DD143998B1 - AGENTS FOR THE CONTROL OF PHYTOPATHOGENOUS FUNGI WITH EFFICIENCY IN FUNGICIDESIS - Google Patents

Description

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Agent for controlling phytopathogenic fungi with efficacy in fungicide resistance

The invention relates to an agent for controlling phytopathogenic fungi, which has a pronounced synergistic effect and unfolds its full fungicidal action even in fungicide resistance and is counteracted by the use of the formation of fungicide resistance. In particular, benzimidazole fungicides whose mixtures according to the invention with surfactants are preferably used as liquid formulations for the application of shoots in cereal, fruit, vegetable and ornamental plants _o

In addition to this application, the range of application of plant hygiene and plant care products can also be extended with the addition of insecticides, bactericides, viricides, herbicides, minerals, trace elements, agents for controlling biological processes »

Fungal diseases cause annual crop losses estimated at about $ 20 billion. The use of fungicides is a crucial factor in exploiting the high earning potential of our crops. "With approximately one year of worldwide use of fungicides, the fungicide has been used for about 12 years

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Phenomenon of fungicide resistance in phytopathogenic fungi in the foreground. Similar phenomena in pest organisms, the populations that are resistant to insecticides, acaricides and antibiotics always build up quickly when the active substances in the metabolism attack relatively specific, entomologists, bacteriologists, human and veterinary have been known for decades. Especially for the group of benziraidazole fungicides, which include the active substances benomyl, carbendazim, thiabendazole, fuberidazole, thiophanate and thiophanatmethyl, and which are the first systemic fungicides with a broad spectrum of activity, resistance symptoms with frequent "cross-resistance" were found in various fungal pathogens. also observed against other drugs.

SCHRÖDER and PROVVIDENTI (1969), BURTH (1973), PETERSON (1973) and IIDA (1975) report resistance phenomena in Sphaerotheca fuliginea to benomyl, associated with "cross-resistance" to thiophanate.

VARGA (1973) also described resistance to benomyl and thiophanate methyl in the presence of Erysiphe graminis, with "cross-resistance" to thiabendazole. Numerous reports of resistance formation, in particular against Benomyl J, are also found for Yenturta inaequalis, Botrytis cinerea, Penicillium spp, Fusarium spp., Verticillium spp. etc. (HOFFMAM and KIEBACHER, 1976; FEHRMAUN, 1976). In addition, resistance symptoms have become known, among other things, in preparations based on dimethirimol, ethirimol and triforine. Since no loss of virulence was observed for a number of important fungal pathogens with the formation of resistance, for example against benomyl (HOFFMANN and KIEBACHER, 1976), their economic importance is very great. In apple cultivation, the proportion of benzimidazole fungicides in the treatment sequence against apple powdery mildew and scab must not exceed 20%. When first signs of resistance occur, the use of the corresponding fungicides completely forbids. The current state of prevention of fungicide resistance is listed below. "

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1. Use of mixed preparations based on active ingredients with different mechanisms of action

2. Alternating spraying with preparations based on fungicides with different mechanisms of action (fungicide rotation)

3. Use of chemical analogs of fungicidal agents z. B. stereoisomeric forms of tridemorph or triforins

4 · Use of fungicides with several attacking species in the fungal metabolism, eg. B. Tridemorph

In addition, insecticides are known to be synergistically involved in causing resensitization (DDT with synergist DMC or WARF). This possibility is not yet available with fungicides.

Clay Tensxden is known to require the penetration of various substances (simple ions, macromolecules) through biological membranes. Thus, e.g. the uptake of herbicides in the plant cell can be increased by surfactants. Similar effects are also exploited when systemic fungicidal wetting agents (Wolfen E or Synergid) are added to the spraying bristles 0, which then cause an improvement in the effect. The mixtures of fungicides with the above-mentioned wetting agents lead in all cases, where there is no resistance, zv / ar to a certain better distribution and adhesion of SpritzbrUhe on the plant, but not in the occurrence of fungicide resistance to improve the fungicidal activity against the corresponding pathogen.

The following mechanisms are known as the cause of resistance formation:

- Change in the permeability of the plasmalemma

- Detoxification of the active ingredient or reduced conversion of a non-toxic precursor into the active substance

- Bypassing of the inhibited metabolic step

- Reduction of the affinity of the site of action

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The aim of the invention is to develop a composition for controlling phytopathogenic fungi with fungicide-resistance activity, which, with minimal phytotoxicity, allows maximum fungicidal action and eliminates the above-mentioned resistance mechanisms.

It has surprisingly been found that mixtures of fungicides, in particular benzimidazole fungicides, with surfactants, which are preferably to be understood as nonionic surfactants, allow an excellent control even with resistance of the fungal pathogens against the corresponding fungicide and also showed an exceeding beyond the described extent effectivity · This effect can be achieved if otherwise unusable high proportions of certain surfactants are used as a mixed component for the formulation of pesticides. These surfactants are according to the invention not only synergists, but also resensitizers when resistance occurs. The mixtures according to the invention develop, for example, when using fungicides such as benzimidazoles (benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate, thiophanate-methyl, etc.), pyrimidine derivatives (ethirimol, dimethirimol, pyrazophos), piperasine derivatives (triforines) ₈ Morpholine derivatives (Dodemorph, Tridemorph, Aldimorph), triazole derivatives (Tridimefon, Fenarimol, Nuarimol, Triadimenol), Metalaxyl and Dithiocarbamate their very good fungicidal activity, preferably in shoot application. Suitable surfactants are polyglycol ethers, alkylsulfonates, alkylarylsulfonates and mixtures thereof, nonionic surfactants from the group of nonyl and / or dodecylphenol ethoxylates having an ethoxide oxide content of from 35 to 90% by weight, preferably from 50 to 80% by weight, are particularly suitable. An optimal effect is achieved with a mixing ratio of fungicide: surfactant * 1: 1.5 to 1: 5; In some cases, a ratio of up to 1:20 has been proven. The most favorable effect is then achieved

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if a surfactant mixture in the above proportions with 1.5 to 2.5 parts of surfactant (80 % ethylene oxide) is used.

The mixtures of the invention are brought with the usual carriers and additives in a form suitable for the application.

It has been found that, preferably, liquid formulations develop the best effect against resistant fungal S _c hader lively. This effect can be positively influenced by the addition of suitable formulation auxiliaries, such as solvents (DMSO, DMF, triazetin), which are already known as penetration aids, and oils. The erfindungsgeraäßen funds additives of insecticides, bactericides, viricides, herbicides, minerals, trace elements and agents for controlling biological processes can be further admixed by their purpose for plant hygiene and plant care is extended the application of the preferably aqueous spray mixtures can by a variety of techniques respectively.

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Außfübr-ungsbeisgiele

Example 1:

An agent according to the invention has the following composition (agent I):

5.0% by weight of benomyl 60.0% by weight of dodecylphenyl polyglycol ether with an ethylene oxide

proportion of 60% by weight 30.0% by weight of DMSO

5.0% by weight of dioctyl phthalate

Example 2:

Another agent according to the invention has the following composition (agent II):

5.0% by weight of carbendazim 30.0% by weight of nonylphenyl polyglycol ether with an ethylene oxide

share of 50 percent, "% 15.0 wt. _# -% Dodecylphenylpolyglycolether with an ethylene ·

content of 70 percent by _e - 20.0 wt%, -% DMP 20.0 wt .-% Triacetin 10.0 wt "-% paraffin oil

Example 3:

Another agent according to the invention has the following composition (Agent III):

15.0% by weight of carbendazim 35.0% by weight of alkylphenyl polyglycol ether with an ethylene oxide

content of 55% by weight 14.0% by weight of alkylphenyl polyglycol ether with an ethylene oxide

proportion of 64 wt .-% 10.0 wt _e -% n-butanol 10.0 wt, -% Triacetin

5.0% by weight of dibutyl phthalate 10.0% by weight of spindle oil 1.0 part of 5S Antaphron HE 30

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Example 4:

A fourth agent according to the invention has the following composition (Agent IV):

15.0 wt _'9 -% Carbendazim

40.0% by volume of alkylphenyl polyglycol ether with an ethylene oxide

proportion of 55 wt .-% 20.0 wt _# -% ethylene oxide with a Alkylphenylpolyglycolether

proportion of 64% by weight І5І0% by weight n-butanol 10% by weight ethylene glycol

Example 5:

Another agent according to the invention has the following composition (Agent V):

15 % by weight of thiabendazole

28% by weight of alkylphenyl polyglycol ether with an ethylene oxide

proportion of 55 wt .-% 15 ^ _ö 0 wt -% Alkylphenylpolyglycolether with a Ethylenozid

proportion of 64 wt% ~ 15.0 wt wt .-% n-butanol 5.0 -..% hexanetriol 7.0 wt .-% spindle oil

Example 6:

Another agent according to the invention has the following composition (Agent VI):

20 ^ 0 Gem '.-% thiophanate-methyl

10% by weight of phenyl tartaramide sodium salt

2OjO GeWo% Alkylphenylpolyglycolether with an ethylene oxide

share of 60 Gev / .-%

10 ^ 0 % by weight of ethylene glycol

15.0% by weight of n-butanol

25 ^ 0% by weight of xylene

Example 7:

Another erfindungsos agent has the following composition (means VII);

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25, 0% by weight of ethirimol 25 i 0 gff.-fo Alkylphenylpolyglycolether with an ethylene oxide

content of 55% by weight of 14% to 0% by weight of allcylphenyl polyglycol ether with an ethylene oxide

content of 64% by weight 16% Geyr ', -% n-butanol 4 »0 GeWe% octadecylamine 2 ° 0% by weight aluminum stearate U, o% by weight paraffin oil

Example 8:

Another agent according to the invention has the following composition (Agent VIII):

15.0% by weight of nuarimol 25% by weight of sulfosuccinate 15% by weight of 0% by weight of alkylphenyl polyglycol ether having an ethylene oxide

proportion of 55 wt .-% 15jO wt -% ethylene glycol І5І0 _e wt -% Triacetin

5 ^ 0 wt _# -% Dioctyl phthalate 10 ^ 0 wt .-% mineral oil

Example 9J

Another agent according to the invention has the following composition (Agent IX):

20% by weight of metalaxyl 30% by weight of alkylphenyl polyglycol ether having an ethylene oxide

content of 55% by weight 13.0% by weight of alkylphenyl polyglycol ether with an ethylene oxide

proportion of 64 wt, -% 20.0 wt -% silicate support S _t 0 wt -% n-butanol 5.0 wt -% of spindle oil 3 ^ 0 wt .-%... Oleic acid methyl tauride sodium

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Example 10:

Another agent according to the invention has the following composition (agent X):

20.0% by weight of bletalaxyl 25.0% by weight of alkylphenyl polyglycol ether having an ethylene oxide

content of 55% by weight 10.0 % by weight of alkylphenyl polyglycol ether with an ethylene oxide

content of 64% by weight 10.0% by weight n-butanol 5.0% by weight spindle oil 3.0% by weight triazetin 2.0% by weight ethylene glycol 3.0% by weight sulfosuccinate

2.0% by weight of dibutyl phthalate 20.0% by weight of silicate carrier

Example 11:

Another agent according to the invention has the following composition (agent XI):

30.0% by weight of mancozeb

5.0 g / t% oleic acid methyltauride sodium

8.0 % by weight of alkylbenzenesulfonate butylamine salt

30.0% by weight of alkylphenyl polyglycol ether with an ethylene oxide

proportion of 55 % by weight

_E 12.0 wt -% n-butanol

5.0 parts by weight of dibutyl phthalate

10.0% by weight of mineral oil

Example 12:

Greenhouse cucumbers are infected with a benomyl-resistant strain of Sphaerotheca fuliginea (Bad) Salmon and treated once weekly with selected test agents. The fungicidal effect of the test agents after 5 treatments is shown in Table 1 »The fungicidal efficacy was calculated from the score on the degree of infestation. The egg results clearly show that the agents according to the invention I and

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II the comparator Benlate, which is practically ineffective, are highly superior. Only the sulfur-based test agent still shows a very good action against the benomyl-resistant cucumber mildew.

Table 1: Fungicidal action of the agents according to the invention in comparison with commercial preparations against Sphaerotheca fuliginea in benziraidazole resistance to greenhouse cucumbers after shoot application.

variant active substance active substance efficiency concentration Means I benomyl 0.025 % 98 % Means II carbendazim 0.025 % 99 % Benlate benomyl 0.025 % 7% Benlate benomyl 0.050 % 7 % Sickosul sulfur 0,180 % 99 %

Example 13:

Barley plants are treated at one leaf stage with a benomyl-resistant strain of Erysiphe graminis DC f. sp. hordei Marchai breed C-12 infected and treated dripping wet after 24 hours with selected test equipment. The fungicidal action of the test equipment is shown in Table 2. The fungicidal efficiency was determined from the score on the degree of infestation. The results show that benomyl-resistant barley mildew can be combated very well with the agents according to the invention, while benzimidazole-based commercial preparations such as benlate and derosal fail. Only the commercial preparation Calizin on the active ingredient of Tridemorph allows a comparable control success.

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Table 2: Fungicidal activity of the invention Міѣѣеі compared with, commercial preparations for barley powdery mildew in Benzimidazolresistenz after shoot application

variant active substance active ingredient " efficiency concentration Means I benomyl 250 ppm 100 % 50 ppm 91 % Means II carbendazim 250 ppm 100 % 50 ppm 87 % Benlate benomyl 250 ppm 30 % 50 ppm 0 % Thicoper Carbendasim 250 ppm 0 % 50 ppm 0 % Calixin tridemorph 250 ppm 100 % 50 ppm 92 %

Example 14:

Wheat plants are in the single leaf stage with a breed mixture of Erysiphe graminis DC f. sp. tritici Marchai infected and treated dripping wet with selected test equipment after 24 hours. The fungicidal action of the test equipment is shown in Table 3. The fungicidal efficiency was determined as in Example 7. The results show the superiority of the agents according to the invention over the benzimidazole-based commercial preparations.

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Table 3: Fungicidal action of the agents according to the invention in comparison with commercial preparations for wheat powdery mildew after shoot application

variant active substance active substance efficiency concentration Means I benomyl 250 ppm 100 % 50 ppm 94 % Means II carbendazim 250 ppm 100 % 50 ppm 96 % Means III carbendazim 250 ppm 100 % 50 ppm 90 % Medium ГУ carbendazim 250 ppm 100 % 50 ppm 89 % Chinoin-foundations benomyl 250 ppm 56 % zol 50 WP 50 ppm 12 % Thicoper carbendazim 250 ppm 25 % 50 ppm 0 %

Example 15 г

Apple trees of the "Jonathan" variety are treated 9 times with selected test agents against infestation with Podosphaera leucotricha in the spray sequence. The fungicidal action of the test agents is shown in Table 4. The fungicidal efficiency was determined from the score on the degree of infestation

 The agent of the invention is superior to the commercial preparation on the same active ingredient in the treatment of leaf infestation and allows a very good control of leaf infestations · The shoot tip infestation is reduced approximately equally by both test means.

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Table. 4: Fungicidal action of an agent according to the invention in comparison with the commercial preparation BMK against Podosphaera leucotricha on apple trees of the variety "Jonathan"

Variant active ingredient

Drug Pit Efficiency Concentration against leaf infestation

UK II _ O, 04 0? /O 85 % 96 % medium carbendazim 04  % 4 % 70 % BMK carbendazim 5%

Example 16:

Apple trees of the "Gelber Köstlicher" variety are treated with Venturia ineequalis by spraying 9 times with selected test equipment. The fungicidal action of the test equipment is shown in Table 5. The fungicidal efficiency was calculated according to the credit score on the infestation degree. As can be seen from the test results, the agent according to the invention has a much better fungicidal activity compared to the commercial preparation based on the same active ingredient (BMK) and the commercial preparation Saprol.

Table 5: Fungicidal activity of an agent according to the invention in comparison with commercial preparations against Venturia inaequalis on apple trees of the variety "Gelber Köstlicher"

variant

active substance

drug concentration

efficiency

Means III carbendazim 0.04% 92 % BMK carbendazim 0.04 % 50 % Saprol triforine 0.04 % 78 %

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Example 17:

Barley plants are treated at one-leaf stage with an ethirimol-tolerant strain of Erysiphe g-raminis DC f. вр. hordei Marchai was infected and treated dripping wet after 24 hours with selected test equipment. The fungicidal action of the test equipment is shown in Table 6. The fungicidal efficiency was determined from the score on the degree of infestation. From the results it can be seen that the ethirimol-resistant mildew can be very well combated with the agents according to the invention, while the commercial preparation Milgo · E fails. The commercial preparation calixin on the active ingredient basis of Tridemorph allows a comparable control success,

Table 6: fungicidal action of an agent according to the invention in comparison with commercial preparations against ethirimol-resistant barley powdery mildew after shoot application

variant active substance active substance efficiency concentration Means VII ethirimol 250 ppm 99 % 50 ppm 85 % Milgo E ethirimol 250 ppm 45 % 50 ppm 0% Calixin tridemorph 250 ppm 100 % 50 ppm 90 %

Example 18:

Wheat plants are in the single leaf stage with a race mixture (R 3/16/17/18) of Erysiphe graminis DC f. sp. tritici marchai infected and treated dripping wet with selected test agents after 24 hours. The fungicidal action of the test equipment is shown in Table 7. The fungicidal efficiency was determined from the score on the degree of infestation. The results show the considerable superiority of the agents according to the invention over the commercial preparations to corresponding

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Activity basis.

Table 7: Fungicidal effect of agents according to the invention in comparison with commercial preparations on a corresponding active ingredient basis against veeeye mildew after shoot application

variant active substance drug efficiency concentration Means V thiabendazole 250 ppm 100 % 50 ppm 92 % Tecto 60 thiabendazole 250 ppm 55 % 50 ppm 21 % Means VI Thiophanate-methyl 250 ppm 100 % 50 ppm 90 % Cercobin M Thiophanate-methyl 250 ppm 45 % 50 ppm 10 % Means VII ethirimol 25 ppm 98% 5 ppm 85% Milgo E ethirimol 25 ppm 65 % 5 ppm 42 % Means VIII nuarimol 25 ppm 100 % 5 ppm 87 % Trimidal nuarimol 25 ppm 60 % 5 ppm 35 %

Example 19:

Potted tomato plants with 4 to 5 developed leaves are sprayed dripping wet in the greenhouse with aqueous dispersions of the fungicidal formulations according to the invention. 5 days after the artificial infection with sporangia of Phytophthora infestans (Mont.) De Bary, the test evaluation is carried out by scoring the leaf infestation and calculating the percentage

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the infestation area on the entire leaf area (infestation level). From this the efficiency is determined. The results in Table 8 show that the agents according to the invention have a clear superiority in their fungicidal activity against Ridomil spray powder.

Table 8: Fungicidal activity of the agents according to the invention in comparison with a commercial preparation against Phytophthora infestans on tomatoes after shoot application

variant

active substance

drug concentration

efficiency

Means IX metalaxyl 800 ppm 100 % [7211a] 200 ppm 96 % 50 ppm 46 % 12.5 ppm 0 % Mean X metalaxyl 800 ppm 100% [7211b] 200 ppm 27 % 50 ppm 0 % 12.5 ppm 0 % Ridomil 25 WP metalaxyl 800 ppm 14 % 200 ppm 0 % 50 ppm 0 % 12.5 ppm 0 % Mean XI mancozeb 200 ppm 100 % 50 ppm 100 % 12.5 ppm 60 % bc Mancozeb 80 mancozeb 200 ppm 85 % 50 ppm 45 % 12.5 ppm 12 % bc Maneb 80 maneb 200 ppm 98 % 50 ppm 52 % 12.5 ppm 20 %

Claims (8)

1 · Agent for controlling phytopathogenic fungi with efficacy in fungicide resistance and pronounced synergistic effect, characterized in that fungicides with otherwise unusually high levels of surfactants (mixing ratio 1: 1.5 to 1: 20) mixed and with the usual carriers and additives be brought into a suitable form for the application. 2. Means according to item 1, characterized in that benzimidazole derivatives are preferably used as the fungicidal component. 3. Means according to item 1, characterized in that preferably nonionic surfactants are used as the surfactant component. 4 * Composition according to item 1, characterized in that the surfactants used as the mixing component are preferably Alkylphenylpolyglycclether having an ethylene oxide content of 35 to 90 Gsv / .i-%, in particular from 50 to 80% by weight. 5 * Agent according to item 1, characterized in that when using Alkylphenylpolyglycolether with an ethylene oxide content of 50 to 80 wt .-% Tewvidmisehungen be used in which the ratio of surfactants with 50 wt .-% ethylene oxide to surfactants with 80 wt. % Is 1.5 to 2.5: 1. 6. Composition according to item 1, characterized in that the mixing ratio between fungicide and surfactant (mixture) component is preferably 1: 2 to 1: 5. 7 · Agent according to item 1, characterized in that preferably liquid formulations are used, whereby the effect is influenced by the use of suitable solvents. 8 "Means according to item 1", characterized in that the means are additionally IncektiSiUe ₁ Bakfc iz riz, ide _f viricides, herbicides, 213257 Minerals, trace elements and means for controlling biological processes in suitable concentrations individually or in combination ·