UA79217C2 - Fungicidal mixture containing triazolopyrimidine derivative, agent based thereon and method for combating rice pathogens - Google Patents

Abstract

The invention relates to fungicidal mixtures for combating rice pathogens containing in the form of active agents 1) a triazolopyrimidine derivative of formula (I) and 2) fenhexamid of formula (II) at a synergistically effective quantity and to a method for combating rice pathogens by the compound of formula (I) and the compound of formula (II) mixtures and the use the compound of formula (I) with the compound of formula (II) for producing such mixtures and agents containing said mixtures (I), (II).

Description

Description of the invention

The present invention relates to fungicidal mixtures for combating rice pathogens, which contain as active 2 components 1) a triazolopyrimidine derivative of the formula sn, !

Glass 70 m Sme I ne v ta 2) phenhexamide of the formula IYI ton n KA, ra g s

SA h-sk, in a synergistically effective amount. high school

In addition, the invention relates to a method of combating rice pathogens using mixtures of compound | with compound II and the use of compound | with compound II to obtain similar mixtures, as well as means that (o) contain these mixtures.

Compound Y, namely 5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)-(1,2,A)triazolo|1,5-a|)pyrimidine , its preparation and its effect against pathogenic fungi are known from literary sources | see UMO 98/466071.

Compound II, M-(2,3-dichloro-4-hydroxyphenyl)-1-methylcyclohexanecarboxamide, its preparation and its action against pathogenic fungi are also known from literature sources | see publication of Rhos. Hg. Stor Rgoi. Sopi - Revsiv journal, 1998, volume 2, page 327; common name: phenhexamid, Reppehatiiai.

Phenhexamide is known on the market mainly for the fight against Vouigiyizrega! on vines and (22) special crops. with. | 2, , 2, and -

Mixtures of triazolopyrimidine derivatives with phenhexamide are generally known from EP-A 988 790. Compound | included in the general content of this document, but not specifically mentioned. Therefore, the combination of the compound | Phenhexamide is new.

Synergistic mixtures known from (ER-A 988 790) are described as fungicidally active against various diseases on grain, fruit and vegetable crops, such as powdery mildew on wheat and barley or gray rot on apple trees. -in

Due to the special conditions of cultivation of rice plants, fungicides for rice must meet different requirements than fungicides used in the cultivation of grain or fruit crops. Significant differences lie in the method of application: in the case of rice crops, along with foliar treatment, the fungicide is usually applied to the soil directly during or shortly after sowing. The fungicide enters the plant through the root and is transported in the plant sap to the parts of the plant to be protected. In this regard, high -1 systemic activity for rice fungicides is necessary. When growing grain and fruit crops, the fungicide is usually applied to the leaves or fruits, so systemicity plays a much smaller role in these crops. se) Different pathogens are typical for rice than for grain or fruit crops. Rugisciagia ogulae and Sogiisit

GF zazakia (synonym of KPigosiopia zoiapi) are the causative agents of significant diseases on rice plants. KPigosiopia zoiapi is the only agricultural pathogen from the subclass Adagisotuseidae. This fungus infects the plant not like most other fungi through spores, but by mycelial infection. As a result, the experience of fungicidal action in the cultivation of fruit and grain crops cannot be used in relation to rice crops.

Practical experience in agriculture has shown that the repeated or exclusive use of one active substance 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 substance. Effective fight against

GF) with such mushrooms with the corresponding active substance is then no longer possible.

In order to reduce the risk of selection of resistant strains of mushrooms, mixtures of various active substances are usually used to combat pathogenic fungi. The combination of active substances with different mechanisms of action 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 with as low as possible rates of consumption of active substances, the basis of this invention was the task of improving the effect of mixtures against pathogenic fungi.

Accordingly, the above mixtures were developed. In addition, it was established that with simultaneous and joint or separate use of compounds I and compounds I, or with sequential use of compounds | and II compounds are better able to fight rice pathogens than individual compounds.

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

As other active substances in the above sense suitable, in particular, are fungicides selected from the group that includes: - acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl, - amine derivatives, such as aldimorph, dodemorph, fenpropidine, guazatin, iminoctadine or tridemorph, - antibiotics such as cycloheximide, griseofulvin, cazugamycin, natamycin, polyoxin or streptomycin, - azoles such as bitertanol, bromoconazole, ciproconazole, difenoconazole, dinitroconazole, enilconazole, 70 fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, myclobutanil, penconazole, propiconazole, prochlorac, prothioconazole, simeconazole, tetraconazole, triadimefon, triadimenol, triflumizole, or triticonazole. - dicarboxyimides such as myclozolin or procymidone - dithiocarbamates such as ferbam, nabam, metham, propineb, polycarbamate, ziram or zineb - heterocyclic compounds such as anilazine, boscalid, carbendazim, carboxin, oxycarboxin, ciazofamide, dazomet , famoxadone, fenamidone, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, pyroquilon, silthiofam, thiabendazole, thifluzamide, thiadinil, tricyclazole or triforin, - nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl, - phenylpyrroles such as fenpiclonil or fludioxonil, - sulphur, - other fungicides such as acibenzolar-3-methyl, carpropamide, chlorothalonil, cyflufenamide, cimoxanil, diclomesin, diclocimet, dietofencarb, edifenphos, etaboxam, fentin acetate, phenoxanil, ferimzone , fluazinam, fosetyl, hexachlorobenzene, metrafenone, pencicuron, propamocarb, phthalide, toloclofos-methyl, quintocene or zoxamide, sc - strobilurins such as rluoxastrobin, methominostrobin, orysastrobin or pyraclostrobin, - sulfenic acid derivatives, such as captafol, (8) - cinnamic acid amides and analogues, such as rlumetover.

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

Sh or two fungicides PP and IM. mixtures of compounds I and II with component I are better. Especially the best mixtures of compounds and PI.

Mixtures of compounds and II, respectively, simultaneous joint or separate use of compounds | and compounds II - are distinguished by excellent action against rice pathogens from the class Avsotuse(ez, YuOeshegotuse(ev and s

Vasidiotuse (ez. They can be used for processing seed material, as well as soil and foliar fungicides. me)

It is preferable to use compounds I and I by spraying the leaves. The application can also be carried out using granules or by dusting the soil.

They are of particular importance for the control of pathogenic fungi on rice plants and on their seed material, such as Viroiagis and Juogespwiega species as well as Rugisshagia ogulae. In particular, they are suitable for combating rice smut, which is caused by Rugisciagia ogugaye. "

In addition, the combination according to the invention compounds | and II is also suitable for the control of other pathogens, such as Zeriogia and Rissipia species on cereals and APHegpagia and Vouigia species on

And vegetable, fruit crops and vines. and?" Compound I and compound I can be used simultaneously together or separately or sequentially one after the other, and the order of application when used separately does not generally affect the success of the treatment.

Compound I and compound II are usually used in a mass ratio from 100:1 to 1:100, preferably from -I 201 to 1:50, in particular from 10:1 to 1:10.

The components of PI and, if necessary, IM are mixed with compound I, usually in a ratio of 20:1 to 1:20. and, Consumption rates of mixtures according to the invention are, depending on the type of compound and the desired effect, from 5g/ha to 2000g/ha, better from 50 to 1500g/ha, best from 50 to 750g/ha.

Consumption norms of the compound | correspond, as a rule, from 1 to 1000Og/ha, better, from 10 to 750g/ha, in particular - from 20 to 5OOg/ha. "M The rates of consumption of compound II are, as a rule, from 1 to 100 Og/ha, preferably from 10 to 750 g/ha, in particular from 20 to 500 g/ha.

When processing seed material, in general, consumption rates of the mixture from 1 to 1000g/100Okg of seed are used

Grains, mostly, from 1 to 750g/100OKkg, especially from 5 to 500g/100OKkg.

In the fight against pathogenic fungi for rice plants, separate or joint application is carried out

Ф) compounds I and II or mixtures of compounds I and II by means of spraying or pollination of seeds, seedlings, plants or soil before or after sowing of plants or before or after germination of plants.

Mixtures according to the invention, respectively, compounds | and I can be translated into ordinary 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 compound 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. As 65 solvents/auxiliary agents are suitable, mainly: - water, aromatic solvents (e.g. boiMevzvo products, xylene), paraffins (e.g. crude oil fractions), alcohols (e.g. methanol, butanol, pentanol, benzyl alcohol), ketones ( eg cyclohexanone, gamma-butyrolactone), pyrrolidones (M-methylpyrrolidone, M-octylpyrrolidone), acetates (glycol diacetate), glycols, fatty acid dimethyl amides, fatty acids and fatty acid esters. In principle

Mixtures of solvents can also be used; - fillers, such as natural rocks (for example, kaolins, alumina, talc, chalk) and synthetic rocks (for example, highly dispersed silicic acid, silicates); emulsifiers such as nonionic and anionic emulsifiers (for example, polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants such as lignin sulfite spent alkali or 7/0 M methylcellulose.

Alkaline, alkaline earth, ammonium salts of lignin sulfonic acid, phenol sulfonic acid, naphthalene sulfonic acid, dibutyl naphthalene sulfonic acid, alkyl aryl sulfonate, alkyl sulfonate, alkyl sulfate, sulfate of fatty alcohols, fatty acids and sulfated glycol ethers of fatty alcohols, followed by condensation products of sulfonated naphthalene or its derivatives with 7/5 with formaldehyde, condensation products of naphthalene, respectively naphthalene sulfonic acid with phenol or formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenolpolyglycol ether, tributylphenylpolyglycol ether, tristerylphenylpolyglycol ether, alkylaryl polyether alcohols, condensates of alcohol and fatty alcohol/ethylene oxide, ethoxylated castor oil , polyoxyethylene alkyl ether or polyoxypropylene, polyglycol ether acetate of lauryl alcohols, sorbitol ester, spent lignin sulfite alkalis or methyl cellulose.

For the production of direct spraying solutions, emulsions, pastes or oil dispersions, fractions of mineral oils with an average - high boiling point, such as kerosene or diesel oil, then coal oils, as well as oils (oils) of vegetable or animal origin, aliphatic, are suitable , cyclic or aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their chemical derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar solvents, e.g. dimethylsulfoxide, M-methylpyrrolidone or water. and)

A powder, a preparation for spraying and dusting can be obtained by mixing or co-grinding the active substances with a solid carrier.

Granules, for example, coated, impregnated or homogeneous, are usually obtained by combining food-active substances with a solid filler. As solid fillers, for example, mineral earths are used, such as silica gel, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics , as well as fertilizers such as ammonium sulfates, ammonium phosphates, ammonium nitrates, ureas and vegetable products such as, for example, cereal flour, tree bark flour, wood flour and nut shell flour, cellulose powder or other solid fillers. uh-

The finished compositions generally contain from 0.01 to 9 wt.9o, preferably from 0.1 to 30 wt.9o of the active substance. Active substances are used with purity from 9090 to 100905, preferably from 9595 to 10090 (according to the NMR spectrum).

Examples of compositions: 1. Products for dilution with water "

A) Water-soluble concentrates (51) with 1Omas. parts of the compound 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) 20 wt. parts of the compound according to the invention are dissolved in cyclohexanone with the addition of a dispersant, for example polyvinylpyrrolidone. When diluted in water, a dispersion is obtained.

C) Emulsifiable concentrates (EC) se) 15 wt. parts of the compound according to the invention are dissolved in xylene with the addition of Ca-dodecyl benzene sulfonate and castor oil ethoxylate (595 each). When diluted in water, an emulsion is formed.

O) Emulsions (EMU, EF) - 4Omas. parts of the compound according to the invention are dissolved in xylene with the addition of "M Ca-dodecylbenzene sulfonate and castor oil ethoxylate (5956 each). This emulsion 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 the compound according to the invention are crushed with the addition of a dispersant and a wetting agent

F) agent and water or 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 granulate and water-soluble granulate (M/S, 50) in BOMs. parts of the compound 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) 65-75 mass. parts of the compound 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. 2. Products for direct use

H) Powders (OR) 5 wt. parts of the compound according to the invention are finely ground and thoroughly mixed with 9595 fine kaolin. In this way, a means for spraying is obtained.

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

Oh, bBmas. parts of the compound according to the invention are finely ground and bound with 95.595 fillers.

Extrusion, spray drying, or 7/0 fluidized bed processing are common methods used for this. Granulate is obtained for direct use.

C) BIM - solutions (ОЙ) 10 mass. parts of the compound 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 preparative forms or in the forms that /5 are prepared from them, for example, prepared in the form of solutions intended for direct spraying, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, preparations for dusting , dusting preparations or granules and can be applied by spraying, fine-drop spraying, dusting, dusting or watering. The forms of application depend on the purpose of application, but in all cases, the most thin and uniform distribution of the active substances according to the invention should be ensured.

Aqueous compositions can be prepared from emulsion concentrates, pastes or wetting powders (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. Concentrates suitable for dilution with water can also be prepared, which consist of active substances and wetting agents, adhesive compositions, dispersants or emulsifiers or oil. (8)

Concentrations of active substances in compositions can vary in a wide 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 of M with the use of OKha-I om/-Moishte (CIM), and it is possible to use compositions with more than 95wt.9o of the active substance or even the active substance without impurities. -

Oils of various types, wetting agents, impurities, 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 of 1:10 to 10:11. (22)

Compounds And! and II, respectively, mixtures or corresponding compositions are used in such a way that pathogenic fungi or plants, seeds, soil, surfaces, materials and premises subject to protection from them are 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 mixtures can be shown using the following experiments:

The active substances are prepared separately or together as a basic solution with 0.25 wt. 90% of the active substance in acetone or dimethyl sulfoxide. To this solution, add 1 mass of 90% Opirego emulsifier (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and dilute with water to the desired concentration.

Example of application - Effectiveness against rice spotting caused by Sospiobroisz thioureapyl during protective treatment -I Leaves of rice sprouts grown in pots of the "Tai-Mopud 67" variety are sprayed with an aqueous suspension of the active substance in the following concentration until the formation of drops. The next day, the plants are inoculated with an aqueous suspension of spores of Sospioboish5 thiuareapyv. After that, the experimental plants are placed for two days in a chamber at a temperature of 22-242C and a relative humidity of 95-9995. Then visually determine the degree of damage on the 5th leaves. - The assessment is carried out by determining the affected surface of the leaves in percentage. These percentage values list "And in efficiency.

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

MU-(1-A/B).100, where

A corresponds to the defeat of treated plants by fungi in 95 and

B corresponds to the damage by fungi of untreated (control) plants at 90. o At the efficiency equal to 0, damage to treated plants corresponds to damage to 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 K.5. SoiBu, 60 Meeaz 15, 20-22 (1967)) and compared with established effectiveness.

Colby's formula:

E-khnu-kh.u/100, where

E - the expected efficiency, expressed in 956 relative to the untreated control, when using a mixture of active substances A and B with concentrations a and b; 65 x - efficiency, expressed in 95 relative to the untreated control, when using the active substance A with concentration a;

y - efficiency, expressed in 95% relative to the untreated control, when using the active ingredient B with concentration b.

As comparative compounds, known (from EP-A 988,790) mixtures of phenhexamide compounds A and

A: n, se,

There is, and you are. EE n" g nbonn Go st A ge iy y nece (1 with M still o

Table A

Example Active substance (Concentration of active substance in spray solution Effectiveness in 95 relative to untreated (ppm) control 19 1 Control (8595 lesions) (untreated) 2 16 17

And the 5th

A Comparison A 16 53

A 29 5 Comparison B 16 A

A 5 with more 6)

Table B

Example (Mixture of active substances Established effectiveness Calculated effectiveness")

Concentration in

The ratio of the components of the mixture

NO 76 17 -- 16bzh4mln.h dl s 7 IN 88 17 Ge»! 1641 bmln.h that -

IN 70 5 41 bmln.h

AND

") efficiency calculated according to the Colby formula -

Table C;» ;

Example (Mixture of active substances Established effectiveness Calculated effectiveness")

Concentration - The ratio of the components of the mixture

Ach 29 53 (Se) 16bzh4mn.h 41 ime) 10 ANI 17 53 1641bmn.h - 11 "I 11 Ach 17 29 41bmn.h

AND

12 Vni 53 1 16bhx4mln.h 41 (F, 13 Vni 53 1 zhk ko 1641bmln.h 11 14 Vni 1 5 bo d1bmlnoch

AND

") calculated according to the Colby formula, efficiency v5 From the results of the experiments, it follows that the mixtures according to the invention, due to strong synergism, show significantly higher efficiency than the known (from EP-A 988,790) mixtures of phenhexamide, despite the fact that the comparative compounds at comparable rates costs are more effective than compounds I.

Claims (9)

The formula of the invention 1. Fungicidal mixture containing 1) triazolopyrimidine derivative of the formula I CH» () and E She | with M - chi mya 2 -- E M M s and 2) phenhexamide of the formula ІІ ОН (PI d ! (1) d NM s y si s sn, o 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. A fungicidal agent that contains a liquid or solid filler and a mixture according to claims 1 or 2. -- 4. A method of combating rice pathogens, which is characterized by the fact that fungi, their growing space or plants, soil or seed material to be protected from fungi are treated with an effective amount of compound I and compound I according to claim 1. (is) 5. The method according to claim 4, which differs in that compounds I and II according to claim 1 are introduced simultaneously, namely jointly or separately or sequentially one after the other. 6. The method according to claim 4, which differs in that the mixture according to claim 1 or 2 is used in an amount from 5 g/ha to 2000 g/ha. 7. The method according to claims 4 or 5, which differs in that the mixture according to claims 1 or 2 is used in an amount from 1 to 20 1000 g/100 kg of seed material. from the village 8. Seed material containing the mixture according to claims 1 or 2 in an amount from 1 to 1000 g/100 kg. 9. Use of compound I and compound II according to claim 17 for obtaining a means suitable for combating pathogenic fungi. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated -I microcircuits", 2007, M 7, 25.05.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. se) has) - 50 that F) has) 60 b5