JP2666100B2 - 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 The present invention relates to a novel 2-pesticide useful as a pesticide such as an insecticide, an acaricide, and a fungicide.
The present invention relates to an acylamino-2-thiazoline compound and a method for producing the same.

[0002]

DESCRIPTION OF THE PRIOR ART The 2-acylamino-2-thiazoline compound 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-
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]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, the novel 2-acylamino-2-thiazoline compound has a remarkable activity of controlling pests against pests. And found that the present invention was completed. That is, the first invention provides a compound (I) of the following formula:

[0005]

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(Wherein, X represents a hydrogen atom, a halogen atom or a lower alkyl group). A second invention provides a compound (II) of the following formula:

[0007]

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

[0009]

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(Wherein X is as defined above; Y
Represents a halogen atom. The present invention relates to a process for producing the above compound (I), which comprises reacting the compound (I) with the compound (I). The third invention relates to a pesticidal composition containing the compound (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, and a compound (III) which is a raw material for the production thereof [for example, pyridinecarboxylic acids or reactive compounds thereof. ], The substituent X and its substitution position are as follows.

X includes a hydrogen atom, a halogen atom, a lower alkyl group and the like. As the halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a chlorine atom and a bromine atom are preferable. In a lower alkyl group (for example, a linear or branched one having 1 to 6 carbon atoms), it preferably has 1 carbon atom.
4 to 4 are preferred; a methyl group is more preferred.

The substitution position of X is not particularly limited.
And / or 6-position is preferred. The synthesis of compound (I) can be usually carried out by reacting compound (II) as a raw material with compound (III) in a solvent in the presence of a base as shown below.

[0014]

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(In the formula, X and Y have the same meanings 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, Chlorinated or unchlorinated aromatic, aliphatic and cycloaliphatic hydrocarbons such as petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane Ethers such as diethyl ether, tetrahydrofuran and dioxane; ketones such as acetone and methyl ethyl ketone; methanol;
Alcohols such as ethanol and ethylene glycol or hydrates thereof; N, N-dimethylformamide;
Amides such as N, N-dimethylacetamide;
Organic bases such as triethylamine, pyridine, N, N-dimethylaniline, and the like; 1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; and mixtures of the above-mentioned solvents.

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.

Examples of the base include organic bases such as triethylamine, pyridine, N, N-dimethylaniline and the like; alkali metal alkoxides such as sodium methoxide and sodium ethoxide; sodium amide, sodium hydroxide, water Examples thereof include inorganic bases such as potassium oxide, potassium carbonate, sodium carbonate, and sodium hydride.

The amount of the base used is the same as that of the compound (I
It can be used in a molar amount of 0.0001 to 5 times that of I).

The reaction temperature is not particularly limited, but is usually in the range of 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 compound (III) used is the same as that of the compound (I)
The compound (III) is used in an amount of 0.5 to 2 moles, preferably 0.8 to 1.5 times the mole of the compound (I).

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 can be produced using thiourea.

The compound (III) used in the present invention can be prepared, for example, according to the method described in J. Am. Chem. S
oc. , 70, p. 502 (1946) according to the method described in the following formula (IV);

[0023]

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(Wherein, X has the same meaning as described above.)
By using a pyridinecarboxylic acid represented by the following formula as shown in the following formula.

[0025]

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(Wherein, X has the same meaning as described above.)
As the compound (III), for example, each compound (III) [compound (III) ₁ to (III) ₉ having the type of each substituent corresponding to compounds 1 to 9 shown in Table 1 is referred to. For example, the compound (III) ₁ is the same as the compound (II)
In the formula represented by I), X represents a chlorine atom, and Y represents a halogen atom. ].

Furthermore, in the synthesis of compound (I), in addition to the method described above, compound (III) is one of pyridine carboxylic acids, and therefore pyridine carboxylic acid is used in place of compound (III). (For example, acid anhydrides and esters corresponding to pyridinecarboxylic acids) can be synthesized in the same manner as described above.

Further, the compound (I) can also be synthesized by reacting the compound (II) with the compound (IV) in a solvent in the presence of a reaction aid such as dicyclohexylcarbodiimide.

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, recrystallization, various chromatographic techniques and the like. Can be appropriately purified by the above-mentioned means.

As the compound (I), for example, each of the compounds (I) [compounds (I) ₁ to (I) ₉ having the types of the substituents corresponding to the compounds 1 to 9 shown in Table 1 .
For example, the compound (I) ₁ means that X in the formula represented by the compound (I) is a hydrogen atom. ].

Examples of the pests which are effective in controlling compound (I) include agricultural and horticultural pests (eg, Hemiptera (hoppers, leafhoppers, aphids, whiteflies, etc.),
Lepidoptera (Coleoptera, Scarabaeidae, Coleoptera, Pests, Scarab beetles, Pieris beetle, etc.), Coleoptera (Tenebrionidae, Weevil, Chrysomelidae, Scarabaeidae, etc.) Family pests), sanitary pests (e.g., flies, mosquitoes, cockroaches, etc.), stored pests (e. G. And agricultural and horticultural pathogens (for example, wheat rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato late blight, etc.).

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.

Examples of surfactants and dispersants which can be used to improve the performance of the agent, such as adhesion to animals and plants, improvement of absorption, and dispersion, emulsification and spreading of drugs, include alcohol sulfates and alkyls. 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 agent, 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 diluted to an appropriate concentration and applied to various uses by spraying them onto plant foliage, soil, or the surface of paddy fields, or directly applying them, depending on the purpose.

[0037]

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-dichloroisonicotinylamino) -4,4-bis (trifluoromethyl)-
Synthesis of 5- (tetrafluoroethylidene) -2-thiazoline (compound 6) 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1 g) and triethylamine (0.2 g) were dissolved in toluene (10 ml), and the starting compound (III) ₆ , 2,6-dichloroisonicotinyl 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 the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
The residue was purified by eluting with toluene, ethyl acetate = 20: 1) to obtain 0.5 g of the target compound as colorless crystals.

(2) 2- (2-fluoroisonicotinylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 7) 2-imino-4,4-bis (trifluoromethyl) -5
- (tetrafluoro ethylidene) -1,3-thiazolidine the (1 g) and triethylamine (0.2 g) was dissolved in toluene (10 ml), raw material compound _(III) is ₇ 2-fluoro-isonicotinoyl chloride (0. 4
g) was added slowly, and the mixture was stirred at room temperature for 5 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 the solvent was distilled off under reduced pressure. The obtained oil was subjected to column chromatography (Wakogel C-2).
The residue was purified by eluting with toluene, ethyl acetate = 20: 1) to obtain 0.5 g of the target compound as colorless crystals.

(3) Synthesis of other compounds (I) in Table 1 Other compounds (I) in Table 1 were synthesized according to the above-mentioned production method.

[0043]

[Table 1]

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 were added 10 parts by weight of toxanone (trade name; manufactured by Sanyo Chemical Industries), 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 The water-dispersible powder of compound (I) shown in Table 1 prepared according to Example 2 contains a surfactant (0.01%). 50 each with water
Diluted to 0 ppm, and 3 parts of soybean leaf in each of these chemicals.
It was immersed for 0 second, put one by one into each plastic cup, and air-dried. 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 evaluation of the insecticidal effect depends on the range of the insecticidal rate.
Stage (A: 100%, B: 99-80%, C: 79-6)
0%, D: 59% or less). Note that Japanese Patent Application Laid-Open No.
The following formula (V) described in No. 57371:

[0049]

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The same efficacy test was examined using a comparative preparation prepared by using the compound represented by the above formula in the same manner as described above. Table 2 shows the results.

[0051]

[Table 2]

(2) Efficacy test against Conaga (a kind of moth) Each wettable powder of compound (I) shown in Table 1 prepared according to Example 2 was added to water containing a surfactant (0.01%) for 30 times each.
It was diluted to 0 ppm, and cabbage leaf pieces (5 cm × 5 cm) were immersed in each of these chemical solutions for 30 seconds, 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.
After 2 days, the number of live and dead insects in each cup was counted to determine the insecticidal rate. The results of the evaluation of the insecticidal effect are shown in Table 3 together with the results obtained using the comparative preparation described in the above (I) by the four-step evaluation method described in the above (I).

[0053]

[Table 3]

(3) Efficacy test on adult female spider mite (Acari: Tetranychidae) Each wettable powder of compound (I) shown in Table 1 prepared according to Example 2 was washed with water containing a surfactant (0.01%) by 300 p.
pm, and each bean leaf piece (diameter: 20 mm) in which 10 adult female spider mites were parasitized was immersed in each of these drug solutions for 15 seconds. Next, each of these leaf pieces was placed at 25 ° C.
After 3 days, the number of live and dead insects in each leaf piece was counted to determine the acaricidal rate. The results of the evaluation of the acaricidal effect
The results obtained using the comparative preparation described in (1) above are shown in Table 4 by the four-step evaluation method described in (1).

[0055]

[Table 4]

(4) Wheat Rust Control Efficacy Test (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 the compound (I) shown in Table 1 prepared according to Example 2 was diluted to 500 ppm with water containing a surfactant (0.01%).
Sprayed 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 in six stages (0: the whole diseased, 1: the lesion area was about 60%, and 2: the lesion area was about 40%) as compared with the degree of the lesion in the untreated section. 3: The lesion area is about 20%, 4: The lesion area is 10% or less, 5: No lesion). In addition, the same efficacy test was examined using a comparative preparation in which the compound (V) described in the above (1) was the same as the preparation (3). Table 5 shows the results.

[0058]

[Table 5]

[0059]

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

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshinori Yamanaka 5-1978 Ogushi, Ube City, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Examiner at Ube Research Laboratory Shintaro Takahara (56) References JP-A-5-86041 (JP, A) JP-A-5-112546 (JP, A) JP-A-58-57371 (JP, A)

Claims (3)

(57) [Claims] (1) The following formula: (In the formula, X represents a hydrogen atom, a halogen atom, or a lower alkyl group.) 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, X has the same meaning as in claim 1; Y represents a halogen atom). The compound represented by formula (I) according to claim 1 is reacted with the compound represented by formula (I). -A process for producing an acylamino-2-thiazoline compound. 3. 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.