DD217960A3 - MEANS FOR CONTROLLING PHYTOPATHOGENOUS FUNGI AND BACTERIA - Google Patents

Abstract

The invention relates to synergistic mixtures for combating phytopathogenic fungi and bacteria from antimicrobially active derivatives of the phenol of general formula I, wherein R 1 is bromine or chlorine, R 2 is methyl or ethyl, R 3 is hydrogen, sodium, potassium, calcium, barium or ammonium and R 4 is hydrogen, Bromine, chlorine, methyl, ethyl or alkyl having up to 5 carbon atoms and fumigants. formula

Description

Title of the invention

Means for controlling phytopathogenic fungi and bacteria

Field of application of the invention

The invention relates to synergistic, acting mixtures of antimicrobial compounds and fungicides which can be used for the chemical control of phytopathogenic fungi and bacteria.

Non-synergistic fungicides and systemic fungicides, in particular benzimidazole fungicides, metalaxyl or dithiocarbamates, their mixtures according to the invention with antimicrobially active compounds are used. for use against mycoses and bacterioses in cereal, fruit, potato, vegetable and ornamental crops. In addition to this application, the range of use of the agents for plant hygiene and plant care may also include suspensions of insecticides, bactericides, viricides, herbicides, sikkants, Minerals, trace elements and means of controlling biological processes in suitable concentrations, individually or in combination

Characteristic of the known technical solutions

Mycoses and bacterial sprouts of crops cause annual crop losses and losses of stored crops estimated at more than $ 20 billion. In addition to breeding measures, the use of pesticides is of decisive importance for the exhaustion of the high herbicidal potency of crops and for the protection of the stored crop · For many P-plant diseases, no sufficiently effective or sufficiently practicable solutions are known (mixed rags on stored material, hindranges in orchards etc.). It is known that phenol derivatives such as chlorophenol, eresol, chlorocresol, pentachlorophenol, benzylphenol, benzylchlorophenol, thymol are antimicrobially active and therefore can be used as potent potential combiners for fungicides to increase the activity and broaden the spectrum of action. Disadvantages of these compounds are the sometimes very high phytotoxicity and Y / ary toxin toxicity, which excludes their use in crop protection.

Synergistic mixtures of 2-chloro-6-methyl-4-benzylphenol with fungicides have already been proposed. These mixtures are distinguished by very good antimicrobial and antifungal activity. Disturbing for certain fields of application is the acid smell of Z-chloro-e methyl - ^ - benzylphenol. In addition, the low water solubility of 2-chloro-6-methyl-4-benzylphenol can lead to difficulties in the preparation and use of preparations.

Object of the invention ₍

The aim of the invention is to develop new crop protection agents for controlling phytopathogenic fungi and bacteria which, with minimal phytotoxicity and minimal toxicity to warm-blooded animals, have a maximum fungicidal and bactericidal action and the lowest possible odor.

Explanation of the essence of the invention

The invention has for its object to develop agents for controlling phytopathogenic fungi and bacteria, which are suitable for use against difficult-to-fight mycoses or bacterioses, especially in mixed infections of crops, and which have minimal phytotoxicity and minimal toxicity to warm-blooded animals.

It has surprisingly been found that mixtures of antimicrobial compounds of the general formula I with various fungicides, in particular BenζimidazoIfungiciden, metalaxyl or dithiocarbamates allow an excellent control of fungal and bacterial pests individually or in mixed infections and also a measure described above for the individual corresponding compounds: beyond the effect of increasing

In the general formula I mean:

R. Bromine or chlorine

R _{2 is} methyl or ethyl

Ε-, 'hydrogen, sodium, potassium, calcium,

'Barium, ammonium as well

R. hydrogen, bromine, chlorine, methyl, ethyl

, or alkyl having up to 5 C atoms ·

Examples of active compounds of the general formula I or their salts with sodium, potassium, calcium, barium and ammonium are the compounds in Table 1.

(I)

Table 1: Phenol derivatives of the general formula I

Derivative- bromine ^E 2 H No. bromine H 1 bromine -methyl 4'-ethyl 2 bromine ethyl 4'-isbpropyl 3 bromine -methyl 4 ^f - ± 3opropyl 4 bromine ethyl 4'-Bromo 5 - bromine -methyl 4'-Bromo β ^! , bromine -methyl 4'-Chloro 7 bromine ethyl 4'-Chloro 3 bromine -methyl 4'-methyl 9 bromine ethyl 4'-ethyl 1.0 -Chlorine -methyl 4'-methyl 1.1 chlorine ethyl 4'-ethyl 12 chlorine -methyl Ή:. 13 chlorine -methyl 4'-isopropyl  14 chlorine ethyl 4'-isopropyl 15 chlorine -methyl 4'-Bromo 16 chlorine ethyl 4'-Bromo 17 chlorine -methyl 4'-Chloro 18 μ bromine ethyl 4'-tert. butyl 19 chlorine ethyl 4'-tert.butyl 20 -methyl 21 -methyl

The synergistic effect of these mixtures can be achieved if the formulations use dissolution ratios of compounds of the general formula I: fungicide of 100: 1 to 1: 100, an optimal effect being obtained in the treatment of mixed pilipidal and bacterial infections A mixture ratio of compounds of the general: Formula I: Fungicide from 1:50 to 1: 5, reached · Non-systemic fungicides such as, for example, pentachloronitrobenzene, sulfur, zineb, maneb, mancozeb, captan, captafol, are used.

/ Copper oxide chloride and systemic fungicides such as ζ. Thiabendazone, fuberidazole, benomyl and metalaxyl. Benzimidazoles, metalaxyl or dithocarbamates are preferably used for the treatment of fungal and bacterial mixed infractions against skin disorders in fruit production, etc. The mixtures according to the invention are brought into a form suitable for use with the customary carriers and additives. The erfiadungsgemäßen funds additives of insecticides, bactericides, tartaricides, sikkanten, 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 liquors to the vegetable sprout or to the treatment of agricultural or horticultural crop can be carried out by a variety of techniques. ,

EXAMPLES

It has been found that various types of formulation (wettable powders, dusts, solutions, suspensions, emulsion concentrates, etc.) can be used and give the advantageous effect. These formulations contain a mixture by Type $ e AU3 an active compound of general formula I, and a fungicide, one or more inert carriers (e.g., kaolin, mica, bentonite, sepiolite, diatomaceous earth, synthetic silica, etc.), wetting agents, dispersing - or emulsifiers (eg »lignosulfonates, pinaphthalmethan-disulfonates, polyvinyl sulfonates, alkyl succinates, sodium sulfite, alkylbenzenesulfonates, alkylphenyl polyglycol ethers, etc.)? Adhesives (eg, polyvinyl alcohols, vegetable and animal waxes, albumins, dextrins, guram arabic, natural and synthetic resins, etc.) _f solvents (eg, DMSO, DMl, HMPT, triacetin, propylene glycol, etc.), oils ( mineral and triglycerides) and, if necessary, buffers. Especially for the production of wettable powders or dusts grinding aids may be necessary in addition to other inert carriers, in which case substances such as chalk powder, quartz powder,

Clays, natural silicates or salts, such as sodium sulfate, sodium bicarbonate, sodium phosphates, sodium thiosulfate and sodium carbonate are used · '

•. ~ f

Example 1 to 10 <.

Samples according to the invention formulated as wettable powders have the following composition %

Mean I ·:>

4% by weight of derivative no. 15 50% by weight of carbeodazim

40 wt -.% Kaolin '

3% by weight of waste liquor powder,

3% by weight ethoxylated alkylphenyl polyglycol ether

Means II

5% by weight of derivative no. 1 30% by weight thiabendazole

55% by weight of calcium carbonate

5% by weight sodium lignin sulfonate

5 wt -.% Ethoxylated alkylphenyl polyglycol ethers

Means III

4 wt, - # Derivative-Hr. 15 50 Gew, - # Carbendazim

6% by weight of propylene glycol

30 wt -.% Synthetic silica

4% by weight of waste liquor powder

δ wt .- ^. ethoxylated Alkylphenylpolyglykolether

Mean IY. ·.

5 wt -.% Derivative no. 15 30 wt .- # thiabendazole

5% by weight ethylene glycol

40% by weight of synthetic silicic acid

12% by weight of dinaphthalmethane dibasulfonate

3% by weight of polyvinyl acetate

5% by weight of N-oleylvinyl acidaurate

Means 7

Derivative-Hr. 15

Metalaxyl.

synthetic silicic acid

sodium dioctylsulfosuccinate

hydrogenated sodium silicoaluminate

NatriumligDiDsulfonat

ethoxylated Alkylphenylpropylglykolether

Derivative no. 14

maneb

precipitated silica

SaoliD

sodium lauryl sulfate

liatriumligDiusulfonat

The ivat no.15

Manoozeb,

kaolin

Hatriumdioctylsulfosucoinat

hydrogenated sodium silicoaluminate

Sodium lignosulfonate -

ethoxylated Alkylpheaylpolyglykolether

Derivative No. «1

Ziaeb ''

kaolin

Sodium _{dioctylsulfosuccinate Λ}

hydrogenated sodium silicoaluminate sodium lignosulfonate wt .- # ethoxylated Alkylphenylpolyglykolether

30 Weight "-% Wt .- ^ Wt .- ^ Wt .- ^ 20 Wt .- ^ Wt .- ^ Wt .- # Weight % 32 Weight % Wt .- ^ Wt .- ^ Wt .- ^ 3 Wt .- ^ Weight % Wt .- ^ Wt .- ^ 8th Wt .- ^ Wt .- # Wt .- ^ Wt .- ^ 4 Wt .- ^ Wt .- ^ Wt .- ^ Wt .- ^ 3 Wt .- ^ Mean 711 Weight % Mean TI 40 Middle Till 30 20 40 30 22 20 8th 3 22 25 8th 3 3 4 8th 4 3 4

Means IX

4 parts by weight 4 50 parts by weight 40 parts by weight 3 parts by weight 3 parts by weight

Mean X

25% by weight, 30% by weight, 35 % by weight

5 wt

 5 wt.

Derivative no. ' Tkio phaDat-me 13iyl Saoliu

Sulphite wastewater dispenser ·

ethoxylated AlkylpheDylpolyglykolether

Sulfur diatomaceous earth SuIfitablaugepulyer ethoxylated

Examples 11 to 19

SrfiDaungsgemäi3e means formulated as suspensions have the following compositions: ',

Mean XI

30 wt -.% Derivative no.

3% by weight of carbendazim

19% by weight of ethylene glycol 25% by weight of butanol

3 parts Metaupon

20% by weight ethoxylated alkylphenyl polyglycol ethers

Mean XII

30% by weight, 34% by weight, 10% by weight

4 wt.

6 wt -.% 1 wt .- ^

Deriyat no.

captan

ethoxylated all-phenylpolyglycol ether Pr ο py.l narrow lyko dibutyl phthalate

Iriazetin,

Antaphron NE

Mean XII] Weight % Wt .- # Weight % Weight- l C. , , ' Wt .- ^ Derivative no. 14 · 10 Wt .- $ Wt .- $ Wt .- ^ Wt .- ^ Derivative no. 1 ' · Wt .- ^ Sulfur '^'. 5 Weight % Wt .- ^ Wt .- ^ Wt .- ^ Cu atearat Wt .-% synthetic silica 10 Wt .- ^ Wt .- ^ Wt .- # Wt .- ^ Dimethylarainoethanol Wt .- ^ spindle oil 20 Wt .- ^ 4 parts by weight Wt .- ^ Weight % DMSO ^s . Weight -4i ethoxylated Alkylphenylpolyglykolether 20 Wt .- ^ Wt .- ^ Means XYI % By weight MethylhexaliE 35 Means XIY Means XY 12 Wt .- ^ ethoxylated Alkylphecylpolyglykolether 5 10 15 5 5 15 Derivative no. 1 ' 10 25 6 sulfur 25 30 2 Dimethylaminοethano1 25 30 5 DMSO 30 45 xylene ethoxylated alkylphenyl polyglycol ether Derivative no. 1 griseofulvin Dim e t hy lam in ο e t han ο 1 DMSO · ethoxylated Alkylphenylpolyglykolether Derivative no. 1 Kupferoxidehlorid synthetic silica Propylene glycol. , hydroxymethyl ethoxylated Alkylphenylpolyglykolether water Mean XYII> * '' 5 5 10 50 30

Agent X7III

25% by weight of derivative no. 1

25 wt .- $ Tridemorph

16% by weight of propylene glycol '<',.,

34% by weight & ethoxylated alkylphenyl polyglycol ether

Means XIX. , ; ....

20% by weight of derivative no. 1

20% by weight of metalaxyl

30% by weight & propylene glycol

10% by weight & DMSO

20% by weight ethoxylated alliglyl phenyl polyglycol ether

Example 20: Test on potato tubers in the laboratory

Zur.Anwendung .come the inventive agent III, 2-chloro-6-methyl-4- (4'-isopropyldieliayl) -PpiieEol brought with customary formulation auxiliaries in an applicable form and Thicoper. These formulations and the comparator carendazimide-based thicoper are tested in a laboratory test against Fusarium blight (Fusarium spp.), Bacterial wet rot (Erwinia spp.) And mixed rot (Fusarium spp. + Erwinia spp.) On Adretta tubers after artificial infection fungicidal efficiency of the test equipment is shown in Table 2 · The fungicidal efficiency was determined from the degree of infestation. The inventive agent III is in the fungicidal action against the three Fäületypen significantly above the fungicidal efficiency of the individual substances. Particularly noteworthy is the excellent action against bacterial wet rot and Mi3chfäule, which are extremely difficult to combat.

TABLE 2 Fungicidal activity of .Mittels III according to the invention in comparison to 2-Ch.lor-6-methyl-4- (4 ¹ -isopropylbenzyl) -phenol and Thicoper against Fusarium blight (Fusariura (derivative-No. 15) spp.), bacterial wet rot (Srwinia spp.), and mixed rot (Fusarium spp. + Erwinia spp.) on "Adretta" potato tubers after artificial infection under laboratory conditions

variant Application rate (active substance) per ton Efficiency Fusarium blight (in%) hate rot Mixed. lazy Agent III (derivative No. 15 + carbendazim) 10 g + 125 g 90 100 100 Derirat no. 15 10g 30 40 1.0 Carbendazim (Thicoper) 125 g 70 1Q 10

Example 21 Testing of the Mixtures according to the Invention Against Powdery Mildew Q2ryslj) graminis DC)

The mixtures according to the invention (agents XI, XIII, XT) which contain the active ingredients 2-chloro-6-methyl-4- (4 ^L -isopropylbenzyl) -ph.enol (derivative no. 15) and 2-bromo-6-methyl 4-benzylphenol (derivative No. 1) are brought into an applicable form with conventional formulation adjuvants and thicopers are used for the experiments. To carry out the experiment, wheat plants in the bin leaf stage with Srysiphe graminis DC f. sp. tritici marchai infected and treated dripping wet after 24 hours with the selected remedies. The fungicidal efficiency was determined from the score on the degree of infestation.

The mixtures according to the invention show a marked synergistic effect. While 'with the mixing components in Sinzelanwendung only an insufficient effect is achieved, with the mixtures of the invention excellent cereal moth control under laboratory conditions is possible.

Table 3: Fungicidal action of the agents XI, XIII and XY according to the invention against powdery mildew (Erysiphe graminis DC, for example tritici Marchai)

Variant drug concentration efficiency

(in ppm) (in 9 &)

100

Mean XI. 750 Derirat-Nr..15 + 250 + Carbendazim Means XIII 300 Derivative no. 1 + 150 + Cu stearate Medium XT 300 Derirat no. 1 + 150 + GrofoofulTin carbendazim 250 (Tkiooper) 150 Cu stearate 150 G-riseofulrim 750 Derivative no. 15 300 Derivative no. 1

100

35 20 65 31 35

Example 22: Testing of the mixtures according to the invention against Botrytis spp on tulips

With the mixtures according to the invention (agents XI and XII), tulip bulbs infected with Botrytis spp. Are treated by being dipped in aqueous broth. These tulip bulbs were planted in the autumn and checked the next spring for symptoms of illness caused by 3otrytis spp. The results of these investigations are shown in Table 4. It was found that the mixtures according to the invention gave an excellent control result.

Table 4: Fungicidal activity-of the mixtures according to the invention against Botrytis spp. on tulip bulbs

variant Application skonzentr at ion 0.15 efficiency (in #)  + 0.05 (in 55) Mean XI Derirat no. 15 1.00 98 + Carbendazim + 0.50 Mean XII Derivative No. 1 92 + Captan

Example 23: Testing of the mixtures according to the invention (agents YII, YIII and XIY) against Phytophthora infestans

Tomato leaves are treated dripping wet with the mixtures according to the invention and then infected with Phytophthora infestans. The fungicidal action of the test equipment is shown in Table 5. The fungicidal efficiency was calculated by counting the infection sites on the degree of infestation. As can be seen from the Yersuchsergebnissen, Gemi3ohe invention have excellent fungicidal activity. It is to be expected that in the case of the mixture according to the invention with metalaxyl the risk of the formation of resistance to the active substance metalaxyl is reduced or avoided by virtue of the combination with an antimicrobial compound of the general formula I

Table 5: Fungicidal effect of mixtures according to the invention and Yergleichsmittel against 3Phytoph.th.ora infestans on tomato leaves

Variant Efficiency Conversion Efficiency

(in ppm) - (in #).

Mean 711 150 92

Medium Till '150, SO

Means XIY. 150 93

Mancozeb ^;

(beroema-Mancozeb 80) 50 51

Ziaeb - _v

(beroema-Ziceb 90) 50 " ^c '20

Metalax ^ l.

(Ridomil 25 WP) -50 45

Claims (4)

Srfindungsanspruch 1. A composition for controlling phytopathogenic fungi and bacteria in cereal, potato, fruit, vegetable and ornamental crops, characterized in that they synergistically acting mixtures of antimicrobially active derivatives of phenol of general formula I, * CD wherein S _{-1 is} bromine or chlorine, R _{2 is} methyl or ethyl, R is hydrogen, sodium, potassium, calcium, barium or ammonium, and H. hydrogen, bromine, chlorine, methyl, ethyl or alkyl having up to 5 carbon atoms with Exception of the combination R.sup.1 = chlorine, R.sup.p = methyl, R.sup.4 = hydrogen and R.sup.4, denote hydrogen or chlorine and contain fungicides. 2. Composition according to item 1, characterized in that they contain as fungicides Benzimidazolfungizide, metalaxyl or dithiocarbamates. 3. Composition according to item 1, characterized in that the mixing ratio between the antimicrobially active ^ Derivatives of the phenol of general formula I and the fungicidal (mixture component 100: 1 to 1: 100, preferably when used against fungal and bacterial mixed infections 1:, 50 to 1: 5., ' 4 "Composition according to item 1, characterized in that the means for expanding the Sinsatzbreite, for plant hygiene and plant care additionally insecticides, bactericides, viricides, herbicides, sikkanten, minerals, trace elements and means for controlling biological processes in suitable concentrations individually or in combinations contain.