JP2710084B2 - 1- (Thiazolin-2-yl) -3-benzoylurea compound, its production method and pesticide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel 1- (thiazolin-2-yl) -3- useful as a pesticide.
The present invention relates to a benzoylurea compound and a method for producing the same.

[0002]

2. Description of the Prior Art Since the 1- (thiazolin-2-yl) -3-benzoylurea compound of the present invention is a novel compound, its pest control activity is not known.

[0003]

An object of the present invention is to provide a novel 1-
An object of the present invention is to provide a (thiazolin-2-yl) -3-benzoylurea 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, a novel 1- (thiazolin-2-yl) -3-benzoylurea compound has been developed for pests. Thus, the present invention has been found to have a remarkable controlling activity. That is, the first invention provides a compound (I) of the following formula:

[0005]

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(Wherein X represents a halogen atom, lower alkyl group, lower alkoxy group, lower haloalkyl group, lower haloalkoxy, nitro group, acetyl group or cyano group; Y represents an oxygen atom or a sulfur atom; n Represents an integer of 0 to 5; or, when n is 2, Xn represents an unsaturated 6 fused to a benzene ring together with the carbon atom to which they are attached.
1- (thiazolin-2-yl) represented by the following formula:
-3-Benzoylurea compound. 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, Y and n have the same meanings as described above). The present invention also relates to a process for producing the above-mentioned compound (I), characterized by reacting with a compound represented by the formula:

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 1- (thiazolin-2-yl) -3-benzoylurea compound [compound (I)],
The production material [benzoyl isocyanate (III-
I) or benzoyl isothiocyanates (III-
2) X, Y, n and X in [Compound (III)]
The substitution positions of n are as follows.

X includes a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy group, a nitro group, an acetyl group, a cyano group, and the like; a halogen atom (eg, a chlorine atom , Iodine atom, bromine atom, fluorine atom, etc.), preferably chlorine atom, bromine atom, fluorine atom; lower alkyl group (for example, linear or branched one having 1 to 6 carbon atoms) It 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.

Examples of Y include an oxygen atom and a sulfur atom. Examples of n include an integer of 0 to 5; preferably 1 or 2. The substitution position of Xn is not particularly limited;
Good place.

When n is 2, Xn, together with the carbon atom to which they are bonded, can represent an unsaturated 6-membered ring bonded to a benzene ring; preferably, together with the benzene ring, α-naphthyl It is preferred to form a group or a β-naphthyl group.

The synthesis of the compound (I) of the present invention is generally carried out as shown below, usually using the compound (II) as a raw 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.

[0017]

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(In the formula, X, Y 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. For example, benzene, toluene, xylene, methyl Chlorinated or non-chlorinated aromatics and aliphatics such as naphthalene, petroleum ether, ligroin, hexane, chlorobenzene, dichlorobenzene, methylene chloride, chloroform, dichloromethane, dichloroethane, trichloroethylene, cyclohexane,
Alicyclic hydrocarbons; ethers such as diethyl ether, tetrahydrofuran, dioxane; ketones such as acetone, methyl ethyl ketone; N, N
Amides such as -dimethylformamide, N, N-dimethylacetamide; organic bases such as triethylamine, pyridine, N, N-dimethylaniline;
1,3-dimethyl-2-imidazolidinone; dimethyl sulfoxide; a mixture of the above-mentioned solvents, and the like.

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.

The base used as the catalyst is not particularly restricted but includes, for example, triethylamine, 4- (N, N-
Dimethylamino) pyridine, pyridine, N, N-dimethylaniline, DBU (1,8-diazabicyclo [5.
4.0] undec-7-ene) and the like.

The compound 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.
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-I) wherein Y is an oxygen atom in compound (III) used in the present invention is described, for example, in Org. Synth. , 46, 16 (1963), etc., according to the following formula.

[0026]

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(Wherein X and n have the same meanings as described above). In the compound (III) used in the present invention, the compound (III-2) wherein Y is a sulfur atom is exemplified by, for example,
J. Am. Chem. Soc. , 61, 632 (193)
According to the method described in 9) and the like, it can be produced by performing the reaction as shown in the following formula.

[0028]

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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 29 shown in Tables 1 to 3. (Compounds (III) ₁ to (III)
_{No. 29} . [For example, the compound (III) corresponding to the compound number 1 is replaced with the compound (II)
I) Called ₁ . And, the compound (III) ₁ is the compound represented by the formula (III) wherein Xn is 2,6-C
It means that l ₂ and Y are oxygen atoms. ].

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, Tables 1 to 3
Each compound consisting of the kind of each substituent corresponding to the compound numbers 1 to 29 shown therein [referred to as compounds 1 to 29. [For example, compound (I) corresponding to compound number 1 is referred to as compound 1. Compound 1 is represented by the formula (I) wherein Xn is 2,6-C
is l _2, which means that Y is an oxygen atom. ].

Examples of the pests which can be controlled by the compound (I) of the present invention include agricultural and horticultural pests [eg, Hemiptera (Orthoptera, Lepidoptera, Aphids, Whiteflies, etc.) and Lepidoptera (Coleoptera) , 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, 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, for example, 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 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 sprayed on the foliage of plants, soil, or the surface of paddy fields, or applied directly to various applications depending on the purpose.

[0038]

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) Synthesis of 1- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -3- (2,6-difluorobenzoyl) urea 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1.0 g) was dissolved in toluene (10 ml), and 2,6-difluorobenzoyl isocyanate (0.4 g) as a raw material compound was added. Stirred for hours. After the reaction, 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.

(2) 1- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -3- (2-chlorobenzoyl)
Synthesis of urea 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1.0 g) was dissolved in toluene (10 ml), and 2-chlorobenzoyl isocyanate (0.4 g) as a raw material compound was added, followed by stirring at room temperature for 3 hours. did. After the reaction,
The solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 0.7 g of the target compound as colorless crystals.

(3) 1- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -3- (2-methylbenzoyl)
Synthesis of urea 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1.0 g) is dissolved in toluene (10 ml), 2-methylbenzoyl isocyanate (0.3 g) as a raw material compound is added, and the mixture is stirred at room temperature for 3 hours. did. After the reaction,
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) Synthesis of 1- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -3- (2-methoxybenzoyl) urea Imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1.0 g) was dissolved in toluene (10 ml), and 2-methoxybenzoyl isocyanate (0.4 g) as a raw material compound was added, followed by stirring at room temperature for 3 hours. did. After the reaction,
The solvent was distilled off under reduced pressure. The obtained pale yellow crystals were recrystallized from toluene-n-hexane to give 0.7 g of the target compound as colorless crystals.

(5) 1- [4,4-bis (trifluoromethyl) -5- (tetrafluoroethylidene) -2-thiazolin-2-yl] -3- (2-nitrobenzoyl)
Synthesis of urea 2-imino-4,4-bis (trifluoromethyl) -5
-(Tetrafluoroethylidene) -1,3-thiazolidine (1.0 g) is dissolved in toluene (10 ml), 2-nitrobenzoyl isocyanate (0.4 g) as a raw material compound is added, and the mixture is stirred at room temperature for 3 hours. did. After the reaction,
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.

(6) Other compounds (I) in Tables 1 to 3
Compound (I) according to any one of methods (1) to (5)
Was synthesized.

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 against Spodoptera litura Compound (I) prepared according to Example 2 and shown in Tables 1 to 3
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). The following compounds described in JP-A-58-57371

[0050]

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Using a comparative preparation having the same formulation as above, the same efficacy test was examined, and the results obtained were taken as comparative examples. Table 4 shows the results.

[0052]

[Table 4]

(2) Efficacy test for Conaga (Compound I) shown in Tables 1-3 prepared according to Example 2
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 results of the evaluation of the insecticidal effect are shown in Table 5 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).

[0054]

[Table 5]

(3) Efficacy test for Pleurotus terrestris (Compound I) prepared according to Example 2 and shown in Tables 1 to 3
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 each was covered with a lid. The cup was allowed to stand in a constant temperature room at 25 ° C. 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 are shown in Table 6 by the four-step evaluation method described in the above (1) together with the comparative examples obtained using the comparative preparation described in the above (1).

[0056]

[Table 6]

[0057]

The novel 1- (thiazoline-2-) of the present invention
The yl) -3-benzoylurea compound is an agricultural chemical useful as a pesticide.

[Table 1]

[Table 2]

[Table 3]

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Yoshinori Yamanaka 5-1978 Kogushi, Obe-shi, Ube City, Yamaguchi Prefecture Ube Industries, Ltd. Examiner in the 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)

Claims (3)

(57) [Claims] (1) The following formula: (Wherein X is a halogen atom, a lower alkyl group, a lower alkoxy group, a lower haloalkyl group, a lower haloalkoxy,
Y represents an oxygen atom or a sulfur atom; n represents an integer of 0 to 5; or, when n is 2, Xn represents, together with the carbon atom to which they are bonded, a nitro group, an acetyl group or a cyano group; 1- (thiazolin-2-yl) -3-benzoylurea compound represented by the formula (1) which represents an unsaturated 6-membered ring fused to a benzene ring. 2. The following formula: And a 2-iminothiazolidine compound represented by the following formula: (Wherein, X, Y and n have the same meanings as in claim 1). 1- (Thiazolin-2-yl) -3 according to claim 1, wherein the compound is reacted. −
A method for producing a benzoylurea compound. 3. The 1- (thiazoline-2-) according to claim 1,
A pest control agent comprising an yl) -3-benzoylurea compound as an active ingredient.