Fungicidal Compositions

Abstract

A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A) and B) in a synergistically effective amount, wherein component A) is a compound of formula (I), wherein R1 is difluoromethyl or trifluoromethyl and R2 is C1-C6alkyl, C1-C4alkoxy-C1-C6 alkyl or C1-C6 haloalkyl; or a tautomer of such a compound; and component B) is a compound selected from compounds known for their fungicidal and/or insecticidal activity, is particularly effective in controlling or preventing fungal diseases of useful plants.

Description

FORMULATION EXAMPLES

Wettable powders	a)	b)	c)
active ingredient [I:comp B) =	25%	50%	75%
1:3(a), 1:2(b), 1:1(c)]
sodium lignosulfonate	5%	5%	—
sodium lauryl sulfate	3%	—	5%
sodium diisobutylnaphthalenesulfonate	—	6%	10%
phenol polyethylene glycol ether	—	2%	—
(7-8 mol of ethylene oxide)
highly dispersed silicic acid	5%	10%	10%
Kaolin	62%	27%	—

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders that can be diluted with water to give suspensions of the desired concentration.

	Powders for dry seed treatment	a)	b)	c)
	active ingredient [I:comp B) =	25%	50%	75%
	1:3(a), 1:2(b), 1:1(c)]
	light mineral oil	5%	5%	5%
	highly dispersed silicic acid	5%	5%	—
	Kaolin	65%	40%	—
	Talcum	—		20

The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording powders that can be used directly for seed treatment.

Emulsifiable concentrate
active ingredient (I:comp B) = 1:6) 10%
octylphenol polyethylene glycol ether 3%
(4-5 mol of ethylene oxide)
calcium dodecylbenzenesulfonate  3%
castor oil polyglycol ether (35 mol of ethylene oxide) 4%
Cyclohexanone                    30%
xylene mixture                   50%

Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water.

	Dusts	a)	b)	c)
	Active ingredient [I:comp B) =	5%	6%	4%
	1:6(a), 1:2(b), 1:10(c)]
	talcum	95%	—	—
	Kaolin	—	94%	—
	mineral filler	—	—	96%

Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed.

Extruder granules
Active ingredient (I:comp B) = 2:1) 15%
sodium lignosulfonate            2%
carboxymethylcellulose           1%
Kaolin                           82%

The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.

Coated granules
Active ingredient (I:comp B) = 1:10) 8%
polyethylene glycol (mol. wt. 200) 3%
Kaolin                           89%

The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.

Suspension concentrate
active ingredient (I:comp B) = 1:8) 40%
propylene glycol                 10%
nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6%
Sodium lignosulfonate            10%
carboxymethylcellulose           1%
silicone oil (in the form of a 75% emulsion in water) 1%
Water                            32%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Flowable concentrate for seed treatment
active ingredient (I:comp B) = 1:8) 40%
propylene glycol                 5%
copolymer butanol PO/EO          2%
tristyrenephenole with 10-20 moles EO 2%
1,2-benzisothiazolin-3-one (in the form of a 20% solution in 0.5%
water)
monoazo-pigment calcium salt     5%
Silicone oil (in the form of a 75% emulsion in water) 0.2%
Water                            45.3%

The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.

Slow Release Capsule Suspension

28 parts of a combination of the compound of formula I and a compound of component B), or of each of these compounds separately, are mixed with 2 parts of an aromatic solvent and 7 parts of toluene diisocyanate/polymethylene-polyphenylisocyanate-mixture (8:1). This mixture is emulsified in a mixture of 1.2 parts of polyvinylalcohol, 0.05 parts of a defoamer and 51.6 parts of water until the desired particle size is achieved. To this emulsion a mixture of 2.8 parts 1,6-diaminohexane in 5.3 parts of water is added. The mixture is agitated until the polymerization reaction is completed.

The obtained capsule suspension is stabilized by adding 0.25 parts of a thickener and 3 parts of a dispersing agent. The capsule suspension formulation contains 28% of the active ingredients. The medium capsule diameter is 8-15 microns.

The resulting formulation is applied to seeds as an aqueous suspension in an apparatus suitable for that purpose.

BIOLOGICAL EXAMPLES

A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components.

The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S. R. “Calculating synergistic and antagonistic responses of herbicide combination”. Weeds, Vol. 15, pages 20-22; 1967):

ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture

X=% action by active ingredient A) using p ppm of active ingredient

Y=% action by active ingredient B) using q ppm of active ingredient.

According to COLBY, the expected (additive) action of active ingredients A)+B) using p+q ppm of active ingredient is

$E=X+Y-\frac{X·Y}{100}$

If the action actually observed (O) is greater than the expected action (E), then the action of the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms the synergism factor SF corresponds to O/E. In the agricultural practice an SF of ≧1.2 indicates significant improvement over the purely complementary addition of activities (expected activity), while an SF of ≦0.9 in the practical application routine signals a loss of activity compared to the expected activity.

Example B-1

Action Against Botrytis cinerea on Grapes

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48-72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the grape plants are inoculated by spraying a spore suspension (1×10⁶ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% relative humidity in a greenhouse the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-2

Action Against Septoria tritici on Wheat

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment

2 week old wheat plants cv. Riband are treated with the formulated test compound (0.2% active ingredient) in a spray chamber. One day after application, wheat plants are inoculated by spraying a spore suspension (10×10⁵ conidia/ml) on the test plants. After an incubation period of 1 day at 23° C. and 95% relative humidity, the plants are kept for 16 days at 23° C. and 60% relative humidity in a greenhouse. The disease incidence is assessed 18 days after inoculation. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-3

Action Against Pyricularia oryzae on Rice

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment

Rice leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-4

Action Against Alternaria solani (Early Blight)

a) Fungal Growth Assay

Conidia—harvested from a freshly grown colony—of the fungus were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia in	Fenpropidin	in %	in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0667	—	—	50	—
0.0074	—	—	40	—
0.0025	—	—	17	—
—	0.600	—	0	—
—	0.067	—	0	—
—	0.002	—	0	—
0.0667	0.002	50	62	1.2
0.0074	0.002	40	51	1.3
0.0025	0.600	17	26	1.5
0.0025	0.067	17	22	1.3
0.0025	0.002	17	22	1.3

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia in	Fludioxonil	in %	in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0074	—	—	46	—
0.0025	—	—	26	—
0.0008	—	—	0	—
—	0.067	—	25	—
—	0.022	—	0	—
—	0.007	—	0	—
—	0.002	—	0	—
0.0074	0.002	46	56	1.2
0.0025	0.067	45	55	1.2
0.0025	0.022	26	41	1.6
0.0025	0.002	26	38	1.4
0.0008	0.067	25	54	2.1
0.0008	0.007	0	23	>100

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia in	Propiconazole	in %	in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0667	—	—	60	—
0.0003	—	—	6	—
0.0001	—	—	6	—
—	0.007	—	0	—
0.0667	0.007	60	76	1.3
0.0003	0.007	6	11	1.9
0.0001	0.007	6	11	1.9

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia	Cyproconazole	in %	in %	Factor SF
in ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0074	—	—	27	—
0.0008	—	—	0	—
0.0001	—	—	0	—
—	0.600	—	15	—
—	0.007	—	0	—
—	0.002	—	3	—
0.0074	0.007	27	40	1.5
0.0074	0.002	29	38	1.3
0.0008	0.600	15	26	1.7
0.0001	0.600	15	18	1.2

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia	Azoxystrobin	in %	in %	Factor SF
in ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0025	—	—	18	—
0.0008	—	—	0	—
0.0003	—	—	0	—
0.0001	—	—	0	—
—	0.067	—	31	—
—	0.022	—	0	—
0.0025	0.022	18	23	1.3
0.0008	0.067	31	39	1.3
0.0003	0.067	31	37	1.2
0.0001	0.067	31	43	1.4

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia in	Chlorotalonil	in %	in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0025	—	—	22	—
0.0003	—	—	4	—
—	0.600	—	6	—
—	0.002	—	9	—
0.0025	0.600	26	33	1.2
0.0025	0.002	24	35	1.5
0.0003	0.600	10	14	1.5

Control of Alternaria solani
Dosage in mg active ingredient/liter final medium
		Expected	Observed
		control	control	Synergy
Cpd Ia in	Cyprodinil in	in %	in %	Factor SF
ppm	ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0025	—	—	11	—
0.0008	—	—	0	—
—	0.067	—	30	—
—	0.022	—	0	—
—	0.007	—	0	—
—	0.002	—	3	—
0.0025	0.022	11	20	1.7
0.0025	0.007	11	15	1.3
0.0025	0.002	14	24	1.7
0.0008	0.067	30	43	1.4

b) Protective Treatment

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (2×10⁵ conidia/ml) on the test plants. After an incubation period of 3 days at 20° C. and 95% relative humidity in a growth chamber the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-5

Action Against Pyrenophora teres (Net Blotch)

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-6

Action Against Venturia inaegualis on Apple

a) Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 144 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment

4 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the apple plants are inoculated by spraying a spore suspension (4×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 21° C. and 95% relative humidity the plants are placed for 4 days at 21° C. and 60% relative humidity in a greenhouse. After another 4 day incubation period at 21° C. and 95% relative humidity the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-7

Action Against Pythium ultimum (Damping Off)—Fungal Growth Assay

Mycelial fragments of the fungus, prepared from a fresh liquid culture, were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-8

Action Against Leptosphaeria nodorum (Glume Blotch)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Fenpropidin	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.2000	—	—	32	—
0.0667	—	—	21	—
0.0222	—	—	9	—
—	0.022	—	0	—
—	0.007	—	4	—
0.2000	0.022	32	38	1.2
0.0667	0.022	21	28	1.4
0.0222	0.007	12	16	1.3

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Fludioxonil	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0667	—	—	10	—
0.0222	—	—	0	—
0.0074	—	—	0	—
—	0.067	—	9	—
—	0.002	—	7	—
0.0667	0.067	18	31	1.8
0.0667	0.002	16	30	1.8
0.0222	0.067	9	28	3.1
0.0074	0.067	9	23	2.6

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Propiconazole	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0222	—	—	5	—
0.0025	—	—	0	—
0.0003	—	—	0	—
0.0001	—	—	0	—
—	0.022	—	11	—
—	0.002	—	12	—
0.0222	0.022	16	21	1.4
0.0222	0.002	16	25	1.6
0.0025	0.022	11	18	1.6
0.0003	0.022	11	19	1.6
0.0001	0.022	11	20	1.7

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Cyproconazole	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.2000	—	—	30	—
0.0667	—	—	20	—
0.0222	—	—	5	—
—	0.067	—	4	—
—	0.007	—	0	—
—	0.002	—	3	—
0.2000	0.007	30	36	1.2
0.2000	0.002	32	44	1.4
0.0667	0.007	20	24	1.2
0.0667	0.002	22	30	1.4
0.0222	0.067	9	24	2.6
0.0222	0.002	8	21	2.6

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Azoxystrobin	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0667	—	—	9	—
0.0074	—	—	0	—
0.0025	—	—	0	—
0.0001	—	—	2	—
—	0.007	—	14	—
—	0.002	—	5	—
0.0667	0.002	14	31	2.3
0.0074	0.002	5	18	3.8
0.0025	0.007	14	20	1.4
0.0001	0.007	16	20	1.3

Control of Leptosphaeria nodorum
Dosage in mg active ingredient/liter final medium
		Expected	Observed	Synergy
Cpd Ia in	Chlorotalonil	control in %	control in %	Factor SF
ppm	in ppm	(% Cexp)	(% Cobs)	% Cobs/% Cexp
[mg/L]	[mg/L]	expected	observed	Factor
0.0667	—	—	17	—
0.0222	—	—	6	—
—	0.067	—	6	—
—	0.022	—	0	—
—	0.007	—	0	—
—	0.002	—	1	—
0.0667	0.067	22	30	1.4
0.0667	0.022	17	25	1.5
0.0667	0.007	17	27	1.6
0.0667	0.002	17	33	1.9
0.0222	0.067	12	24	2.0

Example B-9

Action Against Pseudocercosporella herpotrichoides var. acuformis (Eyespot/Cereals) —Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 72 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-10

Action Against Ustilago maydis (Corn Smut)—Fungal Growth Assay

Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of the test compounds into a microtiter plate (96-well format) the nutrient broth containing the fungal spores was added. The test plates were incubated at 24° C. and the inhibition of growth was determined photometrically after 48 hrs. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-11

Action Against Phytophthora infestans (Late Blight) on Tomato—Protective Treatment

Tomato leaf disks are placed on water agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-12

Action Against Plasmopara viticola (Downy Mildew) on Grape Vines—Protective Treatment

Grape vine leaf disks are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 7 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-13

Action Against Botrytis cinerea (Grey Mould) on Beans—Protective Treatment

Bean leaf disks are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-14

Action Against Erysiphe graminis f.sp. hordei (Barley Powdery Mildew) on Barley—Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-15

Action Against Erysiphe graminis f.sp. tritici (Wheat Powdery Mildew) on Barley—Protective Treatment

Barley leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-16

Action Against Puccinia recondita (Brown Rust) on Wheat

a) Protective Treatment of Leaf Segments

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 9 days after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment of Plants

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (1×10⁵ uredospores/ml) on the test plants. After an incubation period of 2 days at 20° C. and 95% relative humidity the plants are kept in a greenhouse for 8 days at 20° C. and 60% relative humidity. The disease incidence is assessed 10 days after inoculation. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-17

Action Against Septoria nodorum on Wheat

a) Protective Treatment of Leaf Segments

Wheat leaf segments are placed on agar in multiwell plates (24-well format) and sprayed with test solutions. After drying, the leaf disks are inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound is assessed 96 hrs after inoculation as preventive fungicidal activity. The fungicide interactions in the combinations are calculated according to COLBY method.

b) Protective Treatment of Plants

1 week old wheat plants cv. Arina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the wheat plants are inoculated by spraying a spore suspension (5×10⁵ conidia/ml) on the test plants. After an incubation period of 1 day at 20° C. and 95% relative humidity the plants are kept for 10 days at 20° C. and 60% relative humidity in a greenhouse. The disease incidence is assessed 11 days after inoculation. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-18

Action Against Podosphaera leucotricha (Powdery Mildew) on Apple—Protective Treatment

5 week old apple seedlings cv. McIntosh are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after, the application apple plants are inoculated by shaking plants infected with apple powdery mildew above the test plants. After an incubation period of 12 days at 22° C. and 60% relative humidity under a light regime of 14/10 hours (light/dark) the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-19

Action Against Erysiphe graminis (Powdery Mildew) on Barley—Protective Treatment

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the barley plants are inoculated by shaking powdery mildew infected plants above the test plants. After an incubation period of 6 days at 20° C./18° C. (day/night) and 60% relative humidity in a greenhouse the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-20

Action Against Botrytis cinerea on Tomatoes—Protective Treatment

4 week old tomato plants cv. Roter Gnom are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the tomato plants are inoculated by spraying a spore suspension (1×10⁵ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% relative humidity in a growth chamber the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-21

Action Against Helminthosporium teres (Net Blotch) on Barley—Protective Treatment

1 week old barley plants cv. Regina are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. Two days after application, the barley plants are inoculated by spraying a spore suspension (3×10⁴ conidia/ml) on the test plants. After an incubation period of 4 days at 20° C. and 95% relative humidity in a greenhouse the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

Example B-22

Action Against Uncinula necator (Powdery Mildew) on Grapes—Protective Treatment

5 week old grape seedlings cv. Gutedel are treated with the formulated test compound (0.02% active ingredient) in a spray chamber. One day after application, the grape plants are inoculated by shaking plants infected with grape powdery mildew above the test plants. After an incubation period of 7 days at 26° C. and 60% relative humidity under a light regime of 14/10 hours (light/dark) the disease incidence is assessed. The fungicide interactions in the combinations are calculated according to COLBY method.

The combinations according to the invention exhibit good activity in all of the above examples.

A further aspect of the instant invention is a method of controlling phytopathogenic diseases on useful plants or plant propagation material thereof, which comprises applying to said plant propagation material, preferrably seeds, a fungicidally effective amount of a compound of formula I, especially a compound of formula Ia, Ib, Ic, Id or Ie, or a tautomer of such a compound.

Claims

1. A method of controlling phytopathogenic diseases on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof a combination of components A) and B) in a synergistically effective amount, wherein

2. A method according to claim 1, wherein component A) is a compound of formula I, wherein R1 is difluoromethyl.

3. A method according to claim 1, wherein component A) is a compound of the formula Ia

4. A method according to claim 1, wherein component A) is a compound of the formula Ib

5. A method according to claim 1, wherein component A) is a compound of the formula Ic

6. A method according to claim 1, wherein component A) is a compound of the formula Id

7. A method according to claim 1, wherein component A) is a compound of the formula Ie

8. A method according to claim 1, wherein component B) is selected from the group consisting of a strobilurin fungicide, selected from the group consisting of Azoxystrobin, Dimoxystrobin, Fluoxastrobin, Kresoxim-methyl, Metominostrobin, Orysastrobin, Picoxystrobin, Pyraclostrobin; Trifloxystrobin and a compound of formula B-6

9. A method according to claim 1, wherein component B) is selected from the group consisting of Azoxystrobin; Picoxystrobin; Cyproconazole; Difenoconazole; Propiconazole; Fludioxonil; Cyprodinil; Fenpropimorph; Fenpropidin; a compound of formula F-1

10. A method according to claim 1, wherein component B) is selected from the group consisting of Azoxystrobin; Cyproconazole; Propiconazole; Cyprodinil; Chlorothalonil; Fludioxonil and Fenpropidin.

11. A fungicidal composition comprising a combination of components A) and B) according to claim 1 in a synergistically effective amount, together with an agriculturally acceptable carrier, and optionally a surfactant.

12. A fungicidal composition comprising a combination of components A) and B) according to claim 1 together with an agricultural acceptable carrier, and optionally a surfactant, wherein the weight ratio of A) to B) is between 2000:1 and 1:1000.

13. A method of protecting natural substances of plant and/or animal origin, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said natural substances of plant and/or animal origin or their processed forms a combination of components A) and B) according to claim 1 in a synergistically effective amount.