JP2730020B2 - N- (thiazolin-2-yl) -N'-phenylurea derivative, process for producing the same and pest control agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel N- (thiazolin-2-yl) -N 'which is useful as a pesticide.
A phenylurea derivative and a method for producing the same.

[0002]

2. Description of the Prior Art Since the N- (thiazolin-2-yl) -N'-phenylurea derivative of the present invention is a novel compound, its pest control activity is not known.

[0003]

The object of the present invention is to provide a novel N-
An object of the present invention is to provide a (thiazolin-2-yl) -N'-phenylurea 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 N- (thiazolin-2-yl) -N′-phenylurea derivative is useful for pests. The present inventors have found that they have a remarkable controlling activity, and have completed the present invention. That is, the present invention is as follows. The first invention has the following formula:

[0005]

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Wherein X represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a nitro group or a cyano group;
Or an integer of 5; or when n is 2, Xn represents an unsaturated 6-membered ring fused to a benzene ring together with the carbon atom to which they are attached, and N- (thiazoline-2-
Yl) -N′-phenylurea derivative (I). The second invention has the following formula:

[0007]

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

[0009]

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(Wherein X and n have the same meanings as described above) (III)
And a method for producing an N- (thiazolin-2-yl) -N′-phenylurea derivative represented by the above formula (I). A third invention provides the following formula:

[0011]

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Wherein the 2-amino-2-thiazoline derivative (IV) represented by the formula (III) is reacted with the phenyl isocyanate represented by the formula (III). -(Thiazolin-2-yl)-
The present invention relates to a method for producing an N′-phenylurea derivative.

The fourth invention relates to a pesticidal composition containing an N- (thiazolin-2-yl) -N′-phenylurea derivative represented by the above formula (I) as an active ingredient.

Hereinafter, the present invention will be described in detail. The substitution positions of X, n and Xn in the above-mentioned target compound, a novel N- (thiazolin-2-yl) -N′-phenylurea derivative (I), and its production raw material [phenyl isocyanates (III)] It is as follows.

Examples of X include a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy, a nitro group, a cyano group, and the like; a halogen atom (eg, a chlorine atom, In the case of an iodine atom, a bromine atom, a fluorine atom, etc.), a chlorine atom, a bromine atom and a fluorine atom are preferred; in the case of a lower alkyl 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, more preferably a methyl group; a lower alkoxy group (for example, 1 to 6 carbon atoms)
Is preferably a straight-chain or branched one having 1 to 4 carbon atoms, more preferably a methoxy group; a lower haloalkyl group (for example, chlorine atom, iodine) Straight-chain or branched having 1 to 6 carbon atoms having a halogen atom such as an atom, bromine atom or fluorine atom), preferably a straight-chain or branched having 1 to 4 carbon atoms. And more preferably a trifluoromethyl group. A lower haloalkoxyl 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) preferably has 1 to 4 carbon atoms. And a trifluoromethoxy group is more preferable.

N can be an integer of 0 to 5; preferably 1 or 2.

The substitution position of Xn is not particularly limited;
Preferably, the 3-position or 4-position is good.

The compound (I) of the present invention can be produced, for example, by the following synthesis method 1 or synthesis method 2.

(Synthesis method 1)

The synthesis of the compound (1) of the present invention is generally carried out as follows, using the compound (II) as a starting material and the compound (II)
And I) in a solvent or in the absence of a solvent. Also, to accelerate the reaction,
Bases are often used as catalysts.

[0021]

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(In the formula, X and n 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, 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; amides such as N, N-dimethylformamide, N, N-dimethylacetamide; triethylamine, pyridine, N ,
Organic bases such as N-dimethylaniline; 1,3-
Dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above solvents, and the like.

The amount of the solvent used depends on the amount of the compound (I
It can be used such that the concentration of I) is in the range of 5 to 80% by weight, but it is preferable to use the compound B in a concentration of 10 to 70% by weight.

The base used as a catalyst is not particularly restricted but includes, for example, triethylamine, pyridine, N,
Organic bases such as N-dimethylaniline, DBU and the like can be mentioned.

The amount of the compound used can be 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.

Compound (III) used in the present invention is described, for example, in Org. Synth. , II, 453 (1943).
According to the method described in, for example, the method can be carried out as shown in the following formula.

[0030]

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(Wherein X and n have the same meanings as described above.) Examples of the compound (III) include the types of substituents corresponding to the compound numbers 1 to 17 shown in Tables 1 and 2. [Compounds (III) ₁ to (III)
No. ₁₇ . [For example, compound (III) corresponding to compound No. 1 is replaced with compound (II)
Called ₁ . The compound (III) ₁ means that Xn in the compound (III) is H. ].

(Synthesis Method 2) The compound (I) of the present invention can be synthesized by a synthesis method 1 using the compound (IV) instead of the compound (II) as a raw material. 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 and filtration, and if necessary, recrystallization and various chromatographic techniques. Can be appropriately purified by the above-mentioned means.

Compounds (I) include, for example, those described in Tables 1-2.
Compounds (hereinafter, referred to as Compounds 1 to 17) consisting of the types of the substituents corresponding to Compound Nos. 1 to 17 shown therein may be mentioned [for example, Compound (I) corresponding to Compound No. 1 may be a compound Called 1. The compound 1 means that Xn in the compound (I) is H. ].

The pests which are effective in controlling the compound (I) of the present invention include agricultural and horticultural pests [for example, Hemiptera (Orthoptera, Lepidoptera, Aphids, Whiteflies, etc.) and Lepidoptera (Cycoridae) , 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).

Examples of the carrier include 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 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 a suitable 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.

[0041]

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) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(4-chlorophenyl)
Synthesis of Urea (Compound 2) According to Synthesis Method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (2.
0 g) was dissolved in toluene (10 ml), and 4-chlorophenyl isocyanate (1.4 g) as a raw material compound was dissolved.
Was added and stirred at room temperature for 3 hours. After the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 1.6 g of the target compound as colorless crystals.

(2) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(1-naphthyl) urea (compound 3) According to the synthesis method 1, the following synthesis was performed. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) was dissolved in toluene (10 ml), 1-naphthyl isocyanate (0.5 g) as a raw material compound was added, and the mixture was stirred at room temperature for 3 hours. After the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 0.5 g of the target compound as colorless crystals.

(3) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(4-tolyl) urea (compound 4) According to the synthesis method 1, the following synthesis was performed. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) was dissolved in toluene (10 ml) and 4-tolyl isocyanate (0.3 g) as a raw material compound was added.
Stir at room temperature for 3 hours. After the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 0.6 g of the target compound as colorless crystals.

(4) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(3-isopropoxyphenyl) urea (compound 8) Synthesis According to synthesis method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) was dissolved in toluene (10 ml), and 3-isopropoxyphenyl isocyanate (0.4 g) as a raw material compound was added, followed by stirring at room temperature for 3 hours. After the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were dissolved in toluene-n
By recrystallizing from -hexane, 0.2 g of the target compound was obtained as colorless crystals.

(5) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(3-trifluoromethylphenyl) urea ( Synthesis of compound 9) According to the synthesis method 1, it was synthesized as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) was dissolved in toluene (10 ml), and 3-trifluoromethylphenyl isocyanate (0.5 g) as a raw material compound was added, followed by stirring at room temperature for 3 hours. After the reaction,
The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 1.0 g of the target compound as colorless crystals.

(6) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(4-bromophenyl)
Synthesis of Urea (Compound 7) According to Synthesis Method 1, synthesis was performed as follows. 2-imino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -1,3-thiazolidine (1.
0 g) was dissolved in toluene (10 ml), and the starting compound 4-bromophenyl isocyanate (0.4 g) was dissolved.
Was added and stirred at room temperature for 3 hours. After the reaction, the reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure.
The obtained pale yellow crystals were recrystallized from toluene-n-hexane to obtain 1.1 g of the target compound as colorless crystals.

(7) N- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -N '-(4-trifluoromethoxyphenyl) urea ( Synthesis of Compound 12) According to Synthesis Method 2, the compound was synthesized as follows. 2-Amino-4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazoline (1.0 g)
Was dissolved in toluene (10 ml), 4-trifluoromethoxyphenyl isocyanate (0.4 g) as a raw material compound was added, and the mixture was stirred at room temperature for 3 hours. After the reaction,
The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 0.5 g of the target compound 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 Atlas) and 2 parts by weight of sodium ligninsulfonate After uniform mixing, a small amount of water was added and kneaded, the mixture was 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 Atlas) and Demol (trade name) ; Made by Kao Atlas) 0.5 part by weight,
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) Test for controlling efficacy against Spodoptera litura (Preventive effect) A wettable powder of the target compound (I) shown in Tables 1-2 prepared according to Example 2 was replaced with a surfactant (0.01%). The soybean leaves were immersed in their respective chemical solutions for 30 seconds each, diluted into 500 ppm, placed in a plastic cup, and air-dried. Then, after releasing 10 second instar larvae of the cutworm, Spodoptera litura, into each of those cups and covering the cups,
It was left in a constant temperature room at 5 ° C., and the number of live and dead insects in each cup was counted to determine the mortality. The evaluation of the drug effect was performed in four stages (A: 100%, B: 99 to 80) depending on the range of the mortality.
%, C: 79 to 60%, D: 59% or less). Table 3 shows the results.

(2) Test for controlling efficacy against Japanese moth (preventive effect) A wettable powder of the target compound (I) shown in Tables 1-2 prepared according to Example 2 was added to a surfactant (0.01%). Diluted to 300 ppm with water containing cabbage leaf (5 x 5 cm)
Was immersed in a plastic cup for 30 seconds and air-dried. Then, in each of those cups, 10 third instar larvae of Conaga
After releasing the heads one by one and closing the lid, it was left in a constant temperature room at 25 ° C. for 2 days, and the number of live and dead insects in each cup was counted to determine the mortality. The results are shown in Table 4 by the four-step evaluation method described in (1).

[0058]

The N- (thiazolin-2-yl) of the present invention
The -N'-phenylurea derivative has an excellent pest control effect.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

Continuation of the front page (72) Inventor Yoshinori Yamanaka 5-19 Kogushi, Ogushi, Ube City, Yamaguchi Prefecture Examiner, Ube Research Institute, Ube Industries, Ltd. Shinichi Naito

Claims (4)

(57) [Claims] (1) The following formula: (Wherein, X represents a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a nitro group or a cyano group; n represents an integer of 0 to 5; Xn represents an unsaturated 6-membered ring condensed to a benzene ring together with the carbon atom to which they are attached), N- (thiazolin-2-yl)-
N′-phenylurea derivatives. 2. The following formula: And a 2-iminothiazolidine derivative represented by the following formula: (Wherein X and n have the same meanings as in claim 1), and are reacted with a phenyl isocyanate represented by the formula (1).
A method for producing a (thiazolin-2-yl) -N'-phenylurea derivative. 3. The following formula: And a 2-amino-2-thiazoline derivative represented by the following formula: (Wherein X and n have the same meanings as in claim 1), and are reacted with a phenyl isocyanate represented by the formula (I).
A method for producing a (thiazolin-2-yl) -N'-phenylurea derivative. 4. The method according to claim 1, wherein N-
A pest control agent comprising a (thiazolin-2-yl) -N'-phenylurea derivative as an active ingredient.