Fungicide mixtures and method for control with phytopathogenic fungi

FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes a fungicide mixture containing carbamate of the formula (Ia):

and copper-containing fungicide taken in synergistically active amount. Also, invention describes a method for control of phytopathogenic fungi and applying compounds for a synergistic mixture eliciting the fungicide properties. Fungicide mixtures provide inhibition of phytophthora infection in tomato plants.

EFFECT: improved method for control, valuable fungicide properties of mixtures.

8 cl, 6 tbl, 3 ex

 

The present invention relates to a fungicidal mixture, which contains

A. 1) a carbamate of the formula Ia,

where X is CH and N, n is 0, 1 or 2 and R is halogen, C1-C4-alkyl and C1-C4-halogenated, and residues R may be different if n is 2,

and

b) copper-containing fungicide active ingredient (II) in a synergistically effective amount.

In addition, the invention relates to a method of combating phytopathogenic fungi by mixtures of compounds I and II and to the use of compounds I and II for obtaining such compounds.

The compounds of formula I, their reception and their activity against phytopathogenic fungi known from various sources (WO-A 96/01, 256; WO-A 96/01, 258).

Also known application of copper-containing compounds for combating phytopathogenic fungi.

With regard to the reduction of consumption norms and improving spectrum of the known compounds I and II of the present invention is the task of developing such mixtures at reduced application rates of the active substance have improved activity against phytopathogenic fungi (cineracea mix).

In accordance with that were developed above mixture. In addition, it was found that simultaneous, namely joint and separate use of the compounds I is II or successive application of the compounds I and II, the best you can to fight against phytopathogenic fungi than the individual compounds.

Formula Ia represents, in particular, carbamates, in which the combination of the substituents corresponds to one row of table 1.

Especially preferred compounds I.12, I.23, I.32 and I.38.

The compounds of formula I because of the basic nature of the contained nitrogen atoms capable of forming salts or adducts with organic or inorganic acids or with metal ions.

Examples of inorganic acids are halogen acids, such as pterodroma acid, chlorodane acid, bromatologia acid and iododerma acid, sulfuric acid, phosphoric acid and nitric acid.

As organic acids are suitable, for example, formic acid, carbonic acid and alcamovia acids such as acetic, triperoxonane, trichloroacetic and propionic acid, and also glycolic acid, titanova acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic (sulfonic acids with unbranched or branched alkylamino radicals with 1 to 20 carbon atoms), aresult the acid or ridiculously (aromatic radicals, such as phenyl and naphthyl, which carry one or two sulfonic acids), alkylphosphonate acids (phosphonic acids with unbranched or branched alkyl radicals with 1 to 20 carbon atoms), arylphosphonate acid or aryldiazonium acid (aromatic residues, such as phenyl and naphthyl, which carry one or two phosphonic acid radical), and alkyl, respectively, aryl residues may bear other substituents, such as, for example, p-toluensulfonate, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

As metal ions are suitable, in particular ions of the elements of the first to eighth sub-groups, especially chromium, manganese, iron, cobalt, Nickel, copper, zinc and along with the second main group, primarily calcium and magnesium, elements of the third and fourth main group, in particular aluminum, tin and lead. The metals may be, if necessary, with different inherent valence.

As copper-containing fungicide active substance (II) is suitable in General known, commercially available fungicides. In particular, suitable copper-containing fungicides selected from the group comprising copper hydroxide, copper oxide, oxychloride - copper sulfate, copper sulfate, Aksenovo copper, bis-(3-fenilsalitsilat)copper, digit asin-disulfate copper, trihydroxy-chloride of copper(II) dichloride and the copper dimethyldithiocarbamate(III).

Upon receipt of the compounds used is preferably pure active ingredients I and II, to which it is possible to admix other active agents against phytopathogenic fungi or against other pests, such as insects, arachnids or nematodes, or herbicide or growth regulating active ingredients or fertilizers.

Mixtures of the compounds I and II, respectively, of the compounds I and II are applied simultaneously together or separately, have excellent activity against a broad spectrum of phytopathogenic fungi, in particular from the class of records of Ascomycetes, basidiomycetes, phykomycets and deuteromycetes. They may have partially systemic activity and can therefore also be used as deciduous and as soil fungicides.

They have a special importance when dealing with a multitude of fungi on various cultivated plants, such as cotton, vegetable crops (for example Ogurtsova, beans, tomatoes, potatoes and pumpkin crops), barley, turfgrass, oat, banana, coffee, maize, fruit, rice, rye, soybeans, wheat, vines, ornamental plants, sugar cane, and many seeds.

In particular, they are suitable for dealing with the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on cereals Kul is Urach, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin cultures, Podosphaera leucotricha on apples, Uncinula necator on grape vines, Puccinia species on cereals, Rhizoctonia species on cotton, rice and Janine, Ustilago-Arten on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea (grey mould) on strawberries, vegetables, ornamental plants and grape vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley. Pyricularia oryzae on rice. Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on grape vines, Pseudoperonospora species on hops and cucumbers, Altemaria species on vegetable and fruit crops, Mycosphaerella species in bananas and Fusarium species and Verticillium.

They are applicable also in the protection of materials (for example, protection of wood), for example against Paecilomyces variotii.

The compounds I and II can be made simultaneously, namely, jointly or separately, or sequentially, and the sequence in case of separate application generally does not affect the success of treatment.

The compounds I and II are usually applied in a weight ratio of from 1:1 to 1:1000, preferably 1:1 to 1:100, in particular from 1:3 to 1:10.

The consumption rates of the mixtures according to the invention is primarily in agricultural crops, depending on the type and desired effect from 0.01 to 5 kg/ha, preferably 0.05 to d is 3.5 kg/ha, in particular, from 0.1 to 2.0 kg/ha

This expenditure rate for connection I is from 0.01 to 2.5 kg/ha, preferably from 0.05 to 2.5 kg/ha, in particular from 0.1 to 1.0 kg/ha

The consumption rates of the compounds II are respectively from 0.1 to 10 kg/ha, preferably from 0.5 to 5 kg/ha, in particular from 0.5 to 2.0 kg/ha

In the processing of seed grain in General apply the norms of flow of the mixture from 0.001 to 250 g/kg of seed grain, preferably from 0.01 to 100 g/kg, in particular from 0.01 to 50 g/kg

When combating phytopathogenic fungi on plants separate or joint treatment compounds I and II or of the mixtures of the compounds I and II is carried out by spraying or dusting the seeds, the plants or the soils before or after sowing the plants or before or after germination of the plants. The fungicidal synergistic mixtures according to the invention, respectively the compounds I and II can be prepared, for example, in the form intended for direct spray solutions, powders or suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, products for dusting, preparations for powder or granules and can be applied by spraying, atomized spraying, dusting, dusting or irrigation. Processing technology and used forms hung the t from the target application, but in all cases must be ensured to the maximum fine and uniform distribution of the mixtures according to the invention.

Preparative form get in a known manner, for example by the addition of solvents and/or excipients. Usually admixed inert additives, such as emulsifiers and dispersing agents.

As surface-active substances suitable alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, such as ligninsulfonate, phenolsulfonate, naphthalenesulfonate, dibutylaminoethanol, as well as the fatty acid series, alkyl sulphonates and alkylarylsulfonates, alkyl sulphates, laurilefirsulfat and sulfates of fatty alcohols, and salts of sulfated hexa-, hepta - and octadecanol or glycolethers fatty alcohol series, condensation products from sulphonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene, respectively naphthalenesulfonic with phenol or formaldehyde, polyoxyethyleneglycol ether, ethoxylated isooctyl, octyl - or Nonylphenol, alkylphenol or tributyltinchloride ether, alkylarylsulfonate alcohols, isotridecyl alcohol, condensates of ethylene oxide fatty alcohol series, ethoxylated castor oil, polyoxyethyleneglycol ether or polyoxypropylene, polyglycolether the initial acetate laurynovich alcohols, ester of sorbitol, ligninsulfonate waste alkali or methylcellulose.

Powder, preparation for spraying and dusting can be obtained by mixing or jointly grinding the compounds I and II or of the mixtures of the compounds I and II with a solid filler.

The granulate (e.g., coated, impregnated or homogeneous) are obtained usually by connecting to the active substance or active substances with a solid filler.

As fillers, respectively solid carriers are, for example, mineral earths, such as silica gel, silicic acids, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, milled plastics, and fertilizers such as ammonium sulphate, ammonium phosphates, ammonium nitrate, urea and vegetable products, such as, for example, flour of cereals, flour, tree bark, wood flour and flour a nutshell, cellulose powder or other solid fillers.

Preparative forms contain in General from 0.1 to 95 wt.% preferably from 0, 5 to 90 wt.% compounds I or II, respectively, a mixture of compounds I and II active substances are applied with a purity of from 90 to 100%, preferably from 95 to 100% (according to NMR spectrum or EHVK).

The use of compounds I, Il is II, mixtures or the corresponding preparative forms is carried out in such a way that phytopathogenic fungi, their space habitat (biotope) or protected from them plants, seeds, soil, surfaces, materials or spaces treated fungicide effective amount of the mixture, respectively, compounds I and II with separate entry.

Treatment can be performed before or after the defeat of phytopathogenic fungi.

Application example

Synergistic efficacy of the mixtures according to the invention can be shown by the following experiments.

The active substance is prepared separately or jointly as a 10%emulsion of 63 wt.% cyclohexanone and 27 wt.% emulsifier and in accordance with the desired concentration of the dilute with water.

Action against Phytophthora infestans (phytophthoras)

Leaves grown in pots of tomato varieties "Grβe Fleischtomate" abundantly, to the formation of droplets were sprayed with an aqueous suspension prepared from a source solution containing 10% active ingredient, 63% cyclohexanone and 27% emulsifier. The next day, the leaves were infected with an aqueous suspension of zoospores of Phytophthora infestans. After that, the experimental plants were placed in a saturated steam chamber with a temperature of between 16 and 18°C. After 6 days on the untreated, but infected control plants late blight is asville so much that defeat could be determined visually in %.

The evaluation was made by determining the affected surfaces of the leaves in percent. These percentage values were calculated in efficiency. Efficiency () is determined by the Abbott's formula:

W=(1-α)·100/β,

in which α corresponds to defeat mushrooms treated plants in %; and

β corresponds to defeat mushrooms untreated (control) plants in %.

When efficiency is equal to 0, the defeat of the treated plants corresponds to the efficiency of the untreated plants; efficiency equal to 100, the treated plants are not of defeat.

The expected effectiveness of the mixtures of the active substance is determined by the formula Colby [R. S. Colby, Weeds 15, 20-22 (1967)] and compared with the established effectiveness.

Formula Colby: E=x+y-x·y/100

E expected efficacy, expressed in %of the untreated control when using a mixture of active substances a and B at concentrations of a and b.

x is the efficacy, expressed in %of the untreated control, when using active substance And with concentration.

y is the efficacy, expressed in %of the untreated control, when using active substance B with b concentration.

The results are presented in tables 2 and 3.

Table 2
Approx.Deistvuushie substanceThe concentration of the active substance in the solution for spraying in part./millionEfficiency in % of the untreated control
1VControl (untreated)(100% loss)0
2VCompound I.32280
  130
  0,530
  0,250
3VII.1 = Cobroxin of Tihonov. the copper sulfate10010
    
  500
  250
  12,50

Table 3
Bsp.The mixture according to the inventionThe observed effektivnostithe calculated efficiency*)
4 1 frequent./million I.32 + 100 ppm million II.1 (a mixture of 1: 100)9537
50,5 frequent./million I.32 + 50 part./million II.1 (a mixture of 1: 100)8030
60,25 frequent./million I.32 + 25 ppm million II.1 (a mixture of 1:100)500
72 frequent./million I.32 + 100 ppm million II.1 (a mixture of 1: 50)9782
81 frequent./million I.32 + 50 part./million II.1 (a mixture of 1:50)9530
90,5 frequent./million I.32 + 25 ppm million II.1 (a mixture of 1:50)9330
102 frequent./million I.32 + 50 part./million II.1 (a mixture of 1:25)10080
111 frequent./million I.32 + 25 ppm million II.1 (a mixture of 1:25)9730
120,5 frequent./million I.32 + 12,5 frequent./million II.1 (a mixture of 1:25)9730
30) calculated by the formula Colby

From the results it follows that the observed (installed) efficiency at all mixture ratios higher than calculated by the formula Colby efficiency.

Application example 2. Effective against Phytophthora infestans

Leaves grown in pots of tomato varieties "Grβe Fleischtomate St. Pierre" abundantly, to the formation of droplets were sprayed with an aqueous suspension, prepared from the original solution containing 10% active ingredient, 63% cyclohexanone and 27% emulsifier. The next day, the leaves were infected with cold water suspension of zoospores of Phytophthora infestans with a density of 0.25×106spores/ml. After that, the experimental plants were placed in a saturated steam chamber with a temperature of between 16 and 18°C. After 6 days on the untreated, but infected control plants late blight has evolved so much that defeat could be determined visually in %.

Certain visually percentage share of the affected surfaces are translated into efficiency as % of untreated control. Efficiency of 0 corresponds to the same defeat that and untreated control efficiency equal to 100, corresponds to the defeat at 0%. The expected effectiveness of the mixture of active substances is determined by the Colby formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, pp. 20-22, 1967) and compared with the observed efficiency.

As component II is used rejonowy copper sulphate si(HE2)·CuSO4(may be purchased under the trade name Ciproxin).

The results of the experiments presented in the following tables 4 and 5.

Table 4
Approx.The active ingredientConcentration in ppm millionEffektivnosti % nearabout. control
13Vwithout hitting(87% loss)0
14Vconnection I.2328
  10
  0,50
  0,258
  0,1250
15Vconnection I.3820
  10
    
  0,58
16Vcompound II2008
  1008
  508
  258
  12,50

Tablica
Approx.The mixture according to the invention (conc. in frequent./million)The observed efficiencyThe calculated efficiency
172 frequent./million I.23 + 200 mil. $ II5415
181 frequent./million I.23 + 100 ppm million II428
190,125 frequent./million I.23 + 12,5 frequent./million II310
202 frequent./million I.23 + 100 ppm million II3115
212 frequent./million I.38 + 200 ppm million II778
221 frequent./million I.38 + 100 ppm million II428
232 frequent./million I.38 + 100 ppm million II778
241 frequent./million I.38 + 50 part./million II318
252 frequent./million I.38 + 50 part./million II658
261 frequent./million I.38 + cast./million II548
270,5,part./million I.38 + 12,5 frequent./million II298
* calculated by the Colby formula

From the results of the latter is AET, the installed efficiency in all mixture ratios higher than calculated in advance according to the Colby formula.

An example of biological tests

Prepare the initial solution containing 0.25 wt.% the active substance in acetone or DMSO. To the resulting solution was added 1 wt.% emulsifier of Unipetrol EL (wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenol). The original solution of the active substance is diluted with water corresponding to the specified concentration.

Application example 3

Activity when protective treatment from defeat blight (brown rot) of tomato, caused by the fungus Phytophthora infestans

Leaves of tomato plants in pots were intensively sprayed with an aqueous suspension with the following concentrations of active compounds. The next day, the leaves were infected with an aqueous suspension of spores of Phytophthora infestans. Then the plants were placed in a chamber saturated with water vapor at a temperature of from 18 to 20°C. After 6 days on infected, but untreated protective composition of the control plants brown rot was developed so that the degree of destruction was determined visually in %.

Table 6
Akimune substance/combinationConc. part./millionRatio Action (exp.) (%)Action Rasch. by ColbySynergismThe degree of synergism
Control (naobr. Rast.)  90%   
Pyraclostrobin2 78   
Coprosat100

50
 11

0
   
The copper oxide100

50
 11

0
   
Hydroxide copper100

50
 11

0
   
Pyraclostrobin/coprosat2+1001:5010080Yes20
Pyraclostrobin/coprosat2+501:259778Yes19
Pyraclostrobin/copper oxide2+1001:5010080Yes20
Pyraclostrobin/oxide IU the and 2+501:259778Yes19
Pyraclostrobin/hydroxide copper2+1001:509780Yes17
Pyraclostrobin/hydroxide copper2+501:259478Yes16

1. Fungicidal mixture containing

a) a carbamate of the formula Ia

where X is CH and N, n is 0,1 or 2 and the remainder R is halogen, C1-C4-alkyl and C1-C4-halogenated, and residues R may be different if n is 2;

b) copper containing fungicide of the formula II selected from the group comprising copper hydroxide, copper oxide, oxychloride - copper sulfate, copper sulfate, Aksenovo copper, bis-(3-fenilsalitsilat) copper, dehydratin-disulfate copper, trihydroxy - chloride of copper(II)dichloride, the copper dimethyldithiocarbamate(III) and 3 C satellite(OH)2·CuSO4in synergistic effective amounts.

2. The fungicidal mixture according to claim 1, characterized in that it contains a carbamate of the formula Ia, where X is CH.

3. The fungicidal mixture according to claim 1, characterized in that the weight ratio of compound Ia to the compound II is 1:1 to 1:1000.

4. Way of dealing with phytopathol nimi mushrooms, wherein the phytopathogenic fungi space of their growth or protected from them plants, seeds, soil, surfaces, materials or spaces treated with a compound of formula Ia no to claim 1 and a compound of formula II according to claim 1, and compounds Ia and II according to claim 1 are used simultaneously or sequentially in a synergistic effective amount.

5. The method according to claim 4, characterized in that the compound of formula Ia according to claim 1 and the compound II according to claim 1 are applied simultaneously, namely, either together or separately.

6. The use of compounds Ia according to claim 1 to obtain fungicide acting synergistic mixture according to claim 1.

7. The use of compound II according to claim 1 to obtain fungicide acting synergistic mixture according to claim 1.

8. Tool for use in the composition of the mixture according to claim 1.



 

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FIELD: organic chemistry, fungicides.

SUBSTANCE: invention describes a fungicide mixture containing carbamate of the formula (Ia):

and copper-containing fungicide taken in synergistically active amount. Also, invention describes a method for control of phytopathogenic fungi and applying compounds for a synergistic mixture eliciting the fungicide properties. Fungicide mixtures provide inhibition of phytophthora infection in tomato plants.

EFFECT: improved method for control, valuable fungicide properties of mixtures.

8 cl, 6 tbl, 3 ex

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