CA2132048A1

CA2132048A1 - Fungicidal mixtures

Info

Publication number: CA2132048A1
Application number: CA002132048A
Authority: CA
Inventors: Horst Wingert; Bernd Muller; Hubert Sauter; Eberhard Ammermann; Gisela Lorenz; Reinhold Saur; Klaus Schelberger; Manfred Hampel
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1993-09-24
Filing date: 1994-09-14
Publication date: 1995-03-25
Also published as: JP3630724B2; CN1111090A; CN1126029A; JPH07165509A

Abstract

Fungicidal mixtures Abstract A fungicidal mixture containing a) the oxime ether carboxamide of the formula I

Description

BASF Aktiengesellschaft 931555 O.Z. 0050/44323 21320~

Fungicidal mixtures The present invention relates to a fungicidal mixture which con-5 tains a) the oxime ether carboxamide of the formula I

C=NOCH3 and b) a dithiocarbamate (II) selected from the group - manganese ethylenebis(dithiocarbamate) (zinc complex) (IIa), - manganese ethylenebis(dithiocarbamate) (IIb), - zinc ammoniate ethylenebis(dithiocarbamate) (IIc) and - zinc ethylenebis(dithiocarbamate) (IId) 25 in a synergistically active amount.
The invention additionally relates to processes for controlling harmful fungi using mixtures of the compounds I and II and the use of the compound I and the compounds II for the production of 30 mixtures of this type.
The compound of the formula I, its preparation and its action against harmful fungi are disclosed in the literature (EP-A 477 631).
The dithiocarbamates II (IIa: common name: mancozeb, US-A 3,379,610; IIb: common name: maneb, US-A 2,504,404; IIc:
former common name: metiram, US-A 3,248,400; IId: common name:
zineb, US-A 2,457,674), their preparation and their action 40 against harmful fungi are likewise known.
With respect to a decrease in the application rates and an im-provement of the spectrum of action of known compound3, the pres-ent invention is based on mixtures which, with a reduced total 45 amount of applied active compo~nds, have an improved action -against harmful fungi (synergistic mixtures).

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BASF Aktiengesellschaft 931555 0.Z. 0050/44323 21320~8 Accordingly, the mixtures defined at the beginning have been found. It has-additionally been found that on simultaneous joint or separate application of the compound I and the compounds II or on application of the compound I and the compounds II in succes-5 sion, harmful fungi can be controlled better than with the indi-vidual compounds.
The compound of the formula I can be present in the E or the Z
configuration with respect to the C=X double bond (with respect 10 to the carboxylic acid function group). Accordingly, it can be used in the mixture according to the invention in each case ei-ther as the pure ~ or Z isomer or as an ~/Z isomer mixture. The E/Z isomer mixture or the E isomer is preferably used, the E iso-mer being particularly preferred.
~ecause of the basic character of the NH group, the compound I is ab~e to form salts or adducts with inorganic or organic acids or with metal ions.
20 ~xamples of inorganic acids are hydrohalic acids such as hydro-fluoric acid, hydrochloric acid, hydrobromic acid and hydriodic acid, sulfuric acid, phosphoric acid and nitric acid.
Suitable organic acids are, for example, formic acid, carbonic 25 acid and alkanoic acids such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid and also glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids having straight-chain or branched alkyl radicals 30 having 1 to 20 carbon atoms), arylsulfonic acids or -disulfonic acids (aromatic radicals such a~ phenyl and naphthyl which carry one or two sulfonic acid groups), alkylphosphonic acids (phos-phonic acids having straight-chain or branched alkyl radicals having 1 to 20 carbon atoms), arylphosphonic acids or -diphos-~5 phonic acids (aromatic radicals ~uch as phenyl and naphthyl whichcarry one or two phosphoric acid radicals), the alkyl and aryl radicals being able to carry further substituents, eg. p-toluene-sulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxy-benzoic acid, 2-acetoxybenzoic acid etc.

Suitable metal ions are in particular the ions of the elements of the second main group, in particular calcium and magnesium, of the third and fourth main group, in particular aluminum, tin and lead, as well as of the first to eighth subgroup, in particular 45 chromium, manganese, iron, cobalt, nickel, copper, zinc and oth-ers. The metal ions of the elements of the subgroups of the fourth period are particularly preferred. The metals can in this ., : : . , .

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case be present in the different valencies applicable to them.
Preferably, the pure active compounds I and II are employed in the preparation of the mixtures, to which, if required, further 5 active compounds against harmful fungi or other pests such as in-sects, arachnids or nematodes, or alternatively herbicidal or growth-regulating active compounds or fertilizers, can be ad-mixed.
10 The mixtures of the compounds I and II and the simultaneous joint or separate use of the compounds I and II are distinguished by an outstanding action against a wide spectrum of phytopathogenic fungi, in particular from the Ascomycetes and Basidiomycetes class. In some cases they are systemically active and can there-15 fore also be employed as foliar and soil fungicides.
They have particular importance for the control of a multiplicityof fungi on various crop plants such as cotton, vegetable plants (eg. cucumbers, beans and cucurbit~), barley, grass, oats, cof-20 fee, maize, fruit plants, rice, rye, soybean, grape, wheat, deco-rative plants, sugar cane and a multiplicity of seeds.
In particular, they are suitable for the control of the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) on ce-25 reals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cu-curbits, Podosphaera leucotricha on apples, Puccinia species on cereals, Rhizoctonia species on cotton and lawns, Ustilago spe-cies on cereals and sugar cane, Venturia inaequalis (scab) on ap-ples, Helminthosporium species on cereals, Septoria nodorum on 30 wheat, Botrytis cinerea (gray mold) on strawberries and vines, Cercospora arachidicola on groundnuts, Pseudocercosporella herpo-trichoides on wheat and barley, Pyricularia oryzae on rice, Phy-tophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Alternaria species on vegetables and fruit and also Fu-35 sarium and Verticillium species.
They are additionally applicable in the protection of materials ;~
(eg. wood preservation), for example against Paecilomyces variotii.

The compounds I and II can be applied ~imultaneously ~ointly or separately, or in succession, the sequence in the case of sepa-rate application in general having no effect on the control suc-cess.
The compounds I and II are customarily applied in a weight ratio of from 2000:1 to 5:1, preferably from 1000:1 to 5:1, in BASF Aktienges~llschaft 931555 O.Z. 0050/4g3~3 213~48 particular from 500:1 to 5:1 (II:I).
Depending on the type of effect desired, the application rates of the mixtures according to the invention are from 0.005 to 5 0.5 kg/ha~, preferably from 0.01 to 0.5 kg/ha, in particular from 0.01 to 0.3 kg/ha, for the compound I. The application rates for the compound~ II are correspondingly from 0.1 to 10 kg/ha, pre-rerably from 0.5 to 5 kg/ha, in particular from 1 to 4 kg/ha.
10 In the treatment of seed, application rateQ of mixture of from 0.001 to 100 g/kg of seed, preferably from 0.01 to 50 g/kg, in particular from 0.01 to 10 g/kg, are generally used.
If harmful fungi which are pathogenic for plants are to be con-15 trolled, the separate or joint application of the 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 soil before or -after sowing of the plants or before or after emergence of the -~
plants.
The fungicidal synergistic mixtures according to the invention and the compounds I and II can be prepared, for example, in the form of directly sprayable solutions, powder~ and ~uspensions or in the form of high-percentage aqueous, oily or other suspen-25 sions, dispersions, emulsions, oil dispersions, pastes, dustingcompositions, brcadcasting compositions or granules and applied by spraying, atomizing, dusting, broadcasting or watering. The application form is dependent on the intended use; it should in each case guarantee a dispersion of the mixture according to the 30 invention which i8 as fine and uniform as possible.
The formulations are prepared in a manner known per se, eg. by addition of solvents and/or carriers. Inert additives such as emulsifiers or dispersants are customarily admixed to the 35 formulations.
Suitable surface-active substances are the alkali metal, alkaline earth metal or ammonium salts of aromatic sulfonic acids, eg.
lignosulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid 40 and dibutylnaphthalene~ulfonic acid, as well as of fatty acids, alkyl- and alkylarylsulfonates, alkyl-, lauryl ether and fatty alcohol sulfates, and also salts of sulfated hexa-, hepta- and octadecanols or fatty alcohol glycol ethers, condensation prod-ucts of sulfonated naphthalene and its derivatives with formalde-45 hyde, condensation products of naphthalene or of naphthalenesul-fonic acids with phenol and formaldehyde, polyoxyethylene octyl-- phenol ethers, ethoxylated isooctyl-, octyl- or nonylphenol, - ..

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alkylphenol or tributylphenyl polyglycol ethers, alkylaryl poly-ether alcohols, i otridecyl alcohol, fatty alcohol-ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene or polyoxy-propylene alkyl ethers, lauryl alcohol polyglycol ether acetate, 5 sorbitol-esters, lignin-sulfite waste liquors or methylcellulose.
Powder, broadcasting and dusting compositions can be prepared by mixing or joint grinding of the compounds I or II or the mixture of the compounds I and II with a solid carrier.
Granules (eg. coated, impregnated or homogeneous granules) are customarily prepared by binding the active compound or the active compounds to a solid carrier.
lS Fillers or solid carriers used are, for example, mineral earths such as silica gel, silicic acids, silicates, talc, kaolin, lime-stone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastic~, and fertilizers such as ammonium sulfate, ammonium 20 phosphate, ammonium nitrate, ureas and vegetable products such a cereal flour, tree bark meal, wood meal and nutshell meal, cellu-lose powder or other solid carriers.
The formulations in general contain from 0.1 to 95 % by weight, 25 preferably from 0.5 to 90 % by weight, of one of the compounds I
or II or the mixture of the compounds I and II. The active com-pounds are in this case employed in a purity of from 90 % to 100 %, preferably from 95 ~ to 100 % (according to NMR spectrum or HPLC).
The compounds I or II and the mixtures or the corresponding for-mulations are applied by treating the harmful fungi or the plants, seeds, 80ils, surfaces, materials or space~ to be kept free from them with a fungicidally active amount of the mixture, -~
35 or of the compounds I and II in the case of separate application.
Application can be carried out before or after attack by the harmful fungi.
Examples of the synergistic action of the mixtures according to ~ 40 the invention against harmful fungi.
It was possible to show the fungicidal action of the compounds and of the mixtures by the following tests:
45 The active compounds were prepared separately or jointly as a 20%
strength emulsion in a mixture of 70% by weight of cyclohex-anone, 20% by weight of Nekanil~ L~ (Lutensol~ AP6, wetting agent ",,.~ . . :. .... .~ , : - : .
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BASF Aktiengesellschaft 931555 O.Z. 0050/44323 , 2132048 having emulsifier and dispersant action based on ethoxylated al-kylphenols) and 10% by weight of Emulphor~ EL (Emulan~ EL, emul-sifier based on ethoxylated fatty alcohols) and accordingly diluted to the desired concentration with water.
Assessment fo~lowed determination of the attacked leaf areas in percent. These percentage values were converted into degrees of action. The degrees of action of the active compound mixtures to be expected were determined according to the Colby formula lO [R.S. Colby, Weeds 15, (1967) 20-22] and compared with the de-grees of action observed.
Colby formula:
E = x + y - x X y/100 E is the degree of action to be expected, expressed in ~ of the untreated control, when using the mi~ture of the active compounds A and B in the concentrations a and b x is the degree of action, expressed in ~ of the untreated control, when using the active compound A in the concentration a 25 y is the degree of action, expressed in % of the untreated control, when using the active compound ~ in the concentration b At a degree of action of 0, the attack of the treated plants cor-30 responds to that of the untreated control plants; at a degree of action of 100 the treated plants showed no attack.
Activity against Fusarium culmorum on wheat 35 Primary leaves of wheat of the variety Kanzler which has been grown in pots were sprayed until dripping wet with aqueous spray liquor which contained 80% of active compound and 20% of emulsi-fier in the dry matter. On the following day, they were inocu-lated with a spore suspension of Fuisarium culmorum and then ~ 40 placed in a climatic chamber having high atmospheric humidity (> 90~) at 22-24-C. After 6 days, the extent of symptom develop-ment was asses~ed visually.

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BASF Aktiengesellschaft 931555 O.Z. 0050/44323 2~320~8 Active compound Active compound con- Degree of action in centration in the ~ of the untreated spray liquor in ppm control Control (untreated) _ 0 5 I. - 750 41 .

_ II. 750 0 _ _ _ 10 Mixture according to degree of action degree of action the invention observed calculated*) I + II 750 + 750 61 41 1:1 mixture I + II 500 + 500 41 21 15 1:1 mixture I + II 750 + 75 41 21 10:1 mixture _ .
I + II 75 + 750 41 21 1:10 mixture .
Active compound Active compound con- Degree of action in centration in the % of the untreated : :
spray liquor in ppm control :-~
_ _ Control (untreated) _ 0 ::~
_ I. 500 21 25 III. 500 0 Mixture according to degree of action degree of action the invention observed calculated*) ~:
_ I + III 500 + 500 41 21 ~:~
1:1 mixture I + III 500 + 50 41 21 10:1 mixture I + III 50 + 500 68 1:10 mixture _ 35 *) calculated by the Colby formula From the results of the test it emerges that the degree of action observed in all mixture ratios is higher than the degree of action forecast by the Colby formula.

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Claims

1. A fungicidal mixture containing a) the oxime ether carboxamide of the formula I
and b) a dithiocarbamate (II) selected from the group - manganese ethylenebis(dithiocarbamate) (zinc complex) (IIa), - manganese ethylenebis(dithiocarbamate) (IIb), - zinc ammoniate ethylenebis(dithiocarbamate) (IIc) and - zinc ethylenebis(dithiocarbamate) (IId) in a synergistically active amount.

2. A fungicidal mixture as claimed in claim 1, containing the oxime ether carboxamide of the formula I as claimed in claim 1 and manganese ethylenebis(dithiocarbamate) (zinc com-plex) (IIa).

3. A fungicidal mixture as claimed in claim 1, containing the oxime ether carboxamide of the formula I as claimed in claim 1 and manganese ethylenebis(dithiocarbamate) (IIb).

4. A fungicidal mixture a claimed in claim 1, containing the oxime ether carboxamide of the formula I as claimed in claim 1 and zinc ammoniate ethylenebis(dithiocarba-mate) (IIc).

5. A fungicidal mixture as claimed in claim 1, containing the oxime ether carboxamide of the formula I as claimed in claim 1 and zinc ethylenebis(dithiocarbamate) (IId).

6. A fungicidal mixture as claimed in claim 1, wherein the weight ratio of the compound II to the compound I is from 2000:1 to 5:1.

7. A process for controlling harmful fungi, which comprises treating the harmful fungi, their environment or the plants, seeds, soils, surfaces, materials or spaces to be kept free from them with the compound of the formula I as claimed in claim-1 and the compound of the formula II as claimed in claim 1.

8. A process as claimed in claim 7, wherein the compound I as claimed in claim 1 and the compound II as claimed in claim 1 are applied simultaneously jointly or separately, or in suc-cession.

9. A process as claimed in claim 7, wherein the harmful fungi, their environment or the plants, seeds, soils, surfaces, ma-terials or spaces to be kept free from them are treated with from 0.005 to 0.5 kg/ha of the compound I as claimed in claim 1.

10. A process as claimed in claim 7, wherein the harmful fungi, their environment or the plants, seeds, soils, surfaces, ma-terials or spaces to be kept free from them are treated with from 0.1 to 10 kg/ha of a compound II as claimed in claim 1.

11. A method of using the compound I as claimed in claim 1 for the production of fungicidally active synergistic mixtures as claimed in claim 1.

12. A method of using a compound II as claimed in claim 1 for the production of fungicidally active synergistic mixtures as claimed in claim 1.