CN1309897A - Unsaturated oximino ether bactericide - Google Patents

Abstract

The present invention relates to the bactericidal compound of the unsaturated oxime ether structure of the general formula (I) and its stereoisomer. In the formula, X ₁ -X ₅ are selected from hydrogen, halogen, alkyl, alkoxy, nitro, haloalkyl. Compared with the existing unsaturated oxime ether fungicides, they have better fungicidal activity.

Description

Unsaturated oxime ether fungicides

The invention belongs to agricultural fungicide.

A fungicide with an unsaturated oxime ether structure is reported in Chinese patent publication CN1191670A. These compounds with unsaturated oxime ether structure have broad-spectrum activity—it can be used to prevent and control diseases caused by various fungi such as Phycomycetes, Oomycetes, Ascomycetes and Deuteromycetes on various crops. However, the development of modern agriculture and horticulture requires us to continue to innovate and develop agricultural fungicides with smaller doses and more outstanding efficacy.

In order to obtain effective compounds that can control various fungal diseases at a smaller dose, the inventors have continued to carry out a large amount of research work on the basis of the aforementioned inventions, and synthesized and screened out unsaturated compounds with general formula (I). Compounds with an oxime ether structure. These compounds have broad-spectrum bactericidal activity, and compared with the compounds disclosed in the prior art, they have higher bactericidal activity and good control effect at a lower dosage, thus completing the present invention.

The present invention relates to derivatives of unsaturated oxime ethers useful as fungicides, processes for their preparation and compositions containing these compounds.

The present invention provides unsaturated oxime ether compounds with general formula (I) and stereoisomers thereof:

In the formula, X ₁ -X ₅ are selected from hydrogen, halogen, alkyl, alkoxy, nitro, haloalkyl.

Halogen includes fluorine, chlorine, bromine and iodine.

In the compounds of the present invention, due to the carbon-carbon double bond and the carbon-nitrogen double bond connecting different substituents can form geometric isomers (respectively use E and Z to represent different configurations), and the present invention includes E-type isomers and Z-isomers and mixtures thereof in any proportion.

The present invention can be illustrated by the compounds in Table (I) below, but the present invention is not limited.

Table (I) serial number _{x1 x2 x3 x4 x5} 1 2-Cl 3-H 4-H 5H 6-Cl 2 2-Cl 3-Cl 4-H 5H 6-H 3 2-Cl 3-H 4-Cl 5-H 6-H 4 2-Cl 3-H 4-H 5-Cl 6-H 5 2-H 3-Cl 4-Cl 5-H 6-H 6 2-H 3-Cl 4-H 5-Cl 6-H 7 2-Cl 3-Cl 4-Cl 5-H 6-H 8 2-Cl 3-Cl 4-H 5-Cl 6-H 9 2-Cl 3-Cl 4-H 5-H 6-Cl 10 2-Cl 3-H 4-Cl 5-Cl 6-H 11 2-Cl 3-H 4-Cl 5-H 6-Cl 12 2-H 3-Cl 4-Cl 5-Cl 6-H 13 2-Cl 3-Cl 4-Cl 5-Cl 6-H 14 2-Cl 3-Cl 4-Cl 5-H 6-Cl 15 2-Cl 3-Cl 4-H 5-Cl 6-Cl 16 2-Cl 3-Cl 4-Cl 5-Cl 6-Cl 17 2-F 3-H 4-H 5H 6-F 18 2-F 3-F 4-H 5H 6-H 19 2-F 3-H 4-F 5-H 6-H 20 2-F 3-H 4-H 5-F 6-H twenty one 2-H 3-F 4-F 5-H 6-H twenty two 2-H 3-F 4-H 5-F 6-H twenty three 2-Br 3-H 4-H 5H 6-Br twenty four 2-Br 3-Br 4-H 5H 6-H 25 2-Br 3-H 4-Br 5-H 6-H 26 2-Br 3-H 4-H 5-Br 6-H 27 2-H 3-Br 4-Br 5-H 6-H 28 2-H 3-Br 4-H 5-Br 6-H 29 2-Br 3-Br 4-Br 5-H 6-H 30 2-Br 3-Br 4-H 5-Br 6-H 31 2-Br 3-Br 4-H 5-H 6-Br 32 2-Br 3-H 4-Br 5-Br 6-H 33 2-Br 3-H 4-Br 5-H 6-Br 34 2-H 3-Br 4-Br 5-Br 6-H 35 2-Br 3-Br 4-Br 5-Br 6-H 36 2-Br 3-Br 4-Br 5-H 6-Br 37 2-Br 3-Br 4-H 5-Br 6-Br 38 2-Br 3-Br 4-Br 5-Br 6-Br 39 2-Cl 3-H 4-H 5H 6-F 40 2-Cl 3-F 4-H 5H 6-H 41 2-F 3-Cl 4-H 5H 6-H 42 2-Cl 3-H 4-F 5-H 6-H 43 2-F 3-H 4-Cl 5-H 6-H 44 2-F 3-H 4-H 5-Cl 6-H 45 2-Cl 3-H 4-H 5-F 6-H 46 2-H 3-Cl 4-F 5-H 6-H 47 2-H 3-F 4-Cl 5-H 6-H 48 2-H 3-Cl 4-H 5-F 6-H 49 2-F 3-Cl 4-Cl 5-H 6-H 50 2-Cl 3-F 4-Cl 5-H 6-H 51 2-Cl 3-Cl 4-F 5-H 6-H 52 2-F 3-F 4-Cl 5-H 6-H 53 2-Cl 3-F 4-F 5-H 6-H 54 2-F 3-Cl 4-F 5-H 6-H 55 2-F 3-F 4-F 5-H 6-H 56 2-F 3-Cl 4-H 5-Cl 6-H 57 2-Cl 3-F 4-H 5-Cl 6-H 58 2-Cl 3-Cl 4-H 5-F 6-H 59 2-F 3-F 4-H 5-Cl 6-H 60 2-Cl 3-F 4-H 5-F 6-H 61 2-F 3-Cl 4-H 5-F 6-H 62 2-F 3-F 4-H 5-F 6-H 63 2-F 3-Cl 4-H 5-H 6-Cl 64 2-Cl 3-F 4-H 5-H 6-Cl 65 2-Cl 3-Cl 4-H 5-H 6-F 66 2-F 3-F 4-H 5-H 6-Cl 67 2-F 3-Cl 4-H 5-H 6-F 68 2-Cl 3-F 4-H 5-H 6-F 69 2-F 3-F 4-H 5-H 6-F 70 2-F 3-H 4-Cl 5-Cl 6-H 71 2-Cl 3-H 4-F 5-Cl 6-H 72 2-Cl 3-H 4-Cl 5-F 6-H 73 2-F 3-H 4-F 5-Cl 6-H 74 2-F 3-H 4-Cl 5-F 6-H 75 2-Cl 3-H 4-F 5-F 6-H 76 2-F 3-H 4-F 5-F 6-H 77 2-F 3-H 4-Cl 5-H 6-Cl 78 2-Cl 3-H 4-F 5-H 6-Cl 79 2-F 3-H 4-F 5-H 6-Cl 80 2-F 3-H 4-Cl 5-H 6-F 81 2-F 3-H 4-F 5-H 6-F 82 2-F 3-F 4-H 5-F 6-F 83 2-F 3-F 4-F 5-F 6-F 84 2-Cl 3-H 4-H 5H 6-CH3 85 2-CH3 3-H 4-Cl 5-H 6-Cl 86 2-Cl 3-H 4-CH3 5-H 6-Cl 87 2-CH3 3-H 4-CH3 5-H 6-Cl 88 2-CH3 3-H 4-Cl 5-H 6-CH3 89 2-CH3 3-H 4-CH3 5-H 6-CH3 90 2-Br 3-H 4-Cl 5-H 6-Cl 91 2-Cl 3-H 4-Br 5-H 6-Cl 92 2-Br 3-H 4-Br 5-H 6-Cl 93 2-Br 3-H 4-Cl 5-H 6-Br 94 2-Br 3-H 4-H 5H 6-F 95 2-F 3-H 4-Br 5-H 6-Br 96 2-Br 3-H 4-F 5-H 6-Br 97 2-F 3-H 4-F 5-H 6-Br 98 2-F 3-H 4-Br 5-H 6-F 99 2-Cl 3-H 4-H 5H 6-OCH3 100 2-OCH3 3-H 4-Cl 5-H 6-Cl 101 2-Cl 3-H 4-OCH3 5-H 6-Cl 102 2-OCH3 3-H 4-OCH3 5-H 6-Cl 103 2-OCH3 3-H 4-Cl 5-H 6-OCH3 104 2-Cl 3-H 4-H 5H 6-NO2 105 2-NO2 3-H 4-Cl 5-H 6-Cl 106 2-Cl 3-H 4-NO2 5-H 6-Cl 107 2-NO2 3-H 4-Cl 5-H 6-NO2 108 2-Cl 3-H 4-H 5H 6-CF3 109 2-Cl 3-H 4-CF3 5-H 6-Cl 110 2-Cl 3-Cl 4-CF3 5-H 6-CF3 111 2-F 3-H 4-H 5H 6-CF3 112 2-Cl 3-H 4-H 5H 6-I

The compound of the general formula (I) of the present invention can be prepared by the steps shown in the following reaction formula. wherein X is as defined above and Z is a leaving group such as halogen (chloro, bromo or iodo).

Compounds of general formula (IV) can be prepared by treating general formula (III ) shown in the oxime, and then add the compound of general formula (II).

The oxime of general formula (Ⅲ) can be by corresponding α, β unsaturated ketone and hydroxylamine hydrochloride in suitable solvent (such as methanol or ethanol), and there is the reaction under the existence of suitable base (such as sodium hydroxide or potassium carbonate) get.

European patent application EP254426 describes compounds of general formula (II) in (E) configuration in which Z is bromine.

The compound of the general formula (I) can be easily obtained by reacting the compound of the general formula (IV) with an aqueous solution of methylamine.

The compounds of the present invention are more effective fungicides. They are systemically active and useful as foliar and soil fungicides. Especially suitable for the control of the following plant diseases:

Rice blast (Pyricularia oryzae); wheat stripe rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rusts; barley stripe rust (Puccinia striiformis), leaf rust (Puccinia recandita) and other rusts; barley and wheat powdery mildew, Cucumber powdery mildew, apple powdery mildew and grape powdery mildew.

Wheat sheath blight and glume blight (Septoria nodorum). Helminthias elongatum, Cephalosporium, Septoria, Sclerotinia, Pseudocercosporella herpotrichoides and Gaeumannomyces graminis on cereals. Cercospora arachidicola on peanuts and Cercosporidium personata on sugar beets, soybeans and other Cercospora spp. Tomatoes, cucumbers, Botrytic cinerea. Artichokes on vegetables such as cucumbers. Anthracnose on cucumber, apple scab, downy mildew on cucumber, downy mildew on grape, Phytophthora on potato and tomato, Thanatephorus cucumeris on rice and other Rhizoctonia on other hosts such as wheat and barley, vegetables.

The invention also provides a process for the preparation of a composition as defined above by mixing a compound of general formula (I) and at least one carrier. Such compositions may contain a single compound of the invention or a mixture of several compounds.

The compositions according to the invention preferably contain from 1 to 99% by weight of active ingredient. The carrier of the present invention is a substance that satisfies the following conditions: it can be conveniently applied to the locus to be treated after being formulated with the active ingredient, for example, it can be a plant, seed or soil; or it can be convenient for storage, transportation or handling. The carrier may be solid or liquid, including substances that are usually gaseous but compressed into liquid, and any carrier commonly used in formulating insecticidal and fungicidal compositions may be used.

Suitable solid carriers include natural and synthetic clays and silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite and mica, calcium carbonate, calcium sulfate, ammonium sulfate; Silicon and synthetic calcium or aluminum silicates; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl chloride and styrene polymers and copolymers; solid polychlorinated phenols; bitumen; waxes such as Beeswax, paraffin.

Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexyl ketone; ethers; aromatic hydrocarbons such as benzene, toluene, and xylene; and mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchlorethylene and trichloroethane. Often, mixtures of these liquids are also suitable.

Insecticidal and fungicidal compositions are usually diluted prior to application. The presence of a small amount of surfactant carrier aids in the dilution process. In the composition of the present invention, at least one carrier is contained, preferably a surfactant is used as the carrier. For example the composition may contain at least two carriers, at least one of which is a surfactant.

A surfactant can be an emulsifying agent, a dispersing agent or a wetting agent; it can be a nonionic or an ionic surfactant. Suitable surfactants include sodium or calcium salts of polyacrylic acid and lignosulfonic acid; condensation products of fatty acids or fatty amines or amides with at least 12 carbon atoms in the molecule and ethylene oxide and/or propylene oxide; Glycol, sorbitol, sucrose or pentaerythritol fatty acid esters and condensates of these esters with ethylene oxide and/or propylene oxide; fatty alcohols or alkylphenols such as p-octylphenol or p-octylcresol with epoxy Condensates of ethane and/or propylene oxide; sulfates or sulfonates of these condensation products; alkali metal or alkaline earth metal salts, preferably sodium salts, of sulfuric acid or sulfonates containing at least 10 carbon atoms in the molecule; For example sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium sulfonated castor oil, sodium alkylaryl sulfonate such as sodium dodecylbenzenesulfonate.

Examples of compositions according to the invention are wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. Wettable powders usually contain 25, 50 or 75% (by weight) of active ingredient, and usually contain 3-10% (by weight) of dispersant in addition to solid inert carrier, and 0-10% (by weight) can be added if necessary. ) stabilizers and/or other additives such as penetrants or adhesives. Dusts are usually formulated as powder concentrates having a composition similar to wettable powders but without dispersants, which are further diluted in the field with solid carriers to give compositions usually containing 0.5-10% by weight of active ingredient. Granules are typically prepared in sizes of 10 and 100 mesh (1.676-0.152 mm), and may be prepared by agglomeration or injection techniques. Typically, granules contain 0.5-75% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, slow-release modifiers. So-called "dry flowable powders" consist of relatively small granules having a relatively high concentration of active ingredient. Emulsifiable concentrates usually contain, in addition to solvents, co-solvents when required, 1-50% W/V active ingredients, 2-20% W/V emulsifiers and 0-20% W/V other additives such as stabilizers, penetrants Agents and corrosion inhibitors, suspension concentrates usually contain 10-75% (weight) of active ingredients, 0.5-15% (weight) of dispersants, 0.1-10% (weight) of other additives such as antifoaming agents, corrosion inhibitors agent, stabilizer, penetrant and adhesive.

Aqueous dispersions and emulsions, such as compositions obtained by diluting the wettable powders or concentrates according to the invention with water, are also within the scope of the invention. Said emulsions may be of the water-in-oil or oil-in-water type.

By adding one or more other fungicides to the composition, it can have a wider spectrum of activity than the compound of general formula (I) alone. In addition, other fungicides may have a synergistic effect on the fungicidal activity of the compounds of general formula (I). Examples of fungicide compounds that may be included in the compositions of the present invention are: myclobutanil, triclofenac, benomyl, carbendazim, chlorothalonil, king copper, Bordeaux mixture, fennel, biguanide octyl salt, soil fungus Xiao, Fuji No. 1, Kasugamycin, Mancozeb, Maneb, Zinc, Doxymycin, Zinc Methyl, Thioprazine Methyl, Thiram, Tridemorph, Dienoyl phylloline etc.

Suitable insecticides which may be mixed with the compounds of the present invention to form compositions include dimethoate, omethoate, chlorpyrifos, chlorpyrifos-methyl, methamidophos, monocrotophos, fenthion, phoxim, pyraflucarb, imidacloprid And pyrethroids such as fenvalerate, fenpropathrin, fluvalinate, cyhalothrin, etc.

Compared with the unsaturated oxime ether fungicides disclosed in the prior art, the compound of the present invention has better fungicidal activity. The compounds in the Chinese Patent Publication CN1191670A are effective when the concentration of the compound to be tested is 100 mg/L in the control effect test of various fungal diseases; and the compounds provided by the present invention are 1/4 or even 1 /16, its bactericidal activity is still much better than the reference compound. This excellent bactericidal effect has enabled the inventors of the present invention to achieve the purpose of inventing an effective compound that can control various fungal diseases at a smaller dose, and has completed another step in the field of unsaturated oxime ether fungicides. an important invention.

The present invention is illustrated below with specific examples, but the present invention is not limited.

Synthetic example

Synthesis of Example 1 Compound 1

17.5 g (0.1 mole) of 2,6-dichlorobenzaldehyde was dissolved in 100 ml of acetone, and 5 g of 10% aqueous sodium hydroxide solution was added dropwise thereto, and the temperature was kept not exceeding 40° C. during the dropwise addition. Stirring was continued for one hour after the dropwise addition. The mixture was poured into water, extracted with ethyl acetate, washed with water three times, dried and concentrated to obtain 20.4 g of a light yellow oily substance, namely 2,6-dichlorostyryl methyl ketone, with a yield of 94.9%.

10 g (0.0465 mol) of 2,6-dichlorostyryl methyl ketone, 7.77 g of hydroxylamine hydrochloride (0.093 mol) and 12.9 g (0.093 mol) of potassium carbonate were refluxed in 150 ml of ethanol for 3 hours. The reaction mixture was concentrated, diluted with water and extracted with ethyl acetate. The combined extracts were dried and concentrated to obtain 9.3 g of 2,6-dichlorostyryl methyl ketone oxime as a light yellow solid. Yield 86.93%.

At room temperature, 2.3 g (0.01 mol) of 2,6-dichlorostyryl methyl ketoxime in N,N-dimethylformamide (10 ml) was added dropwise to 0.4 g (0.01 mol) of Sodium N,N-dimethylformamide suspension (10 mL). Half an hour later, a solution of 2.86 g (0.01 mol) of (E)-methyl 2-(bromomethyl)benzoylformate-O-methyloxime in N,N-dimethylformamide (10 ml) was added to Stirring of the reaction mixture was continued at room temperature for 2 hours. The mixture was poured into water and extracted twice with ethyl acetate. The combined extracts were washed 3 times with water, then dried and concentrated to obtain a crude product. Column chromatography was performed using a mixture of ethyl acetate and petroleum ether (1:5) as the eluent to obtain 1.28 g of light yellow oil, with a yield of 29.43%.

0.75 g (0.00172 moles) of the above compound and 40% aqueous solution of methylamine in a molar ratio of 3 times were heated to reflux overnight in 50 ml of methanol, extracted twice with ethyl acetate after concentration, the combined extracts were washed with water three times, and then dried , and concentrated to obtain 0.55 g of the title compound as a white solid with a yield of 73.3%. Melting point 131-133°C

NMR data: 2.03 (3H unimodal) 2.82-2.87 (3H bimodal) 3.87 (3H unimodal) 4.97 (2H unimodal) 6.5-6.6 (1H multimodal) 6.71 (2H unimodal) 6.80-7.50 (7H multimodal peak)

Example 2 Synthesis of compound 2

17.5 grams (0.1 moles) of 2,3-dichlorobenzaldehyde were dissolved in 100 milliliters of acetone, and 5 grams of 10% sodium hydroxide aqueous solution was added dropwise, and the temperature was kept no more than 40 ° C during the dropping process, and then continued to stir One hour. The mixture was poured into water, extracted with ethyl acetate, washed with water three times, dried and concentrated to obtain 20.2 g of light yellow oily 2,3-dichlorostyryl methyl ketone, with a yield of 93.9%.

10 g (0.0465 mol) of 2,3-dichlorostyryl methyl ketone, 7.77 g of hydroxylamine hydrochloride (0.093 mol) and 12.9 g (0.093 mol) of potassium carbonate were refluxed in 150 ml of ethanol for 3 hours. The reaction mixture was concentrated, diluted with water and extracted with ethyl acetate. The combined extracts were dried and concentrated to obtain 9.5 g of 2,3-dichlorostyryl methyl ketone oxime as a light yellow solid with a yield of 88.8%.

At room temperature, 2.3 g (0.01 mol) of 2,3-dichlorostyryl methyl ketoxime in N,N-dimethylformamide (10 ml) was added dropwise to 0.4 g (0.01 mol) of hydroxide Sodium N,N-dimethylformamide suspension (10 mL). Half an hour later, a solution of 2.86 g (0.01 mol) of (E)-methyl 2-(bromomethyl)benzoylformate-O-methyloxime in N,N-dimethylformamide (10 ml) was added to Stirring of the reaction mixture was continued at room temperature for 2 hours. The mixture was poured into water and extracted twice with ethyl acetate. The combined extracts were washed 3 times with water, then dried and concentrated to obtain a crude product. Column chromatography was performed using a mixture of ethyl acetate and petroleum ether (1:5) as the eluent to obtain 1.38 g of light yellow oil, with a yield of 31.73%.

0.75 g (0.00172 moles) of the above compound and 40% aqueous solution of methylamine in a 3-fold molar ratio were heated to reflux overnight in 50 ml of methanol, extracted twice with ethyl acetate after concentration, and the combined extracts were washed three times with water, and then dried , and concentrated to obtain 0.65 g of the title compound as viscous oil with a yield of 86.63%.

NMR data: 2.04 (3H unimodal) 2.82-2.87 (3H bimodal) 3.89 (3H unimodal) 5.01 (2H unimodal) 6.5-6.6 (1H multimodal) 6.70 (2H unimodal) 6.80-7.50 (7H multimodal peak)

Example 3 Synthesis of compound 3

17.5 grams (0.1 moles) of 2,4-dichlorobenzaldehyde were dissolved in 100 milliliters of acetone, and 5 grams of 10% sodium hydroxide aqueous solution was added dropwise thereto, and the temperature was kept no more than 40°C during the dropping process, and then continued to stir for a while. Hour. The mixture was poured into water, extracted with ethyl acetate, washed with water three times, dried and concentrated to obtain 20.6 g of light yellow oily 2,4-dichlorostyryl methyl ketone with a yield of 95.8%.

10 g (0.0465 mol) of 2,4-dichlorostyryl methyl ketone, 7.77 g of hydroxylamine hydrochloride (0.093 mol) and 12.9 g (0.093 mol) of potassium carbonate were refluxed in 150 ml of ethanol for 3 hours. The reaction mixture was concentrated, diluted with water and extracted with ethyl acetate. The combined extracts were dried and concentrated to obtain 9.1 g of 2,4-dichlorostyryl methyl ketone oxime as a light yellow solid with a yield of 85.06%.

At room temperature, 2.3 g (0.01 mol) of 2,4-dichlorostyryl methyl ketoxime in N,N-dimethylformamide solution (10 ml) was added dropwise to 0.4 g (0.01 mol) of hydroxide Sodium N,N-dimethylformamide suspension (10 mL). Half an hour later, a solution of 2.86 g (0.01 mol) of (E)-methyl 2-(bromomethyl)benzoylformate-O-methyloxime in N,N-dimethylformamide (10 ml) was added to Stirring of the reaction mixture was continued at room temperature for 2 hours. The mixture was poured into water and extracted twice with ethyl acetate. The combined extracts were washed 3 times with water, then dried and concentrated to obtain a crude product. Column chromatography was performed using a mixture of ethyl acetate and petroleum ether (1:5) as the eluent to obtain 1.35 g of light yellow oil, with a yield of 31.04%.

0.75 g (0.00172 moles) of the above compound and 40% aqueous solution of methylamine in a molar ratio of 3 times were heated to reflux overnight in 50 ml of methanol, extracted twice with ethyl acetate after concentration, the combined extracts were washed with water three times, and then dried , and concentrated to obtain 0.63 g of the title compound as viscous oil with a yield of 83.96%.

NMR data: 2.03 (3H unimodal) 2.82-2.87 (3H bimodal) 3.88 (3H unimodal) 5.01 (2H unimodal) 6.4-6.6 (1H multimodal) 6.68 (2H unimodal) 6.75-7.50 (7H multimodal peak)

Example 4 Synthesis of compound 17

14.2 grams (0.1 moles) of 2,6-difluorobenzaldehyde were dissolved in 100 milliliters of acetone, and 5 grams of 10% sodium hydroxide aqueous solution was added dropwise, and the temperature should be kept no more than 40°C during the dropping process, and the stirring was continued One hour. The mixture was poured into water, extracted with ethyl acetate, washed with water three times, dried and concentrated to obtain 15.7 g of light yellow oily 2,6-difluorostyryl methyl ketone, with a yield of 86.26%.

8.46 g (0.0465 mol) of 2,6-difluorostyryl methyl ketone, 7.77 g of hydroxylamine hydrochloride (0.093 mol) and 12.9 g (0.093 mol) of potassium carbonate were refluxed in 150 ml of ethanol for 3 hours. The reaction mixture was concentrated, diluted with water and extracted with ethyl acetate. The combined extracts were dried and concentrated to obtain 7.91 g of 2,6-difluorostyryl methyl ketone oxime as a light yellow solid. Yield 86.37%.

At room temperature, 1.97 g (0.01 mol) of 2,6-difluorostyryl methyl ketoxime in N,N-dimethylformamide solution (10 ml) was added dropwise to 0.4 g (0.01 mol) of hydroxide Sodium N,N-dimethylformamide suspension (10 mL). Half an hour later, a solution of 2.86 g (0.01 mol) of (E)-methyl 2-(bromomethyl)benzoylformate-O-methyloxime in N,N-dimethylformamide (10 ml) was added to Stirring of the reaction mixture was continued at room temperature for 2 hours. The mixture was poured into water and extracted twice with ethyl acetate. The combined extracts were washed 3 times with water, then dried and concentrated to obtain a crude product. Column chromatography was performed using a mixture of ethyl acetate and petroleum ether (1:5) as the eluent to obtain 1.18 g of light yellow oil, with a yield of 29.35%.

0.75 g (0.00186 moles) of the above compound and 40% aqueous solution of methylamine in a 3-fold molar ratio were heated to reflux overnight in 50 ml of methanol, extracted twice with ethyl acetate after concentration, and the combined extracts were washed with water three times, then dried , and concentrated to obtain 0.51 g of the title compound as viscous oil with a yield of 68.17%.

NMR data: 2.01 (3H unimodal) 2.82-2.88 (3H bimodal) 3.87 (3H unimodal) 4.97 (2H unimodal) 6.6-7.40 (10H multimodal)

Example 5 Synthesis of compound 39

15.8 grams (0.1 moles) of 2-chloro-6-fluorobenzaldehyde were dissolved in 100 milliliters of acetone, and 5 grams of 10% aqueous sodium hydroxide solution was added dropwise thereto, and the temperature was kept no more than 40°C during the dropping process, and then continued to stir One hour. The mixture was poured into water, extracted with ethyl acetate, washed with water three times, dried and concentrated to obtain 15.7 g of light yellow oily 2-chloro-6-fluorostyryl methyl ketone, with a yield of 79.34%.

9.23 g (0.0465 mol) of 2-chloro-6-fluorostyryl methyl ketone, 7.77 g of hydroxylamine hydrochloride (0.093 mol) and 12.9 g (0.093 mol) of potassium carbonate were refluxed in 150 ml of ethanol for 3 hours. The reaction mixture was concentrated, diluted with water and extracted with ethyl acetate. The combined extracts were dried and concentrated to obtain 8.38 g of 2-chloro-6-fluorostyryl methyl ketone oxime as a pale yellow solid. Yield 84.41%.

At room temperature, 2.14 g (0.01 mol) of 2-chloro-6-fluorostyryl methyl ketoxime in N,N-dimethylformamide solution (10 ml) was added dropwise to 0.4 g (0.01 mol) hydrogen Sodium oxide in N,N-dimethylformamide suspension (10 mL). Half an hour later, a solution of 2.86 g (0.01 mol) of (E)-methyl 2-(bromomethyl)benzoylformate-O-methyloxime in N,N-dimethylformamide (10 ml) was added to The reaction mixture was stirred at room temperature for 2 hours. The mixture was poured into water and extracted twice with ethyl acetate. The combined extracts were washed 3 times with water, then dried and concentrated to obtain a crude product. Column chromatography was performed using a mixture of ethyl acetate and petroleum ether (1:5) as the eluent to obtain 1.24 g of light yellow oil, with a yield of 29.63%.

0.75 g (0.00179 moles) of the above compound and 40% aqueous solution of methylamine in a 3-fold molar ratio were heated to reflux overnight in 50 ml of methanol, extracted twice with ethyl acetate after concentration, and the combined extracts were washed three times with water, then dried , and concentrated to obtain 0.59 g of the title compound as viscous oil with a yield of 78.85%.

NMR data: 2.02 (3H unimodal) 2.83-2.88 (3H bimodal) 3.87 (3H unimodal) 4.97 (2H unimodal) 6.4-7.40 (10H multimodal)

recipe example

Example 6

10 parts (weight) of compound 1 were dissolved in the following mixture containing 90 parts (weight) of xylene, 6 parts (weight) of nonylphenol ethoxylates, 2 parts (weight) of dodecyl An emulsifiable concentrate was prepared from calcium benzenesulfonate and 2 parts by weight of the addition product of 40 moles of ethylene oxide and 1 mole of castor oil (active compound content 9%).

Bioassay example

Example 7

Some compounds were tested for bactericidal activity. The method is as follows: the test compound is dissolved in a 1:1 mixture of acetone and methanol, and then diluted to a desired concentration with a 2:1:1 mixture of water, acetone and methanol (volume ratio). This solution was sprayed on the plants to be tested and allowed to dry for 2 hours, and inoculated with pathogens one day later. The activity is calculated as a percentage relative to the blank control, and is divided into four grades: A, B, C, and D. The control rate is 90%-100% for grade A, the control rate for 75%-90% is grade B, and the control rate is 50%-75%. It is grade C, and the control rate is 0%-50% is grade D

Cucumber powdery mildew

Inoculate one day after application. Place them in the greenhouse for about 7 days after inoculation for investigation. The test results are shown in Table (2)

Table 2) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 D. 6 D. Comparative compound 2(5) 25 D. 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 C 6 D. Comparative compound 6(7) 25 D. 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 D. 6 D. Comparative compound 10(13) 25 D. 6 D. Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 D. 6 D. Comparative compound 13(40) 25 D. 6 D. Comparative compound 14(42) 25 D. 6 D. Comparative compound 15(45) 25 D. 6 D. CK - o - -

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

At a concentration of 25 mg/l, the control rate of the compound of the present invention is A grade, and only the control rate of compound 5 is C grade in the reference compound, and all the others are D grade; at a concentration of 6 mg/l, the control rate of the compound of the present invention Class A, all control compounds are basically ineffective. It can be seen from the test results that the compound of the invention has good control effect on cucumber powdery mildew, which is obviously better than that of the reference compound.

rice blast

Inoculate one day after application. After inoculation, keep it moist in the humidity box for 36 hours to facilitate infection, move it into the greenhouse, and investigate after about 7 days. The test results are shown in Table (3)

table 3) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 B 6 D. Comparative compound 2(5) 25 C 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 C 6 D. Comparative compound 6(7) 25 D. 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 B 6 C Comparative compound 10(13) 25 B 6 D. Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 C 6 C Comparative compound 13(40) 25 B 6 D. Comparative compound 14(42) 25 D. 6 D. Comparative compound 15(45) 25 D. 6 D. CK - o

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

Under the 25mg/l concentration, the control rate of the compound of the present invention is A grade, and all contrast compound control rates are all below B grade; Under the 6mg/l concentration, the compound control rate of the present invention is A grade, and all contrast Compounds are largely ineffective. It can be seen from the test results that the compound of the invention has good control effect on rice blast, which is obviously better than that of the reference compound.

Cucumber Botrytis

Inoculate one day after application. After inoculation, place it in a constant temperature and humidity box for about 5 days and then investigate. The test results are shown in Table (4)

Table 4) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 D. 6 D. Comparative compound 2(5) 25 B 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 D. 6 D. Comparative compound 6(7) 25 C 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 D. 6 D. Comparative compound 10(13) 25 B 6 C Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 D. 6 D. Comparative compound 13(40) 25 C 6 C Comparative compound 14(42) 25 B 6 D. Comparative compound 15(45) 25 B 6 C CK 25 D. 6 D.

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

Under the 25mg/l concentration, the control rate of the compound of the present invention is A grade, and all contrast compound control rates are all below B grade; Under the 6mg/l concentration, the compound control rate of the present invention is A grade, and all contrast The compounds are all below grade C. It can be seen from the test results that the control effect of the compound of the invention on cucumber gray mold is obviously better than that of the reference compound. wheat leaf rust

Inoculate one day after application. After inoculation, it was placed in the greenhouse for about 10 days and then investigated. The test results are shown in Table (5)

table 5) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 B 6 C Comparative compound 2(5) 25 C 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 C 6 D. Comparative compound 6(7) 25 D. 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 B 6 D. Comparative compound 10(13) 25 B 6 D. Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 B 6 D. Comparative compound 13(40) 25 B 6 D. Comparative compound 14(42) 25 B 6 D. Comparative compound 15(45) 25 D. 6 D. CK - o

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

Under the 25mg/l concentration, the control rate of the compound of the present invention is A grade, and all contrast compound control rates are all below B grade; Under the 6mg/l concentration, the compound control rate of the present invention is A grade, and all contrast Compounds are largely ineffective. It can be seen from the test results that the control effect of the compound of the invention on wheat leaf rust is obviously better than that of the reference compound. wheat powdery mildew

Inoculate one day after application. After inoculation, they were placed in the greenhouse for about 7 days and then investigated. The test results are shown in Table (6)

Table (6) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 C 6 D. Comparative compound 2(5) 25 C 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 B 6 D. Comparative compound 6(7) 25 D. 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 B 6 C Comparative compound 10(13) 25 B 6 D. Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 C 6 D. Comparative compound 13(40) 25 B 6 D. Comparative compound 14(42) 25 D. 6 D. Comparative compound 15(45) 25 D. 6 D. CK - o

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

Under the 25mg/l concentration, the control rate of the compound of the present invention is A grade, and all contrast compound control rates are all below B grade; Under the 6mg/l concentration, the compound control rate of the present invention is A grade, and all contrast Compounds are largely ineffective. It can be seen from the test results that the compound of the invention has good control effect on wheat powdery mildew, which is obviously better than that of the reference compound. Cucumber Anthracnose

Inoculate one day after application. After inoculation, they were placed in the greenhouse for about 7 days and then investigated. The test results are shown in Table (7)

Table (7) compound Concentration (mg/l) active Concentration (mg/l) active 1 25 A 6 A 17 25 A 6 A 39 25 A 6 A Control compound 1(4) 25 B 6 C Comparative compound 2(5) 25 C 6 D. Comparative compound 3(6) 25 D. 6 D. Comparative compound 4(10) 25 D. 6 D. Comparative compound 5(2) 25 C 6 C Comparative compound 6(7) 25 D. 6 D. Comparative compound 7(9) 25 D. 6 D. Comparative compound 8(11) 25 D. 6 D. Comparative compound 9(12) 25 B 6 D. Comparative compound 10(13) 25 B 6 D. Comparative compound 11(19) 25 D. 6 D. Comparative compound 12(23) 25 B 6 D. Comparative compound 13(40) 25 B 6 D. Comparative compound 14(42) 25 B 6 B Comparative compound 15(45) 25 D. 6 D. CK - o

*The reference compound is the compound in CN1191670A, and the number in the patent compound table is in the brackets.

At a concentration of 25 mg/l, the control rate of the compound of the present invention is A grade, and all control compounds are below the B grade; at a concentration of 6 mg/l, the control rate of the compound of the present invention is A grade, only the control compound The control rate of 14 was grade B, and all other control compounds were basically ineffective. It can be seen from the test results that the compound of the invention has good control effect on cucumber anthracnose, which is obviously better than that of the reference compound.

Claims (9)

1, unsaturated oximino ether bactericide is characterized in that the present invention has the unsaturated oxime ether structure and the stereoisomer thereof of general formula (I):

X in the formula ₁-X ₅Be selected from hydrogen, halogen, alkyl, alkoxyl, nitro, alkylhalide group.

Halogen comprises fluorine, chlorine, bromine and iodine.

2, compound according to claim 1 is characterized in that: X in the formula (I) ₁-X ₅Have at least two to be selected from halogen, alkyl, alkoxyl, nitro, alkylhalide group.

3, compound according to claim 1 and 2 is characterized in that: X in the formula (I) ₁, X ₅Be selected from halogen, X ₂-X ₄Be selected from hydrogen, halogen, alkyl, alkoxyl, nitro, alkylhalide group.

4, compound according to claim 1 and 2 is characterized in that: X in the formula (I) ₁, X ₅Be selected from halogen, X ₂-X ₄Be hydrogen.

5, compound according to claim 4 is characterized in that: X in formula (I) ₁, X ₅Be chlorine, X ₂-X ₄During for hydrogen, described compound is N-methyl 2-[2-((((1-methyl-3-(2 ', 6 '-dichlorophenyl)-2-acrylic) amino) oxygen base) methyl) phenyl]-2-methoxyl group imido grpup acetamide, structural formula is:

6, compound according to claim 4 is characterized in that: X in formula (I) ₁Be chlorine, X ₂-X ₄Be hydrogen, X ₅During for fluorine, described compound is N-methyl 2-[2-((((1-methyl-3-(2 '-chloro-6 '-fluorophenyl)-2-acrylic) amino) oxygen base) methyl) phenyl]-2-methoxyl group imido grpup acetamide, structural formula is:

7, compound according to claim 4 is characterized in that: X in formula (I) ₁, X ₅Be fluorine, X ₂-X ₄During for hydrogen, described compound is N-methyl 2-[2-((((1-methyl-3-(2 ', 6 '-difluorophenyl)-2-acrylic) amino) oxygen base) methyl) phenyl]-2-methoxyl group imido grpup acetamide, structural formula is:

8, a kind of microbicide compositions is characterized in that: it is that active component and other agricultural go up acceptable carrier or thinner that said composition contains the compound described in the claim 1.

9, the compound of general formula of the present invention (I) or its preparation can be used for preventing and treating on various crops by multiple fungus-caused diseases such as Phycomycetes, Oomycete, Ascomycetes and deuteromycetes.