JP2666099B2 - 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, a lower alkyl group or a phenyl group.) The present invention relates to a 2-acylamino-2-thiazoline compound represented by the following formula: (II):

[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. In the novel 2-acylamino-2-thiazoline compound [compound (I)] as the target compound and the compound (III) as a raw material for the production, the substitution positions of X, Y and X are as follows.

X includes a hydrogen atom, a halogen atom, a lower alkyl group or a phenyl group. 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. Lower alkyl groups (for example, having 1 carbon atom
6 to 6), preferably a straight or branched one having 1 to 4 carbon atoms; more preferably a methyl group.

The phenyl group may be substituted or unsubstituted, but is preferably a substituted phenyl group; the substituent is preferably a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, Iodine atom etc.), more preferably a chlorine atom; the position of the substituent is preferably the 4-position; and the phenyl group substituted by a halogen atom is preferably a 4-chlorophenyl group.

Examples of Y include a halogen atom (for example, those described above for X); preferably, a chlorine atom.

The substitution position of X is not particularly limited.
3-position, 4-position or 5-position is preferred for thiophenecarboxylic acid derivatives; 5-position is preferred for 3-thiophenecarboxylic acid derivatives. 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.

[0016]

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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 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; 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 determined by the amount of the compound (I
It can be used in an amount of 0.001 to 5 times the molar amount of I).

The reaction temperature is not particularly limited, but is usually in the range from room temperature to the boiling point of the solvent used.
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 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. Can be manufactured.

The compound (III) used in the present invention is, for example, as described in J. Am. Chem. S
oc. 68, p. 2599 (1946), and the like, compound (IV) of the following formula;

[0025]

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(Wherein, X has the same meaning as described above.)
Can be produced by using a thiophene carboxylic acid represented by the following formula as shown in the following formula.

[0027]

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(Wherein X and Y have the same meanings as described above). As the compound (III), for example, each of the substituents corresponding to the compounds 1 to 8 shown in Table 1 Compound (III) [Compound (III) ₁ to (III) ₈
Called. For example, the compound (III) ₁ means that X in the formula represented by the compound (III) is a hydrogen atom and Y is a chlorine atom. ].

Furthermore, in the synthesis of compound (I), in addition to the method described above, compound (III) is one of the reactive derivatives of thiophene carboxylic acids, and thus thiophene is used instead of compound (III). It can be synthesized in the same manner as described above using another reactive derivative of a carboxylic acid (for example, an acid anhydride or an ester corresponding to a thiophene carboxylic acid).

Further, compound (I) can also be synthesized by reacting compound (II) with 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 and various chromatographic techniques. Can be appropriately purified by the above-mentioned means.

As the compound (I), for example, each compound (I) [compound (I) ₁ to (I) ₈ consisting of each substituent type corresponding to compounds 1 to 8 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 that can be controlled by the 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 (for example, flies, mosquitoes, cockroaches, etc.), stored grain pests (e. G. Agricultural and horticultural pathogens (eg, wheat rust, barley powdery mildew, cucumber downy mildew, rice blast, tomato late blight, 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 that 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. 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 agent 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 the foliage of plants, soil, or the surface of paddy fields, or directly applying them, depending on the purpose.

[0039]

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- (5-bromo-2-thenoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 3) 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (3 g) and triethylamine (0.6 ml) are dissolved in toluene (30 ml), and the starting compound (III) ₃
5-bromo-2-thiophenecarbonyl chloride (1.4 g) was gradually added, and the mixture was stirred 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 purification with the aid of 00, toluene: ethyl acetate = 20: 1) to give 0.9 g of the target compound as colorless crystals.

(2) 2- (3-methyl-2-thenoylamino) -4,4-bis (trifluoromethyl) -5
Synthesis of (tetrafluoroethylidene) -2-thiazoline (compound 4) 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1 g) and triethylamine (0.2 ml) are dissolved in toluene (10 ml), and the starting compound (III) ₃
3-methyl-2-thiophenecarbonyl chloride (0.5 g) was gradually added, and the mixture was stirred 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).
The residue was purified by eluting with toluene, ethyl acetate = 20: 1) to obtain 0.2 g of the target compound 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 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 (1) by the four-step evaluation method described in the above (1).

[0053]

[Table 3]

(3) Efficacy test against Pleurotus terrestris A. 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 50 times each.
The solution was diluted to 0 ppm, and 1 ml of each of these chemical solutions was evenly dropped on filter paper (7.8 cm in diameter, 1 sheet) in each plastic cup and air-dried. 10 in each of these cups
Release the head of Hirata Kokusutomodoki (adult) and cover it.
It was left in a constant temperature room at 25 ° C., and after 5 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
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) 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 mixed with water containing a surfactant (0.01%) for 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 insecticidal effect, together with the results obtained using the comparative preparation described in the above (1), were evaluated by the four-step evaluation method described in the above (1).
Shown in

[0057]

[Table 5]

(5) Test for Control Effect on Wheat Leaf Rust (Preventive Effect) Wheat (cultivar: Kobushi wheat) was grown 10 per pot in a plastic flowerpot having a diameter of 6 cm, and the seedlings were grown at 1.5-leaf stage. 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 plot. 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 (1) was the same as the preparation (4). Table 6 shows the results.

[0060]

[Table 6]

[0061]

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

[Table 1]

Continuing from the front page (72) Inventor Yoshinori Yamanaka 5-1978 Kogushi, Ube City, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Ube Research Laboratory Examiner 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, a lower alkyl group or a phenyl 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.