Fungicidal active compound combinations

Abstract

There are described new active compound combinations of a compound of the formula (I) with known fungicidal active compounds, and their use for combating phytopathogenic fungi.

Description

The present application relates to new active compound combinations which are composed, on the one hand, of a compound of the formula I

and, on the other hand, of other known fungicidal active compounds and which are highly suitable for combating phytopathogenic fungi.

It has already been disclosed that the compound of the formula (I) has fungicidal properties (cf. EP-A 339418). The activity of the substance is good; however, it leaves something to be desired in some cases when used at low application rates.

It has furthermore already been disclosed that a large number of azol derivatives, aromatic carboxylic acid derivatives, morpholin compounds and other heterocycles can be employed for combating fungi (cf. K.H. Büchel “Pflanzenschutz und Schädlingsbekämpfung”[Plant Protection and Pest Control], pages 87, 136, 140, 141 and 146 to 153, Georg Thieme Verlag, Stuttgart 1977). However, the action of the substances in question is not always satisfactory when used at low application rates.

It has now been found that the new active compound combinations of a compound of the formula I

and

(A) bupyrimate (Nimrod) and/or

(B) carbozoline (Serinal) and/or

(C) quinomethionate and/or

(D) cyprodinyl and/or

(E) dinocap and/or

(F) epoxiconazole and/or

(G) fenpropidin and/or

(H) fenpiclonil and/or

(I) fluquinconazole and/or

(K) guazatine and/or

(L) 8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4,5]decane-2-methaneamine and/or

(M) (E)-α-(methoxyimino)-N-methyl-2-phenoxy-benzacetamide and/or

(N) (E)-α-(methoxyimono)-N-methyl-2-(2,5-dimethyl-phenoxy-methyl)-benzacetamide and/or

(O) 1-methylethyl[2-methyl-1-[[[1-(4-methylphenyl)ethyl]amino]carbonyl]propyl]-carbamate and/or

(P) N-[5-(2-methoxy-pyridinyl)]-cyclopropane-carboxamide and/or

(Q) bromuconazole and/or

(R) organic Cu preparations, and/or Cu oxyquinolate and/or inorganic Cu preparations, with the exception of Cu oxychloride, and/or

(S) cyproconazole and/or

(T) diniconazole and/or

(U) dodine and/or

(V) ethirimol and/or

(W) fenarimol and/or

(X) fenbuconazole and/or

(Y) fenpicionil and/or

(Z) fentin acetate and fentin hydroxide and/or

(α) imazalil and/or

(β) imibenconazole and/or

(χ) kasugamycin and/or

(δ) maneb and/or

(ε) metconazole and/or

(ω) nuarimol and/or

(π) oxycarboxin and/or

(I) polyoxin and/or

(II) propamocarb and/or

(III) propiconazole and/or

(IV) pyrazophos and/or

(V) pyrifenox and/or

(VI) tetraconazole and/or

(VII) thiabendazole and/or

(VIII) triazoxide and/or

(IX) triflumizole and/or

(X) triforine and/or

(XI) triticonazole and/or

(XII) zineb and/or

(XIII) ziram and/or

(XIV) cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol and/or

(XV) diethirimol and/or

(XVI) edifenphos and/or

(XVII) fluoromide and/or

(XVIII) perfurazoate and/or

(XIX) pencycuron have very good fungicidal properties which complement each other as synergists.

The active compound of the formula (I) has been disclosed (EP-A-339 418). The components also present in the combinations according to the invention are equally known.

Besides the active compound of the formula (I), the active compound combinations according to the invention comprise at least one active compound from amongst compounds (A) to (XIX). Preferred components in the mixture are compounds (A) to (P). In addition, the mixture may also comprise other fungicidally active components.

The synergistic effect is particularly pronounced when the active compounds are present in the active compound combinations according to the invention in certain ratios by weight. However, the ratios by weight of the active compounds in the active compound combinations can be varied within a relatively wide range. In general, 0.01 to 50, preferably 0.25 to 20, parts by weight of compounds (A) to (XIX) are used per part by weight of active compound of the formula (I).

In particular, the number of parts by weight of the components in the mixture which are used per part by weight of the compound of the formula (I) are as indicated below:

(A) 0.1 to 50, preferably 0.25 to 20,

(B) 0.1 to 50, preferably 0.25 to 20,

(C) 0.1 to 50, preferably 0.1 to 20,

(D) 0.1 to 50, preferably 0.25 to 10,

(E) 0.1 to 50, preferably 0.25 to 20,

(F) 0.01 to 10, preferably 0.025 to 5,

(G) 0.1 to 50, preferably 0.25 to 20,

(H) 0.01 to 10, preferably 0.025 to 5,

(I) 0.01 to 20, preferably 0.025 to 20,

(K) 0.01 to 20, preferably 0.025 to 20,

(L) 0.1 to 50, preferably 1 to 50,

(M) 0.01 to 10, preferably 0.025 to 10,

(N) 0.01 to 10, preferably 0.025 to 10,

(O) 0.1 to 50, preferably 0.5 to 50,

(P) 0.1 to 50, preferably 0.1 to 20,

(Q) 0.01 to 10, preferably 0.025 to 5,

(R) 1 to 50, preferably 1 to 20,

(S) 0.01 to 10, preferably 0.025 to 5,

(T) 0.01 to 10, preferably 0.025 to 5,

(U) 0.1 to 50, preferably 0.25 to 20,

(V) 0.1 to 50, preferably 0.25 to 20,

(W) 0.1 to 50, preferably 0.25 to 20,

(X) 0.01 to 10, preferably 0.025 to 5,

(Y) 0.01 to 10, preferably 0.025 to 5,

(Z) 0.1 to 50, preferably 0.25 to 20,

(α) 0.01 to 10, preferably 0.025 to 5,

(β) 0.01 to 10, preferably 0.025 to 5,

(χ) 0.1 to 50, preferably 0.25 to 20,

(δ) 0.1 to 50, preferably 0.25 to 20,

(ε) 0.01 to 10, preferably 0.025 to 5,

(ω) 0.1 to 50, preferably 0.25 to 20,

(π) 0 1 to 50, preferably 0.25 to 20,

(I) 0.1 to 50, preferably 0.25 to 20,

(II) 0.1 to 50, preferably 0.25 to 20,

(III) 0.01 to 10, preferably 0.025 to 5,

(IV) 0.1 to 50, preferably 0.25 to 20,

(V) 0.1 to 50, preferably 0.25 to 20,

(VI) 0.01 to 10, preferably 0.025 to 5,

(VII) 0.01 to 10, preferably 0.025 to 5,

(VIII) 0.1 to 50, preferably 0.25 to 20,

(IX) 0.01 to 10, preferably 0.025 to 5,

(X) 0.1 to 50, preferably 0.25 to 20,

(XI) 0.01 to 10, preferably 0.025 to 5,

(XII) 0.1 to 50, preferably 0.25 to 20,

(XIII) 0.1 to 50, preferably 0.25 to 20,

(XIX) 0.1 to 50, preferably 0.25 to 20,

(XV) 0.1 to 50, preferably 0.25 to 20,

(XVI) 0.1 to 50, preferably 0.25 to 20,

(XVII) 0.1 to 50, preferably 0.25 to 20,

(XVIII) 0.1 to 50, preferably 0.25 to 20, and

(XIX) 0.1 to 50, preferably 0.25 to 20.

The active compound combinations according to the invention have very good fungicidal properties and can be employed mainly for combating phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.

The active compound combinations according to the invention are particularly suitable for combating cereal diseases, such as Erysiphe, Cochliobolus, Pyrenophora and Leptosphaeria, and against fungal attack in vegetables, grape vines and fruit, for example against Venturia in applies, Botrytis in beans and Phytophthora in tomatoes.

The good tolerance, by plants, of the active compound combinations at the concentrations required for combating plant diseases permits treatment of above-ground parts of plants, of vegetative propagation materials and seed, and of the soil.

The active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very find capsules in polymeric substances and in coating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixing the active compounds, or active compound combinations, with extenders, that is, liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulphoxide, as well as water. By liquefied gaseous extenders or carriers are meant liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide. As solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-disperse silica, alumina and silicates. As solid carriers for granules there are suitable: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. As emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates as well as albumen hydrolysis products. As dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

The formulations in general comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.

The active compound combinations according to the invention can be present in the formulations as a mixture with other known active compounds, such as fungicides, insecticides, acaricides and herbicides, as well as in mixtures with fertilizers or plant growth regulators.

The active compound combinations can be used as such or in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders and granules.

They are used in the customary manner, for example by watering, spraying, atomizing, scattering as a powder for dry seed treatment, a solution for seed treatment, a water-soluble powder for seed treatment or a water-dispersible powder for slurry treatment, or by incrusting.

In the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range. They are, in general, between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02% by weight, are required at the place of action.

The good fungicidal, synergistically mutually complementing action of the active compound combinations according to the invention can be demonstrated by the examples which follow. While the individual active compounds show shortcomings with regard to the fungicidal activity, the activity of the combinations exceeds a simple additive effect.

A synergistic effect in fungicides is always present when the fungicidal activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.

The expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S. R., “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 15, pages 20-22, 1967).

If

X is the degree of effectiveness expressed in % of the untreated control when applying active compound A at a concentration of m ppm,

Y is the degree of effectiveness expressed in % of the untreated control when applying active compound B at a concentration of n ppm,

E is the expected degree of effectiveness expressed in % of the untreated control when applying active substances A and B at a concentration of m and n ppm,

then $$ E = X + Y - X · Y 100 .

If the actual fungicidal activity exceeds the calculated value, then the activity of the combination is superadditive, i.e. a synergistic effect exists. In this case, the degree of effectiveness which was actually observed must be greater than the value for the expected degree of effectiveness (E) calculated from the abovementioned formula:

EXAMPLES

Botrytis Test (Beans)/protective

To produce a suitable preparation of active compound, either commercially available formulations of active compound (individual active compound or active compound combinations) or one part by weight of active compound is mixed with 4.7 parts by weight of solvent (acetone) and 0.3 parts by weight of emulsifier (alkyl-aryl polyglycol ether), and the mixture is diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound until dripping wet. After the spray coating has dried on, 2 small pieces of agar covered with Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened humid chamber at 20° C. 3 days after the inoculation, the size of the infected spots on the leaves is evaluated.

To demonstrate synergism between the active compounds used in this experiment, the results were evaluated by the method described by Colby (see above).

Active compounds, active compound concentrations and test results can be seen from the tables which follow.

TABLE 1
Botrytis test (beans)/protective
	Active compound	Degree of
	concentration	effectiveness in % of
Active compound	in ppm	the untreated control
(I)	5	29
Quinomethionate	50	0
Mixture according to the invention:
(I)		5
+		+		63
Quinomethionate		50
Expected value calculated by Colby's formula	29
(see above)
(I)	5	29
Fenpropidin	50	0
Mixture according to the invention:
(I)		5
+		+		90
Fenpropidin		50
Expected value calculated by Colby's formula	29
(see above)
(I)	5	29
Fludioxonil	1	5
Mixture according to the invention:
(I)		5
+		+		85
Fludioxonil		1
Expected value calculated by Colby's formula	33
(see above)
(I)	5	29
Fluquinconazole	25	29
Mixture according to the invention:
(I)		5
+		+		81
Fluquinconazole		25
Expected value calculated by Colby's formula	50
(see above)
(I)	5	29
(N)	12.5	64
Mixture according to the invention:
(I)		5
+		+		85
(N)		12.5
Expected value calculated by Colby's formula	74
(see above)
(I)	5	29
(M)	25	28
Mixture according to the invention:
(I)		5
+		+		55
(M)		25
Expected value calculated by Colby's formula	49
(see above)
(I)	5	29
(L)	200	0
Mixture according to the invention:
(I)		5
+		+		78
(L)		200
Expected value calculated by Colby's formula	29
(see above)
(I)	5	29
(O)	200	19
Mixture according to the invention:
(I)		5
+		+		81
(O)		200
Expected value calculated by Colby's formula	42
(see above)
(I)	5	29
Sodium hydroxymethyl	200	32
sulphinate
Mixture according to the invention:
(I)		5
+		+
Sodium hydroxymethyl-		200		86
sulphinate
Expected value calculated by Colby's formula	52
(see above)
(I)	5	29
Ciprodinyl	5	5
Mixture according to the invention:
(I)		5
+		+		46
Ciprodinyl		5
Expected value calculated by Colby's formula	33
(see above)

Example 2

Agar Plate Test with Penicillium custosum

Nutrient medium used:

39 parts by weight of potato dextrose agar

20 parts by weight of agar

are dissolved in 1,000 ml of distilled water and the solution is kept in an autoclave at 121° C. for 20 minutes.

Solvent:

50 parts by weight of acetone

950 parts by weight of water

Ratio of the amount of solvent to nutrient medium: 1:100

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent.

The concentrate is thoroughly mixed, in the stated ratio, with the liquid nutrient medium, and the mixture is poured into Petri dishes.

When the nutrient medium has cooled and solidified, the plates are inoculated with the following microorganisms and are incubated at about 21° C.: Penicillium custosum.

Evaluation is carried out after 6 days, the inhibition of growth being used as a measure of the action of the products.

In this test, the compounds employed according to the invention perform clearly better than the prior art.

TABLE
Agar plate test with Penicillium custosum
	Active compound	Degree of
	concentration	effectiveness in % of
Active compound	in ppm	the untreated control
(I)	100	24
Guazatine	100	9
Mixture according to the invention:
(I)		100
+		+		56
Guazatine		100
Expected value calculated by Colby's formula	31
(see above)

Example 3

Erysiphe Test (Barley)/protective

To produce a suitable preparation of active compound, commercially available formulations of active compound are diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate shown.

After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%, in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

TABLE
Erysiphe test (barley)/protective
	Application rate of	Degree of effectiveness in
Active compound	active compound in g/ha	% of the untreated control
Prior art: (I)	125	18
Iminoctadine triacetate “Befran”	125	27
Mixture according to the invention:
(I) + iminoctadine triacetate	62.5	55
	+62.5

Example 4

Erysiphe Test (Wheat)/protective

To produce a suitable preparation of active compound, commercially available formulations of active compound are diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate shown.

After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%, in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

TABLE
Erysiphe test (wheat)/protective
		Degree of
	Application	effectiveness
	rate of active	in % of the un-
Active compound	compound in g/ha	treated control
Prior art: (I)	125	25
Quinomethionate “Morestan”	125	9
Mixture according to the invention:
(I) + quinomethionate	62.5	41
	+62.5

Example 5

Leptosphaeria nodorum Test (Wheat)/protective

To produce a suitable preparation of active compound, commercially available formulations of active compound are diluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with the preparation of active compound at the application rate shown.

After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C. and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

TABLE
Leptosphaeria nodorum test (wheat)/protective
	Application	Degree of
	rate of active	effectiveness
	compound in	in % of the un-
Active compound	g/ha	treated control
Prior art: (I)	125	57
Epoxiconazole “Opus”	125	57
Mixture according to the invention:
(I) + epoxiconazole	62.5	100
	+62.5

Example 6

Erysiphe Test (Barley)/curative

To produce a suitable preparation of active compound, commercially available formulations of active compound are diluted with water to the desired concentration.

To test for curative activity, young plants are dusted with spores of Erysiphe graminis f.sp. hordei. 48 hours after the inoculation, the plants are sprayed with the preparation of active compound at the application rate shown.

The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%, in order to promote the development of mildew pustules.

Evaluation is carried out 7 days after the inoculation.

To demonstrate synergism between the active compounds used in this experiment, the results were evaluated by the method described by R. S. Colby (Calculating Synergistic and Antagonistic Responses of Herbicides Combinations: Weeds 15, 20-22, 1967). The expected degree of effectiveness in % of the untreated control was calculated using the equation $$ E = x + y - x · y 100

in which x and y denote, respectively, the degree of effectiveness—expressed in % of the untreated control—obtained by the two preparations when used separately.

If the actually observed degree of effectiveness of the active compound combination exceeds the value calculated for the expected degree of effectiveness (E) using the abovementioned formula, then there is a superadditive, i.e. synergistic, effect.

TABLE
Erysiphe test (barley)/curative
	Application rate of	Degree of effectiveness in
Active compound	active compound in g/ha	% of the untreated control
Prior art: (I)	20	25
	10	66
	actually observed degree of
	effectiveness after using the	expected degree of effectiveness
	mixture, in % of the	(E) after using the mixture, in %
Mixture according to the invention:	untreated control	of the untreated control
(I) + KWG 4168	100	75
	20
	+10

Example 7

Fusarium nivale Test (Wheat)/seed Treatment

The active compounds are used as a powder for dry seed treatment. They are prepared by extending the active compound in question with rock meal to give a finely pulverulent mixture which guarantees uniform distribution on the seed surface.

To carry out the seed treatment, the infected seed and the seed-dressing product are shaken for 3 minutes in a sealed glass flask.

2×100 wheat kernels are sown in standard soil at a depth of 1 cm and grown in the greenhouse at a temperature of approximately 10° C. and a relative atmospheric humidity of approximately 95% in seed boxes which are exposed to the light for 15 hours per day.

Approximately 3 weeks after sowing, the plants are evaluated for snow blight symptoms.

TABLE
Fusarium nivale test (wheat)/seed treatment
	Application rate of	Degree of
	active compound in	effectiveness in % of
Active compound	mg/kg of seed	the untreated control
Prior art: (I)	100	22
	25	0
Guazatine	100	55
Fenpiclonil	25	6
“CGA 142705”
Mixture according to the invention:
(I) + guazatine	50	65
	+50
(I) + fenpiclonil	12.5	31
	+12.5

Example 8

Drechslera graminea Test (Barley)/seed Treatment (syn. Helminthosporium gramineum )

The active compounds are used as a powder for dry seed treatment. They are prepared by extending the active compound in question with rock meal to give a finely pulverulent mixture which guarantees uniform distribution on the seed surface.

To carry out the seed treatment, the infected seed and the seed-dressing product are shaken for 3 minutes in a sealed glass flask.

The seed, embedded in screened, moist standard soil in sealed Petri dishes, is exposed to a temperature of 4° C. for 10 days in a refrigerator. This triggers germination of the barley and, if appropriate, of the fungal spores. 2×50 pregerminated barley kernels are subsequently sown in standard soil at a depth of 3 cm and grown in a greenhouse at a temperature of approximately 18° in seed boxes which are exposed to the light for 15 hours per day.

Approximately 3 weeks after sowing, the plants are evaluated for symptoms of barley leaf stripe.

TABLE
Drechslera graminea test (barley)/seed treatment
(syn. Helminthosporium gramineum )
	Application	Degree of
	rate of	effectiveness
	active compound	in % of the
Active compound	in mg/kg of seed	untreated control
Prior art: (I)	100	43
	50	41
Ethirimol	100	8
Fenpiclonil	50	41
“CGA 142705”
Mixture according to the
invention:
(I) + ethirimol	50	54
	+50
(I) + fenpiclonil	25	69
	+25

Claims

1. A fungicidal composition comprising a synergistic fungicidally effective amount of a combination of a first compound and a second compound, wherein said first compound is a compound of the formula (I)) and said second compound is cyprodinil (d),and wherein said second compound is present in said fungicidal composition in an amount ranging from 0.1 to 50 parts by weight of said first compound in said fungicidal composition.

2. A method of combating fungi comprising administering to the fungi or fungus habitat a fungicidally effective amount of a synergistic fungicidal composition according to claim 1.