UA80067C2 - Fungicidal mixture containing triazolopyrimidine derivative and agent based thereon for fighting against rice pathogens - Google Patents

Abstract

The invention relates to fungicidal mixtures for fighting against rice pathogens, comprising in the form of active agents 1) a triazolopyrimidine derivative of formula (I) and 2) phthalimide derivative of formula (II) selected from a group a) captan of formula (IIa) and b) folpet of formula (IIb) in a synergistically efficient quantity. Said invention also relates to a method for fighting against rice pathogens by means of the compound (I) with the compound (II), to the use of the compound (I) with the compound (II) for producing the inventive mixtures and the agents containing said mixtures. .

Description

Description of the invention

This invention relates to fungicidal mixtures that contain as active components 9 1) a triazolopyrimidine derivative of the formula 70 NK shima and 2) one phthalimide derivative II selected from the group that includes a) captan of the formula Pa (- thuja and

TD "Ya, Sha, 9 school and o

C) folpet of the formula Ir i i yu Zh n-vov, yiv y

ChK and o not) o in a synergistically effective amount. at

In addition, the invention relates to a method of combating rice pathogens using mixtures of compound | with the compound |I and the use of the compound | with compound I to obtain similar mixtures, as well as means containing these mixtures.

Compound 1, 5-chloro-6-(2,4,6-trifluorophenyl)-7--4-methyl and piperidin-1-yl)-(1,2,Agriazolo|1,5-a|pyrimidine, (Its preparation and its effect against pathogenic fungi are known from literary sources | see UMO 98/466071.

Phthalimide derivatives II, 2-trichloromethylsulfanyl-Za,4,7,7a-tetrahydroisoindole-1,3-dione (Pa; common name: Kaptan, Sariap) and 2-trichloromethylsulfanylisoindole-1,3-dione (IB; common name : folpet, RoiYire)), their preparation and their action against pathogenic fungi are also known from literary sources m (5 2 553 770; 0052 553 771; 05 2 553 776). Derivatives of phthalimide II have long established themselves on the market as fungicides, mainly against Ootuseg.

Mixtures of triazolopyrimidine derivatives with captan are generally proposed in the document (EP-A 988 790). The compound is included in the general content of this document, but not specifically mentioned. Therefore, the combination of the compound | with captan so is new. Folpet is not mentioned in (ER-A 988 790). o The synergistic mixtures described in EP-A 988 790 are effective against various diseases on grain, fruit and vegetable crops, especially against powdery mildew on wheat and barley or gray rot on apple trees. (c) The fungicidal effect of known mixtures cannot always be completely satisfactory.

Fu 50 For the possibility of effective control of rice pathogens at low consumption rates, the invention is based on the task of achieving greater effectiveness of control against pathogenic fungi when using a reduced total amount of active substances.

Due to the special conditions of cultivation of rice plants, a fungicide for rice must meet different requirements than fungicides used in the cultivation of grain or fruit crops. Significant differences are in the method of application: in the case of rice crops, the fungicide is usually applied to the soil immediately during or shortly after sowing. The fungicide enters the plant through the root and is transported with the plant sap to the parts of the plant to be protected. In this regard, high systemic activity for rice fungicides is necessary. When growing grain and fruit crops, the fungicide is usually applied to the leaves or fruits, therefore, in these crops, the systemic effect of the active substance plays a much smaller role. 60 Different pathogens are typical for rice than for cereals or fruit crops. Rugisciagia ogugae and Sogpisit zazakii (synonym of KPigosiopia zoiapi) are causative agents of significant diseases of rice plants. KPygosiopia zoiYapi is the only important pathogen in agriculture from the subclass Adagisotuseiidae. This fungus affects the plant not like most other fungi through spores, but through mycelial infection.

As a result, the known information about fungicidal activity in the cultivation of grain and fruit crops 65 cannot be applied to rice crops.

Practical experience in agriculture has shown that the repeated or exclusive use of certain active substances in the fight against pathogenic fungi in many cases leads to the rapid selection of such fungal strains that have developed natural or adopted resistance to the corresponding active substances. Effective fight against such mushrooms with appropriate active substances is then impossible.

In order to reduce the danger of selection of resistant strains of mushrooms, mixtures of different active substances are used mainly to combat pathogenic fungi at this time. The combination of active substances can ensure the success of the fight for a long time.

Taking into account the effective prevention of the development of resistance and the effective fight against rice pathogens, the basis of this invention was the task of developing mixtures that, with a reduced total amount of 7/0 of the active substances used, show better effectiveness against pathogenic fungi.

Accordingly, the above mixtures were developed. It was unexpectedly found that the mixture according to the invention of the triazolopyrimidine derivative | with derivatives of phthalimide I have significantly higher efficiency against rice pathogens than those known from (EP-A 988 790) a mixture of structurally similar triazolopyrimidines

And, accordingly, B with captain.

Eh I" in what B

In addition, it was established that with simultaneous joint or separate use of the compound | and compound II or when sequentially using compound I and compound II is better able to fight rice pathogens than individual compounds.

It is preferable to use pure active substances in the preparation of mixtures and Pa or II, to which, depending on the need, other active substances that are active against pathogenic fungi or other pests, such as insects, arachnids or nematodes, or herbicidal or re-regulating active substances or fertilizers can be mixed. high school

As other active substances in the above sense suitable, in particular, fungicides selected from the group that includes: o - acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl, - amine derivatives, such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine , guazatin, iminoctadine, spiroxamine or trideform, - anilinopyrimidines such as pyrimethanil, mepanipyrim or cyprodinil, - 3o - antibiotics such as cycloheximide, griseofulvin, kazugamycin, natamycin, polyoxin or treptomycin, (Ce) - azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxyconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, o metconazole, myclobutanil, penconazole, propiconazole, prochlorac, prothioconazole, simeconazole, tebuconazole, (SU tetraconazole, triadimefon , triadimenol, triflumizole or triticonazole, - dicarboximides such as iprodione, myclozolin, procymidone or vinclozolin, 09 - dithiocarbamates such as ferbam, on bam, maneb, mancozeb, metham, metiram, propineb, polycarbamate, thiram, ziram or zineb, - heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, du cyazofamide, dazomet, dithianone, famoxadone, phenamidon . fungicides such as bordeaux liquid, copper acetate, copper oxychloride, copper hydroxide, copper oxide, (basic) copper sulfate, copper oxychloride-sulfate, - nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl, bo 15 - phenylpyrroles, such as fenpiclonil or fludioxonil, - sulfur, (ab) - other fungicides, such as acibenzolar-B-methyl, benthiawalicarb, carpropamide, chlorothalonil, ciflefenamide, o cymoxanil, dazomet, diclomesin, diclocimet, dietofencarb, edifenphos, et aboxam, phenhexamide, phenytin-acetate, phenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, (o) 50 metrafenone, pencicuron, propamocarb, phthalide, toloclofos-methyl, quintocene or zoxamide, -h - strobilurins, such , such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, methominostrobin, orysastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, - sulfenic acid derivatives such as captafol, dichlofluanid or tolylfluanid, - cinnamic acid amides and analogs such as dimethomorph, flumetover or flumorph

In one embodiment of the mixture according to the invention, one more fungicide is mixed with compounds I and II

GF) PI or two fungicides PI and IM. 7 The best mixtures of compounds I and II with one component PI.

Mixtures of compounds I and Ia or Ir are especially preferable.

Mixtures of compounds and II, respectively, simultaneous joint or separate use of compounds | and II 60 compounds are characterized by a good effect against rice pathogens from the class Avzsotuseiez, YuOeshegotuseifev and

Vasidiotuse (ez. They are highly systemic and can be used for seed treatment, as well as foliar and soil fungicides.

They are of particular importance for the control of pathogenic fungi such as Viroiagis and Ogespziega species, as well as Rugisciaga ogulae on rice plants and on their seed material. In particular, they are suitable for the fight against rice seedling, which is caused by Rugisciagia.

In addition, the combination according to the invention compounds | and II is also suitable for combating other pathogens, such as Zeriogia and Rissipia species on cereals and AKegpagia and Vouigia species on vegetable, fruit crops and grapevines.

Compounds I and compounds Na or Ir may be applied simultaneously together or separately or sequentially one after the other, and the order of separate application generally does not affect the success of the treatment.

Compounds I and compounds Pa or B are usually used in a mass ratio from 100:1 to 1:100, preferably from 10:1 to 1:50, in particular from 5:1 to 1:20.

Consumption rates of mixtures according to the invention are, depending on the specific compound and the desired effect, from 5 g/ha to 2000 g/ha, preferably from 50 to 1500 g/ha, in particular from 50 to 10000 g/ha.

Consumption rates of compound I are usually from 1 to 1500 g/ha, preferably from 10 to 1200 g/ha, in particular from 20 to 90 Og/ha.

The rates of consumption of compound Ma, respectively, B are, as a rule, from 1 to 2000 g/ha, preferably from 10 to 1500 g/ha, in particular, from 20 to 100 Og/ha.

When processing seed material, in general, consumption rates of the mixture from 1 to 1000g/10Okg of seed grain are used, preferably from 1 to 200g/100Okg, in particular, from 5 to 100g/10Okg.

In the fight against fungi pathogenic to rice plants, separate or joint application of compounds I and compounds Na or IB or mixtures of compound I and compounds Na or Ir is carried out by spraying or dusting seeds, seedlings, plants or soil before or after planting plants or before or after how the plants germinated. It is better if the compounds are applied together or separately by spraying the leaves. The compounds can be applied by applying granular herbicides or dusting the soil.

Mixtures according to the invention, respectively, compounds | and I can be translated into conventional compositions, for example, solutions, emulsions, suspensions, powders, fine powders, pastes and granules. The form of application depends on the purpose of application. In any case, it should ensure a thin and uniform distribution of the compounds according to the invention.

Compositions according to the invention can be prepared in a known manner, for example, by diluting the active substance with solvents and/or fillers, optionally with the use of emulsifiers and dispersants. Suitable solvents/auxiliary agents are mainly: water, aromatic solvents (e.g. dyes, xylene), paraffins (e.g. crude oil fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones ( for example, cyclohexanone, ix, gamma-butyrolactone), pyrrolidones (M-methylpyrrolidone, M-octylpyrrolidone), acetates (glycol diacetate), glycols, o dimethyl amides of fatty acids, fatty acids and esters of fatty acids. In principle, mixtures of solvents can also be used; o fillers, such as natural rock flour (for example, kaolin, alumina, talc, chalk) and synthetic rock flour (for example, highly dispersed silicic acid, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example, polyoxyethylene fatty alcohols, alkylsulfonates and arylsulfonates) and dispersants such as lignin sulfite spent alkali or methylcellulose. "

Alkaline, alkaline earth, ammonium salts of ligninsulfonic acid, pt») with phenolsulfonic acid, naphthalene sulfonic acid, dibutylnaphthalene sulfonic acid, alkylaryl sulfonates are suitable as surfactants. alkyl sulfonates, alkyl sulfates, sulfates of fatty alcohols, fatty acids and sulfated glycol ethers and fatty alcohols, then condensation products of sulfonated naphthalene or its derivatives with formaldehyde, condensation products of naphthalene, respectively naphthalene sulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,

Go! alkylphenolpolyglycol ether, tributylphenylpolyglycol ether, tristerylphenylpolyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated o castor oil, polyoxyethylene alkyl ether or polyoxypropylene, polyglycol ether acetate of lauryl alcohols, o sorbitol ester, lignin sulfate spent alkali.

For the preparation of directly spraying solutions, emulsions, pastes or oil dispersions, mineral oil fractions with medium to high boiling points, such as kerosene or diesel oil, further "M coal oils, as well as oils (oils) of vegetable or of animal origin, aliphatic, cyclic or aromatic hydrocarbons, for example, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalene or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, for example, dimethyl sulfoxide, M- methylpyrrolidone or water.

A powder, a preparation for spraying and dusting can be obtained by mixing or co-grinding (Ф, active substances with a solid filler. ka Granules, for example, coated, impregnated or homogeneous, are usually obtained by combining the active substances with a solid filler. vo How solid fillers are used, for example , mineral earths such as silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, and fertilizers such as ammonium sulfates, ammonium phosphates, ammonium nitrates, ureas and vegetable products such as, for example, cereal flour, tree bark flour, tree flour and nut shell flour, cellulose powder or other solid fillers. 65 The finished compositions contain a total of 0.01 to 9U5wt.9o is better from 0.1 to ZOwt.9o of the active substance. The active substances are used with a purity from 9090 to 100905, better from 9595 to 10090 (per s NMR spectrum).

Examples of compositions (preparative forms) are: 1. Products for dilution with water

A) Water-soluble concentrates (51) wt. parts of active compounds according to the invention are dissolved in water or in a water-soluble solvent.

Alternatively, wetting agents or other auxiliary agents are added. When diluted in water, the active substance dissolves.

B) Dispersible concentrates (OS) 2Omas. parts of active compounds according to the invention are dissolved in cyclohexanone with the addition of 7/0 dispersant, for example, polyvinylpyrrolidone. When diluted in water, a dispersion is obtained.

C) Emulsifiable concentrates (EC) 15 wt. parts of active compounds according to the invention are dissolved in xylene when added

Ca-dodecylbenzenesulfonate and castor oil ethoxylate (595 each). When diluted in water, an emulsion is formed.

O) Emulsions (EMU, EF) 40 wt. parts of active compounds according to the invention are dissolved in xylene when added

Sa-dodecylbenzenesulfonate and castor oil ethoxylate (5 95 each). This mixture is introduced into water using an emulsifying device (Shigafshgah) and brought to a homogeneous emulsion. When diluted in water, an emulsion is formed.

E) Suspensions (5C, OB) 20 mass. parts of active compounds according to the invention are crushed by adding a dispersant and a wetting agent and water or an organic solvent in a ball mill with a stirrer. When diluted in water, a stable suspension of the active substance is formed.

E) Water-dispersible granules and water-soluble granules (M/S, 50)

Bomas parts of the active compounds according to the invention are finely ground with the addition of a dispersant and a wetting agent and with the help of technical devices (for example, an extrusion device, a spray tower, a fluidized bed) a granulate is obtained that is dispersed in water or dissolves in water. When diluted in water, a stable dispersion or solution of the active substance is formed. b) Water-dispersible powder and water-soluble powder (MUR, ZR) M zo 75 mass. parts of the active compounds according to the invention are ground with the addition of a dispersant and a wetting agent, as well as silica gel in a rotor-stator mill. When diluted in water, a stable dispersion or solution of the active substance is formed. o 2. Products for direct use

H) Powders (OR) about 5 wt. parts of the active compounds according to the invention are finely ground and thoroughly mixed with 95 95 parts of fine kaolin. In this way, a means for spraying is obtained.

I) Granulates (OK, BO, BO, MO)

Oh, b5 mass. parts of the active compounds according to the invention are finely ground and bound with 95.5 95 fillers.

The usual method used for this is extrusion, spray drying or fluidized bed processing. Granulate is obtained for direct use. in c U) BI M-solutions (OG)

And 1Omas. parts of the active compounds according to the invention are dissolved in an organic solvent, for example, xylene. Receive a product for direct use.

Active substances can be used as such, in the form of their preparation forms or in the forms prepared from them, for example, in the form of solutions intended for direct spraying, in the form

Go! powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusting preparations, dusting preparations or granules and may be applied by spraying, fine-drop spraying, dusting, dusting or watering. The forms that are used depend on the purpose of application, but in all cases, the most thin and uniform distribution of the mixtures according to the invention should be ensured.

Me, Aqueous compositions can be prepared from concentrates of emulsions, pastes or wetting powders "M (powders for spraying, oil dispersions) by adding water. To obtain emulsions, pastes or oil dispersions, substances can be homogenized as such or dissolved in oil or solvent in water with the help of wetting agents, adhesive compositions, dispersants or emulsifiers. However, there may also be prepared concentrates that are suitable for dilution with water, and which consist of active substances and a wetting, adhesive, dispersing or emulsifying agent or oil. (F, Concentrations of active substances in ready-to-use preparations can vary in a wide ka range.In general, such concentrations are from 0.0001 to 1095, preferably from 0.01 to 1905.

Active substances can also be used with great success according to the method of low volumes because of the use of Oga-Hom-Mointe (SHUM), and it is possible to use compositions with more than 95% by weight of the active substance or even the active substance without impurities.

Oils of various types, wetting agents, activating additives, herbicides, fungicides, other pesticides, bactericides can be mixed with the active substances if necessary immediately before use (mixture in the tank). These agents can be mixed with the agents according to the invention in a mass ratio from 1:10 to 101. 65 Compounds I! and II, respectively, mixtures or corresponding compositions are applied in such a way that pathogenic fungi or plants, seeds, soil, surfaces, materials and premises subject to protection from them,

treated with a fungicidally active amount of the mixture, respectively, compounds | and II when separately introduced.

The application can be carried out before or after damage by pathogenic fungi.

The fungicidal activity of the mixtures and the corresponding compounds can be demonstrated by the following experiments.

The active substances are prepared separately or together as a basic solution with 0.25 wt.9% of the active substance in acetone or dimethyl sulfoxide. To this solution, add 1 wt.9o of the Opirego emulsifier (? EG! (a wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and dilute with water to the desired concentration. 70 Example of application - protective effectiveness against rice smut caused by Rugisiiagia ogugae.

The leaves of rice sprouts of the "Tai-Mopud 67" variety grown in pots are sprayed with an aqueous suspension of the active substance in the concentration below until the formation of drops. The next day, the plants are inoculated with an aqueous suspension of Rugisiiagia ogugae spores. Then the experimental plants are placed in a chamber at a temperature of 22 - 2490 and a relative humidity of 95 - 9995 for six days. Then visually determine the degree of development of the lesion on 7/5 leaves.

The assessment is carried out by determining the affected surface of the leaves in percentage. These percentage values are listed in efficiency as 95 relative to the untreated control:

Efficiency (MU) is calculated according to the Abot formula:

MU - (1 -o/r)x 100, where o corresponds to fungal damage to treated plants at 9o and p corresponds to fungal damage to untreated (control) plants at 905.

At an efficiency equal to 0, the lesion of treated plants corresponds to the lesion of untreated control plants; at an efficiency equal to 100, the treated plants have no damage.

The expected effectiveness of mixtures of active substances is determined by the Colby formula, see publication of Soir K.5. "s (Saiisciatspod zupegdivis apa apiadopiviis gezropzevs oi Pegriside SotrBipaiop5z, MUeeaz 15, 20-22 (1967) " and o are compared with the established efficiency.

Colby's formula:

E - x -- y-hu100, where

E - the expected efficiency, expressed in 956 relative to the untreated control, when using a mixture of 3 units of active substances A and B with concentrations a and b; x - efficiency, expressed in 95% relative to the untreated control, when using the active substance A with the th-th concentration of a; "in y - efficiency, expressed in 95% relative to the untreated control, when using the active substance B with concentration b. at

As comparative compounds, compounds A and B known from the captan mixtures described in (ЕР-А 988 790) were used: (se) not in

А in « с - " - с Table А я 00000001 snnnnannini p Individual active substances substances in the solution relative to so for spraying the untreated (million parts) control o yuu pvzhurayutya write po t non o vv

Ge, in 11111 4 tp 007 substances in the solution for spraying mly relative to the untreated control, in 00000808 o POLI POLON POLO NO PO po yu

PI POLYA POL I am UNN in (pedvkoytav 111111110853016 7 PP v11111v

Table B 65 Mixtures according to the invention

Example Mixture of active substances | Installed | Calculated

Concentration efficiency efficiency")

The ratio of the components of the mixture 1 joint 11

PI POS ON PO PO

8 | nevy 1 lvzmnia 11 c PI PO ON PO PO in inv vv 0 ovnemnia r inv t5 rolevamnia

PI PE and PO NO ") efficiency calculated by the Colby formula

Table C

Comparative experiments - Combinations of active substances known from (ER-A 988 7901 (Example | Mixture of active substances Concentration Ratio of mixture components | Determined efficiency Calculated efficiency") in (ав) ") calculated according to the Colby formula efficiency ав)

From the results of the experiments, it follows that the mixtures according to the invention at comparable consumption rates show significantly higher efficiency than the mixtures with captan known from EP-A 988 790, although the comparative compounds, as individual active substances, are more effective in comparison with compound I .

Claims (13)

Formula of the invention shsh h» 1. Fungicidal mixture containing "1) triazolopyrimidine derivative of the formula Na 1 (ee) o E E (av) M i (about) M. More h R IC SI and | that 2) one phthalimide derivative II, selected from the group that includes F) a) captan of the formula Pa ko y ; Pa bo Sn, IV) and 65 B) folpet of the formula IB about , po-e m--yass somewhat about in a synergistically effective amount. 2. Fungicidal mixture according to claim 1, which contains a compound of the formula | and the compound of formula I in a mass ratio of 100:1 to 1:100. 3. Fungicidal mixture according to claim 1 or 2, which contains captan of the formula Pa according to claim 1 as a phthalimide derivative. 4. Fungicidal mixture according to claim 1, which is used to combat rice pathogens. 5. Fungicidal mixture according to claim 1 or 2, which contains folpet of the formula NAME according to claim 1 as a phthalimide derivative. 6. Fungicidal agent, which contains a liquid or solid filler and a mixture according to any of claims 1-5. 7. A method of combating rhizopathogenic harmful fungi, which differs in that the fungi, their growing space or plants, soil or seed material to be protected from them, are treated with an effective amount of a mixture of compound I and one of compounds II according to claim 1. 8. The method according to claim 7, which differs in that compounds I! and II according to claim 1 are applied simultaneously, namely jointly or separately, or sequentially one after the other. 9. The method according to claim 7, which differs in that the mixture according to any of claims 1-5 is used in an amount from 5 g/ha to 2000 g/ha. 10. The method according to claim 7 or 8, which differs in that the mixture according to any of claims 1-5 is used in an amount from 1 to 1000 g/100 kg of seed material. 11. The method according to any one of claims 7-9, which is characterized by the fact that they fight with Rulisc/ata ogugaye. with 12. Seed material containing the mixture according to any of claims 1-5 in an amount from 1 to 1000 g/100 kg. at 13. Use of compound I and compound II according to claim 1 to obtain a fungicide according to claim 6. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated microcircuits", 2007, M 12, 10.08.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. "so "c) "c) d) shi s . and? (ee) («c) («c) b 50 that F) has) 60 b5