KR100574351B1 - Fungicidal composition for agriculture and horticulture having a 4-quinolinone derivative - Google Patents

Abstract

The present invention relates to a horticultural germicide composition comprising a 4-quinolinone derivative of the formula (1) as an active ingredient and a pharmaceutically acceptable carrier, wherein the composition of the present invention has a selectively high bactericidal effect against a wide range of plant pathogens. Indicates.

Where

R ₁ to R ₄ are each independently hydrogen, halogen, C _1-6 linear or C _3-4 branched alkyl group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _1-3 thioalkoxy Group, C _1-3 halothioalkoxy group, C _1-3 haloalkyl group, nitro group, cyano group, aryl group, aryloxy group, aryl sulfone group, C _1-3 alkoxycarbonyl group, carboxyl group or heterocyclic group,

R ₅ is C _1-6 linear or C _3-4 branched alkyl or aryl group,

R ₆ is a C _1-6 linear or C _3-4 branched alkyl group; Aryl group; Or hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, a benzyl group unsubstituted or substituted with a C _1-3 haloalkyl group,

n is 0 or 1;

Description

FUNGICIDAL COMPOSITION FOR AGRICULTURE AND HORTICULTURE HAVING A 4-QUINOLINONE DERIVATIVE}

The present invention relates to agrohorticultural fungicide composition comprising a 4-quinolinone derivative having an excellent bactericidal effect against plant pathogens.

As a horticultural fungicide for preventing plant diseases, synthetic compounds having various chemical structures have been used, which has contributed greatly to the development of agriculture. However, some of the existing fungicide compounds have never been satisfactory in the regulation of activity and stability, and in particular, the development of a fungicide with a new structure is required due to its resistance to the known fungicides.

Accordingly, the present inventors have continued to study compounds having a bactericidal effect, and as a result, 4-quinolinone derivatives having a sulfanyl group or a sulfoxy group at the 2-position of the quinolinone derivatives are selectively high bactericidal effects against a wide range of plant pathogens. The present invention has been found to exhibit pesticidal effects.

It is therefore an object of the present invention to provide agrohorticultural fungicide compositions comprising compounds having a broad and optionally high bactericidal effect against plant pathogens.

In order to achieve the above object, the present invention provides a horticultural fungicide composition comprising a 4-quinolinone derivative of the formula 1 and a pharmaceutically acceptable carrier:

Formula 1

Where

R ₁ to R ₄ are each independently hydrogen, halogen, C _1-6 linear or C _3-4 branched alkyl group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _1-3 thioalkoxy Group, C _1-3 halothioalkoxy group, C _1-3 haloalkyl group, nitro group, cyano group, aryl group, aryloxy group, aryl sulfone group, C _1-3 alkoxycarbonyl group, carboxyl group or heterocyclic group,

R ₅ is C _1-6 linear or C _3-4 branched alkyl or aryl group,

R ₆ is a C _1-6 linear or C _3-4 branched alkyl group; Aryl group; Or hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, a benzyl group unsubstituted or substituted with a C _1-3 haloalkyl group,

n is 0 or 1;

As used herein, aryl is hydrogen, halogen, C _1-4 linear or C _3-4 branched alkyl group, C _1-3 haloalkyl group, C _1-3 alkoxy group or C _1-3 haloalkoxy group Or phenyl unsubstituted or substituted with a cyano group or a nitro group.

As used herein, the term heterocyclic group is a cyclic group containing a hetero atom selected from nitrogen, oxygen, and sulfur.

Hereinafter, the present invention will be described in more detail.

4-quinolinone derivatives of the general formula (1) according to the present invention, as can be seen in the following scheme 1, by cyclizing the ketene S, N-acetal of the general formula (II) according to a known method -Alkylthio-4-quinolinones (India Journal of Chemical Section B, Vol 30B, 1991 560-562), compounds of formula (Ia) can also be prepared by oxidation It can be prepared with 2-alkyl sulfoxy-4-quinolinone.

Wherein R ₁ to R ₅ are as defined above and R ₆ ′ is a C _1-6 linear or C _3-4 branched alkyl group; Or a benzyl group substituted or unsubstituted with hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, a C _1-3 haloalkyl group, and R ₇ is a methyl group or an ethyl group.

Oxidation reactions of compounds of formula (Ia) to compounds of formula (Ib) include peroxy compounds such as hydrogen peroxide; organic hydroperoxides such as t-butyl hydroperoxide; aromatic or aliphatic percarboxylic acids such as m-chloro peroxy benzoic acid, peroxy acetic acid or permono phthalic acid; Or a mixture thereof, and in addition, it may be performed using an oxidizing agent such as organic peracid heavy metal oxide or inorganic oxyacid. Such oxidizing agents may be used in an amount of at least 1 equivalent, preferably 1 to 1.2 equivalents based on the compound of formula (Ia), and there is no particular limitation on the amount used.

Solvents that can be used in the oxidation reaction include water; Halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride and chlorobenzene; Fatty acids such as acetic acid and propionic acid; Alcohols such as methyl alcohol and ethyl alcohol; Or mixtures thereof.

The oxidation reaction takes place at 0 to 130 ° C, preferably 20 to 60 ° C. If the reaction temperature is less than 0 ℃ there is a problem that the reaction time is long, if the reaction temperature exceeds 130 ℃ there is a problem that the solvent boils over.

In addition, according to the present invention, as shown in Scheme 2, when the compound of formula (Ib) is heat substituted by mercaptan (HSR ₆ ″) of formula (III), the compound of formula (Ia ′) Is obtained, which is then oxidized in the same manner as in Scheme 1 to obtain a compound of formula (Ib ').

Wherein R ₁ to R ₅ and R ₆ ′ are as defined above, R ₆ ″ is an aryl group; or hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, C _{1 Or} a benzyl group unsubstituted or substituted with a _-3 haloalkyl group.

The heating substitution reaction may be carried out in the presence or absence of a solvent, and solvents that may be used in the substitution reaction include paraffin oil; Benzenes such as xylene and dichlorobenzene; Amides such as dimethylformamide and dimethyl acetamide; N, N-dialkylanilines such as N, N-dimethyl aniline, N, N-diethyl aniline and the like; Ethers such as diphenyl ether and the like or mixtures thereof.

In addition, when the reaction temperature is 140 to 250 ° C, preferably 160 to 200 ° C, the substitution reaction occurs well. If the reaction temperature is less than 100 ° C the reaction proceeds too slowly, if it exceeds 250 ° C the yield is low due to the generation of by-products.

Meanwhile, according to the present invention, the ketene S, N-acetal compound of Formula II, which is a starting material, is substituted phenylisothiocyanate (IV), β-keto ester (V) and leaving as shown in Scheme 3 below. It can be prepared from an alkyl compound (VI) to which a group is attached (Tetrahedron 59 (9), 1557-1564 (2003)).

Wherein R ₁ to R ₇ are as defined above and Y is chlorine, bromine, iodine, C _1-6 linear or C _3-4 branched alkyl group or arylsulfonate group.

The 4-quinolinone derivative of Formula 1 according to the present invention, prepared by the above method, exhibits a high control effect against a wide range of plant pathogens, including blasting, paperback disease, gray mold disease, late blight, and the like. It also has excellent control effect against pathogens resistant to. It also has insecticidal effects against lepidopteran pests such as cabbage moths and spotted mites.

According to the present invention, the compound of formula 1 of the present invention is used as the active ingredient in an amount of about 0.01 to 90% by weight based on the weight of the total composition, so as to dissolve or disperse in a liquid or liquefied gas carrier, or It may be formulated as a horticultural fungicide or insecticide composition by mixing or adsorbing on a solid carrier, and such compositions may be prepared as emulsions, wetting agents, powders, granules, sprays and the like.

In addition, the composition according to the invention may comprise suitable auxiliaries such as emulsifiers, suspending agents, electrodeposition agents, penetrants, wetting agents, store agents, stabilizers and the like, if necessary.

Specific examples of 4-quinolinone derivatives of formula 1 according to the present invention are shown in Table 1 below:

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are not intended to limit the invention only.

Example 1 Synthesis of 2-methylthio-3-acetyl-4-quinolinone (Compound 1)

In a nitrogen atmosphere, 0.8 g (20 mmol) of 60% sodium hydride was added to 60 ml of anhydrous dimethylformamide, cooled to 0 ° C., and 2.32 g (20 mmol) of methyl acetoacetate was added dropwise with stirring, followed by stirring at room temperature for 30 minutes. After cooling the mixture to 0 ° C., 2.7 g (20 mmol) of phenylisothiocyanate was added thereto, and the mixture was stirred at room temperature for 1 hour. The mixture was cooled to 0 ° C., and then 2.84 g (20 mmol) of methane iodide was added thereto and stirred at room temperature for 1 hour. The stirred reaction mixture was added to 100 g of ice water, and the resulting solid was filtered and dried. The solid was poured into 50 ml of o-dichlorobenzene and stirred for 40 minutes while refluxing. The product was concentrated by distillation under reduced pressure, and 50 ml of n-hexane was added thereto, and the resulting solid was filtered and dried to obtain the target compound in 83% yield.

¹ H NMR (DMSO-d ₆ ): δ 10.7 (s, 1H), 8.2 ~ 7.15 (m, 4H), 2.65 (s, 3H), 2.53 (s, 3H)

Example 2: Synthesis of 2-methylthio-3-acetyl-7-methoxy-4-quinolinone (compound 2)

The target compound was obtained in the same manner as in Example 1 using m-methoxyphenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (CDCl ₃ ): δ 10.49 (s, 1H), 8.18 ~ 6.68 (s, 3H), 3.8 (s, 3H), 2.64 (s, 3H), 2.53 (s, 3H)

Example 3: Synthesis of 2-methylthio-3-acetyl-8-chloro-4-quinolinone (3)

Using o-chlorophenylisothiocyanate instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ ): δ 8.2-7.25 (m. 3H), 2.67 (s, 3H), 2.59 (s, 3H).

Example 4: Synthesis of 2-methylthio-3-acetyl-5,8-dichloro-4-quinolinone (Compound 4)

2,4-dichlorophenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 7.7 (d, J = 9.0, 1H), 7.27 (d, J = 9.0, 1H), 2.64 (s, 3H), 2.52 (s, 3H)

Example 5: Synthesis of 2-methylthio-3-acetyl-6-methoxy-4-quinolinone (Compound 5)

P-methoxyphenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ ): δ 10.68 (s, 1H), 7.93-6.95 (m, 3H), 3.83 (s, 3H), 2.63 (s, 3H), 2.59 (s, 3H)

Example 6: Synthesis of 2-methylthio-3-acetyl-6-fluoro-4-quinolinone (compound 7)

P-fluorophenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.1-7.2 (m, 3H), 2.62 (s, 3H), 2.55 (s, 3H)

Example 7: Synthesis of 2-methylthio-3-acetyl-8-fluoro-4-quinolinone (compound 8)

O-fluorophenylisothiocyanate was used in place of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 6.13 to 7.1 (m, 3H), 2.65 (s 3H), 2.57 (s, 3H)

Example 8: Synthesis of 2-methylthio-3-butyryl-8-chloro-4-quinolinone (Compound 9)

O-chlorophenylisothiocyanate and ethyl butyryl acetate were used in place of phenylisothiocyanate and methylacetoacetate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (CDCl ₃ ): δ 8.52 ~ 8.05 (m, 3H), 2.76 (t, J = 7.0, 2H), 2.45 (s, 3H), 1.72 (m, 2H), 0.95 (t, J = 7.0 , 3H)

Example 9: Synthesis of 2-methylthio-3-acetyl-8-methyl-4-quinolinone (Compound 11)

Using o-tolylisothiocyanate instead of phenylisothiocyanate, the target compound was obtained in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ ): δ 15.6 (s, 1H), 8.06 ~ 7.3 (m, 3H), 2.93 (s, 3H), 2.69 (s, 3H), 2.65 (s, 3H)

Example 10 Synthesis of 2-methylthio-3-benzoyl-8-chloro-4-quinolinone (Compound 12)

The desired compound was obtained in the same manner as in Example 1 using o-chlorophenylisothiocyanate and ethyl benzoyl acetate instead of phenylisothiocyanate and methylacetoacetate.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.3 ~ 7.2 (m, 8H), 2.65 (s, 3H)

Example 11: Synthesis of 2-methylthio-3-acetyl-6-chloro-8-trifluoromethyl-4-quinolinone (Compound 13)

4-chloro-2-trifluoromethylphenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.3 (s, 1H), 8.12 (s, 3H), 2.67 (s, 3H)

Example 12 Synthesis of 2-methylthio-3-acetyl-8-methoxycarbonyl-4-quinolinone (Compound 16)

The target compound was obtained in the same manner as in Example 1 using 2-methoxycarbonylphenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.0 to 8.9 (m, 4H), 2.66 (s, 3H), 2.60 (s, 3H)

Example 13: Synthesis of 2-methylthio-3-acetyl-6-chloro-7-nitro-4-quinolinone (Compound 21)

Using the 3-nitro-4-chlorophenylisothiocyanate instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 11.4 (s, 1H), 7.73 ~ 8.13 (m, 2H), 2.7 (s, 3H), 2.43 (s, 3H)

Example 14 Synthesis of 2-methylthio-3-acetyl-8-cyano-4-quinolinone (Compound 22)

The desired compound was obtained in the same manner as in Example 1 using 2-cyanoanophenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 7.6-8.7 (m, 3H), 2.7 (s, 3H), 2.13 (s, 3H)

Example 15 Synthesis of 2- (4-t-butylbenzylthio) -3-acetyl-6-chloro-8-trifluoromethyl-4-quinolinone (Compound 23)

The desired compound was obtained in the same manner as in Example 1, using 4-chloro-2-trifluoromethylphenylisothiocyanate and 4-t-butylbenzylchloride instead of phenylisothiocyanate and iodinemethane.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.52 (d, 1H), 7.95 (d, 1H), 7.35 (s, 4H), 4.6 (s, 2H), 2.73 (s, 3H), 1.27 (s, 9H)

Example 16: Synthesis of 2-methylthio-3-acetyl-6-t-butyl-4-quinolinone (compound 24)

4-t-butylphenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 10.83 (s, 1H), 7.73 (d, 2H), 8.23 (s, 1H), 2.63 (s, 3H), 2.6 (s, 3H), 1.37 (s, 9H)

Example 17 Synthesis of 2-methylthio-3-acetyl-5,6,7,8-tetrachloro-4-quinolinone (Compound 27)

Using the 2,3,4,5-tetrachlorophenylisothiocyanate instead of phenylisothiocyanate, the target compound was obtained in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 7.96 (s, 1H), 2.66 (s, 3H), 2.43 (s, 3H)

Example 18 Synthesis of 2-methylthio-3-acetyl-8-trifluoromethyl-4-quinolinone (Compound 29)

2-Trifluoromethylphenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (DMSO-d ₆ + CDCl ₃ ): δ 8.63 (m, 1H), 8.06 (m, 1H), 2.7 (s, 3H), 2.6 (s, 3H)

Example 19: Synthesis of 2-methylthio-3-acetyl-6-fluoro-8-trifluoromethyl-4-quinolinone (Compound 33)

The target compound was obtained in the same manner as in Example 1 using 4-fluoro-2-trifluoromethylphenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (CDCl ₃ ): δ 15.63 (s, 1H), 7.73-8.16 (m, 1H), 2.97 (s, 3H), 2.7 (s, 3H)

Example 20 Synthesis of 2-methylthio-3-acetyl-7-fluoro-8-trifluoromethyl-4-quinolinone (Compound 34)

2-Tfifluoromethyl-3-fluorophenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (CDCl ₃ ): δ 7.83-8.1 (m, 2H), 7.1-7.68 (m, 1H), 2.93 (s, 3H), 2.72 (s, 3H).

Example 21 Synthesis of 2-methylthio-3-acetyl-6-bromo-8-trifluoromethyl-4-quinolinone (Compound 35)

The desired compound was obtained in the same manner as in Example 1 using 4-bromo-2-trifluoromethylphenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (CDCl ₃ ): δ 15.6 (s, 1H), 8.53 (s, 1H), 8.1 (s, 1H), 2.93 (s, 3H), 2.7 (s, 3H)

Example 22 Synthesis of 2-methylthio-3-acetyl-6-chloro-7-trifluoromethyl-4-quinolinone (Compound 36)

3-Trifluoromethylphenylisothiocyanate was used instead of phenylisothiocyanate to obtain the target compound in the same manner as in Example 1.

¹ H NMR (CDCl ₃ ): δ 2.7 (s, 3H), 2.92 (s, 3H), 8.1-8.3 (m, 2H), 15.57 (s, 1H)

Example 23 Synthesis of 2-methylthio-3-acetyl-6-hexyl-4-quinolinone (Compound 37)

The desired compound was obtained in the same manner as in Example 1 using 4-hexylphenylisothiocyanate instead of phenylisothiocyanate.

¹ H NMR (CDCl ₃ ): δ 7.57 to 8.07 (m, 3H), 2.83 (s, 3H), 2.67 (s, 3H), 1.16 to 1.8 (m, 10H), 0.78 to 0.97 (m, 3H).

Example 24 Synthesis of 2-methylthio-3-acetyl-6,7,8-trifluoro-4-quinolinone (Compound 38)

Using the 2,3,4-trifluorophenylisothiocyanate instead of phenylisothiocyanate, the target compound was obtained in the same manner as in Example 1.

¹ H NMR (CDCl ₃ ): δ 15.73 (s, 1H), 7.6 ~ 7.93 (m, 1H), 2.97 (s, 3H), 2.73 (s, 3H)

Example 25 Synthesis of 2- (2,4dichlorobenzylthio) -3-acetyl-6-chloro-8-trifluoromethyl-4-quinolinone (Compound 39)

The desired compound was obtained in the same manner as in Example 1 using 4-chloro-2-trifluoromethylphenylisothiocyanate and 2,4-dichlorobenzylchloride instead of phenylisothiocyanate and iodinemethane.

¹ H NMR (CDCl ₃ ): δ 15.68 (s, 1H), 8.57 (m, 1H), 8.17 (m, 1H), 7.67 ~ 7.03 (m, 4H), 4.87 (s, 2H), 2.97 (s, 3H)

Example 26 Synthesis of 2-methylsulfoxy-3-acetyl-8-chloro-4-quinolinone (Compound 91)

After 2-methylthio-3-acetyl-8-chloro-4-quinolinone (26.7 g, 0.1 mol) (Compound 3) obtained in Example 3 was added to 200 ml of ethyl alcohol, magnesium monoperoxy was added thereto. A solution of phthalate (29.7 g, 0.1 mol) in 150 ml of water was slowly added dropwise at room temperature. After completion of the dropwise addition, the reaction temperature was increased to 50 ° C. and reacted at 50 ° C. for 2 hours. After the reaction, ethyl alcohol was distilled off, 500 ml of water was added thereto, and the produced solid was filtered. The filtered solid was recrystallized using 100 ml of ethyl alcohol to obtain a target compound in a yield of 3.2 g (82%).

¹ H NMR (CDCl ₃ ): δ 8.3 ~ 7.5 (m, 3H), 3.1 (s, 3H), 2.8 (s, 3H)

Example 27 Synthesis of 2-methylsulfoxy-3-acetyl-6-methoxy-4-quinolinone (Compound 92)

The 2-methylthio-3-acetyl-6-methoxy-4-quinolinone (2.6 g, 0.01 mol) (Compound 5) obtained in Example 5 was added to 10 ml of acetic acid, and the mixture was stirred under a temperature of 80 캜. , 30% hydrogen peroxide solution (2.83 g, 0.025 mol) was added dropwise and stirring continued at 80 ° C. for 30 minutes. After the reaction was completed, the reaction product was cooled, poured into 500 g of ice water, and the resulting solid was filtered and dried to obtain the target compound in a yield of 2.3 g (85%).

¹ H NMR (CDCl ₃ ): δ 7.9 ~ 7.3 (m, 3H), 3.9 (s, 3H), 3.0 (s, 3H), 2.8 (s, 3H)

Example 28 Synthesis of 2-methylsulfoxy-3-acetyl-5,8-dichloro-4-quinolinone (Compound 93)

Using the 2-methylthio-3-acetyl-5,8-dichloro-4-quinolinone (3.0 g, 0.01 mol) (Compound 4) obtained in Example 4 to the target compound in the same reaction as in Example 26 Obtained in a yield of 2.4 g (78%).

¹ H NMR (CDCl ₃ ): δ 8.0 ~ 7.0 (m, 2H), 3.1 (s, 3H), 2.75 (s, 3H)

Example 29: Synthesis of 2-methylsulfoxy-3-acetyl-8-fluoro-4-quinolinone (compound 97)

2.0 g of the target compound was obtained in the same manner as in Example 27, using the 2-methylthio-3-acetyl-8-fluoro-4-quinolinone (2.5 g, 0.01 mol) (Compound 8) obtained in Example 7. Obtained in a yield of (79%).

¹ H NMR (CDCl ₃ ): δ 8.3 ~ 7.0 (m, 4H), 3.05 (s, 3H), 2.82 (s, 3H)

Example 30 Synthesis of 2-methylsulfoxy-3-acetyl-6-chloro-8-trifluoromethyl-4-quinolinone (Compound 98)

The same process as in Example 26 using the 2-methylthio-3-acetyl-6-chloro-8-trifluoromethyl-4-quinolinone (3.4 g, 0.01 mol) (Compound 13) obtained in Example 11 above. To yield the desired compound in a yield of 2.9 g (85%).

¹ H NMR (CDCl ₃ ): δ 11.25 (s, 1H), 8.0 (d, 1H), 8.6 (d, 1H), 3.0 (s, 3H), 2.75 (s, 3H)

Example 31 Synthesis of 2-methylsulfoxy-3-acetyl-8-trifluoromethyl-4-quinolinone (Compound 102)

The desired compound was prepared in the same manner as in Example 26 using 2-methylthio-3-acetyl-8-trifluoromethyl-4-quinolinone (3.0 g, 0.01 mol) (Compound 29) obtained in Example 18. Obtained in a yield of 2.5 g (82%).

¹ H NMR (CDCl ₃ ): δ 11.25 (s, 1H), 7.52 ~ 8.78 (m, 3H), 3.03 (s, 3H), 2.87 (s, 3H)

Example 32 Synthesis of 2-methylsulfoxy-3-acetyl-8-cyano-4-quinolinone (104)

Using the 2-methylthio-3-acetyl-8-cyano-4-quinolinone (2.6 g, 0.01 mol) (Compound 22) obtained in Example 15, the target compound was obtained in the same manner as in Example 26. Obtained in g (68%).

¹ H NMR (CDCl ₃ ): δ 7.6-8.67 (m, 4H), 3.01 (s, 1H), 2.67 (s, 3H)

Example 33 Synthesis of 2- (p-chlorophenyl) thio-3-acetyl-5,8-dichloro-4-quinolinone 182

2-Methylsulfoxy-3-acetyl-5,8-dichloro-4-quinolinone (3.2 g, 0.01 mol) (Compound 93) and p-chlorothiophenol (1.73 g, 0.012 mol) obtained in Example 28. ) Was stirred at 200 ° C and heated for 30 minutes, and then the temperature of the reactant was slowly cooled to 100 ° C, dissolved in 15 ml of toluene, and then cooled to room temperature. The resulting crystals were filtered and dried to afford the desired compound in 3.3 g (83%) yield.

¹ H NMR (CDCl ₃ ): δ 7.2 ~ 8.3 (m, 6H), 3.00 (s, 3H)

Example 34 Synthesis of 2- (p-chlorophenyl) sulfoxy-3-acetyl-5,8-dichloro-4-quinolinone (Compound 184)

2- (p-chlorophenyl) thio-3-acetyl-5,8-dichloro-4-quinolinone (1 g, 0.0025 mol) (Compound 182) obtained in Example 33 was added with 5 ml of acetic acid and hydrogen peroxide (30%, 0.57 g, 0.005 mole) was added to the mixture, which was stirred for 30 minutes at 100 ° C., and then added to 50 g of ice water, and the resulting solid was filtered and dried to obtain the desired compound in a yield of 0.8 g (73%).

¹ H NMR (DMSO-d _6, CDCl ₃ ): δ 7.2-8.3 (m, 6H), 3.05 (s, 3H)

Sterilization Effect Test Example

To investigate the protective effect against plant pathogens, 25 mg of test compound was dissolved in 10 ml of acetone, 90 ml of 250 ppm aqueous solution of Tween 20 was added to the solution, and the concentration was adjusted to 250 ppm. 50 ml of foliar spray was applied to host plants. The sprayed plants were left at room temperature for 24 hours to volatilize the solvent and water. The plants (test group) and untreated plants (control group) treated with the disinfectant composition as described above were inoculated with specific plant pathogens as shown in the following test examples, and left for the same period under the same conditions (humidity and temperature). The control area (Control Value,%) was calculated as shown in Equation 1 by obtaining the leaf area ratio of the leaf (obtained from the ratio of the disease area ratio prepared based on the ratio of the measured area of the leaf to the leaf area). All experiments were repeated twice, and the higher the control value, the better the sterilization effect.

Control value (%) = (1- (Length of treatment area / lesion area of control)) × 100

Test Example 1: bactericidal effect on rice blast

Strains of pathogens ( Pyricularia oryzae ) were inoculated in rice bran agar medium (Rice Polish 20g, dextrose 10g, agar 15g, distilled water 1L) and incubated for 2 weeks in a 26 ℃ incubator. The surface of the medium in which the pathogen was grown was scraped with a rubber gallbladder to remove airborne hyphae, and spores were formed for 48 hours on a shelf of 25 to 28 ° C. in which a fluorescent lamp was turned on. Germ inoculation was sprayed sufficiently to flow into the Nakdong rice (3-4 leaf stage) susceptible to rice blast, after making a spore suspension (10 ⁶ spores / ml of spores) of a certain concentration using sterile distilled water. The inoculated rice was incubated for 24 hours in a dark state, and the disease area ratio of leaves was determined by inducing the disease for 5 days in a constant temperature and humidity chamber at a relative humidity of 90% or higher and 26 ± 2 ° C. At this time, the lesion area formed on the fully developed leaf just below the top leaf of 3-4 leaf rice was measured.

Test Example 2: The bactericidal effect on the rice leaf blight blight

Put the appropriate amount of wheat bran into 1L culture bottle, sterilize, inoculate agar pieces of pathogen ( Rhizoctonia solani ) grown on potato agar medium for 3 days, and finely crush the cultured mycelium masses. (5cm) and inoculated evenly in a constant temperature and humidity room with 28 ± 1 ℃ and relative humidity of 80% or more for 5 days to determine the lesion area ratio of leaves of 2-3 leaf seedlings.

Test Example 3: bactericidal effect on tomato gray mold

Strains ( Botrytis cinerea ) isolated from tomatoes were inoculated in potato agar medium (PDA) and plated in an incubator at 25 ° C. to incubate for 15 days under light dark conditions to form spores. Spores formed in the medium were put in 10ml of distilled water per plate, scraped with a brush, and then spores were filtered with gauze to harvest spores, and the spore concentration was 10 ⁶ / ml, and then sprayed on single-leaf cucumbers. This was induced for 3 days in a humidified room at 20 ° C (please confirm), and the lesion area ratio of one leaf was obtained.

Test Example 4: bactericidal effect against tomato late blight

Phytophthora infestans were placed on V-8 juice agar medium (V-8 juice 200ml, CaCO ₃ 4.5g, agar 15g, distilled water 800ml) and light treated at 20 ℃ for 16 hours and dark treated for 14 hours. Spores were harvested after incubation. At this time, sterile distilled water was added to the plate and shaken to separate the zygote sac from the flora, and then, the 4-stage piece of cloth was used to filter the stool sac. Adjust the concentration of strained sachets to 10 ⁵ pcs / ml and inoculate the inoculum to tomato seedlings for 1 day in a 20 ° C. chamber, and then transfer to a constant temperature and humidity room with a temperature of 20 ° C. and a relative humidity of 80% or more. After 1 day of onset, the lesion area ratio of one and two leaves of tomato was examined.

Test Example 5: bactericidal effect on wheat rust

The pathogen ( Puccinia recondita ) was used for direct passage to plants in the laboratory. For subculture and pharmacological investigation of strains, 15 seed grains (silver onions) were seeded in a disposable pot (diameter: 6.5 cm), and spores were inoculated by sprinkling the wheat of one leaf grown for 7 days in a greenhouse. The inoculated one-leafed wheat was incubated for one day in a 20 ° C. humidity chamber, and then transferred to a constant temperature and humidity chamber at a relative humidity of 70% and 20 ° C. for 10 days to induce onset, and then the leaf area ratio of the leaves was determined.

Test Example 6: bactericidal effect on barley powdery mildew

The pathogen ( Erysiphe graminis f.sp.hordei ) was used by passage in the laboratory. For subculture and pharmacological investigation of strains, seedlings of 15 barley seeds (East barley No. 1) were seeded in a disposable pot (diameter: 6.5 cm), and grown on a barley barley grown for 7 days in a greenhouse (25 ± 5 ℃). After inoculating the powdery mildew spores, it was transferred to a constant temperature and humidity room of 50% relative humidity and 22 to 24 ° C to induce the onset for 7 days, and then the leaf area ratio of the leaves was determined.

The control value was calculated by substituting the lesion area ratios of the treated and control leaves measured in Test Examples 1 to 6, and the results are shown in Table 2 as the activity index.

Insecticidal Effect Test Example

In order to investigate the insecticidal effect of the 4-quinolinone derivative according to the present invention, 25 mg of the test compound was dissolved in 5 ml of acetone, and then mixed with 45 ml of a 100 ppm aqueous solution of Triton-X-100, a surfactant, The test drug obtained by adjusting the concentration to 250 ppm was sprayed on each adult. On the other hand, the control group was treated with acetone-surfactant-distilled water solution containing no test compound. Thus, after leaving the test group and the control group for the same period of time under the same conditions (humidity and temperature) as in the following test example, the mortality rate (%) was calculated as shown in Equation 2 from the results obtained, and all the experiments Each repeat was repeated three times.

Mortality rate (%) = (100-surviving appendix)

Test Example 7: Insecticidal effect on Nilaparvata lugens stal

Raise susceptible Nilaparvata lugens stalls bred indoors without spraying insecticides in an acrylic cage (26 cm wide, 29 cm long and 20 cm high) with the same reproductive nymphs to have a final adult density of approximately 500 per cage. Were bred indoors using Dongjin rice in a constant temperature room (temperature 27 ± 1 ℃, relative humidity 50 ± 5%, light conditions of 16 females, 8 females).

For insecticidal testing, first, 6 seedlings (cultivar: Dongjin), 5-7 cm long, are rolled with cotton wool, inserted into a test tube (31 cm in diameter, 15 cm in height), and then inoculated with 20 adult adults. The test drug prepared beforehand was sprayed twice by placing a nozzle of a micro atomizer (a single injection amount of 0.0254 ± 0.0005 ml) in the center of the inlet. Subsequently, the mortality rate was examined after 24 hours and 48 hours while the test tube was kept in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions 16 people 8 cancer). At this time, when the stimulation with the tip of the brush did not show a reflex action was considered as the death.

Test Example 8: Insecticidal effect on peach aphid ( Myzus persicae sulzer )

Peach or aphid ( Myzus persicae sulzer ), which was raised for 2 years without spraying pesticides indoors, was smoked in a constant temperature room (temperature 21 ± 1 ℃, relative humidity 50 ± 5%, light conditions 16 people, 8 cancers). Indoor breeding using), and the insects were notified.

For the insecticidal test, first, 50 ml of the test drug with a concentration of 500 ppm and tobacco leaf (variety: NC-82) cut into a circular shape of 9 cm in diameter were immersed for 30 seconds and dried in the wind for 30 minutes, followed by 9 cm petri dish. I put it. Subsequently, 20 worms were inoculated into tobacco leaves treated with the respective drugs, and then stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 people 8 and 24 hours). The mortality rate was later examined. When irritated with a thin brush tip, no reflexes were considered dead.

Test Example 9: Insecticidal effect on Chinese cabbage moth ( Plutella Xylostella Linnaeus )

The average density per breeding box was 500 for the Chinese cabbage moth ( Plutella Xylostella Linnaeus ), which was raised using a cabbage in a constant temperature room (temperature 27 ± 1 ℃, relative humidity 50 ± 5%, 8 females in the light condition) without using insecticide. As many as three breeding, three larvae were disclosed.

For the pesticidal test, first, the cabbage leaves were cut into 6 cm diameter circles, soaked in a test drug having a concentration of 500 ppm for 36 seconds, and then dried in the wind for 30 minutes. The leaves thus treated were placed in a Petri dish each 6 cm in diameter, and then 10 larvae of 3 larvae were inoculated. Subsequently, the petri dishes were covered with a lid and stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 patients, 8 cancers), and the mortality rate was examined after 24 and 48 hours. Death was considered to not show reflexes when stimulated with a thin brush tip.

Test Example 10: Insecticidal effect on spotted mite ( Tetranychus urticae koch )

The insecticide susceptible mite ( Tetranychus urticae koch ) was bred indoors using kidney beans in a constant temperature room (temperature 23 ± 1 ° C, relative humidity 50 ± 5%, light conditions of 16 people, 8 cancers), and their loyalty was disclosed. .

For the insecticidal test, first, the boiled agar solution (agar content of 0.5%) was poured into the chaile to a depth of about 1 cm, cooled and hardened, and then the kidney beans were fixed on it. 40 adults were inoculated and 3 ml of test drug with a concentration of 500 ppm was sprayed using a micro sprayer. Subsequently, the mortality was examined through a microscope after 24 hours and 48 hours, respectively, while keeping the saale in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, light conditions of 16 people 8 cancers). Death was considered to show no reflex when stimulated.

The mortality measured from Test Examples 7 to 10 is shown in Table 3 below.

Compound number A light bulb Peach aphid Chinese cabbage moth Spotted mite 13 28 29 30 33 34 38 --20 10 0 5 0 --0 0 25 75 30 -90 90 20 40 60 80 100-100 100 100 100 100

As can be seen from the results of Tables 2 and 3, the composition comprising the 4-quinolinone derivative according to the present invention not only has a wide range of bactericidal effects against plant pathogens, but also shows excellent insecticidal effects against insecticidal effects, especially spotted mites. Have

Claims (2)

Farming horticultural fungicide composition comprising a 4-quinolinone derivative of Formula 1 and a pharmaceutically acceptable carrier: Formula 1

Where R ₁ to R ₄ are each independently hydrogen, halogen, C _1-6 linear or C _3-4 branched alkyl group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _1-3 thioalkoxy Group, C _1-3 halothioalkoxy group, C _1-3 haloalkyl group, nitro group, cyano group, aryl group, aryloxy group, aryl sulfone group, C _1-3 alkoxycarbonyl group, carboxyl group or heterocyclic group, R ₅ is C _1-6 linear or C _3-4 branched alkyl or aryl group, R ₆ is a C _1-6 linear or C _3-4 branched alkyl group; Aryl group; Or hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, a benzyl group unsubstituted or substituted with a C _1-3 haloalkyl group, n is 0 or 1; Agrohorticultural insecticide composition comprising a 4-quinolinone derivative of Formula 1 and a pharmaceutically acceptable carrier: Formula 1

Where R ₁ to R ₄ are each independently hydrogen, halogen, C _1-6 linear or C _3-4 branched alkyl group, C _1-3 alkoxy group, C _1-3 haloalkoxy group, C _1-3 thioalkoxy Group, C _1-3 halothioalkoxy group, C _1-3 haloalkyl group, nitro group, cyano group, aryl group, aryloxy group, aryl sulfone group, alkoxycarbonyl group, carboxyl group or heterocyclic group, R ₅ is C _1-6 linear or C _3-4 branched alkyl or aryl group, R ₆ is a C _1-6 linear or C _3-4 branched alkyl group; Aryl group; Or hydrogen, halogen, a C _1-6 linear or C _3-4 branched alkyl group, a benzyl group unsubstituted or substituted with a C _1-3 haloalkyl group, n is 0 or 1;