Fungicidal compositions comprising 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and an azole

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 compound of formula I ##STR00001## wherein R is hydrogen or methoxy; Q is ##STR00002## R.sub.1 is hydrogen, halogen or C.sub.1-C.sub.6alkyl; R.sub.2 is hydrogen, halogen, C.sub.1-C.sub.6alkyl, C.sub.2-C.sub.6alkenyl, C.sub.3-C.sub.6alkinyl, C.sub.3-C.sub.6cycloalkyl-C.sub.3-C.sub.6alkinyl, halophenoxy, halophenyl-C.sub.3-C.sub.6alkinyl, C(C.sub.1-C.sub.4alkyl)=NO—C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.6haloalkyl, C.sub.1-C.sub.6haloalkoxy, C.sub.2-C.sub.6haloalkenyl, or C.sub.2-C.sub.6haloalkenyloxy; R.sub.3 is hydrogen, halogen, C.sub.1-C.sub.6alkyl; R.sub.4, R.sub.5 and R.sub.6, independently from each other, are hydrogen, halogen or —≡—R.sub.7; with the proviso that at least one of R.sub.4, R.sub.5 and R.sub.6 is different from hydrogen; R.sub.7 is hydrogen, C.sub.1-C.sub.6alkyl, C.sub.1-C.sub.6haloalkyl or C.sub.1-C.sub.4alkoxyalkyl; and R.sub.8 is hydrogen or methoxy; and agrochemically acceptable salts/isomers/structural isomers/stereoisomers/diastereoisomers/enantiomers/tautomers and N-oxides of those compounds; 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.

Claims

1. A fungicidal composition, comprising: (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole, wherein the weight ratio of (A) to (B1) is 1:4 to 4:1, or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole, wherein the weight ratio of (A) to (B2) is 1:4 to 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole, wherein the weight ratio of (A) to (B3) is 1:4 to 4:1.

2. A method of controlling phytopathogenic fungi on useful plants or on propagation material thereof, which comprises applying to the useful plants, the locus thereof or propagation material thereof (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole, wherein the weight ratio of (A) to (B1) is to 1:4 to 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole, wherein the weight ratio of (A) to (B2) is 1:4 to 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole, wherein the weight ratio of (A) to (B3) is 1:4 to 4:1.

3. A method of protecting natural substances of plant and/or animal origin from phytopathogenic fungi, which have been taken from the natural life cycle, and/or their processed forms, which comprises applying to said the natural substances of plant and/or animal origin or their processed forms (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole, wherein the weight ratio of (A) to (B1) is to 1:4 to 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole, wherein the weight ratio of (A) to (B2) is 1:4 to 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole, wherein the weight ratio of (A) to (B3) is 1:4 to 4:1.

4. The fungicidal composition according to claim 1, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole.

5. The fungicidal composition according to claim 1, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole.

6. The fungicidal composition according to claim 1, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole.

7. The fungicidal composition according to claim 1, wherein, (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole or (B3) tebuconazole are present at a weight ratio of from 2:1 to 1:2.

8. The method according to claim 2, wherein 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole or (B3) tebuconazole are applied to the useful plants, the locus thereof or propagation material thereof at a weight ratio of from 2:1 to 1:2.

9. The method according to claim 3, wherein 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole or (B3) tebuconazole are applied to the natural substances of plant and/or animal origin or their processed forms at a weight ratio of from 2:1 to 1:2.

10. A fungicidal composition, comprising: (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole, wherein the weight ratio of (A) to (B1) is about 1:4 to about 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole, wherein the weight ratio of (A) to (B2) is about 1:4 to about 4:1; or (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole, wherein the weight ratio of (A) to (B3) is about 1:4 to about 4:1.

11. The fungicidal composition according to claim 10, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole.

12. The fungicidal composition according to claim 10, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole.

13. The fungicidal composition according to claim 10, wherein the composition comprises (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole.

14. The fungicidal composition according to claim 1, wherein the weight ratio of (A) to (B1) is to 1:4 to 4:1.

15. The method according to claim 2, wherein the weight ratio of (A) to (B1) is 1:4 or 4:1.

16. The method according to claim 3, wherein the weight ratio of (A) to (B1) is 1:4 or 4:1.

17. The fungicidal composition according to claim 1, wherein the weight ratio of (A) to (B1) is about 1:4 or about 4:1.

18. The fungicidal composition according to claim 1, wherein the only fungicides in the fungicidal composition are (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B1) difenoconazole.

19. The fungicidal composition according to claim 1, wherein the only fungicides in the fungicidal composition are (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B2) prothioconazole.

20. The fungicidal composition according to claim 1, wherein the only fungicides in the fungicidal composition are (A) 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid methoxy-[1-methyl-2-(2,4,6-trichlorophenyl)-ethyl]-amide and (B3) tebuconazole.

Description

FORMULATION EXAMPLES

(1) TABLE-US-00003 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% —

(2) 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.

(3) TABLE-US-00004 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

(4) 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.

(5) TABLE-US-00005 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%

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

(7) TABLE-US-00006 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%

(8) 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.

(9) TABLE-US-00007 Extruder granules Active ingredient (I:comp (B) = 2:1) 15% sodium lignosulfonate 2% carboxymethylcellulose 1% Kaolin 82%

(10) 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.

(11) TABLE-US-00008 Coated granules Active ingredient (I:comp (B) = 1:10) 8% polyethylene glycol (mol. wt. 200) 3% Kaolin 89%

(12) 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.

(13) TABLE-US-00009 Suspension concentrate active ingredient (I:comp (B) = 1:8) 40% propylene glycol 10% nonylphenol polyethylene glycol ether (15 mol of ethylene 6% oxide) Sodium lignosulfonate 10% carboxymethylcellulose 1% silicone oil (in the form of a 75% emulsion in water) 1% Water 32%

(14) 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.

(15) TABLE-US-00010 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 0.5% in water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2% Water 45.3%

(16) 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.

(17) Slow Release Capsule Suspension

(18) 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.

(19) 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.

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

Biological Examples

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

(22) 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):

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

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

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

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

(27) $E=X+Y-\frac{X.Math.Y}{100}$

(28) 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 0/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.

(29) Liquid Culture Tests in Well Plates:

(30) Mycelia fragments or conidia suspensions of a fungus, prepared either freshly from liquid cultures of the fungus or from cryogenic storage, were directly mixed into nutrient broth. DMSO solutions of the test compound (max. 10 mg/ml) was diluted with 0.025% Tween20 by factor 50 and 10 μl of this solution was pipetted into a microtiter plate (96-well format). The nutrient broth containing the fungal spores/mycelia fragments was then added to give an end concentration of the tested compound. The test plates were incubated in the dark at 24° C. and 96% rh. The inhibition of fungal growth was determined visually after 2-7 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check was calculated.

Example B1

Fungicidal Action Against Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture (Gray Mould)

(31) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels 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 visually 3-4 days after application.

Example B2

Fungicidal Action Against Pythium ultimum/Liquid Culture (Seedling Damping Off)

(32) Mycelia fragments and oospores of a newly grown liquid culture 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 mycelia/spore mixture was added. The test plates were incubated at 24° C. and the inhibition of growth was determined visually 2-3 days after application.

Example B3

Fungicidal Action Against Sclerotinia sclerotiorum/Liquid Culture (Cottony Rot)

(33) Mycelia fragments of a newly grown liquid culture 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 material was added. The test plates were incubated at 24° C. and the inhibition of growth was determined visually 3-4 days after application.

Example B4

Fungicidal Action Against Mycosphaerella arachidis (Cercospora arachidicola)/Liquid Culture (Early Leaf Snot)

(34) 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 visually 4-5 days after application.

Example B5

Fungicidal Action Against Tapesia yallundae W-Type (Pseudocercosporella herpotrichoides)/Liquid Culture (Eyespot)

(35) 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 visually 3-4 days after application.

Example B6

Fungicidal Action Against Mycosphaerella graminicola (Septoria tritici)/Liquid Culture (Septoria Blotch)

(36) 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 visually 4-5 days after application.

Example B7

Fungicidal Action Against Fusarium culmorum/Liquid Culture (Head Blight)

(37) 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 visually 3-4 days after application.

Example B8

Fungicidal Action Against Thanatephorus cucumeris (Rhizoctonia solani)/Liquid Culture (Foot Rot, Damping-Off)

(38) Mycelia fragments of a newly grown liquid culture 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 material was added. The test plates were incubated at 24° C. and the inhibition of growth was determined visually 3-4 days after application.

(39) Leaf Disk or Leaf Segment Tests in Well Plates:

(40) Leaf disks or leaf segments of various plant species were cut from plants grown in the greenhouse. The cut leaf disks or segments were placed in multiwell plates (24-well format) onto water agar. The leaf disks were sprayed with a test solution before (preventative) or after (curative) inoculation. Compounds to be tested were prepared as DMSO solutions (max. 10 mg/ml) which were diluted to the appropriate concentration with 0.025% Tween20 just before spraying. The inoculated leaf disks or segments were incubated under defined conditions (temperature, relative humidity, light, etc.) according to the respective test system. A single evaluation of disease level was carried out 3-9 days after inoculation, depending on the pathosystem. Percent disease control relative to the untreated check leaf disks or segments was then calculated.

Example B9

Fungicidal Action Against Plasmopara viticola/Grape/Leaf Disc Preventative (Late Blight)

(41) Grape vine leaf disks were placed on water agar in multiwell plates (24-well format) and sprayed with the formulated test compound diluted in water. The leaf disks were inoculated with a spore suspension of the fungus 1 day after application. The inoculated leaf disks were incubated at 19° C. and 80% rh under a light regime of 12 h light/12 h darkness in a climate cabinet and the activity of a compound was assessed as percent disease control compared to untreated when an appropriate level of disease damage appears in untreated check leaf disks (6-8 days after application).