KR101414006B1 - Fused pyrazine derivative and insecticide composition comprising same - Google Patents

Abstract

상기 화학식에서, X, Y, Z, Ar 및 W은 명세서에서 정의한 바와 같다.The pyrazine fused ring derivative of the formula (1) or a salt thereof and the insecticidal composition containing the pyrazine fused ring derivative of the formula (1) are excellent in the control effect against various insects of insects, especially the cabbage moth,
Formula 1

In the above formulas, X, Y, Z, Ar and W are as defined in the specification.

Description

FIELD OF THE INVENTION [0001] The present invention relates to pyrazine-bonded ring derivatives and pesticide compositions containing the pyrazine-

FIELD OF THE INVENTION The present invention relates to pyrazine bond ring derivatives having an insecticidal effect on moths, ferns, and insecticidal compositions containing the same.

As a conventional insecticide, carbamate insecticides or organophosphorus insecticides can be mentioned. These insecticides inhibit acetylcholinesterase and exert their effects. However, pesticides resistant to these insecticides have been used for a long time, and it has become necessary to develop insecticides with new mechanism of action. The ryanodine receptor, a calcium ion channel, has emerged as a new target to control pests.

Because calcium homeostasis plays a particularly important role in muscle contraction, pesticides that bind to the ranodine receptor inhibit insect feeding and lead to coma or paralysis leading to death.

To date, commercially available insecticides that bind to ryanodine receptors are flubendiamide (Phoenix ^TM , Takumi ^TM , EP 1380209), discovered by Nihon Nohyaku and co-developed by Bayer Crop Science A1) and chlorantraniliprole (Rynaxypyr ^TM , WO 01/070671) which is an anthranilamide structure developed by Du Pont.

These two compounds are known to have insecticidal effect by binding to the ranodine receptor and disturbing the calcium ion pathway. Especially, it is known that the insecticidal action against moths is strong, but the chlorantranil leafs have insecticidal effect only on moths and beetles The disadvantage is that the spectrum is narrow.

Companies such as Syngenta, Sumitomo, Ishihara Sangyo Kaisha and Nissan have developed a variety of derivatives including Bayer and DuPont. And 100 patents have been filed. However, two types of flubendiamide and chloranthraniliprole are commercially available.

EP 1380209 A1 (Nihon Nohyaku Co., Ltd.) Jan. 14, 2004. WO 01/070671 A2 (EI. DU PONT DE NEMOURS AND COMPANY).

Accordingly, an object of the present invention is to provide a novel pyrazine-linked ring derivative having insecticidal activity against various insect pests, including moths and falcons, and a pesticide composition containing the same.

According to the above object, the present invention provides a pyrazine fused ring derivative represented by the following formula (1) or a salt thereof:

Formula 1

In this formula,

W is CH or N;

X, Y and Z are each independently H, hydroxy, cyano, halogen, C _1-6 alkyl, C _1-6 alkoxy, -C (= O) -NH- R 1, or -NH-C (= O) -OR < ² >;

R ¹ and R ² are each independently selected from the group consisting of H, C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-6 cycloalkyl, 3-6 membered hetero Cycloalkyl, or C _2-4 lactonyl, wherein said alkyl, alkoxy, alkenyl, and alkynyl are each independently selected from the group consisting of hydroxy, cyano, halogen, and C _1-3 alkoxy Lt; / RTI >

Ar is C _6-12 aryl or 5-11 membered heteroaryl, wherein said aryl and heteroaryl each optionally substituted with one to three halogens and consisting of C _1-3 alkyl, halogen and nitro Lt; RTI ID = 0.0 > 1, < / RTI >

Wherein said heterocycloalkyl and heteroaryl each independently comprise 1 to 3 heteroatoms selected from the group consisting of N, O, and S;

According to another aspect of the present invention, there is provided an insecticidal composition comprising, as an active ingredient, a pyrazine fused ring derivative of Formula 1 or a salt thereof.

Also, the present invention provides a method for controlling insects by treating the pyrazine fused ring derivative of Formula 1 or a salt thereof with a crop or a habitat thereof

INDUSTRIAL APPLICABILITY The pyrazine bond ring derivative according to the present invention and the insecticidal composition containing it can exhibit an excellent insecticidal effect against various insect pests of insects, especially moths such as Chinese cabbage moth, Tobacco spider moth,

Hereinafter, the present invention will be described more specifically.

In one example of the pyrazine fused ring derivative compound of Formula 1 according to the present invention, W is CH.

According to another example of the compound of formula (I) of the present invention,

Wherein W is CH;

Wherein X and Y are each independently H, hydroxy, cyano, halogen, C _1-6 alkyl, or C _1-6 alkoxy;

Wherein Z is -C (= O) -NH-R 1 or -NH-C (= O) -OR 2 , and;

Wherein R ¹ and R ² are each independently selected from the group consisting of H, C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-6 cycloalkyl, 3-6 membered heterocycloalkyl, or C _2-4 lock tonil, wherein said alkyl, alkoxy, alkenyl, and alkynyl are each independently hydroxy, cyano, 1 to selected from the group consisting of halogen and C _1-3 alkoxy Lt; / RTI > may be substituted with up to three substituents,

Said heterocycloalkyl includes 1 to 3 heteroatoms selected from the group consisting of N, O, and S;

According to another example of the compound of formula (I) of the present invention,

Wherein W is CH;

Each of X and Y is independently halogen, cyano, or C _1-6 alkyl;

Wherein Z is -C (= O) -NH-R 1 or -NH-C (= O) -OR 2 , and;

Wherein R ¹ is C _1-6 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-6 cycloalkyl, or C _2-4 lactonyl, Alkoxy, alkenyl, and alkynyl may each be independently substituted with one to three substituents selected from the group consisting of halogen and C _1-3 alkoxy;

Wherein Ar is C _6-10 aryl or 5-6 membered heteroaryl, wherein said aryl and heteroaryl are each independently selected from the group consisting of halogen, C _1-3 alkyl, trifluoromethyl and nitro, Lt; / RTI > may be substituted with up to three substituents,

Wherein said heteroaryl comprises 1 to 3 heteroatoms selected from the group consisting of N, O and S.

According to another example of the compound of formula (I) of the present invention,

Wherein W is CH;

Wherein X is halogen or cyano;

Wherein Y is halogen or C _1-6 alkyl;

Wherein Z is -C (= O) -NH-R 1 or -NH-C (= O) -OR 2 , and;

Wherein R ¹ is C _1-6 alkyl, C _1-6 alkoxy, C _3-6 cycloalkyl, or C _2-4 lactonyl;

_Wherein R ² is C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, or C _2-6 alkynyl;

Wherein said alkyl and alkynyl may each independently be substituted with one to three halogen or C _1-3 alkoxy,

Wherein Ar is pyridyl or phenyl wherein the pyridyl may be substituted with one to three halogens and wherein the phenyl is optionally substituted with one or more groups selected from the group consisting of halogen, C _1-3 alkyl, trifluoromethyl and nitro Lt; / RTI > to 3 substituents.

Specific examples of the compound of the formula (1) of the present invention are as follows, and salts thereof are also possible:

1) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-2-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

2) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

3) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-4-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

4) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- amides;

5) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3- chloropyridin- amides;

6) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,6- dichloropyridin- Carboxamide;

7) 4- (2-Bromopyridin-3-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

8) 4- (4-Bromopyridin-3-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

9) Preparation of 4- (6-bromopyridin-2-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

10) 4- (6-Bromopyridin-3- yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

11) 4- (3-Bromopyridin-4-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

12) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

13) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

14) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,3-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

15) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

16) Synthesis of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chloro-5-nitrophenyl) pyrrolo [ amides;

17) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- ≪ / RTI >

18) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (4- (trifluoromethyl) phenyl) pyrrolo [ ≪ / RTI >

19) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3- (trifluoromethyl) phenyl) pyrrolo [ ≪ / RTI >

20) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-fluorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

21) 4- (2-bromophenyl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

22) 4- (3-bromophenyl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

23) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chloro-6-fluorophenyl) pyrrolo [ ≪ / RTI >

24) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (o-tolyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

25) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,3-dimethylphenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

26) N- (4-Chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides;

27) N- (4-chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

28) N- (4-Bromo-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >

29) N- (4-Bromo-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4- dichlorophenyl) pyrrolo [1,2- a] pyrazine-3-carboxamide ;

30) A mixture of N- (4-bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [ ;

31) N- (4-Bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >

32) 4- (2-Chloropyridin-3-yl) -N- (4-cyano-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

33) N- (4-Chloro-2- (cyclopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides;

34) 4- (2-Chloropyridin-3-yl) -N- (2,4-dibromo-6- (cyclopropylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >

35) 4- (2-Chloropyridin-3-yl) -N- (2,4-dichloro-6- (cyclopropylcarbamoyl) phenyl) pyrrolo [1,2- a] pyrazine- ;

36) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -5- (2- chloropyridin- 3- yl) imidazo [1,2- a] pyrazine- amides;

37) 2-methoxyethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ Mate;

38) 3-Chloropropyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) phenyl) carbamate ;

39) allyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

40) 2-chloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ ;

41) Synthesis of 2,2,2-trichloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine- ) Phenyl) carbamate;

2-a) pyrazine-3-carboxamido) phenyl) carbamate (42) 2- Mate;

43) hexyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

44) isobutyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

45) methyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

46) heptyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

47) Methyl (5-chloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -3-methylphenyl) carbamate;

48) heptyl (5-chloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -3-methylphenyl) carbamate;

49) Methyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -5-cyano-3-methylphenyl) carbamate;

50) heptyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -5-cyano-3-methylphenyl) carbamate;

51) Methyl (3,5-dibromo-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

2-a) pyrazine-3-carboxamido) phenyl) carbamate < / RTI >;

53) heptyl (3,5-dibromo-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

54) N- (4-Chloro-2- (methoxycarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides; And

55) N- (4-Chloro-2-methyl-6 - ((2- oxotetrahydrofuran-3-yl) carbamoyl) , 2-a] pyrazine-3-carboxamide.

Other specific examples of the compound of the formula (1) of the present invention are as follows, and salts thereof are also possible:

3) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-4-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

4) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- amides;

12) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

13) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

27) N- (4-chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;

31) N- (4-Bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >

37) 2-methoxyethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ Mate;

38) 3-Chloropropyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) phenyl) carbamate ;

39) allyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;

40) 2-chloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ ;

41) Synthesis of 2,2,2-trichloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine- ) Phenyl) carbamate;

2-a) pyrazine-3-carboxamido) phenyl) carbamate (42) 2- Mate; And

43) hexyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate.

In one embodiment of preparing a compound of formula (1) of the present invention, it can be prepared as shown in the following reaction formula (1).

Scheme 1

In the above Reaction Scheme 1, X, Y, Z, and Ar are the same as defined in Formula 1 above.

First, the carboxylic acid compound of formula (3) is dissolved in acetonitrile, aniline compound of formula (2) and 3-picoline are added thereto, methanesulfonyl chloride is added, and the mixture is stirred at room temperature for 12 to 24 hours to obtain compound of formula . The above synthesis method can be referred to PCT Publication No. WO 2007/24833. When the aniline compound wherein X is CN is a starting material, trifluoromethanesulfonyl chloride may be used instead of methanesulfonyl chloride.

Some of the aniline compounds of formula (2), which are starting materials, can be synthesized according to the methods reported in the literature and specifically include 2-amino-5-chloro-N, 3- dimethylbenzamide (PCT Publication No. WO 2009/6061 A2 (Feng, Qi et al., Synthesis and Insecticidal Activities of Novel Anthranilic Diamonds Containing Modified N-Pyridylpyrazoles, Journal of Agricultural and Food Chemistry Amino-5-bromo-N, 3-dimethylbenzamide (see PCT Publication No. WO 2006/62978 A1), 2-amino-5 3-methylbenzamide (see Chinese Patent Publication No. 101659655) and 2-amino-5-cyano-N, 3-dimethylbenzamide (see PCT Publication No. WO 2006/62978 A1) can be synthesized by conventional methods. Other aniline compounds can be synthesized by the following Reaction Schemes 3 to 5.

Further, the carboxylic acid compound of formula (3), which is another starting material, can be synthesized by the reaction scheme 6 below.

In another embodiment of the compound of formula (I) of the present invention, the compound of formula (Ia) may be synthesized by the following reaction scheme (2).

Scheme 2

In the above Reaction Scheme 2, X and Y are as defined in Formula 1 above.

First, 4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxylic acid of Formula 3a and pyridine are dissolved in acetonitrile, methanesulfonyl chloride is added thereto, Lt; / RTI > A solution obtained by dissolving the aminobenzoic acid compound of formula (4) and pyridine in acetonitrile is added thereto, and the mixture is stirred at -5 DEG C to form a solid. After 10 to 20 minutes, methanesulfonyl chloride is further added, the mixture is reacted at room temperature for 4 to 10 hours, and distilled water is added thereto to synthesize a benzoxazinone compound of the formula (5) as a yellow solid. The solids are filtered off, washed with water and dried to give the pure benzoxazinone compound of formula (5).

The above synthesis method is described in George P. Lahm et al., Rynaxy Pyrr, et al., Synthesis of anthranilamide using 3-bromo-1- (3-chloropyridin-2-yl) -1H- pyrazole-5-carboxylic acid : A new insecticidal anthranilic diamide that acts as a potent and selective ryanodine receptor activator, Bioorganic & Medicinal Chemistry Letters , 17, 2007, pp. 627-4-6279.

The benzoxazinone compound of Formula 5 and cyclopropylamine thus obtained are dissolved in THF and reacted at room temperature for 5 to 10 hours to synthesize the compound of Formula 1a.

Among the compounds of formula (4) as starting materials, 2-amino-5-chloro-3-methylbenzoic acid wherein X and Y are Cl and Me, respectively, and 2-amino-3,5-dibromo Benzoic acid, and 2-amino-3,5-dichlorobenzoic acid in which X and Y are both Cl are commercially available.

In one embodiment of preparing the compound of Formula 2, the compound of Formula 2a may be synthesized by the following Reaction Scheme 3.

Scheme 3

In the above Reaction Scheme 3, R ² is the same as defined in Formula 1 above.

First, 3,5-dichloro-2-nitroaniline of formula (6) is added to a chloroformate solvent of formula (7) and refluxed for 20-24 hours, or reacted at 130 ° C for 20-24 hours to obtain a carbamate- Of the nitrobenzene compound can be obtained. Thereafter, the compound of formula (8) is dissolved in THF, and an aqueous solution of sodium hydrosulfite and sodium bicarbonate dissolved therein is added, followed by reaction at room temperature for 2 to 4 hours to obtain an aniline compound of formula (2a) substituted with carbamate.

The 3,5-dichloro-2-nitroaniline of formula (6) can be prepared according to the method described in Vasiliki Giannouli et al., Design, Synthesis, and Evaluation of the Antiproliferative Activity of a Novel Fused Xanthine Anion Derivatives in Human Breast Cancer Cells, Journal of medicinal Chemistry , 50 (7), pp. 1716-1719, 2007). For a method of reducing nitrobenzene to aniline, see US Patent Application Publication No. 2008-0287468 (Ohlmeyer, Michael J. et al).

In another embodiment of preparing the compound of formula 2, the compound of formula 2b may be synthesized by the method of Scheme 4 below.

Scheme 4

In the above Reaction Scheme 4, X, Y and R ² are the same as defined in Formula 1 above.

First, the nitroaniline compound of Formula 9 is dissolved in THF, followed by addition of di-t-butyldicarbonate of Formula 10, addition of 4-dimethylaminopyridine as a catalyst, and reflux reaction for 1 to 5 hours to obtain Boc- Compounds are synthesized.

The obtained nitrobenzene compound of formula (11) is dissolved in a lower alcohol and tin chloride is added thereto, followed by stirring at room temperature for 2 to 4 hours to obtain an aniline compound of formula (12). Alternatively, an aniline compound of formula (12) may be obtained by dissolving the nitrobenzene compound of formula (11) in THF, adding an aqueous solution of sodium hydrosulfite and sodium bicarbonate dissolved therein, and then reacting at room temperature for 1 to 4 hours.

Pyridine and a chloroformate compound are added to the aniline compound of the formula (12) and the mixture is stirred at 80 ° C for 2 to 24 hours to obtain a carbamate-substituted compound of the formula (13). When the chloroformate is 2-bromoethyl chloroformate, the aniline compound of formula (12) is dissolved in dichloromethane, pyridine and 2-bromoethyl chloroformate are added, and the mixture is stirred at room temperature for 4 to 24 hours Carbamate-substituted compound of formula (13) can be obtained.

Then, the compound of formula (13) is dissolved in dichloromethane, TFA is added, and the mixture is stirred at room temperature for 1 to 8 hours to obtain an aniline compound of formula (2b) substituted with carbamate.

Compounds of formula 9 in which X = CN and Y = Me, i.e., 4-amino-3-methyl-5-nitrobenzonitrile are disclosed in PCT Patent Publication No. WO 2007/56155 A1 (CHEMBRIDGE RESEARCH LABORATORIES, INC.) . ≪ / RTI >

In another embodiment of preparing the compound of formula 2 above, the compound of formula 2c may be synthesized by the method of Scheme 5 below.

Scheme 5

In the above Reaction Scheme 5, R ¹ is as defined in Formula 1 above.

First, 6-chloro-8-methyl-1H-benzo [d] [1,3] oxazine-2 of formula (15) is obtained from 2-amino- , 4-dione. For the synthesis method, reference can be made to PCT Publication No. WO 2007/43677 Al (SUMITOMO CHEMICAL COMPANY LIMITED).

Benzo [d] [1,3] oxazine-2,4-dione of the formula 15 and the amine compound of the formula 16 were dissolved in THF, and diisopropylethylamine Followed by heating at reflux for 10 to 16 hours to obtain an aniline compound of formula (2c).

In this way, the compound of formula 2, for example, 2-amino-5-chloro-N-methoxy-3-methylbenzamide, 2-amino-5-chloro-N- (4,5-dihydrothiazole 2-yl) -3-methylbenzamide, and 2-amino-5-chloro-3-methyl-N- (2-oxotetrahydrofuran-3-yl) benzamide.

In one embodiment of preparing the compound of Formula 3, the compound of Formula 3 may be synthesized by the following Reaction Scheme 6.

Scheme 6

In the above Reaction Scheme 6, Ar and W are as defined in Formula 1 above.

First, an aldehyde compound of formula (17) containing an aromatic ring and methyl 2-azidacetate of formula (18) are dissolved in methanol, the temperature is lowered to -20 ° C and the mixture is stirred for 30 minutes to 1 hour. Sodium methoxide is slowly added. Thereafter, the mixture is stirred for 2 to 4 hours while maintaining the temperature at 0 ° C to obtain methyl 2-arylacrylate of Formula 19 in which the aromatic ring is substituted at the 3-position. Subsequently, the methyl 2-azido-3-aryl acrylate compound of Chemical Formula 19, 1H-pyrrole-2-carbaldehyde (W = CH) and Cs ₂ CO ₃ of Chemical Formula 20 were dissolved in DMF solvent and reacted at room temperature for 24 hours To obtain a methyl pyrrolo [1,2-a] pyrazine-3-carboxylate compound of the formula (21) wherein the aromatic ring is substituted at the 4-position. The methyl pyrrolo [1,2-a] pyrazine-3-carboxylate of Formula 21 was dissolved in a THF / MeOH mixed solution or a THF / H ₂ O mixed solution, and an aqueous NaOH solution was added thereto. To obtain the carboxylic acid compound of formula (3).

Alternatively, the methylimidazo [1,2-a (21) -containing aromatic ring of Formula 21 in which the aromatic ring is substituted at the 5-position by using the 1H-imidazole-2-carbaldehyde (W = ] Pyrazine-6-carboxylate compound, and hydrolyzing the compound to obtain imidazo [1,2-a] pyrazine-6-carboxylic acid compound of formula (3) wherein aromatic is substituted at the 5-position.

In the above method, the process of synthesizing the compound of formula 19 from the compound of formula 17 is described in Organic Syntheses, Vol. 84, pp. 262-271, 2007 and Coll., Preparation of substituted 5-azaindoles: methyl Chloro-1H-pyrrolo [3,2-C] pyridine-2-carboxylate, Vol.11, pp.802-810, -Chloropyridin-3-yl) acrylate can be referred to.

Further, the process of synthesizing the compound of Formula 20 from the compound of Formula 19 is described in Wenteng Chen et al., Domino Approach for Synthesis of pyrrolo [1,2-a] pyrazine from Vinyl Azides, Organic Letters , 2010, vol 1,2-a] pyrazine-3-carboxylate having introduced therein a substituted or unsubstituted phenyl group from an ethyl 2-azidacrylate compound, Can be referred to.

The present invention also provides an insecticidal composition comprising, as an active ingredient, an effective amount of the compound of formula (I) or a salt thereof together with a carrier.

In addition, the present invention provides a method for controlling insects by treating a compound according to Formula 1 or a salt thereof with a crop or a habitat thereof.

The pyrazine bond ring derivative of the present invention and the insecticidal composition containing the pyrazine bond ring derivative of the present invention can exert an excellent insecticidal effect against various insect pests of insects, especially moths such as Chinese cabbage moth, Tobacco spider moth,

Hereinafter, the present invention will be described in detail with reference to the following examples. The following examples are illustrative of the present invention only and are not intended to limit the scope of the present invention.

Examples 1 to 12

The same procedures as in Example 13 were repeated, except that in Step 1, instead of 2,4-dichlorobenzaldehyde, each Ar-CHO compound having the substituent Ar described in the following Table 1 was used to prepare the compounds 1 to 12. The ¹ H NMR results of the respective products are summarized in Table 1 below.

Example 13: Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [ amides

Step 1. Preparation of methyl 2-azido-3- (2,4-dichlorophenyl) acrylate

A solution of 2,4-dichlorobenzaldehyde (2.00 g, 11.4 mmol) and methyl 2-azidacetate (2.63 g, 22.9 mmol, 2.0 eq) was dissolved in MeOH (10 mL). The temperature of the reaction was reduced to -20 < 0 > C and after 30 minutes NaOMe (6.2 mL, 28.5 mmol, 2.5 eq) was slowly added dropwise thereto. Thereafter, the mixture was stirred for 2 hours while keeping the temperature at 0 캜, and the reaction was confirmed by TLC after 1 hour. The reaction is ice and sat. NH ₄ Cl solution, and the resulting solid was filtered. The solid was dissolved in CH ₂ Cl ₂ , dried over MgSO ₄ , filtered again, and distilled under reduced pressure to give the title compound (2.4 g, yield: 77%).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 8.17 (d, 1H, J = 8.6Hz), 7.43 (d, 1H, J = 2.0Hz), 7.30 (d, 1H, J = 1.7Hz), 7.22 (s, 1H), < / RTI > 3.94 ( s , 3H)

Step 2. Synthesis of methyl 4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-

(2.00 g, 7.35 mmol), 1 H -pyrrole-2-carbaldehyde (769 mg, 8.08 mmol, 1.1 eq) synthesized in the above step 1 and methyl 2-azido-3- (2,4-dichlorophenyl) ) And Cs ₂ CO ₃ (2.63 g, 8.08 mmol, 1.1 eq) were added to DMF solvent, and the mixture was stirred at room temperature for 24 hours. Distilled water was added thereto and extracted with CH ₂ Cl ₂ . The organic layer was dried over MgSO ₄ and filtered to remove the solvent by distillation under reduced pressure. This was separated by column chromatography (EtOAc / hexane = 1: 9 -> 2: 8 -> 5: 5) to give the title compound (300 mg, yield: 13%).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 8.94 (s, 1H), 7.65 (d, 1H, J = 1.8Hz), 7.47 (dd, 1H, J = 8.3Hz, 2.0Hz), 7.31 (d, 1H, J = 8.3 Hz), 7.01-6.94 ( m , 3H), 3.94 ( s , 3H)

Step 3. Preparation of 4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-

(600 mg, 1.87 mmol) and NaOH (374 mg, 9.74 mmol, 5.0 eq) synthesized in the above Step 2 were added to a solution of methyl 4- (2,4-dichlorophenyl) pyrrolo [ Dissolved in a THF / H ₂ O mixed solvent (2: 1, v / v), and stirred at room temperature for 24 hours. After completion of the reaction was confirmed by TLC, the pH was adjusted to 1 to 2 with 1N HCl. This was extracted with CH ₂ Cl ₂ and the organic layer was dried over MgSO ₄ and filtered. Finally, the solvent was removed to give the title compound (570 mg, yield: 99%).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 8.94 (s, 1H), 7.65 (d, 1H, J = 1.8Hz), 7.47 (dd, 1H, J = 8.3Hz, 2.0Hz), 7.31 (d, 1H, J = 8.3 Hz), 7.01-6.94 ( m , 3H)

Step 4. Synthesis of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2- a] pyrazine-

Synthesized in the above Step 3 4- (2,4-dichlorophenyl) pyrrolo [1,2-a] adding to CH ₃ CN (5mL) on-3-carboxylic acid (676mg, 2.2mmol), 2- here Amino-5-chloro-N, 3-dimethylbenzamide (437 mg, 2.2 mmol) and 3-picoline (615 mg, 6.6 mmol) were added. Methanesulfonyl chloride (378 mg, 3.3 mmol) was added to the mixture, and the mixture was stirred at room temperature for 12 hours. The solid formed during the reaction was filtered and washed with CH ₃ CN and distilled water to give the title compound as a yellow solid (264 mg, yield: 25%).

At this time, 2-amino-5-chloro-N, 3-dimethylbenzamide used as the starting compound was synthesized by the method disclosed in PCT Publication No. WO 2009/6061 A2.

^{1 H NMR (300MHz, DMSO-} D 6) δ 10.85 (s, 1H), 9.10 (s, 1H), 8.47 (d, 1H, J = 4.6Hz), 7.86 (d, 1H, J = 1.8Hz), 7.61 (dd, 1H, J = 1.6, 8.0Hz), 7.55 (d, 1H, J = 8.3Hz), 7.44 (d, 1H, J = 2.1Hz), 7.39 (d, 1H, J = 2.4Hz), 7.17 (dd, 1H, J = 1.1, 4.0Hz), 7.11 (d, 1H, J = 2.4Hz), 7.05 (dd, 1H, J = 2.8, 4.0Hz), 2.70 (d, 3H, J = 4.6Hz ), 2.12 (s, 3H)

Examples 14 to 25

The same procedure was repeated as in the following Example 13 except that in Step 1, instead of 2,4-dichlorobenzaldehyde, each Ar-CHO compound having the substituent Ar described in the following Table 1 was used to prepare the compounds 14 to 25. The ¹ H NMR results of the respective products are summarized in Table 1 below.

The structures and NMR data of the compounds 1 to 25 are summarized in Table 1 below.

Examples 26 to 32

The same procedure as in Example 13 was repeated except that in Step 1, each Ar-CHO compound having the substituent Ar described in the following Table 2 was used instead of 2,4-dichlorobenzaldehyde, and 2-amino-5- Using the compound of the following formula 2d instead of chloro-N, 3-dimethylbenzamide, compounds 26 to 32 were prepared. The ¹ H NMR results of the respective products are summarized in Table 2 below.

2d

Wherein X, Y and R < ¹ > are as set forth in Table 2 below.

Example 33: N- (4-Chloro-2- (cyclopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- Carboxamide

D) [l, 2-a] pyrazin-3-yl) -8-methyl-4H-benzo [ , 3] oxazin-4-one

(80 mg, 0.29 mmol, 1.0 eq) and pyridine (40 μL, 0.50 mmol, 1.7 eq) were added to a solution of 4- (2- chloropyridin-3-yl) pyrrolo [ (ACN, 1.0 mL) to prepare a solution, and the prepared solution was slowly added dropwise to a solution of MsCl (29 μL, 0.37 mmol, 1.3 eq) in ACN (1.0 mL) at -5 ° C for 5 minutes , And stirred for 5 minutes to obtain a reaction product. A solution of 2-amino-5-chloro-3-methylbenzoic acid (54.2 mg, 0.29 mmol, 1.0 eq) and pyridine (82 μL, 0.87 mmol, 3.0 eq) in ACN (1.0 mL) Lt; RTI ID = 0.0 > -5 C < / RTI > to produce some solids. After 15 min, MsCl (0.029 mL, 0.38 mmol, 1.3 eq) was further added, and the mixture was slowly stirred at room temperature for 4 hours. To the mixture was added distilled water (2.0 mL). When a yellow solid was formed, it was filtered, washed several times with water and then dried to obtain the title compound (70 mg, yield: 57%) as a yellow solid.

^{1 H NMR (300MHz, DMSO)} δ 9.14 (d, J = 1.8Hz, 1H), 8.66 (dd, J = 4.3, 2.2Hz, 1H), 8.12 (dd, J = 7.6, 1.9Hz, 1H), 7.88 (s, 1H), 7.75 (s, 1H), 7.69-7.63 (m, 2H), 7.18 (s, 1H), 7.13-7.08 (m,

Step 2. Synthesis of N- (4-chloro-2- (cyclopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin-3- yl) pyrrolo [ Vox amide

Pyrazolo [1,2-a] pyrazin-3-yl) -8-methyl-4H-benzo [d ] [1,3] oxazin-4-one (70 mg, 0.17 mmol, 1.0 eq) and cyclopropylamine (0.012 ml, 0.17 mmol, 1 eq) were dissolved in THF (3.0 mL) and stirred at room temperature for 5 hours. To the solution was added distilled water (15 mL), and the mixture was stirred at room temperature for 20 minutes. When a yellow solid was formed, it was filtered, washed several times with water and then dried to obtain the title compound (40 mg, yield: 51%) as yellow solid.

^{1 H NMR (300MHz, DMSO)} δ 10.69 (s, 1H), 9.11 (s, 1H), 8.56 (dd, J = 4.8, 2.0Hz, 1H), 8.48 (s, 1H), 8.02 (dd, J = (D, J = 7.6 Hz, 1H), 7.41 (d, J = 2.6 Hz, 1H), 7.31 J = 3.8 Hz, 2H), 7.15 (d, J = 2.6 Hz, 1H), 7.06 (t, J = 3.3 Hz, 1H), 2.73 (dq, J = 7.6, 3.9 Hz, 1H) J = 7.0, 2.8 Hz, 2H), 0.47 (q, J = 3.5 Hz, 2H).

Examples 34 and 35

The procedure is identical to that of Example 33, but using in step 1 2-amino-3,5-dibromobenzoic acid and 2-amino-3,5-dichlorobenzoic acid , Compounds 34 and 35 were prepared. The ¹ H NMR results of the respective products are summarized in Table 2 below.

Example 36

The same procedure was repeated as in the above Example 13 except that 2-chloropyridine-3-carbaldehyde was used instead of 2,4-dichlorobenzaldehyde in Step 1, and instead of 1 H -pyrrole-2-carbaldehyde in Step 2 1 H -imidazole-2-carbaldehyde, compound 36 was prepared. The ¹ H NMR results of the product are summarized in Table 2 below.

The structures and NMR data of the compounds 26 to 36 are summarized in Table 2 below.

Examples 37 to 44

The same procedure was repeated as in Example 45, except that in Step 1, the respective R ² -OC (= O) -Cl compounds having substituents R ² described in Table 3 below were used instead of methyl chloroformate to give compounds 37 to 44 . The ¹ H NMR results of each product are summarized in Table 3 below.

Example 45: Methyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) phenyl) carbamate

Step 1. Methyl (3,5-dichloro-2-nitrophenyl) carbamate

3,5-Dichloro-2-nitroaniline (150 mg, 0.72 mmol) and methyl chloroformate (2.0 mL, 0.36 M) were added to the vial and stirred under reflux for 24 hours. After completion of the reaction, the chloroformate was removed by vacuum distillation, distilled water (30 mL) was added, and the mixture was extracted with ethyl acetate (30 mL x 2), dried over MgSO ₄ and concentrated under reduced pressure. Then, the product was separated by silica gel column chromatography (EA / Hex = 1: 4) to obtain the title compound (79 mg, yield: 42%) as yellow solid.

The starting material, 3,5-dichloro-2-nitroaniline, is described in Vasiliki Giannouli et al., Design, Synthesis, and Evaluation of the Antiproliferative Activity of a Novel Fused Xanthine Anion Derivatives in Human Breast Cancer Cells, Journal of medicinal Chemistry , 2007, 50 (7), pp. 1716-1719.

¹ H NMR (300 MHz, CDCl ₃ )? 8.24 (s, IH), 7.71 (s, IH), 7.23 (s, IH), 3.81 (s, 3H).

Step 2. Methyl (2-amino-3,5-dichlorophenyl) carbamate

To the 20 mL vial was added methyl (3,5-dichloro-2-nitrophenyl) carbamate (79 mg, 0.3 mmol) synthesized in the above step 1 and THF (1.5 mL, 0.2 M) and stirred. A solution of sodium hydrosulfite (603 mg, 2.7 mmol, 9.0 eq) and sodium bicarbonate (227 mg, 2.7 mmol, 9.0 eq) in H ₂ O (3 mL, 0.1 M) was added. MeOH (0.5 mL) was added thereto, followed by stirring at room temperature for 2 hours. After completion of the reaction, THF and MeOH were removed with a vacuum distillation apparatus, and the mixture was extracted with ethyl acetate (30 mL × 2), dried over MgSO _4, and concentrated under reduced pressure. The product was then purified by silica gel column chromatography (EA / Hex = 1: 4) to give the title compound (30 mg, yield: 43%) as an amber solid.

¹ H NMR (300 MHz, CDCl ₃ )? 7.34 (s, IH), 7.15 (s, IH), 6.41 (s, IH), 4.04 (s, 2H), 3.79

Step 3. Synthesis of methyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [

The procedure of Step 4 of Example 13 was repeated except that 4- (2-chloropyridin-3-yl) piperidine was used instead of 4- (2,4-dichlorophenyl) pyrrolo [ (2-amino-3,5-dichlorophenyl) pyridine synthesized in Step 2 above instead of 2-amino-5-chloro-N, ) Carbamate to give the title compound as a slightly yellow solid (yield: 48%). ≪ RTI ID = 0.0 >

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 10.22 (s, 1H), 8.90 (s, 1H), 8.62 (d, J = 4.8Hz, 1H), 7.83 (s, 1H), 7.77 (d, J = 7.1 1H), 7.02 (s, 2H), 3.73 (s, 3H), 7.71 (s, 1H), 7.50-7.43 (m,

Example 46

The same procedure was repeated as in Example 45 below, except that in Step 1, heptyl chloroformate was used instead of methyl chloroformate to prepare 46. [ The ¹ H NMR results of the product are summarized in Table 3 below.

The structures and NMR data of the compounds 37 to 46 are summarized in Table 3 below.

Examples 47 to 49

The same procedure as in Example 50 was repeated, except that the compound of the formula 9 was used instead of 4-amino-3-methyl-5-nitrobenzonitrile in the step 1, and the compound of the formula 9 was used instead of heptyl chloroformate in the step 3 Using each R ² -OC (= O) -Cl compound having the described substituent R ² , compounds 47-49 were prepared. The ¹ H NMR results of the respective products are summarized in Table 4 below.

Formula 9

Wherein X and Y are as set forth in Table 4 below.

Example 50: Synthesis of heptyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) Mate

Step 1. Synthesis of di-t-butyl (4-cyano-2-methyl-6-nitrophenyl) imidodicarbonate

4-Amino-3-methyl-5-nitrobenzonitrile (10.6 g, 60 mmol) was dissolved in THF (0.5 M, 120 mL). Di-t-butyl dicarbonate (28.8 g, 2.2 eq, 132 mmol) and 4-dimethylaminopyridine (1.47 g, 0.2 eq, 12 mmol) were added thereto and heated under reflux for 1 hour. After completion of the reaction, the solvent was removed under reduced pressure, distilled water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. Thereafter, the resultant product was separated by silica gel column chromatography (EA: Hex = 1: 9 -> 1: 4) to obtain the title compound (21.6 g, yield: 95%) as an ivory solid.

At this time, the 4-amino-3-methyl-5-nitrobenzonitrile used as the starting compound was synthesized by the method disclosed in PCT Publication No. WO 2007/56155 A1.

¹ H NMR (300 MHz, CDCl ₃ )? 8.15 (s, IH), 7.80 (s, IH), 2.37 (s, 3H), 1.41 (s,

Step 2. Synthesis of di-t-butyl (2-amino-4-cyano-6-methylphenyl) imidodicarbonate

Di-t-butyl (4-cyano-2-methyl-6-nitrophenyl) imidodicarbonate (3.77 g, 10 mmol) synthesized in the above step 1 was dissolved in THF (0.2 M, 50 ml). A solution prepared by dissolving sodium hydrosulfite (15.7 g, 9 eq, 90 mmol) and sodium bicarbonate (7.56 g, 90 mmol) in H ₂ O (0.1 M, 100 mL) was added thereto. MeOH (17 mL) was then added and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, THF and MeOH were removed under reduced pressure, brine was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. Thereafter, the resultant was separated by silica gel column chromatography (EA: Hex = 1: 2) to obtain the title compound (2.90 g, yield: 83%) as a white solid.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 6.89 (s, 1H), 6.85 (s, 1H), 3.89 (s, 2H), 2.15 (s, 3H), 1.41 (s, 18H).

Step 3. Preparation of t-butyl t-butoxycarbonyl (4-cyano-2 - (((heptyloxy) carbonyl) amino) -6- methylphenyl) carbamate

To a solution of di-t-butyl (2-amino-4-cyano-6-methylphenyl) imidodicarbonate (104 mg, 0.3 mmol) synthesized in step 2 above was added pyridine (0.24 mL, 3 mmol, 10 eq) and heptyl chloroformate 0.11 mL, 0.6 mmol, 2 eq.) Were added. The mixture was stirred at room temperature for 10 minutes and then at 80 DEG C for 2 hours. After completion of the reaction, distilled water was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over MgSO ₄ and concentrated under reduced pressure. The residue was then separated by silica gel column chromatography (EA: Hex = 1: 9) to obtain the title compound (146 mg, yield: 99%) as a colorless liquid.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 8.31 (s, 1H), 7.22 (s, 1H), 6.74 (s, 1H), 4.17 (t, J = 6.7Hz, 2H), 2.21 (s, 3H), 1.69-1.65 (m, 2H), 1.38 (s, 18H), 1.32-1.21 (m, 8H), 0.89 (t, J = 5.9 Hz, 3H).

Step 4. Heptyl (2-amino-5-cyano-3-methylphenyl) carbamate

Butyl (4-cyano-2 - (((heptyloxy) carbonyl) amino) -6-methylphenyl) carbamate (416 mg, 0.85 mmol) synthesized in the above step 3 was dissolved in CH ₂ Cl ₂ (3.0 mL), TFA (1.95 mL, 30 eq, 25.5 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Then sat. NaHCO ₃ was added and extracted with CH ₂ Cl _{2. The} organic layer was dried over MgSO ₄ and concentrated under reduced pressure to give the title compound (245 mg, yield: 99%) as a white solid.

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 7.41 (s, 1H), 7.24 (s, 1H), 6.06 (s, 1H), 4.24 (brs, 2H), 4.17 (t, J = 6.7Hz, 2H), 2.20 (s, 3H), 1.74-1.60 (m, 2H), 1.40-1.23 (m, 8H), 0.89 (t, J = 6.4Hz, 3H).

Step 5. Synthesis of heptyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2- a] pyrazine-3- carboxamido) -5- cyano-3- methylphenyl) carbamate

The procedure of Step 4 of Example 13 was repeated except that 4- (2-chloropyridin-3-yl) pyridine was used instead of 4- (2,4-dichlorophenyl) pyrrolo [ Pyrrolo [1,2-a] pyrazine-3-carboxylic acid was used instead of 2-amino-5-chloro-N, -3-methylphenyl) carbamate and using trifluoromethanesulfonyl chloride instead of methanesulfonyl chloride, the title compound was obtained as a pale yellow solid (yield: 24%).

_{^{1 H NMR (300MHz, CDCl 3}} ) δ 10.05 (s, 1H), 8.89 (s, 1H), 8.62 (d, J = 4.8Hz, 1H), 8.04 (s, 1H), 7.77 (d, J = 7.4 7.01 (t, J = 7.0 Hz, 1H), 7.50-7.42 (m, 2H), 7.28 2H), 2.37 (s, 3H), 1.70-1.61 (m, 2H), 1.36-1.23 (m, 8H), 0.90-0.84 (m, 3H).

Examples 51 to 53

The same procedure was repeated as in Example 50, except that 2,4-dibromo-6-nitrobenzenamine was used in place of 4-amino-3-methyl-5-nitrobenzonitrile in step 1 and heptyl Compounds 51 to 53 were prepared using the respective R ² -OC (= O) -Cl compounds having the substituent R ² described in Table 4 instead of the chloroformate. The ¹ H NMR results of the respective products are summarized in Table 4 below.

The structure and NMR data of the compounds 47 to 53 are summarized in Table 4 below.

Examples 54 and 55

The procedure of Example 13 was repeated except that 2-amino-5-chloro-N-methoxy-3-methylbenzamide and 2-amino- Using 2-amino-5-chloro-N- (tetrahydro-3-oxofuran-2-yl) -3-methylbenzamide, compounds 54 and 55 were prepared. The ¹ H NMR results of the respective products are summarized in Table 5 below.

The structure and NMR data of compounds 54 and 55 are summarized in Table 5 below.

Active Test Example

For the compounds prepared in the above examples, the insecticidal activity against the Chinese cabbage moth, Tobacco rubrum, and Lawn mallard were measured using the following bioassay.

Test Example 1: Chinese cabbage moth ( Plutella xylostella ) (Insecticidal activity)

The cabbage moths were collected in the vicinity of Gyeongju in 2000, The leaf of the cabbage (Daiya) was cut into 5.8 cm in diameter, and then dipped in a 5% acetone solution diluted with the agent for 30 seconds to sufficiently shade. The shaded cabbage leaves were placed in a petri dish (diameter 8.8 cm) with a filter paper, and three recipients of three cabbage moths moths were inoculated three times. The live embryos were examined at 24 hours and 48 hours after inoculation, while they were stored under the light condition of 16: 8 hours, 25 ± 1 ℃, and relative humidity of 50 to 60%. In some cases, the live embryos were examined at 72 and 96 hours after inoculation. The control value is expressed as the following formula (1) and (2), and the density after the treatment is corrected on the basis of the density before treatment and converted to the corrected insecticide rate for the untreated treatment (refer to A method of computing effectiveness of an insecticide. J. Econ, Entomol 18: 265-267, Abbott, 1925).

Equation 1

Controlling = (untreated biodegradation - treatment biodegradation) / untreated biodegradation x 100

Equation 2

Lacticity = Density after treatment / Density before treatment x 100

Each compound obtained in Examples 4, 12, 13, 27, 31, 37, 38, 39, 40, 41 and 42 was treated with 100 ppm by the above test method to examine the insecticidal activity against Chinese cabbage moth As a result, all of them showed more than 80% control after 4 days.

Test Example 2: Tobacco spider room ( Spodoptera litura ) (Insecticidal activity)

The tobacco caterpillars were collected in the vicinity of Gyeongju in 2009, and then reared in the breeding room. The leaf of the cabbage (Daiya) was cut into 5.8 cm in diameter, and then dipped in a 5% acetone solution diluted with the agent for 30 seconds to sufficiently shade. The shaded cabbage leaves were placed in a petri dish (diameter 8.8 cm) with a filter paper, and the tobacco budworm larvae were inoculated three times with 10 livers each. The samples were stored under light conditions of 16: 8 hours, 25 ± 1 ℃ and relative humidity of 50 ~ 60%. The live embryos were examined 24 hours, 48 hours, 72 hours, and 96 hours after inoculation. As shown in Equations (1) and (2) above, the control of the individual is expressed by correcting the post-treatment density based on the pre-treatment density and converting it into corrected insecticidal rate for non-treatment.

The compound obtained in Example 43 was treated with 100 ppm by the above test method to examine the insecticidal activity against the tobacco budworm larvae. As a result, the control value was over 80% after 4 days.

Test Example 3: Laodelphax striatellus ) (Insecticidal activity)

Leucocytes were collected in the vicinity of Gyeongju in 2007 and then used in the breeding room. The seedlings of rice (Dongjin) were plated in cotton, put into a test tube (diameter 5 cm x height 17.5 cm), and then 10 adult ladybug adults were inoculated and sprayed with a small sprayer after 24 hours of inoculation. It was stored under the light condition of 16: 8 hours, temperature of 25 1 캜, and relative humidity of 50 - 60%, and the live water was examined after 24 hours and 48 hours. As shown in Equations (1) and (2) above, the control agent corrects the density after treatment based on the density before treatment and converts the density to the corrected insecticidal rate for non-treatment.

Each compound obtained in Examples 3, 4 and 13 was treated with 100 ppm by the above test method, and the insecticidal activity against the spermatozoa was examined. As a result, the control value was over 80% after 2 days.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken by way of limitation, It is to be understood that the invention may be practiced within the scope of the appended claims.

Claims (9)

A pyrazine fused ring derivative represented by the following formula (1) or a salt thereof:
Formula 1

In this formula,
W is CH or N;
X and Y are each independently selected from the group consisting of H, hydroxy, cyano, halogen, C _1-6 alkyl, C _1-6 alkoxy, -C (= O) -NH-R ¹ or -NH- OR ² wherein R ¹ and R ² are each independently selected from the group consisting of H, C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-6 cycloalkyl, and 3-6 heterocycloalkyl or C _2-4 lock tonil the original, wherein said alkyl, alkoxy, alkenyl and alkynyl days each independently selected from hydroxy, cyano, halogen and the group consisting of C _1-3 alkoxy 1 Lt; / RTI > to 3 substituents;
Z is -C (= O) -NH-R ¹ or -NH-C (= O) -OR ² wherein R ¹ and R ² are each independently C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, C _2-6 alkynyl, C _3-6 cycloalkyl or C _2-4 lactonyl, wherein said alkyl, alkoxy, alkenyl and alkynyl are each independently selected from the group consisting of halogen and C _1-3 alkoxy ≪ / RTI >
Wherein Ar is C _6-10 aryl or 5-6 membered heteroaryl wherein each of said aryl and heteroaryl is optionally substituted with 1 to 3 substituents independently selected from the group consisting of halogen, C _1-3 alkyl, trifluoromethyl, and nitro; ≪ / RTI >
Wherein said heterocycloalkyl and heteroaryl each independently comprise 1 to 3 heteroatoms selected from the group consisting of N, O, and S;
The method according to claim 1,
Wherein W is CH.
The method according to claim 1,
Wherein W is CH;
Wherein X and Y are each independently H, hydroxy, cyano, halogen, C _1-6 alkyl, or C _1-6 alkoxy.
The method according to claim 1,
Wherein W is CH;
Wherein X and Y are each independently halogen, cyano, or C _1-6 alkyl.
The method according to claim 1,
Wherein W is CH;
Wherein X is halogen or cyano;
Wherein Y is halogen or C _1-6 alkyl;
Wherein Z is -C (= O) -NH-R < ^{1 >} Or -NH-C (= O) -OR < ² > ego;
Wherein R ¹ is C _1-6 alkyl, C _1-6 alkoxy, C _3-6 cycloalkyl, or C _2-4 lactonyl;
_Wherein R ² is C _1-8 alkyl, C _1-6 alkoxy, C _2-6 alkenyl, or C _2-6 alkynyl;
Wherein said alkyl and alkynyl may each independently be substituted with one to three halogen or C _1-3 alkoxy,
Wherein Ar is pyridyl or phenyl wherein the pyridyl may be substituted with one to three halogens and wherein the phenyl is optionally substituted with one or more groups selected from the group consisting of halogen, C _1-3 alkyl, trifluoromethyl and nitro Lt; / RTI > to 3 substituents.
The method according to claim 1,
The pyrazine fused ring derivative of formula (1) is any one of the following compounds:
1) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-2-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
2) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
3) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-4-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
4) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- amides;
5) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3- chloropyridin- amides;
6) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,6- dichloropyridin- Carboxamide;
7) 4- (2-Bromopyridin-3-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
8) 4- (4-Bromopyridin-3-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
9) Preparation of 4- (6-bromopyridin-2-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
10) 4- (6-Bromopyridin-3- yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
11) 4- (3-Bromopyridin-4-yl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
12) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
13) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
14) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,3-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
15) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
16) Synthesis of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chloro-5-nitrophenyl) pyrrolo [ amides;
17) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- ≪ / RTI >
18) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (4- (trifluoromethyl) phenyl) pyrrolo [ ≪ / RTI >
19) Preparation of N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (3- (trifluoromethyl) phenyl) pyrrolo [ ≪ / RTI >
20) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-fluorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
21) 4- (2-bromophenyl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
22) 4- (3-bromophenyl) -N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
23) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chloro-6-fluorophenyl) pyrrolo [ ≪ / RTI >
24) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (o-tolyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
25) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,3-dimethylphenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
26) N- (4-Chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides;
27) N- (4-chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
28) N- (4-Bromo-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >
29) N- (4-Bromo-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4- dichlorophenyl) pyrrolo [1,2- a] pyrazine-3-carboxamide ;
30) A mixture of N- (4-bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [ ;
31) N- (4-Bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >
32) 4- (2-Chloropyridin-3-yl) -N- (4-cyano-2-methyl-6- (methylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
33) N- (4-Chloro-2- (cyclopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides;
34) 4- (2-Chloropyridin-3-yl) -N- (2,4-dibromo-6- (cyclopropylcarbamoyl) phenyl) pyrrolo [ ≪ / RTI >
35) 4- (2-Chloropyridin-3-yl) -N- (2,4-dichloro-6- (cyclopropylcarbamoyl) phenyl) pyrrolo [1,2- a] pyrazine- ;
36) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -5- (2- chloropyridin- 3- yl) imidazo [1,2- a] pyrazine- amides;
37) 2-methoxyethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ Mate;
38) 3-Chloropropyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) phenyl) carbamate ;
39) allyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
40) 2-chloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ ;
41) Synthesis of 2,2,2-trichloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine- ) Phenyl) carbamate;
2-a) pyrazine-3-carboxamido) phenyl) carbamate (42) 2- Mate;
43) hexyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
44) isobutyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
45) methyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
46) heptyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
47) Methyl (5-chloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -3-methylphenyl) carbamate;
48) heptyl (5-chloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -3-methylphenyl) carbamate;
49) Methyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -5-cyano-3-methylphenyl) carbamate;
50) heptyl (2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) -5-cyano-3-methylphenyl) carbamate;
51) Methyl (3,5-dibromo-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
2-a) pyrazine-3-carboxamido) phenyl) carbamate < / RTI >;
53) heptyl (3,5-dibromo-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
54) N- (4-Chloro-2- (methoxycarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [1,2- a] pyrazine- amides; And
55) N- (4-Chloro-2-methyl-6 - ((2- oxotetrahydrofuran-3-yl) carbamoyl) , 2-a] pyrazine-3-carboxamide.
The method according to claim 1,
The pyrazine fused ring derivative of formula (1) is any one of the following compounds:
3) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (pyridin-4-yl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
4) N- (4-Chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2- chloropyridin- amides;
12) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2-chlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
13) N- (4-chloro-2-methyl-6- (methylcarbamoyl) phenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
27) N- (4-chloro-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2,4-dichlorophenyl) pyrrolo [1,2-a] pyrazine-3-carboxamide;
31) N- (4-Bromo-2- (isopropylcarbamoyl) -6-methylphenyl) -4- (2- chloropyridin- 3- yl) pyrrolo [ ≪ / RTI >
37) 2-methoxyethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ Mate;
38) 3-Chloropropyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine-3-carboxamido) phenyl) carbamate ;
39) allyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate;
40) 2-chloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [ ;
41) Synthesis of 2,2,2-trichloroethyl (3,5-dichloro-2- (4- (2-chloropyridin-3- yl) pyrrolo [1,2- a] pyrazine- ) Phenyl) carbamate;
2-a) pyrazine-3-carboxamido) phenyl) carbamate (42) 2- Mate; And
43) hexyl (3,5-dichloro-2- (4- (2-chloropyridin-3-yl) pyrrolo [1,2-a] pyrazine-3-carboxamido) phenyl) carbamate.
8. An insecticidal composition comprising as an active ingredient a compound according to any one of claims 1 to 7.
A method for controlling insects by treating a compound according to any one of claims 1 to 7 to a crop or its habitat.