JP2710083B2 - 2-Acylamino-2-thiazoline derivatives, their preparation and pest control agents - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel 2-acylamino-2-thiazoline derivative useful as a pesticide and a method for producing the same.

[0002]

DESCRIPTION OF THE PRIOR ART The 2-acylamino-2-thiazoline derivative of the present invention is a novel compound, and its pest control activity is not known.

[0003]

An object of the present invention is to provide a novel 2-
An object of the present invention is to provide an acylamino-2-thiazoline derivative, a method for producing the same, and a pesticidal composition containing the same as an active ingredient.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a novel 2-acylamino-2-thiazoline derivative has a remarkable controlling activity against pests. This led to the completion of the present invention. That is, the present invention is as follows. The first invention provides the following formula (I):

[0005]

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Wherein Ar is 1 to 5 halogen atoms,
Lower alkoxy group, lower alkyl group, nitro group, lower haloalkyl group, cyano group, phenyloxy group optionally substituted with a halogen atom, aralkyloxy group optionally substituted with a halogen atom, lower alkylamino group, hydroxy A phenyl group which may be substituted by a group, a carboxyl group, a lower haloalkoxy group, a lower alkylsulfonyl group, a lower alkylthio group or a methylenedioxy group, and a naphthyl group which may have a substituent;
Represents an oxygen atom or a sulfur atom; R represents a hydrogen atom or a lower alkyl group. The present invention relates to a 2-acylamino-2-thiazoline derivative represented by the following formula: A second invention provides the following formula (II):

[0007]

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A 2-iminothiazolidine derivative represented by the following formula (III):

[0009]

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(Wherein Ar has the same meaning as described above), wherein the compound represented by the formula (I) is reacted with a benzoic acid or a reactive derivative thereof. (IV):

[0011]

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(In the formula, Ar has the same meaning as in claim 1.) The present invention relates to a method for producing a 2-acylamino-2-thiazoline derivative represented by the formula: A third invention provides the following formula (V):

[0013]

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(Wherein, R has the same meaning as described above.)
Reacting a 2-amino-2-thiazoline derivative represented by the formula with a benzoic acid represented by the formula (III) or a reactive derivative thereof, wherein the compound represented by the formula (I) is represented by the following formula: (VI):

[0015]

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(Wherein Ar and R are as defined in claim 1). The present invention also relates to a method for producing a 2-acylamino-2-thiazoline derivative represented by the formula: The fourth invention is
The compound represented by the above formula (I) is characterized in that the compound represented by the above formula (VI) is thiolated, and the compound represented by the following formula (VII):

[0017]

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(Wherein Ar and R are as defined in claim 1). The present invention also relates to a method for producing a 2-thioacylamino-2-thiazoline derivative represented by the formula: The fifth invention relates to a pesticidal composition containing the compound represented by the formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. Compounds represented by the above formulas (I) to (VII) [hereinafter referred to as compounds (I) to (VII). ], The novel compound [(I), (IV), (V
I), (VII)] and its production raw materials [(II), (II)
The symbols (Ar, R, X) used in [I), (V) and (VI)] are as follows.

Examples of Ar include a phenyl group and a naphthyl group which may have a substituent. Examples of the substituent include a halogen atom, a lower alkoxy group, a lower alkyl group, a nitro group, a lower haloalkyl group, a cyano group, a phenyloxy group optionally substituted with a halogen atom, and an aralkyl optionally substituted with a halogen atom. Examples include an oxy group, a lower alkylamino group, a hydroxy group, a carboxyl group, a lower haloalkoxy group, a lower alkylsulfonyl group, a lower alkylthio group, and a methylenedioxy group.

The preferred substituents are as follows: As the halogen atom (for example, chlorine atom, iodine atom, bromine atom, fluorine atom and the like), chlorine atom, bromine atom and fluorine atom are preferable.

The lower alkoxy group has 1 to 1 carbon atoms.
6, more preferably a linear or branched one of 1-4, more preferably a methoxy group.

The lower alkyl group has 1 to 6 carbon atoms,
More preferably, a linear or branched one of 1-4 is preferable.

A lower haloalkyl group (for example, chlorine atom,
Straight or branched one having 1 to 6 carbon atoms having a halogen atom such as an iodine atom, a bromine atom and a fluorine atom)
Is preferably a linear or branched one having 1 to 4 carbon atoms, more preferably a trifluoromethyl group.

The phenyloxy group which may be substituted with a halogen atom (for example, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom, etc.) is preferably a 4-fluorophenoxy group or a phenoxy group.

The aralkyloxy group which may be substituted with a halogen atom (for example, a chlorine atom, an iodine atom, a bromine atom, a fluorine atom, etc.) is preferably a benzyloxy group, a phenethyloxy group, a phenyloxypropyl group or the like. Preferably, a benzyloxy group is good.

The lower alkylamino group (for example, a linear or branched one having 1 to 6 carbon atoms) is preferably a linear or branched one having 1 to 4 carbon atoms, and more preferably dimethyl. Amino groups are preferred.

A lower haloalkoxy group (for example, a linear or branched one having 1 to 6 carbon atoms having a halogen atom such as a chlorine atom, an iodine atom, a bromine atom and a fluorine atom) has 1 to 1 carbon atoms. 4 is preferably a linear or branched one, more preferably a trifluoromethoxy group,
-Chloro-1,1,2-trifluoroethoxy group is preferred).

The lower alkylsulfonyl group (for example, a linear or branched group having 1 to 6 carbon atoms) is preferably a linear or branched group having 1 to 4 carbon atoms, and more preferably methane. A sulfonyl group is preferred.

A lower alkylthio group (for example, a linear or branched one having 1 to 6 carbon atoms) has 1 carbon atom.
4 to 4 are preferred, and a methylthio group is more preferred.

The number of substituents may be an integer of 0 to 5, and the position of the substituent is not particularly limited.
Preferred numbers and positions are as follows. The halogen atom is
They are 2, 3, 4, 5 and / or 6th. In a lower alkoxy group, it is 3-position. In a lower alkyl group, it is 4-position. In the nitro group, it is at the 3,4 and / or 5 position. In lower haloalkyl groups, it is at the 3,4 and / or 5 position. In the cyano group, it is 4-position.

The phenyloxy group which may be substituted with a halogen atom is at the 3- and / or 4-position. In an aralkyloxy group optionally substituted with a halogen atom,
Third place. In a lower alkylamino group, it is 3-position.
In the hydroxy group, it is at the 3-position. In the carboxyl group,
6th place. In lower haloalkoxy groups, it is at position 4 and / or 5. In a lower alkylsulfonyl group, it is 4-position. In a lower alkylthio group, it is 4-position.

Examples of R include a hydrogen atom and a lower alkyl group. The lower alkyl group may be a straight or branched one having 1 to 6, more preferably 1 to 4 carbon atoms. And more preferably a methyl group.
X includes an oxygen atom, a sulfur atom, and the like.

Examples of the reactive derivative of benzoic acid which is the starting compound (III) used for producing the compound (I) of the present invention include, for example, acid anhydrides and acid chlorides of carboxylic acids corresponding to benzoic acids Alternatively, an acid bromide or a carboxylic acid ester (a carboxylic acid methyl ester, a carboxylic acid ethyl ester, a carboxylic acid phenyl ester, etc.) can be mentioned; however, a carboxylic acid acid anhydride or an acid chloride is preferable. Compound (I) can be produced, for example, by any of the following production methods 1 to 3.

(Synthesis Method 1) In the synthesis of the compound (IV) of the present invention, as shown below, usually, the starting compounds (II) and (III) are reacted in a solvent in the presence of a reaction assistant. This can be done by causing

[0036]

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(In the formula, Ar has the same meaning as described above.) The solvent is not particularly limited as long as it does not directly participate in the present reaction. For example, benzene, toluene, xylene, methylnaphthalene, petroleum ether , Chlorinated or unchlorinated aromatic, aliphatic, cycloaliphatic hydrocarbons such as, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane; diethyl Ether, tetrahydrofuran,
Ethers such as dioxane; ketones such as acetone, methyl ethyl ketone; alcohols such as methanol, ethanol, ethylene glycol and the like or hydrates thereof; N, N-dimethylformamide, N,
Amides such as N-dimethylacetamide; organic bases such as triethylamine, pyridine, N, N-dimethylaniline; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; be able to.

The amount of the solvent used depends on the amount of the compound (I
The compound (II) can be used in such a manner that the concentration of I) is in the range of 5 to 80% by weight.
Is preferably used in such a manner that the concentration thereof becomes 10 to 70% by weight.

As a reaction assistant, bases (for example, triethylamine, pyridine, 4- (N, N-dimethylamino) pyridine, N, N-dimethylaniline, 1,8-diazabicyclo [5.4.0] undeca- Organic bases such as 7-ene and the like; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; sodium amide, sodium hydroxide, potassium hydroxide,
Inorganic bases such as potassium carbonate, sodium carbonate and sodium hydride), dehydrating agents [for example, dicyclohexylcarbodiimide, 1-ethyl-8- (8-dimethylaminopropyl) carbodiimide hydrochloride, 1,1-carbodiimidazole, Phosphorus chloride, phosphorus trichloride, phosphorus oxychloride, thionyl chloride, phosgene].

The reaction assistant can be used in an amount of 0.001 to 5 times the molar amount of the compound (II).

The reaction temperature is not particularly limited, but is usually in the range from room temperature to the boiling point of the solvent used or lower.
The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 24 hours.

The amount of the starting compound used is 0.5 to 2 times the molar amount of the compound (III) with respect to the compound (II).
Preferably it is 0.8 to 1.5 times mol.

The compound (II) used in the present invention can be prepared, for example, from perfluoro- (2-methyl-2-pentene) according to the method described in JP-A-58-57371.
And the like, and can be easily produced using thiourea.

The compound (III) used in the present invention is, for example, as described in J. Am. Chem. Soc. , 1934, 1406
According to the method described on the page, etc., it can be produced by performing as shown in the following formula.

[0045]

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(Wherein Ar has the same meaning as described above.) The compound (III) includes, for example, the types of the respective substituents corresponding to the compound numbers 1 to 47 shown in Tables 1 to 5. Each compound [compound (III) ₁ to (III)
_{No. 47} . [For example, the compound (III) corresponding to the compound No. 1 is replaced with the compound (II)
I) Called ₁ . Compound (III) ₁ is the compound represented by the formula (III) wherein Ar is 2,6-F
It means that it is a _2- phenyl group. ].

(Synthesis Method 2) The compound (VI) of the present invention can be synthesized by the synthesis method 1 using the compound (V) instead of the compound (II) as a raw material. The compound (V) used in the present invention can be prepared by isomerizing the compound (II) in sulfuric acid or perfluoro- (2-methyl-2) according to the method described in JP-A-58-57371. -Pentene) and N-methylthiourea.

(Synthesis method 3) Compound (VII) of the present invention was synthesized by reacting compound (VI) with phosphorus pentasulfide as shown below.
It can be carried out by thionation with an S agent such as Lawesson's reagent or hydrogen sulfide.

[0049]

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(Ar and R have the same meanings as described above.) The solvent is not particularly limited as long as it does not directly participate in the reaction, and examples thereof include benzene, toluene, xylene, methylnaphthalene, petroleum ether, Chlorinated or unchlorinated aromatic, aliphatic, alicyclic hydrocarbons such as ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane; diethyl ether , Tetrahydrofuran,
Ethers such as dioxane; alcohols such as methanol, ethanol, ethylene glycol and the like or hydrates thereof; dimethyl sulfoxide; carbon disulfide;
Mixtures of the above solvents can be mentioned.

The amount of the solvent used may be such that the concentration of compound (VI) is in the range of 5 to 80% by weight, but preferably the concentration of compound (VI) is 10 to 70% by weight. % Should be used.
Although the reaction temperature is not particularly limited, it is generally in the range of room temperature to the boiling point of the solvent to be used or lower, and it is preferable to heat the mixture in the temperature range of the boiling point or lower.

The reaction time varies depending on the above-mentioned concentration and temperature, but can usually be carried out for 0.3 to 24 hours.
After completion of the reaction, the target compound (I) produced as described above is subjected to ordinary post-treatments such as extraction, concentration and filtration, and if necessary, by known means such as recrystallization and various types of chromatography. It can be appropriately purified.

As the compound (I), for example, Tables 1 to 5
Compounds (hereinafter referred to as Compounds 1 to 47) consisting of the types of the substituents corresponding to Compound Nos. 1 to 47 shown therein can be mentioned [for example, Compound (I) corresponding to Compound No. 1 It is referred to as Compound 1. And this compound 1
Means that R in the formula represented by the compound (I) is H, X is O, and Ar is a 2,6-F ₂ phenyl group. ].

Examples of the pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests (eg, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.) and lepidoptera (armyworms) , Scarabaeidae, Coleoptera, Pestiformes, Scarabaeidae, Pieris beetle, etc., Coleoptera (Tenebrionidae, Weevils, Chrysomelidae, Scarabaeidae, etc.), Acari (Acari: Tetranychidae, Tetranychidae, etc.) )], Sanitary pests (for example, flies, mosquitoes, cockroaches, etc.), stored grain pests (e. G. For example, wheat leaf rust, barley powdery mildew, cucumber downy mildew, rice blast, toma Epidemics, etc.) can be mentioned.

The pesticidal composition of the present invention has a remarkable insecticidal property.
It has an acaricidal / bactericidal effect and contains at least one compound (I) as an active ingredient. Compound (I)
Can be used alone, but usually, a carrier, a surfactant, a dispersant, an adjuvant, etc. are blended by a conventional method (eg, powder, emulsion, fine granule, granule, wettable powder, oil-based Prepared as a composition such as a suspension or an aerosol).

Examples of the carrier include solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea; hydrocarbons (kerosene, mineral oil, etc.), aromatic carbon Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene Liquid carriers such as glycol acetate, dibutyl maleate, etc.), alcohols (methanol, n-hexanol, ethylene glycol, etc.), polar solvents (dimethylformamide, dimethyl sulfoxide, etc.), water, etc .; air, nitrogen, carbon dioxide, freon, etc. Body carrier (in this case, can be mixed injection) out and the like.

Surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement in absorption, dispersion, emulsification and spreading of drugs, include alcohol sulfates and alkyls. Sulfonates, ligninsulfonates, polyoxylene glycol ethers and the like can be mentioned. In order to improve the properties of the preparation, for example, carboxymethylcellulose, polyethylene glycol, gum arabic and the like can be used as an auxiliary agent.

In the preparation of the present preparation, the above-mentioned carrier, surfactant, dispersant and auxiliary can be used alone or in an appropriate combination depending on the respective purposes.
When the compound (I) of the present invention is formulated, the concentration of the active ingredient is usually from 1 to 50% by weight in the emulsion, and usually from 0.3 to 0.3 in the powder.
25 to 25% by weight, usually 1 to 90% by weight for wettable powders, usually 0.5 to 5% by weight for granules, 0.5 to 5% by weight for oils and 0.1 to 5% by weight for aerosols. is there.

These preparations can be used for various purposes by diluting them to an appropriate concentration and spraying them on the foliage of plants, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments of the present invention will be specifically described below.
Note that these examples do not limit the scope of the present invention. Example 1 [Synthesis of Compound (I)]

(1) 2- (2,6-difluorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of-(tetrafluoroethylidene) -2-thiazoline (compound 1)

According to the synthesis method 1, it was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (0.8 g), triethylamine (1 ml)
Then, a catalytic amount of 4- (N, N-dimethylamino) pyridine was dissolved in toluene (10 ml), and 2,6-difluorobenzoyl chloride (0.5 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) is extracted from the reaction mixture with ethyl acetate, washed with water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-200, toluene: ethyl acetate = 10: 1).
The resulting product was purified by elution to give 0.5 g of the target compound (I) as colorless crystals.

According to the synthesis method 2, the compound was synthesized as follows. 2-amino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (0.4 g), triethylamine (1 ml) and a catalytic amount of 4- (N, N-dimethylamino) Pyridine was dissolved in toluene (10 ml), and 2,6-difluorobenzoyl chloride (0.2 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 10: 1) to obtain 0.3 g of the target compound (I) as colorless crystals.

(2) Synthesis of 2-benzoylamino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 2) According to Synthesis Method 1, synthesized as follows. did. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (0.
7 g) and triethylamine (1 ml) were added to toluene (1
0 ml), and benzoyl chloride (0.
3 g) was gradually added, and the mixture was stirred at room temperature for 3 hours. After the reaction,
From the reaction mixture, the target compound (I) was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, elution with toluene: ethyl acetate = 10: 1) to obtain 0.4 g of the target compound (I) as colorless crystals.

(3) Synthesis of 2- (4-chlorobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 3) It was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (4.
0 g) and triethylamine (1.5 ml) were dissolved in toluene (15 ml), and 4-chlorobenzoyl chloride (2.5 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) is obtained from the reaction mixture.
Was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-200,
Purification with toluene: n-hexane = 3: 2) gave 0.93 g of the target compound (I) as colorless crystals.

(4) Synthesis of 2- (2-chlorobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 4) It was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (40 ml), and a solution of 2-chlorobenzoyl chloride (1.3 g) dissolved in toluene (10 ml) was gradually added thereto under cooling, and the mixture was added at room temperature for 4 hours. Stirred. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: n-hexane = 3: 2 elution) to obtain 0.21 g of the target compound (I) as colorless crystals.

(5) Synthesis of 2- (3-chlorobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 5) It was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (2.0 ml) were dissolved in toluene (20 ml), and 3-chlorobenzoyl chloride (2.0 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) is obtained from the reaction mixture.
Was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were washed with n-hexane to give 0.51 g of the target compound (I) as colorless crystals.

(6) Synthesis of 2- (2-methoxybenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 6) It was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and triethylamine (0.4 ml) were dissolved in toluene (10 ml), and 2-methoxybenzoyl chloride (0.7 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: n-hexane = 3: 2) to give the target compound (I) as a colorless crystal in 0.2%.
g was obtained.

(7) Synthesis of 2- (4-methylbenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 7) It was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (0.
5 g) and triethylamine (1.0 ml) were dissolved in toluene (10 ml), and 4-methylbenzoyl chloride (0.3 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) is obtained from the reaction mixture.
Was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-200,
Purification with toluene: ethyl acetate = 10: 1) gave 0.3 g of the target compound (I) as colorless crystals.

(8) 2- (2,6-dichlorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 8) According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (0.
5 g) and triethylamine (1.0 ml) were dissolved in toluene (10 ml), and 2,6-dichlorobenzoyl chloride (0.4 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: ethyl acetate = 10: 1) to give 0.4 g of the target compound (I) as colorless crystals.
g was obtained.

(9) 2- (3,5-dichlorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 9) According to Synthesis Method 1, the compound was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (10 ml), and 3,5-dichlorobenzoyl chloride (1.5 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: ethyl acetate = 10: 1) to give 0.4 g of the target compound (I) as colorless crystals.
g was obtained.

(10) 2- (3,4-dichlorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of-(tetrafluoroethylidene) -2-thiazoline (Compound 10) According to Synthesis Method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
1 g) and triethylamine (1.0 ml) were dissolved in toluene (10 ml), and 3,4-dichlorobenzoyl chloride (1.0 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: ethyl acetate = 10: 1) to give the target compound (I) as colorless crystals in 0.9%.
g was obtained.

(11) 2- (4-nitrobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 1
Synthesis of 1) According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (0.
5 g) and triethylamine (1.0 ml) were dissolved in toluene (10 ml), and 4-nitrobenzoyl chloride (0.5 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) is obtained from the reaction mixture.
Was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-200,
Purification with toluene: ethyl acetate = 10: 1) gave 0.2 g of the target compound (I) as colorless crystals.

(12) 2- (4-t-butylbenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 12) According to Synthesis Method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and triethylamine (0.4 ml) were dissolved in toluene (10 ml), and 4-t-butylbenzoyl chloride (0.9 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: ethyl acetate = 10: 1) to give 0.2 g of the target compound (I) as colorless crystals.
1 g was obtained.

(13) 2- (3-methoxybenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 13) According to Synthesis Method 1, the compound was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and triethylamine (0.4 ml) were dissolved in toluene (10 ml), and 3-methoxybenzoyl chloride (0.7 g) was gradually added thereto, followed by stirring at room temperature for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
00, toluene: n-hexane = 3: 2) to give the target compound (I) as a colorless crystal in 0.2%.
1 g was obtained.

(14) Synthesis of 2- (3-trifluoromethylbenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 14) Were synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (40 ml), and 3-trifluoromethylbenzoyl chloride (1.5 g) was added to toluene (10 ml).
The solution dissolved in 1) was gradually added under cooling, and stirred at 103 ° C. for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
-200, toluene: n-hexane = 3: 2 elution) to obtain 0.44 g of the target compound (I) as colorless crystals.

(15) 2- (3-nitrobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 1
Synthesis of 5) According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (40 ml), and a solution of 3-nitrobenzoyl chloride (1.3 g) in toluene (10 ml) was gradually added thereto under cooling. Stir for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: n-hexane = 3: 2) to give 0.32 g of the target compound as colorless crystals.

(16) Synthesis of 2- (4-trifluoromethylbenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 16) Were synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (40 ml), and 4-trifluoromethylbenzoyl chloride (1.5 g) was dissolved in toluene (10 ml).
The solution dissolved in 1) was gradually added under cooling, and stirred at 103 ° C. for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
-200, toluene: n-hexane = 3: 2 elution) to obtain 0.6 g of the target compound (1) as colorless crystals.

(17) 2- (3-fluorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 17) According to Synthesis Method 1, the compound was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and dicyclohexylcarbodiimide (2.4)
g) is dissolved in dichloromethane (10 ml), and 3
-Fluorobenzoic acid (1.6 g) was added to dichloromethane (1
(0 ml) was gradually added and stirred at room temperature for 3 hours. After the reaction, the reaction mixture was filtered, the target compound (I) was extracted from the obtained mother liquor with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-200, toluene: n-hexane =
(3: 2 elution) to give 0.5 g of the target compound (I) as colorless crystals.

(I8) 2- (4-cyanobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 2
Synthesis of 0) According to the synthesis method 1, it was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (1.0 ml) were dissolved in toluene (40 ml), and a solution of 4-cyanobenzoyl chloride (1.2 g) dissolved in a mixture of toluene (10 ml) and dichloromethane (2 ml) was cooled. The mixture was gradually added under reduced pressure and stirred at 103 ° C. for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: n-hexane = 3: 2) to give 1.15 g of the target compound as colorless crystals.

(19) 2- (4-fluorobenzoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (Compound 21) According to Synthesis Method 1, the compound was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) and triethylamine (0.6 ml) were dissolved in toluene (40 ml), and a solution of 4-fluorobenzoyl chloride (0.8 g) dissolved in toluene (10 ml) was gradually added thereto under cooling. Stir for 3 hours. After the reaction, the target compound (I) is obtained from the reaction mixture.
Was extracted with ethyl acetate, washed with water and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting oil was subjected to column chromatography (Wakogel C-200,
Purification with toluene: n-hexane = 3: 2) gave 1.53 g of the target compound (I) as colorless crystals.

(20) 2- (3-bromobenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 2
Synthesis of 3) According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (5.
0 g) and triethylamine (1.5 ml) were dissolved in toluene (80 ml), and a solution of 3-bromobenzoyl chloride (2.9 g) in toluene (10 ml) was gradually added thereto under cooling. Stir for 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, eluted with toluene: n-hexane = 3: 2) to give 0.96 g of the target compound (I) as colorless crystals.

(21) Synthesis of 2- (3-trifluoromethoxybenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 36) Were synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) and triethylamine (0.6 ml) were dissolved in toluene (10 ml), and 3-trifluoromethoxybenzoyl chloride (0.5 g) was dissolved in toluene (10 g).
ml) is gradually added under cooling to a solution of 103 ° C.
For 3 hours. After the reaction, the target compound (I) was extracted from the reaction mixture with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography (Wakogel C-200, toluene: n-hexane = 3: 2 elution) to obtain 0.7 g of the target compound (I) as colorless crystals.

(22) 2-[(4-trifluoromethyl) thiobenzoylamino] -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2
-Synthesis of thiazoline (compound 37) According to the synthesis method 3, it was synthesized as follows. 2- (4
-Trifluoromethylbenzoylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (1 g) in xylene (10 m
l), and phosphorus pentasulfide (0.2 g) was added thereto.
Heated to reflux for an hour. After the reaction, the target compound (I) was extracted from the reaction mixture with toluene, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C).
-200, toluene: n-hexane = 3: 2 elution) to obtain 0.5 g of the target compound (I) as colorless crystals.

Example 2 [Preparation of preparation] (1) Preparation of granules 5 parts by weight of compound 1, 35 parts by weight of bentonite, 57 parts by weight of talc, 1 part by weight of Neoperex powder (trade name; manufactured by Kao Corporation) And 2 parts by weight of sodium ligninsulfonate were uniformly mixed, then kneaded by adding a small amount of water, and then granulated and dried to obtain granules.

(2) Preparation of wettable powder 10 parts by weight of compound 1, 70 parts by weight of kaolin, 18 parts by weight of white carbon, 1.5 parts by weight of Neoperex powder (trade name, manufactured by Kao Corporation) and Demol (trade name) Name; manufactured by Kao Corporation)
Then, it was pulverized to obtain a wettable powder.

(3) Preparation of Emulsion To 20 parts by weight of Compound 1 and 70 parts by weight of xylene, 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries) was added, mixed uniformly, and dissolved to obtain an emulsion. .

(4) Preparation of powder 5 parts by weight of compound 1, 50 parts by weight of talc and kaolin 4
5 parts by weight were uniformly mixed to obtain a powder.

Example 3 [Efficacy test] (1) Efficacy test against Spodoptera litura Compound (I) prepared according to Example 2 and shown in Tables 1 to 5
Each wettable powder was diluted to 500 ppm with water containing a surfactant (0.01%), soybean leaves were immersed in each of these chemicals for 30 seconds, placed one by one into each plastic cup, and air-dried. did. In each of these cups, ten cutworm armyworms (2nd instar larvae) were released, covered, left in a constant temperature room at 25 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal effect was evaluated in four stages (A: 100%, B: 99-80%, C: 7) according to the range of the insecticidal rate.
9 to 60%, D: 59% or less). Incidentally, the following formula (VII) described in Japanese Patent Application Laid-Open No. 58-57371
I):

[0089]

Embedded image

Using a comparative preparation obtained by preparing the compound (VIII) shown in the above in the same manner as described above, a similar efficacy test was examined, and the results obtained were taken as comparative examples. Table 6 shows the results.

(2) Efficacy test for Conaga Compound (I) prepared according to Example 2 and shown in Tables 1 to 5
Was diluted to 300 ppm with water containing a surfactant (0.01%), and cabbage leaf pieces (5 cm x 5 cm) were immersed in each of these chemical solutions for 30 seconds, and one piece was placed in each plastic cup. One by one and air-dried. In each of these cups, release 10 moths (3rd instar larvae) and cover them.
It was left in a constant temperature room at 5 ° C., and two days later, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The insecticidal effect is shown in Table 7 by the four-step evaluation method described in the above (1) together with the comparative example obtained using the comparative preparation described in the above (1).

(3) Efficacy test for Pleurotus terrestris (Compound (I) shown in Tables 1 to 5 prepared according to Example 2)
Is diluted to 500 ppm with water containing a surfactant (0.01%), and 1 ml of each of these chemicals is evenly dropped on filter paper (diameter 7.8 cm, 1 sheet) in each plastic cup. And air-dried. In each of these cups, 10 mosquitoes were released and capped. After leaving them in a constant temperature room at 25 ° C., the number of live and dead insects in each cup was counted after 5 days to determine the insecticidal rate. The insecticidal effect is shown in Table 8 by the four-step evaluation method described in the above (1) together with the comparative example obtained using the comparative preparation described in the above (1).

(4) Efficacy test against adult female spider mite (Acari: Tetranychidae) Compound (I) prepared according to Example 2 and shown in Tables 1 to 5
Each hydration agent in water containing a surfactant (0.01%).
Each bean leaf (20 m in diameter) diluted to 0 ppm and infested with 10 adult female spider mites in each of these solutions
m) for 15 seconds. Next, each leaf piece was left in a constant temperature room at 25 ° C., and after 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The acaricidal effect is shown in Table 9 by the four-step evaluation method described in the above (1) together with the comparative example obtained using the comparative preparation described in the above (1).

(5) Test for Control Effect on Wheat Leaf Rust (Preventive Effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm. Each wettable powder of compound (I) shown in Tables 1 to 5 prepared according to Example 2 was added to a surfactant (0.01
%), And diluted with water to 500 ppm, and these chemicals were sprayed at 20 ml per pot. These were cultivated in a glass greenhouse for 2 days, and then a spore suspension of wheat leaf rust (7 × 10 ⁴ spores / ml) was uniformly spray-inoculated on the plant. Next, these were grown in a glass greenhouse for one week, and the degree of wheat rust spots appearing on each first leaf was investigated. The evaluation of the bactericidal effect was carried out by comparing the degree of the lesion with the non-treated section in six stages (0: the whole disease, 1: the lesion area was about 60%, 2: the lesion area was about 40%, 3:
Lesion area is about 20%, 4: Lesion area is 10% or less,
5: no lesion). In addition, using a comparative preparation obtained by preparing compound (VIII) in the same manner as described above,
The results obtained by examining the same efficacy test were used as comparative examples. Table 10 shows the results.

(6) Test for controlling efficacy against barley powdery mildew (preventive effect) Barley (cultivar: black wheat) was grown 10 per pot in a plastic flower pot having a diameter of 6 cm, and a young plant at the 1.5 leaf stage Each of the wettable powders of the compound (I) shown in Tables 1 to 5 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%). The chemical was sprayed at a rate of 20 ml per pot. These were cultivated in a glass greenhouse for 2 days, and then barley powdery mildew spores were collected from the diseased leaves and sprinkled evenly over each plant for inoculation. Next, these were grown in a glass greenhouse for one week, and the degree of barley powdery mildew spots that appeared on each first leaf was investigated. The bactericidal effect is shown in Table 11 by the six-step evaluation method described in the above (5) together with the comparative example obtained using the comparative preparation described in the above (5).

[0096]

According to the present invention, a novel 2-acylamino-2-
Thiazoline derivatives are useful agricultural chemicals as pesticides.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

[Table 11]

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshinori Yamanaka 5-1978 Kogushi, Obe-shi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Examiner at Ube Research Laboratory Yoshie Okabe (56) References JP-A-58-57371 (JP, A) JP-A-5-4979 (JP, A)

Claims (5)

(57) [Claims] (1) The following formula: (In the formula, Ar is substituted with 1 to 5 halogen atoms, lower alkoxy group, lower alkyl group, nitro group, lower haloalkyl group, cyano group, phenyloxy group optionally substituted with halogen atom, halogen atom. An optionally substituted aralkyloxy group, lower alkylamino group, hydroxy group, carboxyl group, lower haloalkoxy group, lower alkylsulfonyl group, lower alkylthio group or methylenedioxy group; X represents an optionally substituted naphthyl group; X represents an oxygen atom;
R represents a hydrogen atom or a lower alkyl group; ). 2-Acylamino-2-thiazoline derivatives represented by the formula: 2. The following formula: And a 2-iminothiazolidine derivative represented by the following formula: (Wherein Ar has the same meaning as in claim 1). The compound represented by formula (I) according to claim 1, wherein the compound is reacted with a benzoic acid or a reactive derivative thereof. The following formula: (Wherein, Ar has the same meaning as described in claim 1.) A method for producing a 2-acylamino-2-thiazoline derivative represented by the formula: 3. The following formula: (Wherein R is as defined in claim 1) and a 2-amino-2-thiazoline derivative represented by the following formula: (Wherein Ar has the same meaning as in claim 1). The compound represented by formula (I) according to claim 1, wherein the compound is reacted with a benzoic acid or a reactive derivative thereof. The following formula: (Wherein, Ar and R are as defined in claim 1)
A method for producing a 2-acylamino-2-thiazoline derivative represented by the formula: 4. The following formula: (Wherein, Ar and R are as defined in claim 1)
2. The formula (I) according to claim 1, wherein the 2-acylamino-2-thiazoline derivative represented by the formula (1) is thiolated.
In a compound represented by the following formula: (Wherein, Ar and R are as defined in claim 1)
A method for producing a 2-thioacylamino-2-thiazoline derivative represented by the formula: 5. A compound represented by the formula (I) according to claim 1,
A pest control agent comprising an acylamino-2-thiazoline derivative as an active ingredient.