UA81091C2 - Fungicidal mixture containing triazolopyrimidine derivative, agent and method for controlling phytopathogenic fungi, seed - Google Patents

Abstract

The inventive fungicide mixtures contain as active components 1) a triazolopyrimidine derivative of formula (I) and 2) at least one component of formula (II), wherein variables have the following meanings: A is O or N, B is N or a direct bond, G is C or N, R1 is alkyl, R2 is alkoxy and R3 is halogen, wherein said mixtures contain the components in the synergically effective amount thereof. A method for controlling pathogenic fungi using the compound (I) and compound (II) mixtures, the use of the compound (I) with the compound (II) for producing said mixtures and mixture-containing agents are also disclosed (I).

Description

Description of the invention

The present invention relates to fungicidal mixtures containing as active components 2 1) a triazolopyrimidine derivative of the formula

WITH

70 ME, E ge meh ro | E and manta 2. 2) at least one compound of the formula ЕІІІ 20 ЕІІ c

Angle

And in

Ii, ch 25 in which the variables have the following meaning: Ge)

A means O or M;

B stands for M or direct connection;

C means C or M;

B" means CgC,-alkyl; -- 30 B2 means C-C,-alkyl; and Ge)

ВZ means halogen, о in a synergistically effective amount.

In addition, the invention relates to a method of combating pathogenic fungi with mixtures of compound I! with mixed - with 5 product IP and application of the compound | with mixed product I to obtain similar mixtures, as well as with means containing these mixtures.

Compound I, 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 is known from publications (see international application UUO 98/46607|.

Compounds of the formula II, their preparation and their action against pathogenic fungi are also known from literary sources (MO « 40 9З1/А86Ва; UMO 02/094797; MO 03/14103І. 2 с Mixtures of triazolopyrimidines with other active substances are generally known from documents (ЕР- А 988 790 and 05 6 268 3711. Taking into account the reduction of consumption norms and the expansion of the spectrum of action of known compounds, the basis of this invention was the task of developing mixtures that, with reduced total amounts of introduced active substances 45, show a better effect against pathogenic fungi (synergistic mixtures) . o In accordance with this, the above mixtures were developed. In addition, it was established that with the simultaneous joint or separate use of compound I and compound II or with the sequential application of compound I! and - compound II, it is possible to fight pathogenic fungi better than with separate compounds ( synergistic mixtures). o Mixtures of compound | and compound II, respectively, simultaneous joint or separate application of compound | and 50 compound II differ in red action against a wide range of phytopathogenic fungi, in particular from the class of ise) Azsotuseiez, Oeshegotuseiez, Ootuseiez and Vavzidiotuse (evz. They can be used for the protection of sk plants as foliar and soil fungicides.

They are of particular importance in the control of large numbers of fungi on various cultivated plants, such as bananas, cotton, vegetable crops (for example, cucumbers, legumes and pumpkin crops), barley, turf, oats, coffee, potatoes, corn, fruit crops, rice, rye, soybeans, tomatoes, grapes, wheat, ornamental plants, sugar cane and on a large number of seeds. (F) In particular, they are suitable for the control of the following phytopathogenic fungi: Vishtegia dgatipiz (true powdery mildew) on wheat, Eguzirpe sispogaseagit and Zryaegoipesa IShidipea on pumpkin plants,

Rodozrnaega Ieisoigisna on apple trees, Opsipsha pesaiog on grapevines, species of Ryssipia on cereals, species of 60 KPigosiopia on cotton, rice and turf, species O8i(Shado on cereals and sugar cane, Mepishgia ipaedsaiyz on apple trees, Viroiagis and Yuogesyziega on cereals, rice and turf , Zeriogia podogyta on wheat,

Voiguiiz sipegea on strawberries, vegetables, decorative crops and vines, Musozrpaegeiia species on banana crops, strawberries, groundnut and cereals, RzecydosegsozrogeiIa Pegroihispoidesz on wheat and barley, Rugisiiagia ogulae on rice, Rpuiorpiyoga ip'ezwiape on potatoes and tomatoes, Rzepozroga vyfdorego species On pumpkin plants and hops, Riaztoraga myisoia on vines, species of AKegpag on vegetable and fruit crops, as well as species of Ryzagisht and Megisiit.

In addition, they are suitable for protecting materials (e.g. protecting wood), such as against

Raesiiotusez of magic.

Compound | and compound I can be introduced simultaneously together or separately or sequentially, moreover

Queuing when applied separately generally does not affect processing success.

The definitions used for formula II are collective concepts that have meaning for the following substituents: halogen: means fluorine, chlorine, bromine and iodine; alkyl: means a saturated, straight or branched hydrocarbon residue having from 70 1 to 4 carbon atoms, for example, C1-C1-alkyl, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1- methylpropyl, 2-methylpropyl or 1,1-dimethylethyl.

Compounds of formula II, in which VE! means n-propyl or n-butyl, particularly n-propyl, are preferred.

Along with this, especially preferred are compounds of formula II, in which KZ means iodine or bromine, in particular, iodine.

Formula II represents especially the compounds of formulas 11.1, 11.2 and II. Z: o pf shk o poviche SO dym on Sche Le ikh ME: ve Ot in which variables have values as for the formula HER.

The compound of formula 1.1, in which B" means n-propyl, K?2 means n-propoxy and KZ means iodine, is also known under the common name "proquinazid" (compound 11.1-1). Mixtures of compounds of the formula | and proquinazid is the best form of implementation of this invention.

Along with this, mixtures containing a compound of the formula | and the compound of formula 1I.2, is the best form of implementation of the invention. high school

Mixtures of compounds I| and one of the following compounds of formula 1I.2 are preferable: o - »

F

"in)

Another form of implementation of the invention is a mixture of compound I and one of the following compounds of formula 11.3: - зв со « и шчи - :» 5 со или («c) со 50 Mixtures of compound I with compounds 11.3-6 or 11.3-12, especially 1I.3-6, are better.

When preparing mixtures, it is desirable to use pure compounds I and II, to which you can mix, if necessary, "6 other active substances against pathogenic fungi or other pests, such as insects, arachnids or nematodes, or herbicidal or re-regulating active substances or fertilizers.

As other active substances in the above sense suitable, in particular, fungicides selected from the group that includes: 29 - acylalanines, such as benalaxyl, metalaxyl, ofurace or oxadixyl,

GF! - amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidine, guazatin, iminoctadine, spiroxamine or tridemorph, co - anilinopyrimidines such as pyrimitanil, mepanipyrim or cyprodinil, - antibiotics such as cycloheximide, griseofulvin, kazugamycin, natamycin, polyoxin or streptomycin, bo - azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinitroconazole, enilconazole, epoxyconazole, fenbuconazole, fluquiconazole, flusilazole, flutriafol, hexaconazole, imazalil, ipconazole, metconazole, myclobutanil, penconazole, propiconazole, prochlorac , prothioconazole, simeconazole, tetraconazole, tebuconazole, triadimefon, triadimenol, triflumizole or triticonazole, - dicarboximides such as iprodione, myclozolin or vinclozolin, b5 - dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metham, metiram, propineb, polycarbamate, thiram, ziram or zineb,

- heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, ciazofamide, dazomet, dithianone, famoxadone, phenamidon, fenarimol, fuberidazole, flutolanil, furametpir, isoprothiolane, mepronil, nuarimol, probenazole, pyroquilon, silthiofam, thiabendazole , thifluzamide, thiophanate-methyl, thiadinil, tricyclazole or triforin, - copper-containing fungicides such as Bordeaux liquid, copper acetate, copper oxychloride or basic copper sulphate, - nitrophenyl derivatives such as binapacryl, dinocap, dinobuton or nitrophthalisopropyl, - phenylpyrroles, such as fenpiclonil or fludioxonil, - sulfur, 70 - other fungicides, such as acibenzolar-B-methyl, benthiavalicarb, carpropamide, chlorothalonil, cyflufenamide, cymoxanil, diclomezin, diclocimet, dietofencarb, edifenphos, etaboxam, phenhexamide, fentin- acetate, phenoxanil, ferimzone, fluazinam, phosphoric acid, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenone, pencicuron, propamocarb, phthalide, toloclofos-methyl, quint ocene or zoxamide, - strobilurins such as azoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, /5 methominostrobin, oryzastrobin, picoxystrobin, pyraclostrobin or trifloxystrobin, - sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet or tolifluanid, - amides of cinnamic acid and analogues such as dimethomorph, flumetover or flumorph.

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

Sh or two fungicides HER and IM.

Mixtures of compounds I and II with component III are the best. Mixtures of compounds I and HER are especially preferable.

Compound I and compound II are usually used in a mass ratio of from 100:1 to 1:100, preferably from 20:1 to 1:20, especially preferably from 10:1 to 1:10.

Components I and, if necessary, IM are mixed with compound I if necessary in a ratio of 20:1 to 1:20. high school

Consumption rates of mixtures according to the invention are, depending on the type of compound and the desired effect, from 5g/ha to 1000g/ha, preferably from 50 to 900g/ha, in particular from 40 to 750g/ha. (8)

Consumption norms of the compound | are, respectively, usually from 1 to 1000 g/ha, preferably from 10 to 3900 g/ha, in particular from 20 to 750 g/ha.

The rate of consumption of compound II is, as a rule, from 1 to 100 Og/ha, preferably from 10 to 900 Og/ha, in particular from 20 to 75 Og/ha.

When processing seed material, in general, consumption rates of mixtures from 1 to 100g/100Okg of Me seed material are used, preferably from 1 to 750g/10Okg, in particular from 5 to 500g/1O0Okg. at

The method of combating pathogenic fungi is carried out with the help of separate or joint application of compound I and compound I or mixtures of compound I and compound I by spraying or dusting seed material, plants or soil before or after sowing plants, or before or after plants got off co

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 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 . Solvents/excipients are suitable, mainly: and? - water, aromatic solvents (e.g., petroleum products, xylene), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol, pentanol, benzyl alcohol), ketones (e.g., cyclohexanone, gamma-butyrolactone), pyrrolidones ( M-methylpyrrolidone, M-octylpyrrolidone), acetates (glycol diacetate), glycols,

Go! dimethyl amides of fatty acids, fatty acids and esters of fatty acids. In principle, mixtures of solvents can also be used; - - fillers, such as natural rocks (for example, kaolins, alumina, talc, chalk) and o synthetic rocks (for example, highly dispersed silicic acid, silicates); emulsifiers such as 5or Nonionic and anionic emulsifiers (for example, ethers of polyoxyethylene fatty alcohols, and alkylsulfonates and arylsulfonates) and dispersants such as lignin sulfite spent alkalis or

Kk methylcellulose.

Alkaline, alkaline earth, ammonium salts of lignin sulfonic acids, phenol sulfonic acids, naphthalene sulfonic acids, dibutylnaphthalene sulfonic acids, alkylaryl sulfonates, alkyl sulfonates, alkyl sulfates, sulfates of fatty alcohols, fatty acids and sulfated glycol ethers of fatty alcohols, and condensation products of sulfonated naphthalene or its derivatives are suitable as surfactants. with

F) formaldehyde, condensation products of naphthalene, respectively naphthalene sulfonic acid with phenol or formaldehyde, polyoxyethylene octyl phenol ether, ethoxylated isooctyl phenol, octyl phenol, nonyl phenol, alkylphenol polyglycol ether, tributyl phenyl polyglycol ether, tristeryl phenyl polyglycol ether, boron alkylaryl polyester 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 obtaining solutions, emulsions, pastes or oil dispersions that are sprayed directly, suitable fractions of mineral oils with an average - high boiling point, such as kerosene or diesel oil, further 65 coal oils, as well as oils (oils) of vegetable or animal origin , aliphatic, cyclic or aromatic hydrocarbons such as toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents such as dimethylsulfoxide, M-methylpyrrolidone or water.

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

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 ammonium sulfates, ammonium phosphates, ammonium nitrates, ureas, and vegetable products such as grain flour, tree bark flour, wood flour and nut shell flour, cellulose powder or other solid fillers.

Ready-made compositions generally contain from 0.01 to 95% by weight, preferably from 0.1 to 30% by weight of the active substance. Active substances are used with purity from 9095 to 10095, preferably from 9595 to 10095 (according to the NMR spectrum). 15 Examples for compositions: 1. Products for dilution in water

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

Alternatively, a wetting agent or other auxiliary agents are added. When diluted in water, the active substance dissolves 2%.

B) Dispersible concentrates (OS) 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) of 15 wt. parts of the compound according to the invention are dissolved in xylene when added

Sa-dodecylbenzenesulfonate and castor oil ethoxylate (5 95 each). When diluted in water, i) an emulsion is formed.

O) Emulsions (EMU, EF) wt. parts of the compound according to the invention are dissolved in xylene with the addition of "-zo Ca-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. An emulsion is formed when Me is diluted in water. at

E) Suspensions (5C, OB) 20 wt. parts of the compound according to the invention are crushed by adding a dispersant and a wetting agent (87

From the agent and water or organic solvent in a ball mill with an agitator. 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 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) and 75 wt. 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. o 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 o kaolin. In this way, a means for spraying is obtained.

I) Granules (OK, BO, BO, MO) se) 0.5 wt. parts of the compound according to the invention are finely ground and bound with 95.595 fillers. Extrusion, spray drying, or fluidized bed processing are common methods used for this. Granulate is obtained for direct use.

U) BIM - solutions (ОЙ) 5B 10 wt. parts of the compound according to the invention are dissolved in an organic solvent, for example, xylene.

Receive a product for direct use.

F) Active substances can be used as such, in the form of their preparative forms or in the forms that 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, because dusting preparations or granules 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 65 (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, 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, preferably from 0.01 to 1905.

Active substances can also be used with great success according to the method of low volumes of application 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. 70 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.

Compounds And! and II, respectively, mixtures or corresponding compositions are used in such a way that pathogenic fungi or plants, seeds, soil, surfaces, materials or premises subject to protection from them are treated with a fungicidally active amount of the mixture, respectively, compounds I! and II when used separately.

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

The fungicidal effect of a compound or mixture can be shown using 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. Imas.9o of Opirego emulsifier is added to this solution. EG. (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and diluted with water according to the desired concentration.

Application example - Effectiveness against powdery mildew of wheat caused by Eguzirpe Isyn. Vitegia) dgatipiv gta zresiaiiv. Tiyisi with 5-day protective treatment

The leaves of wheat sprouts of the "Kaplieg" variety grown in pots are sprayed with an aqueous suspension with the following concentration of the active substance until the formation of drops. The suspension or emulsion is prepared as above. 5 days after the application of the active substance, the plants are dusted with powdery mildew spores (Eguzirpe |zup. Vishtegia| dgatipiv yogta zresiaiiiv. igyisi). The experimental plants are then placed in a greenhouse with a temperature from 20 to 242C and a relative humidity of 60-9095. After 7 days, the degree of development of powdery mildew on the entire surface of plant leaves is determined visually in 9Uo. "--

Visually determined values of the percentage of the affected leaf surface are listed in the efficiency as 90 relative to the untreated control: o

Efficiency (MU) is calculated according to Abot's formula: o

MU t (1 -o/8)-100, where sa. corresponds to fungal damage to treated plants in 95 and -- p corresponds to fungal damage to untreated (control) plants in 905. (ee)

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 Soyru K.5. "

UUeeadvs 15, 20-22 (1967)| and compared with established efficiency.

Colby's formula: - c E -x nu-xUu/100, where "» E is the expected efficiency, expressed in 95% relative to the untreated control, when using a mixture 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 a concentration of a; so y - efficiency, expressed in 95% relative to the untreated control, when using the active substance B with - concentration b. (ав) Table A (se) 50 Individual active substances to it

POH renovany in solution relative to cheobrov- for ooprzhuvuevnia | lazy contule! with no 100 henvol 111-110 t damage) o 7 (yuvryuven! 111111 yu pe niya PO YN PO NYA vv v vm viyu rondo and Olya PO NYA NOTES 51315011yu 65 vm

Table B

Mixtures according to the invention 000000 Concentration efficiency efficiency) 01 bhalf ratio/ 111111 000 juomponenivmixtures 1 ns ot ke PO POL to 1 raezhavminya 11 ni a . PO PO 1 0rovyulavminyai 111

PI PI i PI PO i she i shi i poh s 1 roavyuviinya 1

PI PE EN FIELDS PO

Concentration (effectiveness, effectiveness")

Drink NIE EN NI ZY o nn u NI nn nn and MON - zo nyny Ek No PO and nyny

Oootetnna and rve oh nrnny | her "-

From the results of the experiments it follows that the mixture according to the invention Due to strong synergism

They show much higher efficiency than could be expected from the previous calculation according to Colby's formula.

Claims (12)

The formula of the invention "- c 1. Fungicidal mixture containing c" 1) triazolopyrimidine derivative of the formula с () АХ (ее) Бе; - Sh-E «so g E -x Meems and 2) at least one compound of the formula ІІІ (c) ; (I) Z C E! she has two that Al: in 60 What in which A means O or M, B means M or a direct bond, C means C or M, 65 "B" means C.-C.-alkyl, B? means C.-C .-Alkoxy and VZ means halogen, in a synergistically effective amount. 2. Fungicidal mixture according to claim 1, which contains as a compound of formula I compound 11.1-1 (proquinazid) o (P.1-1). so sen 2. di M al YANU to Z. Fungicidal mixture according to claim 1, which contains as a compound of formula II a compound of formula 1I.2 o ; (1.2) Z Г E! where B" means n-propyl or n-butyl, B" means methoxy, ethoxy or isopropoxy and EZ means iodine. 4. The fungicidal mixture according to claim 1, which contains as a compound of the formula II the compound of the formula 1.3 (c); (3) c z - (o) no -E a b2 in which -- 3o B" means n-propyl or n-butyl, Ge) B? means ethoxy, n-propoxy, isopropoxy or n-butoxy and o BZ means bromine or iodine. 5. Fungicidal mixture according to any of claims 1-4, which contains a compound of the formula | and the compound of the formula HER in a mass ratio of 100:1 to 1:100. co 6. An agent containing a solid or liquid carrier and a mixture according to any of claims 1-5. 7. The method of combating phytopathogenic fungi, which differs in that the fungi, their growing space or plants, soil or seed material to be protected from damage by them, are treated with an effective amount of compound I and compound I according to claim 1. 8. The method according to claim 7, which differs in that compounds I and II according to claim 1 are introduced simultaneously, namely jointly or with c separately or sequentially. 9. The method according to claim 7 or 8, which differs in that compounds I! and II according to claim 1 or mixtures according to any of paragraphs . and? 1-5 are used in amounts from 5 g/ha to 1000 g/ha. 10. The method according to any of claims 7-9, which differs in that compounds I and II according to claim 1 or mixtures according to any of claims 1-5 are used in an amount from 1 to 1000 g/100 kg of seed material. Go! 11. Seed material containing the mixture according to any of claims 1-5 in an amount from 1 to 1000 g/100 kg. 12. Use of compounds I and II according to claim 1 to obtain a means suitable for combating pathogenic fungi. (c) Official Bulletin "Industrial Property". Book 1 "Inventions, useful models, topographies of integrated circuits and microcircuits", 2007, M 19, 26.11.2007. State Department of Intellectual Property of the Ministry of Education and Science of Ukraine. F) name) 60 b5