KR100613688B1 - 2-amino-4-quinolinone derivative and fungicidal composition for agriculture and horticulture comprising same - Google Patents

Abstract

The present invention relates to a novel 2-amino-4-quinolinone derivative of formula (I), which is useful as an agricultural horticultural fungicide, which selectively shows high bactericidal effect against a wide range of plant pathogens. In addition, agricultural and horticultural fungicide compositions comprising the compound as a active ingredient and a pharmaceutically acceptable carrier can be used against a wide range of plant pathogens.

<Formula 1>

Where

R ₁ to R ₄ are hydrogen, halogen, C _1-10 linear or branched alkyl group, C _1-6 linear or branched haloalkyl group, C _1-10 linear or branched alkoxy group, phenyl group, phenoxy group , Benzyl group, nitro group or cyano group;

R ₅ is a C _1-6 linear or branched alkyl group, a C _3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group;

R ₆ is hydrogen or a saturated or unsaturated C _1-5 linear or branched alkyl group;

R ₇ is hydrogen,

또는 -CH₂CN 이며, 여기에서

Or -CH ₂ CN, where

R ₈ to R ₁₆ are each hydrogen, halogen, saturated or unsaturated C _1-6 linear or branched alkyl group, substituted or unsubstituted phenyl group, alkoxyalkyl group or (R ₁₉ ) ₃ Si, wherein R ₁₉ is C _{1 -5} linear or branched alkyl groups;

R ₁₇ and R ₁₈ are each hydrogen or a C _1-5 linear or branched alkyl group,

X and X 'are each C _1-3 alkoxy, C _1-3 thioalkoxy, or together form -O- (CH ₂ ) rO-, -S- (CH ₂ ) rS-,

Y is O, S or S = O,

Z is a heterocyclic group,

m is an integer from 0 to 4,

n, p, q, and r are integers of 1-4, respectively.

Description

2-amino-4-quinolinone derivative and agricultural horticultural fungicide composition comprising the same {2-AMINO-4-QUINOLINONE DERIVATIVE AND FUNGICIDAL COMPOSITION FOR AGRICULTURE AND HORTICULTURE COMPRISING SAME}

The present invention relates to a novel 4-quinolinone derivative having a good bactericidal effect against plant pathogens and agrohorticultural fungicide composition comprising the same.

Recently, research is being actively conducted to synthesize new compounds that are safer and more environmentally safe than existing fungicides. For example, Korean Patent Application Nos. 2004-35181 and 2004-60083 of the present inventors 4-quinolinone derivatives having a different structure from the fungicide of and having excellent bactericidal or insecticidal effects have been published. However, these compounds did not satisfy sufficient bactericidal or pesticidal effects against some pathogens.

Accordingly, the present inventors conducted a more continuous study, and found that when the 2-position of the quinolinone derivative is substituted with an amine group having an unsaturated group or a hetero atom-containing group, it exhibits a stronger and broader bactericidal or insecticidal effect as well as a herbicidal effect. The present invention has been completed.

Accordingly, it is an object of the present invention to provide novel 2-amino-4-quinolinone derivatives which are environmentally safe with remarkably superior bactericidal, insecticidal and herbicidal effects as compared with the prior art.

In order to achieve the above object, the present invention provides a novel 4-quinolinone derivative of the formula (1) useful as an agricultural horticultural bactericidal, insecticide or herbicide:

Where

R ₁ to R ₄ are hydrogen, halogen, C _1-10 linear or branched alkyl group, C _1-6 linear or branched haloalkyl group, C _1-10 linear or branched alkoxy group, phenyl group, phenoxy group , Benzyl group, nitro group or cyano group;

R ₅ is a C _1-6 linear or branched alkyl group, a C _3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group;

R ₆ is hydrogen or a saturated or unsaturated C _1-5 linear or branched alkyl group;

R ₇ is hydrogen,

또는 -CH₂CN 이며, 여기에서

Or -CH ₂ CN, where

R ₈ to R ₁₆ are each hydrogen, halogen, saturated or unsaturated C _1-6 linear or branched alkyl group, substituted or unsubstituted phenyl group, alkoxyalkyl group or (R ₁₉ ) ₃ Si, wherein R ₁₉ is C _{1 -5} linear or branched alkyl groups;

R ₁₇ and R ₁₈ are each hydrogen or a C _1-5 linear or branched alkyl group,

X and X 'are each C _1-3 alkoxy, C _1-3 thioalkoxy, or together form -O- (CH ₂ ) rO-, -S- (CH ₂ ) rS-,

Y is O, S or S = O,

Z is a heterocyclic group,

m is an integer from 0 to 4,

n, p, q, and r are integers of 1-4, respectively.

Hereinafter, the present invention will be described in detail.

Preferred examples of 2-amino-4-quinolinone derivatives according to the present invention are compounds in which R ₇ has an unsaturated group such as alkene, acetylene, allene and the like.

2-amino-4-quinolinone derivatives of the general formula (1) according to the present invention, as can be seen in the following scheme 1, of the 2-alkyl sulfoxy-4-quinolinone of the formula (II) It can be prepared by reacting an amine compound:

Wherein R ₁ to R ₇ are as defined in Formula 1, and R ₂₁ is an alkyl group of C _1-3 .

The reaction is an inert solvent such as ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, dioxane and diphenyl ether; Hydrocarbons such as benzene, toluene, xylene and ligroin; Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; Esters such as ethyl acetate, ethyl propionate and the like; Chlorobenzenes such as monochlorobenzene and dichlorobenzene; And aprotic polar solvents such as N, N-dimethylform amide, diethylsulfoxide and the like. In addition, pyridine or trialkylamine can be used in the reaction as a base and a solvent.

The reaction may be carried out at 0 to 260 ° C, but is preferably carried out at room temperature to the boiling point of the solvent, the reaction time depends on the reaction temperature, but 0.5 to 48 hours is preferred.

The compound of formula II is hydrogen peroxide synthesized by a known method (see RC Anand & AK Sinha, India Journal of Chemistry, 30B , 560-562 (1991); and Korean Patent No. 295819). And oxidizing agents such as acetic acid peroxide or m-chloroperoxide.

On the other hand, when the amine compound of the formula (III) is used in the form of an acid addition salt, it is used after being treated with 1 to 2 equivalents of an inorganic base such as trialkylamine, potassium carbonate, sodium hydroxide and the like for acid removal.

After the completion of the reaction, when the amine compound of the formula (III) is used in a form other than an acid addition salt, the target product can be directly obtained by distilling the solvent under reduced pressure, and in the case of using the acid addition salt, the solvent is distilled under reduced pressure. Next, water is added to dissolve the resulting salt, extracted with an organic solvent such as methylene chloride, chloroform or ethyl acetate, and then the solvent is distilled under reduced pressure to obtain the desired product.

In addition, Compound (Ib), which is a kind of the compound of Formula 1 according to the present invention, may be obtained by acid hydrolysis of Compound (Ia) as in Scheme 2 below:

Wherein R ₁ to R ₆ are as defined in Formula 1, and R ₂₀ is an alkyl group of C _1-3 .

The acid hydrolysis reaction is carried out in an acid solution of 5 to 70%, wherein the usable acid is an inorganic acid such as hydrochloric acid, sulfuric acid or the like or an organic acid such as acetic acid or propionic acid, and the reaction temperature may be from room temperature to boiling point.

The desired product obtained is an alcohol such as methanol or ethanol; Esters of organic acids such as ethyl acetate or methyl acetate; Hydrocarbons such as pentane or hexane; Solvents, such as ether, such as ethyl ether or tetrahydrofuran, may be recrystallized by using alone or in combination, or may be easily separated and purified by a method such as column chromatography.

The compounds of the present invention exhibit high therapeutic and prophylactic antimicrobial properties against a broad spectrum of plant pathogens. Examples of such pathogens include Pyricularia oryzae of rice, Rhizoctonia solani of rice, Botrytis cinerea of cucumber, Sphaerotheca fuliginea of cucumber, and Pseudoperonospora cube of cucumber. ), downy mildew of grape fungus (Plasmopora viticola), Station pathogens of tomato (Phytophthora infestans), kkaessi pattern germs (Cochliobolus miyabeanus), brown pattern germs of peanut (Cercopora arachidicola), powdery mildew fungus of barley (Erysiphe graminis), wheat red rust ( Puccinia recondita ) and Puccinis graminis of wheat, and the compounds according to the invention show excellent effects, in particular against rice fever and wheat rust.

In addition, the compounds according to the invention are sanitary pests, such as flies, mosquitoes and wheels, agricultural pests, for example, Lodelphax striztellus Fallen , Nilaparvata lugens stal , Sogatella furcifera Horvath , Nephetettix cincticeps Uhler ), stink bugs such as Trialeurodes vaporariorum and Myzus persicae Sulzer , Phyllonorycter ringonella Matsumura , Plutella zylostella Curtis , Lepidoptera pests such as Pseudaletia separata Walker , Thief moth ( Hamestra brassicae Linne ), Tobacco macromoth ( Spodoptera litura Fablicius ), Chinese cabbage butterfly ( Pieris rapaecrucivora Boisdubal ) and Tetranychus urticae koch the Coleoptera pests such as (Oulema oryzae Kuwayama) and rice root weevil (Echinocnemus squameus Billberg), huini cigarettes and bow And are effective against pests such as home, especially to some Lepidoptera such as cabbage moth and T. urticae shows an excellent effect with respect to the charge.

In addition, the compounds according to the invention can be used as herbicides after germination, for example, in various weeds, for example, wheatgrass ( Agropyron smit hii ), dianthus (Digitaria sangulanis (L.) Scop. ), And US panicum dichotomiflorum Michx. It is effective for Solanum nigrum L. , Aeschynomene indica L. , Abutilon avicennae Gaertn , Xanthium strumarium L. and Calystegia japonica Choisy . The effect is noticeable.

In addition, the compounds according to the present invention various non weeds using herbicides in rice plants in paddy conditions, for example barnyard grass (E.oryzieola), ladle ring (S. juncoides), water Tradescantia (M. vaginalis), beech It exhibits herbicidal effect on Cyperus serotinus and Sagittaria pygmaea . Especially, it shows good effect on paddy grass, water stilt, and you.

According to the present invention, the compound of formula (I) of the present invention contains about 0.01 to 90% by weight, preferably about 1 to 40% by weight, based on the weight of the composition, as an active ingredient, suitable solid or liquid carriers and surfactants, diluents It can be formulated into agricultural compositions by mixing with other suitable auxiliaries such as electrodeposition agents, synergists, adhesives, dispersants and the like, which can be prepared as emulsions, wetting agents, powders, granules, powders and the like.

Solid carriers that can be used in the present invention include talc, clay, bentonite, pyrophyllite, kaolin, diatomaceous earth, silica and the like; Liquid carriers include water, methanol, ethanol, acetone, diethylformamide, ether, benzene, xylene, toluene, naphtha and the like; Surfactants include nonionic surfactants such as polyoxyethylene alkylphenyl ethers and polyoxyethylene fatty acid esters, anionic surfactants such as alkylbenzenesulfonates, lignin sulfonates and dynaphthylmethanesulfonates; Adhesives include polyvinyl alcohol, carboxymethyl cellulose (CMC), gum arabic and the like.

In addition, the composition according to the present invention can be used to sterilize agricultural products, seedlings, seeds, as well as soil, and used in combination with other agrochemicals or nutrients such as insecticides, fungicides, herbicides, plant growth regulators, acaricides and the like. Can be.

Specific examples of 2-amino-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 6-Chloro-3-cyclopropanecarbonyl-2- (2,2-dimethoxyethylamino) -8-trifluoromethyl-4-quinolinone (Compound 9)

6-Chloro-3-cyclopropanecarbonyl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (377 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) It was added to 2 ml of furan and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the remaining solid was recrystallized in ethanol to obtain 335 mg (yield 80%) of the title product.

¹ H NMR (CDCI ₃ ): δ 0.7-1.2 (m, 4H), 3.4 (s, 6H), 3.6-3.8 (m, 1H), 4.4 (t, 1H), 4.5-4.9 (m, 2H), 7.7 (d, 1H), 8.8 (d, 1H), 9.5 (br, 1H), 11.6 (br, 1H)

Example 2: Synthesis of 6-chloro-2- (2,2-dimethoxyethylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 10)

Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and 2,2-dimethoxyethylamine (105 mg, 1 mmol) The reaction was carried out to give 307 mg (73% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.5 (d, 6H), 3.6-3.8 (m, 1H), 3.8 (s, 6H), 4.4 (t, 1H), 4.5-4.9 (m, 2H), 8.1 ( d, 1H), 8.8 (d, 1H), 9.9 (br, 1H), 12.2 (br, 1H)

Example 3: Synthesis of 3-acetyl-6-chloro-2- (N-methyl-N'-propazylamino) -8-trifluoromethyl-4-quinolinone (Compound 13)

Example 1 from 3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (351 mg, 1 mmol) and N-methyl-N'-propazylamine (69 mg, 1 mmol) The same reaction was carried out to give 235 mg (66% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 2.6 (t, 1H), 3.0 (s, 3H), 3.4 (m, 3H), 4.6 (d, 2H), 8.2 (d, 1H), 8.6 (d, 1H) , 14.0 (br, 1H)

Example 4: Synthesis of 3-acetyl-2- (N-methyl-N'-propazylamino) -8-trifluoromethyl-4-quinolinone (Compound 16)

The same reaction as in Example 1 was carried out from 3-acetyl-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (317 mg, 1 mmol) and N-methyl-N'-propazylamine (69 mg, 1 mmol). This gave 235 mg (66% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 2.5 (t, 1H), 2.9 (s, 3H), 3.3 (s, 3H), 4.5 (d, 2H), 7.4 (t, 1H), 8.2 (d, 1H) , 9.6 (br, 1H)

Example 5 Synthesis of 6-Chloro-3-cyclopropanecarbonyl-2-propazylamino-8-trifluoromethyl-4-quinolinone (Compound 22)

The same reaction as in Example 1 was carried out from 6-chloro-3-cyclopropanecarbonyl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (377 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). This gave 265 mg (72% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.3-1.6 (m, 4H), 2.9 (t, 1H), 3.9-4.3 (m, 1H), 4.6 (q, 2H), 8.2 (d, 1H), 8.8 ( d, 2H), 12.4 (br, 1H)

Example 6: Synthesis of 3-acetyl-6-chloro-2-propazylamino-8-trifluoromethyl-4-quinolinone (Compound 25)

The title product was subjected to the same reaction as in Example 1 from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (351 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). 284 mg (83% yield) were obtained.

¹ H NMR (CDCI ₃ ): δ 2.9 (t, 1H), 3.0 (s, 3H), 4.54 (q, 2H), 8.0 (d, 1H), 8.7 (d, 2H), 12.3 (br, 1H)

Example 7: Synthesis of 6-chloro-2- (3,3-diethoxypropylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 33)

Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and 3,3-diethoxypropylamine (147 mg, 1 mmol) The reaction was carried out to obtain 335 mg (yield 78%) of the title product.

¹ H NMR (CDCI ₃ ): δ 0.7-1.5 (m, 12H), 2.0-2.40 (m, 2H), 3.2-4.0 (m, 6H), 4.2 (m, 1H), 4.7 (t, 1H), 7.8 (d, 1 H), 8.0 (br, 1 H). 11.9 (br, 1 H)

Example 8: Synthesis of 6-chloro-3-isobutyryl-2- (3-oxopropylamino) -8-trifluoromethyl-4-quinolinone (Compound 34)

To 6-chloro-2- (3,3-diethoxypropylamino) -isobutyryl-8-trifluoromethyl-4-quinolinone (33) (462 mg, 1 mmol) was added 20 ml of an aqueous 80% acetic acid solution, Heated at 70 ° C. for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with 20 ml of water and 30 ml of ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off. The remaining solid was purified by chromatography using a mixed solvent of n-hexane and ethyl acetate as eluent to obtain 280 mg (72% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.3 (d, 6H), 3.1 (t, 2H), 3.7 (q, 2H), 4.2 (m, 1H), 7.8 (d, 1H), 8.5 (d, 1H) , 9.1 (br, 1H). 10.0 (s, 1H), 11.2 (br, 1H)

Example 9: Synthesis of 2-allylamino-6-chloro-3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 37)

The same reaction as in Example 1 was carried out from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and allylamine (57 mg, 1 mmol). 279 mg (75% yield) of product were obtained.

¹ H NMR (CDCI ₃ ): δ 1.2 (d, 6H), 4.0-4.6 (m, 3H), 5.3-5.6 (m, 3H), 7.8 (d, 1H), 8.1 (br, 1H), 8.6 ( d, 1H), 12.1 (br, 1H)

Example 10 Synthesis of 3-acetyl-6-chloro-8-trifluoromethyl-2- (3-trimethylsilylpropazylamino) -4-quinolinone (Compound 46)

20 ml of 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-trimethylsilylpropazamineamine hydrochloride (164 mg, 1 mmol) tetrahydrofuran After adding to the triethylamine excess and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure. The remaining solid was dissolved in 20 ml of dichloromethane, washed with 20 ml of water, dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. The remaining solid was recrystallized in ethanol to give 330 mg (80% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 0.2 (s, 9H), 2.7 (s, 3H), 4.3 (d, 2H), 6.8 (d, 1H), 8.5 (br, 1H), 8.6 (d, 1H) , 12.0 (br, 1H)

Example 11 Synthesis of 6-Chloro-2-propazylamino-3-propionyl-8-trifluoromethyl-4-quinolinone (Compound 48)

The same reaction as in Example 1 was carried out from 6-chloro-2-methylsuloxy-3-propionyl-8-trifluoromethyl-4-quinolinone (365 mg, 1 mmol) and propazylamine (55 mg, 1 mmol). 310 mg (87% yield) of product was obtained.

¹ H NMR (CDCI ₃ ): δ 1.2 (t, 3H), 2.7 (t, 1H), 3.4 (q, 2H), 4.3 (d, 2H), 7.9 (d, 1H), 8.6 (br, 1H) , 8.7 (d, 1 H), 12.2 (br, 1 H)

Example 12 Synthesis of 3-acetyl-6-chloro-2- (1,1-dimethylpropazylamino) -8-trifluoromethyl-4-quinolinone (Compound 55)

Same as Example 1 from 3-acetyl-6-chloro-2-methyl sulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 1,1-dimethylpropazamine (83 ml, 1 mmol) The reaction was carried out to give 322 mg (87% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.5 (s, 6H), 2.5 (t, 1H), 2.6 (s, 3H), 7.7 (m, 1H), 8.4 (m, 1H), 9.1 (br, 1H) , 12.0 (br, 1H)

Example 13: Synthesis of 3-acetyl-6-cholo-2- (phenylallylamino) -8-trifluoromethyl-4-quinolinone (Compound 66)

The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-phenylallylamine (133 mg, 1 mmol). 286 mg (68% yield) of the title product were obtained.

¹ H NMR (CDCI ₃ ): δ 2.8 (s, 3H), 4.3 (t, 2H), 6.0-6.7 (m, 2H), 7.4 (s, 5H), 7.7 (d, 1H), 8.1 (br, 1H), 8.5 (d, 1H), 12.1 (br, 1H)

Example 14 Synthesis of 6-chloro-2- (2-chloroallylamino) -3-propionyl-8-trifluoromethyl-4-quinolinone (Compound 80)

The same reaction as in Example 1 was carried out from 6-chloro-2-methyl sulfoxy-3-propionyl-8-trifluoromethyl-4-quinolinone (365 mg, 1 mmol) and 2-chloroallylamine (92 mg, 1 mmol). This gave 279 mg (71% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.2 (t, 2H), 3.3 (q, 2H), 4.2 (d, 2H), 5.6 (s, 2H), 7.8 (d, 1H), 8.0 (br, 1H) , 8.5 (d, 1H), 12.3 (br, 1H)

Example 15 Synthesis of 6-Chloro-2- (N-methyl-N'-propazylamino) -3-isobutyryl-8-trifluoromethyl-4-quinolinone (Compound 98)

Example 1 from 6-chloro-3-isobutyryl-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (379 mg, 1 mmol) and N, N'-dipropazamine (93 mg, 1 mmol) The reaction was carried out to obtain 290 mg (71% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ1.2 (d, 6H), 2.3 (t, 2H), 4.0-4.3 (m, 1H), 4.3 (d, 4H), 8.0 (d, 1H), 8.3 (d , 1H), 13.1 (br, 1H)

Example 16: Synthesis of 3-acetyl-6-chloro-2- (3-phenylpropazylamino) -8-trifluoromethyl-4-quinolinone (Compound 104)

The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-phenylpropazylamine hydrochloride (167 mg, 1 mmol). This gave 305 mg (73% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 2.7 (t, 1H), 4.5 (d, 2H), 7.5 (s, 5H), 7.8 (d, 1H), 8.6 (d, 2H), 12.0 (br, 1H)

Example 17 Synthesis of 3-acetyl-6-chloro-2- (3-ethoxypropylamino) -8-trifluoromethyl-4-quinolinone (Compound 107)

The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 3-ethoxypropylamine (103 mg, 1 mmol). This gave 278 mg (71% yield) of the title product.

¹ H NMR (CDCI ₃ ): δ 1.2 (t, 3H), 2.1 (q, 2H), 2.7 (s, 3H), 3.3-3.8 (m, 6H), 7.7 (d, 1H)

Example 18 Synthesis of 3-acetyl-6-chloro-2-methylthioethylamino-8-trifluoromethyl-4-quinolinone (Compound 114)

The same reaction as in Example 1 was carried out from 3-acetyl-6-chloro-2-methylsuloxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and methylthioethylamine (91 mg, 1 mmol). 287 mg (76% yield) of product were obtained.

¹ H NMR (CDCI ₃ ): δ 2.15 (s, 3H), 2.7 (s, 3H), 2.8 (t, 2H), 3.6 (q, 2H), 7.7 (br, 1H), 8.1 (br, 1H) , 8.5 (br, 1H), 12.0 (br, 1H)

Example 19 Synthesis of 3-acetyl-6-chloro-2- [2- (fluorophenyl) -2,3-butadienylamino] -8-trifluoromethyl-4-quinolinone (Compound 126)

3-acetyl-6-chloro-2-methylsulfoxy-8-trifluoromethyl-4-quinolinone (350 mg, 1 mmol) and 2- (4-fluorophenyl) -2,3-butadienylamine ( 163 mg, 1 mmol) was added to 20 ml of tetrahydrofuran and stirred at room temperature for 24 hours. After the reaction was completed, the solvent was distilled off under reduced pressure, and the remaining solid was recrystallized in ethanol to obtain 369 mg (yield 82%) of the title product.

¹ H NMR (CDCI ₃ ): δ 2.6 (s, 3H), 3.6 (t, 2H), 5.2 (t, 2H), 7.2 (m, 4H), 7.8 (d, 1H), 8.5 (br, 1H) , 8.6 (d, 1H), 11.8 (br, 1H).

Sterilization Effect Test Example

To investigate the protective effect against plant pathogens, 10 mg of test compound was dissolved in 10 ml of acetone, 90 ml of a 100 ppm aqueous solution of Tween 20 was added to the solution, and the concentration was adjusted to 100 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. Thus, plants (test group) and untreated plants (control group) treated with the fungicide composition 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 disease area ratio of each leaf (obtained from the ratio of disease area ratio prepared based on the ratio of the measured disease area 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 fever

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 in a wet room, and the disease area ratio of the leaves was obtained by inducing the onset for 5 days in a constant temperature and humidity room with 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. The spores formed on the medium were put in 10 ml of distilled water per plate, scraped with a brush, and then spores were filtered with gauze to harvest spores. The spore concentration was 10 ⁶ / ml, and then sprayed on single-leaf cucumbers. This was induced for 3 days in a 20 ℃ wet room to determine the lesion area ratio of one leaf.

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. chamber, and then transferred to a constant temperature and humidity chamber at a relative humidity of 70% and 20 ° C. to induce the disease for 10 days, and then calculated the leaf area ratio of the leaves.

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, seeded 15 barley seeds (East barley No. 1) in a disposable pot (diameter: 6.5 cm) and seeded on barley plants 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 2-amino-4-quinolinone derivative according to the present invention, 25 mg of test compound was dissolved in 5 ml of acetone, and 45 ml of 100 ppm aqueous solution of Triton-X-100, a surfactant, was used. After mixing, the test drug obtained by adjusting the concentration to 500 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 습 C, relative humidity 50 ± 5%, 8 females in the light condition), and the adult females were observed 4 days after hatching.

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 saliva did not show a reflex action was considered as a death.

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

Peach or aphid ( Myzus persicae sulzer ), which was bred for 2 years without spraying insecticide indoors, was smoked in a constant temperature room (temperature 21 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions 16 persons 8 cancers). 82) was used to breed indoors, 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. 20 worms were then 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 48 hours. Mortality was examined after time. 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 cage for the cabbage moth ( Plutella Xylostella Linnaeus ) was raised in a constant temperature room (temperature 27 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions 16 females, 8 cancers) using a cabbage. About 500 animals were bred and 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. The petri dishes were then covered with a lid and stored in a constant temperature room (temperature 25 ± 1 ° C., relative humidity 50 ± 5%, 8 females in 16 light conditions), 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 )

Tetranychus urticae koch of the insecticide susceptible strain was bred indoors using a kidney bean leaf in a constant temperature room (temperature 23 ± 1 ㅀ C, relative humidity 50 ± 5%, light conditions of 16 females, 8 cancers). It was.

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 storing the saale in a constant temperature room (temperature 25 ± 1 ° C, relative humidity 50 ± 5%, light conditions 16 people 8 cancer). Death was considered to show no reflex when stimulated.

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

Herbicide effect test example

This time, the herbicidal effects of the 2-amino-4-quinolinone derivatives according to the present invention were investigated.

The appropriate amount of fertilizer sterilized a sandy soil mix, and then, the test port was em in (to condition:: 348cm ² paddy conditions 115cm ^2), wherein the number of ports used by the field conditions sugar compound 2-port, in the non-condition 1 It was a port. Next, seeds or underground diameters such as sorghum, blood, wheat, barley, American total ground, crows, larvae, motherbirds, skewers, buckthorns, etc., as field crops and weeds, are placed in pots of field conditions; As crops and weeds, seed, such as rice, paddy, beetle, snare, tadpole rings, and water canes, were sown in pots of rice fields, and then poured into fine soil and placed in a greenhouse. 1 day after sowing in soil before germination, 9-14 days after sowing in foliage after germination, test compound was prepared so that the dose would be 4kg / ha (field condition: 14mg / port, paddy condition: 4mg / port). After dissolving in the same amount of acetone, the test soil was sprayed with 14 ml of paddy and field conditions, respectively. After the treatment, grow at room temperature for 2-3 weeks, and then remove the herbicidal effect from the morphological and physiological criteria (0% no herbicidal effect; 10-30% slight herbicidal effect; 40-60% moderate effect; 70-90% severe effect). And 100% complete herbicidal effect). The herbicidal effects in the evaluated field conditions and paddy conditions are shown in Tables 4 and 5, respectively.

As can be seen from the results of Tables 2 to 5, the composition comprising the 2-amino-4-quinolinone derivatives according to the present invention has a wide bactericidal spectrum, and in particular, has an excellent effect on wheat rust and rice fever, It has a selective insecticidal effect on pests such as moths and spotted mites, and has a good herbicidal effect on field weeds and paddy fields.

Claims (4)

2-Amino-4-quinolinone derivatives of Formula Formula 1

Where R ₁ to R ₄ are hydrogen, halogen, C _1-10 linear or branched alkyl group, C _1-6 linear or branched haloalkyl group, C _1-10 linear or branched alkoxy group, phenyl group, phenoxy group , Benzyl group, nitro group or cyano group; R ₅ is a C _1-6 linear or branched alkyl group, a C _3-6 cycloalkyl group, a phenyl group, a phenoxy group or a benzyl group; R ₆ is hydrogen or a saturated or unsaturated C _1-5 linear or branched alkyl group; R ₇ is hydrogen,

Or -CH ₂ CN, where R ₈ to R ₁₆ are each hydrogen, halogen, saturated or unsaturated C _1-6 linear or branched alkyl group, phenyl group, halogen substituted phenyl group, C _1-3 alkoxyalkyl group or (R ₁₉ ) ₃ Si, wherein R ₁₉ is a C _1-5 linear or branched alkyl group), R ₁₇ and R ₁₈ are each hydrogen or a C _1-5 linear or branched alkyl group, X and X 'are each C _1-3 alkoxy, C _1-3 thioalkoxy, or together form -O- (CH ₂ ) rO-, -S- (CH ₂ ) rS-, Y is O, S or S = O, Z is a 5-membered nitrogen-containing heterocyclic group, m is an integer from 0 to 4, n, p, q, and r are integers of 1-4, respectively. Agrohorticultural fungicide composition comprising the 2-amino-4-quinolinone derivative according to claim 1 as an active ingredient and a pharmaceutically acceptable carrier. Agrohorticultural insecticide composition comprising the 2-amino-4-quinolinone derivative according to claim 1 as a active ingredient and a pharmaceutically acceptable carrier. A herbicide composition for agrohorticulture, comprising the 2-amino-4-quinolinone derivative according to claim 1 as a active ingredient and a pharmaceutically acceptable carrier.