MXPA99000808A - Fungicidal compositions containing n-acetonyl benzami - Google Patents

Abstract

The present invention relates to fungicidal compositions and their use as a method for controlling phytopathogenic fungi, which comprises the application of a compound selected from N-acetonylbenzamide, fungicidally active, and a second compound, fungicidally active, selected from a fungicide of Acylalanine type, seed wings of plants, the foliage of plants or the growth medium of plants. The compositions and method of use provide a higher fungicidal activity compared to the separate use of the same compounds.

Description

FUNGICIDAL COMPOSITIONS CONTAINING N-ACETONYLBENZAMIDES The present invention relates to new fungicidal compositions and their use as a method to control phytopathogenic fungi in plants. It is always advisable to improve products that can be used by farmers in order to combat fungal diseases of crops and, in particular, diseases caused by fungi of the class of Oomycetes. It is also always advisable to reduce the doses of chemical products disseminated in the environment, to combat attacks of fungi in crops, in particular by reducing the doses of applications of the products. It is also always advisable to increase the number of antifungal products available to farmers, in order that they find, among these products, one that is the best suited for the specific use of the farmer. An object of the invention is thus to provide novel fungicidal compositions that are useful against the problems discussed above. Another object of the invention is to propose novel fungicidal compositions that are useful in the treatment, preventive and curative, of diseases caused by fungi of the Oomycetes class. Still another object of the invention is to propose novel fungicidal compositions, which are of improved efficacy against mildew and / or late blight caused by Oomycetes. Still another object of the invention is to propose novel fungicidal compositions having an improved efficacy against pubescent downy mildew in the vine and other crops and / or late blight in tomatoes and potatoes. It has been found that these objects can be achieved, partially or totally, by means of the fungicidal compositions, according to the present invention. The patents of E. U. A., Nos. 5,304,572 and 5,667,333 describe applying the mixtures of the N-acetonyl-benzamides, described therein, with other fungicidal compounds. It has now been discovered that the application of the N-acetonyl-benzamides, described in these patents, in combination with other selected fungicidal compounds, unexpectedly provides a high fungicidal activity and is effective in controlling the phytopathogenic fungi in lower dose amounts of N-acetonylbenzamide than those described in U.S. Patent No. 5,304,572. Although the patent of E. U. A., No. 5,677,333 describes the use of the N-acetonylbenzamides, in combination with the bis-thiocarba- ethylene, cymoxanil and dimethomorph, to unexpectedly deliver the high fungicidal activity, the synergistic combinations of this invention are not described or suggested in that patent.

In a first embodiment of this invention, a composition is provided, which comprises: (a) a fungicidally effective amount of a first fungicidally active compound, having the formula (I): or a salt, agronomically acceptable, thereof, wherein: R1 and R3 are each, independently, halogen or (C1-C4) alkyl; R2 is (C1-C4) alkyl, (C2-C4) alkenyl, (C2-C6) alkynyl, (C1-C4) alkoxy or cyano; R and R5 are each, independently, a hydrogen atom or (C1-C4) alkyl, with the proviso that at least one of R4 and R5 is (C2-C4) alkyl; and X is halogen, thiocyano or isothiocyano; (b) an amount, fungicidally effective, of a second compound, fungicidally active, which is an acylalanine-type fungicide, such as the enantiomer R of metalazil, the racemic mixture of metalalxyl, oxadixyl, furalaxyl, benalazil, ofurace and ciprofuram; Y (c) an agronomically acceptable carrier.

In a second embodiment of this invention, a method for controlling phytopathogenic fungi in a plant is provided, which comprises the application of: (a) a fungicidally effective amount of a first fungicidally active compound having the formula (I) : (I) or a salt, agronomically acceptable, thereof, wherein: R1 and R3 are each, independently, halogen or (C1-C4) alkyl; R2 is (C1-C4) alkyl, (C2-C4) alkenyl, alkynyl (C2-C6), (C1-C4) alkoxy or cyano; R4 and R5 are each, independently, a hydrogen atom or (C1-C4) alkyl, with the proviso that at least one of R4 and R5 is (C2-C4) alkyl; and X is halogen, thiocyano or isothiocyano; (b) a fungicidally effective amount of a second compound, fungicidally active, which is an acylalanine-type fungicide, such as the R-enantiomer of metalazil, the racemic mixture of metalalxyl, oxadixyl, furalaxyl, benalazil, ofurace and ciprofuram; Y (c) an agronomically acceptable carrier, to the seeds of the plant, to the foliage of the plant or to the growth medium of the plant.

When R4 and R ^ are different, the optical enantiomers of the compounds of the present invention are possible, due to the presence of an asymmetric carbon atom, which binds R4 and R ^. It is known that many biologically active compounds have optical enantiomers, one of which is more active than the other.

Similarly, for the compounds used in the method of the present invention, the biological activity of one enantiomer can exceed that of the other enantiomer, as described in EP 0 816 330 Al, of January 7, 1998.

"(C 1 -C 4) alkyl" means an alkyl group, straight or branched chain, having from one to four carbon atoms per group, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, secondary butyl and tertiary butyl. "(C2-C4) alkenyl" means a straight or branched chain alkenyl group having from two to four carbon atoms per group, and includes, for example, ethenyl, 2-propenyl, 2-butenyl, 1-methyletenyl , 2-methyl-2-propenyl, and the like. "Alkynyl (C2-C6)" means a straight or branched chain alkynyl group, having from two to six carbon atoms per molecule, and includes, for example, ethynyl, 2-propynyl, 2-butynyl and the like. "Halogen" means chlorine, fluorine, bromine and iodine. "(C 1 -C 4) alkoxy" means a straight or branched chain alkoxy group having from one to four carbon atoms per group, and includes, for example, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy , isobutoxy, secondary butoxy and tertiary butoxy.

"Ciano" means a group that has the formula structure of -CN. "Tiociano" means a group that has the formula structure -SCN. "Isothiocyan" means a group that has the structural formula -NCS. Agronomically acceptable salts include, for example, metal salts, such as sodium, potassium, calcium and magnesium salts, ammonium salts, such as isopropyl ammonium salts, and trialkylsulfonium salts, such as triethylsulfonium salts. The first fungicidally active compound can be a simple compound of the formula (I) or, alternatively, it can be a mixture of compounds of the formula (I). Suitable compounds of the formula (I) include, but are not limited to: N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-methylbenzamide, N- [3 '- (1'-chloro-3' -methyl-2 '-oxopentan)] -3,5-dichloro-4-ethylbenzamide, N- [3' - (1'-chloro-3'-methyl) -2 '-oxopentan)] -3,5-dichloro-4-ethoxybenzamide, N- [3' - (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro- 4- methoxybenzamide, N- [3 '- (1' -chloro-3 '-methyl-2' -oxopentan)] -3,5-dichloro-4-cyanobenzamide, and N- [3 '- (1'-chloro-3' - methyl-2 '-oxopentan)] -3,5-dibromo-4-methylbenzamide. In a preferred embodiment, the first fungicidally active compound is an N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-methylbenzamide. N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dibromo-4-cyanobenzamide, or mixtures thereof. More preferably, the first fungicidally active compound is N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-methylbenzamide.

Suitable compounds that function as the second fungicidally active compound include, but are not limited to: the R-enantiomer of metalaxyl, the racemic mixture of metalazyl, the racemic mixture of meta-allyl, oxadixyl, furalaxyl, benalazil, ofurace and ciprofuram. In a preferred embodiment, the second compound, fungicidally active, is selected from the group consisting of the R-enantiomer of metalaxyl, oxadixyl, ofurace and benalaxyl. The method of the present invention may, optionally, also comprise the application of other compounds having biological activity, for example, additional fungicidally active compounds or compounds having herbicidal activity or insecticidal activity, to the seed of the plant, to the foliage of the plant or to the growth medium for the plant. The method of the present invention is useful for the control of phytopathogenic fungi in crops and the first and second fungicidally active compounds can be applied as a soil fungicide, as a seed protector, as a foliar fungicide or as a combination of they. In a preferred embodiment, the first and second fungicidally active compounds are applied to the growth medium of the plant, to the seed of the plant or to the foliage of the plant, at dose rates from 2 parts by weight (pep) up to 90 pep , more preferably from 5 to 75 pep,. of the first active compound fungicidally, per 100 pbw of the combined amount of the first and second fungicidally active compounds, and 10 to 98 pbw, more preferably 25 to 95 pbp of the second fungicidally active compound per 100 pbw of the combined amount of the first and second fungicidally active compounds. As a soil fungicide, the first and second fungicidally active compositions can be incorporated into the soil or applied to the soil surface at a dose rate of about 0.25 to 5 kg of the first compound active fungicidally, and from 0.25 to 5 kg of the second active compound fungicidally, per hectare. As a seed protector, the first and second active compounds fungicide are coated on the seeds at a dose rate of about 0.5 kilogram (kg) up to 5 kg of the first fungicidally active compound, and 0.5 to 5 kg of the second fungicidally active compound , per 100 kg of seed. As a foliar fungicide, the first and second fungicidally active compounds are applied to the foliage of the plant at a dose rate of 0.01 kg per hectare up to 5 kg per hectare of the first active compound fungicidally, and a dose regime of 0.01 kg per hectare up to 5 kg per hectare of the second fungicidally active compound. In a preferred embodiment, the first fungicidally active compound is applied to the foliage of the plant at a dose rate of 0.05 kg per hectare to approximately 0.5 kg per hectare. In a preferred embodiment, the second fungicidally active compound is applied to the foliage of the plant at a dose rate of 0.05 kg per hectare up to 5.0 kg per hectare. The first and second fungicidally active compounds can be applied to the foliage of the plant as pulverized fungicides, by commonly employed methods, such as conventional high volume hydraulic sprays, low volume sprays, air jets, sprays air and dust. While the dilution and rate of application will depend on the type of equipment employed, the method and frequency of the desired application and the disease to be controlled, the effective amount is typically around 0.1 to 5.0 kg, preferably 0.2 to 5.0 kg. , from both the first and second active compounds, per hectare. The first and second fungicidally active compounds can be applied simultaneously or in sequence. In a preferred embodiment, the first and second fungicidally active compounds are applied simultaneously to the growth medium of the plant, to the seed of the plant, the foliage of the plant, or a combination thereof, as a composition comprising a mixing the first active compound fungicidally and the second active compound fungicidally. In a preferred embodiment, the mixture includes from 2 to 90 pbw of a first active compound fungicidally and from 10 to 98 pbw of a second active compound fungicidally, per 100 pbw of the mixture. In an alternative embodiment, the first and second fungicidally active compounds are applied in sequence to the seed of the plant, the foliage of the plant or the growth medium of the plant, with application of the second compound after the application of the first compound, for up to 72 hours. The compounds can be applied in any order, or the first active compound fungicidally followed by the second active compound fungicidally or, alternatively, the second fungicidally active compound is applied followed by the first fungicidally active compound. The method of the present invention is useful in controlling certain phytopathogenic fungi, particularly fungi of the Oomycetes class, and provides high fungicidal activity and relatively low phytotoxicity. The method of the present invention is particularly effective in controlling fungi Oopiycetes of the genera Phytophthora, Plasmopara, Peronospora, Albugo and Pseudopernospore, and even more particularly against the organisms of these genera, which cause diseases, such as late blight in tomatoes and potatoes, and the pubescent millidium in life and other crops, which include, for example, Phytophthora infestans, Plasmopara vi tícola Y Pseudoperonospora cubensis. For each of the purposes described above, the first and second fungicidally active compounds can be used in the technical or pure form, as prepared, as solutions or as formulations. The compounds are usually taken in a carrier or formulated to make them suitable for subsequent use as fungicides. For example, the compounds can be formulated as powders that are mixed with water, dry powders, emulsifiable concentrates, powders, granular formulations, aerosols or emulsion concentrates that can flow. In such formulations, the compounds are diluted with a liquid or solid carrier and, when dry, suitable surfactants are incorporated. It is usually convenient, in particular in the case of foliar spray formulations, to include adjuvants, such as soaking agents, spreading agents, dispersing agents, tackifiers, adhesives and the like, in accordance with agricultural practices. Such adjuvants, commonly used in the art, can be found in McCutcheon's "Emulsifiers and Detergents", McCutcheon's "Emulsifiers and Detergents / Functional Materials" and McCutcheon's "Functional Materials", all published annually by the McCutcheon Division of McCutcheon. MC Publishing Company (New Jersey). In general, the compositions used in this invention can be dissolved in suitable solvents, such as acetone, methanol, ethanol, dipiethylformamide or dimethyl sulfoxide, and such solutions are diluted with water. The concentrations of the first and second active compounds combined in the solution can vary from 1 to 90%, with a preferred range being from 5 to 50%. For the preparation of emulsifiable concentrates, the compositions used in the invention can be dissolved in suitable organic solvents or a mixture of solvents, together with an emulsifying agent, which allows the dispersion of the first and second active compounds in water. The concentration of the first and second active compounds combined in the emulsifiable concentrates is usually from 10 to 90% and in concentrates in emulsion that can flow, this can be as high as 75%. Water-mixable powders, suitable for spraying, can be prepared by mixing the composition with a finely divided solid, such as inorganic clays, silicates and carbonates, and silicas and with the incorporation of soaking agents, tackifiers and / or dispersing agents in such mixtures. The concentration of the first and second active compounds combined in such formulations is usually in the range of 20 to 98%, preferably 40 to 75%. The powders are prepared by mixing the composition of the present invention, or its salts and complexes, with finely divided inert solids, which may be organic or inorganic in nature. Useful inert materials for this purpose include botanical flours, silica, silicates, carbonates and clays. A convenient method of preparing a powder is to dilute a powder mixable in water with a finely divided carrier. The powder concentrations contain from 20 to 80% of the first and second active compounds combined and are commonly obtained and subsequently diluted to a use concentration of 1 to 10%. The method of the present invention, in which an N-acetonylbenzamide and a second fungicidally selected active compound, are applied to the seeds of plants, foliage of plants or to the growth medium of the plants, unexpectedly provides a greater activity fungicide compared to the same compounds used separately. The results provided by the mixtures were compared with the predicted results, which were calculated using the formula indicated by SR Colby in Pitees, 1967, 15, 20-22 ("Colby's formula") of the results obtained using each of the compounds individually. The predicted results are also provided in the following Examples. These examples, tables and experimental procedures are provided for the practitioner's guidance and do not mean limitations of the scope of the invention, which is defined by the claims.

Example 1: Test, in vitro, for the control of Phytophthora capsici, with the use of N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro- 4-methylbenzamide (Compound A) and the R enantiomer of metalaxyl (Compound B) Dilution series of Compounds A and B were prepared in dimethyl sulfoxide (DMSO) and parts Aliquots of each were added to 25 ml of melted potato dextrose agar, at 50 ° C, to give the appropriate concentrations shown in the following table. Immediately after adding the compounds, the melted agar was emptied into a Petri dish or plate, 9 cm in diameter, and allowed to harden. The final concentration of DMSO in all plates was 0.25%. The control plates contained DMSO but no other compound. The plates were inoculated in the center with 1 μl of a zoospore suspension of Phytophthora capsici (ATCC 15399, available from the American Type Culture Collection, Rockville, Maryland, E.U.A.), containing 5 x 10 ^ zoospores per milliliter. Three replica plates were used for each treatment. The diameters of the fungal colonies were measured after growing for 7 days at 25 ° C and two measurements were taken from each plate. Growth inhibition was calculated by comparing the growth in the treatments with Compound A and / or B, with the growth in the controls. The degree of inhibition (observed) was expressed as a percentage in the following Table 1. The percent inhibition predicted in the treatments containing both Compound A and B, were calculated using the Colby Formula.

Table 1 - Control of Phytophthora capsici Example 2: Test, in vitro, for the control of Phytophthora capsici with the use of N-3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro-4- methylbenzamide (Compound A) and oxadixyl (Compound C) The experimantal procedure and analyzes are as described in Example 1 and the results are presented in Table 2.

Table 2 - Control of Phytophthora capsici Example 3: Test, in vitro, to control Phytophthora capsici, with the use of N- [3 '- (1'-c-oro-3' -methyl-2'-oxopentan)] -3,5-dichloro-4 -methylbenzamide (Compound A) and Ofurace (Compound D) The experimental procedure and analyzes are as described in Example 1 and the results are presented in Table 3.

Table 3 - Control of Phytophtora capsici Example 4: Test, in vitro, to control Phytophthora capsici, with the use of N- [2 '- (1'-chloro-3' -metxl-2'-oxopentan)] -3,5-dichloro-4 -methylbenzamide (Compound A) and Benalaxyl (Compound E) The experimental procedure and analyzes are as described in Example 1 and the results are presented in Table 4.

Table 4 - Control of Phytooph hour capsici

Claims (15)

1. CLAIMS 1. A composition, which includes: (a) a quantity, fungicidally effective, of a first compound, fungicidally active, having the formula: or a salt, agronomically acceptable, of the same, in which: R! and R3 are each, independently, halogen or (C1-C4) alkyl; R2 is (C1-C4) alkyl, (C2-C4) alkenyl, (C2-C6) alkynyl, (C1-C4) alkoxy or cyano; R4 and R5 are each, independently, a hydrogen atom or (C1-C4) alkyl, with the proviso that at least one of R4 and R5 is (C2-C4) alkyl; and X is halogen, thiocyano or isothiocyano; (b) a fungicidally effective amount of a second compound, fungicidally active, which is an acylalanine type fungicide; and (c) an agronomically acceptable carrier.
2. 2. The composition of claim 1, wherein the first compound, fungicidally active, is selected from the group consisting of: N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3, 5-dichloro-4-methylbenzamide, N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-ethylbenzamide, N- [3' - (1 '-chloro-3' -methyl-2 '-oxopentan)] -3,5-dichloro-4-ethoxy-benzamide, N- [3' - (1'-chloro-3 '-methyl-2' -oxopentan)] - 3, 5-dichloro-4-methoxybenzamide, N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-cyanobenzamide, and N- [3' - (1 '-chloro-3' -methyl-2 '-oxopentan)] -3,5-dibromo-4-methylbenzamide, or a mixture thereof.
3. 3. The composition of claim 2, wherein the first compound, fungicidally active, is selected from the group consisting of: N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro-4-methylbenzamide. N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dibromo-4-cyanobenzamide, or mixtures thereof.
4. 4. The composition of claim 3, wherein the first compound, fungicidally active, is N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro- 4- methylbenzamide.
5. 5. The composition of one of claims 1 to 4, wherein the second compound, fungicidally active, is selected from the group consisting of: the R-enantiomer of metalaxyl, the racemic mixture of metalaxyl, oxadixyl, furalaxyl, benalaxyl, ofurace and ciprofuram.
6. 6. The composition of claim 5, wherein the second compound, fungicidally active, is selected from the group consisting of: the R-enantiomer of metalaxyl, oxadixyl, ofurace and benalaxyl.
7. 7. A method for controlling phytopathogenic fungi in a plant, which comprises the application of: (a) a fungicidally effective amount of a first fungicidally active compound having the formula (I): or a salt, agronomically acceptable, of the same, in which: R! and R3 are each, independently, halogen or (C1-C4) alkyl; R2 is (C1-C4) alkyl, (C2-C4) alkenyl, (C2-C6) alkynyl, (C1-C4) alkoxy or cyano; R4 and R5 are each, independently, a hydrogen atom or (C1-C4) alkyl, with the proviso that at least one of R4 and R5 is (C2-C4) alkyl; and X is halogen, thiocyano or isothiocyano; (b) a fungicidally effective amount of a second fungicidally active compound, which is an acylalanine type fungicide; and (c) an agronomically acceptable carrier, to the seeds of the plant, to the foliage of the plant or to the growth medium for the plant.
8. 8. The method of claim 7, wherein the first compound, fungicidally active, is selected from the group consisting of: N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3, 5-dichloro-4-methylbenzamide, N- [3 '- (1'-chloro-3'-methyl-2'-oxopentan)] -3,5-dichloro-4-ethylbenzamide, N- [3' - (1 '-chloro-3' -methyl-2 '-oxopentan)] -3,5-dichloro-4-ethoxybenzamide, N- [3' - (1'-chloro-3 '-methyl-2' -oxopentan)] - 3, 5-dichloro-4-methoxybenzamide, N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro-4-cyanobenzamide, and N- [3 ' - (1 '-chloro-3' -methyl-2 '-oxopentan)] -3,5-dibromo-4-methylbenzamide, and mixtures thereof.
9. 9. The method of claim 8, wherein the first compound, fungicidally active, is selected from the group consisting of: N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3, 5-dichloro-4-methylbenzamide. N- [3 '- (1' -chloro-3 '-methyl-2' -oxopentan)] -3,5-dibromo-4-cyanobenzamide, or mixtures thereof.
10. 10. The composition of claim 9, wherein the first compound, fungicidally active, is N- [3 '- (1'-chloro-3' -methyl-2'-oxopentan)] -3,5-dichloro- 4- methylbenzamide.
11. 11. The method according to one of claims 7 to 10, wherein the second compound, fungicidally active, is selected from the group consisting of the R-enantiomer of metalaxyl, the racemic mixture of metalaxyl, oxadixyl, furalaxyl, benalaxyl, ofurace and ciprofuram.
12. 12. The composition of claim 11, wherein the second compound, fungicidally active, is selected from the group consisting of the R-enantiomer of metalaxyl, oxadixyl, ofurace and benalaxyl.
13. 13. The method of claim 11, wherein the phytopathogenic fungi belong to the Oomycetes class, and are of the genus Phytophthora, Plasmopara, Peronospora, Albugo or Pseudoperonospora.
14. 14. The method of claim 11, wherein the plant is a potato plant, a tomato plant, a vine plant or a cucumber plant.
15. 15. The method of claim 11, wherein the applied amounts of the first second compound, fungicidally active, are from 2 pairs by weight up to 90 parts by weight of the first compound, fungicidally active, and from 10 parts by weight up to 98 parts by weight of the second fungicidally active compound, per 100 parts by weight of the combined amount of the first and second fungicidally active compounds.