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

IS 2 142 000 T3

DESCRIPTION

Derivatives of methoxyiminoacetic acid and agricultural and horticultural fungicides that contain them as an active ingredient.

The present invention relates to a new derivative of methoxyiminoacetic acid and to an agricultural / horticultural fungicide containing it as an active ingredient.

Certain derivatives of methoxyiminoacetic acid are known to possess biological activities including fungicidal activities. For example, EP 398692 describes a compound of the formula:

<img file="ES2142000T3_D0001.tif" />

Furthermore, in documents WO92 / 13830 and EP 463488 a compound of formula is described:

<img file="ES2142000T3_D0002.tif" />

Furthermore, document EP 499823 describes a compound of formula:

<img file="ES2142000T3_D0003.tif" />

Likewise, document EP515901 describes a compound of formula:

<img file="ES2142000T3_D0004.tif" />

IS 2 142 000 T3

However, such compounds are not always satisfactory as agricultural / horticultural fungicides, as will be demonstrated in subsequent Test Examples.

Under such circumstances, the inventors turned their attention to said methoxyiminoacetic acid derivatives and conducted extensive studies on them. As a result, it has been successfully found that a derivative of methoxyiminoacetic acid with a specific structure possesses strong fungicidal activity as well as excellent systemic and residual activity for plants, which completes the present invention.

Following the above, the essentiality of the present invention resides in a derivative of methoxyiminoacetic acid represented by the following formula (1):

<img file="ES2142000T3_D0005.tif" />

wherein X represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 4 carbon atoms, or an alkoxy group of 1 to 4 carbon atoms; R¹ represents a hydrogen atom, an alkyl group of 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 it as an active ingredient.

Detailed description of the invention

The present invention will now be described in detail.

The methoxyiminoacetic acid derivative of the present invention is that represented by formula (I) above. In the above formula (l), X represents a hydrogen atom; a halogen atom (eg, fluorine, chlorine, bromine); an alkyl group of 1 to 4 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl); or an alkoxy group of 1 to 4 carbon atoms (eg, methoxy, ethoxy, isopropoxy, n-butoxy). It preferably represents a hydrogen atom or a halogen atom, most preferably it still represents a hydrogen atom.

R¹ represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, 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 (eg phenyl, naphthyl) which may be optionally substituted by the following groups; or a heteroaryl group (eg pyridyl, thienyl, thiazolyl) which may be optionally substituted by the following groups. Preferably, it represents a phenyl group that can be optionally substituted by the following groups, a naphthyl group, a thienyl group that can be optionally substituted by the following groups, or a thiazolyl group that can be optionally substituted by the following groups.

Examples of the substituents of the above-mentioned aryl group include a cyano group; a halogen atom (eg, fluorine, chlorine, bromine); an alkyl group of 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl); an alkenyl group of 2 to 4 carbon atoms (eg ethenyl, propenyl) optionally substituted by a halogen atom; a haloalkyl group of 1 to 4 carbon atoms (eg, trifluoromethyl, difluoromethyl, trichloromethyl, trichlorodifluoroethyl); an alkoxy group of 1 to 6 carbon atoms (eg, methoxy, ethoxy, isopropoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group of carbon 3 to 6 atoms; an alkylcarbonyloxy group of 1 to 7 carbon atoms (eg, acetoxy, propionyloxy, pivaloyloxy) optionally substituted by a halogen atom; an acylamino group of 1 to 7 carbon atoms (eg, acetoamino, propionylamino), optionally substituted by a halogen atom; an alkylthio group of 1 to 6 carbon atoms (e.g. methylthio, ethylthio, isopropylthio,

ES 2 142 000 T3 n-butylthio) optionally substituted by a halogen atom; an aryl group (eg phenyl) optionally substituted by an alkyl group of 1 to 4 carbon atoms or a halogen atom; an aryloxy group (eg, phenoxy) optionally substituted by an alkyl group of 1 to 4 carbon atoms or a halogen atom; an alkylsulfonyloxy group of 1 to 6 carbon atoms (eg, methanesulfonyloxy or ethanesulfonyloxy) optionally substituted by a halogen atom; an alkenyloxide 2 to 6 carbon atom (eg, propenyloxy) group optionally substituted by a halogen atom; and an alkynyloxy group of 2 to 6 carbon atoms (eg, propargyloxy). Among such substituents, the adjacent ones can combine with each other to give, for example, a methylenedioxy or ethylenedioxy group and form a fused ring together with an aryl group. The number of substituents is between 1 and 5, preferably between 1 and 2. If Ar has two or more substituents, these can be the same or different from each other. Preferred examples of substituents of an aryl group include an alkyl group of 1 to 4 carbon atoms, a halogen atom, an alkoxy group of 1 to 4 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine), an acylamino group of 1 to 4 carbon atoms that may be optionally substituted by a halogen atom (preferably fluorine), an alkylthio group of 1 to 3 carbon atoms, an alkylsulfonyloxy group of 1 to 3 carbon atoms which may be optionally substituted by a halogen atom (preferably fluorine) and a trifluoromethyl group.

Examples of the substituents on the aforementioned heteroaryl group include a cyano group; a halogen atom (eg fluorine, chlorine, bromine); an alkyl group of 1 to 6 carbon atoms (eg, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl); a haloalkyl group of 1 to 4 carbon atoms (eg, trifluoromethyl, difluoromethyl, trichloromethyl, dichlorodifluoroethyl); and an alkoxy group of 1 to 6 carbon atoms (eg, methoxy, ethoxy, isopropoxy, n-butoxy) optionally substituted by a halogen atom or a cycloalkyl group of 3 to 6 carbon atoms. The number of substituents, which may be the same or different from each other, is between 1 and 2. Among these substituents, an alkyl group with 1 to 4 carbon atoms, a halogen atom and a trifluoromethyl group can be mentioned as preferred.

Each of the compounds of the present invention is a new compound and can be prepared, for example, following the following reaction scheme:

<img file="ES2142000T3_D0006.tif" />

[in which X, R¹ and Ar are as defined in formula (l) above].

The above formula compound (lb) 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 aforementioned phaormula compounds (V) as starting materials can be produced according to the method described in EP398692, EP499823 or the like.

Each of the compounds of the above formula (lb) exists as isoamers in the methoxyimino fraction. Each isoomer can be separated from the other isoomer from the mixture of isáomers that is usually obtained, by a conventional method such as by column chromatography. Each of the E and Z mixtures or the Z isáomer can be converted to the E isáomer showing high activity, by treatment with an acid (e.g. hydrochloric acid, sulfuric acid, methansulphoanic acid) in an alcohol solvent (e.g. , methanol, ethanol).

The compounds of the present invention thus obtained are each a new compound with excellent fungicidal activity. Said compounds exert excellent preventive effects on various phytopathogenic fungi, which makes them useful as agricultural / horticultural fungicides.

IS 2 142 000 T3

For example, these compounds exert high activity on rice blotch (Pyricularia oryzae), rice pod rust (Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis f. Sp. Tritici) and powdery mildew of barley (E. graminis f. sp. holdei), various blights on the leaves of wheat and barley (eg. Puccinia recondita), gray mold of vegetables and fruit trees (Botrytis cinerea) and late rust of various crops (Phytophthora infestance). They also have a prolonged residual activity and an excellent systemic action in plants, which makes them extremely useful as agricultural / horticultural fungicides.

If the compound of the present invention is intended to be used as an agricultural / horticultural fungicide, it can be applied as such. However, it is preferable to formulate said compound in the form of, for example, an emulsifiable concentrate, wettable powder, powder or granules by mixing with adjuvants in a conventional manner to thereby ensure effective dispersion of the active ingredient in the application.

If it is intended to formulate the agricultural / horticultural fungicide according to the present invention in the form of an emulsifiable concentrate, between 10 and 80 parts by weight (hereinafter referred to as "parts") are mixed in a suitable proportion (preferably between 10 and 70 parts). of the compound of the present invention, between 10 and 90 parts (preferably between 20 and 80) of a solvent and between 3 and 20 parts (preferably between 5 and 15 parts) of a surfactant. For use, the mixture obtained is diluted with water to a defined concentration and applied by, for example, spraying.

If the agricultural / horticultural fungicide of the present invention can be used in the form of a wettable powder, between 5 and 80 parts (preferably between 10 and 70 parts) of the compound of the present invention are mixed in suitable proportion, between 10 and 90 parts (preferably between 20 and 80 parts) of a filler and between 1 and 20 parts (preferably between 3 and 15 parts) of a surfactant. For its use, the mixture obtained is diluted with, for example, water to a defined concentration and applied in a similar way to the case of the emulsifiable concentrate.

If it is intended to use the agricultural / horticultural fungicide of the present invention in powder form, between 0.1 and 10 parts (preferably between 1 and 5 parts) of the compound of the present invention are mixed uniformly with between 90 and 99.9 parts (preferably 95-99 parts) of a filler (eg kaolin, bentonite, talc).

The agricultural / horticultural fungicide of the present invention may further contain other active ingredients such as bactericides, insecticides and acaricides, provided that the effects of the active ingredient of the present invention are not impaired thereby.

The agricultural / horticultural fungicide of the present invention can be suitably used in both foliar application and submerged application. In the case of foliar application, the agricultural / horticultural fungicide is usually formulated as an emulsifiable concentrate or a wettable powder and diluted with water to provide a concentration of the active ingredient between 10 and 1000 ppm. Subsequently, it is applied in a proportion of between 100 and 5000 l per 1 ha.

To illustrate the present invention in greater detail, the following examples would be provided. However, it should be understood that the present invention is not limited thereto, but various changes can be made 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-trilfluoromethylacetophenone hydrazone and 7.5 ml of ethanol heated under reflux for 3 hours. After concentration in vacuo, said residue was chromatographed on SiO2 to provide 2.48 g of the title compound (86.6% yield).

Compounds number 86, 87, 89 and 90 of Table 1 were synthesized by repeating the above procedure, except that the starting material was altered.

IS 2 142 000 T3

TABLE 1

<img file="ES2142000T3_D0007.tif" />

<td>Compound No.</td><td>B</td><td>(Y) n</td><td>Property</td>

<td> 86</td><td>N = C (CH3)</td><td>3-CH3</td><td>97-104 ° C</td>

<td> 87</td><td>N = C (CH3)</td><td>3-Cl</td><td>117-118.5 ° C</td>

<td> 88</td><td>N = C (CH₃)</td><td>3-CF3</td><td>138-138.5 ° C</td>

<td> 89</td><td>N = C (CH3)</td><td>4-Cl</td><td>129-132 ° C</td>

<td> 90</td><td>N = C (CH3)</td><td>4-CF3</td><td>141-144 ° C</td>

* Although there are E and Z isomers in the methoxyimino fraction, only the properties of the E isiomers are given in the table above.

The data from ¹H-NMR of the compounds obtained are the following:

[TABLE 1]

Data of ¹H-NMR of compound number 86 (CDCl3); 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).

Data of ¹H-NMR of compound number 87 (CDCl3); 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).

Data of ¹H-NMR of compound number 88 (CDCl₃); 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 compound with excellent fungicidal activity. Said compounds are particularly effective in the control of phytopathogenic fungi, which makes them extremely useful as agricultural / horticultural fungicides.

For example, these compounds exert high activity on rice blight (Pyricularia oryzae), rice pod rust (Rhizoctonia solani), powdery mildew of wheat (Erysiphe graminis f. Sp. Tritici) and powdery mildew of barley (E. graminis f. sp. hodei), various blights on the leaves of wheat and barley (eg. Puccinia recondita), gray mold of vegetables and fruit trees (Botrytis cinerea) and late rust of various crops (Phytophthora infestance). They also have a prolonged residual activity and an excellent systemic action in plants, which makes them extremely useful as agricultural / horticultural fungicides.

Although the invention has been described in detail and with reference to specific embodiments thereof, it would be apparent to any person skilled in the art that various changes and modifications can be made therein without departing from the spirit or scope thereof.