JP2710082B2 - 2-acylamino-2-thiazoline compound, production method thereof and pest control agent - 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 compound useful as a pesticide and a method for producing the same.

[0002]

2. Description of the Prior Art As a related compound of the 2-acylamino-2-thiazoline compound of the present invention, 2-acetamido-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline is disclosed in Japanese Patent Application Laid-Open No. 58-1983. 5737
Although it is described in JP-A No. 1, there is no description about its use as a pesticide (biological test). In addition, 2 of the present invention
Since -acylamino-2-thiazoline compounds are novel compounds, their pest control activity is not known.

[0003]

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

[0004]

The present inventors have conducted studies to solve the above-mentioned problems, and as a result, a novel 2-acylamino-2-thiazoline compound has a remarkable activity for controlling 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, R is a cycloalkyl group having 3 to 10 carbon atoms which may have an alkyl group having 1 to 3 carbon atoms, or a carbon atom which may have a phenyl group. An alkenyl group having 2 to 5 carbon atoms, an alkyl group having 1 to 6 carbon atoms (excluding an acetyl group) which may have a phenyl group, and a haloalkyl group having 1 to 4 carbon atoms. ]. A second invention provides the following formula (II):

[0007]

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

[0009]

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(Wherein, R has the same meaning as described above.)
And a method for producing a 2-acylamino-2-thiazoline compound represented by the formula (I), characterized by reacting the compound with an aliphatic carboxylic acid represented by the formula (I) or a reactive compound thereof. A third invention provides the following formula (IV):

[0011]

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Wherein the 2-acylamino-thiazoline compound represented by the formula (I) is reacted with the compound (III).
The present invention relates to a method for producing a 2-thiazoline compound.

The fourth invention relates to a pesticidal composition comprising a 2-acylamino-2-thiazoline compound represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. A novel 2-acylamino-2-thiazoline compound [Compound (I)] which is the above-mentioned target compound, a compound carboxy or a reactive compound [Compound (II
R in I)] is as follows.

R is a cycloalkyl group having 3 to 10 carbon atoms which may have an alkyl group having 1 to 3 carbon atoms, or a cycloalkyl group having 2 to 3 carbon atoms which may have a phenyl group. Examples thereof include five alkenyl groups, an alkyl group having 1 to 6 carbon atoms which may have a phenyl group (excluding an acetyl group), and a haloalkyl group having 1 to 4 carbon atoms. .

In the cycloalkyl group having 3 to 10 carbon atoms which may have an alkyl group having 1 to 3 carbon atoms, the alkyl group (for example, linear or branched) is: A methyl group is preferred; the number of carbon atoms of the cycloalkyl group is preferably 3 to 8, more preferably 3 to 6; The cycloalkyl group optionally having an alkyl group is, for example, cycloalkyl. Examples thereof include a propyl group, a 1-methylcyclopropyl group, a 2-methylcyclopropyl group, and a cyclohexyl group.

In the alkenyl group having 2 to 5 carbon atoms which may have a phenyl group, those having a phenyl group include, for example, styryl groups; those having no phenyl group Preferably has 2 or 3 carbon atoms; examples of those having no phenyl group include a 1-propenyl group.

In an alkyl group having 1 to 6 carbon atoms which may have a phenyl group (for example, a linear or branched alkyl group), those having a phenyl group include, for example, a benzyl group, Diphenylmethyl group; and those having no phenyl group, preferably those having 2 to 4 carbon atoms (excluding acetyl group); and those having no phenyl group include, for example, ,
Ethyl group, propyl group, i-propyl group, butyl group, i
-Butyl group and the like.

A haloalkyl group having 1 to 4 carbon atoms; a halogen atom (for example, a chlorine atom, an iodine atom,
A bromine atom, a fluorine atom, etc.), preferably a chlorine atom; preferably 1 to 3 carbon atoms, more preferably 1 or 2 carbon atoms; haloalkyl groups such as chloromethyl, dichloro Examples include a methyl group.

Examples of the reactive compound of the aliphatic carboxylic acid which is the compound (III) used as a raw material for producing the compound (I) of the present invention include, for example, an acid anhydride of a carboxylic acid corresponding to the aliphatic carboxylic acid. , Acid chlorides or acid bromides, or carboxylic acid esters (eg, carboxylic acid methyl ester, carboxylic acid ethyl ester, carboxylic acid phenyl ester, etc.); preferably carboxylic acid anhydrides or acid chlorides. Good. The compound (I) of the present invention was synthesized by the following synthesis method 1 and synthesis method 2.
Can be done by

(Synthesis Method 1) In the synthesis of the compound (I) 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

[0022]

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

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 the reaction assistant, bases (for example, organic bases such as triethylamine, pyridine, 4-N, N-dimethylaminopyridine, N, N-dimethylaniline, etc .; sodium methoxide, sodium ethoxide, etc.) Alkali metal alkoxides; inorganic bases such as sodium amide, sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium hydride, etc.) and dehydrating agents [for example, dicyclohexylcarbodiimide, 1-ethyl-8- (8- Dimethylaminopropyl) carbodiimide hydrochloride, 1,1-carbodiimidazole, phosphorus pentachloride, 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 within a temperature range from room temperature to the boiling point of the solvent used or less.
It is preferable to heat within a temperature range not higher than the boiling point. 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 is prepared by using perfluoro- (2-methyl-2-pentene) or the like and thiourea according to the method described in, for example, JP-A-58-57371. And can be easily manufactured.

The compound (III) used in the present invention may be, for example, an acid chloride of a carboxylic acid corresponding to an aliphatic carboxylic acid, as described in Org. Syn. Coll. , 3 volumes, 1
According to the method described on page 69 (1955) and the like, the compound can be produced by performing the reaction according to the following formula.

[0031]

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(Wherein, R has the same meaning as described above.)
As compound (III), for example, each compound (III) [compound (III) _1- (III) consisting of each substituent type corresponding to compounds 1 to 14 shown in Tables 1 and 2
No. ₁₄ . For example, the compound (III) ₁ means that R in the formula represented by the compound (III) is a cyclohexyl group. ].

(Synthesis Method 2) The compound (I) of the present invention can be synthesized by the synthesis method 1 using the compound (IV) in place of the starting compound (II). Compound (IV) used in the present invention can be synthesized by isomerizing compound (II) in sulfuric acid according to the method described in JP-A-58-57371.

After completion of the reaction, the target compound (I) produced as described above is subjected to ordinary post-treatments such as extraction, concentration, filtration and the like, and if necessary, recrystallization, various chromatographic techniques and the like. Can be appropriately purified by the above-mentioned means.

As the compound (I), for example, each compound (I) [compounds 1 to 14] consisting of each substituent type corresponding to compounds 1 to 14 shown in Tables 1 and 2. For example, the compound 1 means that R in the formula represented by the compound (I) is a cyclohexyl group. ].

Examples of the pests that 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 rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato 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).

As the carrier, for example, solid carriers such as talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, slaked lime, silica sand, ammonium sulfate, urea, etc .; hydrocarbons (kerosene, mineral oil, etc.), aromatic hydrocarbons Hydrogen (benzene, toluene, xylene, etc.), chlorinated hydrocarbons (chloroform, carbon tetrachloride, etc.), ethers (dioxane, tetrahydrofuran, etc.), ketones (acetone, cyclohexanone, isophorone, etc.), esters (ethyl acetate, ethylene, etc.) 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, absorption, and dispersion, emulsification and spreading of drugs, include, for example, alcohol sulfates, alkylsulfates and the like. Sulfonate, lignin sulfonate, polyoxyethylene glycol ether 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 appropriate combination, respectively, according to 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 diluted to an appropriate concentration and applied to various uses by spraying them on the foliage of plants, soil, or the water surface of paddy fields, or directly applying them, depending on the purpose.

[0042]

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-Cyclohexanecarbonylamino-4,4-
Synthesis of bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 1) According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
8 g), triethylamine (2 ml) and a catalytic amount of 4-
N, N-dimethylaminopyridine was dissolved in toluene (10 m
l), and cyclohexanecarbonyl chloride (0.7 g) as a raw material compound (III) ₁ 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 purified by column chromatography (Wakogel C-200, eluted with toluene) to give 0.8 g of the target compound (I) as colorless crystals.

(2) 2-cyclopropanecarbonylamino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (compound 6)
According to the synthesis method 1, the following synthesis was performed. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
3g) and triethylamine (1 ml) were added to toluene (5
ml), and cyclopropanecarbonyl chloride (0.3 g) as a raw material compound (III) ₆ 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-200, toluene: ethyl acetate = 1).
(0: 1 elution) to give 1.1 g of the target compound (I) as colorless crystals.

(3) Synthesis of 2- (1-methylcyclopropanecarbonylamino) -4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 12) Were synthesized as follows. 2-amino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolidine (1.2
g), triethylamine (1 ml) and a catalytic amount of 4-
N, N-dimethylaminopyridine was dissolved in toluene (15 m
was dissolved in l), a raw material of the compound _{(III) 12} 1-
Methylcyclopropanecarbonyl chloride (0.6
g) was added slowly and stirred at room temperature for 3 hours. 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 purified by column chromatography (Wakogel C-200, eluted with toluene) to obtain 0.4 g of the target compound (I) as colorless crystals.

(4) 2-chloroacetylamino-4,4
Synthesis of -bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (Compound 9) According to Synthetic Method 1, it 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 the starting compound (III) was added thereto.
₉ is a chloroacetyl chloride (0.4 g) was added slowly under cooling solution in toluene (5 ml), and stirred for further 3 hours at 50 ° C. 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 purified by column chromatography (Wakogel C-200, eluted with toluene) to obtain 0.4 g of the target compound (I) as colorless crystals.

Example 2 [Preparation of preparation] (1) Preparation of granule 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 on adult female spider mite, Tetranychus urticae Each wettable powder of compound (I) shown in Tables 1 and 2 prepared according to Example 2 was treated with a surfactant (0.01 %), And each bean leaf piece (diameter: 20 mm) in which ten adult female spider mites were parasitized was immersed in each of these chemical solutions 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 mite-killing effect was evaluated in four stages (A: 100) according to the range of the insecticidal mite rate.
%, B: 99-80%, C: 79-60%, D: 59%
Below). The following compound (V) described in JP-A-58-57371

[0051]

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Using a comparative preparation having the same formulation as above, a similar efficacy test was examined, and the results obtained were taken as comparative examples. Table 3 shows the results.

[0053]

[Table 3]

(2) Test for controlling efficacy against rice blast (preventive effect) Ten rice plants (variety: Nipponbare) are grown per pot in a plastic flower pot having a diameter of 6 cm, and are transformed into 1.5-leaf seedlings. The wettable powder prepared according to Example 2 from the compound (I) shown in Tables 1 and 2 was diluted to 500 ppm with water containing a surfactant (0.01%) and sprayed in an amount of 20 ml per pot. . After spraying, the plants were cultivated in a glass greenhouse for 2 days, and then a suspension of conidia of rice blast fungi was prepared, and the suspension was inoculated evenly onto plant leaves. After inoculation, the plants were grown for 5 days in a humidified room at 28 ° C., and the degree of rice blast lesions appearing on the leaves was examined. The evaluation of the bactericidal effect was 6 compared to the degree of the untreated section.
Stage (0: overall diseased, 1: lesion area is about 60%,
2: Lesion area is about 40%, 3: Lesion area is about 20%, 4: Lesion area is 10% or less, 5: Lesion is not found. ). As the comparative preparation, a preparation using the compound (V) as in the above (1) was used. Table 4 shows the results.

[0055]

[Table 4]

[0056]

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

[Table 1]

[Table 2]

 ──────────────────────────────────────────────────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) JP-A-5-86041 (JP, A) JP-A-5-112546 (JP, A)

Claims (4)

(57) [Claims] (1) The following formula: [Wherein, R represents a cycloalkyl group having 3 to 10 carbon atoms which may have an alkyl group having 1 to 3 carbon atoms, or a carbon atom having 2 to 3 carbon atoms which may have a phenyl group. It represents an alkyl group having 1 to 6 carbon atoms (excluding an acetyl group) which may have 5 alkenyl groups or a phenyl group, or a haloalkyl group having 1 to 4 carbon atoms. ]
A 2-acylamino-2-thiazoline compound represented by the formula: 2. The following formula: And a 2-iminothiazolidine compound represented by the following formula: (Wherein, R is as defined in claim 1) or an aliphatic carboxylic acid or a reactive compound thereof, represented by the formula (1), wherein the 2-acylamino-2-thiazoline according to claim 1 is reacted. Preparation of the compound. 3. The following formula: And a 2-amino-2-thiazoline compound represented by the following formula: (Wherein, R is as defined in claim 1) or an aliphatic carboxylic acid or a reactive compound thereof, represented by the formula (1), wherein the 2-acylamino-2-thiazoline according to claim 1 is reacted. Preparation of the compound. 4. The compound represented by the formula (I) according to claim 1,
A pest control agent containing an acylamino-2-thiazoline compound as an active ingredient.