Methoxyiminoacetic acid derivative and agricultural/horticultural fungicide containing the same as active ingredient

Abstract: A methoxyiminoacetic acid derivative represented by the following formula (I): wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group and an agricultural/horticultural fungicide containing the same as an active ingredient.

Description: This invention relates to a novel methoxyiminoacetic acid derivative and an agricultural/horticultural fungicide containing the same as an active ingredient. It has been known that certain methoxyiminoacetic acid derivatives have biological activities including fungicidal activities. For example, a compound of the formula: is described in EP 398692. Further a compound of the formula: is described in WO92/13830 and EP 463488. Furthermore, a compound of the formula: is described in EP 499823. Also, a compound of the formula: is described in EP515901. However, these compounds are not always satisfactory as an agricultural/horticultural fungicide, as will be shown in Test Examples hereinafter. Under these circumstances, the present inventors have paid their attention to these methoxyiminoacetic acid derivatives and conducted extensive studies thereon. As a result, it has successfully been found out that a methoxyiminoacetic acid derivative having a specific structure has a potent fungicidal activity as well as an excellent systemic and residual activity for plants, thus completing the present invention. Accordingly, the gist of the present invention resides in a methoxyiminoacetic acid derivative represented by the following formula (I): wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group and an agricultural/horticultural fungicide containing the same as an active ingredient. DETAILED DESCRIPTION OF THE INVENTION Now, the present invention will be described in detail. The methoxyiminoacetic acid derivative of the present invention is the one represented by the above formula (I). In the above formula (I), X represents a hydrogen atom; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); or an alkoxy group having 1 to 4 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy). It preferably represents a hydrogen atom or a halogen atom, still preferably a hydrogen atom. R 1 represents hydrogen atom; an alkyl group having 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); a cyano group; or a trifluoromethyl group. It preferably represents a hydrogen atom, a cyano group or a methyl group. Ar represents an aryl group (for example, phenyl, naphthyl) which may be optionally substituted by the following groups; or a heteroaryl group (for example, pyridyl, thienyl, thiazolyl) which may be optionally substituted by the following groups. It preferably represents a phenyl group which may be optionally substituted by the following groups, a naphthyl group, a thienyl group which may be optionally substituted by the following groups, or a thiazolyl group which may be optionally substituted by the following groups. Examples of the substituents for the above-mentioned aryl group include a cyano group; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); an alkenyl group having 2 to 4 carbon atoms (for example, ethenyl, propenyl) optionally substituted by a halogen atom; a haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl, difluoromethyl, trichloromethyl, dichlorodifluoroethyl); an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms; an alkylcarbonyloxy group having 1 to 7 carbon atoms (for example, acetoxy, propionyloxy, pivaloyloxy) optionally substituted by a halogen atom; an acylamino group having 1 to 7 carbon atoms (for example, acetoamino, propionylamino) optionally substituted by a halogen atom; an alkylthio group having 1 to 6 carbon atoms (for example, methylthio, ethylthio, iso-propylthio, n-butylthio) optionally substituted by a halogen atom; an aryl group (for example, phenyl) optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an aryloxy group (for example, phenoxy) optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an alkylsulfonyloxy group having 1 to 6 carbon atoms (for example, methanesulfonyloxy or ethanesulfonyloxy) optionally substituted by a halogen atom; an alkenyloxy group having 2 to 6 carbon atoms (for example, propenyloxy) optionally substituted by a halogen atom; and an alkynyloxy group having 2 to 6 carbon atoms (for example, propargyloxy). From among these substituents, those adjacent to each other may be combined together to give, for example, a methylenedioxy or ethylenedioxy group and form a fused ring together with an aryl group. The number of substituents is from 1 to 5, preferably from 1 to 2. When Ar has two or more substituents, they may be the same or different each other. Preferable examples of substituents for an aryl group include an alkyl group having 1 to 4 carbon atoms, a halogen atom, an alkoxy group having 1 to 4 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine), an acylamino group having 1 to 4 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine), an alkylthio group having 1 to 3 carbon atoms, an alkylsulfonyloxy group having 1 to 3 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine) and a trifluoromethyl group. Examples of the substituents for the above-mentioned heteroaryl group include a cyano group; a halogen atom (for example, fluorine, chlorine, bromine); an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl); a haloalkyl group having 1 to 4 carbon atoms (for example, trifluoromethyl, difluoromethyl, trichloromethyl, dichlorodifluoroethyl); and an alkoxy group having 1 to 6 carbon atoms (for example, methoxy, ethoxy, iso-propoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms. The number of substituents, which may be the same or different each other, is from 1 to 2. Among these substituents, an alkyl group having 1 to 4 carbon atoms, a halogen atom and a trifluoromethyl group may be cited as preferable ones. The compounds of the present invention are each a novel one and can be prepared, for example, in accordance with the following reaction scheme: [wherein X, R 1 and Ar are as defined in the above formula (I)]. The compound of the above formula (I-b) can be obtained by reacting the benzaldehyde derivative represented by the above formula (V) with the corresponding hydrazone derivative in an inert solvent such as an alcohol. The above-mentioned compounds of formula (V) as starting materials can be produced in accordance with the method described in EP398692, EP499823 or the like. The compounds of the above formula (I-b) each exists as isomers at the methoxyimino moiety. Each isomer can be separated each other from the mixture of isomers which is obtained usually, by a coventional manner such as column chromatography. Each of E-, Z-mixture or Z-isomer can be converted to the E-isomer which shows high activities, by treating with an acid (for example, hydrochloric acid, sulfuric acid, methanesulfonic acid) in an alcohol solvent (for example, methanol, ethanol). The compounds of the present invention thus obtained are each a novel one having an excellent fungicidal activity. They exert excellent preventive effects on various phytopathogenic fungi, which makes them useful as an agricultural/horticultural fungicide. For example, these compounds exert high activity on rice blast ( Pyricularia oryzae ), rice sheath blight ( Rhizoctonia solani ), wheat powdery mildew ( Erysiphe graminis f. sp. tritici ) and barley powdery mildew ( E. graminis f. sp. hodei ), various leaf rusts of wheat and barley (e.g., Puccinia recondita ), gray mold of vegetables and fruit trees ( Botrytis cinerea ) and late blight of various crops ( Phytophthora infestance ). Further, they have prolonged residual activity and excellent systemic action in plants, which makes them highly useful as an agricultural/horticultural fungicide. When the compound of the present invention is to be used as an agricultural/horticultural fungicide, it may be applied as such. However, it is preferable to formulate said compound into, for example, emulsifiable concentrate, wettable powder, dust or granules by blending with adjuvants in a conventional manner to thereby ensure the effective dispersion of the active ingredient at the application. When the agricultural/horticultural fungicide according to the present invention is to be formulated into an emulsifiable concentrate, 10 to 80 parts by weight (hereinafter referred to as "parts") (preferably 10 to 70 parts) of the compound of the present invention, 10 to 90 parts (preferably 20 to 80 parts) of a solvent and 3 to 20 parts (preferably 5 to 15 parts) of a surfactant are mixed together at an appropriate ratio. At the usage, the obtained mixture is diluted with water to a definite concentration and applied by, for example, spraying. When the agricultural/horticultural fungicide of the present invention is to be used as a wettable powder, 5 to 80 parts (preferably 10 to 70 parts) of the compound of the present invention, 10 to 90 parts (preferably 20 to 80 parts) of a filler and 1 to 20 parts (preferably 3 to 15 parts) of a surfactant are mixed together at an appropriate ratio. At the usage, the obtained mixture is diluted with, for example, water to a definite concentration and applied, similar to the case of the emulsifiable concentrate. When the agricultural/horticultural fungicide of the present invention is to be used as a dust, 0.1 to 10 parts (preferably 1 to 5 parts) of the compound of the present invention is uniformly mixed with 90 to 99.9 parts (preferably 95 to 99 parts) of a filler (for example, kaolin, bentonite, talc). The agricultural/horticultural fungicide of the present invention may further contain other active ingredients such as bactericides, insecticides and miticides, so long as the effects of the active ingredient of the present invention are not deteriorated thereby. The agricultural/horticultural fungicide of the present invention can be suitably used either in foliar application or in submerged application. In the case of foliar application, the agricultural/horticultural fungicide is usually formulated into an emulsifiable concentrate or a wettable powder and diluted with water so as to give a concentration of the active ingredient of from 10 to 1,000 ppm. Then it is applied at a ratio of 100 to 5000 l per 1 ha. To further illustrate the present invention in greater detail, the following Examples will be given. However, it is to be understood that the present invention is not restricted thereto but various changes may be restored within the scope thereof. SYNTHESIS EXAMPLE 1 Synthesis of methyl 2-[2-{4-(3-trifluoromethylphenyl)-2,3-diaza-1,3-pentadienyl}phenyl]-2-methoxyiminoacetate (compound No. 88 in Table 1): A mixture comprising 1.5 g (6.75 mmol) of methyl 2-(2-formylphenyl)-2-methoxyiminoacetate, 1.37 g (6.75 mmol) of m-trifluoromethylacetophenone hydrazone and 7.5 ml of ethanol was heated under reflux for 3 hours. After vacuum concentration, the residue was chromatographed over SiO 2 to give 2.48 g of the title compound (yield: 86.6 %). The compounds No. 86, No. 87, No. 89 and No. 90 in Table 1 were synthesized by repeating the above-mentioned procedure except altering the starting material. * Although E- and Z-isomers at the methoxyimino moiety exist, the properties of the E-isomers alone are given in the above table. 1 H-NMR data of the obtained compounds are as follows. [Table 1] 1 H-NMR data of compound No. 86 (CDCl 3 ); 2.41 (3H, s), 2.46 (3H, s), 3.82 (3H, s), 4.03 (3H, s), 7.23-7.35 (3H, m), 7.48-7.54 (2H, m), 7.66 (1H, d), 7.73 (1H, s), 7.87 (1H, dd), 8.37 (1H, s) 1 H-NMR data of compound No. 87 (CDCl 3 ); 2.44 (3H, s), 3.81 (3H, s), 4.03 (3H, s), 7.26 (1H, dd), 7.31-7.43 (2H, m), 7.48-7.54 (2H, m), 7.76 (1H, d), 7.86 (1H, dd), 7.91 (1H, s), 8.37 (1H, s) 1 H-NMR data of compound No. 88 (CDCl 3 ); 2.49 (3H, s), 3.82 (3H, s), 4.03 (3H, s), 7.27 (1H, dd), 7.51 (2H, dd), 7.54 (1H, d), 7.67 (1H, d), 7.87 (1H, dd), 8.06 (1H, d), 8.19 (1H, s), 8.39 (1H, s) Each of the compounds of the present invention is a novel one having an excellent fungicidal activity. It is particularly effective in controlling phytopathogenic fungi, which makes it highly useful as an agricultural/horticultural fungicide. For example, these compounds exert high activity on rice blast ( Pyricularia oryzae), rice sheath blight ( Rhizoctonia solani ), wheat powdery mildew (Erysiphe graminis f. sp. tritici) and barley powdery mildew (E. graminis f. sp. hodei), various leaf rusts of wheat and barley (e.g., Puccinia recondita), gray mold of vegetables and fruit trees (Botrytis cinerea) and late blight of various crops (Phytophthora infestance). Further, they have prolonged residual activity and excellent systemic action in plants, which makes them useful as an agricultural/horticultural fungicide. While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims: A methoxyiminoacetic acid derivative represented by the following formula (I ): wherein X represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms; R 1 represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cyano group or a trifluoromethyl group; and Ar represents an optionally substituted aryl group or an optionally substituted heteroaryl group. The methoxyiminoacetic acid derivative as claimed in Claim 1, wherein Ar represents an aryl group optionally substituted by 1 to 5 substituents which may be the same or different and, when the aryl group has 2 or more substituents, those adjacent to each other may be combined together to give a methylenedioxy or ethylenedioxy group and form a fused ring together with the aryl group, said substituents being selected from the group consisting of a cyano group; a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkenyl group having 2 to 4 carbon atoms optionally substituted by a halogen atom; a haloalkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom or a cycloalkyl group having 3 to 6 carbon atoms; an alkylcarbonyloxy group having 1 to 7 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 7 carbon atoms optionally substituted by a halogen atom; an alkylthio group having 1 to 6 carbon atoms optionally substituted by a halogen atom; an aryl group optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an aryloxy group optionally substituted by an alkyl group having 1 to 4 carbon atoms or a halogen atom; an alkylsulfonyloxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom; an alkenyloxy group having 2 to 6 carbon atoms optionally substituted by a halogen atom; and an alkynyloxy group having 2 to 6 carbon atoms; or a heteroaryl group optionally substituted by 1 to 2 substituents which may be the same or different, said substituents being selected from the group consisting of a cyano group; a halogen atom; an alkyl group having 1 to 6 carbon atoms; a haloalkyl group having 1 to 4 carbon atoms; and an alkoxy group having 1 to 6 carbon atoms optionally substituted by a halogen atom; or a cycloalkyl group having 3 to 6 carbon atoms. The methoxyiminoacetic acid derivative as claimed in 1 or 2, wherein X represents a hydrogen atom or a halogen atom; R 1 represents a hydrogen atom, a cyano group, a trifluoromethyl group or an alkyl group having 1 to 4 carbon atoms; and Ar represents a phenyl or naphthyl group optionally substituted by one or more substituents being selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an alkylthio group having 1 to 3 carbon atoms; an alkylsulfonyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom; or a trifluoromethyl group, or a thienyl or thiazolyl group optionally substituted by one or more substituents selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; or a trifluoromethyl group. The methoxyiminoacetic acid derivative as claimed in claim 1, 2 or 3. wherein X represents a hydrogen atom; R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and Ar represents a naphthyl group or a phenyl group optionally substituted by one or more substituents being selected from the group consisting of a halogen atom; an alkyl group having 1 to 4 carbon atoms; an alkoxy group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an acylamino group having 1 to 4 carbon atoms optionally substituted by a halogen atom; an alkylsulfonyloxy group having 1 to 3 carbon atoms optionally substituted by a halogen atom; or a trifluoromethyl group. The methoxyiminoacetic acid derivative as claimed in claim 1, 2, 3 or 4, wherein X represents a hydrogen atom; R 1 represents an alkyl group having 1 to 4 carbon atoms; and Ar represents a phenyl group substituted by one or more substituents being selected from the group consisting of a halogen atom, an alkyl group having 1 to 4 carbon atoms and a trifluoromethyl group. An agricultural/horticultural fungicide containing a methoxyiminoacetic acid derivative as claimed in any of claims 1 to 5 as an active ingredient.

Inventors: KATSURADA MANABU, ODA MASATSUGO, TOMITA HIROFUMI, KATSURADA, MANABU, ODA, MASATSUGO, TOMITA, HIROFUMI
Applicants: MITSUBISHI CHEM CORP, MITSUBISHI CHEMICAL CORPORATION
Application year: 1993
Main classification: C07C251
IPC codes: A01N37, C07C251