MXPA96005685A - Compounds of 2- (phenyl-substituted) -2-alcoxyimin-n-alkylacetamide fungicides that contains them - Google Patents

Abstract

The present invention relates to a compound of the formula (IB): characterized in that A2 is 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl , 6-trifluoromethyl-2-pyridyl, 6-methoxy-2-pyridyl, 6-isopropoxy-2-pyridyl, 6-methylthio-2-pyridyl, 5-chloro-3-trifluoromethyl-2-pyridyl, 6-methoxy-3 -trifluoromethyl-2-pyridyl, 6-isopropoxy-3-trifluoromethyl-2-pyridyl, 6-chloro-4-trifluoromethyl-2-pyridyl, 3,5,6-trichloro-4-trifluoromethyl-2-pyridyl, 6-chloro -3,5-di (trifluoromethyl) -2-pyridyl, 6-methoxy-5-trifluoromethyl-2-pyridyl, 6-isopropoxy-5-trifluoromethyl-2-pyridyl, 6-methylamino-5-trifluoromethyl-2-pyridyl, or 3,6-dichloro-5-trifluoromethyl-2-pyridyl, and indicates a configuration of E or Z isomer, or a mixture thereof, or a salt thereof.

Description

COMPOUNDS OF 2- (FENBL SUBSTITUTED) -2-ALCOXYIMIN-N- ALKYLACETAMIDE AND FUNGICIDES THAT CONTAIN THEM Technical Field The present invention relates to the compounds of 2- (substituted phenyl) -2-alkoxyimino-N-alkylacetamide and to fungicides containing them, in particular, to a composition for controlling Pseudocercosporella herpotrichoides.

Background of the Invention Certain alkoxyiminoacetamide derivatives are known to have fungicidal activity against certain pathogens (JP-A 3-246268, JP-A 4-182461). However, its fungicidal activity against the wheat eyespot (Pseudocercosporella herpotri choides), which is a serious pathogen of wheat, is unknown.

The present invention aims to provide a novel compound having a broad fungicidal spectrum and potent activity for controlling activity particularly against Pseudocercosporella herpotri the choides, and a novel composition for controlling Pseudocercosporella herpotrichoides. REF: 23471 DESCRIPTION OF THE INVENTION The authors of the present invention have studied intensively to achieve the above objective. As a result, it has been found that the compounds of 2- (substituted phenyl) -2-alkoxyimino-N-alkylacetamide have potent fungicidal activity against Pseudocercosporella herpotrichoides and that the a novel compound 2- (substituted phenyl) -2- Methoxyimino-N-methyl-acetamide included in the above compounds not only has a potent fungicidal activity against the Pseudocercosporella herpotri choides but also has a broad fungicidal spectrum. Thus, the present invention has been completed.

The present invention provides: (1) A compound of the formula (I-A) (I -A) wherein A is a 3, 4-dimethylphenyl or 3,5-dimethylphenyl and ~ indicates a configuration of an E or Z isomer or a mixture thereof; (2) A compound of the formula (I-B) (I-B) where A2 is 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 6-methoxy-2- pyridyl, 6-isopropoxy-2-pyridyl, 6-methylthio-2-pyridyl, 5-chloro-3-trifluoromethyl-2-pyridyl, 6-methoxy-3-trifluoromethyl-2-pyridyl, 6-isopropoxy-3- trifluoromethyl-2-piridiilo, 6-chloro-4-trifluoromethyl-2-pyridyl, 3, 5, 6-trichloro-4-trifluoromethyl-2-pyridyl, 6-chloro-3, 5-di (trifluoromethyl) -2 -pyridyl, 6-methoxy-5-trifluoromethyl-2-pyridyl, 6-isopropoxy-5-trifluorometi1-2-pyridyl, ß-methylamino-5-trifluoromethyl-2-pyridyl, 3,6- dichloro-2-trifluoromethyl -pyridyl or 2-quinolyl and ~ indicates a configuration of an E or Z isomer or a mixture thereof, or a salt thereof; (3) A compound according to item (2) above, wherein A is 3-tr? Fluoromet? L-2-pyridyl or 5-chloro-3-trifluoromethyl-2-pyridyl, or a salt thereof; (4) A fungicidal composition comprising as an active ingredient a compound of the formula (I-A) or (I-B) or a salt thereof; (5) A composition for controlling the Pseudocercosporella herpotrichoides, which comprises as an active ingredient a compound of the formula (I-A) or (I-B ") or a salt thereof; (6) A composition for controlling the Pseudocercosporella herpotri choides, which comprises as an active ingredient a compound of the formula (I): (I) wherein A is an optionally substituted phenyl, an optionally substituted pyridyl or an optionally substituted quinolyl 1 2, R and R are the same or different and are alkyl, n is 0 or 1, and ~ indicates a configuration of a E or Z isomer or a mixture thereof, or a salt thereof; Y (7) A composition according to subsection (6) above wherein R 1 and R 2 are methyl.

The term "lower" used herein means having from 1 to 8 carbon atoms, preferably from 1 to 6 carbon atoms, more preferably from 1 to 4 atoms. carbon, unless otherwise indicated. ' A in the formula (I-B) is preferably 3-trifluoromethyl-2-pyridyl or 5-chloro-3-trifluoromethyl-2-pyridyl. Optionally substituted pyridyl and optionally substituted quinolyl represented by A in the formula (I) may have a bond to the oxygen atom in any possible position, but preferably have the bond in the 2-position. Each optionally substituted phenyl, optionally substituted pyridyl, and optionally substituted quinolyl represented by A is substituted or unsubstituted by 1 to 5. substituents, more preferably 1 to 3 substituents, in any possible position. The substituent is selected from, for example, lower alkyl (e.g., methyl, ethyl, propyl, butyl, etc.), lower alkenyl (e.g., vinyl, allyl, crotyl, etc.), alkynyl lower (eg, ethynyl, propargyl, butynyl, etc.), cycloalkyl (eg, cyclopropyl, cyclopentyl, cyclohexyl, etc.), cycloalkenyl (eg, cyclopentenyl, cyclohexenyl, etc.) , lower alkanoyl (eg, acetyl, propionyl, isobutyryl, etc.), lower alkylsilyl (eg, methylsilyl, ethylsilyl, propylsilyl, butylsilyl, etc.), halogenated lower alkyl (eg, trifluoromethyl, trichloromethyl, chloromethyl, 2-bromoethyl, 1,2-dichloropropyl, etc.), alkylamino (lower) (eg, methylamino, ethylamino, etc.), dialkylamino lower (e.g. ., dimethylamino, diethylamino, etc.), lower alkylthio (eg, methylthio, ethylthio, etc.), phenyl, lower alkylphenyl (eg, benzyl, phenethyl, etc.), lower alkenylphenyl (e.g. ., styryl, cinnamyl, etc.), lower alkylfuryl (e.g., 3-furylmethyl, 2-furylethyl, etc.), lower alkenylfuryl (e.g., 3-furylvinyl, 2-furyl-lily, etc.), halogen (eg, fluoro, chloro, bromo, iodo), nitro, cyano, OR 4 [wherein R 4 is hydrogen, lower alkyl (e.g., methyl, ethyl, propyl, etc.), lower alkenyl ( eg, vinyl, allyl, crotyl, etc.), lower alkynyl (eg, ethynyl, 2-propynyl, 3-butynyl, etc.), lower alkanoyl (eg, acetyl, propionyl butyryl, etc.), phenyl lower alkoxyphenyl (e.g., 3-methoxyphenyl, 4-ethoxyphenyl, etc.), nitrophenyl (e.g., 3-nitrophenyl, 4-nitrophenyl, etc. .), lower alkylphenyl (eg, benzyl, phenethyl, phenylpropyl etc.), cyanophenylalkyl (eg, 3-cyanophenylmethyl, 4-cyanophenylethyl, etc.), benzoyl, tetrahydropyranyl, pyridyl, trifluoromethylpyridyl, pyrimidinyl, benzothiazolyl, quinolyl, lower benzoylalkyl (eg, benzoylmethyl, benzoylethyl, etc.), benzenesulfonyl or lower alkylbenzene sulfonyl (eg, toluenesulfonyl, etc.), -CH2-Z-R5 (wherein Z is -O-, -S- or -NR6- (in which R is hydrogen or lower alkyl), R is phenyl, halophenyl, (e.g., 2-chlorophenyl, 4-fluorophenyl, etc.), lower alkoxyphenyl (e.g., 2-methoxyphenyl, 4-ethoxyphenyl, etc. ), pyridyl or pyrimidinyl} , etc. In particular, preferred are halogen, halogenated lower alkyl, lower alkoxy, lower alkylthio and lower alkylamino. The alkyl examples represented by R 1 and R 2 they include alkyl having from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc. In particular, methyl and ethyl are preferred and methyl is particularly preferred. The compound of the formula (I-A), (I-B) or (I) is any of its E or Z isomer and a mixture thereof.

This is indicated by the wavy line - in the formulas. Each of these compounds is preferably its E-isomer since the E-isomer has a more potent fungicidal activity. The compound of the formula (I) is preferably the compound of the formula (I-A) or (I-B). Further below are the preferred processes for producing the compound of the formula (I) including a compound of the formula (I-A) or (I-B). The compound of the formula (I) wherein n is 0 (ie, the compound (V) in Scheme 1) can be prepared, for example, according to Scheme 1.

Scheme 1 (II) (III) (IV) (V) wherein each symbol is as defined above, and A is preferably A1, and R1 and R are preferably methyl. wherein each symbol is as defined above, and A is preferably A 1, and R 1 and R 2 are preferably methyl.

That is, the carboxylic acid (II) is reacted with thionyl chloride or phosgene in a solvent such as a hydrocarbon (eg, benzene, toluene, etc.) to give the acid chloride (III). subsequently, the acid chloride (III) is subjected to a condensation reaction with an alkyl isocyanide (e.g., methyl isocyanide, etc.) in the absence of a solvent or in an inert solvent (e.g., benzene, toluene, etc.). The resulting compound is then subjected to hydrolysis in the presence or absence of a base (e.g., sodium hydroxide, etc.) or an acid (e.g., hydrochloric acid, etc.), if necessary in a solvent hydrophilic (eg, acetone, tetrahydrofuran, etc.), to give the α-ketoamide (IV) (see JP-A 5-331124). The resulting α-ketoamide (IV) is then reacted with an alkoxyamine (eg, methoxylamine, etc.) or a salt thereof in an alcohol solvent (eg, methanol, etc.) to give the desired compound (V) (see JP-A 3-246268). The compound (V) thus obtained can be separated and purified by conventional methods (e.g., chromatography, recrystallization, etc.). The compound of the formula (I) wherein n is 1 can be prepared for example by the method shown in the following substituted as A in the formula (I) but the compound (VIII) having another optionally substituted pyridyl, optionally substituted phenyl or quinolyl optionally substituted as A can be prepared in a similar manner.

Scheme 2 wherein X is hydrogen or a substituent of A described above, R is alkyl, (e.g., methyl, ethyl, n-propyl, isopropyl, butyl, etc.), Y is an oxygen atom, a sulfur atom or R'N (in which R 'is hydrogen or alkyl such as methyl, ethyl, propyl, butyl, etc.), and the other symbols are as defined above. First, the compound (VI) is reacted with optionally substituted 2,6-dichloropyridine in a solvent (eg, dimethylformamide, tetrahydrofuran, etc.) in the presence of a base [e.g. sodium hydride, alkali carbonate (eg, sodium carbonate, potassium carbonate, etc.), alkali hydroxide (eg, sodium hydroxide, potassium hydroxide, etc.), etc.] give the compound (VII) (see JP-A 3-246268, JP-A 4-182461). Subsequently, the resulting compound (VII) is reacted with the compound (X) or a metal salt thereof in an organic solvent or an organic solvent containing water (e.g., methanol, ethanol, tetrahydrofuran, etc.) to give the desired compound (VIII). The amount of the compound (X) to be used is 1 to 3 mol, preferably 1.0 to 1.2 mol, per mol of the compound (VII). The reaction temperature is from 0 to 120 ° C, preferably 50 to 100 ° C and the reaction time is from 1 hour to 30 hours, preferably from 5 hours to 20 hours.

Alternatively, the compound (VIII) can be prepared by reacting the compound (VI) with the compound (IX) according to the method described in JP-A 3-246268 or JP-A 4-182461.

The compound (VIII) thus obtained can be separated and purified by conventional methods (e.g., chromatography, recrystallization, etc.).

The compound of the formula (I) used in the present invention has a potent fungicidal activity against the Pseudocercosporella herpotrichoides and is useful as a composition for controlling the Pseudocercosporella herpotrichoides.

The compound of the formula (I-A) or (I-B) of the present invention shows potent fungicidal activity against the Pseudocercosporella herpotrichoides. It is also effective against a wide variety of phytopathogenic fungi in crop plants (eg, rice, wheat, barley, rye, corn, common millet, millet, buckwheat, soybean, red bean (Australian tree (redbean)) , peanuts, etc.), fruit trees (eg, citrus fruits, grapes, apples, pears, peaches, etc.), vegetables (eg, cucumber, eggplant, tomatoes, squash, beans, etc.), etc. ., or seeds thereof. It is also effective against phytopathogenic fungi on land. A) Yes, has a broad fungicidal spectrum. Specifically, it shows potent fungicidal activity against Pseudocercosporella herpotrichoides, Pyricularia oryzae, Rhizoctonia solani, Erysiphe graminis, Puccinia spp. , Sphaerotheca fuliginea, Erysiphe cichoracearum, Phytophthora infestans, Pseudoperonospora cubensis, Peronospora manshurica, Plasmopara tícola, Botrytis cinerea of vegetables, grape, etc., Pythium aphanidermatu, Sclerotinia sclerotiorum of alforjón, soybean, rapeseed, etc., Cortici um rolfsii of soybean , kidney beans (redbean), potatoes, peanuts, etc. Therefore the compound of the formula (I-A) or (I-B) is useful as a fungicide, particularly as agricultural fungicides, preferably as a composition for controlling the Pseudocercosporella herpotrichoides.

The application of the compound of the formula (I) used in the present invention, (including the compound of the formula (IA) or (IB) can be carried out in the plants by any conventional method such as spraying, diffusion or dispersion of the active compound The application can also be done through the treatment of the seeds of the plants, the soil where the plants grow, the soil where the seeds are sown, rice fields or water for dew or perfusion with the active compound. performed before or after infection with phytopathogenic fungi in plants.

The compound can be used in a conventional formulation form suitable for agricultural fungicides such as solutions, wetting powders, emulsions, suspensions, concentrated liquid preparations, tablets, granules, aerosols, microgranules, pastes, powders, etc.

Such a formulation form can be prepared in a conventional manner by mixing at least one compound of the present invention with an appropriate liquid or solid carrier (s) or vehicle (s) and, if necessary, an appropriate adjuvant (s) ( eg, surfactants, spreaders, dispersants, stabilizers, etc.) to improve the dispersibility and other properties of the active ingredient.

Examples of solid carriers or diluents include botanical materials (e.g., flour, tobacco stem powder, soybean powder, walnut hull powder, vegetable powder, sawdust, bran, powdered bark, powdered cellulose, vegetable extract residue) fibrous materials (eg paper, corrugated cardboard, old rags), artificial plastic powder (eg kaolin, bentonite, fuller's earth), talc other inorganic materials (pyrophyllite, sericite , pumice, sulfur powder, activated carbon), chemical fertilizers (eg, ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride), etc.

Examples of liquid carriers or diluents include water, alcohols (e.g., methanol, ethanol), ketones (e.g., acetone, methyl ethyl ketone), ethers (e.g., diethyl ether, dioxane, cellosolve, tetrahydrofuran) ) aromatic hydrocarbons (eg, benzene, toluene, xylene, methylnaphthalene), aliphatic hydrocarbons (eg, gasoline, kerosene, lamp oil), esters, nitriles, acidic amides (eg, dimethylformamide, ethylacetamide, etc.), halogenated hydrocarbons (eg, dichloroethane, carbon tetrachloride), etc. Examples of surfactants include alkyl sulphates, alkyl sulfonates, alkylaryl sulfonates, polyethylene glycol, ethers, polyhydric alcohol esters, etc. Examples of spreaders or dispersants include casein, gelatin, powdered starch, carboxymethyl cellulose, gum arabic, alginic acid, lignin, bentonite, molasses, polyvinyl alcohol, pine oil, agar, etc. Examples of stabilizers include PAP (a mixture of isopropylphosphate), tricresyl phosphate (TCP), tolu-balsam oil, epoxidized oil, surfactants, fatty acids and their esters, etc.

The composition of the present invention may contain other fungicides, insecticides, herbicides or fertilizers in addition to the above ingredients. In general, the above composition contains at least one compound of the formula (I) of the present invention in a concentration of 1 to 95% by weight, preferably 2.0 to 80% by weight. The composition can be used as such or in diluted form. Approximately 1.0 g to 5.0 Kg / hectare, preferably about 2 g to 100 g / ha, of the compound of the present invention is used in a concentration of usually about 1 to 50,000 ppm, preferably about 100 to 5,000 ppm.

EXAMPLES The following test examples and experiments further illustrate the present invention in detail, but should not be considered to limit the scope of the invention.

Example 1 Synthesis of (E) -2- (2- (6-methoxypyridin-2-yloxymethyl) phenyl] -2-methoxy-imino-N-methylacetamide (Compound No. 6) A solution of 28% sodium methoxide-methanol (1. 16g) was added to (E) -2- [2- (6-chloropyridin-2-yloxymethyl) phenyl] -2-methoxyimino-N-methylacetamide (400 mg ), and the mixture was heated under reflux with stirring for 4 hours. The mixture was neutralized with IN hydrochloric acid and water was added. The mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give the title compound (61 mg), mp = 81-82 ° C.

Example 2 Synthesis of (E) -2- [2- (6-methylthiopyridin-2-yloxymethyl) phenyl] -2-methoxy-imino-N-methylacetamide (Compound No.8) (E) -2- [2- (6-chloropyridin-2-yloxymethyl) phenyl] -2-methoxyimino-N-methylacetamide (1.2 g) was dissolved in tetrahydrofuran (10 ml) and sodium thiomethoxide (1 g) was added. ). The mixture was heated under reflux with stirring for 5 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give the title compound (800 mg), mp = 130-132 ° C.

Example 3 Synthesis of (E) ~ 2- [2 ~ (6-methylamino-5-trifluoromethylpyridin-2-yloxy-methyl) phenyl] -2-methoxyimino-N-methylacetamide (Compound No. 17) A solution of 40% methylamine-methanol (10 mL) was added to (E) -2- [2- (6-chloro-5-trifluoromethylpyridin-2-yloxymethyl) phenyl] -2-methoxyimino-N-methylacetamide (402 mg ), and the mixture was stirred at 100 ° C for 17 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give the title compound (379 mg), p. f. = 66-67 ° C.

Example 4 In the same manner as described above, the compounds of Table 1 were synthesized. All the compounds in Table 1 are E-isomers. Table 1 also lists the physical properties of the compounds obtained in the previous examples Table 1 Example 5 Synthesis of (E) -2- [2 ~ (3,4 ~ dimethylphenoxy) phenyl] -2-methoxyimino-N-methylacetamide The (E) -2- (3,4-dimethylphenoxy) benzoic acid (3.0 g) was suspended in toluene (7 ml) and thionyl chloride (1.62 g) and 3 drops of dimethylformamide were added. The mixture was stirred at 60 ° C for 1 hour. Toluene was evaporated under reduced pressure, methyl isocyanide (610 mg) was added and the mixture was stirred at 60 ° C overnight. Additional methyl isocyanide (610 mg) was added and the mixture was stirred for 2 hours. 5N Hydrochloric acid (10 mL) and acetone (13 mL) were added and the mixture was stirred for 2 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by means of column chromatography on silica gel to give (E) -2- [2- (3,4-dimethylphenoxy)) phenyl] -2-oxo-N-methylacetamide (2.98 g). i- MRÍCDCla) ppm: 2.23 (6H, s), 2.88 (3H, d, J = 4.9Hz), 6.60 (lH, brs), 6.74 (3H, m), 7.09 (1H, d, J = 7.9Hz) , 7.12 (lH, td, J = 7.9,1.2Hz), 7.42 (lH, td, J = 7.3, 1.8Hz) (1H, dd, J = 7.3, 1.8Hz).

(E) -2- [2- (3, 4-dimethylphenoxy)) phenyl] -2-oxo-N-methyl-acetamide (2.58 g) and methoxylamine hydrochloride (916 mg) were dissolved in methanol (50 ml). ) and the mixture was heated under reflux with stirring overnight. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give the title compound (2.00 g), p. f. = 98-100 ° C. Example 6 Synthesis of (E) -2- [2- (3,5-dimethylphenoxy) phenyl] -2-methoxyimino-N-methylacetamide The 2- (3,5-dimethylphenoxy) benzoic acid (3.0 g) was suspended in toluene (7 ml) and thionyl chloride (1.62 g) and 3 drops of dimethylformamide were added. The mixture was stirred at 60 ° C for 1 hour. Toluene was evaporated under reduced pressure, methyl isocyanide (1.00 g) was added and the mixture was stirred at 60 ° C overnight. 5N Hydrochloric acid (10 mL) and acetone (13 mL) were added and the mixture was stirred for 2 hours. Water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give 2- [2- (3,5-dimethylphenoxy)) phenyl] -2-oxo-N-methylacetamide (2.28 g).

^ -NMRÍCDCls) PPm: 2.28 (3H, s), 2.88 (3H, d, J = 4.8Hz), 6.61 (lH, brs), 6.68 (2H, s), 6.78 (lH, s), 6.87 (1H, d, J = 7.3Hz), 7.14 (lH, td, J = 7.3.1.2Hz), 7.44 (1H, td, J = 7.3, 1.8Hz), 7.74 (lH, dd, J = 7.3.1.8Hz).

The 2- [2- (3,5-dimethylphenoxy)) phenyl] -2-oxo-N-methylacetamide (2.58 g) and the methoxylamine hydrochloride (1.52 g) were dissolved in methanol (50 ml) and the mixture it was heated under reflux with stirring overnight. Water was added, and the mixture was extracted with ethyl acetate. The organic layer was washed with saturated brine and dried, and then the solvent was evaporated. The resulting oil was purified by column chromatography on silica gel to give the title compound (1.96 g), m.p. = 90-91 ° C.

Example 7 Synthesis of (E) -2- [2- (2-quinolinyloxymethyl) phenyl] -2-methoxyimino-N-methylacetamide The (E) -2- [2- (hydroxymethyl) phenyl] -2-methoxyimino-N-methyl-acetamide (0.44 g, 2 mmol) was dissolved in dry DMF (4 mL). 60% sodium hydride (0.10 g, 2.4 mmol) was added at room temperature, the mixture was stirred for 10 minutes, and then 2-chloroquinoline (0.36 g, 2.2 mmol) was added at room temperature. The resulting mixture was allowed to stand at room temperature overnight and saturated brine was added. The mixture was extracted with ethyl acetate and dried over magnesium sulfate, and the solvent was evaporated under reduced pressure. The resulting crude product was purified by column chromatography on silica gel (ethyl acetate-n-hexane) to give the title compound (0.46 g) as an oil. 1 H-NMR (in CDCl 3) ppm: 2.88 (lH, d, J = 4.9Hz), 3.93 (3H, s), 5.43 (2H, s), 6.64 (lH, br s), 6.86 (1H, d, J = 8.8Hz), 7.25 (lH, m), 7.34-7.45 (3H, m), 7.59-7.69 (2H, m), 7.71 (1H, d, J = 7.8Hz), 7.83 (lH, d, J = 7.8Hz), 8.00 (1H, d, J = 8.8Hz).

The following experiments illustrate the effects of control of the foliar application of the various compounds of the present invention on the different diseases of plants.

Experimental Method All tests were done to evaluate the effects of control (preventive) except the test for the Pseudocercosporella herpotrichoides. This is the tests were carried out by spraying a liquid sample to a test plant and inoculating the plant with a pathogen 24 hours later. A test compound was dissolved in a small amount of N, N-dimethylformamide and the solution was diluted to a given concentration with distilled water containing a dispersant to prepare a liquid sample. The percentage of the control was calculated according to the following equation: Percentage of control (%) =. { (severity, number of injuries, etc. on untreated site-severity, number of injuries, etc. on treated site) / severity, number of injuries, etc. on untreated land} x 100 Test Example 1 Effect of Control on Pseudocercosporella herpotrichoides Wheat seeds (see v. NORIN No. 61) were planted in plastic crucibles (each 11 cm in diameter), followed by cultivation at 15 ° C for 1 week. The Pseudocercosporella herpotrichoides grown on sterilized oat seeds was put together with the seeds at the base of the wheat stem to inoculate the test plant with the pathogen. After the inoculation, the test plant was developed for three more weeks in the same greenhouse. When a homogenous development of the disease was observed in the lower part of the stem of the seedlings or of the plants that grew from the wheat seeds, a solution or suspension of the test compound was sprayed. After the treatment, the test plant was developed for 4 more weeks in the same greenhouse, and then the severity of the disease was verified. Compound A is (E) -2-2 - / - 5-trif luoro-methylpyridin-2-yloxymethyl) phenyl-2-methoxyimino-N-methylacetamide (see JP-A 3-246268). Compound B is (E) -2- / 2- (6-chloro-pyridin-2-yloxymethyl) f-enyl-2-methoxyimino-N-methylacetamide (see JP-A 4-182461). The wheat seedlings were uprooted to assess the expansion of the lesion of the first internode of the stem. The criteria for the assessment were grouped into 5 grades and the severity of the disease was determined to calculate the percentage of control. Results are shown in table 2.

Table 2 Effect of control on the Pseudocercosporella herpotrichoides by application to foliage Compound No. (percentage of Control) (%)) 250 pi 125 ppm 62.5 ppm 3 82 63 46 9 82 68 51 Compound A 45 24 13 Compound B 28 21 24 Test Example 2 Effect of Control on Pyricularia oryzae The plants that have grown from the rice seed in two weeks (c.v .: AICHIASAHI) were transplanted into plastic cups (each 9 cm in diameter). A solution or suspension of the test compound was sprayed onto the foliage of the rice seedlings. Inoculation of the pathogen was carried out by spraying on the treated foliage a conidium suspension of Pyricularia oryzae grown in an oatmeal medium. After inoculation, the test plant was kept in a humid chamber (28 ° C, 100% R.H.) for 24 hours and then in a greenhouse for 5 days. Six days after the inoculation, the number of lesions in the leaves of the inoculated plant was measured to calculate the percentage of the control. The results are shown in table 3. Table 3 Effect of control on Pyricularia oryzae by application in Compound No. foliage at 500 ppm (percentage of control (%)) 1 97 2 97 3 100 4 90 5 100 6 90 7 97 9 100 10 97 11 97 12 90 14 97 15 97 16 90 18 97 Test Example 3 Control effect on dusty cucumber mold (Sphaerotheca fuliginea) The cucumber seeds (c.v .: TSUKUBASHIROIBO) were planted in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A solution or suspension of the test compound was sprayed onto the surface of its first leaves. The pathogen was inoculated by spraying on the treated leaves a conidium suspension of Sphaerotecha fuliginea which had been cultivated on the leaves of the cucumber. After inoculation, the plants were kept in a greenhouse at 20 ° C. Ten days after the inoculation, the infected area of the leaves was observed and the percentage of the control was calculated. The results are shown in table 4. Table 4 Effect of control on Sphaerothecafitliginea by application of Compound No. on the foliage at 500 ppm (percentage of control (%)) 1 100 2 100 3 100 4 100 5 100 6 100 7 100 8 100 9 100 10 100 11 100 12 100 13 100 14 100 15 100 16 100 18 100 Test Example 4 Effect of Control over Botrytis cinerea The cucumber seeds (c.v .: TSUKUBASHIROIBO) were planted in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A solution or suspension of the test compound was sprayed onto the surface of its first leaves, and mycelial discs of Botrytis cinerea grown on a medium of sucrose agar of potato were placed on the surface of the treated leaves to inoculate the seedlings with the pathogen. After inoculation, the plants were kept in a humid chamber at 20 ° C for 2 days. The diameter of the lesions around the inoculum was measured and the percentage of the control was calculated. The results are shown in table 5.

Table 5 Effect of control on Botrytis cinerea by application in Compound No. foliage at 500 ppm (percentage of control (%)) 1 70 2 70 3 70 5 70 9 70 Test Example 5 Effect of Control on Pseudoperonospora cubensis Cucumber seeds (c.v .: TSUKUBASHIROIBO) were seeded in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A solution or suspension of the test compound was sprayed onto the surface of its first leaves, and a zoosporangia suspension of Pseudoperonospora cubensis grown on the cucumber leaves was added dropwise onto the surface of the treated leaves to inoculate the test plants with the pathogen. After inoculation, the plants were kept in a humid chamber at 20 ° C for 10 days. Subsequently, the increased diameters of the lesions around the inoculated part were measured and the percentage of the control was calculated. The results are shown in table 6. Table 6 Effect of control on Pseudoperonospora cubensis by Compound No. application on foliage at 500 pjp (% J ^ 1 100 2 100 3 100 4 100 5 100 6 100 8 100 9 100 10 100 11 100 12 100 13 90 14 100 15 90 16 100 18 100 Test Example 6 Effect of Control on Erysiphe graminis f. sp. tri tici Wheat seeds (c.v .: NORIN No. 61) were planted in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A solution or suspension of the test compound was sprayed on the seedlings, and a conidium of Erysiphe graminis f. sp. Tri-tici cultivated on the wheat leaves was added dropwise on the test plants to inoculate the plants with the pathogen. After inoculation, the plants were kept in a greenhouse at 20 ° C. Ten days after the inoculation, the infected area was observed on the inoculated leaves and the percentage of the control was calculated. The results are shown in table 7.

Table 7 Effect of control on Erysiphe graminis f. sp. tritici by Compound No. application on foliage at 500 ppm (percentage of control (%)) 1 100 2 99 3 97 4 90 5 100 6 100 7 97 8 97 9 100 10 97 11 97 12 90 13 90 14 100 15 97 16 97 18 90 Test Example 7 Effect of Control on Puccinia coronata The oat seeds (c.v .: PC-38) were seeded in plastic cups (each 9 cm in diameter), followed by cultivation for 2 to 3 weeks. A solution or suspension of the test compound was sprayed on the seedlings. Spores of Puccinia coronata grown on the oat leaves in about 5 parts (by weight) were diluted with talc and sprayed onto the treated test plants to inoculate the plants with the pathogen. After inoculation, the plants were kept in a humid chamber at 20 ° C for 1 day and then in a greenhouse for 9 days ° C. The infected area was observed on the leaves and the percentage of the control was calculated. The results are shown in table 8.

Table 8 Effect of control on Puccinia coronata by application in Compound No. foliage at 500 ppm (percentage of control (%)) 1 100 2 99 5 100 6 97 7 100 8 90 9 100 10 97 11 97 15 100 16 97 18 90 It is evident from Table 2 that the compound of the present invention shows a very potent control activity against the Pseudocercosporella herpotrichoides, which has been very difficult to control. Furthermore Tables 3 to 8 clearly show that the compound of the present invention has a very broad fungicidal spectrum and exhibits a potent control activity against diseases caused by oomycetes, basidiomycetes, ascomycetes, deuteromycetes, etc. Thus, by applying the compound of the present invention to the Pseudocercosporella herpotrichoides, for example, which has been very difficult to control, the compound of the invention can control not only the Pseudocercosporella herpotrichoides, but also the dusty mold and mildew. which are important diseases of wheat, barley, oats, rye, etc. and that become problematic due to the appearance of their resistant cells. The compound of the invention can thus become a very useful drug for controlling diseases in the cultivation of wheat, barley, oats, rye, etc. The present invention thus provides novel compounds having a broad fungicidal spectrum and a potent fungicidal activity particularly against the Pseudocercosporella herpotrichoides, and a novel composition for controlling the Pseudocercosporella herpotrichoides. It is noted that in relation to this date, the best method known by the applicant to carry out the aforementioned invention, is the conventional one for the manufacture of the objects to which it relates.

Having described the invention as above, property is claimed as -contained in the following: "-

Claims (7)

1. A compound of the formula (I-A): (I-A) characterized in that A is a 3,4-dimethylphenyl or 3,5-dimethylphenyl and ~ denotes a configuration of an E isomer or Z or a mixture thereof.
2. 2. A compound of the formula (I-B) dB) 2 characterized in that A is 3-chloro-2-pyridyl, 5-chloro-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 6-trifluoromethyl-2-pyridyl, 6-methoxy -2-pyridyl, 6-isopropoxy-2-pyridyl, 6-methylthio-2-pyridyl, 5-chloro-3-trifluoromethyl-2-pyridyl, 6-methoxy-3-trifluoromethyl-2-pyridyl, 6-isopropoxy-3 -trifluoromethyl-2-pyridyl, 6-chloro-4-trifluoromethyl-2-pyridyl, 3,5,6-trichloro-4-trifluoromethyl-2-pyridyl, 6-chloro-3,5-di (trifluoromethyl) - 2-pyridyl, 6-methoxy-5-5-trifluoromethyl-2-pyridyl, 6-isopropoxy-5-trifluoromethyl-2-pyridyl, 6-methylamino-5-trifluoromethyl-2-pyridyl,, 6-dichloro-5-trifluoromethyl -2- pyridyl or 2-quinolyl and ~ indicates a configuration of. a E or Z isomer or a mixture thereof, or a salt thereof.
3. 3. A compound according to claim 2, characterized in that A is 3-tpfluoromet? L-2-pyridyl or 5-chloro-3-trifluoromethyl-2-pyridyl, or a salt thereof.
4. 4. A fungicidal composition characterized in that it comprises as an active ingredient a compound of the formula (I-A) or (I-B) or a salt thereof.
5. 5. A composition for controlling the Pseudocercosporella herpotrichoides, characterized in that it comprises as an active ingredient a compound of the formula (I-A) or (I-B) or a salt thereof.
6. 6. A composition for controlling the Pseudocercosporella herpotrichoides, characterized in that & 'comprises as an active ingredient a compound of the formula (I): (I) wherein A is an optionally substituted phenyl, an optionally substituted pyridyl or an optionally substituted quinolyl, R 1 and R 2 are the same or different and are alkyl, n is 0 or 1, and indicates a configuration of a E or Z isomer or a mixture thereof, or a salt thereof.
7. 7. A composition according to claim 6, characterized in that R 1 and R 2 are methyl. twenty