WO2019156425A1 - Pyrazole carboxamide compound containing organosulfur group and pesticide composition containing pyrazole carboxamide compound - Google Patents

Abstract

The present invention relates to a novel pyrazole carboxamide compound containing an organosulfur group, a pesticide composition containing the pyrazole carboxamide compound, and a method for controlling pests by using the pesticide composition. The compound according to the present invention is useful in the control of various insect pests, especially moths, such as Plutella xylostella and Spodoptera litura, and planthoppers, such as Laodelphax striatellus.

Description

Pyrazole carboxamide compound containing organosulfur group and pesticide composition containing same

The present invention relates to novel compounds having insecticidal effects on various pests of insects and to insecticide compositions containing the same.

Examples of the pesticides used in the past include carbamate insecticides or organophosphorus insecticides, and these insecticides exhibit an effect by inhibiting acetylcholinesterase. However, with the use of these pesticides for a long time, resistant pests appeared, and the development of pesticides with a new mechanism of action was needed, and the calcium ion channel, ryanodine receptor, has emerged as a new target for controlling pests.

Because homeostasis of calcium plays an important role, particularly in muscle contraction, pesticides that bind to liadinodine receptors inhibit pest ingestion and cause coma or paralysis, leading to death.

To date, commercially available insecticides that bind to the lyanodine receptor have been discovered by Nihon Nohyaku and co-developed by Bayer Crop Science, flubendiamide, Phoenix ^TM , Takumi ^TM , EP 1380209 A1. Chlorantraniliprole, Rynaxypyr ^™ , WO 01/070671 and cyantraniliprole, Cyazypyr ^™ , WO 04 / 067528).

These compounds are known to exhibit potent insecticidal effects on moths, by binding to the lianodine receptor and disrupting calcium ion channels.

A variety of companies include Bayer and Du Pont, including Syngenta, Sumitomo, Ishihara Sangyo Kaisha, and Nissan. More than 100 patents have been filed for the development of derivatives, but only three are commercially available: flubendiamide, chloranthraniliprole and cyanthraniliprole.

Recently, the EU pointed out a neonicotinoid insecticide pesticide as one of the causes of the decline in honeybee populations, and accordingly, the EU Food and Drug Administration published a study related to the above in January 2013. Based on these findings, the EU Commission proposed a ban on the use of three substances: imidacloprid, clothianidin and thiamethoxam. The vote was to decide whether or not to take the final ban. In Korea, the Environmental Promotion Agency and the National Assembly, especially the Agriculture Promotion Agency, have shown a position to respond proactively before these problems arise. As described above, in the development of pesticide pesticides, safety of insects and bees as well as insects has become important. Chloranthraniliprolol, developed by DuPont, has a bee acute contact toxicity of only> 4μg / bee (LD ₅₀ ), which requires the development of a safer pesticide.

On the other hand, in the development of pesticides, the half-life of soil residues is considered along with bee acute contact toxicity. The half-life of chlorantraniliprole remains in the soil for about 180 days and poses a risk to the environment. In addition to the stability of honeybees, the shorter soil retention period requires the development of pesticides that are safer for the environment.

It is an object of the present invention to provide novel compounds, hydrates thereof, solvates thereof or salts thereof which exhibit pesticidal activity against various pests and are safe for insects and can be used as active ingredients in insecticide compositions with a short soil residence period.

Another object of the present invention is to provide an insecticide composition containing the compound, a hydrate thereof, a solvate thereof or a salt thereof as an active ingredient.

Still another object of the present invention is to provide a method for controlling pests by treating the pesticide composition to a crop or a habitat thereof.

In order to achieve the above object, a compound of Formula 1, a hydrate thereof, a solvate thereof, or a salt thereof is provided, and the compound of Formula 1 is a pyrazole carboxamide compound comprising an organosulfur group:

[Formula 1]

In Chemical Formula 1,

At least one of A and B

, And the other is hydrogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{3- 10} cycloalkyl alkylamino, C _{1- 10} alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C _{1 - 10} alkyl, hydroxy, carbamoyl, C _{1- 10} alkylcarbamoyl, cyano, nitro or halogen, wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl can each independently be further substituted with one or more halogens;

X is absent or oxygen;

Y is absent or is oxygen or NR ';

R 'is cyano, C _{1- 10} alkyl, C _{1- 10} alkyl carbonyl, C _{6- 20} aryl-carbonyl or C _{3- 10} cycloalkyl-carbonyl, wherein said alkyl, alkylcarbonyl, arylcarbonyl, cycloalkyl carbonyl group is a halogen, a halo-C _{1 - 10} alkyl, cyano, C _1- C ₁₀ alkoxy and _6- with one or more substituents selected from ₂₀ aryl may be further substituted, and;

R is C _{1- 10} alkyl, C _{6- 20} aryl, or C _{3- 10} cycloalkyl;

R ₁ is hydrogen or C _{1- 10} alkyl;

R ₂ is halogen, cyano, amino, hydroxy, mercapto, cyano, thio, C _{1- 10} alkyl, halo C _1-10 alkyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{1- 10} alkyl, halo C _{1 - 10} alkoxy, C _{1- 10} alkylthio, C _{1- 10} alkyl amino, C _{6- 20} aryl amino, C _1-10 alkyl, C _6-20 arylamino, C _{1- 10} alkyl aminocarbonyl, C _{6- 20} aryl, C _{6- 20} aryloxy, halo-C _{6 - 20} aryl, or halo C _6-20 aryloxy Is;

R ₃ is C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 -10} alkyl, C _{3- 10} cycloalkyl, amino, ₁₀ is alkyl, hydroxy, cyano, halogen or nitro, _{- 1-} C ₁₀ alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C ₁ Wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl may each independently be further substituted with one or more halogens;

Ar ₁ is a C _{6- 20} aryl, or C _{3- 20} heteroaryl, wherein said aryl and heteroaryl are each independently selected from halogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _1-10 alkoxy, halo C _{1 - 10} alkyl, halo C _{1 - 10} alkoxy, hydroxy and cyano may be further substituted with one or more substituents selected from the group consisting of a furnace;

The heteroaryls each independently include one or more heteroatoms selected from nitrogen, oxygen and sulfur.

Also provided is an insecticide composition containing the compound of Formula 1, a hydrate thereof, a solvate thereof, or a salt thereof as an active ingredient.

Also provided is a method of controlling pests by treating the pesticide composition to crops or their habitats.

The compound of the formula (1), its hydrate, its solvate or its salt is a novel compound, and the pesticide composition containing it as an active ingredient is a variety of pests, especially moths such as Chinese cabbage moth, tobacco germweed moth, and extinct species such as larvae It has a good insecticidal effect and is safe for insect bees and has a short soil life and is environmentally friendly.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated more concretely. Unless otherwise defined in the technical terms and scientific terms used at this time, have a meaning commonly understood by those of ordinary skill in the art to which the present invention belongs, unnecessarily obscure the subject matter of the present invention in the following description Description of known functions and configurations that may be omitted.

A pyrazole carboxamide compound, a hydrate thereof, a solvate thereof, or a salt thereof including an organosulfur group represented by Formula 1 is disclosed:

[Formula 1]

In Chemical Formula 1,

At least one of A and B

, And the other is hydrogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{3- 10} cycloalkyl alkylamino, C _{1- 10} alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C _{1 - 10} alkyl, hydroxy, carbamoyl, C _{1- 10} alkylcarbamoyl, cyano, nitro or halogen, wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl can each independently be further substituted with one or more halogens;

X is absent or oxygen;

Y is absent or is oxygen or NR ';

Y is oxygen or NR;

R 'is cyano, C _{1- 10} alkyl, C _{1- 10} alkyl carbonyl, C _{6- 20} aryl-carbonyl or C _{3- 10} cycloalkyl-carbonyl, wherein said alkyl, alkylcarbonyl, arylcarbonyl, cycloalkyl carbonyl group is a halogen, a halo-C _{1 - 10} alkyl, cyano, C _1- C ₁₀ alkoxy and _6- with one or more substituents selected from ₂₀ aryl may be further substituted, and;

R is C _{1- 10} alkyl, C _{6- 20} aryl, C _{3- 10} cycloalkyl, halo-C _{1 - 10} alkyl or cyano;

R ₁ is hydrogen or C _{1- 10} alkyl;

R ₂ is halogen, cyano, amino, hydroxy, mercapto, cyano, thio, C _{1- 10} alkyl, halo C _1-10 alkyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{1- 10} alkyl, halo C _{1 - 10} alkoxy, C _{1- 10} alkylthio, C _{1- 10} alkyl amino, C _{6- 20} aryl amino, C _1-10 alkyl, C _6-20 arylamino, C _{1- 10} alkyl aminocarbonyl, C _{6- 20} aryl, C _{6- 20} aryloxy, halo, C _{6 -20} aryl group or a halo C _6-20 aryloxy Is;

R ₃ is C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 -10} alkyl, C _{3- 10} cycloalkyl, amino, ₁₀ is alkyl, hydroxy, cyano, halogen or nitro, _{- 1-} C ₁₀ alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C ₁ Wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl may each independently be further substituted with one or more halogens;

Ar ₁ is a C _{6- 20} aryl, or C _{3- 20} heteroaryl, wherein said aryl and heteroaryl are each independently selected from halogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _1-10 alkoxy, halo C _{1 - 10} alkyl, halo C _{1 - 10} alkoxy, hydroxy and cyano may be further substituted with one or more substituents selected from the group consisting of a furnace;

The heteroaryls each independently include one or more heteroatoms selected from nitrogen, oxygen and sulfur.

As used herein, the term "alkyl" refers to a monovalent straight or pulverized saturated hydrocarbon radical consisting solely of carbon and hydrogen atoms, which may have from 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Examples of such alkyl radicals include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl and the like.

As used herein, the term “aryl” refers to an organic radical derived from an aromatic hydrocarbon by one hydrogen removal, wherein a single or fused ring contains 4 to 7, preferably 5 or 6 ring atoms, as appropriate for each ring. It includes a system, including a form in which a plurality of aryl is connected by a single bond. Specific examples include, but are not limited to, phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, and the like.

As used herein, the term “heteroaryl” refers to an aryl group containing 1 to 4 heteroatoms selected from N, O and S as the aromatic ring skeleton atom, and wherein the remaining aromatic ring skeleton atom is carbon. Monocyclic heteroaryl and polycyclic heteroaryl condensed with one or more benzene rings, and may be partially saturated. In addition, heteroaryl in the present specification also includes a form in which one or more heteroaryl is connected by a single bond. Examples of the heteroaryl group include pyrrole, quinoline, isoquinoline, pyridine, pyrimidine, oxazole, thiazole, thiadiazole, triazole, imidazole, benzoimidazole, isoxazole, benzoisoxazole, thiophene, Benzothiophene, furan, benzofuran and the like.

As used herein, the term “halo” or “halogen” refers to a halogen group element and includes, for example, fluoro, chloro, bromo and iodo.

The term “cycloalkyl” herein is a monovalent saturated carbocyclic radical composed of one or more rings, which may have 3 to 10 carbon atoms, preferably 3 to 7 carbon atoms. Specific examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.

The term "alkoxy" as used herein is an -O-alkyl radical, which may have 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms. Here 'alkyl' is as defined above. Specific examples include, but are not limited to, methoxy, ethoxy, isopropoxy, butoxy, isobutoxy, t-butoxy and the like.

In Formula 1, at least one of A and B

, And the other is hydrogen, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{3- 7} cycloalkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, C _{1- 6} alkylthio, C _{6- 12} aryl, C _{6- 12} aryloxy, C _{6- 12} aryl C _{1 - 6} alkyl, hydroxy, carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen; X is absent or oxygen; Y is absent or is oxygen or NR '; R 'is cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _1-6 alkylcarbonyl, halo C _{1 - 6} alkylcarbonyl or C _{3- 7} cycloalkyl carbonyl gt; R is C _{1- 6} alkyl, C _{3- 7} cycloalkyl, halo C _{1 - 6} alkyl or cyano; R ₁ is hydrogen or C _{1- 6} alkyl; R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, or C _{3- 7} cycloalkyl; R ₃ is C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{3- 7} cycloalkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, C _{1- 6} alkylthio, C _{6- 12} aryl, C _{6- 12} aryloxy, C _{6- 12} aryl C _{1 - 6} alkyl, hydroxy, cyano, nitro, or halogen; Ar ₁ is a C _{3- 12} heteroaryl, wherein said heteroaryl group is halogen, C _{1- 6} alkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkyl, halo C _{1 - 6} alkoxy, hydroxy and cyano consisting of It may be further substituted with one or more substituents selected from the group.

The compound of Formula 1 may be specifically represented by the following Formula 2 or Formula 3.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3,

R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

R ₁ is hydrogen or C _{1- 6} alkyl;

R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

Ar ₁ is pyridyl with or without halogen.

The compound of Formula 1 may be represented by the following Formula 4, Formula 5, Formula 6 or Formula 7.

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

In Chemical Formulas 4 to 7,

R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

R ₁ is hydrogen or C _{1- 6} alkyl;

R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

Ar ₁ is pyridyl with or without halogen.

The compound of Formula 1 may be represented by Formula 8, Formula 9, Formula 10 or Formula 11 more specifically.

[Formula 8]

[Formula 9]

[Formula 10]

[Formula 11]

In Chemical Formulas 8 to 11,

R 'is cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkylcarbonyl or halo C _{1 - 6} alkylcarbonyl, and;

R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

R ₁ is hydrogen or C _{1- 6} alkyl;

R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

Ar ₁ is pyridyl with or without halogen.

The compound of Formula 1 may be specifically selected from the following compound group, but is not limited thereto.

(1) 3-bromo-N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

(2) 3-chloro-N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide ;

(3) N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole- 5-carboxamide;

(4) 3- (2,2,2-trifluoroethoxy) -N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl ) -1H-pyrazole-5-carboxamide;

(5) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -1H-pyrazole-5-car Copyamide;

(6) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -1H-pyrazole-5-carbox Amide;

(7) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

(8) 3- (2,2,2-trifluoroethoxy) -1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) Phenyl) -1H-pyrazole-5-carboxamide;

(9) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-car Copyamide;

(10) 3-chloro-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

(11) N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

(12) N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (2,2,2-trifluoro Methoxy) -1H-pyrazole-5-carboxamide;

(13) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -1H-pyrazole-5- Carboxamide;

(14) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -1H-pyrazole-5-car Copyamide;

(15) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -3- (trifluoromethyl) -1H-pyra Sol-5-carboxamide;

(16) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -3- (2,2,2-trifluoro Ethoxy) -1H-pyrazole-5-carboxamide;

(17) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -N-methyl-1H-pyrazole -5-carboxamide;

(18) 3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H -Pyrazole-5-carboxamide;

(19) 3-Chloro-N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H- Pyrazole-5-carboxamide;

(20) N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoro Methyl) -1H-pyrazole-5-carboxamide;

(21) N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -3- (2,2 , 2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

(22) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl)- 1H-pyrazole-5-carboxamide;

(23) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1H -Pyrazole-5-carboxamide;

(24) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -3- (trifluoro Rhomethyl) -1H-pyrazole-5-carboxamide;

(25) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -3- (2, 2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

(26) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-car Copyamide;

(27) 3-chloro-N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

(28) N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

(29) N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (2,2,2-trifluoro Methoxy) -1H-pyrazole-5-carboxamide;

(30) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -1H-pyrazole-5- Carboxamide;

(31) 3-Chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -1H-pyrazole-5-car Copyamide;

(32) 1- (3-Chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -3- (trifluoromethyl) -1H-pyra Sol-5-carboxamide;

(33) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -3- (2,2,2-trifluoro Ethoxy) -1H-pyrazole-5-carboxamide;

(34) 3-bromo-N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- ( 3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

(35) 3-Chloro-N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3 -Chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

(36) N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3-chloropyridine- 2-yl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide;

(37) N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3-chloropyridine- 2-yl) -3- (2,2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

(38) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1H-pyrazole-5-carboxamide;

(39) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl)- S-methylsulfinimidoyl) phenyl) -1H-pyrazole-5-carboxamide;

(40) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulphine Imidoyl) phenyl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide;

(41) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulphine Imidoyl) phenyl) -3- (2,2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

(42) 3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H -Pyrazole-5-carboxamide;

(43) 3-bromo-N- (4-chloro-2-methyl-6- (S-methyl-N- (2,2,2-trifluoroacetyl) sulfonimidoyl) phenyl) -1- ( 3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

(44) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-4- (methylthio) phenyl) -1H-pyrazole-5-carboxamide;

(45) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-4- (methylsulfinyl) phenyl) -1H-pyrazole-5-carboxamide;

(46) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1H-pyrazole- 5-carboxamide;

(47) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl)- 6-methylphenyl) -1H-pyrazole-5-carboxamide;

(48) 3-bromo-N- (4- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1 H-pyrazole- 5-carboxamide;

(49) 3-bromo-N- (4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridine- 2-yl) -1H-pyrazole-5-carboxamide;

(50) 3-bromo-N- (2-carbamoyl-4- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

(51) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-carbamoyl-4- (N-cyano-S-methylsulfinimidoyl) phenyl) -1H-pyra Sol-5-carboxamide;

(52) 3-bromo-N- (2-carbamoyl-4- (N-cyano-S-methylsulfonimidoyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyra Sol-5-carboxamide;

(53) N- (2- (methylcarbamoyl) -6-methyl-4- (methylthio) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole- 5-carboxamide;

(54) N- (2- (methylcarbamoyl) -6-methyl-4- (methylsulfonyl) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole -5-carboxamide;

(55) N- (2- (methylcarbamoyl) -6-methyl-4- (methylsulfinyl) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole -5-carboxamide;

(56) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2- (methylcarbamoyl) -4- (N- (2,2,2-trifluoroacetyl)- S-methylsulfinimidoyl) -6-methylphenyl) -1H-pyrazole-5-carboxamide;

(57) 3-bromo-N- (2- (methylcarbamoyl) -4- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridine-2- Yl) -1H-pyrazole-5-carboxamide;

(58) 3-bromo-N- (2- (methylcarbamoyl) -4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfonimidoyl) -6-methylphenyl)- 1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide; And

(59) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-thiocyanatophenyl) -1H-pyrazole-5-carboxamide.

In addition, a method for preparing a pyrazole carboxamide compound comprising an organosulfur group of the formula (1) is disclosed.

Scheme 1 is illustrated as a method of preparing the compound of Formula 1, but the following preparation method does not limit the method of preparing the compound of Formula 1. It is apparent that the preparation method of Reaction Scheme 1 is merely an example, and may be easily modified by those skilled in the art according to specific substituents.

Scheme 1

In Scheme 1, A, B, R ₁ to R ₃ and Ar ₁ are the same as defined in Chemical Formula 1.

The aniline compound a can be prepared based on the synthesis of references ( Bioorg . Med . Chem . 2006, 14 , 5678 and J. Med . Chem . 2002, 45 , 2229 and Org . Lett . 2012, 14 , 5334) The carboxylic acid compounds b are described in references (WO 2004/033468 and WO 2004/11447 and Chin. J. Chem . 2009, 27 , 579 and J. Agric . Food Chem . 2012, 60 , 7565 and Chin. J. Chem . 2012, 30 , 1748).

In one embodiment, sulfide compound 1 may be prepared by amide coupling reaction of compounds a-1 and b-1 based on the synthesis method of the known patent (WO2013 / 168967).

In one embodiment, sulfide compound 1 may be prepared by oxidizing sulfide compound 1 produced by an amide coupling reaction between an aniline compound and a carboxylic acid compound, and the oxidation reaction may be performed by MMPP · 6H ₂ O (Magnesium monoperoxyphthalate hexahydrate, MMPP 6H ₂ O).

In one embodiment, the sulfide compound 1 produced by the amide coupling reaction of the aniline compound and the carboxylic acid compound is prepared by using a known synthesis method ( Org . Lett . 2007, 9 , 3809). cyano sulfilimine) compound 18 can be prepared.

In one embodiment, N-trifluoroacetyl sulfinamine ( Org . Lett . 2004, 6 , 1305) using a known synthesis method ( Org . Lett . 2004, 6 , 1305) produced by the amide coupling reaction of an aniline compound with a carboxylic acid compound N-trifluoroacetyl sulfilimine compound 34 and sulfoxide compound 26 can be prepared.

In one embodiment, N-cyano sulfoxylamine ( Org. Lett . 2007, 9 , 3809 and Org . Lett . 2007, 9 , 2951) is synthesized using known synthesis from N-cyano sulfpyrimin compound 18 ( Org. N-cyano sulfoximine) compound 42 can be prepared.

In one embodiment, a known synthesis from N-cyano sulfoximine compound 42 ( Org. Lett . 2004, 6 , 1305, Org . Lett . 2007, 9 , 3809 and Org . Lett . 2007, 9 , 2951) N-trifluoroacetyl sulfoximine Compound 43 can be prepared.

The scope of the present invention includes not only the compound of Formula 1, but also a form of a hydrate thereof, a solvate thereof, or a salt thereof. The salt is preferably a salt of an agriculturally suitable inorganic or organic acid, for example bromic acid, hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, acetic acid, butyric acid, fumaric acid, lactic acid, maleic acid, malonic acid, oxalic acid, propionic acid, salicylic acid, Acid-addition salts with tartaric acid, 4-toluenesulfonic acid or valeric acid. The hydrate is a compound of the present invention or salt thereof comprising a stoichiometric or non-stoichiometric amount of water bound by a non-covalent intermolecular force. it means. By solvate is meant a compound of the present invention or a salt thereof comprising a stoichiometric or nonstoichiometric amount of solvent bound by noncovalent intermolecular forces. Preferred solvents therefor are volatile, non-toxic solvents.

Also disclosed are pesticidal compositions containing an effective amount of a compound of Formula 1, a hydrate thereof, a solvate thereof, or a salt thereof as an active ingredient.

When the compound of formula 1 is used as the active ingredient of the pesticide, it may be used by itself or in the form of a salt without addition of any other ingredients and may be used with a suitable carrier and / or additive. Suitable carriers and additives may be solid or liquid, and include natural or recycled materials, solvents, dispersants, wetting agents, adhesives, binders and / or fertilizers used in conventional formulations. When used as a pesticide, the compound of formula 1 may be prepared according to conventional methods in the form of a conventional formulation, for example powders, emulsions, granules, dispersions, sprays, solutions or suspensions. It may also be prepared from bottle dips and spray races used in the preparation of fluids.

The composition may also be obtained according to conventional methods for the complete mixing and / or grinding of the compound of formula 1 by addition of a suitable carrier and an inert dispersant or solvent to the active substance. The carrier may be a pharmaceutically acceptable carrier, and examples thereof include kaolin, talc, dolomite, feldspar, diatomaceous earth, calcium carbonate and the like.

The dosage of the compound of Formula 1 may be determined by factors such as the amount or growth of pests and the preparation.

In addition, a method of controlling pests by treating a compound of Formula 1, a hydrate thereof, a solvate thereof, or a salt thereof with a crop or a habitat thereof is disclosed.

The pests are preferably moths or extinct species, and more specifically, Chinese cabbage moth, tobacco germweed moth, and larvae.

The insecticide composition containing the compound of Formula 1, its hydrate, solvate or salt thereof has excellent insecticidal effects against various pests of insects, especially moths such as Chinese cabbage moth, tobacco germweed moth, and extinct species such as larvae. While exerting it, it is safe for insect bees and the like.

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, this is presented as an example of the present invention by any means is not limited by the scope of the present invention, the scope of the present invention is defined only in accordance with the claims below.

Example

Example 1 3-Bromo- N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1 H- pyrazole-5-carboxamide (Compound 1) Manufacture

Aniline compound a-1 (33.0 g, 0.176 mol), carboxylic acid compound b-1 (58.6 g, 0.194 mol), and 3-picoline (32 mL, 0.35 mol) were dissolved in anhydrous MeCN (300 mL), followed by MsCl (21 mL, 0.26 mol) was slowly added dropwise at 0 ° C. The reaction mixture was stirred at room temperature for 24 hours, then extracted with EtOAc and washed with aqueous NaHCO ₃ solution. The resulting solid compound was filtered with hexane and a small amount of EtOAc to give the title compound 1 (68.5 g).

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.44-8.46 (m, 1H), 7.85-7.88 (m, 1H), 7.54 (s, 1H), 7.32-7.39 (m, 1H), 6.97-7.01 (m, 2H), 2.40 (s, 3H), 2.16 (s, 3H).

Example 2 3-Bromo- N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide (Compound 9 ) Synthesis

Sulphide Compound 1 (7.6 g, 0.016 mol) was dissolved in 10 mL of CH ₂ Cl ₂ / MeOH (1: 1), and 18.5 g (0.048 mol) of MMPP.6H ₂ O was slowly added at 0 ° C. The reaction mixture was reacted at room temperature for one day, extracted with EtOAc, and the organic layer was washed with NaHCO ₃ aqueous solution and dried over anhydrous MgSO ₄ . The resulting solid compound was washed with EtOAc to give the title compound 9 quantitatively.

¹ H NMR (300 MHz, CDCl ₃ ) δ 8.92 (s, 1H), 8.39-8.41 (m, 1H), 7.85-7.89 (m, 2H), 7.51-7.52 (m, 1H), 7.38-7.42 (m, 1H), 7.05 (s, 1H), 3.05 (s, 3H), 2.25 (s, 3H).

Example 3 (E) -3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H Preparation of -pyrazole-5-carboxamide (Compound 18)

50 mg (0.1 mmol) of sulfide compound 1, 6 mg (0.15 mmol) of H ₂ NCN, 15 mg (0.13 mmol) of t-BuOK and 30 mg (0.17 mmol) of NBS were dissolved in 1 mL of MeOH and reacted at 0 ° C. for 10 minutes. . The reaction mixture was extracted with EA, dried over anhydrous Na ₂ SO ₄ and purified by silica gel column chromatography to give the title compound 18 (5 mg, 10% yield).

¹ H NMR (300 MHz, CDCl ₃ ) δ 10.44 (s, 1H), 8.42-8.44 (m, 1H), 7.73-7.83 (m, 1H), 7.43-7.44 (m, 1H), 7.35-7.40 (m, 3H), 2.75 (s, 3H), 2.27 (s, 3H).

Example 4 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -1 H-pyrazole-5-carboxamide (Compound 26 ) And (E) -3-bromo-N- (4-chloro-2-methyl-6- (S-methyl-N- (2,2,2-trifluoroacetyl) sulfinimidoyl) phenyl) -1- (3-chloropyridin Preparation of -2-yl) -1H-pyrazole-5-carboxamide (Compound 34)

100 mg (0.212 mmol) of sulfide compound 1, 48 mg (0.424 mmol) of 2,2,2-trifluoroacetamide, 34 mg (0.847 mmol) of MgO, 2.3 mg (2.5 mol%) of Rh ₂ (OAc) ₂ and 102 mg (0.318 mmol) of PhI (OAc) ₂ were dissolved in anhydrous CH ₂ Cl ₂ and reacted at 0 ° C. for 2 hours. The reaction mixture was extracted with EA, dried over anhydrous Na ₂ SO ₄ , and purified by silica gel column chromatography to give the title compound sulfoxide compound 26 (21 mg, 20% yield) and N-trifluoroacetyl sulfyrimine compound. 34 (62 mg, 50% yield) was obtained.

Sulfoxide compound 26: ¹ H NMR (300 MHz, CDCl ₃ ) δ 9.78 (s, 1H), 8.43-8.45 (m, 1H), 7.83-7.86 (m, 1H), 7.35-7.39 (m, 1H), 7.24 -7.31 (m, 3 H), 2.71 (s, 3 H), 2.18 (s, 3 H).

N-trifluoroacetyl sulfinamine compound 34: ¹ H NMR (300 MHz, CDCl ₃ ) δ 10.19 (s, 1H), 8.45-8.47 (m, 1H), 7.83-7.86 (m, 1H), 7.50-7.51 (m, 1 H), 7.27-7.44 (m, 3 H), 2.93 (s, 3 H), 2.02 (s, 3 H).

Example 5 3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5 Preparation of -carboxamide (Compound 42)

N-Cyano Sulpyrimine Compound 18 (83 mg, 0.162 mmol), m-CPBA (60 mg, 0.24 mmol) and K ₂ CO ₃ (45 mg, 0.32 mmol) were dissolved in 2 mL of MeOH and reacted at room temperature for 1 hour. 1N HCl aqueous solution was added dropwise to the reaction mixture at 0 ° C., extracted with EA, and dried over anhydrous Na ₂ SO ₄ . Purification by silica gel column chromatography gave the title compound 42 (37 mg, 43% yield).

¹ H NMR (300 MHz, CDCl ₃ ) δ 9.40 (s, 1H), 8.38-8.40 (m, 1H), 7.85-7.89 (m, 2H), 7.60-7.61 (m, 1H), 7.35-7.43 (m, 1H), 7.22 (s, 1 H), 3.28 (s, 1 H), 2.25 (s, 3 H).

Example 6 3-bromo-N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methyl-sulfonimidoyl) phenyl) -1- (3-chloropyridin Preparation of -2-yl) -1H-pyrazole-5-carboxamide (Compound 43)

N-cyano sulfoximine compound 42 (125 mg, 0.24 mmol) was dissolved in 4 mL of CH ₂ Cl ₂ , TFAA (0.1 mL, 0.71 mmol) was slowly added dropwise, and the reaction was performed at room temperature for 4 hours. The solvent was removed under reduced pressure, and the resulting solid compound was filtered and the filtrate was crystallized with CH ₂ Cl ₂ / ether / n-hexane to give the title compound 43 (33 mg, 23% yield).

¹ H NMR (300 MHz, DMSO) δ 10.57 (s, 1H), 8.48-8.49 (m, 1H), 8.20-8.23 (m, 1H), 7.97-8.01 (m, 1H), 7.86-7.88 (m, 1H ), 7.60-7.65 (m, 1H), 7.40-7.42 (m, 1H), 3.45 (s, 3H), 2.20 (s, 3H).

[Examples 7 to 59]

The compounds 1 to 59 of Table 1 were prepared according to the methods of Examples 1 to 6, and the identification data of the prepared compounds is shown in Table 2 below.

TABLE 1

TABLE 2

In order to determine the activity of the compound prepared in the above Example, the insecticidal activity against Chinese cabbage, moth and tobacco larvae and larvae were measured using the bioassay described below.

Unless otherwise specified, test solutions are prepared as follows: Example compounds are dissolved in desired mixtures in a mixture of 1: 1 (vol: vol) distilled water: acetone. Test solutions are prepared on the day of use and generally at a concentration of ppm (wt / vol).

Test Example 1 Insecticidal Activity Test of Tobacco Taraxacum (Spodoptera litura) (leaf Dipping Method)

Tobacco gelling moths were collected near Gyeongju and used individuals bred in cages. The leaves of cabbage (diamond) were made into slices of 5.8 cm in diameter, and then dipped in 5% acetone solution diluted with the drug to be tested for 30 seconds to be sufficiently dry. The dried cabbage leaves were placed on a filter paper-clad petri dish (8.8 cm in diameter) and inoculated twice with 10 tobacco germweed moths. These were stored under light conditions of 16: 8 hours, 25 ± 1 ° C., and relative humidity of 50-60%, and the viable cell numbers of tobacco giant seminars were examined 24, 48, 72 and 96 hours after inoculation. The control value of the subject was expressed after converting the density after the treatment based on the density before the treatment and converting it as a corrected insecticidal rate for no treatment, and the results are shown in Table 3 below (Reference: A method of computing the effectiveness .. of an insecticide J. Econ Entomol 18:.. 265 ~ 267 Abbott, 1925).

[Equation 1]

Control Value = (Untreated Viability-Treated Viability) / Untreated Viability × 100

[Equation 2]

Viability = Density after treatment / Density before treatment × 100

A: 60 to 100% after 96 hours, B: 30 to 60% after 96 hours, C: 10 to 30% after 96 hours

TABLE 3

In particular, compounds 1, 2, 3, 4, 7, 10, 11, 12, 18, 19, 20, 21, 23, 26, 34, and 56 were treated in an amount of 50 ppm to control the insecticidal activity against As a result of the test, after 96 hours, all showed excellent control value of 60% or more.

Test Example 2 Chinese cabbage moth ( Plutella) Insecticidal activity test on xylostella ) (leaf dipping method)

Chinese cabbage moths were collected in the vicinity of Gyeongju, and then used in the cages. The leaves of cabbage (diamond) were made into slices of 5.8 cm in diameter, and then dipped in 5% acetone solution diluted with the drug to be tested for 30 seconds to be sufficiently dry. Dried cabbage leaves were placed on a filter paper-clad petri dish (8.8 cm in diameter) and inoculated three times with three worms of Chinese cabbage moth. It was stored under light conditions of 16: 8 hours, 25 ± 1 ° C., and 50-60% relative humidity, and the viable numbers of Chinese cabbage moths were examined 24 and 48 hours after inoculation. In some cases, viable numbers of Chinese cabbage moths were examined 72 and 96 hours after inoculation. The control value was expressed by converting the density after the treatment based on the pretreatment density as shown in Equations 1 and 2 below and converting it as a corrected insecticidal rate for no treatment (see Equations 1 and 2 above).

As a result of testing the insecticidal activity against the Chinese cabbage moth by treating compounds 9 and 18 in an amount of 50 ppm by the test method as described above, all showed excellent control value of 60% or more after 96 hours.

Test Example 3 Insecticidal Activity against Laodelphax striatellus (Spray Method)

The larvae were collected near Gyeongju, and then used for breeding animals in cages. Rice seedlings are rolled with cotton wool, placed in a test tube (5cm in diameter x 17.5cm in height), inoculated with 10 adult larvae, and sprayed with a small atomizer with a 5% acetone solution diluted with the drug to be tested 24 hours after inoculation. It was. It was stored under conditions of 16: 8 hours, temperature 25 ± 1 ° C., and 50-60% relative humidity, and the viable insects after 24 hours and 48 hours were examined. The control agent corrects the density after the treatment based on the density before the treatment as shown in Equations 1 and 2, and converts the result into a corrected insecticidal rate for no treatment.

As a result of testing the pesticidal activity against the larvae by treating the compounds 9 and 18 in an amount of 50 ppm by the test method as described above, all showed excellent control value of 60% or more after 96 hours.

Test Example 4 Acute Contact Toxicity Test on Bees (Apis mellifera)

To identify acute toxicity using apis mellifera Rural Development Administration Notification No. 2016-46 "Ecology and Methods of Environmental Ecotoxicity Test-Acute Contact Toxicity Test for Bees" and the OECD Guidelines "Honeybees, Acute Contact Toxicity Test" (No. 214, adopted: September 21, 1998).

The bees were reared for about 4 months in the bee breeding area. Feeding during the breeding period was prepared 50% sugar solution (W / W) was supplied to 1 L / small phase more than once / week. Cylindrical test made of stainless steel wire (15cm long and 5cm in diameter) by transferring more than 110% of the number of birds required for the test 4 hours before the test material treatment to bee reared in the bee breeding space for about 4 months. Ten animals each were placed in a container and purified under the same environmental conditions as the toxicity test. Fasting did not occur in the route of administration of the test substance.

Screening of individuals for group separation was performed using anesthesia bee and CO ₂ gas. During the acclimation period, mortality occurrence, temperature and humidity were measured and recorded, and under the dark conditions except for the observation time. During the acclimatization period, no mortality was found, the condition was good, the temperature was 24.5 ~ 25.0 ℃ and the humidity was 57.5 ~ 58.0%.

Concentration-specific test material treatment method was treated with 1 μl of each test solution directly to the honeybee chest using a micro syringe. The anesthesia of the honeybees was separated into groups, and the honeybees contained in the test containers were placed in an anesthesia container and anesthetized using CO ₂ gas. At this time, the anesthesia time was controlled by an investigator, and the anesthesia time was adjusted to 40 to 50 seconds, and the test substance (Compound 9) was administered by anesthesia.

Toxicity studies were performed with 200 μg / bee on the basis of dosage, solvent control and no treatment control and 30 bees per test dose were exposed. 1, 4, 24 and 48 hours after exposure, the number of mortality and toxic symptoms were observed.

On the day of the experiment, mortality and toxic symptoms were observed for 1 hour and 4 hours after the test substance (Compound 9) treatment and for 48 hours at 24 hours (± 1 hour) from the next day. Lethality was considered lethal because there was no response or no antennae or leg movement. Lethal subjects were not removed until the end of the experiment.

As a result of testing acute contact toxicity and acute feeding toxicity to bees on the compounds prepared in the Example, it was measured as> 100 μg / bee (LD ₅₀ , Honey bee), which is a claw developed by DuPont Acute Contact Toxicity of Lantraniliprole and Cyantraniliprole 0.1–4 μg / bee (LD ₅₀ , Honey bee) there was.

Test Example 5 General Toxicity Measurement

The general toxicity of Compound 9 of the present invention was determined by GINAPATH (Eurofins, AnaPath, Accelera three CRO consortium).

Acute Oral Toxicity (OECD423): LD ₅₀ > 2,000 mg / kg bw

Acute Dermal Toxicity (OECD402): LD ₅₀ > 2,000 mg / kg bw

Acute Skin Irritation (OECD 405): Non-irritation

Acute Eye Irritation (OECD 405): Non-irritation

Bacterial Reverse Mutation, Ames Test (OECD 471): Negative

In vitro Chromosomal Abberation Assay (OECD 473): Negative

In vivo Mictonucleus assay (OECD 474): Negative

Test Example 6 Log P Measurement

log P represents the concentration ratio of the compound dissolved in each solution when the compound is dissolved in water and octanol as shown in Equation 3 below, and the log P value of each compound is measured at a pH in which the compound is present in a neutral state. It is listed in Table 4 below.

[Equation 3]

log P = log ([solute] octanol / [solute] water)

TABLE 4

As a result of analyzing the chemical properties of the compounds prepared in Examples, most log P values were determined to be 3.04 to 4.95, which is chlorantraniliprole and cyanthraniliprole developed by Dupont. Compared with the log P value of 5.25 of cyantraniliprole, it is more than 1 ~ 2 lower. In general, when the log P value is 0.5 lower, the half-life in soil can be estimated to be shortened by 3 months. Therefore, the half-life of Chloranthraniliprole, developed by DuPont, remains about 180 days without being decomposed in the soil for a long time, and thus poses a risk to the environment. It is estimated that the environmental safety is high.

Test Example 7 Equilibrium solubility measurement using μSOL

Equilibrium solubility was measured using a UVspectrometer (see Pharm. Res., 2000, 17, 85-89. (Part 2 in pSOL series)). The solubility values of each compound are listed in Table 5 below.

 TABLE 5

The compounds prepared in the Examples showed high aqueous solubility compared to the solubility values of 10.4 μg / mL and 179 μg / mL of chlorantraniliprole and cyantraniliprole. In other words, while the control compound remains in the soil and poses a risk to the environment, the compound of the present invention is estimated to be quickly washed down with water in the soil and thus have high environmental safety.

The compound of the formula (1), its hydrate, its solvate or its salt is a novel compound, and the pesticide composition containing it as an active ingredient is a variety of pests, especially moths such as Chinese cabbage moth, tobacco germweed moth, and extinct species such as larvae It has a good insecticidal effect and is safe for insect bees and has a short soil life and is environmentally friendly.

Claims (8)

1. A compound represented by Formula 1, a hydrate thereof, a solvate thereof, or a salt thereof:

   [Formula 1]

   

   In Chemical Formula 1,

   At least one of A and B

   

   , And the other is hydrogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{3- 10} cycloalkyl alkylamino, C _{1- 10} alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C _{1 - 10} alkyl, hydroxy, carbamoyl, C _{1- 10} alkylcarbamoyl, cyano, nitro or halogen, wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl can each independently be further substituted with one or more halogens;

   X is absent or oxygen;

   Y is absent or is oxygen or NR ';

   R 'is cyano, C _{1- 10} alkyl, C _{1- 10} alkyl carbonyl, C _{6- 20} aryl-carbonyl or C _{3- 10} cycloalkyl-carbonyl, wherein said alkyl, alkylcarbonyl, arylcarbonyl, cycloalkyl carbonyl group is a halogen, a halo-C _{1 - 10} alkyl, cyano, C _1- C ₁₀ alkoxy and _6- with one or more substituents selected from ₂₀ aryl may be further substituted, and;

   R is C _{1- 10} alkyl, C _{6- 20} aryl, C _{3- 10} cycloalkyl, halo-C _{1 - 10} alkyl or cyano;

   R ₁ is hydrogen or C _{1- 10} alkyl;

   R ₂ is halogen, cyano, amino, hydroxy, mercapto, cyano, thio, C _{1- 10} alkyl, halo C _1-10 alkyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 - 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{1- 10} alkyl, halo C _{1 - 10} alkoxy, C _{1- 10} alkylthio, C _{1- 10} alkyl amino, C _{6- 20} aryl amino, C _1-10 alkyl, C _6-20 arylamino, C _{1- 10} alkyl aminocarbonyl, C _{6- 20} aryl, C _{6- 20} aryloxy, halo-C _{6 - 20} aryl, or halo-C _{6 - 20} aryloxy Is;

   R ₃ is C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _{3- 10} cycloalkyl, C _{3- 10} cycloalkyl, C _{1 -10} alkyl, C _{3- 10} cycloalkyl, amino, ₁₀ is alkyl, hydroxy, cyano, halogen or nitro, _{- 1-} C ₁₀ alkoxy, C _{1- 10} alkylthio, C _{6- 20} aryl, C _{6- 20} aryloxy, C _{6- 20} aryl C ₁ Wherein said alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy, aryl, aryloxy and arylalkyl may each independently be further substituted with one or more halogens;

   Ar ₁ is a C _{6- 20} aryl, or C _{3- 20} heteroaryl, wherein said aryl and heteroaryl are each independently selected from halogen, C _{1- 10} alkyl, C _{2- 10} alkenyl, C _{2- 10} alkynyl, C _1-10 alkoxy, halo C _{1 - 10} alkyl, halo C _{1 - 10} alkoxy, hydroxy and cyano may be further substituted with one or more substituents selected from the group consisting of a furnace;

   The heteroaryls each independently include one or more heteroatoms selected from nitrogen, oxygen and sulfur.
2. The method of claim 1,

   At least one of the A and B

   

   , And the other is hydrogen, C _{1- 6} alkyl, halo C _{1 -6} alkyl, C _{3- 7} cycloalkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, C _{1- 6} alkylthio, C _{6- 12} aryl, C _6-12 aryloxy, C _{6- 12} aryl C _{1 - 6} alkyl, hydroxy, carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

   X is absent or oxygen;

   Y is absent or is oxygen or NR ';

   R 'is cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkylcarbonyl, halo C _{1 - 6} alkylcarbonyl or C _{3- 7} cycloalkyl carbonyl gt;

   R is C _{1- 6} alkyl, C _{3- 7} cycloalkyl, halo C _{1 - 6} alkyl or cyano;

   R ₁ is hydrogen or C _{1- 6} alkyl;

   R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, or C _3-7 cycloalkyl;

   R ₃ is C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{3- 7} cycloalkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkoxy, C _1-6 alkylthio, C _{6- 12} aryl, C _{6- 12} aryloxy, C _{6- 12} aryl C _{1 - 6} alkyl, hydroxy, cyano, nitro, or halogen;

   Ar ₁ is a C _{3- 12} heteroaryl, wherein said heteroaryl group is halogen, C _{1- 6} alkyl, C _{1- 6} alkoxy, halo C _{1 - 6} alkyl, halo C _{1 - 6} alkoxy, hydroxy and cyano consisting of A compound, a hydrate thereof, a solvate thereof, or a salt thereof, which may be further substituted with one or more substituents selected from the group.
3. The method of claim 1,

   A compound represented by the following Chemical Formula 2 or Formula 3, a hydrate thereof, a solvate thereof, or a salt thereof:

   [Formula 2]

   

   [Formula 3]

   

   In Chemical Formulas 2 and 3,

   R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

   R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

   R ₁ is hydrogen or C _{1- 6} alkyl;

   R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

   R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

   Ar ₁ is pyridyl with or without halogen.
4. The method of claim 1,

   A compound represented by the following formula (4), (5), (6) or (7), a hydrate thereof, a solvate thereof, or a salt thereof:

   [Formula 4]

   

   [Formula 5]

   

   [Formula 6]

   

   [Formula 7]

   

   In Chemical Formulas 4 to 7,

   R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

   R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

   R ₁ is hydrogen or C _{1- 6} alkyl;

   R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

   R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

   Ar ₁ is pyridyl with or without halogen.
5. The method of claim 1,

   A compound represented by the following Chemical Formula 8, Chemical Formula 9, Chemical Formula 10, or Chemical Formula 11, a hydrate thereof, a solvate thereof, or a salt thereof:

   [Formula 8]

   

   [Formula 9]

   

   [Formula 10]

   

   [Formula 11]

   

   In Chemical Formulas 8 to 11,

   R 'is cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkylcarbonyl or halo C _{1 - 6} alkylcarbonyl, and;

   R ₄ and R ₅ are each independently a hydrogen, a carbamoyl, C _{1- 6} alkyl-carbamoyl, cyano, nitro, or halogen;

   R is C _{1- 6} alkyl, halo C _{1 - 6} alkyl or cyano;

   R ₁ is hydrogen or C _{1- 6} alkyl;

   R ₂ is halogen, cyano, C _{1- 6} alkyl, halo C _{1 - 6} alkyl, C _{1- 6} alkoxy or halo C _{1 - 6} alkoxy;

   R ₃ is C _{1- 6} alkyl or halo C _{1 - 6} alkyl;

   Ar ₁ is pyridyl with or without halogen.
6. The method of claim 1,

   The compound is any one selected from the group of compounds, hydrates thereof, solvates thereof or salts thereof:

   (1) 3-bromo-N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

   (2) 3-chloro-N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide ;

   (3) N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole- 5-carboxamide;

   (4) 3- (2,2,2-trifluoroethoxy) -N- (4-chloro-2-methyl-6- (methylthio) phenyl) -1- (3-chloropyridin-2-yl ) -1H-pyrazole-5-carboxamide;

   (5) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -1H-pyrazole-5-car Copyamide;

   (6) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -1H-pyrazole-5-carbox Amide;

   (7) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) phenyl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

   (8) 3- (2,2,2-trifluoroethoxy) -1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylthio) Phenyl) -1H-pyrazole-5-carboxamide;

   (9) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-car Copyamide;

   (10) 3-chloro-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

   (11) N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

   (12) N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (2,2,2-trifluoro Methoxy) -1H-pyrazole-5-carboxamide;

   (13) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -1H-pyrazole-5- Carboxamide;

   (14) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -1H-pyrazole-5-car Copyamide;

   (15) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -3- (trifluoromethyl) -1H-pyra Sol-5-carboxamide;

   (16) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfonyl) phenyl) -3- (2,2,2-trifluoro Ethoxy) -1H-pyrazole-5-carboxamide;

   (17) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfonyl) phenyl) -1- (3-chloropyridin-2-yl) -N-methyl-1H-pyrazole -5-carboxamide;

   (18) 3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H -Pyrazole-5-carboxamide;

   (19) 3-Chloro-N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H- Pyrazole-5-carboxamide;

   (20) N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoro Methyl) -1H-pyrazole-5-carboxamide;

   (21) N- (4-chloro-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -3- (2,2 , 2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

   (22) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl)- 1H-pyrazole-5-carboxamide;

   (23) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1H -Pyrazole-5-carboxamide;

   (24) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -3- (trifluoro Rhomethyl) -1H-pyrazole-5-carboxamide;

   (25) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -3- (2, 2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

   (26) 3-bromo-N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-car Copyamide;

   (27) 3-chloro-N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carbox Amide;

   (28) N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (trifluoromethyl) -1H-pyrazole -5-carboxamide;

   (29) N- (4-chloro-2-methyl-6- (methylsulfinyl) phenyl) -1- (3-chloropyridin-2-yl) -3- (2,2,2-trifluoro Methoxy) -1H-pyrazole-5-carboxamide;

   (30) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -1H-pyrazole-5- Carboxamide;

   (31) 3-Chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -1H-pyrazole-5-car Copyamide;

   (32) 1- (3-Chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -3- (trifluoromethyl) -1H-pyra Sol-5-carboxamide;

   (33) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (methylsulfinyl) phenyl) -3- (2,2,2-trifluoro Ethoxy) -1H-pyrazole-5-carboxamide;

   (34) 3-bromo-N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- ( 3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

   (35) 3-Chloro-N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3 -Chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

   (36) N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3-chloropyridine- 2-yl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide;

   (37) N- (4-chloro-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1- (3-chloropyridine- 2-yl) -3- (2,2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

   (38) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl) phenyl) -1H-pyrazole-5-carboxamide;

   (39) 3-chloro-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl)- S-methylsulfinimidoyl) phenyl) -1H-pyrazole-5-carboxamide;

   (40) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulphine Imidoyl) phenyl) -3- (trifluoromethyl) -1H-pyrazole-5-carboxamide;

   (41) 1- (3-chloropyridin-2-yl) -N- (4-cyano-2-methyl-6- (N- (2,2,2-trifluoroacetyl) -S-methylsulphine Imidoyl) phenyl) -3- (2,2,2-trifluoroethoxy) -1H-pyrazole-5-carboxamide;

   (42) 3-bromo-N- (4-chloro-2- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1H -Pyrazole-5-carboxamide;

   (43) 3-bromo-N- (4-chloro-2-methyl-6- (S-methyl-N- (2,2,2-trifluoroacetyl) sulfonimidoyl) phenyl) -1- ( 3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

   (44) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-4- (methylthio) phenyl) -1H-pyrazole-5-carboxamide;

   (45) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-methyl-4- (methylsulfinyl) phenyl) -1H-pyrazole-5-carboxamide;

   (46) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4- (N-cyano-S-methylsulfinimidoyl) -6-methylphenyl) -1H-pyrazole- 5-carboxamide;

   (47) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfinimidoyl)- 6-methylphenyl) -1H-pyrazole-5-carboxamide;

   (48) 3-bromo-N- (4- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridin-2-yl) -1 H-pyrazole- 5-carboxamide;

   (49) 3-bromo-N- (4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridine- 2-yl) -1H-pyrazole-5-carboxamide;

   (50) 3-bromo-N- (2-carbamoyl-4- (methylthio) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide;

   (51) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2-carbamoyl-4- (N-cyano-S-methylsulfinimidoyl) phenyl) -1H-pyra Sol-5-carboxamide;

   (52) 3-bromo-N- (2-carbamoyl-4- (N-cyano-S-methylsulfonimidoyl) phenyl) -1- (3-chloropyridin-2-yl) -1H-pyra Sol-5-carboxamide;

   (53) N- (2- (methylcarbamoyl) -6-methyl-4- (methylthio) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole- 5-carboxamide;

   (54) N- (2- (methylcarbamoyl) -6-methyl-4- (methylsulfonyl) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole -5-carboxamide;

   (55) N- (2- (methylcarbamoyl) -6-methyl-4- (methylsulfinyl) phenyl) -3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole -5-carboxamide;

   (56) 3-bromo-1- (3-chloropyridin-2-yl) -N- (2- (methylcarbamoyl) -4- (N- (2,2,2-trifluoroacetyl)- S-methylsulfinimidoyl) -6-methylphenyl) -1H-pyrazole-5-carboxamide;

   (57) 3-bromo-N- (2- (methylcarbamoyl) -4- (N-cyano-S-methylsulfonimidoyl) -6-methylphenyl) -1- (3-chloropyridine-2- Yl) -1H-pyrazole-5-carboxamide;

   (58) 3-bromo-N- (2- (methylcarbamoyl) -4- (N- (2,2,2-trifluoroacetyl) -S-methylsulfonimidoyl) -6-methylphenyl)- 1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxamide; And

   (59) 3-bromo-1- (3-chloropyridin-2-yl) -N- (4-cyano-2-thiocyanatophenyl) -1H-pyrazole-5-carboxamide.
7. A pesticide composition containing as an active ingredient a compound according to any one of claims 1 to 6, a hydrate thereof, a solvate thereof or a salt thereof.
8. A method of controlling pests by treating the pesticide composition according to claim 7 to a crop or a habitat thereof.