JP2007522110A - Sterilization mixture - Google Patents

Abstract

The present invention relates to a bactericidal mixture containing as active ingredients 1) a triazolopyrimidine derivative of formula (I) and 2) phenpropidine of formula (II) in a synergistic amount. The present invention also relates to a method of controlling pathogenic fungi using a mixture of Compound I and Compound II, the use of Compound I and Compound II to produce such a mixture, and a product comprising the mixture of the present invention.

Description

As an active ingredient, the present invention
1) Formula I

Triazolopyrimidine derivatives, and 2) Formula II

Fenpropidin,
It relates to a sterilizing mixture comprising a synergistic amount.

  Furthermore, the present invention relates to a method for controlling harmful fungi using a mixture of compound I and compound II, the use of compound I and compound II to prepare such a mixture, and a composition comprising these mixtures .

  Compound I, 5-chloro-7- (4-methylpiperidin-1-yl) -6- (2,4,6-trifluorophenyl)-[1,2,4] triazolo [1,5-a] pyrimidine Its preparation and its action against harmful fungi are known from the literature (WO 98/46607).

  Compound II, 1- [3- (4-tert-butylphenyl) -2-methylpropyl] piperidine, its preparation and its action on harmful fungi are likewise known from the literature (DE OS 27 52 096; US 4 202 894; Generic name: Fenpropidin).

  Mixtures of triazolopyrimidine and other active compounds are known in general form from EP-A 988 790 and US 6 268 371.

  The synergistic mixture described in EP-A 988 790 is described to show bactericidal activity against various diseases of cereals, fruits and vegetables, in particular wheat and barley powdery mildew or apple gray mold. The mixture described in US 6 268 371 is described to show bactericidal activity, in particular bactericidal activity against rice pathogens. However, their bactericidal activity against harmful fungi belonging to the class of Oomycetes is not satisfactory.

  Since oomycetes are biologically closer to algae than fungi, the biological behavior of oomycetes is clearly different from that of Ascomycetes, Deuteromycetes, and Basidiomycetes. Therefore, what is known about the bactericidal activity of active compounds against "fungi" such as ascomycetes, incomplete fungi and basidiomycetes can only be applied to oomycetes to a very limited extent.

  Oomycetes cause economically relevant damage to various crops. In many areas, infection by Phytophthora infestans during the cultivation of potatoes and tomatoes is the most serious plant disease. In the case of grape cultivation, it is greatly damaged by grape downy mildew (peronospora).

  Based on practical experience in agriculture, repeated application of only a single active compound for the control of harmful fungi often quickly leads to a strain of said fungus with natural or adaptive developed resistance to the active compound Shown to be selected. As a result, it is no longer possible to effectively control these fungi with the active compound.

  Recently, a mixture of different active compounds is preferably used to control harmful fungi in order to reduce the risk of selecting resistant strains. By combining active compounds having different mechanisms of action, it is possible to ensure effective control over a relatively long period of time.

  The object of the present invention is to effectively take measures against tolerance of phytopathogenic harmful fungi, particularly harmful fungi belonging to the class of oomycetes, and to effectively control the fungi with the smallest possible application amount. The object is to provide a mixture having improved activity against harmful fungi while reducing the total amount of active compound applied.

  We have found that this object is achieved by the mixture defined above. Furthermore, we can achieve with individual compounds by applying Compound I and Compound II simultaneously, ie together or separately, or by applying Compound I and Compound II sequentially. It has been found that it is possible to control harmful fungi better than that (synergistic mixture).

  The use of a mixture of Compound I and Compound II, or Compound I and Compound II simultaneously, ie together or separately, results in a wide range of phytopathogenic fungi, especially ascomycetes, imperfect fungi, oomycetes and basidiomycetes It is excellent in that it is highly active against fungi belonging to the fungal class. They can be used for crop protection as fungicides acting on leaves and soil.

  They include bananas, cotton, vegetable species (eg, cucumbers, beans and gourds), barley, pasture, oats, coffee, potatoes, corn, fruit seeds, rye, soybeans, tomatoes, grapes, wheat, ornamental plants, sugar cane, And particularly important for controlling many fungi in various cultivated plants such as rice and many seeds.

  They are particularly suitable for controlling the following phytopathogenic fungi: cereals Blumeria graminis (powdery mildew), gourds Erysiphe cichoracearum and Sphaerotheca friginea (Sphaerotheca fuliginea), apple Podosphaera leucotricha, grapes Uncinula necator, cereal Puccinia sp., cotton, rice and pasture Rhizoctonia sp., cereals and sugarcane (Ustilago) sp., Venturia inaequalis, cereals, rice and pasture Bipolaris and Drechslera sp., Wheat septoria nodorum, strawberries, vegetables, ornamental plants And grape gray fungus (Botrytis cinerea), banana, lacquer Pseudocercosporella herpotrichoides, Pyricularia oryzae, potato and tomato phytofutra infestance, gourd and gourd pseudoperono Spora (Pseudoperonospora) sp., Grape downy mildew (Plasmopara viticola), vegetable and fruit Alternaria sp., And Fusarium and Verticillium sp.

  In particular, they control the harmful fungi belonging to the class of oomycete in various crop plants such as vegetable plants (eg cucumbers, beans and gourds), in particular the potato and tomato plague caused by phytofutra infestans, and It is particularly suitable for controlling grape downy mildew caused by downy mildew (Plasmopara viticola).

  They can also be used, for example, to protect materials (eg, wood protection) against Paecilomyces variotii.

  Compound I and Compound II can be applied simultaneously, i.e. together or separately, or sequentially, in the case of separate applications, the order generally has no effect on the outcome of the control measures. Don't give.

  When preparing said mixture, it is preferred to use pure active compounds I and II, if necessary further active compounds against harmful fungi or against other pests such as insects, spiders or nematodes, or weeding Alternatively, growth regulating active compounds or fertilizers can be added.

Further active compounds suitable in the above sense are in particular the following groups:
・ Acylalanine such as benalaxyl, offurace, oxadixyl,
-Amine derivatives such as aldimorph, dodemorph, guazatine, iminoctadine, tridemorph,
Anilinopyrimidines such as pyrimethanil, mepanipyrim, cyprodinil,
-Antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin,
・ Bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxiconazole, fenbuconazole fenbuconazole), fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, microbutanil, penconazole (Penconazole), propiconazole, prochloraz, prothioconazole, simeconazole, tetraconazole, triazimephone triadimefon), triadimenol (triadimenol), triflumizole (triflumizole), azoles such as triticonazole (triticonazole),
・ Dicarboximide such as microcloline, procymidone,
Dithiocarbamates such as ferbam, nabam, metam, propineb, polycarbamate, ziram, zineb,
Anilazine, boscalid, oxycarboxin, cyazofamid, dazomet, famoxadone, fenamidone, fuberidazole, flutolanil, frametapil (Furametpyr), isoprothiolan, mepronil, nuarimol, nuarimol, probenazole, pyroquilon, silthiofam, thiabendazole, thifluzamide, thifluzamide, thiazinyl (Tricyclazole), heterocyclic compounds such as triforine,
-Nitrophenyl derivatives such as binapacryl, dinobuton, nitrophthal-isopropyl,
・ Acibenzolar-S-methyl, carpropamid, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, ifiphos, enphos (Ethaboxam), fentin-acetate, phenoxanil, ferimzone, fosetyl, hexachlorobenzene, metrafenone, propamocarb, phthalide, torquelophos -Other fungicides such as toloclofos-methyl, quintozene, zoxamid,
A strobilurin, such as fluoxastrobin, metominostrobin, orysastrobin or pyraclostrobin,
・ Sulfenic acid derivatives such as captafol,
An active compound selected from cinnamides and similar compounds, such as flumetover.

  In one embodiment of the mixture of the present invention, another fungicide III or two fungicides III and IV are added to compounds I and II. A mixture of compounds I and II and component III is preferred. Particularly preferred are mixtures of compounds I and II.

  In another preferred embodiment of the mixture of the present invention, the fungicide III is an azole fungicide.

  Compound I and Compound II can be applied simultaneously, i.e. together or separately, or sequentially, in the case of separate applications, the order generally has no effect on the outcome of the control measures. Don't give.

  Compound I and compound II are usually applied in a weight ratio of 100: 1 to 1: 100, preferably 20: 1 to 1:20, in particular 10: 1 to 1:10.

  Component III and, where appropriate, Component IV is optionally added to Compound I in a ratio of 20: 1 to 1:20.

  Depending on the type of compound and the required effect, the application rates of the mixtures according to the invention are 5 g / ha to 1000 g / ha, preferably 50 to 900 g / ha, in particular 50 to 750 g / ha.

  Similarly, the application rates of compound I are generally 1-1000 g / ha, preferably 10-900 g / ha, in particular 20-750 g / ha.

  Similarly, the application rate of compound II is generally 1-1000 g / ha, preferably 10-500 g / ha, in particular 40-350 g / ha.

  In the treatment of seeds, the application rate of the mixture is generally 1 to 1000 g / 100 kg of seed, preferably 1 to 200 g / 100 kg, in particular 5 to 100 g / 100 kg.

  In the control of harmful fungi, the application of Compound I and Compound II separately or together, or the application of a mixture of Compound I and Compound II can be carried out before or after planting or before or after plant germination. Carried out by spraying or dusting seeds, plants or soil. The compound is preferably applied by spraying on the leaves.

  The mixtures or compounds I and II according to the invention can be converted into customary formulations, for example solutions, emulsions, suspensions, powders, dusts, pastes and granules. The application form depends on the particular purpose, but in any case it must ensure a fine and uniform distribution of the compounds according to the invention.

  The formulations are prepared in a known manner, for example by diluting the active compounds with solvents and / or carriers, optionally with emulsifiers and dispersants. Suitable solvents / additives are basically as follows.

-Water, aromatic solvents (eg, Solvesso products, xylene), paraffins (eg, mineral oil fractions), alcohols (eg, methanol, butanol, pentanol, benzyl alcohol), ketones (eg, cyclohexanone, gamma- Butyrolactone), pyrrolidone (NMP, NOP), acetate (glycol diacetate), glycol, fatty acid dimethylamide, fatty acid and fatty acid ester. In principle, solvent mixtures can also be used.

-Carriers such as ground natural minerals (eg kaolin, clay, talc, chalk) and ground synthetic minerals (eg highly dispersed silica, silicates); nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohols) Emulsifiers such as ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignosulfite waste liquors and methylcellulose.

  Suitable surfactants include lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid, dibutyl naphthalene sulfonic acid, alkyl aryl sulfonate, alkyl sulfate, alkyl sulfonate, fatty alcohol sulfate, fatty acid and sulfated fatty alcohol glycol ether alkali. Metal salts, alkaline earth metal salts and ammonium salts. In addition, condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenyl ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributyl Phenyl polyglycol ether, tristearyl phenyl polyglycol ether, alkylaryl polyether alcohol, alcohol and fatty alcohol / ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sorbitol ester, Diagnostics sulfite waste liquors and methylcellulose.

  Substances suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions include medium to high boiling mineral oil fractions such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin. Aliphatic, cyclic and aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, For example, dimethyl sulfoxide, N-methylpyrrolidone, or water.

  Powders, dusting materials and dusts can be prepared by mixing or pulverizing the active substance with a solid carrier.

  Granules such as coated granules, impregnated granules and uniform granules can be prepared by binding the active compound to a solid carrier. Examples of solid carriers are silica gel, silicate, talc, kaolin, attaclay, limestone, lime, chalk, clot clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, etc. Mineral earths, ground synthetic materials, such as fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and plants such as grain grinds, bark grinds, wood grinds and nut shell grinds Product of origin, cellulose powder and other solid carriers.

  In general, the formulations comprise 0.01 to 95% by weight of active compound, preferably 0.1 to 90%. The active compound is used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR spectrum).

  Examples of preparations are shown below.

1. Products for dilution with water
A) Water-soluble concentrate (SL)
10 parts by weight of the active compound are dissolved in water or a water-soluble solvent. Alternatively, wetting agents or other additives are added. The active compound dissolves when diluted with water.

B) Dispersible concentrate (DC)
20 parts by weight of the active compound are dissolved in cyclohexanone with the addition of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion.

C) Emulsifiable concentrate (EC)
15 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and castor oil ethoxylated (concentration 5% each). Dilution with water gives an emulsion.

D) Emulsion (EW, EO)
40 parts by weight of the active compound are dissolved in xylene with the addition of calcium dodecylbenzenesulfonate and ethoxylated castor oil (5% concentration each). This mixture is introduced into water using an emulsifier (Ultraturrax) to prepare a uniform emulsion. Dilution with water gives an emulsion.

E) Suspension (SC, OD)
In a stirred ball mill, 20 parts by weight of the active compound are ground by adding a dispersing agent, a wetting agent and water or an organic solvent to obtain a fine active compound suspension. Dilution with water gives a stable suspension of the active compound.

F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound are finely ground with the addition of a dispersant and a wetting agent, and water-dispersible or water-soluble granules are prepared using technical equipment (eg injection machines, spray towers, fluidized beds). Dilution with water gives a stable dispersion or solution of the active compound.

G) Water-dispersible powder and water-soluble powder (WP, SP)
75 parts by weight of the active compound are ground in a rotor-stator mill with the addition of a dispersant, a wetting agent and silica gel. Dilution with water gives a stable dispersion or solution of the active compound.

2. Products applied without dilution
H) Dust (DP)
5 parts by weight of active compound are ground finely and intimately mixed with 95% finely divided kaolin. Thereby, a powder agent is obtained.

I) Granules (GR, FG, GG, MG)
0.5 part by weight of the active compound is ground finely and combined with 95.5% carrier. The latest methods are injection, spray drying or fluidized bed. This gives granules to be applied without dilution.

J) ULV solution (UL)
10 parts by weight of the active compound are dissolved in an organic solvent, for example xylene. This gives a product to be applied without dilution.

  The active compounds can be used as such, in the form of their formulations or in the use forms prepared from such formulations, for example solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, powders that can be sprayed directly Can be used by spraying, spraying, dusting, spraying or pouring, in the form of spraying materials or granules. The use forms depend entirely on the intended purpose, but in each case they are intended to ensure the finest possible distribution of the active compounds according to the invention.

  Aqueous use forms can be prepared by adding water to the concentrated emulsion, paste or wettable powder (sprayable powder, oil dispersion). To prepare an emulsion, paste or oil dispersion, the material can be homogenized in water as it is or dissolved in an oil or solvent using a wetting agent, tackifier, dispersant or emulsifier. . Alternatively, concentrates can be prepared that contain the active substance, wetting agent, tackifier, dispersant or emulsifier and, where appropriate, a solvent or oil, such concentrate being suitable for dilution with water. .

  The active compound concentration in the ready-to-use formulation can vary within a relatively wide range. In general, the concentration is from 0.0001 to 10%, preferably from 0.01 to 1%.

  Active compounds can also be used effectively in microdispersion methods (ULV) where it is possible to apply formulations containing more than 95% by weight of active compounds or even to apply active compounds without additives can do.

  Various types of oils, wetting agents, adjuvants, herbicides, fungicides, other insecticides or bactericides can be added to the active compounds, if appropriate, immediately before use (Tank mix). These agents can be mixed with the composition of the present invention in a weight ratio of usually 1:10 to 10: 1.

  Compound I and Compound II, or a mixture or corresponding formulation, is a harmful fungus or plant, seed, soil, area, material or space to be protected from it, mixture or in the case of separate application, Compound I and II. It is applied by treating with an amount effective for sterilization. Application can be carried out before or after infection with harmful fungi.

  The bactericidal action of compounds and mixtures can be demonstrated by the following experiments.

  The active compounds were prepared separately or together as stock solutions containing 0.25% by weight of active compound in acetone or DMSO. 1% by weight of the emulsifier Uniperol® EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenol) was added to this solution and the mixture was diluted with water to the desired concentration.

Example of Use- Aqueous suspension containing active compounds of the following concentrations on the potted leaves of active grape cultivar "Riesling" against grape downy mildew (peronospora) caused by Plasmopara viticola Until sprayed. The next day, an aqueous zoospore suspension of downy mildew was inoculated on the back of the leaves. The grapes were then first placed in a room saturated with 24 ° C. water vapor for 48 hours and then in a 20-30 ° C. greenhouse for 5 days. After this period, the plants were again placed in a humid room for 16 hours to promote the development of the spore stalk. The degree of disease development on the backside of the leaves was then visually measured.

The visually determined percentage of infected leaf area was converted to an effect expressed as a percentage of the untreated control:
The effect (E) is calculated using the Abbot equation as follows:
E = (1−α / β) ・ 100
α corresponds to fungal infection of treated plants expressed in%, and β corresponds to fungal infection of untreated (control) plants expressed in%.

  Effect 0 means that the level of infection of the treated plant is consistent with the level of infection of the untreated control plant, and effect 100 means that the treated plant was not infected.

  The expected effect on a mixture of active compounds was determined and observed using the Colby equation (RSColby, “Calculating synergistic and antagonistic responses of herbicide combinations”, Weeds, 15, 20-22 (1967)). Compare the effect.

Colby's formula:
E = x + y−x · y / 100
E Expected effect expressed as a percentage of the untreated control using a mixture of active compounds A and B at concentrations a and b
x Effect expressed as% of untreated control with active compound A at concentration a
y Effect of active compound B at concentration b as a percentage of the untreated control

  The test results show that the observed effect of the mixtures of the invention on downy mildew is significantly higher than that predicted using the Colby equation at all mixing ratios due to the strong synergism.

Claims (10)

1) Formula I

Triazolopyrimidine derivatives, and 2) Formula II

Fenpropidin,
A sterilizing mixture for controlling harmful fungi containing in a synergistic amount.   The bactericidal mixture according to claim 1, comprising a compound of formula I and a compound of formula II in a weight ratio of 100: 1 to 1: 100.   A composition comprising a liquid or solid carrier and a mixture according to claim 1 or 2.   A method for controlling harmful fungi, comprising treating a fungus, its growth environment, or a seed, soil or plant to be protected from fungal attack with an effective amount of the compound I and the compound II according to claim 1.   5. A process according to claim 4, wherein compounds I and II according to claim 1 are applied simultaneously, i.e. together or separately or sequentially.   The method according to claim 4, wherein the mixture according to claim 1 or 2 is applied in an amount of 5 g / ha to 1000 g / ha.   The method according to any one of claims 4 to 6, wherein harmful fungi belonging to the class of oomycetes are controlled.   The method according to claim 4 or 5, wherein the mixture according to claim 1 or 2 is applied in an amount of 1 to 1000 g / 100 kg of seeds.   Seeds comprising the mixture according to claim 1 or 2 in an amount of 1-1000 g / 100 kg.   Use of compounds I and II according to claim 1 for the preparation of a composition suitable for controlling harmful fungi.