AU2004224838A1 - Fungicides containing methoxy acrylic acid methyl ester compound - Google Patents

Description

Statement I, Shuzhen ZHANG of Beijing Sunhope Intellectual Property Ltd. state that I am the translator of the English language document attached hereto and the said document is a true translation of the specification of international application PCT/CN2004/000226 filed on 19 March 2003. Signed: S hen A Date: 0 S MI Fungicides Containing Methoxy Acrylic Acid Methyl Ester Compound Field of the Invention The present invention relates to a fungicide of methoxy acrylic acid methyl ester, i.e. methyl methoxyacrylate, for agricultural use. More specifically, the present invention relates to a methyl methoxyacrylate compound having excellent fungicidal action, a process for producing it, a composition containing it, and its use as fungicides. Background Art US 4,914,128 have disclosed some methyl methoxyacrylate compounds, furthermore, the fungicidal action thereof has also been disclosed. The present inventors discovered unexpectedly that some compounds represented by the general formula disclosed in US 4,914,128 have extremely high fungicidal action, but their molecular structure are not definitely disclosed. Based on these, the present invention has completed. Methyl methoxyacrylate fungicides are highly effective fungicides for agricultural use, which are obtained by structural modification of the natural compounds. These fungicides exhibit a broad-spectrum fungicidal action, lower biological toxicity and better environmental compatibility. Many companies have researched and discovered several methyl methoxyacrylate fungicides with promising market. This kind of fungicide occupied more and more market shares and was supposed to become the dominating alternative species of triazole fungicides. Summary of the Invention The invention relates to novel methyl methoxyacrylate compound and its preparation methods, to a fungicidal compositions containing the methyl methoxyacrylate and its use as fungicides. The chemical name of methyl methoxyacrylate compound as fungicide is: methyl

I

(E)-2-(2-((2,5-dimethylphenoxy)methylphenyl))-3-methoxyacrylate represented by the following formula: CHC

H

3 C CH3 0 - CH 3 I The compound of the present invention can be prepared by following processes: Process 1 Compound I can be prepared by the following reaction: alkali

CH

3

-

+ 0 0-~~o0

CH

3 0 0. CH el3 C H2 O C H, 3 II III I Compound II can be prepared by following procedures: 2,5-dimethylphenol of formula II and methyl 2 -(2-halomethylphenyl)-3-methoxyacrylate of formula III are added to a suitable solvent, and then a suitable alkali is added, at an appropriate temperature, the mixture reacts for an appropriate period of time to obtain compound I, in which X represents leaving group such as halogen, preferably chlorine, bromine or iodine. Solvent which can be preferably used is acetone or tetrahydrofuran. Said alkali can be organic base or inorganic base. Specific examples of the organic base include triethylamine and pyridine etc., and specific examples of the organic base include sodium hydroxide, potassium hydroxide, sodium hydride, 2 sodium carbonate and potassium carbonate etc. The alkali preferably used in the present invention is sodium carbonate or potassium carbonate. The temperature range preferably used in the above-mentioned reaction is about 0-~100 0 C. Process 2 Compound I can be prepared by the following reactions: alkali Hz + o CH H3 C- H3C ' II IV V C H 3 o e C H 3 C H CO O C H , 0 m eihylating . agent ff' .

alkali H0 1 0. alkali 0 0

CH

3 H 3 C 0

CH

3 ° OC H , O , TH 3 VI I. Compound I can be prepared by the following procedures: 2,5-dimethylphenol of formula II and compound of formula IV are added into a suitable solvent, then an appropriate alkali is added, the mixture reacts for an appropriate period of time at an appropriate temperature to obtain V. In compound IV, X represents leaving group such as halogen, preferably chlorine, bromine or iodine. Suitable alkali and an appropriate amount of methyl formate are respectively added into a solution of V in a suitable solvent. At an appropriate temperature, the mixture reacts for an appropriate period of time to obtain Compound VI. Methylating agent such as dimethyl sulfate or iodomethane etc. is added into a solution of VI in a suitable solvent, followed by adding a suitable alkali. At an appropriate temperature, the mixture reacts for an appropriate period of time to obtain compound I. When producing V, solvent preferably used is acetone and tetrahydrofuran. Said 3 alkali can be organic base or inorganic base. Specific examples of the organic base include triethylamine and pyridine etc., and specific examples of the organic base include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate and potassium carbonate etc. The alkali preferably used in the present invention is sodium carbonate or potassium carbonate. The temperature range preferably used in the reaction is about 0-1 00 0 C. When producing VI, alkali preferably used is sodium methoxide or sodium hydride etc.; solvent preferably used is ether or methanol. The temperature range preferably used in the reaction is about -5-100* C. When producing I, solvent preferably used is acetone or tetrahydrofuran. Said alkali can be organic base or inorganic base. Specific examples of the organic base include triethylamine and pyridine etc., and specific examples of the organic base include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate and potassium carbonate etc. The alkali preferably used in the present invention is sodium carbonate or potassium carbonate. The temperature range preferably used in the reaction is about 0-100 0 C. Compound I of the present invention is an effective fungicide, which is especially effective for controlling the following plant diseases: powdery mildew of wheat and barley, powdery mildew of vegetables, powdery mildew of melons, powdery mildew of fruit trees, powdery mildew of grape, powdery mildew of strawberry, and powdery mildew of flowers; stripe rust, leaf rust and other rust diseases of wheat and barley; downy mildew of cucumber, downy mildew of grape; anthracnose of melons, etc. The invention also provided a fungicidal composition comprising the above-defined compound and the preparation processes thereof. The composition of the invention preferably contains 0.1-99.0% by weight active ingredient of formula I, and suitable carriers and/or surfactants. Process for producing the composition according to the present invention is 4 mixing compound I with at least one carrier. The composition can also contain other active ingredient of pesticides. The carriers of the present invention can be substances that satisfy the following conditions: after mixing the carriers with active ingredient(s), the composition formed are conveniently used to the locations need to be treated, for example, the locations can be plant, seed or soil; or the composition can be advantageous for storing, shipping or operation. Carriers can be solid or liquid, and can be any carrier which is conventionally used in the composition of pesticides and bactericides. Suitable solid carriers include natural and synthetic silicates such as diatomaceous earth, talc, attapulgite, aluminum silicate (kaolin), montmorillonite, and mica; calcium carbonate, calcium sulfate, ammonium sulfate; synthetic oxidized calcium silicate or oxidized aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resin, polyvinyl chloride and styrene polymer and copolymer; solid polychlorophenol; asphalt; waxes such as beeswax, paraffin. Suitable liquid carriers include water; alcohols such as isopropyl alcohol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether; aromatic hydrocarbons such as benzene, toluene, xylene; petroleum fractions such as kerosene and mineral oil; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene and trichloroethane. Generally, the mixture thereof are also appropriate. The composition with other pesticides and bactericides are usually manufactured in concentrated form for shipping convenience. Users should dilute the composition before use. Small amount of surfactant as carrier is helpful for dilution. Therefore, the composition of the present invention preferably contain surfactant. Said surfactant can be emulsifier, dispersant or wetting agent: it can be ionic surfactants or nonionic surfactants such as sodium salt or calcium salt of 5 polyacrylic acid and lignosulfonic acid; fatty acid or fatty amine or amide having at least 12 carbon atoms; condensation compounds of ethylene oxide and/or propylene oxide; fatty acid ester of glycol, sorbitol, sucrose or pentaerythritol, and the condensation compounds thereof with ethylene oxide and/or propylene oxide; fatty alcohol or alkyl phenol such as paraoctyl phenol or the condensation compounds thereof with propylene oxide and/or ethylene oxide; sulfate or sulfonate of the above-mentioned condensation compounds; alkali metal or alkaline earth metal salts of sulfate or sulfonate having at least 10 carbon atoms, and sodium salts such as sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium salt of sulfonated castor oil, sodium salt of alkyl aryl sulfonate such as sodium dodecyl benzene sulfonate are preferable. The specific examples of the composition according to the present invention can be wettable powders, dusts, granules, emulsifiable concentrates, emulsions, suspension concentrates, smoke aerosols and aerosols. Said wettable powders usually contain 20-80wt% active ingredient, and usually contain 2~-10wt% dispersant in addition to solid inert carriers, and adding 0- 10wt% stabilizer and/or other additives such as penetrant or agglutinant if necessary. Said dusts are usually manufactured into dust concentrates and the compositions thereof are similar to the wettable powders except for the existence of dispersant, the dust concentrates can be further diluted with solid carriers in the field before its use, and the compositions obtained by dilution usually contain 0.5- 10wt% active ingredients. Said granules are usually manufactured into 10-100 screen mesh by using conglobation or infusion technology. Said granules usually contain 0.1 80wt% active ingredient and 0 - 10 Owt% other additives such as stabilizer, surfactant, slow release agent etc. Said "flowable dry powder" contains the smaller granules with the relatively higher concentration of the active ingredient. Said emulsifiable concentrates usually contain 1-50% w/v active ingredient, 2-20% w/v emulsifier and 0-20% w/v other additives such as stabilizer, penetrant and corrosion inhibitor in addition to solvent, and may contain cosolvent if necessary. Said suspension concentrates usually contain 10-80wt% active ingredient, 0.5- 15wt% dispersant, 0.1 - 10 Owt% other additives such as defoamer, corrosion inhibitor, stabilizer, penetrant and agglutinant. 6 For water dispersants and emulsions, for example, the compositions obtained by diluting the wettable powders or the concentrates according to the present invention with water are also included in the scope of the present invention. Said emulsions can be W/O-emulsion or O/W-emulsion. A compositions with a boarder-spectrum fungicidal action than that of compound (I) alone are obtained by adding other one or more fungicides thereto. In addition, other fungicides can produce synergism to the fungicidal action of compound (I). Specific examples of the compounds as fungicides which can be added in the compositions of the present invention are captan, thiophal, pyrimethanil, tridemorph, fenarimol, fludioxonil, cuprous oxide, difenoconazole, zineb, mancozeb, thiram, difolatan, iprodione, methyl-dichlozoline, hexaconazole, tebuconazole, pencycuron, cymoxanil, myclobutanil, guazatine acetate, prothiocarb, cyclafuramid, flumorph, flusilazole, SSF-129, picoxystrobin, metrafenone, pyraclostrobin, resveratro, dimoxystrobin, UBF-307, BASF490F, ICIA5504, TH-164, RH7592, diniconazole, flutolanil, carbendazim, benomyl, triadimefon, cyproconazole, diethofencarb, thiophanate-methyl, hymexazol, fenpropimorph, propamocarb, metalaxyl, furalaxyl, benalaxyl, oxadixyl, methasulfocarb, pyrifenox, fenpropidin, mepanipyrim, dimethomorph, fenpiclonil, propiconazole, chlorothalonil, diazinon, cupric sulfate, dichlofluanid, phosethyl-Al, hymexazol and the like. Specific examples of insecticides which can be mixed with the compounds of the present invention to form the compositions are bromopropylate, dicofol, 1605-methyl, 1605, fenitrothion, diazinon, carbosulfan, chlorpyrifos, fipronil, chlorfenapyr, methomyl, monosultap, bisultap, cartap , avermectins, permethrin, cypermethrin, tetramethrin, tefluthrin, cyfluthrin, fenvalerate, cypermethrin, flufenoxuron, triflumuron, chlorfluazuron, fenpyroximate, imidacloprid, fenoxycarb, triazophos, fenazaquin, diafenthiuron, pyridaben, clofentezine etc. Some compounds are synthesized by the inventors in order to control various fungi diseases only using very small amount the compounds, these compounds exhibit a broad-spectrum fungicidal action for controlling the diseases in the plant 7 caused by various fungi such as phycomycetes, oomycetes, ascomycetes and deuteromycetes etc., and a low dosage of these compounds is needed to obtain the satisfactory effect of controlling the diseases due to their excellent biological activity. These compounds exhibit good biological activity not only for controlling powdery mildew, downy mildew and anthracnose, but also for controlling black pox and white rust of grape. The compound provided by the present invention not only has very high biological activity, but also is friendly to environment and has no environmental pollution. Furthermore, the compound can lower cost compared with that of other similar products, and thus is a novel promising fungicide for agricultural use. Description of the Preferred Embodiments Then the present invention will be described more specifically by the following examples. However, the present invention should not be restricted to them in any way. Unless otherwise indicated, all parts in the present invention are by weight. Synthesis example Into a 500ml three-necked flask containing 150ml of anhydrous acetone, 12.2 g of 2,5-dimethly phenol was added at room temperature, then 13.8 g of potassium carbonate was added. The solution was stirred for 20 minutes at room temperature, then 28.5 g of methyl (E)- 2

-[

2 -(bromomethyl)phenyl]-3-methoxyacrylate was slowly added into the reaction mixture. The mixture was refluxed for 3 hours. The reaction mixture was filtered and concentrated in vacuum to give the crude product. The crude product was purified by column chromatography using ethyl acetate: petroleum ether (1:4) as eluant to give 26.08 g of white solid (yield 80%). Melt point: 108-110 0 C 'HNMR:2.235(3H,s), 2.279(3H,s), 3.706(3H,s), 3.835(3H,s), 4.944(2H,s), 6.584(1H,s), 6.655-6.673(1H,d), 7.013-7.032(1H,d), 7.164-7.168(2H,d), 7.300-7.382(2H,m), 7.596(1H,s), 7.617(1H,s) Note: 'HNMR spectrum was recorded using CDCl 3 as solvent. The abbreviation used in the data is as follows: NMR=nucleic magnetic resonance, s=single peak, 8 d=double peaks and m=multiple peaks. Formulation Examples Formulation Example 1 Compound of the present invention (40 kg), diatomaceous earth (53 kg), C12-20 alcohol sulfate (4 kg), and sodium dodecyl benzene sulfonate (3 kg) were homogeneously mixed together and ground to give a wettable powder containing 40% active ingredient. Formulation Example 2 Compound of the present invention (30 kg), xylene (33 kg), dimethylformamide (30 kg), and polyoxyethylene alkylpropyl ether (7 kg) were homogeneously mixed together, and dissolved to give a emulsion containing 30% active ingredient. Formulation Example 3 Compound of the present invention (10 kg), talcum powder (89 kg), and polyoxyethylene alkylpropyl ether (1 kg) were homogeneously mixed together, and ground to give a dust containing 10% active ingredient. Formulation Example 4 Compound of the present invention (5 kg), clay (73 kg), bentonite (20 kg), sodium dioctyl thiosuccinate (1 kg) and sodium phosphate (1 kg) were homogeneously mixed together and ground adequately, then an appropriate amount of water was added, and homogeneously mixed again, granulated and dried to give a granule containing 5% active ingredient. Formulation Example 5 Compound of the present invention (10 kg), sodium lignosulfonate (4 kg), sodium dodecyl benzene sulfonate (1 kg), xanthic acid (1 kg) and water (84 kg) were homogeneously mixed together. The above mixture were ground by wet grind process to give particles with the granularity smaller than 1 micron, and a colloidal suspension containing 10% active ingredient was obtained. Formulation Example 6 9 Compound of the present invention (8 kg), mancozeb (50 kg), kaolin (30 kg), sodium dodecyl benzene sulfonate (4 kg) and sodium lignosulfonate(8 kg) were homogeneously mixed together, and the mixture was adequately ground to give a wettable powder containing 8% active ingredient. Formulation Example 7 Compound of the present invention (1 kg), triazolone (20 kg), kaolin (64 kg), sodium dodecyl benzene sulfonate (6 kg) and sodium lignosulfonate (9 kg) were homogeneously mixed together, and the mixture was adequately ground to give a wettable powder containing 1% active ingredient. Effect examples The compound of the present invention has better biological activity than the known fungicides, can effectively control diseases caused by fungi with a very low dosage, and is particularly effective for controlling following disease: powdery mildew, rust diseases, downey mildew, anthracnose , such as powdery mildew of wheat and barley, powdery mildew of cucumber, powdery mildew of pumpkin, powdery mildew of strawberry, powdery mildew of grape, rust diseases of wheat and barley, downey mildew of grape, downey mildew of cucumber, anthracnose of cucumber. In addition, it can inhibit black pox and white rust of grape to a certain extent. Effect example 1 The prevention and treatment tests for controlling powdery mildew of cucumber (in the green house) The fungicide used in the test was compound I (emulsifiable oil containing 5% of compound I, and six concentrations 10, 5, 2.5, 1.25, 0.625, 0.3125 ppm were designed. To compare with ZA-1963 (i.e. picoxystrobin, manufactured by Syngenta Company, a compound commercially available which had been described in the resemble patent) (emulsifiable oil containing 5% ofZA-1963), six concentrations 10, 5, 2.5, 1.25, 0.625, 0.3125 ppm were designed. To compare with emulsifiable oil containing 20% of triazolone, three concentrations 100, 50, 10 25 ppm were designed. Some pot-grown cucumber healthy seedlings with two opened true leaves, which grew up to the period of two leaves with one bud, were selected and sprayed. 24 hours after spraying with the tested compound, the prevention test was carried out by inoculation; 24 hours after inoculation, the treatment test was carried out by spraying with the tested compound. The inoculated cucumber seedlings were placed into an artificial climate chamber to be cultivated in humidity. The prevention and treatment effect was investigated after 7 days. The results are shown in Table 1. Table 1 Results of tests for controlling powdery mildew of cucumber Concentration Powdery mildew of cucumber Fungicides (ppm) Prevention effect (%) Treatment effect (%) 10 100 98.89 5 100 97.53 Compound Compound 2.5 97.22 88.89 (I) ) 1.25 90.28 85.71 0.625 85.31 64.81 0.315 63.11 29.63 10 98.15 86.11 5 88.89 68.52 ZA-1963 2.5 81.75 36.11 1.25 75.60 23.42 0.625 47.63 8.33 0.315 41.67 0.0 100 100 triazolone 50 81.25 25 45.40 Results of the prevention and treatment tests demonstrate that the prevention effect of compound I is slightly better than the treatment effect thereof. When the concentration of compound I is 0.625 ppm, the prevention effect is 85.31%, while the treatment effect is 64.81%. At the same time, the prevention effect and the treatment effect of compound I are obviously better than that of ZA-1963, especially for the treatment effect. It is clearly that the biological activity of 11 compound I is much better than that of triazolone. Effect example 2 The prevention and treatment tests for controlling powdery mildew of wheat (in the green house) The fungicide ed in the tests was compound I (emulsifiable oil containing 5% of compound I), and six concentrations 25, 12.5, 6.25, 3.125, 1.563, 0.781 ppm were designed. To compare with ZA-1963 (i.e. picoxystrobin, manufactured by Syngenta Company, a compound commercially available which had been described in the resemble patent) (emulsifiable oil containing 5% of ZA-1963), six concentrations 25, 12.5, 6.25, 3.125, 1.563, 0.7815 ppm were designed. To compare with emulsifiable oil containing 20% oftriazolone, three concentrations 100, 50, 25 ppm were designed. Some pot-grown wheat, which grew up to the period of two leaves with one bud, was selected and sprayed. 24 hours after spraying with the tested compounds, the prevention tests were carried out by inoculation; 24 hours after inoculation, the treatment tests were carried out by spraying with the tested compounds. The inoculated wheat was placed into an artificial climate chamber to be cultivated in humidity. The prevention and treatment effect was investigated after 7 days. The results are shown in Table 2. 12 Table 2 Results of tests for controlling powdery mildew of wheat Fungicides Powdery mildew of wheat FungicidesPrevention effect (%) Treatment effect (%) 25 100 100 12.5 100 100 Compound Compound 6.25 100 100 (I) 3.125 100 100 1.563 98.33 97.33 0.781 87.43 84.13 25 100 99.77 12.5 99.60 98.31 ZA-1963 6.25 91.30 82.95 3.125 93.61 73.15 1.563 78.18 71.97 0.781 53.05 38.97 100 triazolone 50 25 Results of the prevention and treatment tests demonstrate that the prevention and treatment effect of compound I is obviously better than that of ZA-1963, especially for the treatment effect. The biological activity of compound I is much better than that of triazolone. Effect example 3 Simulation field tests for controlling powdery mildew of wheat Treating concentrations of compound I were 50, 25, 12.5, 6.25, 3.125 ppm, treating concentrations of the compared fungicide ZA-1963 were the same as these of compound I, while treating concentrations of triazolone were 100, 50, 25 ppm. Cultivating pot-grown wheat to the 4-5-leaf period, and taking its own course to bad until the metaphase of powdery mildew of wheat, the infected leaves were sprayed using the tested compounds with the concentrations mentioned above. The prevention and treatment effect was investigated after 10 days. The results are shown in Table 3. 13 Table 3 Results for controlling powdery mildew of wheat in simulation field test Fungicides Concentration (ppm) Control effect (%) 50 100 25 100 Compound 25 100 12.5 100 6.25 95.60 3.125 70.37 50 93.61 25 83.26 ZA-1963 12.5 64.25 6.25 49.57 3.125 41.83 .100 64.93 Triazolone 50 13.85 Results of the simulation field test demonstrate that the pot-grown wheat when taking its own course to bad until the metaphase was sprayed using compound I, the control effect thereof is still excellent, and the control effect is better than that of the compared fungicides ZA- 1963 and triazolone. Effect example 4 Duration tests Treating concentrations of compound I and ZA-1963 were 50, 25 mg/l. The test object was the powdery mildew of wheat. The pot-grown wheat was sprayed when two true leaves thereof were opened. 24 hours after spraying, E. graminis fsp.tritici of wheat was inoculated to the tested plant, and then the inoculated wheat was placed into the green house to be cultivated in humidity. The control effect was investigated after 7, 10, 15, 20, 25, 30 days. The results are shown in Table 4. 14 Table 4 Results of duration tests Concentration Control effect (%) Fungicides (mg/1) 7days 10days 15days 20days Compound 50 100 100 99.6 88.16 (I) 25 100 100 98.51 87.23 ZA-1963 50 100 100 96.43 85.21 25 100 100 96.31 84.68 The results of duration tests demonstrate that the duration of compound I is slightly longer than that of ZA-1963 when the artificial inoculation is carried out in the green house. Effect example 5 The tests for controlling powdery mildew of pumpkin (in the field) The field tests for controlling powdery mildew of pumpkin were carried out in the sheds at Modem Agriculture District in Shaoxing City, Zhejiang province of China in June 2002. Four concentrations of compound I (aqueous suspension containing 10% of compound I 50, 25, 12.5, 6.25 ppm were designed. To compare with the compared fungicide triazolone EC (20%), the concentration of triazolone EC was 100 ppm. The control test was carried out using water. One treatment was repeated for four times. The effect was investigated after 7 days. The results are shown in Table 5. 15 Table 5 The test results for controlling powdery mildew of pumpkin (in the field) Fungicides Concentration Disease Increment of Fungicides (ppm) index disease index Control effect (%) (ppm) mndex disease index 50 17 1.5 91.8 Compound 25 22.75 1 96.4 (I) 12.5 22.5 2.5 90.9 6.25 23.75 2 92.7 Triazolone 200 20 7.25 72.7 CK 44.25 27.5 27.5 Note: Values in the CK column of the control effect are the increment value of the disease index. It is illustrated from Table 5 that compound I with the concentration of 6.25 ppm has very high activity for controlling powdery mildew of pumpkin, the effect is obviously better than that of the compared fungicide triazolone. Effect example 6 The tests for controlling powdery mildew of cucumber (in the field) The field tests for controlling powdery mildew of cucumber were carried out in the sheds at Modem Agriculture District in Shaoxing City, Zhejiang province of China in June 2002. Four concentrations of compound I (aqueous suspension containing 10% compound I 50, 25, 12.5, 6.25 ppm were designed. To compare with the compared fungicide triazolone EC (20%), the concentration of triazolone EC was 100 ppm. The control test was carried out using water. One treatment was repeated for four times. The effect was investigated after 7 days. The results are shown in Table 6. 16 Table 6 The test results for controlling powdery mildew of cucumber (in the field) Concentration Increment of Control effect Fungicides Disease index (ppm) disease index (%) 50 21.25 0.5 98.6 Compound 25 26.75 1.25 96.5 (I) 12.5 21.25 2.75 92.2 6.25 24.5 2.75 92.2 Triazolone 200 37.25 11 68.8 CK 59.5 35.25 35.25 Note: Values in the CK column of the control effect are the increment value of the disease index. It is illustrated from Table 6 that compound I with the concentration of 6.25 ppm has very high activity for controlling powdery mildew of cucumber, the effect is obviously better than that of the compared fungicide triazolone. Effect example 7 The tests for controlling downey mildew of cucumber (in the green house) Treating concentrations of compound I were 100, 50, 25, 12.5, 6.25, 3.125 ppm, The concentration of the compared fungicide ZA-1963 were same as that. Treating concentration of metalaxy is 500 ppm. Some pot-grown cucumber healthy seedlings with two opened true leaves, which grew up to the period of two leaves with one bud, were selected and sprayed. 24 hours after spraying with the tested compounds, prevention test was carried out by inoculation; 24 hours after inoculation, treatment test was carried out by spraying with the tested compounds. The inoculated seedlings were placed into an artificial climate chamber to be cultivated in humidity. The prevention and treatment effect was investigated after 7 days. The results are shown in Table 7. 17 Table 7 Results of tests for controlling downy mildew of cucumber (in the green house) Fungicides Concentrations (ppm) Control effect (%) 100 100 50 100 Compound 25 100 (I) 12.5 97.18 6.25 91.55 3.125 77.46 100 91.55 50 60.56 Triazolone 25 46.48 12.5 40.84 6.25 26.76 3.125 9.86 metalaxyl 500 70.11 The control effect of compound I is obviously better than that of the compared fungicide ZA-1963 and metalaxyl with the same concentration in the green house. Effect example 8 The tests for controlling downey mildew of grape (in the field) The tests in the field for controlling downy mildew of grape were carried out at the Agriculture Technology Demonstration Farm in Stone Bridge village, Dangtu County, Maanshan city, Anhui province in July 2002. Five concentrations of compound I (emulsifiable oil containing 5% of compound I) 200, 100, 50, 25, 12.5 ppm were designed, treating concentrations of the compared fungicide the wettable powder of Curzate (72%) manufactured by Du Pont was 1000ppm, and another was the blank control test. One treatment was repeated for four times. 7 days after spraying, the effect was investigated. The results are shown in Table 8. 18 Table 8 Results of tests for controlling downy mildew of grape (in the field) Concentration Base before Disease Fungicides (ppm) using fungicides index Control effect (%) (ppm) using fungicides index 12.5 1.61 4.89 50.94 Compound 25 1.89 4.33 62.97 Compound 50 2.00 3.89 68.58 (I) 100 2.28 3.20 77.34 200 2.22 2.47 82.05 Curzate 1000 1.55 1.68 82.49 CK 1.89 11.70 It is demonstrated from the above results that the effect of compound I for controlling downey mildew of grape with the concentration of 200 ppm is comparative with that of the compared fungicide Curzate with the concentration of 1000 ppm. Effect example 9 The tests for controlling downey mildew of cucumber (in the field) The tests in the field for controlling downy mildew of cucumber were carried out at the Agriculture Technology Demonstration Farm in Stone Bridge village, Dangtu County, Maanshan city, Anhui province in July 2002. Five concentrations of compound I (emulsifiable oil containing 5% of compound I) 200, 100, 50, 25, 12.5 ppm were designed, treating concentrations of the compared fungicide the wettable powder of Curzate (72%) manufactured by Du Pont was 1000ppm, and another was the blank control test. One treatment was repeated for four times. 7 days after spraying, the effect was investigated. The results are shown in Table 9. 19 Table 9 Results of tests for controlling downy mildew of cucumber (in the field) Concentration Base before using Disease Fungicides (ppm) fungicides index Control effect (%) (ppm) fungicides mndex 12.5 0.96 3.89 51.38 25 1.07 3.04 65.91 Compound C o 50 1.04 2.59 70.01 (I) 100 0.93 1.84 76.12 200 0.89 1.28 82.67 Curzate 1000 0.93 1.13 85.33 CK 0.78 6.48 It is demonstrated from the above results that the effect of compound I for controlling downey mildew of cucumber with the concentration of 200 ppm is comparative with that of the compared fungicide Curzate with the concentration of 1000 ppm. Effect example 10 The tests for controlling anthracnose of cucumber (in the green house) Treating concentrations of compound I and the compared fungicide ZA-1963 were 500, 250, 125, 62.5, 31.25 ppm. The test object was anthracnose of cucumber. The pot-grown cucumber seedlings were sprayed when they grew up to the period of one true leaf. 24 hours after spraying, the spore suspension of anthracnose was inoculated, then the inoculated seedlings were placed into an artificial climate chamber maintaining the relative humidity of 100% and the temperature of 20 0 C. 24 hours after inoculation, the relative humidity 85% in the artificial climate chamber was maintained. The effect was investigated after 7 days. The results are shown in Table 10. 20 Tablel0 Results of tests for controlling anthracnose of cucumber (in the green house) Fungicides Concentrations (ppm) Control effect (%) 500 98.51 250 89.94 Compound 125 88.02 (I) 62.5 69.83 31.25 68.41 500 93.20 250 86.38 ZA-1963 125 80.94 62.5 73.86 31.25 63.24 The prevention and treatment effect of compound I is slightly better than that of the compared fungicide ZA-1963 with the same concentration in the green house. 21

Claims (9)

1. A fungicidal composition of methoxyl methylacrylate wherein said composition contains a compound represented by formula (I) and its isomers CH 3 \ 0 H 3 C CH 3 O'CH 3 (I)

2. The fungicidal composition according to claim 1, wherein said composition contains 0.1-99.0wt% compound (I) as active ingredient.

3. The fungicidal composition according to claim 1 or 2, wherein said compound (I) can be formulated into emulsions, dusts, wettable powders, suspension and granules.

4. A using method of the fungicidal composition according to any one of claims 1-3, wherein said composition can be used independently or used in a binary or ternary mixing formulations with one or more bactericides, pesticides , herbicides or plant-growth regulators.

5. The using method of the composition according to claim 4, wherein the composition can be used on plants to control diseases of various plants caused by a broad range of fungi such as phycomycetes, oomycetes, ascomycetes and deuteromycetes.

6. The using method of the composition according to claim 4, wherein the composition can be used on plants to control powdery mildew of cereals, powdery mildew of melons, rust diseases of cereals, powdery mildew of vegetables, powdery mildew of fruits, powdery mildew of flowers; downey mildew of cucumber, downey mildew of grape; anthracnose of cucumber. 22

7. A fungicidal compound according to claim 1, said compound is a compound represented by formula (I) and its isomers, CH 3 - 0 -0 H 3 C OCH CH 3 (I)

8. The method for producing the compound according to claim 7, wherein compound (I) can be obtained by the reaction of compound (II) and compound (III) in the present of alkali, Hz .CH 3 \ H + alkali + 0 ' 0 CH, H,C CH3 H3 0' CH, O-CH C II III I in compound (III), X represents leaving group, the reaction can be carried out in solvent if necessary.

9. The method for producing the compound according to claim 7, wherein compound (I) can be prepared by the following reactions: + o alkali + Y 0HC.0 H H ..0 II IV V CH s H HCOOCH. H o mnethylating agent oH a r o o .CHo alkali H CoCH CH H.J C ----- > o1rY alkali .C alkali u OCHH 3 -CH3 3,, VII 23 in compound (IV), X represents leaving group, and a suitable solvent can be added to the reaction if necessary. 24