KR20000024971A - Methoxyacrylate or ethoxyimino acetate derivatives and preparation method thereof and bactericidal composition by using it - Google Patents

Abstract

PURPOSE: A methoxyacrylate or methoxyimino acetate derivatives, manufacturing method thereof and bactericidal composition using them are provided which have a wide range of antifungal effects against pathogenic bacteria for a variety of plants as well as resistant bacteria and not only a penetrating effect into plants but also a preventing and curing effect on a disease. CONSTITUTION: A methoxyacrylate or methoxyimino acetate derivatives of formula I and amino acid substituted oxime have a wide range of antifungal effects against pathogenic bacteria for a variety of plants as well as resistant bacteria, particularly Pyricularia oryzae, and not only a penetrating effect into plants but also a preventing and curing effect on a disease. The compositions can be also used for pathogenic bacteria for a variety of plants with other components. In formula, R1 is H, C1-C3 alkyl, C1-C3 alkylthio-or alkylsulfon-substituted alkyl, phenyl, or benzyl; R2 is C1-C5 alkyl; X is benzyloxy, C1-C3 alkoxy, C1-C3 alkyl, chloro or fluoro of from 1 to 3, C1-C3 trihaloalkyl, or C1-C3 alkyl or alkoxy-substituted or non substituted phenoxy; Z is CH or N.

Description

Methoxyacrylate or methoxyimino acetate derivatives, preparation method thereof and bactericide composition using the same

[Industrial use]

The present invention relates to a methoxyacrylate or methoxyimino acetate derivative, a method for producing the same and a fungicide composition using the same, and more particularly, to a methoxyacrylate or a methoxyimino acetate derivative useful as an agricultural horticultural fungicide.

[Prior art]

Looking at the recent development of pesticides, the development of low-dose, high selectivity, low toxicity and low pollution pesticides are mainstream due to concerns about toxicity to humans or organisms and pollution to the environment. Accordingly, in the fungicide market, the fungicide market made of inorganic and organometallic compounds and organophosphorus compounds is showing signs of stagnation and decline, while the market for penetration transitional fungicides such as azoles and benzenoids continues to grow. However, since the use of these fungicides in large quantities, resistant bacteria that are resistant to them are also rapidly expressed. Therefore, in order to reduce the expression of resistant bacteria, fungicides having a new mechanism of action are excellent in penetrating effects on plants and caused by pests. There is a demand for the development of fungicides with excellent plant prevention and treatment effects.

It is an object of the present invention to provide methoxyacrylate or methoxyimino acetate derivatives having a wide range of bactericidal effects against plant pathogens, including resistant bacteria.

Another object of the present invention is to provide a methoxyacrylate or methoxyimino acetate derivative which is very excellent in preventing and treating diseases of plants caused by pests.

Still another object of the present invention is to provide a method for preparing a methoxyacrylate or methoxyimino acetate derivative useful as the bactericide described above.

Another object of the present invention is to provide a fungicide composition using the compound as an active ingredient.

[Means for solving the problem]

In order to achieve the above object, the present invention provides a methoxy acrylate or methoxyimino acetate derivative of the formula (1).

[Formula 1]

(Wherein

R ₁ is hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkylthio- or alkylsulphone-substituted alkyl group, a phenyl group, or a benzyl group;

R ₂ is a C ₁ -C ₅ alkyl group;

X is benzyloxy, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkyl group, 1 to 3 chloro or fluoro, C ₁ -C ₃ trihaloalkyl group, or C _1-3 alkyl or alkoxy-substituted or substituted Unphenoxy group;

Z is CH or N.)

In another aspect, the present invention is a methoxy acrylate or methoxyimino of the formula (1) comprising the step of reacting a compound of the formula (2) and a compound of the formula (3) using an acid remover and a phase transfer catalyst in a mixed solvent of an inert organic solvent and water Provided are methods for preparing acetate derivatives.

[Formula 2]

[Formula 3]

Wherein R ₁ , R ₂ , X and Z are as defined above and Y is Br or Cl.

In addition, the present invention provides a horticultural germicide composition comprising the compound of formula (1) as an active ingredient.

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

The methoxyacrylate or methoxyimino acetate derivative of the formula (1) of the present invention is a compound having an oxime substituted with an amino acid, as shown in Scheme 1 reacts the oxime substituted with an amino acid of the formula (2) and the compound of the formula (3) Can be prepared. When Z is CH, a methoxyacrylate derivative is produced, and when Z is N, a methoxyimino acetate derivative is produced.

Scheme 1

Wherein R ₁ , R ₂ , X, Y and Z are as defined above.

In the above reaction, the compound of Formula 3 is used in the amount of 1 to 1.2 equivalents based on the compound of Formula 2, and may be trialkylamines such as triethylamine as an acid remover; And inorganic salts such as sodium hydrogen carbonate, potassium carbonate and sodium hydroxide, and the like may be reacted by adding 1 to 2 equivalents based on the compound of Formula 2. In the reaction of Chemical Formula 2 and Chemical Formula 3, it is preferable to react in a mixed solvent of an organic solvent and water using the acid remover and a phase transfer catalyst together in view of the reaction rate. In this case, the acid remover uses 1 to 4 equivalents based on the compound of Formula 2, and the phase transfer catalyst uses a catalytic amount. Here, the phase transfer catalyst means a quaternary amine salt or phosphate such as tricaprylylmethylammonium chloride, which is commercially available as aliquat336.

In addition, examples of the inert organic solvent used in the reaction include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and diphenyl ether; And halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride and methylene chloride, and the like, and these may be used alone or in combination of one or more.

The reaction temperature is -30 to 50 ℃, the reaction time depends on the reaction temperature, but usually 1 to 24 hours is preferred.

Immediately after completion of the reaction, the solvent is distilled off, or water is added to the reaction mixture, followed by extraction with an organic solvent that is insoluble in water such as dichloroethane, dichloromethane, chloroform and ethyl acetate, and then the solvent is distilled. A crude product of methoxyimino acetate derivative is obtained. This crude product may be converted into an alcohol solvent such as methanol and ethanol; Esters of organic acids such as ethyl acetate and methyl acetate; Hydrocarbons such as pentane and hexane; Ethers such as ethyl ether and tetrahydrofuran; And it can be easily separated and purified by recrystallization with a solvent selected from the mixture or by column chromatography.

Meanwhile, according to the present invention, the oxime substituted with the amino acid of Chemical Formula 2 may be prepared by using the benzohydroxymoyl chloride derivative, which is the compound of Formula 4, and the amino acid ester, which is the compound of Formula 5, as starting materials. Can be. Methods for preparing compounds of Formula 4 are described in Journal of Organic Chemistry, Vol. 45, No. 45, pages 3916-3918. As shown in Scheme 2, a method for preparing an oxime substituted with an amino acid of Formula 2 is described in Journal of Heterocyclic Chemistry, Vol. 21, No. 21, No. 2, pages 455-459.

Scheme 2

Wherein R ₁ , R ₂ and X are as defined above

In Scheme 2, the compound of Formula 5 is used in the amount of 1 to 1.2 equivalents based on the compound of Formula 4, and includes trialkylamines such as triethylamine as an acid remover; And inorganic salts such as sodium hydrogen carbonate, potassium carbonate and sodium hydroxide, etc., based on the compound of Formula 4, 1 to 2 equivalents, and 2 to 4 equivalents when the amino acid ester of Formula 5 is an acid addition salt. have.

Examples of the solvent used in the reaction include ethers such as diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane and diphenyl ether; Halogenated hydrocarbons such as dichloroethane, chloroform and carbon tetrachloride; Aprotic polar solvents such as N, N-dimethylformamide, N, N-dimethylformacetamide, N-methylpyrrolidone and dimethyl sulfoxide; And alcohols such as methanol, ethanol, isopropanol and butanol, and the like.

In addition, the reaction temperature is -30 to 50 ℃, the reaction time depends on the reaction temperature, but usually 1 to 24 hours is preferred.

In the same manner as in Scheme 1, the solvent is distilled immediately after completion of the reaction, or water is added to the reaction mixture, followed by extraction with an organic solvent that is insoluble in water such as dichloroethane, dichloromethane, chloroform and ethyl acetate. A crude product of an oxime derivative substituted with the amino acid of formula 2 is obtained. This crude product is an alcohol solvent such as methanol and ethanol; Esters of organic acids such as ethyl acetate and methyl acetate; Hydrocarbons such as pentane and hexane; Ethers such as ethyl ether and tetrahydrofuran; And recrystallized from a solvent selected from the mixtures thereof, or can be easily separated and purified by column chromatography.

The methoxyacrylate or methoxyimino acetate derivative having an oxime substituted with the amino acid of Formula 1 according to the present invention prepared by the above method has high therapeutic and prophylactic antibacterial properties against a broad spectrum of plant pathogens. Indicates. Examples of these bacteria include Piricularia 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, etc., showing excellent bactericidal effects against rice blast, wheat flour and wheat red rust.

According to the present invention, the compound of formula 1 of the present invention is used as an active ingredient in an amount of about 0.01 to 90% by weight based on the weight of the total composition, so that the solid or liquid carrier, surfactant, diluent, electrodeposition agent, synergist, adhesive and dispersant It can be formulated into agricultural fungicide compositions by mixing with suitable adjuvants such as the like.

Solid carriers usable in formulating compositions in the present invention include talc, clay, bentonite, pyrophyllite, kaolin, diatomaceous earth, silica and the like, and liquid carriers include water, methanol, ethanol, acetone, dimethylformamide, ether , Benzene, xylene, toluene and naphthalene, and the like, and nonionic surfactants such as polyoxyethylene alkylphenyl ether and polyoxyethylene fatty acid ester and alkylbenzene sulfonate, lignin sulfonate and dinaphthyl methane Anionic surfactant, such as a sulfonate, etc. are mentioned. In addition, polyvinyl alcohol, carboxymethyl cellulose, gum arabic and the like can be used as the adhesive.

According to the present invention, the disinfectant composition containing the compound of formula 1 of the present invention may be prepared as a powder or a hydrate powder, granules, emulsion concentrates, suspensions, fumigants, gases and pastes, and the like, as well as agricultural products, seedlings and Used to sterilize seeds and the like. For example, the compound of Formula 1 may be uniformly dissolved in a hydrocarbon, acetone or alcohol with a suitable surfactant to prepare an emulsion concentrate or solution, or mixed with an inorganic powder and a suitable surfactant, and fine powder Hydrated powder can be prepared by grinding and homogenizing as much as possible. The composition thus prepared may be diluted with water to a desired concentration, or mixed with inorganic powder, crushed and mixed homogeneously, and used as dust.

In addition, according to the present invention, by mixing the disinfectant composition diluted to contain an effective amount of the compound of formula 1 of the present invention, and other agricultural chemicals such as insecticides, fungicides, herbicides, plant growth regulators and mites, and nutritional substances Can be used.

EXAMPLE

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.

I. Preparation of Oxime Substituted with Amino Acid of Formula 2

(Example 1)

N- [hydroxyimino- (4-chlorophenyl) -methyl] alanine t-butyl ester

60 ml of dry tetrahydrofuran were added to 1.62 g (8.5 mmol) of 4-chlorobenzohydroxymoyl chloride and 1.54 g (8.5 mmol) of alanine t-butyl ester hydrochloride. 2.84 ml (20.4 mmol) of triethylamine diluted with 3 ml of dry tetrahydrofuran were slowly added dropwise to the mixture, followed by reaction at room temperature for 5 hours. When the reaction proceeded, 50 ml of water was added to the product, and extracted three times with 30 ml of ethyl acetate to obtain an organic solvent layer. The organic solvent layer was washed with water, dried over magnesium sulfate and concentrated. This concentrate was purified by silica gel column chromatography to give 1.35 g (53%) of a white solid of the product.

(Example 2)

N- [hydroxyimino- (2,4-dichlorophenyl) -methyl] valine ethyl ester

2.25 g (10 mmol) of 2,4-dichlorobenzohydroxymoyl chloride, 1.82 g (10 mmol) of valine ethyl ester hydrochloride and 3.35 ml (24 mmol) of triethylamine were substantially the same as in Example 1 above. The same procedure was followed to obtain 2.24 g (67%) of a colorless liquid.

(Example 3)

N- [hydroxyimino- (4-methoxyphenyl) -methyl] methionine methyl ester

Substantially the same as in Example 1 except that 2.41 g (13 mmol) of 4-methoxybenzohydroxymoyl chloride, 2.60 g (13 mmol) of methionine methyl ester hydrochloride and 4.35 ml (31.2 mmol) of triethylamine were used To give 1.92 g (47%) of a colorless liquid.

(Example 4)

N- [hydroxyimino- (4-phenoxyphenyl) -methyl] glycine methyl ester

2.72 g (11 mmol) of 4-phenoxybenzohydroxymoyl chloride, 1.38 g (11 mmol) of glycine methyl ester hydrochloride and 3.68 ml (26.4 mmol) of triethylamine were used in the same manner as in Example 1 above. To give 2.00 g (61%) of a purple solid.

(Example 5)

N- [hydroxyimino- (4-methoxyphenyl) -methyl] glycine t-butyl ester

Same as Example 1, except that 0.85 g (4.57 mmol) of 4-methoxybenzohydroxymoyl chloride, 0.77 g (4.57 mmol) of glycine t-butyl ester hydrochloride and 1.53 ml (11 mmol) of triethylamine were used To give 0.88 g (69%) of a white solid.

(Example 6)

N- [hydroxyimino- (4-methoxyphenyl) -methyl] valine t-butyl ester

Same as Example 1, except that 1.01 g (5.43 mmol) of 4-methoxybenzohydroxymoyl chloride, 1.14 g (5.43 mmol) of valine t-butyl ester hydrochloride and 1.82 ml (13.03 mmol) of triethylamine were used. To give 0.80 g (46%) of a colorless liquid.

(Example 7)

N- [hydroxyimino- (4-phenoxyphenyl) -methyl] methionine sulfone t-butyl ester

Same as Example 1, except that 1.57 g (6.33 mmol) of 4-phenoxybenzohydroxymoyl chloride, 1.50 g (6.33 mmol) of methionine sulfone t-butyl ester, and 2.12 ml (15.19 mmol) of triethylamine were used. To give 0.95 g (36%) of a yellow liquid.

The NMR and melting point (mp) of the oxime derivative substituted with the amino acid of Formula 2 prepared by the method of Example 1-7 and the compound of the present invention in addition to the compound were measured, and the results are shown in Tables 1 to 4 below. Shown in In Tables 1 to 4, No. denotes serial numbers to respective compounds for better understanding, and II denotes a compound of Formula 2. In Tables 1 to 4, II-1 is a compound of Example 1, II-18 is Example 2, II-21 is Example 3, II-22 is Example 4, II-27 is Example 5, II-28 is Example 6, II-30 is a compound of Example 7.

[Formula 2]

No. X R ₁ R ₂ NMR (200 MHz, ppm, CDCl ₃ ) mp ( ^o C) II-1 4-Cl Me t-Bu δ 7.35 (m, 4H), 5.63 (br d, 1H), 3.78 (m, 1H), 1.37 (s, 9H), 1.28 (d, J = 6.88 Hz, 3H) White solid II-2 4-Cl i-Bu Me δ 9.55 (br s, 1H), 7.47-7.28 (m, 4H), 5.48 (br d, 1H), 4.59 (m, 1H), 3.70 (s, 3H), 1.73-1.53 (m, 3H), 0.87 (m, 6H) oil II-3 4-Cl (CH ₂ ) ₂ SMe Me δ 7.52-7.30 (m, 4H), 5.27 (br s, 1H), 4.74 (m, 1H), 3.78 (s, 3H), 2.54 (m, 4H), 2.10 (s, 3H) oil II-4 4-Cl CH ₂ C ₆ H ₄ (4-Cl) Et δ 7.27-6.97 (m, 8H), 5.74 (br d, 1H), 4.14 (q, J = 6.79 Hz, 2H), 3.61 (td, J = 6.65, 6.65 Hz, 2H), 3.02-2.78 (m, 2H), 1.20 (t, J = 6.79 Hz, 3H) 176-177 II-5 4-Cl (CH ₂ ) ₂ CO ₂ Et Et δ 7.60 (d, J = 8.55 Hz, 2H), 7.38 (d, J = 8.55 Hz, 2H), 6.22 (br s, 1H), 5.71 (br d, 1H), 4.10 (m, 4H), 3.88 ( m, 1H), 2.60 (m, 1H), 2.39 (m, 1H), 2.31-1.95 (m, 2H), 1.23 (m, 6H) 116-117 II-6 4-Cl CH ₂ CO ₂ Me Me δ 7.67 (d, J = 6.72 Hz, 2H), 7.52 (d, J = 6.72 Hz, 2H), 6.30 (br d, 1H), 5.03 (m, 1H), 3.90 (s, 3H), 3.86 (s , 3H), 3.20-3.02 (m, 2H) oil II-7 4-CF ₃ H Me δ 7.66 (d, J = 8.14 Hz, 2H), 7.57 (d, J = 8.14 Hz, 2H), 6.60 (br s, 1H), 6.84 (br t, 1H), 3.81 (d, J = 1.63 Hz, 2H), 3.70 (s, 3H) 164-165 II-8 4-CF ₃ CH ₂ SCH ₂ C ₆ H ₅ Et δ 7.65 (d, J = 8.44 Hz, 2H), 7.57 (d, J = 8.44 Hz, 2H), 7.25 (m, 5H), 5.88 (br d, 1H), 4.15 (q, J = 7.12 Hz, 2H ), 4.00 (m, 1H), 3.67 (s, 2H), 2.37 (d, J = 6.10 Hz, 2H), 1.23 (t, J = 7.12 Hz, 3H) 155-156

No. X R ₁ R ₂ NMR (200 MHz, ppm, CDCl ₃ ) mp ( ^o C) II-9 4-CF ₃ i-Pr Et δ 7.64 (d, J = 8.24 Hz, 2H), 7.54 (d, J = 8.24 Hz, 2H), 5.70 (d, J = 10.99 Hz, 1H), 4.13 (q, J = 7.12 Hz, 2H), 3.58 (dd, J = 5.90, 10.78 Hz, 1H), 2.04 (m, 1H), 1.20 (t, J = 7.12 Hz, 3H), 0.88 (m, 6H) 104-105 II-10 4-F (CH ₂ ) ₂ SMe Me δ 7.67 (m, 2H), 7.11 (m, 2H), 6.18 (br s, 1H), 5.66 (br d, 1H), 4.23 (m, 1H), 3.67 (s, 3H), 2.74 (t, J = 7.12 Hz, 1H), 2.55 (t, J = 7.12 Hz, 1H), 2.40-2.00 (m, 2H), 2.12 (s, 3H) 122-124 II-11 4-CF ₃ Me Et δ 7.82-7.54 (m, 4H), 5.68 (br d, 1H), 4.12 (q, J = 7.12, 2H), 3.90 (m, 1H), 1.37 (d, J = 7.12 Hz, 3H), 1.20 ( t, J = 7.12 Hz, 3H) 158-159 II-12 4-F i-Bu Me δ 7.57-7.49 (m, 2H), 7.11-7.02 (m, 2H), 5.43 (br d, 1H), 4.63 (m, 1H), 3.75 (s, 3H), 1.79-1.55 (m, 3H), 0.91 (m, 6H) oil II-13 4-F H Me δ 7.44-7.36 (m, 2H), 7.11-7.02 (m, 2H), 5.80 (br s, 1H), 3.78 (br d, 2H), 3.69 (s, 3H) Red solid II-14 3-Me H Me δ 8.60 (br s, 1H), 7.28-7.19 (m, 4H), 5.87 (br s, 1H), 3.77 (s, 2H), 3.65 (s, 3H), 2.31 (s, 3H) 74-76 II-15 3-Me H Et δ 9.03 (br s, 1H), 7.23-7.21 (m, 4H), 5.84 (br s, 1H), 4.12 (q, J = 7.12 Hz, 2H), 3.75 (s, 2H), 2.33 (s, 3H ), 1.18 (t, J = 7.12 Hz, 3H) 73-74 II-16 3-Me i-Pr Me δ 7.29-7.05 (m, 4H), 5.40 (br s, 1H), 4.60 (m, 1H), 3.70 (s, 3H), 1.60 (m, 1H), 0.90-0.87 (m, 6H) oil II-17 2,4-Cl ₂ H Et δ 8.40 (br s, 1H), 7.46-7.26 (m, 3H), 5.85 (br s, 1H), 4.14 (q, J = 7.12 Hz, 2H), 3.65 (d, J = 5.90 Hz, 2H), 1.22 (t, J = 7.12 Hz, 3H) 116-117

No. X R ₁ R ₂ NMR (200 MHz, ppm, CDCl ₃ ) mp ( ^o C) II-18 2,4-Cl ₂ i-Pr Et δ 8.60 (br s, 1H), 7.43 (s, 1H), 7.27 (d, J = 1.02 Hz, 2H), 5.79 (br d, 1H), 4.13 (q, J = 7.12 Hz, 2H), 3.32 ( dd, J = 5.90, 10.58 Hz, 1H), 2.01 (m, 1H), 1.22 (t, J = 7.12 Hz, 3H), 0.89 (t, J = 6.12 Hz, 6H) oil II-19 4-iPr H Et δ 7.37 (d, J = 8.24 Hz, 2H), 7.24 (d, J = 8.24 Hz, 2H), 5.77 (br s, 1H), 4.16 (q, J = 7.12 Hz, 2H), 3.81 (br s, 2H), 2.92 (m, 1H), 1.27-1.22 (m, 9H) 75-76 II-20 4-iPr C ₆ H ₅ Me δ 7.39-7.17 (m, 9H), 5.56 (br d, 1H), 4.90 (br s, 1H), 3.70 (s, 3H), 2.92 (m, 1H), 1.29-1.23 (m, 6H) 138-139 II-21 4-OMe (CH ₂ ) ₂ SMe Me δ 7.44 (d, J = 8.55 Hz, 2H), 6.90 (d, J = 8.55 Hz, 2H), 5.70 (br s, 1H), 4.72 (m, 1H), 3.82 (s, 3H), 3.77 (s , 3H), 2.66-2.46 (m, 4H), 2.08 (s, 3H) oil II-22 4-OC ₆ H ₅ H Me δ 9.67 (br s, 1H), 7.36-6.98 (m, 9H), 5.80 (br s, 1H), 3.76 (br s, 2H), 3.63 (s, 3H) 64-66 II-23 4-OC ₆ H ₅ H Et δ 8.35 (br s, 1H), 7.37-6.96 (m, 9H), 5.78 (br s, 1H), 4.12 (q, J = 7.12 Hz, 2H), 3.76 (br d, 2H), 1.20 (t, J = 7.12 Hz, 3H) oil II-24 4-OC ₆ H ₅ i-Bu Me δ 7.38-6.98 (m, 9H), 5.53 (br d, 1H), 3.87 (m, 1H), 3.61 (s, 3H), 1.71 (m, 2H), 1.52 (m, 1H), 0.80 (dd, J = 6.51, 17.09 Hz, 6H) 128-129 II-25 4-OMe C ₆ H ₅ Me δ 7.36-7.13 (m, 9H), 5.53 (br d, 1H), 4.86 (br s, 1H), 3.79 (s, 3H), 3.66 (s, 3H) 80-81

No. X R ₁ R ₂ NMR (200 MHz, ppm, CDCl ₃ ) mp ( ^o C) II-26 4-OMe Me t-Bu δ 9.05 (br s, 1H), 7.37 (d, J = 8.55 Hz, 2H), 6.88 (d, J = 8.55, 2H), 5.62 (br d, 1H), 3.84 (m, 1H), 3.80 (s , 3H), 1.38 (s, 9H), 1.28 (d, J = 7.12 Hz, 3H) oil II-27 4-OMe H t-Bu δ 7.42 (d, J = 8.85 Hz, 2H), 6.93 (d, J = 8.85 Hz, 2H), 5.80 (br s, 1H), 3.85 (s, 3H), 3.71 (br s, 2H), 1.44 ( s, 9H) 120-121 II-28 4-OMe i-Pr t-Bu δ 7.37 (d, J = 8.34 Hz, 2H), 6.89 (d, J = 8.34 Hz, 2H), 5.66 (br d, 1H), 3.82 (s, 3H), 3.54 (m, 1H), 2.03 (m , 1H), 1.42 (s, 9H), 0.91 (m, 6H) oil II-29 4-OMe (CH ₂ ) ₂ SO ₂ Me t-Bu δ 7.37 (d, J = 8.95 Hz, 2H), 6.93 (d, J = 8.95 Hz, 2H), 5.60 (br s, 1H), 3.94 (m, 1H), 3.84 (s, 3H), 3.11 (br t, 2H), 2.91 (s, 3H), 2.18 (m, 2H), 1.45 (s, 9H) 112-113 oil II-30 4-OC ₆ H ₅ (CH ₂ ) ₂ SO ₂ Me t-Bu δ 7.40-6.96 (m, 9H), 5.65 (br s, 1H), 3.96 (br s, 1H), 3.10 (br t, 2H), 2.88 (s, 3H), 2.17 (m, 2H), 1.42 ( s, 9H)

II. Preparation of methoxyacrylate or methoxyimino acetate derivative having oxime substituted amino acid

(Example 8)

3-methoxy-2- {2-[(1-t-butoxycarbonyl-1-methylamino)-(4-benzyloxyphenyl) -methyleneaminooxymethyl] -phenyl} acrylic acid methyl ester

0.71 g (2 mmol) N- [hydroxyimino- (4-benzyloxyphenyl) -methyl] glycine t-butyl ester, methyl 3-methoxy-2- [2- (bromomethyl) phenyl] acrylate 0.57 g (2 mmol), 15 ml of methylene chloride, 2 ml (2 mmol) of 2N-NaOH, aliquat336 1-2 drops of tricaprylylmethylammonium chloride were added thereto, and reacted for 10 hours while stirring at room temperature. When the reaction was completed, 20 ml of water was added to the obtained product, and extracted three times with 20 ml of methylene chloride to obtain an organic solvent layer. This organic solvent layer was dried over magnesium sulfate and concentrated. This concentrate was purified by silica gel column chromatography to give 0.56 g (50% yield) of a yellow liquid.

(Example 9)

2-methoxyimino-2- {2-[(1-methoxycarbonyl-3-methylsulfanylpropylamino)-(4-benzyloxyphenyl) -methyleneaminooxymethyl] -phenyl} acetic acid methyl ester

0.47 g (1.2 mmol) N- [hydroxyimino- (4-benzyloxyphenyl) -methyl] methionine methyl ester, 0.34 g of methyl 2-methoxyimino-2- [2- (bromomethyl) phenyl] acetate 1.2 mmol) was used in substantially the same manner as in Example 8 to obtain 0.22 g (31%) of a colorless liquid.

(Example 10)

3-methoxy-2- {2-[(1-ethoxycarbonyl-3-methylsulfanylpropylamino)-(4-methoxyphenyl) -methyleneaminooxymethyl] -phenyl} acrylic acid methyl ester

0.36 g (1.1 mmol) N- [hydroxyimino- (4-methoxyphenyl) -methyl] methionine ethyl ester, 0.31 g of methyl 3-methoxy-2- [2- (bromomethyl) phenyl] acrylate ( Substantially the same as in Example 8, except that 1.1 mmol) was used, to obtain a product of 0.22 g (yield: 38%) of a yellow solid.

(Example 11)

3-methoxy-2- {2-[(1-t-butoxycarbonyl-3-methylbutylamino)-(4-methoxyphenyl) -methyleneaminooxymethyl] -phenyl} acrylic acid methyl ester

N- [hydroxyimino- (4-methoxyphenyl) -methyl] leucine t-butyl ester 0.67 g (2 mmol), methyl 3-methoxy-2- [2- (bromomethyl) phenyl] acrylate 0.57 Subsequent to the same procedure as in Example 8 except that g (2 mmol) was used, 0.55 g (yield: 47%) of a yellow liquid was obtained.

(Example 12)

2-methoxyimino-2- {2-[(1-ethoxycarbonyl-3-methylsulfanylpropylamino)-(4-methoxyphenyl) -methyleneaminooxymethyl] -phenyl} acetic acid methyl ester

0.36 g (1.1 mmol) N- [hydroxyimino- (4-methoxyphenyl) -methyl] methionine ethyl ester, 0.31 g of methyl 2-methoxyimino-2- [2- (bromomethyl) phenyl] acetate 1.1 mmol) was used in substantially the same manner as in Example 8, to obtain 0.37 g (63%) of a colorless liquid.

(Example 13)

2-methoxyimino-2- {2-[(1-t-butoxycarbonyl-ethylamino)-(4-chlorophenyl) -methyleneaminooxymethyl] -phenyl} acetic acid methyl ester

0.70 g (2.34 mmol) of N- [hydroxyimino- (4-chlorophenyl) -methyl] alanine t-butyl ester, 0.67 g of methyl 2-methoxyimino-2- [2- (bromomethyl) phenyl] acetate Except that the (2.34 mmol) was used, substantially the same as in Example 8, to obtain 0.65 g (yield: 55%) of a colorless liquid.

(Example 14)

2-methoxyimino-2- {2-[(1-methoxycarbonyl-3-methylbutylamino)-(4-chlorophenyl) -methyleneaminooxymethyl] -phenyl} acetic acid methyl ester

0.63 g (2.11 mmol) N- [hydroxyimino- (4-chlorophenyl) -methyl] leucine methyl ester, 0.60 g (2.11) methyl 2-methoxyimino-2- [2- (bromomethyl) phenyl] acetate Except for using (mmol)), substantially the same as in Example 8 to obtain 0.38 g (yield: 36%) of a colorless liquid.

(Example 15)

3-methoxy-2- {2-[(1-ethoxycarbonyl-2-methylpropylamino)-(4-methoxyphenyl) -methyleneaminooxymethyl] -phenyl} acrylic acid methyl ester

0.36 g (1.21 mmol) N- [hydroxyimino- (4-methoxyphenyl) -methyl] valine ethyl ester, 0.34 g of methyl 3-methoxy-2- [2- (bromomethyl) phenyl] acrylate 1.21 mmol) was used in substantially the same manner as in Example 8 to obtain 0.28 g (yield: 46%) of a colorless liquid.

(Example 16)

3-methoxy-2- {2-[(1-t-butoxycarbonyl-methylamino)-(4-methoxyphenyl) -methyleneaminooxymethyl] -phenyl} acrylic acid methyl ester

N- [hydroxyimino- (4-methoxyphenyl) -methyl] glycine t-butyl ester 0.56 g (2 mmol), methyl 3-methoxy-2- [2- (bromomethyl) phenyl] acrylate 0.57 Subsequent to the same procedure as in Example 8 except that g (2 mmol) was used, 0.53 g (yield: 55%) of a yellow liquid was obtained.

The NMR of the methoxyacrylate or methoxyimino acetate derivative having an oxime substituted with the amino acid of Formula 1 prepared by the method of Examples 8-16 and the compound of Formula 1 of the present invention was measured and the results are shown in the following table. 5-8 is shown. In Table 5-8, No. is a serial number assigned to each compound for better understanding as in Table 1-4, I means a compound of formula (1). In Table 5-8, I-1 is a compound of Example 8, I-3 is Example 9, I-5 is Example 10, I-7 is Example 11, and I-13 is Example 12 and I. -15 is Example 13, I-17 is Example 14, I-22 is Example 15, and I-23 is the compound of Example 16.

[Formula 1]

No. X R ₁ R ₂ Z NMR (200 MHz, ppm, CDCl ₃ ) I-1 4-OCH ₂ C ₆ H ₅ H t-Bu CH δ 7.65-7.61 (m, 1H), 7.56 (s, 1H), 7.50-7.27 (m, 9H), 7.22-7.14 (m, 1H), 6.98 (d, J = 9.28 Hz, 2H), 5.77 (br t, 1H), 5.10 (s, 2H), 5.05 (s, 2H), 3.82 (s, 3H), 3.70 (s, 3H), 3.67 (d, J = 7.7 Hz, 2H), 1.43 (s, 9H ) I-2 4-OCH ₂ C ₆ H ₅ H t-Bu N δ 7.58-7.13 (m, 11H), 6.88 (d, J = 9.02 Hz, 2H), 5.64 (br t, 1H), 5.06 (s, 2H), 4.97 (s, 2H), 4.02 (s, 3H) , 3.80 (s, 3H), 3.63 (d, J = 6.34 Hz, 2H), 1.38 (s, 9H) I-3 4-OCH ₂ C ₆ H ₅ (CH ₂ ) ₂ SMe Me N δ 7.49-7.18 (m, 11H), 6.97 (d, J = 9.26 Hz, 2H), 5.61 (br d, 1H), 5.07 (s, 2H), 5.04 (s, 2H), 4.80-4.67 (m, 1H), 4.04 (s, 3H), 3.82 (s, 3H), 3.79 (s, 3H), 2.62-2.42 (m, 4H), 2.09 (s, 3H) I-4 4-OCH ₂ C ₆ H ₅ (CH ₂ ) ₂ SMe Et N δ 7.49-7.15 (m, 11H), 6.94 (d, J = 9.28 Hz, 2H), 5.58 (br d, 1H), 5.05 (s, 2H), 5.02 (s, 2H), 4.74-4.62 (m, 1H), 4.21 (q, J = 7.12 Hz, 2H), 4.02 (s, 3H), 3.80 (s, 3H), 2.59-2.40 (m, 4H), 2.06 (s, 3H), 1.29 (t, J = 7.12 Hz, 3H) I-5 4-OMe (CH ₂ ) ₂ SMe Et CH δ 7.58 (s, 1H), 7.54-7.48 (m, 1H), 7.43 (d, J = 9.26 Hz, 2H), 7.35 (m, 2H), 7.20-7.10 (m, 1H), 6.88 (d, J = 9.26 Hz, 2H), 5.50 (br d, 1H), 5.03 (s, 2H), 4.68-4.53 (m, 1H), 4.11 (q, J = 7.85 Hz, 2H), 3.79 (s, 3H), 3.75 (s, 3H), 3.70 (s, 3H), 2.02 (s, 3H), 1.26 (t, J = 7.85 Hz, 3H) I-6 4-OMe CH ₂ C ₆ H ₅ Et CH δ 7.60 (s, 1H), 7.56-6.77 (m, 13H), 5.54 (br d, 1H), 5.01 (s, 2H), 4.88 (br q, 1H), 4.18 (q, J = 7.12 Hz, 2H ), 3.78 (s, 3H), 3.76 (s, 3H), 3.67 (s, 3H), 3.02 (m, 2H), 1.26 (t, J = 7.12 Hz, 3H)

No. X R ₁ R ₂ Z NMR (200 MHz, ppm, CDCl ₃ ) I-7 4-OMe i-Bu t-Bu CH δ 7.60 (m, 1H), 7.55 (s, 1H), 7.38-7.27 (m, 4H), 7.14 (m, 1H), 6.87 (d, J = 8.76 Hz, 2H), 5.47 (br d, 1H) , 5.00 (s, 2H), 4.10 (m, 1H), 3.78 (d, 6H), 3.67 (s, 3H), 1.81-1.62 (m, 3H), 1.38 (s, 9H), 0.86-0.76 (m , 6H) I-8 4-OMe CH ₂ C ₆ H ₅ Et N δ 7.48-6.90 (m, 11H), 6.75 (d, J = 9.00 Hz, 2H), 5.47 (br d, 1H), 4.94 (s, 2H), 4.85 (m, 1H), 4.16 (q, J = 7.12 Hz, 2H), 3.98 (s, 3H), 3.73 (s, 6H), 3.05 (d, J = 6.89 Hz, 2H), 1.22 (t, J = 7.12 Hz, 3H) I-9 4-OMe i-Bu Me N δ 7.49-7.17 (m, 6H), 6.86 (d, J = 7.96 Hz, 2H), 5.38 (br d, 1H), 5.02 (s, 2H), 4.67-4.53 (M, 1H), 4.02 (s, 3H), 3.81 (s, 3H), 3.76 (s, 3H), 3.75 (s, 3H), 1.76-1.60 (m, 3H), 0.97-0.90 (d, J = 6.03 Hz, 6H) I-10 4-OMe i-Bu t-Bu N δ 7.63-7.13 (m, 6H), 6.90 (d, J = 8.49 Hz, 2H), 5.42 (br d, 1H), 4.98 (s, 2H), 4.13 (m, 1H), 4.04 (s, 3H) , 3.83 (d, 6H), 1.74 (m, 2H), 1.51 (m, 1H), 1.39 (s, 9H), 0.89-0.79 (m, 6H) I-11 4-OMe Me CH ₂ C ₆ H ₅ CH δ 7.57 (s, 1H), 7.51-7.06 (m, 11H), 6.82 (d, J = 9.28 Hz, 2H), 5.51 (br d, 1H), 5.20 (m, 2H), 4.58 (m, 1H) , 3.77 (d, 6H), 3.68 (s, 3H), 1.37 (d, J = 7.43 Hz, 3H) I-12 4-OMe CH ₂ SCH ₂ C ₆ H ₅ Et N δ 7.62-7.17 (m, 11H), 6.90 (d, J = 8.2 Hz, 2H), 5.95 (br d, 1H), 5.08 (s, 2H), 4.78 (m, 1H), 4.26 (q, J = 7.12 Hz, 2H), 3.99 (s, 3H), 3.82 (s, 3H), 3.77 (s, 3H), 3.74 (s, 2H), 2.97-2.76 (m, 2H), 1.32 (t, J = 7.12 Hz, 3H)

No. X R ₁ R ₂ Z NMR (200 MHz, ppm, CDCl ₃ ) I-13 4-OMe (CH ₂ ) ₂ SMe Et N δ 7.52-7.17 (m, 6H), 6.87 (d, J = 8.72 Hz, 2H), 5.58 (br d, 1H), 5.03 (s, 2H), 4.68 (m, 1H), 4.22 (q, J = 7.30 Hz, 2H), 4.02 (s, 3H), 3.82 (s, 3H), 3.78 (s, 3H), 2.60 (s, 3H), 2.60-2.37 (m, 4H), 2.07 (s, 3H), 1.28 (t, J = 7.30 Hz, 3H) I-14 4-Cl CH ₂ C ₆ H ₅ t-Bu N δ 7.54-6.96 (m, 13H), 5.57 (br d, 1H), 4.93 (s, 2H), 4.00 (s, 3H), 3.91-3.80 (m, 1H), 3.77 (s, 3H), 3.02- 2.76 (m, 2H), 1.33 (s, 9H) I-15 4-Cl Me t-Bu N δ 7.58-7.16 (m, 8H), 5.53 (br d, 1H), 4.98 (s, 2H), 4.40 (s, 3H), 3.83 (s, 3H), 3.78-3.72 (m, 1H), 1.39 ( s, 9H), 1.32 (d, J = 7.16 Hz, 3H) I-16 4-Cl i-Bu Me CH δ 7.59-6.91 (m, 9H), 5.54 (br d, 1H), 5.04 (s, 2H), 4.61 (m, 1H), 3.81 (s, 3H), 3.77 (s, 3H), 3.70 (s, 3H), 1.73-1.52 (m, 3H), 0.93 (d, J = 5.29 Hz, 6H) I-17 4-Cl i-Bu Me N δ 7.51-7.20 (m, 8H), 5.53 (br d, 1H), 5.03 (s, 2H), 4.62 (m, 1H), 4.02 (s, 3H), 3.82 (s, 3H), 3.76 (s, 3H), 1.78-1.62 (m, 3H), 0.94 (d, J = 6.61 Hz, 6H) I-18 4-CF ₃ CH ₂ SCH ₂ C ₆ H ₅ Et CH δ 7.70-7.15 (m, 4H), 6.00 (br d, 1H), 5.11 (s, 2H), 4.75 (td, J = 7.59, 7.59 Hz, 1H), 4.20 (q, J = 7.12 Hz, 2H) , 3.73 (s, 3H), 3.64 (s, 2H), 3.63 (s, 3H), 2.89-2.84 (m, 2H), 1.28 (t, J = 7.12 Hz, 3H) I-19 4-F (CH ₂ ) ₂ SMe Me N δ 7.55-7.03 (m, 8H), 5.61 (br d, 1H), 5.04 (s, 2H), 4.76-4.65 (m, 1H), 4.03 (s, 3H), 3.83 (s, 3H), 3.78 ( s, 3H), 2.60-2.44 (m, 4H), 2.09 (s, 3H)

No. X R ₁ R ₂ Z NMR (200 MHz, ppm, CDCl ₃ ) I-20 4-F i-Pr Me CH δ 7.60 (s, 1H), 7.54-7.06 (m, 8H), 5.53 (br d, 1H), 5.04 (s, 2H), 4.60 (m, 1H), 3.81 (s, 3H), 3.76 (s, 3H), 3.71 (s, 3H), 1.77-1.50 (m, 3H), 0.94-0.87 (m, 6H) I-21 4-OMe (CH ₂ ) ₂ SMe Me CH δ 7.56 (s, 1H), 7.40 (d, J = 8.95 Hz, 2H), 7.30 (m, 2H), 7.14 (m, 2H), 6.86 (d, J = 8.05 Hz, 2H), 5.71 (br d , 1H), 5.01 (s, 2H), 4.67 (m, 1H), 3.78 (s, 3H), 3.77 (s, 3H), 3.75 (s, 3H), 3.68 (s, 3H), 2.45 (m, 4H), 2.05 (s, 3H) I-22 4-OMe i-Pr Et CH δ 7.58 (s, 1H), 7.42 (d, J = 8.75 Hz, 2H), 7.32 (m, 2H), 7.17 (m, 2H), 6.87 (d, J = 8.75 Hz, 2H), 5.67 (br d , 1H), 5.09 (s, 2H), 4.55 (m, 1H), 4.24 (q, J = 7.12 Hz, 2H), 3.80 (s, 6H), 3.69 (s, 3H), 2.23 (m, 1H) , 1.30 (t, J = 7.12 Hz, 3H), 0.91 (d, J = 6.92 Hz, 6H) I-23 4-OMe H t-Bu CH δ 7.60 (m, 1H), 7.55 (s, 1H), 7.37 (d, J = 8.55 Hz, 2H), 7.34-7.29 (m, 2H), 7.15 (m, 1H), 6.88 (d, J = 8.55 Hz, 2H), 5.73 (br t, 1H), 5.01 (s, 2H), 3.80 (s, 3H), 3.79 (s, 3H), 3.66 (s, 3H), 3.63 (d, J = 6.31 Hz, 2H), 1.39 (s, 9H)

Among the compounds shown in Tables 1-8, Compound Nos. I-1, I-3, I-5, I-13, 1-15, 1-22,1-23, II-19, II-22, and II- Using the compound of 23, the bactericidal effect was measured in the following manner.

Bactericidal effect test

To investigate the protective effect against plant pathogens, 25 mg of test compound was dissolved in 10 ml of acetone and the solution was adjusted to 250 ppm by adding 90 ml of a 250 ppm aqueous solution containing Tween 20. This solution was sprayed with 50 ml of foliar onto host plants of a certain size. The sprayed plants were left at room temperature for 24 hours to volatilize the solvent and water. In this way, the plants (treatment) and the untreated plants (control) treated with the fungicide composition were inoculated with specific plant pathogens, respectively, and left for the same period under the same conditions (humidity and temperature) as shown in the following test examples. The control area (Control Value,%) was calculated as shown in Equation 1 by obtaining the disease area ratio (obtained from the diseased area ratio comparison table based on the ratio of the measured disease area (spot caused by disease) to the leaf area). . The higher the control value, the better the sterilization effect.

[Equation 1]

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

Activation Index +++: Control from 81 to 100%

++: Control is 61-80%

+: Control is 41 to 60%

-: Control is 40% or less

(Test Example 1)

Sterilization Effect against Wheat Red Rust

As a pathogen, Puccinia recondita of wheat ( Puccinia recondita ) was used for direct passage to plants in the laboratory. For subculture and pharmacological investigation of strains, seeded wheat seeds (silver onions-Q: Please tell us what is onions) in a single-use pot (6.5 cm in diameter) and seeded in one-leaf wheat grown for 7 days in a greenhouse. The spores were shaken off and inoculated. The inoculated one-leafed wheat was incubated at 20 ° C. for 1 day and then transferred to a constant temperature and humidity chamber of 70% and 20 ° C. for 10 days to induce onset, and then the leaf area ratio of the leaves was determined.

(Test Example 2)

Bactericidal Effect on Barley Powder Disease

Barley powdery mildew ( Erysiphe graminis f.sp.hordei ) was used as a pathogen in the laboratory. For the subculture and pharmacological investigation of strains, seedlings of 15 barley seeds (East barley No. 1) were sown in a disposable pot (diameter: 6.5 cm), and barley was grown for 7 days in a greenhouse (25 ± 5 ^o C) for 7 days. Was inoculated with powdery mildew spores and transferred to a constant temperature and humidity room at a relative humidity of 50% and 22 to 24 ° C to induce the onset for 7 days, and then calculate the area ratio of the leaves.

(Test Example 3)

Sterilization Effect on Rice Blast

As a pathogen, strains of Pyricularia oryzae were inoculated in rice bran agar medium (Rice Polish 20g, dextrose 10g, agar 15g, distilled water 1L) and incubated in a 26 ° C. incubator for 2 weeks. The surface of the medium in which the pathogen was grown was scraped off with a rubber gallbladder to remove aerial hyphae and spores were formed for 48 hours on a fluorescent lamp turned on at 25 to 28 ^° C.

The conidia formed by using a sterile distilled water to make a spore suspension (10 ⁶ / ml) of a certain concentration, and then sprayed this spore suspension sufficiently to flow down to Nakdong rice (3-4 leaves) susceptible to rice blasting bottle Inoculation.

The inoculated rice was incubated for 24 hours in a dark state and induced to develop for 5 days in a constant temperature and humidity room with a relative humidity of 90% or higher and 26 ± 2 ° C. to determine the leaf area ratio of the leaves. 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 4)

Bactericidal Effect on Rice Leaf Stain Disease

A proper amount of bran was placed in a 1 L culture bottle and sterilized, followed by inoculation with agar of Rhizoctonia solani , a pathogen grown on potato dextrose agar media for 3 days. Cultivated mycelium masses were finely ground and inoculated evenly in the pot (5 cm) in which 2-3 leaves of Nakdong rice were grown and induced to develop for 5 days in a constant temperature and humidity room with 28 ± 1 ℃ and relative humidity of 80% or more. The area ratio of the leaves of the seedlings was determined.

(Test Example 5)

Bactericidal Effect on Cucumber Gray Mold Disease

The strain isolated from tomato was inoculated in potato agar medium on the plate ( Botrytis cinerea ), the plate was placed in an incubator at 25 ℃ to incubate for 15 days in the light dark state to form spores. After the spores formed on the medium into the distilled water 10㎖ per plate with a brush scraping the spores harvested by filtering them with spores gaahje and make the spore concentration to be 10 ⁶ / ㎖ was spray inoculated per leaf stage cucumber. This was induced for 3 days in a 20 ° C wet room, and the lesion area ratio of the first lobe was determined.

(Test Example 6)

Bactericidal Effect on Tomato Blight

Phytophthora infestans were inoculated on V-8 juice agar medium (V-8 juice 200 ml, CaCO ₃ 4.5 g, agar 15 g, distilled water 800 ml), light treated at 20 ° C. for 16 hours and dark treated for 8 hours. Spores were harvested after 14 days of incubation. At this time, the sterile distilled water was added to the plate and shaken to separate the zygote sac from the flora, and then the stool sac was filtered using a 4-ply piece of cloth. The concentration of strained strains was adjusted to 10 ⁵ / ml using sterile distilled water, and this inoculum was sprayed with tomato seedlings for 1 day in a 20 ° C. chamber, and then at a temperature of 20 ° C. and a relative humidity of 80% or more. After transferring to the humidity chamber for 4 days, the lesion area ratio of the first and second leaves of the tomato was examined.

The control area was calculated by substituting the lesion area ratios of the treated and control leaves measured in Test Examples 1 to 6 into Equation 1, and the results are shown in Table 9 below using the activity index.

Compound number Wheat Red Rust Wheat flour Rice fever Paddy leaf smear bottle Cucumber gray mold Tomato plague I-1 +++ +++ - - - - I-3 +++ - - - - - I-5 +++ + ++ + + ++ I-13 ++ - - - - - I-15 - +++ +++ - - + I-22 ++ + - - - - I-23 +++ +++ - - - - II-19 +++ - - - + - II-22 + - ++ - ++ - II-23 - - +++ - - - +++: 81 to 100% ++: control 61 to 80% +: 41 to 60% CONTROL-: 40% or less

As shown in Table 9, the compound of the present invention has an excellent bactericidal effect against various plant pathogens, such as wheat red rust disease, barley flour disease, rice fever disease, rice leaf stain disease, cucumber gray mold disease and tomato late blight disease. In particular, it can be seen that it has an excellent effect against wheat rust, barley flour and rice blast.

As described above, the methoxyacrylate or methoxyimino acetate derivative having an oxime substituted with an amino acid and an oxime substituted with an amino acid according to the present invention has a wide range of bactericidal effects against plant pathogens, in particular, rice blast, wheat red Has excellent effects against rust and barley flour. In addition, it is excellent in preventing and treating diseases caused from pathogens as well as invading plants.

Claims (5)

Methoxyacrylate or methoxyimino acetate derivative of the formula [Formula 1] Where R ₁ is hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkylthio- or alkylsulphone-substituted alkyl group, a phenyl group, or a benzyl group; R ₂ is a C ₁ -C ₅ alkyl group; X is benzyloxy, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkyl group, 1 to 3 chloro or fluoro, C ₁ -C ₃ trihaloalkyl group, or C _1-3 alkyl or alkoxy-substituted or substituted Unphenoxy group; Z is CH or N. In the presence of a mixed solvent of an inert organic solvent and water using an acid scavenger and a phase transfer catalyst of the methoxy acrylate or methoxyimino acetate derivative of Manufacturing method. [Formula 1] [Formula 2] [Formula 3] Where R ₁ is hydrogen, a C ₁ -C ₃ alkyl group, a C ₁ -C ₃ alkylthio- or alkylsulphone-substituted alkyl group, a phenyl group, or a benzyl group; R ₂ is a C ₁ -C ₅ alkyl group; X is benzyloxy, C ₁ -C ₃ alkoxy, C ₁ -C ₃ alkyl group, 1 to 3 chloro or fluoro, C ₁ -C ₃ trihaloalkyl group, or C _1-3 alkyl or alkoxy-substituted or substituted Unphenoxy group; Y is Br or Cl; Z is CH or N. The method of claim 2, The use amount of the compound of Formula 3 is 1 to 1.2 equivalents based on the compound of Formula 2. Agrohorticultural fungicide composition containing the compound of formula 1 as an active ingredient. [Formula 1] The method of claim 4, wherein The content of the compound of Formula 1 is 0.01 to 90% by weight of the total horticultural composition for agricultural horticultural fungicides.