)
ulfuron), metosura (methosula)
m), metsulfuron-methyl (metsulfuron-
methyl), nicosulfuron (nicosulfu)
ron), oxasulfuron
n), primisulfuron methyl (primisulfu)
ron-methyl), procarbazone Na salt (pr
ocarbazone-sodium, prosulfuron, pyrazosulfuron-ethyl, rimsulfuron, sulfometuron-methyl
l), sulfosulfuron (sulfosulfuron)
n), triasulfuron
n), tribenuron-methyl (tribenuron-
methyl), tritosulfuron (tritosul)
furon), thifensulfuron-methyl (this)
nsulfuron-methyl, triflusulfuron-methyl
yl), pyribenzonoxi
m), bispyribac-Na salt (bispyribac-
sodium, pyriminobac-methyl (pyrimi)
nobac-methyl, pyrithiobac-sodium, imazameth, imazamethabenz-methyl, imazamox, imazapic (i)
mazapic), imazapyr (imazapyr),
Imazaquin (imazaquin), imazethapyr (i
mazethapyr) Tepraloxydim, alloxydim Na salt (alloxydim-sodiu)
m), clethodim, clodinahop-propargyl (clodinafop-prop)
argyl), cyhalofobutyl (cyhalofo)
p-butyl, diclohopmethyl (diclof)
op-methyl), fenoxaprop-ethyl, fenoxaprop-ethyl, fenoxaprop-ethyl
hyl), fluazifop butyl (fluazifop)
-Butyl), fluazifop-p-butyl (fl
uazipop-p-butyl, haloxyfop-methyl, quizalofop-p-ethyl (quizalofop-p-eth)
yl), sethoxydim, traloxydim

Diflufenic (diflufenic)
an), flurtamone, norflurazone, benzofenap, isoxaflutole, pyrazolate (pyr)
azolate), pyrazoxifen (pyrazox)
yfen), sulcotrion
e), clomazone, mesotrione, isoxachlortor, bialaphos, glufocine
Ammonium salt (glufosinate-ammo)
nium), glyphosat (glyphosat)
e), sulfosate dichlobenil, isoxaben benthiocarb, butyrate
(Butylate), dime pipette (dimep)
iperate), EPTC, esprocarb (esp)
rocarb, molinate, pyributicarb, trilatelate diflufenzopyr bromobutide, DSMA,
MSMA, cafenstrol
l), daimuron, epoprodan, flupoxam (flupox)
am), metobenzuron
n), pentoxazone, piperophos, triaziflam, beflubutamid, benzobicyclone, benzobifenclos, clomeprop, clomepropane, clomepropane, clomeprop, clomeprop, clomeprop, framezap, clomeprop; flora
sulam), indanofan (indanofa)
n), isoxadifen, mesotrione, naproanilide, oxaziclomefone, pesoxyamide, phenothiol
nothiol), pyridafor (pyridafo)
l)

The above compounds were obtained from Farm Chemicals Handbook (Meister Publishing Company) [Far
m Chemical Handbook (Meiste
r Publishing Company) 1995
Annual version of the catalog, Agchem New Compound Review 1995 (Agchem Information Service)
[AG CHEM NEW COMPOUND REVIE
W, VOL. 13, 1995 (AG CHEM INF
ORMATION SERVICE)], Agchem New Compound Review 1997 Edition (Agchem Information Service) [AG CHEM NEW COM
POUND REVIEW, VOL. 15, 1997
(AG CHEM INFORMATION SERVI
CE)], Agchemnu-Compound Review-199
Eighth Edition (Agchem Information Service) [AG
CHEM NEW COMPOUND REVIEW, V
OL. 16, 1998 (AG CHEM INFORMA
AG SERVICE)], Agchem New Compound Review 1999 Edition (Agchem Information Service) [AG CHEM NEW COMPOUN]
D REVIEW, VOL. 17, 1999 (AG CH
EM INFORMATION SERVICE)],
Listed in the Herbicide Research Directory (Hakutosha),
It is described in "Herbicide Research Directory (Hakutosha)". When the compound of the present invention is used as an active ingredient of a herbicide, the treatment amount varies depending on weather conditions, preparation form, treatment time, treatment method, soil conditions, target crops and target weeds, but is usually 0 per hectare. 0.011 g to 20000 g, preferably 1 g to 12000 g. Emulsions, wettable powders, suspensions, concentrated emulsions, wettable powders and the like are usually prepared in a predetermined amount of 10 to 1000 liters per hectare ( If necessary, the mixture is diluted with water (supplemented with an auxiliary such as a spreading agent) and treated, and granules and certain suspending agents are usually treated without dilution. Here, as an auxiliary agent used as needed, in addition to the above-mentioned surfactant, polyoxyethylene resin acid (ester), lignin sulfonate, abietic acid salt, dinaphthylmethane disulfonate, crop oil concentrate ( crop oi
l concentrate), vegetable oils such as soybean oil, corn oil, cottonseed oil, sunflower oil and the like. In addition, the compound of the present invention can be used as a cotton defoliant / desiccant, potato (S
olanumtuberosum) can be used as an active ingredient of a harvesting aid such as a desiccant. In this case, the compound of the present invention is usually formulated in the same manner as when used as an active ingredient of a herbicide, and foliage treatment is carried out alone or in combination with another harvesting aid before harvesting the crop.

[0087]

EXAMPLES The present invention will be described in more detail with reference to Production Examples, Formulation Examples and Test Examples, but the present invention is not limited to these Examples. First, a production example of the compound of the present invention and a production example of a production intermediate are shown. The compound numbers of the compounds of the present invention are the numbers described in Tables 1 to 30 below. Production Example 1: Production of compound 1-1 of the present invention 4- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Production Example 1) 0.43
g, was dissolved in 2.0 ml of N, N-dimethylformamide, and 0.15 g of anhydrous potassium carbonate was added.
After adding 0.17 g of methyl 2-bromopropionate,
Stirred at 70 ° C. for 3 hours. After cooling the reaction to room temperature,
The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- [4- {2-chloro-4-fluoro-
Methyl 5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} phenoxy] propionate [Compound 1-1 of the present invention] 0.39 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 1.61 (d, 3H, J = 6.9 Hz);
52 (s, 3H), 3.77 (s, 3H), 4.70
(Q, 1H, J = 6.7 Hz), 6.31 (s, 1
H), 6.7-6.8 (m, 1H), 6.8-6.9.
(M, 2H), 6.9-7.0 (m, 2H), 7.36
(D, 1H, J = 9.0 Hz)

Production Example 2: Production of compound 2-1 of the present invention 3- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Preparation Example 2) 0.30
g, dissolved in N, N-dimethylformamide (1.4 ml), and anhydrous potassium carbonate (0.10 g) was added thereto.
After adding 0.11 g of methyl 2-bromopropionate,
Stirred at 70 ° C. for 3 hours. After cooling the reaction to room temperature,
The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- [3- {2-chloro-4-fluoro-
Methyl 5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} phenoxy] propionate [Compound 2-1 of the present invention] 0.28 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 1.60 (d, 3H, J = 7.0 Hz);
53 (s, 3H), 3.75 (s, 3H), 4.74
(Q, 1H, J = 6.7 Hz), 6.32 (s, 1
H), 6.5-6.7 (m, 3H), 6.9-7.0.
(M, 1H), 7.1-7.3 (m, 1H), 7.38
(D, 1H, J = 8.9 Hz)

Production Example 3: Production of Compound 3-1 of the Present Invention 2- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
0.23 g of 2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol was dissolved in 6 ml of N, N-dimethylformamide, and 0.22 g of anhydrous potassium carbonate was dissolved.
And 0.13 g of methyl 2-bromopropionate was added under stirring at room temperature, followed by stirring at 80 ° C. for 3 hours. After the reaction solution was cooled to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- [2- {2-
Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl propionate [Compound 3-1 of the present invention]
0.23 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 1.47 (d, 3H, J = 6.8 Hz);
50 (q, 3H, J = 0.7 Hz), 3.6-3.8
(M, 3H), 4.6-4.8 (m, 1H), 6.28
(S, 1H), 6.7-6.8 (m, 1H), 6.8-
6.9 (m, 1H), 6.9-7.1 (m, 1H),
7.1-7.2 (m, 2H), 7.3-7.4 (m, 1
H)

The physical properties of the compound of the present invention produced by the same method as described in Production Example 3 (Production Method 1) are shown below. 2- [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)
Ethyl-1, -2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] propionate [Compound 3-2 of the present invention] ¹ H-NMR (CDCl ₃ / 250M
Hz) δ (ppm): 1.23 (t, 3H, J = 7.1)
Hz), 1.47 (d, 3H, J = 6.8 Hz),
3.50 (s, 3H), 4.1-4.3 (m, 2H),
4.6-4.8 (m, 1H), 6.3-6.4 (m, 1
H), 6.7-7.0 (m, 3H), 7.0-7.2.
(M, 2H), 7.3-7.4 (m, 1H)

[0091] [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy diphenoxy] methyl acetate [Compound 3 of the present invention
-11] Melting point: 116.4 ° C [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy｝ phenoxy] ethyl acetate [Compound 3 of the present invention]
-12] _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 1.26 (t, 3H, J = 7.1 Hz), 3.5
0 (s, 3H), 4.19 (q, 2H, J = 7.2H
z), 4.64 (s, 2H), 6.28 (s, 1H),
6.7-6.8 (m, 1H), 6.9-7.2 (m, 4
H), 7.36 (d, 1H, J = 8.8 Hz)

Production Example 4: Production of Compound 3-189 of the Present Invention Step 1: 2- [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)
Dissolve 0.365 g of methyl-1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenoxy] propionate [Compound 3-1 of the present invention] in 4 ml of 1,4-dioxane, and add concentrated hydrochloric acid with stirring. After adding a mixed solution of 1 ml and water 1 ml, the mixture was heated and stirred under reflux conditions for 5 hours and 45 minutes. After cooling, ice water was added to the reaction solution, ethyl acetate and saturated saline were added thereto, and the mixture was separated. The organic layer was added with aqueous sodium hydrogen carbonate, and the mixture was separated. Was added to make the mixture acidic, ethyl acetate was added, and the mixture was separated. The organic layer was washed with brine, dried over magnesium sulfate, and concentrated to give 2- [2- {2-chloro-4. 0.183 g of -fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} phenoxy] propionic acid was obtained. Was. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 1.53 (d, 3H, J = 6.9 Hz), 3.51
(s, 3H), 4.76-4.83 (m, 1H), 6.3.
2 (d, 1H, J = 3.5 Hz), 6.63 to 6.67
(M, 1H), 7.0 to 7.1 (m, 2H), 7.1 to
7.2 (m, 2H), 7.38 (d, 1H, J = 9.0
Hz)

Step 2: 2- [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)
-1,2,3,6-Tetrahydropyrimidin-1-yl] phenoxydiphenoxy] propionic acid is dissolved in tetrahydrofuran, thionyl chloride is added with stirring, and the mixture is heated and stirred under reflux. Thereafter, the mixture is allowed to cool, concentrated, and dissolved in tetrahydrofuran (hereinafter, referred to as solution A). Tetrahydrofuran is added to 1-pentyl alcohol, solution A is added, and then pyridine is added. After stirring at room temperature, 2% aqueous hydrochloric acid was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer is washed with brine, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 5/1) to give 2- [2- {2-chloro-4-.
Fluoro-5- [3-methyl-2,6-dioxo-4-
Pentyl (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] propionate [Compound 3-189 of the present invention] is obtained.

Production Example 5: Production of Compound 3-20 of the Present Invention Step 1: [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy diphenoxy] methyl acetate [Compound 3 of the present invention
-11] 0.4 g was dissolved in 1,4-dioxane (4 ml), a mixed solution of concentrated hydrochloric acid (1 ml) and water (1 ml) was added with stirring, and the mixture was heated and stirred under reflux for 12 hours. After cooling, ice water was added to the reaction solution, ethyl acetate and saturated saline were added thereto, and the mixture was separated. The organic layer was added with aqueous sodium hydrogen carbonate, and the mixture was separated. To make it acidic,
After adding ethyl acetate, liquid separation was performed. The organic layer was washed with saturated saline, dried over magnesium sulfate, concentrated, and then concentrated.
-{2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
0.252 g of 2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] acetic acid was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.50 (d, 3H, J = 1.2 Hz), 4.66
(S, 2H), 6.31 (s, 1H), 6.69 (d, 1
H, J = 6.5 Hz), 6.98 to 7.20 (m, 4
H), 7.38 (d, 1H, J = 8.8 Hz)

Step 2: [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
After dissolving 1.0 g of phenoxy [phenoxy] acetic acid in tetrahydrofuran, 0.7 ml of thionyl chloride was added with stirring, and the mixture was heated with stirring under reflux for 2 hours. Thereafter, the solution was allowed to cool, concentrated, and dissolved in 3 ml of tetrahydrofuran (hereinafter, referred to as solution B). 0.7 ml of tetrahydrofuran was added to 0.05 g of allyl alcohol, a solution obtained by dividing the solution B into three equal portions was added, and 0.17 ml of pyridine was added.
After stirring at room temperature for 2 hours, 2% aqueous hydrochloric acid was poured into the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 5/1) to give [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4-]. (Trifluoromethyl) -1,2,3,6-
Tetrahydropyrimidin-1-yl] phenoxy {phenoxyacetic acid] allyl [Compound 3-20 of the present invention] 0.08
g was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.50 (d, 3H, J = 1.2 Hz), 4.62
4.64 (m, 2H), 4.68 (s, 2H), 5.
22-5.32 (m, 2H), 5.8-6.0 (m, 1
H), 6.28 (s, 1H), 6.76 (d, 1H, J =
6.5 Hz), 6.91 to 7.14 (m, 4H), 7.
35 (d, 1H, J = 8.6 Hz)

Production Example 6: Production of compound 3-16 of the present invention 2- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-Tetrahydropyrimidin-1-yl] phenoxydiphenol (0.20 g) was dissolved in N, N-dimethylformamide (2 ml), potassium carbonate (0.083 g) was added, and the mixture was stirred at room temperature for 50 minutes. 0.077 g of t-butyl chloroacetate was added thereto, and the mixture was stirred at 40 to 60 degrees for 2 hours. After allowing to cool, ice water was added to the reaction solution, and ethyl acetate and saturated saline were added, followed by separation. The organic layer was washed with saturated saline, dried over magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography (developing solvent: n-
Hexane / ethyl acetate = 6/1) and [2- {2-
Chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] phenoxy {phenoxy] t-butyl acetate [Compound 3-16 of the present invention]
0.39 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 1.44 (s, 9H), 3.49 (d, 3H, J =
1.1 Hz), 4.53 (s, 2H), 6.27 (s, 1
H), 6.80 (d, 1H, J = 6.6 Hz), 6.8-
7.2 (m, 4H), 7.35 (d, 1H, J = 8.9)
Hz) Melting point 55.6 ° C

Production Example 7: Production of compound 3-198 of the present invention [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
1.5 g of phenoxy [phenoxy] acetic acid was dissolved in 6 ml of tetrahydrofuran, 1 ml of thionyl chloride was added with stirring, and the mixture was heated with stirring under reflux for 2 hours and 10 minutes. Thereafter, the mixture was allowed to cool, concentrated, and dissolved in 3 ml of tetrahydrofuran (hereinafter, referred to as solution C). 1 ml of tetrahydrofuran was added to 0.273 g of isobutyl alcohol, and a solution obtained by dividing solution C into three equal portions was added.
Was added. Thereafter, the mixture was stirred at room temperature for 2 hours, 2% hydrochloric acid was added to the reaction solution, ethyl acetate was added, and the mixture was separated. The organic layer was washed with saturated saline and dried over magnesium sulfate. Concentrated. The residue is subjected to silica gel column chromatography (developing solvent: hexane / ethyl acetate = 6/1).
And [2- {2-chloro-4-fluoro-5- [3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
0.34 g of isobutyl [yl] phenoxy} phenoxy] acetate [Compound 3-198 of the present invention] was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 0.89 (d, 6H, J = 6.7 Hz), 1.8 to
2.0 (m, 1H), 3.50 (d, 3H, J = 1.2H
z), 3.92 (d, 2H, J = 6.7 Hz), 4.67
(s, 2H), 6.28 (s, 1H), 6.77 (d, 1
H, J = 6.6 Hz), 6.85 to 7.15 (m, 4
H), 7.36 (d, 1H, J = 8.9 Hz)

Production Example 8: Production of compound 3-11 of the present invention [2- {2-chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl acetate 0.93 g, potassium carbonate 0.3
0.58 g of methyl iodide was added to a mixture of 1 g and 10 ml of N, N-dimethylformamide, and the mixture was stirred at room temperature for 2 hours. 50 ml of diluted hydrochloric acid was added thereto, and the mixture was extracted with ethyl acetate. The organic layer was washed with water and saturated saline. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography to give [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- Methyl (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] acetate [Compound 3-11 of the present invention] (0.82
g) was obtained. _{^{1 H-NMR (CDCl 3/}} 250 MHz) δ (ppm): 3.49-3.50 (m, 3H),
3.73 (s, 3H), 4.66 (s, 2H), 6.28 (s, 1H), 6.76 (d,
1H, J = 6.6 Hz), 6.9-7.2 (m, 4H), 7.36 (d, 1H, J = 8.9
Hz)

Production Example 9: Production of compound 3-12 of the present invention [2- {2-chloro-4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl iodide is added to a mixture of ethyl acetate, potassium carbonate and N, N-dimethylformamide, and the mixture is stirred at room temperature. Dilute hydrochloric acid is added thereto, and the mixture is extracted with ethyl acetate. The organic layer is washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to give [2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6]. [Tetrahydropyrimidin-1-yl] phenoxy} phenoxy] ethyl acetate [Compound 3-12 of the present invention] is obtained.

Production Example 10: Production of compound 1-2 of the present invention 4- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Production Example 1) 100 m
g was dissolved in 1.0 ml of N, N-dimethylformamide, and 42 mg of anhydrous potassium carbonate was added.
46 mg of ethyl 2-bromopropionate was added, and
For 2 hours. After the reaction solution was cooled to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- [4- {2-chloro-4-fluoro-5-
[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
85 mg of ethyl 1-yl] phenoxy {phenoxy] propionate [Compound 1-2 of the present invention] was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 1.27 (t, 3H, J = 7.0 Hz), 1.6
0 (d, 3H, J = 6.9 Hz), 3.52 (s, 3
H), 4.23 (q, 2H, J = 7.0 Hz), 4.6.
8 (q, 1H, J = 6.9 Hz), 6.31 (s, 1
H), 6.7-6.8 (m, 1H), 6.8-6.9.
(M, 2H), 6.9-7.0 (m, 2H), 7.37
(D, 1H, J = 8.9 Hz)

Production Example 11 Production of Compound 1-11 of the Present Invention 4- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Production Example 1) 150 m
g was dissolved in 1.0 ml of N, N-dimethylformamide, 51 mg of anhydrous potassium carbonate was added, 50 mg of methyl bromoacetate was added under stirring at room temperature, and the mixture was stirred at 60 ° C. for 2 hours. After the reaction solution was cooled to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, and [4]
-{2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl acetate [Compound 1-1 of the present invention]
1] 167 mg was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.52 (q, 3H, J = 1.1 Hz), 3.8
1 (s, 3H), 4.62 (s, 2H), 6.32
(S, 1H), 6.74 (d, 1H, J = 6.6H
z), 6.8-6.9 (m, 2H), 6.9-7.0
(M, 2H), 7.37 (d, 1H, J = 8.9 Hz)

Production Example 12: Production of compound 2-11 of the present invention 3- {2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Production Example 2) 100 m
g was dissolved in 1 ml of N, N-dimethylformamide, 34 mg of anhydrous potassium carbonate was added, 37 mg of methyl bromoacetate was added under stirring at room temperature, and the mixture was stirred at 60 ° C for 1 hour. After the reaction solution was cooled to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, and [3-
{2-chloro-4-fluoro-5- [3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
3,6-Tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl acetate [Compound 2-11 of the present invention]
110 mg were obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.53 (q, 3H, J = 0.9 Hz), 3.8
0 (s, 3H), 4.61 (s, 2H), 6.32.
(S, 1H), 6.60 (s, 1H), 6.6-6.7
(M, 2H), 6.92 (d, 1H, J = 6.6H
z), 7.23 (d, 1H, J = 7.9 Hz), 7.3
9 (d, 1H, J = 9.0 Hz)

Production Example 13: Production of compound 5-7 of the present invention 3- {2-cyano-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Production Example 9) 72 mg
Is dissolved in 1.0 ml of N, N-dimethylformamide,
After adding 31 mg of anhydrous potassium carbonate and adding 31 mg of methyl 2-bromopropionate under stirring at room temperature, the mixture was stirred at 70 ° C for 1 hour. After cooling the reaction solution to room temperature, the reaction solution was poured into water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- [3- {2-cyano-4-fluoro-5- [3
-Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
80 mg of methyl [yl] phenoxy @ phenoxy] propionate [Compound 5-7 of the present invention] was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 1.62 (d, 3H, J = 6.8 Hz), 3.5
3 (q, 3H, J = 1.4 Hz), 3.77 (s, 3
H), 4.75 (q, 1H, J = 6.8 Hz), 6.3.
−6.4 (m, 1H), 6.6-6.8 (m, 3H),
6.8-6.9 (m, 1H), 7.2-7.3 (m, 1
H), 7.53 (d, 1H, J = 8.4 Hz)

Production Example 14: Production of compound 5-22 of the present invention 3- {2-cyano-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol (see Intermediate Preparation Example 9) 32 mg
Was dissolved in 0.5 ml of acetonitrile, and 13 mg of methyl bromoacetate and 13 mg of anhydrous potassium carbonate were added.
Stirred at 0 ° C. for 1.5 hours. After cooling the reaction solution to room temperature, the reaction solution was subjected to silica gel column chromatography to obtain [3- {2-cyano-4-fluoro-5- [3-
Methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1-
26 mg of methyl [yl] phenoxy {phenoxy] acetate [Compound 5-22 of the present invention] was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.53 (q, 3H, J = 1.0 Hz), 3.8
1 (s, 3H), 4.63 (s, 2H), 6.32.
(S, 1H), 6.6-6.7 (m, 1H), 6.7-
6.8 (m, 2H), 6.85 (d, 1H, J = 5.9
Hz), 7.2-7.4 (m, 1H), 7.54 (d,
1H, J = 8.4Hz)

Production Example 15: Production of compound 4-19 of the present invention Methyl (2-hydroxyphenoxy) acetate 15.16
g, 2,5-difluoro-4- [3-methyl-2,6-
Dioxo-4- (trifluoromethyl) -1,2,3
A mixture of 29.23 g of 6-tetrahydropyrimidin-1-yl] nitrobenzene (see Intermediate Preparation Example 4), 11.5 g of anhydrous potassium carbonate and 160 ml of N, N-dimethylformamide was stirred at room temperature for 30 minutes and then at 70 ° C. 3
Stirred for hours. 5 g of methyl (2-hydroxyphenoxy) acetate was added and stirred for 1 hour. The reaction solution was poured into 2% aqueous hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated.
The residue was subjected to silica gel column chromatography,
[2- {4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] -2-nitrophenoxydiphenoxy] acetate [Compound 4-
19] 17.8 g were obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.50 (q, 3H, J = 1.0 Hz), 3.7
0 (s, 3H), 4.63 (s, 2H), 6.28
(S, 1H), 6.88 (d, 1H, J = 8.4H
z), 6.93 (d, 1H, J = 6.0 Hz), 7.0
−7.1 (m, 1H), 7.1-7.3 (m, 2H),
7.87 (d, 1H, J = 8.7 Hz)

Production Example 16: Production of compound 3-11 of the present invention 11.02 g of isoamyl nitrite and 45 m of acetonitrile
l of [2- {2-amino-4-fluoro-5-
[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
Methyl 1-yl] phenoxy {phenoxy] acetate (see Intermediate Preparation Example 10) 15.16 g, copper (I) chloride 6.
21 g, copper (II) chloride 12.65 g, acetonitrile 2
The mixture was added dropwise to 50 ml of the mixture at room temperature and stirred for 2 hours. The reaction was poured into 2% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give [2- {2-chloro-4-fluoro-5].
13 g of methyl-[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} phenoxy] acetate [Compound 3-11 of the present invention] I got

The physical properties of the compound of the present invention produced by the same method as described in Production Example 16 (<Step 5-2> of Production Method 5) are shown below. [2- {2,4-difluoro-5- [3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
3,6-tetrahydropyrimidine-1-yl] phenoxy} phenoxy] methyl acetate [present compound 4-20] _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.52 (s, 3H), 3.72 (s, 3H),
4.64 (s, 2H), 6.32 (s, 1H), 6.8
-7.2 (m, 6H)

[0108] [2- {2-bromo-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy diphenoxy] methyl acetate [Compound 4 of the present invention
-21] _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.53 (q, 3H, J = 1.0 Hz), 3.7
2 (s, 3H), 4.65 (s, 2H), 6.33
(S, 1H), 6.72 (d, 1H, J = 6.4H
z), 6.8-7.2 (m, 4H), 7.53 (d, 1
H, J = 8.6 Hz)

Production Example 18: Production of Compound 4-22 of the Present Invention [2- {2-bromo-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy diphenoxy] methyl acetate [Compound 4 of the present invention
-21], a mixture of 1.5 g, copper cyanide 0.34 g and N-methyl-2-pyrrolidone 10 ml was mixed with 170-18.
Stirred at 0 ° C. for 3 hours. After cooling the reaction system to room temperature, water and aqueous ammonia were added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was washed with dilute hydrochloric acid, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography (developing solvent; hexane / ethyl acetate = 3 /
1) to give 5-fluoro-2- (3-methoxyphenoxy)-[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-1 -Yl] cyanobenzene [Compound 4-
22] 0.37 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.49 (q, 3H, J = 0.8 Hz), 3.7
1 (s, 3H), 4.63 (s, 2H), 6.27
(S, 1H), 6.79 (d, 1H, J = 5.8H)
z), 6.87 (d, 1H, J = 8.1 Hz), 7.0
−7.1 (m, 1H), 7.1-7.3 (m, 2H),
7.49 (d, 1H, J = 8.4 Hz)

Intermediate Production Example 1: 4- {2-chloro-4-
Fluoro-5- [3-methyl-2,6-dioxo-4-
Production of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol First step: A mixture of 1.71 g of 4-benzyloxyphenol and 4.0 ml of N, N-dimethylformamide was added dropwise to a mixture of 0.34 g of sodium hydride and 8.5 ml of N, N-dimethylformamide under ice-cooling for 20 minutes. Stirred.
2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-
A mixture of 3.0 g of [tetrahydropyrimidin-1-yl] nitrobenzene (see Intermediate Production Example 4) and 7.0 ml of N, N-dimethylformamide was added dropwise at the same temperature,
Stir for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed once with 1N hydrochloric acid and once with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- (4-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3. 2,6-tetrahydropyrimidin-1-yl] nitrobenzene 2.0 g was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.51 (q, 3H, J = 1.2 Hz), 5.0
4 (s, 2H), 6.31 (s, 1H), 6.87
(D, 1H, J = 5.9 Hz), 6.9-7.1 (m,
4H), 7.3-7.5 (m, 5H), 7.84 (d,
1H, J = 8.6Hz)

Second step: 2- (4-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) was added to a mixture of 2.0 g of iron powder, 6 ml of acetic acid and 0.6 ml of water. ) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene 1.9 g of acetic acid
0 ml of the solution was added dropwise while maintaining the temperature of the reaction solution at 35 ° C. or lower. After completion of the dropwise addition, stirring was continued for 2 hours, and then the reaction solution was filtered through celite and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate and concentrated. The resulting residue was subjected to silica gel chromatography to give 2- (4-benzyloxyphenoxy). ) -5-Fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
1.0 g of 2,3,6-tetrahydropyrimidin-1-yl] aniline was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.51 (q, 3H, J = 1.3 Hz), 5.0
2 (s, 2H), 6.30 (s, 1H), 6.58
(D, 1H, J = 6.9 Hz), 6.62 (d, 1H,
J = 10.8 Hz), 7.3-7.5 (m, 5H)

Step 3: 0.46 g of isoamyl nitrite was added to 2- (4-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] aniline 1.0 g, copper (I) chloride 0.38 g, copper (II) chloride
A mixture of 0.78 g and 14 ml of acetonitrile was dropped at room temperature and stirred for 1 hour. The reaction was poured into 2% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, and ([4-
{2-chloro-4-fluoro-5- [3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
0.73 g of 3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl) benzene was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.51 (s, 3H), 5.03 (s, 2H),
6.30 (s, 1H), 6.74 (d, 1H, J = 6.
5 Hz), 6.9-7.0 (m, 4H), 7.2-7.
5 (m, 6H)

Step 4: ([4- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy [phenoxy] methyl) benzene 0.72 g
2 ml of ethyl acetate, 0.7 ml of ethanol and 10 ml
36% palladium / carbon was added, and the mixture was stirred at room temperature under a hydrogen atmosphere for 5 hours. After purging the reaction system with nitrogen, the reaction solution was filtered over Celite, and the filtrate was concentrated to give 4- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4-. (Trifluoromethyl) -1,2,3,6-
0.48 g of [tetrahydropyrimidin-1-yl] phenoxydiphenol was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.51 (s, 3H), 5.2-5.5 (b, 1
H), 6.30 (s, 1H), 6.6-7.0 (m, 5
H), 7.36 (d, 1H, J = 9.0 Hz)

Intermediate Production Example 2: 3- {2-chloro-4-
Fluoro-5- [3-methyl-2,6-dioxo-4-
Production of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol Step 1: A mixture of 1.71 g of 3-benzyloxyphenol and 4.0 ml of N, N-dimethylformamide was added dropwise to a mixture of 0.34 g of sodium hydride and 8.5 ml of N, N-dimethylformamide under ice cooling. Stirred.
2,5-difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-
A mixture of 3.0 g of [tetrahydropyrimidin-1-yl] nitrobenzene (see Intermediate Production Example 4) and 7.0 ml of N, N-dimethylformamide was added dropwise at the same temperature,
Stir for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed once with 1N hydrochloric acid and once with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2- (3-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3 , 6-tetrahydropyrimidin-1-yl] nitrobenzene 2.4 g. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.53 (q, 3H, J = 1.2 Hz), 5.0
3 (s, 2H), 6.33 (s, 1H), 6.6-6.
7 (m, 1H), 6.7-6.8 (m, 1H), 6.8
−6.9 (m, 1H), 7.01 (d, 1H, J = 6.
1 Hz), 7.2-7.5 (m, 6H), 7.87
(D, 1H, J = 8.6Hz)

Step 2: To a mixture of 2.5 g of iron powder, 8 ml of acetic acid and 0.8 ml of water was added 2- (3-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl 5.)-1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene 2.4 g acetic acid
0 ml of the solution was added dropwise while maintaining the temperature of the reaction solution at 35 ° C. or lower. After completion of the dropwise addition, stirring was continued for 2 hours, and then the reaction solution was filtered through celite and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate and concentrated, and the obtained residue was subjected to silica gel chromatography to give 2- (3-benzyloxyphenoxy) ) -5-Fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
1.5 g of 2,3,6-tetrahydropyrimidin-1-yl] aniline was obtained. Melting point: 67.0 ° C

Step 3: 0.34 g of isoamyl nitrite was added to 2- (3-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] aniline 1.5 g, copper (I) chloride 0.57 g, copper (II) chloride
To a mixture of 1.17 g and 21 ml of acetonitrile was added dropwise at room temperature and stirred for 1 hour. The reaction was poured into 2% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, ([3-
{2-chloro-4-fluoro-5- [3-methyl-2,
6-dioxo-4- (trifluoromethyl) -1,2,2
There was obtained 1.01 g of 3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl) benzene. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.53 (q, 3H, J = 0.9 Hz), 5.0
3 (s, 2H), 6.33 (s, 1H), 6.6-6.
7 (m, 2H), 6.7-6.8 (m, 1H), 6.9
2 (d, 1H, J = 6.5 Hz), 7.2-7.5
(M, 7H)

Step 4: ([3- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Phenoxy [phenoxy] methyl) benzene 1.01 g
To the mixture were added 3 ml of ethyl acetate, 1 ml of ethanol and 50 mg of 10% palladium / carbon, and the mixture was stirred at room temperature for 5 hours under a hydrogen atmosphere. After replacing the reaction system with nitrogen, the reaction solution was filtered over celite, and the filtrate was concentrated to give 3- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4-. 0.68 g of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.52 (s, 3H), 5.5-5.8 (b, 1
H), 6.32 (s, 1H), 6.4-6.5 (m, 1
H), 6.5-6.6 (m, 2H), 6.93 (d, 1
H, J = 6.7 Hz), 7.17 (dd, 1H, J =
8.3, 7.9 Hz), 7.38 (d, 1H, J = 9.
0Hz)

Intermediate Production Example 3: 2- {2-chloro-4-
Fluoro-5- [3-methyl-2,6-dioxo-4-
Production of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol Step 1: A mixture of 4.05 g of 2-benzyloxyphenol and 9.5 ml of N, N-dimethylformamide was added dropwise to a mixture of 0.80 g of sodium hydride and 20 ml of N, N-dimethylformamide under ice cooling, followed by stirring for 30 minutes. . 2,
5-Difluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene (see Intermediate Preparation Example 4) A mixture of 7.1 g and 17 ml of N, N-dimethylformamide was added dropwise at the same temperature, and the mixture was stirred for 1 hour. The reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed once with 1N hydrochloric acid and once with saturated brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2-
(2-benzyloxyphenoxy) -5-fluoro-4-
[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
8.6 g of [1-yl] nitrobenzene were obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.52 (q, 3H, J = 1.1 Hz), 5.0
1 (s, 2H), 6.31 (s, 1H), 6.81
(D, 1H, J = 6.0 Hz), 6.9-7.1 (m,
2H), 7.1-7.4 (m, 7H), 7.78 (d,
1H, J = 8.7Hz)

Step 2: To a mixture of 8.6 g of iron powder, 27 ml of acetic acid and 2.7 ml of water was added 2- (2-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-2,6-dioxo-4- (trifluoromethyl ) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene 8.6 g of acetic acid 2
A 3 ml solution was added dropwise while maintaining the temperature of the reaction solution at 35 ° C. or lower. After completion of the dropwise addition, stirring was continued for 2 hours, and then the reaction solution was filtered through celite and diluted with ethyl acetate. The mixture was neutralized with saturated aqueous sodium hydrogen carbonate, the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate and concentrated, and the resulting residue was subjected to silica gel chromatography to give 2- (2-benzyloxyphenoxy) ) -5-Fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
6.46 g of 2,3,6-tetrahydropyrimidin-1-yl] aniline was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.50 (q, 3H, J = 1.2 Hz), 5.0
6 (s, 2H), 6.29 (s, 1H), 6.57 (d
d, 1H, J = 8.5, 1.6 Hz), 6.9-7.0
(M, 1H), 7.0-7.1 (m, 3H), 7.2-
7.4 (m, 6H)

Step 3: 4.46 g of isoamyl nitrite was added to 2- (2-benzyloxyphenoxy) -5-fluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
2,3,6-tetrahydropyrimidin-1-yl] aniline 6.46 g, copper chloride (I) 2.45 g, copper chloride (I
I) A mixture of 5.04 g and 90 ml of acetonitrile was added dropwise at room temperature and stirred for 1 hour. The reaction was poured into 2% hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography, ([2
-{2-chloro-4-fluoro-5- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
4.6 g of 2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] methyl) benzene were obtained. Melting point: 50.8 ° C Step 4: ([2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
4.5 g of phenoxy [phenoxy] methyl) benzene
To the mixture were added 230 ml of ethyl acetate and 0.46 g of 10% palladium / carbon, and the mixture was stirred at room temperature under a hydrogen atmosphere for 5 hours. After purging the reaction system with nitrogen, the reaction solution was filtered over celite, and the filtrate was concentrated to give 2- {2-chloro-4-fluoro-5- [3-methyl-2,6-dioxo-4-. (Trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol 3.57 g
I got Melting point: 55.4 ° C

Intermediate Production Example 4: 2,5-Difluoro-4
Production of-[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene 1.77 g of 2,4,5-trifluoronitrobenzene and 3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine
94 g was dissolved in dimethyl sulfoxide (10 ml), and anhydrous potassium carbonate (1.52 g) was added at room temperature.
Stirred for hours. After the reaction solution was cooled to room temperature, the reaction solution was poured into ice water and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 2,5-difluoro-4- [3-methyl-2,6-
Dioxo-4- (trifluoromethyl) -1,2,3
6-Tetrahydropyrimidin-1-yl] nitrobenzene 1.51 g was obtained. Melting point: 150 ° C

Intermediate Production Example 5: [2- {2-chloro-4]
Production of methyl -fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenoxy] acetate Step 1: 2.73 g of 2-methoxyphenol and potassium carbonate5.
5 g was added to 20 ml of dimethylformamide, and the temperature was raised to 60 ° C. N- (2,5-difluoro-
4.3 g of 4-nitrophenyl) acetamide and N, N-
A solution consisting of 30 ml of dimethylformamide is added to 60 to 6
It was added dropwise at a temperature of 5 ° C. After stirring for 1 hour, the mixture was cooled to room temperature, poured into water, extracted with ethyl acetate, and the organic layer was washed with diluted hydrochloric acid, washed with water, dried over magnesium sulfate and concentrated to give N- [2
5.52 g of -fluoro-5- (2-methoxyphenoxy) -4-nitrophenyl] acetamide was obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 2.16 (3H, s), 3.78 (3H,
s), 6.85-7.22 (4H, m), 7.75-7.83 (1H, br), 7.83 (1H, d, J
= 10.7Hz), 8.04 (1H, d, J = 6.9Hz)

Step 2: N- [2-fluoro-5- (2-methoxyphenoxy)
After dissolving 5.4 g of [-4-nitrophenyl] acetamide in 50 ml of methylene chloride, 4.7 g of boron tribromide was dissolved.
Was added under ice cooling. After stirring at the same temperature for 2 hours, concentrated hydrochloric acid was added, the mixture was poured into water, extracted with ethyl acetate, the organic layer was washed with water, dried over magnesium sulfate and concentrated. The obtained crystals were washed with t-butyl methyl ether to give N- [2-fluoro-5-
(2-Hydroxyphenoxy) -4-nitrophenyl]
3.2 g of acetamide were obtained. ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 2.20 (3 H, s), 6.33 (1 H, b
s), 6.86-7.23 (4H, m), 7.63 (1H, bs), 7.81 (1H, d, J = 10.
3 Hz), 8.34 (1H, d, J = 6.7Hz)

Step 3: After dissolving 3.02 g of N- [2-fluoro-5- (2-hydroxyphenoxy) -4-nitrophenyl] acetamide in 20 ml of N, N-dimethylformamide, 1.5 g of potassium carbonate was added and the mixture was allowed to stand at room temperature for 1 hour. Stirred. Thereafter, 1.6 g of methyl bromoacetate was added at room temperature. After stirring at the same temperature for 2 hours, the mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with dilute hydrochloric acid, washed with water, dried over magnesium sulfate and concentrated, and the obtained crystals were washed with t-butyl methyl ether and [2- ( 2. Methyl 5-acetylamino-4-fluoro-2-nitrophenoxy) phenoxy] acetate
01 g was obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 2.16 (3H, s), 3.73 (3H,
s), 4.62 (2H, s), 6.95-7.26 (4H, m), 7.71 (1H, bs), 7.85 (1
H, d, J = 10.7Hz), 8.06 (1H, d, J = 6.9Hz)

Step 4: 2.2 g of iron powder was added to a mixture of 40 ml of acetic acid and 40 ml of water, and the temperature was raised to 80 ° C. [2- (5-
Acetylamino-4-fluoro-2-nitrophenoxy) phenoxy] methyl acetate (3.0 g) was added, and the mixture was heated under reflux for 30 minutes. Thereafter, the mixture is poured into water and extracted with ethyl acetate. The organic layer is washed with water, saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated to give methyl [2- (5-acetylamino-2-amino-4-fluorophenoxy) phenoxy] acetate. 2.01 g were obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 2.11 (3H, s), 3.31 to 4.1
5 (2H, br), 3.76 (3H, s), 4.71 (2H, s), 6.54 (1H, d, J = 11.9H
z), 6.90-7.01 (4H, m), 7.17 (1H, bs), 7.69 (1H, d, J = 7.5H
z)

Step 5: To 30 ml of concentrated hydrochloric acid was added methyl [2- (5-acetylamino-2-amino-4-fluorophenoxy) phenoxy] acetate 2.0, and the mixture was stirred at room temperature for 1 hour. Thereafter, an aqueous solution comprising 0.42 g of sodium nitrite and 3 ml of water was added under ice cooling. After stirring at the same temperature for 1 hour, 40 ml of t-butyl methyl ether was added, and 0.85 g of copper (I) chloride was further added.
Was added. After stirring for 30 minutes, water was added and the mixture was extracted with t-butyl methyl ether. The organic layer was washed with water, dried over magnesium sulfate, and concentrated. / 1) and [2- (5-acetylamino-2-chloro-4-
Fluorophenoxy) phenoxy] methyl acetate 0.52
g was obtained. Melting point: 138.9 ° C

Step 6: Boron trifluoride methanol complex / methanol solution 10m
[2- (5-acetylamino-2-chloro-4-
Fluorophenoxy) phenoxy] methyl acetate 0.25
g was added and stirred with heating for 3 hours. Thereafter, the reaction solution was concentrated, the residue was dissolved in ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and concentrated, and methyl [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] acetate [ Intermediate compound A3-22] (0.2 g) was obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 3.74 (3H, s), 3.86 (2H, b
r), 4.70 (2H, s), 6.36 (1H, d, J = 8.21Hz), 6.83-7.09 (5H, m)

Step 7: [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] methyl acetate [intermediate compound A3-2
2], pyridine is added dropwise to a mixture of methyl chloroformate and tetrahydrofuran, and the mixture is stirred at room temperature. Dilute hydrochloric acid is added to the reaction solution, which is extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
Concentrate to obtain methyl [2- (2-chloro-4-fluoro-5-methoxycarbonylaminophenoxy) phenoxy] acetate [intermediate compound A9-22].

Step 8: N, N-Dimethylformamide and sodium hydride are added to ethyl 3-amino-4,4,4-trifluorocrotonate, and the mixture is stirred at 0 ° C. Then, [2-
A mixture of methyl (2-chloro-4-fluoro-5-methoxycarbonylaminophenoxy) phenoxy] acetate [intermediate compound A9-22] and N, N-dimethylformamide is added, and the mixture is stirred at 80 ° C. After the reaction solution was cooled to room temperature, it was poured into a mixture of hydrochloric acid and ice water, and the precipitated crystals were collected by filtration and [2- {2-chloro-4-fluoro-5-
[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
[Phenoxy diphenoxy] methyl acetate is obtained.

Intermediate Production Example 6 [2- {2-chloro-
Preparation of ethyl 4-fluoro-5- [2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenoxy] acetate Step 1: 1.1 g of catechol and 2.76 g of potassium carbonate were added to N, N
-The mixture was added to 20 ml of dimethylformamide and heated to 60 ° C. N- (2,5-difluoro-4-) was added into the mixture.
A solution consisting of 2.16 g of nitrophenyl) acetamide and 10 ml of N, N-dimethylformamide was used for 65-70.
It was added dropwise at a temperature of ° C. After keeping it warm for 1 hour, cool it down to room temperature,
The mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with diluted hydrochloric acid, washed with water, dried over magnesium sulfate and concentrated. The obtained crystals were washed with t-butyl methyl ether to give N- [2-fluoro-5- (2- 2.56 g of [hydroxyphenoxy) -4-nitrophenyl] acetamide were obtained. ¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm): 2.20 (3 H, s), 6.33 (1 H, b
s), 6.86-7.23 (4H, m), 7.63 (1H, bs), 7.81 (1H, d, J = 10.
3 Hz), 8.34 (1H, d, J = 6.7Hz)

Step 2: 9.5 g of iron powder in a mixed solution of 25 ml of acetic acid and 25 ml of water
Was added and the temperature was raised to 80 ° C. 10.0 g of N- [2-fluoro-5- (2-hydroxyphenoxy) -4-nitrophenyl] acetamide and ethyl acetate 10
A solution consisting of 0 ml was added dropwise. After heating under reflux for 1 hour, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water, saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate and concentrated to give N- [4-amino-2-fluoro-5- (2-hydroxyphenoxy). )
7.42 g of [phenyl] acetamide were obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 2.16 (3H, s), 6.48 (1H,
d, J = 11.6Hz), 6.74 ~ 6.78 (2H, m), 6.93 ~ 6.96 (2H, m), 7.35
(1H, bs), 7.47 (1H, d, J = 7.4Hz)

Step 3: After dissolving 7.4 g of N- [4-amino-2-fluoro-5- (2-hydroxyphenoxy) phenyl] acetamide in 30 ml of acetonitrile, copper (II) chloride is added.
5.42 g was added and the mixture was stirred at room temperature. A solution consisting of 4.16 g of t-butyl nitrite and 5 ml of acetonitrile was added dropwise thereto at around room temperature. After stirring at room temperature for 1 hour, the mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with dilute hydrochloric acid, washed with water, dried over magnesium sulfate, and concentrated, and the resulting residue was subjected to silica gel chromatography (developing solvent; hexane / ethyl acetate =
2/1) to give N- [4-chloro-2-fluoro-
3.92 g of 5- (2-hydroxyphenoxy) phenyl] acetamide were obtained. ¹ H-NMR (250 MHz, CDCl ₃ ) δ (ppm): 2.19 (3H, s), 5.72 (1H,
s), 6.70-6.84 (2H, m), 7.01-7.03 (2H, m), 7.23 (1H, d, J = 1
0.3Hz), 7.34 (1H, bs), 8.18 (2H, d, J = 7.4Hz)

Step 4: After N- [4-chloro-2-fluoro-5- (2-hydroxyphenoxy) phenyl] acetamide is dissolved in N, N-dimethylformamide, potassium carbonate is added and the mixture is stirred at room temperature. Thereafter, ethyl bromoacetate is added at room temperature. After stirring at the same temperature, the mixture was poured into water, extracted with ethyl acetate, and the organic layer was washed with dilute hydrochloric acid, washed with water, dried over magnesium sulfate, and concentrated. Amino-2-chloro-4-fluorophenoxy) phenoxy] ethyl acetate is obtained.

Step 5: Ethyl [2- (5-acetylamino-2-chloro-4-fluorophenoxy) phenoxy] acetate is added to a boron trifluoride methanol complex / methanol solution, and the mixture is heated and stirred. Thereafter, the reaction solution was concentrated, the residue was dissolved in ethyl acetate, washed with saturated aqueous sodium hydrogen carbonate, dried over magnesium sulfate, and concentrated, and ethyl [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] ethyl acetate [ Intermediate compound A3-2
3] is obtained.

Step 6: [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] ethyl acetate [intermediate compound A3-2
3], pyridine is added dropwise to a mixture of ethyl chloroformate and tetrahydrofuran, and the mixture is stirred at room temperature. Dilute hydrochloric acid is added to the reaction solution, which is extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
Concentrate to obtain [2- (2-chloro-4-fluoro-5-ethoxycarbonylaminophenoxy) phenoxy] ethyl acetate [intermediate compound A8-23].

Step 7: N, N-Dimethylformamide and sodium hydride are added to ethyl 3-amino-4,4,4-trifluorocrotonate, and the mixture is stirred at 0 ° C. Then, [2-
A mixture of ethyl (2-chloro-4-fluoro-5-ethoxycarbonylaminophenoxy) phenoxy] acetate [intermediate compound A8-23] and N, N-dimethylformamide is added, and the mixture is stirred at 80 ° C. After the reaction solution was cooled to room temperature, it was poured into a mixture of hydrochloric acid and ice water, and the precipitated crystals were collected by filtration, and [2- {2-chloro-5- [2,6-dioxo-4- (trifluoromethyl) ) Ethyl-1,2,3,6-tetrahydropyrimidin-1-yl] -4-fluorophenoxy {phenoxy] acetate is obtained.

Intermediate Production Example 7: [2- {2-chloro-5]
-[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Production of ethyl 4-fluorophenoxy [phenoxy] ethyl acetate Step 1: [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] ethyl acetate [intermediate compound A3-2
3], activated carbon is added to a mixture of trichloromethyl chloroformate and toluene, and the mixture is heated to reflux. The reaction solution is filtered and the solvent is distilled off to obtain ethyl [2- (2-chloro-4-fluoro-5-isocyanato) phenoxy] acetate [intermediate compound A12-23].

Step 2: N, N-Dimethylformamide and sodium hydride are added to ethyl 3-amino-4,4,4-trifluorocrotonate, and the mixture is stirred at 0 ° C. Then, [2-
After adding a mixture of ethyl (2-chloro-4-fluoro-5-isocyanato) phenoxy] acetate [intermediate compound A12-23] and N, N-dimethylformamide, the mixture is stirred at room temperature. The reaction solution was poured into a mixture of hydrochloric acid and ice water,
The precipitated crystals were collected by filtration and [2- {2-chloro-5-
[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
-4-Fluorophenoxy {phenoxy] ethyl acetate is obtained.

Intermediate Production Example 8: [2- {2-chloro-5]
-[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Production of methyl 4-fluorophenoxy [phenoxy] methyl acetate Step 1 Methyl [2- (5-amino-2-chloro-4-fluorophenoxy) phenoxy] acetate (intermediate compound A3-2
2) 4.85 g and ethyl trifluoroacetoacetate 2.8
A solution consisting of 8 g and 40 ml of toluene was azeotropically deethanolated for 6 hours while passing through a molecular sieve 5A. After cooling the reaction mixture, 50 ml of ethyl acetate was added, and the organic layer was washed with concentrated hydrochloric acid, water, and saturated saline. After drying over anhydrous sodium sulfate, the mixture was concentrated under reduced pressure, and the residue was washed with hexane to give crude [2- (5- {3,3
-Dihydroxy-4,4,4-trifluorobutyryl}
Amino-2-chloro-4-fluorophenoxy) phenoxy] methyl acetate 5.82 g was obtained. mp: 165.3 ° C 2) From compound [2h] to [2- {2-chloro-5-
[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Method for producing methyl 4-fluorophenoxy {phenoxy] acetate [compound [3h]] Crude [2- (5- {3,3-dihydroxy-4,4,4-
Methyl trifluorobutyryl {amino-2-chloro-4-fluorophenoxy) phenoxy] acetate [2h]
Acetic acid 4 ml in a solution of 0 g and 3 ml of tetrahydrofuran
Then, 0.87 g of potassium cyanate was added, and the mixture was stirred at room temperature for 6 hours and then heated and refluxed at 120 ° C. for 2 hours. After cooling, 30 ml of water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate, water, and saturated saline, and then dried over anhydrous sodium sulfate. After concentration under reduced pressure, the residue was subjected to silica gel column chromatography to give [2- {2-chloro-
5- [2,6-dioxo-4- (trifluoromethyl)
0.67 g of methyl-1,2,3,6-tetrahydropyrimidin-1-yl] -4-fluorophenoxy {phenoxy] acetate was obtained. [ ¹ H-NMR (250 MHz, CDCl ₃ , TMS δ (ppm)); 3.72 (3H, s), 4.6
5 (2H, s), 6.16 (1H, s), 6.77 (1H, d, J = 6.6Hz), 6.89-7.15 (4
H, m), 7.36 (1H, d, J = 8.9Hz)

[2- (5-Amino-2-chloro-
4-Fluorophenoxy) phenoxy] ethyl acetate [intermediate compound A3-23] to [2- {2-chloro-5-
[2,6-dioxo-4- (trifluoromethyl)-
1,2,3,6-tetrahydropyrimidin-1-yl]
Ethyl-4-fluorophenoxy {phenoxy] acetate can be prepared.

Intermediate Production Example 9: 3- {2-cyano-4-
Fluoro-5- [3-methyl-2,6-dioxo-4-
Production of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol Step 1: 3.53 g of 3-methoxyphenol, 5.12 g of anhydrous potassium carbonate, 2,5-difluoro-4- [3-methyl-
2,6-dioxo-4- (trifluoromethyl) -1,
A mixture of 10 g of 2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene (see Intermediate Preparation Example 4 above) and 40 ml of N, N-dimethylformamide is
Stirred at 60-70 ° C for 2 hours. The reaction solution was poured into a mixture of aqueous hydrochloric acid and ice water, and extracted with ethyl acetate. The organic layer was washed with saturated saline and dried over anhydrous magnesium sulfate.
Concentrated. The residue was subjected to silica gel column chromatography to give 5-fluoro-2- (3-methoxyphenoxy)
4.17 g of -4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.53 (q, 3H, J = 1.2 Hz), 3.7
9 (s, 3H), 6.33 (s, 1H), 6.6-6.
7 (m, 2H), 6.7-6.8 (m, 1H), 7.0
0 (d, 1H, J = 6.1 Hz), 7.2-7.3
(M, 1H), 7.88 (d, 1H, J = 8.6 Hz)

Step 2: 5-fluoro-2- (3-methoxyphenoxy) -4 was added to a mixed solution of 4.5 g of iron powder, 10 ml of acetic acid and 1 ml of water.
-[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] nitrobenzene 4.17 g of acetic acid 10 ml
The solution was added dropwise over 20 minutes. After completion of the dropwise addition, stirring was continued for 2 hours, and then the reaction solution was filtered through celite and diluted with ethyl acetate. After the mixture was washed twice with water, the organic layer was washed successively with saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate and concentrated, and the resulting residue was subjected to silica gel chromatography to give 5-fluoro- 2- (3-methoxyphenoxy) -4- [3-methyl-2,6-dioxo-4-
3.67 g of (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] aniline were obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.52 (q, 3H, J = 1.0 Hz), 3.7
6 (s, 3H), 4.0-4.2 (b, 2H), 6.3
1 (s, 1H), 6.5-6.7 (m, 4H), 6.7
3 (d, 1H, J = 7.0 Hz), 7.1-7.3
(M, 1H)

Step 3: 57 mg of t-butyl nitrite was added to 5-fluoro-2- (3-
Methoxyphenoxy) -4- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6
-Tetrahydropyrimidin-1-yl] aniline 213
mg, 93 mg of copper (I) bromide and 1 ml of acetonitrile were added dropwise at 0 ° C. over 1 hour and stirred for 30 minutes. The temperature was raised to room temperature and stirred for 10 hours. 2% of the reaction solution
The mixture was poured into hydrochloric acid and extracted with ethyl acetate. The organic layer was washed with brine, dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 5-fluoro-2- (3-methoxyphenoxy) -4
75 mg of-[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] bromobenzene were obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.52 (q, 3H, J = 1.2 Hz), 3.7
7 (s, 3H), 6.31 (s, 1H), 6.5-6.
6 (m, 1H), 6.59 (s, 1H), 6.6-6.
7 (m, 1H), 6.86 (d, 1H, J = 6.7H
z), 7.22 (dd, 1H, J = 9.0, 8.7H
z), 7.54 (d, 1H, J = 8.8 Hz)

Step 4: 5-fluoro-2- (3-methoxyphenoxy) -4-
[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
1-yl] bromobenzene 75 mg, copper cyanide 27 m
g and 0.5 ml of N-methyl-2-pyrrolidone were stirred at 170-180 ° C. for 2 hours. After cooling the reaction system to room temperature, water was added to the reaction solution, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated. The residue was subjected to silica gel column chromatography to give 5-fluoro-2- (3-methoxyphenoxy)-
[3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidine-
1-yl] cyanobenzene 57 mg was obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.52 (q, 3H, J = 1.0 Hz), 3.7
9 (s, 3H), 6.31 (s, 1H), 6.67
(S, 1H), 6.6-6.7 (m, 1H), 6.7-
6.8 (m, 1H), 6.84 (d, 1H, J = 5.8
Hz), 7.29 (dd, 1H, J = 9.1, 8.6H)
z), 7.53 (d, 1H, J = 8.4 Hz)

Step 5: 48 μl of boron tribromide is added at 0 ° C. to 5-fluoro-2- (3
-Methoxyphenoxy) -4- [3-methyl-2,6-
Dioxo-4- (trifluoromethyl) -1,2,3
[6-Tetrahydropyrimidin-1-yl] cyanobenzene was dropped into a solution of 57 mg of chloroform in 0.6 ml of chloroform.
After the addition was completed, the reaction solution was heated to room temperature and stirred for 1 hour. The reaction was cooled to 0 ° C. and 1 ml of methanol was added. After evaporating the solvent under reduced pressure, the mixture was diluted with ethyl acetate and adjusted to pH 4 with saturated aqueous sodium hydrogen carbonate. The mixture was extracted with ethyl acetate, and the organic layer was washed with saturated saline, dried over anhydrous magnesium sulfate, and concentrated. The residue was subjected to silica gel column chromatography to give 3- {2-cyano-4-fluoro-5- [3-methyl-2,6-dioxo-4- (trifluoromethyl)].
36 mg of -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxydiphenol were obtained. _{^{1 H-NMR (CDCl 3 /}} 300MHz) δ (pp
m): 3.52 (q, 3H, J = 1.0 Hz), 6.3
2 (s, 1H), 6.3-6.5 (b, 1H), 6.5
−6.6 (m, 1H), 6.6-6.7 (m, 2H),
6.87 (d, 1H, J = 5.8 Hz), 7.21 (d
d, 1H, J = 8.3, 8.1 Hz), 7.51 (d,
1H, J = 8.4Hz)

Intermediate Production Example 10: [2- {2-amino-
4-fluoro-5- [3-methyl-2,6-dioxo-
Production of methyl 4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy {phenoxy] acetate [2- {4-fluoro-5- [3-methyl-2,6] was added to a mixed solution of 19 g of iron powder, 60 ml of acetic acid and 6 ml of water.
-Dioxo-4- (trifluoromethyl) -1,2,2
19.12 g of methyl 3,6-tetrahydropyrimidin-1-yl] -2-nitrophenoxydiphenoxy] acetate
A solution of [the present compound 4-19] in acetic acid (60 ml) was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 4 hours. Then, the reaction solution was filtered through celite and diluted with ethyl acetate.
The mixture was washed successively with water, saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate and concentrated, and the resulting residue was subjected to silica gel chromatography to give [2- {2-amino-4-fluoro- 15.16 g of methyl 5- [3-methyl-2,6-dioxo-4- (trifluoromethyl) -1,2,3,6-tetrahydropyrimidin-1-yl] phenoxy} phenoxy] acetate was obtained. _{^{1 H-NMR (CDCl 3 /}} 250MHz) δ (pp
m): 3.51 (q, 3H, J = 0.9 Hz), 3.7
6 (s, 3H), 4.2-4.4 (b, 2H), 4.6
9 (s, 2H), 6.29 (s, 1H), 6.6-6.
7 (m, 2H), 6.9-7.1 (m, 4H)

Intermediate Production Example 11: [2- (2-chloro-
4-fluoro-5-methoxycarbonylaminophenoxy) phenoxy] methyl acetate [intermediate compound A9-2
2] Manufacturing

Step 1: From N- [4-chloro-2-fluoro-5- (2-hydroxyphenoxy) phenyl] acetamide (see Intermediate Production Example 6, Step 3), the method was described in Intermediate Production Example 5, Step 6. 4-chloro-2-fluoro-5-
(2-Hydroxyphenoxy) aniline [intermediate compound A3-4] was produced. _{^{1 H-NMR (CDCl 3/}} 300 MHz) δ (ppm): 3.76 (bs, 2H), 5.78
(bs, 1H), 6.41 (d, 1H, J = 8.3 Hz), 6.7-6.9 (m, 2
H), 7.0-7.1 (m, 2H), 7.09 (d, 1H, J = 10.2 Hz)

Step 2: N, N was added to a mixture of 4-chloro-2-fluoro-5- (2-hydroxyphenoxy) aniline [intermediate compound A3-4], methyl chloroformate and tetrahydrofuran.
-Add dimethylaniline dropwise and stir at room temperature. Dilute hydrochloric acid is added to the reaction solution, which is extracted with ethyl acetate. The organic layer is washed with brine, dried over anhydrous magnesium sulfate, and concentrated to give 2- (2-chloro-4-fluoro-5-methoxycarbonylaminophenoxy) phenol [intermediate compound A9-4].

Step 3: 2- (2-chloro-4-fluoro-5-methoxycarbonylaminophenoxy) phenol [intermediate compound A9
-4] in N, N-dimethylformamide, add potassium carbonate and stir at room temperature for 1 hour. Thereafter, ethyl bromoacetate is added at room temperature. After stirring at 60 ° C. for 2 hours, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with diluted hydrochloric acid, washed with water, dried over magnesium sulfate and concentrated.
Methyl (2-chloro-4-fluoro-5-methoxycarbonylaminophenoxy) phenoxy] acetate [intermediate compound A9-22] is obtained.

Next, some of the compounds of the present invention will be exemplified. Specific compounds are specified by the compound numbers described in Tables 1 to 37. In addition, the compound of the present invention is not limited to these examples. Compound represented by general formula [I-1] (compound numbers are described in Tables 1 to 9)

Embedded image

[0152]

[Table 1]

[0153]

[Table 2]

[0154]

[Table 3]

[0155]

[Table 4]

[0156]

[Table 5]

[0157]

[Table 6]

[0158]

[Table 7]

[0159]

[Table 8]

[0160]

[Table 9]

Compounds of the formula [I-2] (compound numbers are listed in Tables 10 to 18)

Embedded image

[0162]

[Table 10]

[0163]

[Table 11]

[0164]

[Table 12]

[0165]

[Table 13]

[0166]

[Table 14]

[0167]

[Table 15]

[0168]

[Table 16]

[0169]

[Table 17]

[0170]

[Table 18] Compounds represented by the general formula [I-3] (compound numbers are described in Tables 19 to 27)

Embedded image

[Table 19]

[0171]

[Table 20]

[0172]

[Table 21]

[0173]

[Table 22]

[0174]

[Table 23]

[0175]

[Table 24]

[0176]

[Table 25]

[0177]

[Table 26]

[0178]

[Table 27]

Compounds represented by the general formula [I-4] (compound numbers are listed in Tables 28 to 29)

Embedded image

[0180]

[Table 28]

[0181]

[Table 29]

Compounds represented by the general formula [I-5] (compound numbers are shown in Tables 30 to 31)

Embedded image

[0183]

[Table 30]

[0184]

[Table 31]

Next, some of useful intermediates for producing the compound of the present invention will be exemplified. Specific compounds are:
It is specified by a compound number specified by a combination of a general formula described below and a branch number described in Tables 32-35. (For example, the intermediate compound A1-1 is represented by the general formula [A
1-], wherein substituents X ¹ , X ² and A
Is a substituent described in Branch No. 1 of Table 34. )

Compounds represented by the general formula [A1-] (branch numbers are shown in Tables 32 to 35)

Embedded image Compounds represented by the general formula [A2-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A3-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A4-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A5-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A6-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A7-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A8-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A9-] (branch numbers are shown in Table 32
To Table 35. )

Embedded image Compounds represented by the general formula [A10-] (branch numbers are shown in Table 3
2 to Table 35. )

Embedded image Compounds represented by the general formula [A11-] (branch numbers are shown in Table 3
2 to Table 35. )

Embedded image Compounds represented by the general formula [A12-] (branch numbers are shown in Table 3
2 to Table 35. )

Embedded image

[0187]

[Table 32]

[0188]

[Table 33]

[0189]

[Table 34]

[0190]

[Table 35]

Next, formulation examples will be shown. In addition, this invention compound is shown by the compound number of Table 1-Table 37. Parts are parts by weight. Formulation Example 1 Compounds 1-1 to 1-201, 2-1 to 2-20 of the present invention
1, 3-1 to 3-201, 4-1 to 4-36 and 5-
50 parts of each of 1 to 5-36, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder. Formulation Example 2 Compounds 1-1 to 1-272 and 2-1 to 2-27 of the present invention
2, 3-1 to 3-272, 4-1 to 4-36 and 5-
1 to 5-36, each 10 parts, polyoxyethylene styrylphenyl ether 14 parts, calcium dodecylbenzenesulfonate 6 parts, xylene 35 parts and cyclohexanone 35 parts are mixed well to obtain each emulsion. Formulation Example 3 Compounds 1-1 to 1-201, 2-1 to 2-20 of the present invention
1, 3-1 to 3-201, 4-1 to 4-36 and 5-
1 to 5-36, 2 parts of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 64 parts of kaolin kure are well pulverized and mixed. To obtain the respective granules. Formulation Example 4 Compounds 1-1 to 1-201, 2-1 to 2-20 of the present invention
1, 3-1 to 3-201, 4-1 to 4-36 and 5-
25 parts each of 1 to 5-36, polyvinyl alcohol 10
% Aqueous solution and 25 parts of water are mixed and wet-pulverized until the average particle size becomes 5 μm or less to obtain each suspending agent. Formulation Example 5 1-1 in 40 parts of a 10% aqueous solution of polyvinyl alcohol
-201, 2-1 to 2-201, 3-1 to 3-20
1, each of 4-1 to 4-36 and 5-1 to 5-36
, And emulsified and dispersed by a homogenizer until the average particle size becomes 10 micrometers or less. Then, 55 parts of water are added to obtain each concentrated emulsion.

Next, Test Examples show that the compounds of the present invention are useful as active ingredients of herbicides. In addition, this invention compound is shown by the compound number of Table 1-Table 31. Test Example 1: Upland foliage treatment test Soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and American morning glory, ibis, barnyardgrass and blackgrass were sown and grown in a greenhouse for 9 days. Thereafter, the compounds 1-1 and 2 of the present invention were prepared according to Formulation Example 2.
-1, 3-1, 3-2, 3-11 and 3-12 were made into emulsions, and a predetermined amount thereof was adjusted to 1000 per hectare.
The mixture was diluted with water containing a spreading agent equivalent to 1 liter, and the entire foliage was uniformly treated from above the plant with a sprayer. After the treatment, the plants were grown in a greenhouse for 7 days, and the herbicidal efficacy was examined. As a result, each of Compounds 1-1, 2-1, 3-1 and 3-2, 3-11 and 3-12 was able to completely grow American morning glory, ibis, barnyardgrass and blackgrass at a dose of 125 g / ha. Was suppressed. Test Example 2: Upland soil surface treatment test Soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and American morning glory, ibis, and barnyard grass were sown. Compounds of the present invention 1-1 and 2-1 according to Formulation Example 2
And 3-1 were each made into an emulsion, a predetermined amount of which was diluted with water equivalent to 1000 liters per hectare, and sprayed uniformly over the entire soil surface with a sprayer. After the treatment, the plants were raised in a greenhouse for 7 days, and the herbicidal efficacy was examined. As a result, compound 1-
Each of 1, 2-1 and 3-1 completely inhibited the growth of American morning glory, strawberries and barnyardgrass at a dose of 500 g / ha.

Test Example 3 Field Foliage Treatment Test A cylindrical plastic pot with a diameter of 10 cm and a depth of 10 cm was filled with soil, and American morning glory, ibis and barnyardgrass were sown and grown in a greenhouse for 9 days. Thereafter, the compounds 3-16, 3-20 and 3 of the present invention were prepared according to Formulation Example 2.
Each of -198 was diluted with water containing a spreading agent equivalent to 1000 liters per hectare, and the whole of the foliage was uniformly treated from above the plant with a sprayer. After the treatment, the plants were grown in a greenhouse for 7 days, and the herbicidal efficacy was examined. As a result, Compounds 3-16, 3-20 and 3-1
At a dose of 125 g / ha, each of 98 completely inhibited the growth of morning glory, strawberry and barnyardgrass. Test Example 4: Upland soil surface treatment test The soil was packed in a cylindrical plastic pot having a diameter of 10 cm and a depth of 10 cm, and American morning glory, ibis, barnyardgrass, and blackgrass were sown. Compounds of the Present Invention 3-2, 3-11, 3-12, 3-16, 3-2 according to Formulation Example 2
0 and 3-198 were each made into an emulsion.
Diluted with 1000 liters of water per hectare,
Sprayed evenly over the entire soil surface with a sprayer. After the treatment, the plants were raised in a greenhouse for 7 days, and the herbicidal efficacy was examined. As a result, each of the compounds 3-2, 3-11, 3-12, 3-16, 3-20, and 3-198 completely enhanced the growth of American morning glory, strawberries, barnyardgrass, and blackgrass at a dose of 500 g / ha. Was suppressed.

In the following test examples, the herbicidal efficacy was “0”,
"1", "2", "3", "4", "5", "6",
It is divided into 11 stages of "7", "8", "9" and "10". When the emergence or growth state of the test weed at the time of the survey is no or little different from that of the untreated one, it is regarded as "0", and the test plant is completely withered or the emergence or growth is completely suppressed. What is "10"
And In order to clearly show the characteristics of the compound of the present invention, test results of the following compounds are also described.

Test Example 5: Field Foliage Treatment Test A cylindrical plastic pot having a diameter of 18.5 cm and a depth of 15 cm was filled with soil, chickweed was sowed, and grown in a greenhouse for 29 days. Thereafter, the compound 1 of the present invention was prepared according to Formulation Example 2.
-2 and Control Compound A were each prepared as an emulsion, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 1,000 liters per hectare, and the whole of the foliage was uniformly treated from above the plant with a sprayer. After the treatment, the plants were raised in a greenhouse for 9 days, and the herbicidal efficacy was examined. The results are shown in Table 36.

[0196]

[Table 36] Test Example 6 Soil was packed in a plastic pot of 27 cm long, 19 cm wide and 7 cm deep, and sorghum sorghum (abbreviated as J in the table), Achinonokorogosa (abbreviated as GF in the table), and Inubie (abbreviated as B in the table) , Large Crab Glass (abbreviated as LC in the table), Meriken Acne (BC in the table)
Seeds) and oats (abbreviated as W in the table).
They were raised in a greenhouse for 25 days. Thereafter, each of Compounds 3-11 and 4-22 of the present invention and Control Compounds B and C was made into an emulsion according to Formulation Example 2, and a predetermined amount thereof was diluted with water containing a spreading agent equivalent to 1000 liters per hectare. Diluted,
The whole foliage was uniformly treated from above the plant with a sprayer.
After the treatment, the plants were raised in a greenhouse for 4 days, and the herbicidal efficacy was examined.
The results are shown in Table 37.

[0197]

[Table 37]

[0198]

According to the present invention, an excellent herbicidal effect can be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tomohiko Goto 4-2-1 Takashi Takarazuka-shi, Hyogo Sumitomo Kagaku Kogyo Co., Ltd. F-term (reference) 4H011 AB01 BA01 BB09 BC01 BC05 BC07 BC18 BC19 BC20 DA13 DA15 DA16 DC03 DC04 DC05 DC06 DC08 DD03 DD04 DH02 DH03 DH08 DH10

Claims (23)

[Claims] 1. A compound of the general formula [I] Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Y represents an oxygen atom, a sulfur atom, an imino group or a C1-C3 alkylimino group, R ¹ represents a C1-C3 alkyl group or a C1-C3 haloalkyl group, and R ² represents a C1-C1-alkylimino group. represents a C3 alkyl group, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-
C6 alkyl group, C1-C6 haloalkyl group, C3-C
6 alkenyl group, C3-C6 haloalkenyl group, C3-
C6 alkynyl group, a C3-C6 haloalkynyl group, X ¹ represents a halogen atom, a cyano group, a nitro group,
X ² represents a hydrogen atom or a halogen atom, and X ³ and X
⁴ is each independently a hydrogen atom, a halogen atom, C1
-C6 alkyl group, C1-C6 haloalkyl group, C3-
C6 alkenyl group, C3-C6 haloalkenyl group, C3
-C6 alkynyl group, C3-C6 haloalkynyl group, C
1-C6 alkoxy C1-C6 alkyl group, C1-C6
Alkoxy group, C1-C6 haloalkoxy group, C1-C
Represents a 6 alkoxycarbonyl C1-C6 alkoxy group or a cyano group. A uracil compound represented by the formula: 2. The uracil compound according to claim 1, wherein in the general formula [I], X ¹ is a halogen atom and X ² is a halogen atom. 3. The uracil compound according to claim 1, wherein in the general formula [I], X ¹ is a chlorine atom. 4. The uracil compound according to claim 1, wherein X ² is a fluorine atom in the general formula [I]. 5. In the general formula [I], the substitution position of W on the benzene ring is an ortho position of Y.
3. The uracil compound according to any one of 3. 6. The uracil compound according to claim 1, wherein W is an oxygen atom in the general formula [I]. 7. The uracil compound according to claim ¹ , wherein R ¹ is a methyl group or a CF ₃ group in the general formula [I]. 8. The uracil compound according to claim 1, wherein R ² is a methyl group in the general formula [I]. 9. In the above general formula [I], X ³ and X ⁴
Is a hydrogen atom. The uracil compound according to any one of claims 1 to 7. 10. The uracil compound according to claim 1, wherein R ⁵ is a methyl group or an ethyl group in the general formula [I]. 11. A herbicide comprising the uracil compound according to claim 1 as an active ingredient. 12. A compound of the general formula [VII] Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Y represents an oxygen atom, a sulfur atom, an imino group or a C1-C3 alkylimino group, R ¹ represents a C1-C3 alkyl group or a C1-C3 haloalkyl group, and R ² represents a C1-C1-alkylimino group. X represents a C3 alkyl group, R ⁴ represents a hydrogen atom or a methyl group, X ¹ represents a halogen atom, a cyano group, or a nitro group, X ² represents a hydrogen atom or a halogen atom, and X ³ and X ⁴ are each independently To form a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3-C6 haloalkynyl group, a C1-C6 Alkoxy C1-C6 alkyl group, C1-C6 alkoxy group,
Represents a C1-C6 haloalkoxy group, a C1-C6 alkoxycarbonyl C1-C6 alkoxy group or a cyano group. A uracil compound represented by the formula: 13. The uracil compound according to claim 12, wherein in the general formula [VII], the substitution position of W on the benzene ring is the ortho position of Y. 14. A compound of the general formula [XXXII] Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, X ¹ represents a halogen atom, a cyano group, a nitro group, X ² represents a hydrogen atom or a halogen atom, X ³ And X ⁴ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3-C6 halo. Alkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkyl group Carboxylate a carbonyl C1-C6 alkoxy group or a cyano group. An aniline compound represented by the formula: 15. The aniline compound according to claim 14, wherein in the general formula [XXXII], the substitution position of W on the benzene ring is the ortho position of R ¹⁷ . (16) a compound of the formula [2- (5-amino-2-chloro-4-);
Fluorophenoxy) phenoxy] methyl acetate [17] a compound of the formula [2- (5-amino-2-chloro-4-);
Fluorophenoxy) phenoxy] ethyl acetate 18. A compound of the general formula [XXXIV] Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, R ¹⁸ represents a C1-C6 alkyl group or a phenyl group, X ¹ represents a halogen atom, a cyano group, a nitro group , X ² represents a hydrogen atom or a halogen atom, and X ³ and X ⁴ each independently represent a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 Haloalkenyl group, C3-C6 alkynyl group, C3-C6 haloalkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alcohol Shi group, a C1-C6 haloalkoxy group, C1-C6 alkoxycarbonyl C1-C6 alkoxy group or a cyano group. ] The compound shown by these. 19. The compound according to claim 18, wherein in the general formula [XXXIV], the substitution position of W on the benzene ring is the ortho position of R ¹⁷ . 20. A compound of the general formula [XXXIII] Wherein W is an oxygen atom, a sulfur atom, an imino group or C1
Represents -C3 alkylimino group, R ¹⁷ represents an oxygen atom or a sulfur atom, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ is C1-C6 alkyl group, C1-C6 haloalkyl group, C3-C6 alkenyl group , C3-C6 haloalkenyl group, C3-C6 alkynyl group, a C3-C6 haloalkynyl group, X ¹ represents a halogen atom, a cyano group, a nitro group, X ² represents a hydrogen atom or a halogen atom, X ³ And X ⁴ are each independently a hydrogen atom, a halogen atom, a C1-C6 alkyl group, a C1-C6 haloalkyl group, a C3-C6 alkenyl group, a C3-C6 haloalkenyl group, a C3-C6 alkynyl group, a C3-C6 halo. Alkynyl group, C1-C6 alkoxy C1-C6 alkyl group, C1-C6 alkoxy group, C1-C6 haloalkoxy group, C1-C6 alkyl group Carboxylate a carbonyl C1-C6 alkoxy group or a cyano group. ] The compound shown by these. 21. In the above general formula [XXXIII],
The substitution position of W on the benzene ring is R ¹⁷In the ortho position
21. The compound according to claim 20. 22. In the above general formula [I], R ¹ is a trifluoromethyl group, R ² is a methyl group, R ⁴ is a hydrogen atom, R ⁵ is a methyl group, and X ¹ is a chlorine atom, X ² is a fluorine atom, X ³ is a hydrogen atom, X ⁴ is a hydrogen atom, W is an oxygen atom, Y is an oxygen atom, and W is an oxygen atom. The uracil compound according to claim 1, wherein the substitution position of is a ortho position of Y. 23. In the above general formula [I], R ¹ is a trifluoromethyl group, R ² is a methyl group, R ⁴ is a hydrogen atom, R ⁵ is an ethyl group, and X ¹ is a chlorine atom, X ² is a fluorine atom, X ³ is a hydrogen atom, X ⁴ is a hydrogen atom, W is an oxygen atom, Y is an oxygen atom, and W is an oxygen atom. The uracil compound according to claim 1, wherein the substitution position of is a ortho position of Y.