KR0131009B1 - 1-pyridothiazolyl-3-benzoyl urea derivatives and their preparation method - Google Patents

Abstract

Pyridothiazole(II) and benzoyl isocyanate(III) were reacted in the presence of diluting agents and solvents to give the 1- -pyridothiazolyl-3-benzoyl urea derivatives. Where X1 is carbon, nitrogen, one of X2, X3, X4 and X5 is nitrogen, the other is carbon, R1, R2, R3 and R5 are same or not, H, fluoro, chlorine and bromine, R4 is H, fluoro or Cl, nitro, C1-3 alkyl, C1-3 alkoxy in case of X1= C, no substituents in case of X1= N, R6, R7, R8 and R9 are H, fluoro, chlorine or bromine, nitro, C1-3 alkyl or C1-3 alkoxy in case of X2= X3= X4= X5= C, no substituents in case of X2, X3, X4 or X5 is nitrogen. Thus, 0.29 ml oxalyl chloride was added in a mixture of 1.57 g 2,6-difluorobenzamide and 15 ml dried dichloroethanol, followed by refluxing for 8 hours to give oily 2,6-difluorobenzoyl isocyanate. The ioscyanate was dissolved in 20 ml dried dichloroethane, followed by dropping in a solution 1.85 g 2-amide-6-chloro-4-pyridothiazo and 20 ml dichloroethane at room temperature for 4 hours to give 1.67 g 1-(6-chloro-4-pyridothiazolyl)- 3-(2,6-difluorobenzoyl)urea.

Description

1-pyridothiazolyl-3-benzoyl urea derivative and preparation method thereof

The present invention relates to a novel 1-pyridothiazolyl-3-benzoyl urea derivative represented by the following structural formula (I) having potent insecticidal and bactericidal action, a preparation method thereof, and a pesticide composition containing the same.

In formula (I), X ¹ is carbon or nitrogen, one of X ² , X ³ , X ⁴ and X ⁵ is nitrogen, the other is carbon, and R ¹ , R ² , R ³ and R ⁵ are the same as each other, or Alternatively a hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine and bromine, and R ⁴ is a halogen atom selected from the group consisting of a hydrogen atom, fluorine and chlorine when X ¹ is carbon, a nitro group and a carbon number of 1 to An alkyl group of 3 or an alkoxy group of 1 to 3 carbon atoms, and when X ¹ is nitrogen, there is no dentifrice, and R ⁶ , R ⁷ , R ⁸ and R ⁹ correspond to X ² , X ³ , X ⁴ , respectively; And a halogen atom, a nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms selected from the group consisting of hydrogen atom, fluorine, chlorine and bromine when X ⁵ is carbon, X ² , X ³ When X ⁴ or X ⁵ is nitrogen, there is no substituent.

The existing patent literature discloses some benzoyl urea derivatives that have an insecticidal effect. For example, benzoyl ureide-diphenylethers having insecticidal action are described in US Pat. Nos. 3,992,533 and 4,041,177. Patent 4,148,902 discloses substituted ((phenylamino) carbonyl) pyridine carboxamides, and together with these compositions a method of inhibiting insects is disclosed. In addition, patent documents describing benzoyl urea include U.S. Patent Nos. 4,166,124, 4,083,977 and 4,123,449, and German Patent Publication Nos. 2,901,334 (European Patent No. 013-414) and 3,104,407 (European Patent No. 57-). 888).

Such benzoyl urea derivatives are effectively used as insecticides and fungicides.

It is therefore an object of the present invention to provide novel 1-pyridothiazolyl-3-benzoyl urea derivatives that exhibit pesticidal and bactericidal action.

Another object of the present invention is to provide a method for preparing the 1-pyridothiazolyl-3-benzoyl urea derivative.

Another object of the present invention to provide a pesticide composition containing the 1-pyridothiazolyl-3-benzoyl urea derivative.

The 1-pyridothiazolyl-3-benzoyl urea derivative of the present invention for achieving the above object is represented by the following structural formula (I).

In formula (I), X ¹ is carbon or nitrogen, one of X ² , X ³ , X ⁴ and X ⁵ is nitrogen, the other is carbon, and R ¹ , R ² , R ³ and R ⁵ are the same as each other, or Alternatively a hydrogen atom or a halogen atom selected from the group consisting of fluoro, chlorine and bromine, and R ⁴ is a halogen atom, a nitro group or a carbon number selected from the group consisting of a hydrogen atom, fluoro and chlorine when X ¹ is carbon; When there is an alkyl group having 1 to 3 or an alkoxy group having 1 to 3 carbon atoms, and X ¹ is nitrogen, there is no substituent, and R ⁶ , R ⁷ , R ⁸ and R ⁹ respectively correspond to X ² , X ³ , X ^{When 4} and X ⁵ are carbon, a halogen atom selected from the group consisting of hydrogen atom, fluoro, chlorine and bromine, a nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, X ² , There is no substituent when X ³ , X ⁴ or X ⁵ is nitrogen.

Another object of the present invention is to prepare a 1-pyridothiazolyl-3-benzoyl urea derivative represented by the formula (I) to achieve a pyridothiazole represented by the formula (II) and the following formula (III) And benzoyl isocyanate represented by) in the presence of a diluent or solvent.

In Formulas (II) and (III), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are described above. Same as one.

Pesticide compositions for achieving another object of the present invention comprises an agriculturally effective amount of the 1-pyridothiazolyl-3-benzoyl urea derivative.

Looking at the present invention in more detail as follows.

The 1-pyridothiazolyl-3-benzoyl urea derivative represented by the structural formula (I) according to the present invention is a diluent of the pyridothiazole represented by the following structural formula (II) and the benzoyl isocyanate represented by the following structural formula (III). Or by reacting in the presence of a solvent.

In Formulas (II) and (III), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are described above. Same as one.

The pyridothiazole compounds represented by the above formula (II) can be prepared by the process described in the following document by reacting bromine in an acetic acid solvent with a substituted pyridine represented by the following formula (IV) [J. Pharm, Soc, Japan, 71, 169-72 (1951) and J. Pharm, Soc, Japan, 71, 662-7 (1951)]. The benzoyl isocyanate compound represented by the above structural formula (III) may be a known method or related literatures such as nicotinamide and oxalyl chloride represented by the chinodine benzamide represented by the following structural formula (V) or the following structural formula (IV). J. Org. Chem. 27, 3742, (1962), J, Pesticede, Sci., 17, 7, (1992).

X ² , X ³ , X ⁴ , X ⁵ , R ¹ , R ² , R ³ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ in the above formulas (IV), (V) and (VI) As described above.

In the present invention, amidopyridines represented by the above formula (IV) used as starting materials of the pyridothiazole compound represented by the above formula (II) are, for example, 2-amino-5-chloro, 3-amino-2-chloro, 5-amino-2-chloro, 2-amino-5-bromo, 2-amino-5-nitro, 2-amino-6-nitro-7-methyl, 2,6-dichloro 3-nitro, 2-amino-4,6-dimethyl, 5-amino-2-methoxy, 2-amino or 3-amino pyridine, and the like.

Further, benzamides represented by the structural formula (V) used as starting materials of the benzoyl isocyanate compound represented by the structural formula (III) are, for example, 2-chloro, 2,4-dichloro, 2,4-di Fluoro, 2,6-dichloro, 2,3,4,5,6-pentafluoro, 2,6-difluoro, 2-fluoro, 2-bromo, 2-iodine or 2,3,6 -Trichlorobenzamines, etc., and nicotinamide represented by the above structural formula (IV) used as another starting material is, for example, 2-chloro, 6-chloro, 2-fluoro, 6-fluoro, 2,6-dichloro, 2,6-difluoro, 2-bromo, or 2-iodine nicotinamide.

Meanwhile, in the present invention, most inert organic solvents may be used as diluents or solvents, and in particular, aliphatic and aromatic compounds such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, tetrahydrofuran and chlorobenzene, and Optionally chlorinated hydrocarbons; Ethers such as diethyl ether, dibutyl ether and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; And nitriles such as acetonitrile and propionitrile.

The reaction according to the invention is generally carried out at a temperature range of 0 ° C. to 120 ° C., preferably 10 to 50 ° C. so that the pressure is at normal pressure. The reaction ratio between the pyridothiazole compound represented by the above formula (II) and the benzoyl isocyanate compound represented by the above formula (III) is preferably in a molar ratio of 1: 1, however, an excess of one component can be used to achieve the object of the present invention. It is not affected. However, the use of an excessive amount of one component is disadvantageous economically in terms of industrial or laboratory. The reaction is carried out using the inert solvent at this temperature for 2 hours or more and the product is vacuum filtered. The filtered solid is washed with a solvent used in the reaction or alcohols such as methanol, dried and then recrystallized as necessary to prepare a pure benzoyl urea compound. The products are all in crystalline form and have the correct melting point.

The compound according to the present invention is added to the pesticide composition in an agriculturally effective amount to be used as an insecticide and a fungicide, in particular, as a pesticide inhibits chitin synthesis, thereby preventing the peeling and eradication, and thus low toxicity to mammals. It can also be used to protect cropland, forest land, and stockpiles and is generally active against pests at all growth stages, as well as sensitive and resistant species. As a fungicide, it shows excellent control effect against fungi including rice fever, tomato late blight, wheat red rust.

In particular, 1- (6-chloro-4-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea, 1- (6-chloro-7-pyridothiazolyl) -3- (2 , 6-difluorobenzoyl) urea, 1- (6-chloro-4-pyridothiazolyl) -3- (2,6-dichlorobenzoyl) urea, 1- (6-chloro-4-pyridothiazolyl ) -3- (2-bromobenzoyl) urea, 1- (6-nitro-4-pyridothiazolyl) -3- (2-fluorobenzoyl) urea, 1- (6-chloro-7-pyrido Such as thiazolyl) -3- (2-chlorobenzoyl) urea or 1- (6-chloro-7-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea Benzoyl urea derivatives are active against pests and fungi at all stages of growth, as well as sensitive and resistant species even when added in small amounts to agrochemical compositions.

Hereinafter, the preparation method of the compounds according to the present invention will be described in more detail, but the scope of the present invention is not limited to the following examples.

Example 1

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

To synthesize the isocyanate, 1.57 g (10 mmol) of 2,6-difluorobenzamide and 15 ml of dry dichloroethanol 100 ml flask were placed, followed by slowly injecting 0.29 ml (10.5 mmol) of olsalyl chloride into the syringe at room temperature. If it generates hydrochloric acid gas, it generates heat. The reaction was refluxed for 8 hours, cooled to room temperature, and the reaction solvent and excess oxalyl chloride were removed under vacuum to obtain 2,6-difluorobenzoyl isocyanate in oil form. Oily 2,6-difluorobenzoyl isocyanate is obtained. After dissolving 2,6-difluorobenzoyl isocyanate in oil state in 20 ml of dried dichloroethane, 1.85 g of 2-amide-6-chloro-4-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto at room temperature. After stirring for an hour, the mixture was filtered to obtain 1.67 g (45% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 225 ° C.

Example 2

Preparation of 1- (6-bromo-4-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

After synthesizing 2,6-difluorobenzoyl isocyanate in the same manner as in Example 1, 2.31 g of 2-amino-6-bromo-4-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto. 2.7 g (65% of theory) of the target compound were obtained. It is a white powder and has a melting point of 233 ° C.

Example 3

Preparation of 1- (4-chloro-5-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

After synthesizing 2,6-difluorobenzoyl isocyanate in the same manner as in Example 1, 1.86 g of 2-amino-4-chloro-5-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto. 2.87 g (77% of theory) were obtained. It is an off-white powder with a melting point of 201 캜.

Example 4

Preparation of 1- (6-chloro-7-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

After synthesizing 2,6-difluorobenzoyl isocyanate in the same manner as in Example 1, 1.86 g of 2-amino-6-chloro-7-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto. 2.49 g (67% of theory) were obtained. It is a white powder with a decomposition temperature of 295 ° C.

Example 5

Preparation of 1- (6-nitro-4-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

After synthesizing 2,6-difluorobenzoyl isocyanate in the same manner as in Example 1, 1.96 g of 2-amino-6-nitro-4-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto. 2.42 g (64% of theory) were obtained. It is a pale yellow powder with a melting point of 226 ° C.

Example 6

Preparation of 1- (6-nitro-7-methyl-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea

2,6-difluorobenzoyl isocyanate was synthesized in the same manner as in Example 1, and 2.1 g of 2-amino-6-nitro-7-methyl-4-pyridothiazole was dissolved in 20 ml of dichloroethane and added dropwise thereto. 1.68 g (43% of theory) of the target compound of the present invention were obtained. It is a pale yellow powder with a melting point of 235 ° C.

Example 7

Preparation of 1- (6-nitro-4-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea

To synthesize the isocyanate, 2.11 g (10 mmol) of 2,3,4,5,6-pentafluorobenzamide and 15 ml of dried dichloroethanol 100 ml flask were added, followed by 0.92 ml (10.5 mmol) of oxalyl chloride. Slow injection into a syringe at room temperature generates hydrochloric acid gas and generates heat. The reaction was refluxed for 8 hours, then cooled to room temperature and the reaction solvent and excess oxalyl chloride were removed under vacuum to give 2,3,4,5,6-pentafluorobenzoyl isocyanate in oil form. Dissolve oily 2,3,4,5,6-pentafluorobenzoyl isocyanate in 70 ml of dried dichloroethane, then 1.86 g of 2-amino-6-chloro-4-pyridothiazole in 20 ml of dichloroethane. The mixture was added dropwise and stirred at room temperature for 4 hours, followed by filtration to obtain 2.54 g (60% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 202 캜.

Example 8

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2-fluorobenzoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 1.39 g of 2-fluorobenzamide to synthesize 2-fluorobenzoyl isocyanate and 2-amino-6-chloro-4- 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7 to obtain 2.16 g (62% of theory) of the target compound of the present invention. It is a white powder and its melting point is 203 캜.

Example 9

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (3-fluorobenzoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 1.39 g of 3-fluorobenzamide to synthesize 3-fluorobenzoyl isocyanate and 2-amino-6-chloro-4- 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 2.52 g (72% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 236 ° C.

Example 10

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (4-fluorobenzoyl) urea

In Example 7, 2-fluoro-6-chloro-4- isocyanate was synthesized by replacing 2,3,4,5,6-pentafluorobenzamide with 1.39 g of 4-fluorobenzamide. 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 2.32 g (66% of theory) of the target compound of the present invention. It is a yellow powder with a melting point of 258 ° C.

Example 11

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2-chlorobenzoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 1.56 g of 2-chlorobenzamide to synthesize 2-chlorobenzoyl isocyanate and 2-amino-6-chloro-4-pyrido 1.86 g of thiazole was added dropwise in the same manner as in Example 7, to obtain 2.68 g (73% of theory) of the target compound of the present invention. It is a white powder with a melting point of 220 ° C.

Example 12

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (4-chlorobenzoyl) urea

In Example 7, 4-chlorobenzoyl isocyanate was synthesized by replacing 2,3,4,5,6-pentafluorobenzamide with 1.56 g of 4-chlorobenzamide and 2-amino-6-chloro-4-pyrido 1.86 g of thiazole was added dropwise in the same manner as in Example 7 to obtain 2.2 g (60% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 269 ° C.

Example 13

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2,4-dichlorobenzoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 1.90 g of 2,4-dichlorobenzamide to synthesize 2,4-dichlorobenzoyl isocyanate and 2-amino-6-chloro- 1.86 g of 4-pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 2.88 g (72% of theory) of the target compound of the present invention. It is a white powder and its melting point is 203 캜.

Example 14

Preparation of 1- (6-nitro-4-pyridothiazolyl) -3- (2,6-dichlorobenzoyl) urea

In Example 7, 2,6-dichlorobenzoyl isocyanate was synthesized by replacing 2,3,4,5,6-pentafluorobenzamide with 1.39 g of 2,6-dichlorobenzamide, and 2-amino-6-chloro- 1.86 g of 4-pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 1.58 g (40% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 221 캜.

Example 15

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (4-bromobenzoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 2.0 g of 4-bromobenzamide to synthesize 4-bromobenzoyl isocyanate and 2-amino-6-chloro-4- 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 2.46 g (60% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 268 ° C.

Example 16

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2-bromobenzoyl) urea

In Example 7, 2-bromobenzoyl isocyanate was synthesized by replacing 2,3,4,5,6-pentafluorobenzamide with 2.0 g of 2-bromobenzamide and 2-amino-6-chloro-4- 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7, to obtain 3.14 g (76% of theory) of the target compound of the present invention. It is a white powder with a melting point of 220 ° C.

Example 17

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2-chloronicotinoyl) urea

In Example 7, 2,3,4,5,6-pentafluorobenzamide was replaced with 1.57 g of 2-chloronicotinamide to synthesize 2-chloronicotinoyl isocyanate and 2-amino-6-chloro-4 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7 to obtain 2.70 g (73% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 233 ° C.

Example 18

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (6-chloronicotinoyl) urea

In Example 7, 6-chloronicotinoyl isocyanate was synthesized by replacing 2,3,4,5,6-pentafluorobenzamide with 1.57 g of 6-chloronicotinamide and 2-amino-6-chloro-4 1.86 g of pyridothiazole was added dropwise in the same manner as in Example 7 to obtain 2.16 g (66% of theory) of the target compound of the present invention. It is a white powder and has a melting point of 268 ° C.

Example 19

Preparation of 1- (6-chloro-4-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea

2,3,4,5,6-pentafluorobenzoyl isocyanate was synthesized in the same manner as in Example 7, and 2-amino-6-chloro-7-pyridothiazole was reacted in the same manner as in Example 7. 2.94 g (70% of theory) of the target compound of the present invention were obtained. This is an off-white powder, the decomposition temperature is 270 ℃.

Example 20

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (2-fluorobenzoyl) urea

Synthesizing 2-fluorobenzoyl isocyanate in the same manner as in Example 8 and reacting 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7, 2.62 g of the target compound of the present invention (theoretical value) 74%). It is a white powder with a melting point of 240 ° C.

Example 21

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (3,6-difluorobenzoyl) urea

Synthesizing 3-fluorobenzoyl isocyanate in the same manner as in Example 9 and reacting 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7, 2.32 g of the target compound of the present invention (theoretical value) 55%) was obtained. It is a white powder and has a melting point of 270 ° C.

Example 22

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (2-chlorobenzoyl) urea

Synthesis of 2-chlorobenzoyl isocyanate in the same manner as in Example 11 and 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7 3.12 g (85% of theory) ) It is brown powder and has a melting point of 234 ° C.

Example 23

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (2,4-dichlorobenzoyl) urea

Synthesizing 2,4-dichlorobenzoyl isocyanate in the same manner as in Example 13 and reacting 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7 to 3.12g ( 78% of theory). It is a yellow powder with a melting point of 236 ° C.

Example 24

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (2,6-dichlorobenzoyl) urea

Synthesizing 2,6-dichlorobenzoyl isocyanate in the same manner as in Example 14 and reacting 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7, 2.44 g of the target compound of the present invention ( 61% of theory). It is a purple powder with a melting point of 260 ° C.

Example 25

Preparation of 1- (6-chloro-7-pyridothiazole) -3- (2-bromobenzoyl) urea

In the same manner as in Example 16, 2-bromobenzoyl isocyanate was synthesized, and 2-amino-6-chloro-7-pyridothiazole was reacted in the same manner as in Example 7 to 2.8 g of the target compound of the present invention (theoretical value). 68%) was obtained. It is a gray powder with a melting point of 290 ° C.

Example 26

Preparation of 1- (6-chloro-7-pyridothiazolyl) -3- (2-chloronicotinoyl) urea

Synthesizing 2-chloronicotinoyl isocyanate in the same manner as in Example 17 and reacting 2-amino-6-chloro-7-pyridothiazole in the same manner as in Example 7 3.08g ( 84% of theory). It is a white powder and has a melting point of 233 ° C.

Example 27

Preparation of 1- (6-nitro-4-pyridothiazolyl) -3- (2-fluorobenzoyl) urea

Synthesizing 2-fluorobenzoyl isocyanate in the same manner as in Example 8 and reacting 1.96 g of 2-amino-6-nitro-4-pyridothiazole in the same manner as in Example 7, 1.24 g of the target compound of the present invention (34% of theory). It is a white powder and has a melting point of 228 ° C.

Example 28

Preparation of 1- (4-chloro-5-pyridothiazolyl) -3- (2-fluorobenzoyl) urea

Synthesizing 2-fluorobenzoyl isocyanate in the same manner as in Example 8 and reacting 1.84 g of 2-amino-4-chloro-5-pyridothiazole in the same manner as in Example 7, 2.0 g of the target compound of the present invention (57% of theory). It is a white powder and has a melting point of 212 ° C.

Example 29

Preparation of 1- (6-nitro-4-pyridothiazole) -3- (2-chlorobenzoyl) urea

Synthesizing 2-chloronicotinoyl isocyanate in the same manner as in Example 11 and reacting 2-amino-6-nitro-4-pyridothiazole in the same manner as in Example 7, 1.64 g of the target compound of the present invention ( 43% of theory). It is a white powder and has a melting point of 235 ° C.

Example 30

Preparation of 1- (6-bromo-4-pyridothiazolyl) -3- (2-chlorobenzoyl) urea

In the same manner as in Example 11, 2-chloronicotinoyl isocyanate was synthesized, and 2.3 g of 2-amino-6-bromo-7-pyridothiazole was reacted in the same manner as in Example 7. 2.57 g (62% of theory) were obtained. It is a white powder and has a melting point of 228 ° C.

Example 31

Preparation of 1- (6-bromo-4-pyridothiazolyl) -3- (2-fluorobenzoyl) urea

Synthesizing 2-fluorobenzoyl isocyanate in the same manner as in Example 8 and reacting 2.3 g of 2-amino-6-bromo-4-pyridothiazole in the same manner as in Example 7, target compound 1.18 of the present invention g (30% of theory) was obtained. It is a white powder and has a melting point of 198 ° C.

Example 32

Preparation of 1- (6-nitro-4-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea.

2,3,4,5,6-pentafluorobenzoyl isocyanate was synthesized in the same manner as in Example 7, and 2-amino-6-nitro-4-pyridothiazole was reacted in the same manner as in Example 7. 1.08 g (25% of theory) of the target compound of the present invention were obtained. It is a white powder and has a melting point of 202 캜.

Example 33

Preparation of 1- (6-bromo-4-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea.

2,3,4,5,6-pentafluorobenzoyl isocyanate was synthesized in the same manner as in Example 7, and 2-amino-6-bromo-4-pyridothiazole was reacted in the same manner as in Example 7. 1.00 g (21% of theory) of the target compound of the present invention were obtained. It is a white powder and has a melting point of 221 캜.

Table 1 below describes the final products according to Examples 1 to 33 and their melting points and theoretical yields.

In Table 1, decomposition means decomposition at the temperature.

The benzoyl urea derivative of the present invention prepared by the method as described above to determine how much control effect against pests such as Chinese cabbage moth, tobacco germweed moth, rice fever, tomato late blight, wheat red rust disease Was tested.

[Test Example 1]

Insecticidal activity of Plutella maculipennis

Fresh cabbage leaf disks cut into circles of 5 cm in diameter are immersed in the prepared chemical solution for 30 seconds and then dried in a hood. Put the dried disk into a disposable petri dish of 5cm diameter and inoculate 10 cabbage moth larvae with a fine brush and seal it with a lid to prevent escape.

Pesticides were examined at 24 and 48 hours after storage at 25 ° C, 60% RH. Investigation of the effect of reducing insect growth is carried out after the 48-hour assay, replacing with fresh food, and then examining the abnormal development and insecticidal rate at 96 and 120 hours after treatment with the chemical solution.

Drug evaluation criteria are as follows, and the results are shown in Table 2 below.

5: 100% at 95% or more

4: Control is more than 80% and less than 95%

3: Control is more than 50% and less than 80%

2: Control is more than 30% and less than 50%

1: control is more than 10% and less than 30%

0: Control is less than 10%

[Test Example 2]

Insecticidal Activity Test on Tobacco Spider Moth (Spodoptera spp)

Fresh cabbage leaf discs cut into 5.5 cm or 10 cm in diameter are immersed in the prepared chemical solution for 30 seconds and dried in a hood. Clean dried discs are placed in a disposable petri dish with a diameter of 5.5 cm or 12 cm and inoculated with 5 or 10 tobacco gelatin moth larvae with non-sharp tweezers and sealed with a lid to prevent escape. Pesticides were examined at 24 and 48 hours after storage at 25 ° C, 60% RH. Investigation of the inhibitory effect on insect growth is carried out by replacing the fresh food after the 48-hour assay and the abnormal development and pesticide rate at 96 and 120 hours after the treatment with the chemical solution.

Drug efficacy evaluation criteria are the same as in Test Example 1 and the control results are listed in Table 3 below.

[Test Example 3]

Insecticidal Activity Test on Nilaparvata lugens

After seeding, roots of five Dongjin rice seedlings, 7-8 days old, are wrapped with cotton strips and inserted into the bottom of a glass test tube with a diameter of 3 x 15 cm. Ten adult rice larvae 3-5 days after allegory are collected from a breeding cage using a vacuum pump equipped with a shock absorber and placed in a test tube in which rice seedlings are inserted.

Spray the prepared chemical directly from the entrance of the test tube towards the rice planter attached to the rice husk. After treatment, the entrance of the test tube shall be covered with nylon mesh to prevent the escape of a light bulb. After inoculation, the pesticidal rate of test insects was examined 24 and 48 hours after storage at 25 ° C. and 60% RH.

Drug evaluation criteria are the same as in Test Example 1, the results are shown in Table 4 below.

As a result of the insecticidal test as described above, the activity test was performed by adjusting the concentration of the chemical solution for several kinds of compounds having excellent activity (described in Table 5 below), and the commercialized dimilin and activity (lethality,%) ) Was measured and described in Table 5 below.

[Test Example 4]

Rice Blast Control Test

After the application of polyoxyethylene sorbitan monolaurate (Tween-20, Japan, Junsei Chemical Co., Ltd.) as an electrodeposition agent for attaching the rice leaves of the compounds shown in Table 6, Pathogens were inoculated. As a solvent for dissolving the compound, a reagent of methyl alcohol (M-OH) was prepared as a 250 ppm solution, sprayed on rice seedlings of 3 to 4 leaf stages, and then examined for damage, inoculation, and pathogenesis.

In order to investigate the growth inhibition of the bacteriostatic bacterium bacterium, the agar of P. orizae incubated for 5 days in PDA medium was cured by mixing the dissolved compound at a concentration of 250 ppm in potato agar medium (Difco, Fatato Dextrose Agar). The disk (ø5mm) was placed in the center of the medium and incubated at 26 ° C. for 5 days, and the degree of inhibition of bacterial growth was examined. Inhibition rate was calculated as follows.

The experiment was repeated three times and the results were shown in Table 6, and the results were shown in Table 6 below.

[Test Example 5]

Tomato Late Blight Control Test

The compound shown in Table 7 below was diluted to 250 ppm using 5% acetone and 200 ppm solution of Tween 20. This diluted pesticide was foliaged on tomatoes, dried in a hood and placed in a greenhouse. After being left in the greenhouse for 1 day, the tomato seedlings were spray inoculated with an inoculum of 1 × 10 sporangi a / ml spore concentration, followed by wet treatment. When the untreated plot showed about 80% (area area), the control group was determined to obtain control value. The experiment was carried out four times with three repetitions and the results are shown in Table 7 below. The efficacy evaluation criteria are the same as in Test Example 1.

[Test Example 6]

Wheat Leaf Rust Control Test

Sowing 8 seed seeds in a disposable pot (5cm in diameter) and cultivating in a greenhouse for 7 days to grow single-leafed wheat. The compound shown in Table 8 was dissolved in acetone, and then diluted with Tween 20 solution to prepare a drug at a concentration of 250 ppm. Spray the foliar evenly on wheat, and air-dry in a greenhouse for 1 day, and then inoculate wheat rust spores. The inoculated wheat is stored for 1 day in the dark at 20 ° C with 100% relative humidity, and then transferred to a 20 ± 1 ° C constant temperature and humidity room with 79% relative humidity to induce 10 days of onset. The degree of lesion formation of the leaves was investigated, and the same test was repeated three times and the results are shown in Table 8 below. The efficacy evaluation criteria are the same as in Test Example 1.

As a result of the sterilization test as described above, the activity test was carried out by adjusting the concentration of the chemical solution for several kinds of compounds having excellent activity, and the results are shown in Table 9 below.

Claims (13)

1-pyridothiazolyl-3-benzoyl urea derivative represented by the following general formula (I). In formula (I), X ¹ is carbon or nitrogen, one of X ² , X ³ , X ⁴ and X ⁵ is nitrogen, the other is carbon, and R ¹ , R ² , R ³ and R ⁵ are the same as each other, or Alternatively a hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine and bromine, and R ⁴ is a halogen atom selected from the group consisting of a hydrogen atom, fluorine and chlorine when the X ¹ is carbon, a nitro group, having from 1 to 3 carbon atoms When an alkyl group or an alkoxy group having 1 to 3 carbon atoms and X ¹ is nitrogen, there is no substituent, and R ⁶ , R ⁷ , R ⁸ and R ⁹ are corresponding to X ² , X ³ , X ⁴ and X ^{5, respectively.} When carbon is a halogen atom selected from the group consisting of hydrogen atom, fluorine, chlorine and bromine, a nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, X ² , X ³ , X ⁴ or There is no substituent when X ⁵ is nitrogen. The 1-pyri according to claim 1, wherein the derivative of formula (I) is 1- (6-chloro-4-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea. Dothiazolyl-3-benzoyl urea derivatives. The 1-pyri according to claim 1, wherein the derivative of formula (I) is 1- (6-chloro-7-pyridothiazolyl) -3- (2,6-difluorobenzoyl) urea. Dothiazolyl-3-benzoyl urea derivatives. The 1-pyridothia according to claim 1, wherein the derivative of formula (I) is 1- (6-chloro-4-pyridothiazolyl) -3- (2,6-dichlorobenzoyl) urea. Zolyl-3-benzoyl urea derivatives. The 1-pyridothiazolyl according to claim 1, wherein the derivative of formula (I) is 1- (6-chloro-4-pyridothiazolyl) -3- (2-bromobenzoyl) urea. -3-benzoyl urea derivative. The 1-pyridothiazolyl according to claim 1, wherein the derivative of formula (I) is 1- (6-nitro-4-pyridothiazolyl) -3- (2-fluorobenzoyl) urea. -3-benzoyl urea derivative. The 1-pyridothiazolyl according to claim 1, wherein the derivative of formula (I) is 1- (6-bromo-4-pyridothiazolyl) -3- (2-chlorobenzoyl) urea. -3-benzoyl urea derivative. The method of claim 1, wherein the derivative of formula (I) is 1- (6-chloro-7-pyridothiazolyl) -3- (2,3,4,5,6-pentafluorobenzoyl) urea 1-pyridothiazolyl-3-benzoyl urea derivative. 1-pyridothiazolyl represented by the following general formula (I) characterized by reacting pyridothiazole represented by the following structural formula (II) with benzoyl isocyanate represented by the following structural formula (III) in the presence of a diluent or a solvent. Process for the preparation of -3-benzoyl urea derivative. In formulas (I), (II) and (III), X ¹ is carbon or nitrogen, one of X ² , X ³ , X ⁴ and X ⁵ is nitrogen, and the other is carbon, R ¹ , R ² , R ³ and R ⁵ are the same as or different from each other hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine and bromine, R ⁴ is a halogen atom selected from the group consisting of hydrogen atom, fluorine and chlorine when X ¹ is carbon, A nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and when X ¹ is nitrogen, there is no substituent, and R ⁶ , R ⁷ , R ⁸ and R ⁹ each correspond to X ^2; When X ³ , X ⁴ and X ⁵ are carbon, a halogen atom selected from the group consisting of hydrogen atom, fluorine, chlorine and bromine, a nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, There is no substituent when X ² , X ³ , X ⁴ and X ⁵ are nitrogen. The method of claim 9, wherein the diluent or solvent is selected from aliphatic and aromatic and optionally chlorinated hydrocarbons, such as benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, tichloroethane, tetrahydrofuran and chlorobenzene; Ethers such as diethyl ether, dibutyl ether and dioxane; Ketones such as acetone, methyl ethyl ketone, methyl isopropyl ketone and methyl isobutyl ketone; Or nitriles such as acetonitrile and propionitrile. 1. A process for preparing 1-pyridothiazolyl-3-benzoyl urea derivative represented by the general formula (I). 10. The method for preparing 1-pyridothiazolyl-3-benzoyl urea derivative represented by the general formula (I) according to claim 9, wherein the reaction temperature is 0 to 120 ° C. 10. The compound represented by the general formula (I) according to claim 9, wherein the reaction molar ratio of pyridothiazole represented by the structural formula (II) and benzoyl isocyanate represented by the structural formula (III) is 1: 1. Method for preparing pyridothiazolyl-3-benzoyl urea derivative. A pesticide composition characterized by containing 1-pyridothiazolyl-3-benzoyl urea derivative represented by the following general formula (I). In formula (I), X ¹ is carbon or nitrogen, one of X ² , X ³ , X ⁴ and X ⁵ is nitrogen, the other is carbon, and R ¹ , R ² , R ³ and R ⁵ are the same as each other, or Alternatively a hydrogen atom or a halogen atom selected from the group consisting of fluorine, chlorine and bromine, and R ⁴ is a halogen atom selected from the group consisting of a hydrogen atom, fluorine and chlorine when the X ¹ is carbon, a nitro group, having from 1 to 3 carbon atoms If an alkyl group or an alkoxy group having 1 to 3 carbon atoms and X ¹ is nitrogen, there are no substituents, and R ⁶ , R ⁷ , R ⁸ and R ⁹ respectively correspond to X ² , X ³ , X ⁴ and X ⁵ When carbon is a halogen atom selected from the group consisting of hydrogen atom, fluorine, chlorine and bromine, a nitro group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, X ² , X ³ , X ⁴ or There is no substituent when X ⁵ is nitrogen.