MX2011010392A - Compositions and methods to control fungal pathogens. - Google Patents

Abstract

Disclosed herein are acylhydrazone and semicarbazones derivatives of aldehydes and ketones that may act to attract plant pathogenic zoospores and methods of using these compounds. These compounds include the compound according to Formula 1 : wherein: X is selected from the group consisting of: (CH2)n, 1,3-phenylene and 1,4-phenylene; R1 is selected from the group consisting of iso-butyl, sec -butyl and tert-butyl- CH2; R2 is hydrogen or methyl; and n is equal to 0-25. Upon exposure to water, these compounds release aldehydes or ketones that may attract zoospores. These compounds can be combined with fungicides to form fungicidal formulations that are especially effective against oomycete producing fungal pathogens.

Description

COMPOSITIONS AND METHODS TO CONTROL PATHOGENS OF FUNGI Field of the Invention The different aspects described herein relate to new attractants of fungal zoospores, compositions that release them which may be well suited to the formulation with fungicides in different compositions that can be used in methods to control fungi.

Background of the Invention Economically important plants can be attacked by a diverse range of plant pathogens. Many of these resulting diseases are caused by pseudo oomycete fungi. Many of these diseases caused by oomycete pathogens such as late potato or tomato rust, grape villous mold or vellum vegetable mold diseases can be especially harmful.

The life cycle of many of the pathogens of oomycetes comprises a series of spore forms that are very important in the spread and spread of these diseases. For example, during the asexual life cycle of a number of pseudo-fungal oomycetes, such as Phytophthora infestans, the cause of late rust of potatoes, and Plasmopara viticola, which causes the villous rust of the grapes, the non-mobile spores called sporangia are produced by fungal pathogens. Under suitable conditions, the sporangia content forms additional spores called zoospores. Zoospores have flagella and have the ability to swim in water, that is, they are mobile. Zoospores serve as the main agents of infections swimming towards and enquistándose near the stoma of a plant or other suitable places in the leaf, the stem, the root, the seed and the tubers to infect the plant. In the foliage, the stoma is then entered by the germ tubes from the germinating cysts or in some cases, the germ tube of the encysted zoospora can penetrate directly into the leaf and root surface.

Researchers have identified several known chemicals that attract fungal zoospores. These zoospore attractants can generally be described as a substance or compound that causes a chemotactic response from part of the zoospore. Examples of some zoospore attractant chemicals are described in the article "Fatty acids, aldehydes and alcohols as attractants for zoospores of Phytophthora palmivora" in Nature, volume 217, page 448, by Cameron and Carlile. Additional examples of zoospore attractants can be found in the articles "Biology of Zoospores of Phytophthora" in Phytopathology, volume 60, pages 1128 to 1135 of Hickman and "Chemostatic response of zoospores of five species of Phytophthora" in Phytopathology, volume 63, page 1511 of Khew. The descriptions of each of the aforementioned articles are expressly incorporated by reference to the present description.

Generally, these chemicals or zoospore-attracting substances are produced by the root region of plants and can increase the infection process in the rhizosphere to make it possible for zoospores to locate a spot for infection. It is possible that the foliage of the plant or the specific foliage sites also produce substances that are attractive to zoospores. Substances have been tested for their ability to attract zoospores through chemotaxis using a variety of published methods such as those that employ the capillary tubes that emanate the substance to be tested. These methods are generally applicable and are described in different publications, including: 1. Donaldson, S.P. and J.W. Deacon 1993. New Phytologlst, 123: pages 289 to 295. 2. Tyler, B.M., M-H. Wu, J- Wang, W. Cheung and P.F. Morris. 1996. Applied and Environmental Microbiology, 62: pages 2811 to 2817. 3. Khew, K.l. and G.A. Zentmeyer 1973. Phytopathology, 63: pages 1511 to 1517.

Generally, compounds that are to be tested for their ability to attract zoospores through chemotaxis must have a sufficient solubility in water or, if they have a poor solubility in water, they must be in a suitable physical form or matrix to allow sufficient release of the test compound. Researchers have discovered that certain synthetic or naturally occurring short chain aldehydes and ketones (C4-C8) are potent attractants of zoospores. Furthermore, it has been shown that these aldehydes and ketones improve the effectiveness of fungicides that have inherent effects on the pathogens of the oomycetes when they are applied in admixture with them. However, the utility of most aldehydes and short chain ketones for this purpose is limited by certain physical properties such as high volatility or high solubility in water.

The present disclosure provides new methods and compositions for controlling plant pathogens by oomycete fungi. The composition of the invention generally comprises a composition suitable for controlling oomycete fungi capable of producing zoospores, including the composition of an effective agricultural meritorious amount of a fungicide and at least one zoospora-attractant derivative derived from a ketone zoospore attractant molecule or short chain aldehyde.

Brief Description of the Invention One embodiment is a composition suitable for attracting zoospores of oomycete fungi. The derivative is hydrolyzed in water over time to release a zoospore attractant. An additional embodiment is a mixture of these zoospore attractant derivatives and an agriculturally effective amount of an effective fungicide in oomycete fungi.

One modality is an attractant derivative of zoospora that at the time of its exposure to water releases a zoospore attractant. These attractant derivatives are generally either acylhydrazones or semicarbazones and include compounds selected from the group consisting of Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, and Formula 6 wherein Formula 1 is: where, isobutyl, sec-butyl, or tert-butyl-CH2; R? = H; and n = from 0 to 25; Formula 2 is: where, sec-butyl, or tert-butyl-CH2; and 2 = H; the Formula 3 is: wherein, R = so-butyl, sec-butyl, or tert-butyl-CH2; and R2 = H; Formula 4 is: where, = so-butyl, R2 = H; and R3 = an n-alkyl including from 2 to 25 carbons, excluding n-heptyl or n-undecyl alkyls, or a branched alkyl including from 4 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 3 to at 25 carbons, or a substituted or unsubstituted arylalkyl including from 12 to 26 carbons; or R, = sec-butyl, or tert-butyl-CH2; R2 = H; and R3 = an n-alkyl including from 1 to 25 carbons, or a branched alkyl including from 3 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 7 to 25 carbons, or a substituted or unsubstituted arylalkyl which includes from 7 to 25 carbons, or Ri = so-butyl, R2 = methyl; and R3 = an n-alkyl including 2, 3, 6 and 12 to 25 carbons, or a branched alkyl including from 3 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 3 to 25 carbons, or a substituted or unsubstituted arylalkyl including from 7 to 25 carbons; Formula 5 is: wherein, R 4 = H, alkyl or haloalkyl or alkoxy or alkylthio, or haloalkoxy or haloalkylthio, each including 1 to 4 carbons, or halo, hydroxyl, nitro, carboxylic acid, carboxylic acid derivatives or cyano; and any R n = sec-butyl, or tert-butyl-CH 2; and 2 = H; or R, = iso-butyl; and R2 = methyl; or Formula 6 is: where; R 4 = H, alkyl or haloalkyl or alkoxy or alkylthio, or haloalkoxy or haloalkylthio, each including 1 to 4 carbons, or halo, hydroxyl, nitro, carboxylic acid, carboxylic acid derivatives or cyano; and any R- \ = iso-butyl, sec-butyl, or tert-butyl-CH2; and R2 = H; or R, = iso-butyl; and R2 = methyl.

Another embodiment is a method for controlling a fungal pathogen, comprising the steps of: applying at least one composition according to Formulas 1 through 6, mixed with an agriculturally effective amount of a fungicide to an area adjacent to the fungus pathogen . In one embodiment, the fungal pathogen is an oomycete fungus pathogen and the above mixture is applied to the plant tissue before the fungus pathogen has initiated an infection.

Yet another embodiment is a formulation for the control of a fungus, comprising: at least one compound selected from the group including Formulas 1 to 6 and at least one fungicide. In one embodiment, the fungicide is effective against a fungus that produces mobile zoospores. In one embodiment, one or more fungicides are selected from the group consisting of: mancozeb, maneb, zineb, thiram, propinéb, metiram, copper hydroxide, copper oxychloride, Bordeaux mixture, captan, folpet, amisulbrom, azoxystrobin, trifloxystrobin, picoxystrobin , cresoxima-methyl, fluoxastrobin, pyraclostrobin, famoxadone, fenamidone, metalaxyl, mefenoxam, benalaxyl, cymoxanil, propamocarb, dimetomorf, flumorf, mandipropamide, iprovalicarb, bentiavalicarb-isopropyl, valifenal, zoxamide, etaboxam, ciazofamide, fluopicolide, fluazinam, chlorothalonil, ditianon , fosetyl-A1, phosphorus acid, tolylfluanid, and 4-fluorophenyl (1S) -1- ( { [(1 R, S) - (4-cyanophenyl) ethyl] sulfonyl} methyl) propylcarbamate. In one embodiment, the fungicide is a fungicide that is not based on copper. In a further embodiment, the fungicide can be a compound of Formula I, wherein: wherein R 1 is ethyl, 1-octyl, 1-nonyl, or 3,5,5-trimethyl-1 -hexyl and R 2 is methyl, ethyl, 1-propyl, 1-octyl, trifluoromethyl, or methoxymethyl.

Yet another embodiment is a method for controlling a fungal infection comprising the steps of: providing at least one formulation including at least one compound selected from Formulas 1 to 6, at least one fungicide and applying an agriculturally effective amount of the formulation or mixture to an area adjacent to a fungus. In one embodiment, the mixture including the attractant derivative and the fungicide is applied to at least one of the plant, foliage of the plant, buds, stems, fruits, the area adjacent to the plant, soil, seeds, germinating seeds, roots, liquid and solid growth media, and hydroponic growth solutions.

In one embodiment, the formulation comprises at least one zoospore attractant derivative and at least one effective fungicide in oomycete fungal pathogens, which is adapted to control diseases caused by fungal pathogens oomycetes selected from the group consisting of Phytophthora infestans, Plasmopara viticola , Phytophthora capsici, Pseudoperonospora cubensis, Bremia lactucae, Phytophthora phaseoli, Phytophthora nicotiane var. parasitic, Sclerospora graminicola, Sclerophthora rayssiae, Phytophthora palmivora, Phytophthora citrophora, Sclerophthora macrospora, Sclerqphthora graminicola, Phytophthora cactorum, Phytophthora syringe, Pseudoperonospora humuli, and Albugo candida.

In another embodiment, the zoospore attractant derivative can release zoospore attractants such as C4-C8 aldehydes or ketones selected from the group consisting of isovaleraldehyde, 2-methylbutyraldehyde, valeraldehyde, isobutyraldehyde, butyraldehyde, 4-methylpentanal, 3,3-dimethylbutyraldehyde, 3-methylthiobutyraldehyde, 2-cyclopropylacetaldehyde, 3-methylcrotonaldehyde, 2-ethylcrotonaldehyde, crotonaldehyde, 2-methylcrotonaldehyde, 3-indolecarbaldehyde, furfural (2-furaldehyde), 2-thiophenecarboxaldehyde, 2-ethyl butyraldehyde, cyclopropanecarboxaldehyde, 2,3-dimethylvaleraldehyde, 2-methylvaleraldehyde, tetrahydrofuran-3-carboxaldehyde, cyclopentanecarboxaldehyde, 3-methyl-2-pentanone, 4,4-dimethyl-2-pentanone, 3,3-dimethyl-2-butanone, and 4-methyl-2-pentanone.

It is contemplated that the substances that induce the encystment of the zoospores, such as pectin, a metal ion, and an inorganic compound or an inorganic salt compound selected from the group consisting of Ca, Zn, Mg, Mn, NaN03, KN03, and NaCl can be added to the compositions containing the fungicide and an attractant derivative of zoospores to further improve the control of the disease.

Brief Description of the Figures Figure 1 shows some derivatives of acylhydrazone and semicarbazone of aldehydes and ketones used according to the methods described herein and tested for their ability to attract zoospores.

Figure 2 shows a summary of the data collected by testing the ability of several derivatives of acylhydrazone and semicarbazone of aldehydes and ketones to attract the mobile zoospores of Phytophthora capsici (PHYTCA) and Plasmopara viticola (PLASVI).

Detailed description of the invention In order to promote an understanding of the principles of novel technology, reference will now be made to the different exemplary modalities of the same, and a specific language will be used to describe them. However, it should be understood that there is no limitation of the scope of the novel technology intended by such alterations, modifications, and applications of the additional principles of the novel technology that is being contemplated as would normally occur to an expert in the art with which relates the new technology.

The present invention relates to compounds that are or can form derivatives of zoospore-attracting compounds that release zoospore attractants and can be used to increase the efficacy of fungicides for control the diseases of plants caused by oomycete pathogens. The methods of the present invention comprise contacting a plant that is at risk of becoming diseased with an oomycefe pathogen that produces zoospores with a composition comprising an effective amount of a fungicide and a zoospore-attracting derivative. Alternatively, a mixture of different attractants of zoospores and zoospore-attracting derivatives can be used with a fungicide or a mixture of different fungicides.

Although we do not want to be compromised by any theory, it is considered that the incrustation, coating or surrounded by fungicide particles with an attractant derivative of zoospora to create a concentration gradient of a zoospore attractant around the particle of the fungicide that attracts the zoospores towards the fungicide, could improve the effectiveness of the composition. By attracting zoospores to the fungicide particle, control of the sick area of the fungicide can be increased, possibly by decreasing the amount of fungicide use or by prolonging the period of disease control. Additionally, a wider range of fungicides can be used, including fungicides that have limited redistribution on the plant surface.

Although we do not wish to be compromised by any theory, it is considered that the use of the attractive derivative of zoospores could improve the effectiveness of active zoospore fungicides such as thiocarbamates, mancozeb, maneb, zineb, thiram, propineb, or metiram; copper-based fungicides such as copper hydroxide, copper oxychloride, or Bordeaux blends; phthalimide fungicides such as captan and folpet; amisulbrom; strobilurins such azoxystrobin, trifloxystrobin, picoxystrobin, cresoxim-methyl, fluoxastrobin, pyraclostrobin and others; famoxadone; fenamidone; metalaxyl; mefenoxam; benalaxyl; cymoxanil; propamocarb; dimetomorf; flumorf; mandipropamide; iprovalicarb; benthiavalicarb-isopropyl; valifenal, zoxamide; etaboxam; Ciazofamide; fluopicolide; fluazinam; Chlorothalonil; ditianon; fosetyl-AL, phosphorus acid; tolylfluanid, or aminosulfones such as 4-fluorophenyl (1 S) -1 - ( { [(1 R, S) - (4-cyanophenyl) ethyl] sulfonyl} methyl) propylcarbamate or the following triazolopyrimidine compounds such as those shown in Formula I: I wherein R 1 is ethyl, 1-octyl, 1-nonyl, or 3,5,5-trimethyl-1-hexyl and R 2 is methyl, ethyl, 1-propyl, 1-octyl, trifluoromethyl, or methoxymethyl.

The attractive zoospore attractant derivatives and the The attractants that they release may vary depending on the type of plant, the pathogen of the fungus and the environmental conditions. Typical attractants of zoospores may include, for example, derivatives of C4-C8 aldehydes or C4-C8 ketones. The zoospore attractant derivatives can also be absorbed onto or embedded in an inert substrate such as PergoPak M, corn starch, clay, latex agglomerates, or fertilizer particles.

The zoospore attractant derivatives can be used for purposes such as the controlled release of the attractant molecule. Zoospore attractant derivatives are chemical compounds generally made or derived from zoospore attractant molecules. The zoospore attractant derivatives can be used in combination with zoospore attractants and fungicides. Suitable zoospore attractant derivatives such as acylhydrazone derivatives and semicarbazone derivatives of different aldehydes and ketones may be less volatile and / or water soluble than their corresponding aldehydes or ketones. These derivatives can produce or release the zoospore attractants once the derivative is contacted with water on the surface of a plant or the area adjacent to the plant. Examples of the hydrazone derivative technology are included in PCT Patent Application No. WO20060 6248 and the article entitled "Controlled release of Volatile aldehydes and ketones through the reversible formation of "classical" hydrazone-forming proragances that are becoming dynamic "by Levrand and associates, published in Chemical Communications (Cambridge, UK) (2006) on pages 2965 to 2967 (ISSN: pages 1359 to 7345. The description of each of the above references is expressly incorporated by reference to the present disclosure, and various useful and novel methods for the synthesis of the acylhydrazone and semicarbazone derivatives are provided herein.

Reaction 1, shown below, describes how the generic zoospore attractant derivatives, such as those shown in Formulas 1 through 6, release the zoospore attractants upon contact with water. . The amount of production of the zoospore attractant depends on many factors, among them: the physico-chemical properties of the zoospore attractant derivatives, the composition of the formulation containing the derivative, the presence and duration of water on the surface of the plant , and the temperature, humidity and other environmental conditions in the area of the application. As shown, this hydrolysis reaction is theoretically reversible, but this reversibility under practical agricultural conditions is likely to be low. attractive attractant derivative of of zoospora zoospora Reaction 1 The aforementioned zoospore attractant derivatives when used in combination with fungicides can provide particularly effective control of diseases caused by the pathogens Phytophthora infestans, Plasmopara viticola, Phytophthora capsici, and Pseudoperonospora cubensis. Other pathogens that can also be controlled in a variety of plants such as tomatoes, potatoes, peppers, grapes, cucurbit, lettuce, beans, sip, corn, citrus, grassland, pecan, apples, pears, hops, and crucifiers include: Bremia lactucáe , Phytophthora phaseoli, Phytophthora nicotiane var. parasitic, Sclerospora graminicola, Sclerophthora rayssiae, Phytophthora palmivora, Phytophthora citrophora, Sclerophthora macrospora, Sclerophthora graminicola, Phytophthora cactoru, Phytophthora syringe, Pseudoperonospora humuli, and Albugo candida.

The effective amount of the zoospore attractant derivatives to be used with the fungicide often depends on, for example, the type of plants, the stage of plant growth, the severity of the environmental conditions, the pathogen of the fungus and the conditions of application. Generally, a plant that needs protection against fungus, control or elimination is contacted with an amount of the zoospore attractant derivative of from about one to about 5000 ppm, preferably from about 10 to about 1000 ppm of the zoospore attractant derivative. The contact can be in any effective way. For example, any exposed part of the plant, for example, leaves or stems may be sprayed with the attractant in admixture with effective amounts of a fungicide The attractant derivative may be formulated therein in a suitable agricultural vehicle comprising 1% to 95% by weight of the formulation One or more attractive derivatives can be co-formulated with one or more attractants of zoospores and one or more fungicides as a liquid or a solid wherein the attractants, attractant derivatives, or mixture of one or more attractants or attractant derivatives comprise from 1% to 50% of the formulation.

The attractant derivatives of zoospores improved with the aforementioned fungicides can be applied to the foliage of the plants or the soil or the area adjacent to the plant. Additionally, the zoospore attractant derivatives improved with fungicides can be mixed with, or applied with any combination of herbicides, insecticides, bacteriocides, nematocides, miticides, biocides, termiticides, rodenticides, moluscidas, artropodicides, fertilizers, growth regulators, and pheromones.

Experiments Section The general scheme for the synthesis of the different acylhydrazone and semicarbazone derivatives of different aldehydes and ketones of the present disclosure are shown below in Scheme 1.

Scheme 1 For Scheme 1, R1 is an alkyl, R2 is a hydrogen or a methyl, R3 is an aliphatic group and n is from 0 to 8.

Synthesis of Compounds 10 v 12 Briefly, a mixture of 10.0 g (51.5 mmol) of bis- hydrotide of isophthalic acid, 150 ml_ of absolute ethanol and 124 millimole of aldehyde, were heated to reflux for a time of eight to 24 hours. Analysis by TLC indicated the complete consumption of the starting hydrazide. The mixture was allowed to cool to room temperature for many hours and then filtered. The white solid obtained was washed with ethanol and then dried to constant weight in a vacuum oven at a temperature of 40 ° C to 50 ° C. The isolated solid was analyzed by proton nuclear magnetic resonance spectroscopy and by means of an elemental analysis and the results of these analyzes are consistent with the assigned structure. The melting point was also determined.

Synthesis of Compound 5 Briefly, a 250 ml dry round bottom flask equipped with a magnetic bar, thermometer was charged, and the reflux condenser was charged with 10.0 g (57.4 mmol) of adipic acid dihydrazide, 0.5 mL of glacial acetic acid and 150 mL of absolute ethanol. After most of the solids had dissolved, 13.5 mL (126 mmol) of isovaleraldehyde was added to the flask and then heated to reflux for four hours. The progress of the reaction was carried out by extracting an aliquot of the reaction mixture and analyzing it by HPLC. Once the reaction had proceeded to near completion, the mixture was cooled: at room temperature. The resulting solid was collected by vacuum filtration, rinsed with hexanes and dried under vacuum at a temperature of 40 ° C. Approximately 16 g of a white solid product was isolated (yield 90%). The structure of the product was consistent with the structure of compound 5 determined by the 300 MHz analysis of H NMR and HPLC / MS. The melting point was determined between 204 ° C and 206 ° C. Similar methods were used to produce the compounds from 1 to 9 and compound 11 in Figure 1.

Design of the activity trial through zoospora Referring now to Figure 1, the compounds on the list were evaluated for their ability to attract mobile zoospores from two different fungi Phytophthora capsici (PHYTCA) and Plasmopara viticola (PLASVI). Compounds with sufficient water solubility were tested as 5 mM solutions. The compounds with insufficient solubility in water were ground and formulated as 10% suspension concentrates. The solutions for the suspension concentrates were placed in 1.0 cm Drummond 2 Microcapsule capillary tubes. The tubes were placed in the reservoir of a 12-well plate and held in place with a small drop of Dow Corning vacuum grease.

Briefly, for use in these assays, Phytophthora capsici was cultured on V-agar 8. When the culture was aged 5 to 7 days, and was producing abundant sporangia, the production of zoospores was initiated by adding 15 ml of sterile water to the license plate. After 10 minutes at room temperature, the flooded plate was placed in a refrigerator at a temperature of 4 ° C for 20 minutes. Then the plate was returned to room temperature for a period of 30 to 60 minutes. The zoospore suspension was then filtered through a Whatman 113V filter paper.

In order to start the production of the zoospores of Plasmopara viticola, the sporangia was collected from three leaves of grapes (Vitis vinifera cv Carignane) that were completely infected and that produced an abundant sporulation. The infected leaves were placed in deionized water and the sporangia was dislodged by light brushing; the sheet. The solution including the evacuated sporangium was allowed to settle at room temperature for 10 minutes. The solution was transferred to a refrigerator at a temperature of 4 ° C for 20 minutes and then returned to room temperature for a period of 60 to 90 minutes, at which time large numbers of zoospores were present. The zoospore suspension was then filtered through the Whatman 113V filter paper.

Approximately 1 ml of zoospore suspension was placed in the tanks containing the capillary tubes of chemicals that are to be tested for the attractant activity. After a period of 60 to 90 minutes, the level of attraction was rated by looking at the capillary tube and the solution under a microscope and comparing the number of zoospores that had swum in the capillary tube with the number of the external solution. This proportion was rated semiquantitatively on a scale of 1 to 10, representing the 1 non-accumulation of zoospores within the capillary tube, representing 2 an accumulation of zoospores within the capillary tube approximately equal to the density of zoospores in the external solution, representing the 5 an accumulation of approximately five times the density in the external solution and 10 representing a capillary tube filled with zoospores in a density too numerous to count. The average ratings from one to three were categorized as Light Attraction; the average grades from four to seven were categorized as Moderate Attraction; the average grades from eight to 10 were categorized as High Attraction. These results are summarized in Figure 2. As an alternative to this method, the procedures for determining the attraction of zoospores referred to in the Background are generally applicable and may also be employed.

The compounds of the present invention which have attractive properties of zoospores can be beneficially combined with the number of fungicides, especially fungicides which are active against pathogens by oomycete fungi. Useful fungicides include the group consisting of mancozeb, maneb, zineb, thiram, propineb, metiram, copper hydroxide, copper oxychloride, Bordeaux mixture, captan, folpet, amisulbrom, azoxystrobin, trifloxystrobin, picoxystrobin, cresoxim-methyl, fluoxastrobin, pyraclostrobin, famoxadone, fenamidone, metalaxyl, mefenoxam, benalaxyl, cymoxanil, propamocarb, dimetomorf, flumorf, mandipropamide, iprovalicarb , bentiavalicafb-isopropyl, valifenal, zoxamide, etaboxam, ciazofamide, fluopicolide, fluazinam, chlorothalonil, dithianon, fosetyl-AL, phosphorus acid, tolylfluanid, 4-fluorophenyl (1 S) -1 - ( { [(1 R, S) - (4-cyanophenyl) ethyl] sulfonyl} methyl) propylcarbamate and triazolopyrimidine compounds such as those shown in Formula I: I wherein R 1 is ethyl, 1-octyl, 1-nonyl, or 3,5,5-trimethyl-1 -hexyl and R 2 is methyl, ethyl, 1-propyl, 1-octyl, trifluoromethyl, or methoxymethyl.

The compounds of the present invention are preferably applied in the form of a composition comprising one or more of the compounds of Formulas 1 to 6 with a filologically acceptable carrier. The compositions are either concentrated formulations which are dispersed in water or other liquid for the application, or are powders or granular formulations which are applied without further treatment. The compositions are prepared according to methods that are conventional in the agricultural chemistry art, but which are novel and important due to the presence therein of the compounds of the present invention. Some description of the formulation of the compositions is provided to ensure that agricultural chemicals can easily prepare the desired compositions.

The dispersions in which the compounds are applied are most frequently aqueous suspensions or emulsions prepared from concentrated formulations of the compounds. Said water-soluble, water-suspendable, or emulsifiable formulations are either solid, generally known as wettable powders, or liquids, generally known as emulsifiable concentrates, or aqueous suspensions. The present invention contemplates all vehicles by means of which the compounds of the present invention can be formulated for administration with a fungicide. As will be readily appreciated, any material, to which these compounds can be added, can be used, provided that they yield the desired utility without significant interference with the activity of the compounds of the present invention.

Moisturizing powders, which can be compacted to form water dispersible granules, comprise an intimate mixture of the active compound, an inert carrier, and surfactants. The concentration of the active compound is generally from about 1% to about 95% w / w, and more preferably from about 1% to about 50% w / w. In the preparation of moistenable powder compositions, the active compound may be composed of any of the finely divided solids, such as prophyllite, talc, chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein, gluten , clays of montmorilonita, earth diatomaceous, purified silicates and the like. In such operations, the finely divided vehicle is ground or mixed with the active compound in a volatile organic solvent. Effective surfactants, comprising from about 0.5% to about 10% of the wettable powder, include sulfonated lignins, naphthalene sulfonates, alkylbenzene sulfonates, alkyl sulfates, and nonionic surfactants such as ethylene oxide adducts of alkyl phenols.

The emulsifiable concentrates of the compounds of the present invention comprise a suitable concentration, such as from about 10% to about 50% w / w, in a suitable liquid. The compounds are dissolved in an inert carrier, which is either a water-miscible solvent or a mixture of water-immiscible organic solvents and emulsifiers. The concentrates can be diluted with water and oil to form dew mixtures in the form of oil-in-water emulsions. Useful organic solvents include aromatics, especially the high boiling naphthalenic and olefinic portions of the petroleum such as heavy aromatic naphtha. Other organic solvents may also be used such as, for example, terpene solvents including rosin derivatives, aliphatic ketones, such as cyclohexanone,! or complex alcohols such as 1-ethoxyethanol.

Emulsifiers which can be used to advantage in this description, can be readily determined by those skilled in the art and include various nonionic, anionic, cationic, and amphoteric emulsifiers, or a mixture of two or more emulsifiers. Examples of the nonionic emulsifiers useful for preparing concentrates that can be emulsified include polyalkylene glycol ethers and condensation products of alkyl and aryl phenols, aliphatic alcohols, aliphatic amines, or fatty acids with ethylene oxide, propylene oxides such as phenols alkyl ethoxylates, and carboxylic esters solubilized with polyol or polyalkylene. Cationic emulsifiers include quaternary ammonium compounds and fatty amine salts. Anionic emulsifiers include the oil soluble salts (eg, calcium) of alkylaryl sulfonic acids, oil soluble salts of sulfated polyglycol ethers, and the appropriate salts of polyglycol phosphate ether.

Representative organic liquids which can be used to prepare the emulsifying concentrates of the present invention are aromatic liquids such as xylene, propyl benzene fractions or mixed naphthalene fractions, mineral oils, substituted aromatic organic liquids such as dioctyl phthalate, kerosene, and dialkyl amides of different fatty acids; particularly the dimethyl amides of fatty glycols and glycol derivatives such as n-butyl ether, ethyl ether, or methyl ether of triethylene glycol. Mixtures of two or more organic liquids are also frequently employed in the preparation of concentrates that can be emulsified. Preferred organic liquids are fractions of xylene and propylbenzene, with xylene being the most preferred. The surface active dispersing agents are generally used in liquid compositions and in the amount of 0.1% to 20% by weight of the combined weight of the dispersing agent and the active compound. The active compositions may also contain other compatible additives, for example, plant growth regulators or other biologically active compounds used in agriculture. It is contemplated that substances that induce the encystment of zoospores, such as pectin, a metal ion, and an inorganic compound or inorganic salt selected from the group consisting of Ca, Zn, Mg, Mn, NaN03, KN03, and NaCl, may be added to the compositions containing a fungicide and an attractant derivative of zoospores to further improve the control of the disease.

Aqueous suspensions of the water-soluble compounds of the present invention are dispersed in an aqueous vehicle in a concentration ranging from about 5% to about 50% w / w. Prepare suspensions by finely grinding the compound and mixing it vigorously in a vehicle comprising water and the surfactants selected from the same types mentioned above. Inert ingredients, such as inorganic salts and synthetic or natural gums, can also be added to increase the density and viscosity of the aqueous vehicle. Often the most effective is to grind and mix the compound at the same time by preparing the aqueous mixture and homogenizing it in an implement such as a sand mill, a ball mill, or a piston-type homogenizer.

The compounds can also be applied as granular compositions which are particularly useful for earth applications. Granular compositions generally contain from about 0.5% to about 10% w / w of the dispersant compound in an inert carrier which consists wholly or in large part of an attapulgite, bentonite, diatomite, clay, or a similar, inexpensive substance divided in a thick way Said compositions are generally prepared by dissolving the compound in a suitable solvent and applying it to a granular carrier which has been previously formed; to the appropriate particle size, in the range of about 0.5 mm to about 3 mm. Said compositions can also be formulated by making a donut or paste of the vehicle and the compound, and grinding them, and drying them for obtain the desired granular particle size.

The powders containing the compounds are prepared by simply intimately mixing the compound in a pulverized form with a suitable powdered agricultural vehicle such as, for example, kaolin clay, ground volcanic rock, or the like. The powders may suitably contain about 1% to about 10% w / w of the compound. '| The active compositions may contain adjuvant surfactants to improve placement, wetting; and penetration of the compositions in the harvest and objective organism. These adjuvant surfactants may be optionally employed as a component of the formulation or as a tank mixture. The amount of surfactant adjuvant will vary from 0.01% to 1.0% v / v based on one spray per volume of water, preferably 0.05% to 0.5%. Suitable adjuvant surfactants include ethoxylated nonyl phenols, ethoxylated natural or synthetic alcohols, salts of sulfosuccinic acid esters, ethoxylated organosilicon, ethoxylated fatty amines, and mixtures of surfactants with mineral or vegetable oils.

The composition may optionally include fungicidal combinations which comprise at least: 1% of one or more of the compounds of the present invention with another pesticidal compound. Said pesticide compounds additional can be fungicides, insecticides, nematocides, miticides, arthropodicides, bactericides or combinations thereof which are compatible with the compounds of the present invention in the medium selected for the application, and not antagonistic to the activity of the compounds present. Accordingly, in such embodiments, the other pesticide compound is employed as a supplemental toxicant for the same or for a different pesticidal use. The compounds in combination can generally be present in a ratio of 1:10 to 100: 1.

The present invention includes within its scope methods for the control or prevention of fungal attacks. These methods include the application to the site of the fungi, or a place where infection should be prevented (for example, by applying it to potato, tomato, cucurbit or grape plants), an effective amount of one or more of the compounds of the invention. the present invention and an agriculturally effective amount of the fungicidal active in the oomycete fungus. The compounds 1 of the present invention are suitable for the treatment of different plants while exhibiting little phytotoxicity. The compounds of the present invention are applied by any of a variety of known techniques, either as the compounds or as compositions that include the compounds. For example, the compounds can be applied to the foliage of plants, buds, stems, fruits, areas adjacent to the plants, soil, seeds, seeds in germination, roots, liquid and solid growth media, and hydroponic growth solutions for the control of different fungi without damaging the commercial value of the plants. The materials are applied in the form of any of the types of formulation generally used, for example, in the form of solutions, powders, moistening powders, concentrates that can flow, or concentrates that can be emulsified. These materials are conveniently applied in different ways.

The compounds of the present invention have broad ranges of efficacy in fungicidal formulations. The exact amount of the zoospore attractant derivatives to be applied depends not only on the specific zoospore attractant derivative to be applied, but also on the particular action desired, the fungal species to be controlled and the growth stage of the zoospore. the same, as well as the part of the plant or another product that is going to put in contact with the effective ingredient fungicidamente. Therefore, the compounds of the present invention, and compositions containing them, may not be equally effective in similar concentrations or against the same fungal species. The compounds of the present invention and the compositions thereof in admixture with fungicides are effective in plants to inhibit disease and in amounts phytologically acceptable.

Although the novel technology has been illustrated and described in detail in the figures and the previous description, it should be considered as illustrative and not of a restrictive nature, being understood that only the varied modalities of example that have been shown and described and that all changes and modifications that are within the spirit of the new technology are desired to be protected. Also, although the novel technology was illustrated using specific examples, theoretical arguments, accounts, and illustrations, these illustrations and the explanations that accompany them by no means should be construed as limiting technology. All patents, patent applications, and references to texts, scientific treatises, publications, and the like referred to in this application are incorporated herein by reference in their entirety.

Claims (17)

1. A composition selected from the group consisting of Formula 1, Formula 2, Formula 3, Formula 4, Formula 5, and Formula 6 wherein, Formula 1 is: where, Ri = iso-butyl, sec-butyl, or tert-butyl-CH2; R2 = H; Y n = from 0 to 25; Formula 2 is: where, Ri = sec-butyl, or tert-butyl-CH2; Y R2 = H; The Formula 3 is: where, = So-butyl, sec-butyl, or tert-butyl-CH2 R2 = H; Formula 4 is: where, Ri = iso-butyl, R2 = H; Y R3 = an n-alkyl including from 2 to 25 carbons, excluding n-heptyl or n-undecyl alkyls, or branched alkyl including from 4 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 3 to 25 carbons, or a substituted or unsubstituted arylalkyl including from 12 to 26 carbons; or R ^ = sec-butyl, or tert-butyl-CH2;; R2 = H; Y R3 = an n-alkyl including from 1 to 25 carbons, or, a branched alkyl including from 3 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 7 to 25 carbons, or a substituted or unsubstituted arylalkyl which includes from 7 to 25 carbons, or Ri = iso-butyl, R2 = methyl; Y R3 = an n-alkyl including 2, 3, 6 and 12 to 25 carbons, or a branched alkyl including from 3 to 25 carbons, or a substituted or unsubstituted cycloalkyl including from 3 to 25 carbons, or an arylalkyl ui the substituted or unsubstituted which includes from 7 to 25 carbons; Formula 5 is: where, I R 4 = H, alkyl or haloalkyl or alkoxy or alkylthio, or haloalkoxy or haloalkylthio, each including 1 to 4 carbons, or halo, hydroxyl, nitro, carboxylic acid, carboxylic acid derivatives or cyano; and any R-i = sec-butyl, or tert-butyl-CH2; Y R2 = H; or R-i = iso-butyl; Y R2 = methyl; Y Formula 6 is: where; R 4 = H, alkyl, or haloalkyl or alkoxy or alkylthio, or haloalkoxy or haloalkylthio, each including 1 to 4 carbons, or halo, hydroxyl, nitro, carboxylic acid, carboxylic acid derivatives or cyano; and any R! = iso-butyl, sec-butyl, or tert-butyl-CH2; Y R2 = H; or, Ri = iso-butyl; Y R2 = methyl.

2. The composition as described in claim 1, characterized in that R1 is isobutyl and R2; it is hydrogen in Formulas 1, 3, 4, and 6.

3. A method by means of which the compositions as described in claim 1, are used as zoospore attractants of oomycete fungi.

4. The method as described in claim 3, characterized in that the zoospores are spores of at least one fungus selected from the group consisting of Phytophthora infestans, Plasmopara viticola, Phytophthora capsici, Pseudoperonospora cubensis, Bremia lactucae, Phytophthora phaseoli, Phytophthora nicotiane. var. parasitic, Sclerospora graminicola, Sclerophthora rayssiae, Phytophthora palmivora, Phytophthora citrophora, Sclerophthora macrospora, Sclerophthora graminicola, Phytophthora cactorum, Phytophthora syringe, Pseudoperonospora humuli, and Albugo Candida.

5. The method as described in claim 3, characterized in that the zoospores are spores of at least one fungus selected from the group consisting of Phytophthora infestans, Plasmopara viticola, Phytophthora capsici, and Pseudoperonospora cubensis.

6. A method for controlling fungal pathogens, comprising the steps of: providing at least one composition as described in claim 1, and applying an agriculturally effective amount of one or more fungicides applied to the plants.

7. A formulation for the control of a fungus, comprising: at least one composition as described in claim 1, and at least one fungicide.

8. The formulation as described in claim 7, characterized in that the fungicide is effective against a fungus that produces mobile zoospores.

9. The formulation as described in claim 8, characterized in that the fungicide is selected from the group consisting of mancozeb, maneb, zineb, thiram, propineb, metiram, copper hydroxide, oxychloride, copper, Bordeaux mixture, captan, folpet, amisulbrom, azoxystrobin, trifloxystrobin, picoxystrobin, cresoxim-methyl, fluoxastrobin, pyraclostrobin, famoxadone, fenamidone, metalaxyl, mefenoxam, benalaxyl, cymoxanil, propamocárb, dimetomorf, flumorf, mandipropamide, iprovalicarb, bentiavalicarb- isopropyl, valifenal, zoxamide, etaboxam, ciazofamide, fluopicolide, fluazinam, chlorothalonil, dithianon, tolylfluanid, 4-fluorophenyl (1 S) -1 - ( { [(1 R, S) - (4-cyanophenyl) ethyl] sulfonyl .) methyl) propylcarbamate and triazolopyrimidine compounds of Formula I: I wherein R.sub.1 is ethyl, 1-octyl, 1-nonyl, or 3,5,5-tri-meth yl-1-hexyl and R.sub.2 is methyl, ethyl, 1-propyl, 1-octyl, trifluoromethyl, or methoxymethyl.

10. A method to control a fungal infection, comprising the steps of: providing at least one formulation as described in claim 9; Y apply an agriculturally effective amount of the formulation to susceptible plants or to an area underlying a fungus.

11. The formulation as described in claim 7, characterized in that the composition further includes at least one zoospore-attracting derivative.

12. The composition as described in claim 7, characterized in that the fungicide is a non-copper based fungicide.

13. The composition as described in claim 7, characterized in that the fungicide is selected to control diseases caused by pathogens of the oomycete fungus selected from the group consisting of Phytophthora infestans, Plasmopara viticola, Phytophthora capsici, Pseudoperonospora cubensis, Bremia lactucae, Phytophthora phaseoli, Phytophthora nicotlane var. parasitic, Sclerospora graminicola, Sclerophthora rayssiae, Phytophthora palmivora, Phytophthora citrophora, Sclerophthora macrospora, Sclerophthora graminicola, Phytophthora cactorum, Phytophthora syringe, Pseudoperonospora humuli, and Albugo Candida.

14. A method to control plant diseases caused by pathogens of the oomycete fungus that includes the steps of: providing a formulation that includes the composition as described in claim 7, and apply an agriculturally effective amount of the formulation to at least one of the following: the plant, the foliage of the plant, buds, stems, fruits, the area adjacent to the plant, soil, seeds, seeds in germination, roots, liquid and solid growth media, and hydroponic growth solutions.

15. The method as described in claim 14, characterized in that the plant is a plant of grape, potato, tomato, cucumber, cayote, and other cucurbits, cabbage and other cruciferous, lettuce, beans, corn, soybeans, peppers or hops.

16. The formulation as described in claim 11, characterized in that the zoospore attractant derivatives release a C4-C8 aldehyde selected from the group consisting of isovaleraldehyde, 2-methylbutyraldehyde, valeraldehyde, isobutyraldehyde, butyraldehyde, 4-methylpentanal, 3,3- dimethylbutyraldehyde, 3-methylthiobutyraldehyde, 2-cyclopropylacetaldehyde, 3-methylcrotonaldehyde, 2-ethylcrotonaldehyde, crotonaldehyde, 2-methylcrotonaldehyde, 3-indolecarbaldehyde, furfural (2-furaldehyde), 2-thiophenecarboxaldehyde, 2-ethyl butyraldehyde, cyclopropanecarboxaldehyde, 2, 3-dimethylvaleraldehyde, 2-methylvaleraldehyde, tetrahydrofuran-3-carboxaldehyde, and cyclopentanecarboxaldehyde.

17. The formulation as described in claim 11, characterized in that the zoospore attractant derivatives release a C4-C8 ketone.