UA79403C2 - Fungicide mixture and agent, control method, inoculum and use of compounds - Google Patents

Abstract

The invention relates to fungicide mixtures for the control of rice pathogens, containing the following as active ingredients: 1) the triazolopyrimidine derivative of formula (I) and 2) trifloxystrobin of formula (II), in synergistically effective amounts, a method for the control of rice pathogens with mixtures of compound (I) and compound (II), the use of compound (I) and compound (II) for the production of such mixtures and agents comprising 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

IS

VE. and sa (: and 2) trifloxystrobin of formula II

As: There is my v. - with

FI she with Fr

Kk ra I shk! Shk

This is in a synergistically effective amount. -

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 (22) contain these mixtures. them

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 action against pathogenic fungi are known from literary sources | see UMO 98/466071.

Compound II, complex methyl ester of "20 (E)-methoxyimino-"E)-a-(1-(a,.a,o-trifluoro-m-tolyl)ethylideneaminooxy|-o-tolylacetic acid, its preparation and -o its action against pathogenic fungi is also known from literary sources (see ER-A 460 575); common name: TtShohuzigobip (trifloxystrobin). Trifloxystrobin has established itself well on the market, mainly as a fungicide for grain crops against powdery mildew and rust damage caused by

Azsotusegyez, respectively, Vazidiotusegyev. 415 Mixtures of triazolopyrimidine derivatives with trifloxystrobin (СОА-279202) are generally known from document EP-A -1 988 790). Compound I is included in the general context of this document, but not specifically mentioned. Therefore, the combination of compound I with trifloxystrobin is new. is), Synergistic mixtures known from (ER-A 988 790) are effective as fungicides against various diseases of grain, fruit and vegetable crops, such as powdery mildew on wheat and barley or gray rot on apple trees.

Due to the special conditions for the 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 directly to the soil 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. Therefore, high systemic activity is necessary for rice fungicides. In the cultivation of grain and fruit crops the fungicide is usually applied to the leaves or fruit, so systemicity plays a much smaller role in these crops.

Ge Sospioroii5 tiuareapiz and Sogiisitst zazakKii (synonymous KPigosiopia zoiapi) are causative agents of significant diseases of rice plants. Pygosiopia zoyiapi is the only pathogen from the subclass Adagisothuseiidae that is significant in agriculture. This fungus affects the plant not like most other fungi through spores, but through mycelial infection.

As a result, the experience of fungicidal action in the cultivation of fruit and grain crops cannot be used for rice crops.

Practical experience in agriculture has shown that the repeated or exclusive use of a single harmful 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 control of such fungi with the appropriate active substance is then no longer possible.

In order to reduce the danger of selection of resistant strains of mushrooms, conventional mixtures of various active substances are currently used to combat pathogenic fungi. A combination of active substances with a different mechanism 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 with a reduced total amount of active substances introduced.

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

Pure active substances I and II are preferably used when preparing mixtures, 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.

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, dodine, dodemorph, fenpropidine, guazatin , iminoctadine or tridemorph - antibiotics such as cycloheximide, griseofulvin, cazugamycin, natamycin, polyoxin or streptomycin - azoles such as bitertanol, bromoconazole, ciproconazole, difenoconazole, dinitroconazole, epoxyconazole, 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, c - heterocyclic compounds such as anilazine, boscalid, carbendazim, carboxin, oxycarboxin, ciazofamide, dazomet, famoxado n, phenamidon, fuberidazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, and) probenazole, pyroquilon, silthiofam, thiabendazole, typhluzamide, thiadinil, tricyclazole or triforin, - nitrophenyl derivatives, such as binapacryl, dinocap, dinobuton, nitrophthal-isopropyl, - sulphur, sozo - phenylpyrroles such as fenpiclonil or fludioxonil - other fungicides such as acibenzolar-B-methyl, carpropamide, chlorothalonil, cyflufenamide, cimoxanil, o diclomezin, diclocimet, dietofencarb, edifenphos, etaboxam, fentin acetate . such as captafol, cinnamic acid amides and analogs such as rlumetover.

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

Sh or two fungicides PI and IM. "

Mixtures of compounds I and II with component III are better. Especially the best mixtures of compounds | and II. z с Mixtures of compounds I and II, respectively, simultaneous joint or separate use of compound | and compounds II are distinguished by a good effect against rice pathogens from the class Avsotusefez, Yuoeciegotusefev and ;" Vasidiotuse (ez. They can be used for the treatment of seed material, as well as foliar and soil fungicides. It is better to use compounds I and II by spraying the leaves. You can apply the compounds in the form of granules or by dusting the soil. -I They are of special importance when control of pathogenic fungi such as Viroiagis and Ogesnziega spp., as well as Rugisciagia ogugae on rice plants and their seed material.In particular, they are suitable for the control of rice smut caused by Rugisciaga ogula and against rice brown spot caused by caused by their SospioboYiz tiuareapiv.

In addition, combinations of compounds | and II according to the invention are suitable for combating other pathogens, such as, for example, species of Beriogia and Rissipia on cereals and species of Akegpagia and Vouigiii on vegetable, fruit and grape crops

Compounds And! and ITS can 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 processing.

Compound I and compound II are usually used in a mass ratio of 100:1 to 1:100, better, from 20:1 to 1:50, especially better, from 10:1 to 1:10, in particular from 10:1 to 1: 5. (F. The components of IP! and, if necessary, IM are mixed with compound I, usually in a ratio of 20:1 to 1:20. ka The rates of consumption 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 750 g/ha. The rate of consumption of the compound corresponds to, as a rule, from 1 to 1000 g/ha, preferably from 10 to 750 g/ha , in particular, from 20 to 500 g/ha.

The rate of consumption of compound II is, as a rule, from 1 to 1000 g/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 mixtures from 1 to 1000 g/100 kg of seed material are used, preferably from 1 to 750 g/100 kg, in particular, from 5 to 500 g/10Okg. 65 In the fight against pathogenic fungi on rice plants, separate or joint treatment with compounds I and Y or mixtures of compounds I and II is carried out by spraying or dusting seeds, seedlings, plants or soil before or after sowing the plants or before or after the plants have germinated.

Mixtures according to the invention, respectively, compounds I and I can be translated into conventional compositions (preparative forms), 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. Suitable solvents/auxiliary agents are mainly: 70 - water, aromatic solvents (e.g. petroleum 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 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 formaldehyde, condensation products of naphthalene, respectively naphthalene sulfonic acid with phenol or sc formaldehyde, polyoxyethylene octyl phenol ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkylphenol polyglycol ether, tributyl phenyl polyglycol ether, tristeryl phenyl polyglycol ether, and) alkylaryl polyester alcohols, condensates of alcohol and fatty alcohol/ethylene oxide castor oil, ethoxylated oil, polyoxyethylene alkyl ether or polyoxypropylene, polyglycol ether acetate of lauryl alcohols, sorbitol ester, spent lignin sulfite alkali or methyl cellulose. For the production of directly spraying solutions, emulsions, pastes or oil dispersions, fractions of mineral oils with a medium to high boiling point, such as kerosene or diesel oil, as well as coal oils, as well as oils (oils) of vegetable or animal origin, are suitable origin, aliphatic, cyclic or "E aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, strongly polar b" solvents, e.g. dimethylsulfoxide, M-methylpyrrolidone or water. uh-

Powder, drug for spraying and dusting can be obtained by mixing or co-grinding active substances with a solid filler.

Granules, for example, coated, impregnated or homogeneous, are usually obtained by combining 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 sulfates. ammonium, ammonium phosphates, ammonium nitrates, ureas and vegetable products, such as, for example, grain flour and? crops, tree bark flour, tree flour and nut shell flour, cellulose powder or other solid fillers.

The finished compositions generally contain from 0.01 to 95 wt. 90, preferably from 0.1 to 90 wt. 90 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: ise) 1. Products for diluting them with water A) Water-soluble concentrates (51) 10 wt. parts of active compounds according to the invention are dissolved in water or in a water-soluble solvent. o 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 active compounds according to the invention are dissolved in cyclohexanone with the addition of two dispersants, for example, polyvinylpyrrolidone.

When diluted in water, a dispersion is obtained.

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

Sa-dodecylbenzenesulfonate and castor oil ethoxylate (5 95 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 emulsion is introduced into water using an emulsifying device (Shigafshgah) and brought to a homogeneous emulsion. When diluted in water, 65 forms an emulsion.

E) Suspensions (5C, OB)

20 wt. 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 granulate and water-soluble granulate (M/S, 50) 50 wt. 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. 70 b) Water-dispersible powder and water-soluble powder (M/R, ЗР) 75 wt. 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. 2. Products for direct use 15 H) Powders (OR) 5 wt. parts of active compounds according to the invention are finely ground and thoroughly mixed with 95 95 fine kaolin. In this way, a means for spraying is obtained.

I) Granules (OK, BO, SO, MO) 0.5 wt. parts of the active compounds according to the invention are finely ground and bound with 95.5 95 fillers. 2o The usual method used for this is extrusion, spray drying or fluidized bed processing. Granulate is obtained for direct use.

C) BIM - solutions (ОЙ) wt. parts of active compounds according to the invention are dissolved in an organic solvent, for example, xylene. Receive a product for direct use. with

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

Aqueous compositions can be prepared from emulsion concentrates, pastes or wetting powders "E" (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 by

With the help of wetting agents, adhesive compositions, dispersants or emulsifiers. There may also be Kk. prepared concentrates, suitable for dilution with water, consisting of active substances and wetting agents, adhesive compositions, dispersants or emulsifiers or oil.

Concentrations of active substances in compositions can vary in a wide range. In general, such concentrations are from 0.0001 to 1095, better from 0.01 to 1905.

Active substances can also be used with great success according to the method of low volumes with the use of ShIga-I om'-Moishte (SHIM), and it is possible to use compositions with more than 95 wt.95 of the active substance or even the active substance without impurities. z Different types of oils, wetting agents, activating additives, herbicides, fungicides, other pesticides, bactericides, if necessary, can be mixed with the active substances immediately before use (mixture in a tank). These agents can be mixed with the agents according to the invention in a mass ratio of 1:10 to 10:1. -And 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 to be protected from them, and are treated with a fungicidally active amount of the mixture, respectively, compounds | and II when separately introduced. "5" Application can be carried out before or after defeat by pathogenic fungi

The fungicidal activity of mixtures can be shown using the following experiments: o The active substances are prepared separately or together as a basic solution of 0.25 wt.95 of the active substance in acetone c" or dimethyl sulfoxide. To this solution add 1 mass.90 of the emulsifier Opiregoib EG!. (a wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted with water to the desired concentration.

Application example 1 - Protective action against rice smut caused by Rugisciagia ogugae

The leaves of "TaiMopd 67" rice sprouts grown in pots are sprayed with an aqueous suspension in

F) the following concentration of the active substance before the formation of drops. The next day, the plants are inoculated with an aqueous suspension of Rugisciagia ogugae spores. After that, the experimental plants are placed for 6 days in a climatron at a temperature of 22 - 242C and a relative humidity of 95 - 99 95. Then the degree of development of damage on the leaves is visually determined.

The assessment is carried out by determining the affected surface of the leaves in percentage. These percentage values are converted into efficiency.

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

MU - (1 -A/B)X100, where 65 A corresponds to the damage of treated plants by fungi at 9o and

B corresponds to fungal damage of untreated (control) plants in 965.

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 K.5. SoiBu,

Meaves 15, 20-22 (1967)) and compared with 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 active substances A and B with concentrations of a and 6; 76 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, compounds A and B known from the sulfur mixtures described in EP-A 988,790 were used: in. w TE. : "shcha tya and - | into the seam;

What

Table A p

Individual active substances (ge)

Example Active substance Concentration of the active substance in the solution for spraying Effectiveness in 95 relative to the untreated (ppm) control 1 Control (60 95 lesions) (untreated) so 02100010 zo erifluyuyetyu 000000000000640000000000000010002 o « (o) and -

Table B

Mixtures according to the invention

Mixture of active substances Concentration Ratio of components Calculated efficiency") « c 7) efficiency calculated according to the Colby formula - a

Table C - 45 Comparative experiments

Mixture of active substances Concentration Ratio of components Calculated effectiveness")

F PO PI TU MON PO in vna 00000000 o 00001000 (with in tv minya yayu 00310000

PI POP i PO PO p pvzyanya 11010000 50118

You PO PI PON KO o v yu 16 5 16 mln. nn and

FRI PO SOYA MON NO in 7) efficiency calculated according to the Colby formula

It follows from the results of the experiments that the mixtures according to the invention are significantly more effective against rice soot due to strong synergism than the trifloxystrobin mixtures known from EP-A 988 780 comparative compounds. ve Application example 2 - Effectiveness against brown spot of rice caused by Sospiorrhiza: thiuarbeapiz with protective treatment

The leaves of rice sprouts of the "TaiMopd 67" variety grown in pots are sprayed with an aqueous suspension in the following concentration of the active substance until the formation of drops. The next day, the plants are inoculated with an aqueous suspension of spores of Sospiorohyshe thiuareapyv. After that, the experimental plants are placed for 6 days in a climatron at 22 - 249C and 95 - 99 95 relative air humidity. Then visually determine the degree of disease damage to the leaves.

The evaluation is carried out similarly to example 1.

Table O

Separate active substances

Example Active substance Concentration of active substance in solution for spraying Effectiveness in 95 relative to untreated (ppm) control 12 Control (9095 lesions) (untreated) (trifloxystrobic)

Table E

Mixtures according to the invention

Mixture of active substances Concentration Mixture ratio Calculated efficiency") 7) calculated according to the formula

Claims (10)

Formula of the invention (ze) 1. Fungicidal mixture containing 1) triazolopyrimidine derivative of the formula sn | z (o) che - s M -m xx y y y? MU ss -i and c 2) trifloxystrobin formula III III shchi sn, syu om is! o -E m- osn, Po) N., vo in a synergistically effective amount. 2. Fungicidal mixture according to claim 1, which contains a compound of formula I and a compound of formula II in a mass ratio of 100:1 to 1:100. 3. Fungicidal agent, which contains a liquid or solid carrier and a mixture according to any of claims 1 or 2. 4. A method of combating rice-pathogenic fungi, which is characterized by the fact that the fungi, their growth space 65 or plants, soil or seed material to be protected against fungi are treated with an effective amount of compound I and compound II according to claim 1 or the agent according to claim 3. 5. The method according to claim 4, 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. 6. The method according to any of claims 4 or 5, which differs in that the mixture according to claim 1 or 2 or the agent according to item C is used in an amount from 5 g/ha to 2000 g/ha. 7. The method according to any of claims 4 or 5, which differs in that the mixture according to claim 1 or 2 or the agent according to p. C is used in an amount from 1 to 1000 g/100 kg of seed material. 8. The method according to any one of claims 4-7, which is characterized by the fact that they fight against the pathogenic fungus Rugisciagia ogugae or Sospiorohysis tiuareapyv. 70 9. Seed material containing the mixture according to any one of claims 1 or 2 in an amount from 1 to 1000 g/100 kg. 10. Use of compound I and compound II according to claim 1 for obtaining a means suitable for combating rice pathogens. Official bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated 7/5 Microcircuits", 2007, M 8, 11.06.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. c (8) co «c) « (22) i - - c - i? -I se) sh» o 50 syu F) ime) 60 b5