Fungicidal compositions

Abstract

The present invention relates to novel fungicidal compositions for the treatment of phytopathogenic diseases of useful plants, especially phytopathogenic fungi, and to a method of controlling such phytopathogenic diseases on useful plants. In particular compositions suitable for control of diseases caused by phytopathogens comprise a mixture of a compound of formula (I), with a compound selected from compounds known for their fungicidal activity; and a method of controlling diseases on useful plants using such compositions. ##STR00001##

Claims

1. A composition suitable for control of diseases caused by phytopathogens comprising as component (A) 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide or an agrochemically acceptable salt, stereoisomer, diastereoisomer, enantiomer or tautomer thereof; and as component (B) or an agrochemically acceptable salt thereof.

2. The composition according to claim 1, wherein components (A) and (B) are present in a synergistically effective amount.

3. The composition according to claim 1, wherein the weight ratio of (A) to (B) is from 1000:1 to 1:1000.

4. The composition according to claim 1, further comprising an agriculturally acceptable adjuvant and/or carrier.

5. A method of controlling diseases on useful plants or on propagation material thereof caused by phytopathogens, which comprises applying to the useful plants, the locus thereof or propagation material thereof, a composition as defined in claim 1.

Description

FORMULATION EXAMPLES

(1) TABLE-US-00003 Wettable powders a) b) c) active ingredient [I:comp (B) = 1:3(a), 1:2(b), 25%  50% 75% 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) = 1:3(a), 1:2(b), 25% 50% 75% 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) = 1:6(a), 1:2(b),  5%  6%  4% 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 oxide)  6% 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 in 0.5%.sup.  water) monoazo-pigment calcium salt 5% Silicone oil (in the form of a 75% emulsion in water) 0.2%.sup.  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 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) Liquid Culture Tests in Well Plates

(22) 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 photometrically and visually after 2-4 days, depending on the pathosystem, and percent antifungal activity relative to the untreated check was calculated.

(23) Alternaria solanil/Liquid Culture:

(24) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound 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 and visually 2-3 day after application.

(25) Botryotinia fuckeliana (Botrytis cinerea)/Liquid Culture:

(26) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (Vogels broth). After placing a (DMSO) solution of test compound 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 and visually 3 days after application.

(27) Fusarium culmorum/Liquid Culture:

(28) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound 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 and visually 3 days after application.

(29) Gaeumannomyces graminis/Liquid Culture:

(30) Mycelial fragments of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound 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 and visually 3-4 days after application.

(31) Monographella nivalis (Microdochium nivale)/Liquid Culture:

(32) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound 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 and visually 3-4 days after application.

(33) Mycosphaerella graminicola (Septoria tritici)/Liquid Culture:

(34) Conidia of the fungus from cryogenic storage were directly mixed into nutrient broth (PDB potato dextrose broth). After placing a (DMSO) solution of test compound 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 and visually 4 days after application.

(35) Pythium ultimum Seedling Damping Off)/Liquid Culture:

(36) 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.

(37) Results

(38) Representative examples of results from the tests outlined above are shown below in Tables 3 to 38. These data shown that synergistic fungicidal activity is observed for each of the following combinations, a compound of formula (I) and (B1) a compound of formula (II), a compound of formula (I) and a (B2) fenpyrazine, a compound of formula (I) and (B4) oxathiapiprolin, a compound of formula (I) and (B5) tolprocarb, a compound of formula (I) and (B6) flufenoxystrobin, a compound of formula (I) and (B9) the compound of formula (III), a compound of formula (I) and (B10) coumoxystrobin, a compound of formula (I) and (B11) mandestrobin, a compound of formula (I) and B12) tebufloquin, a compound of formula (I) and (B13) triclopyricarb, a compound of formula (I) and (B14) the compound of formula (IV), in tests against one or more of the fungi as outlined above. In each case, the compound of formula (I) tested was compound 1.001 (i.e. 3-(difluoromethyl)-N-methoxy-1-methyl-N-[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide).

(39) TABLE-US-00011 TABLE 3 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II) - in this case wherein R.sup.9 is methyl - against Pythium ultimum in PDB Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition actvity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0063 0.0000 n/a 11  — — — 0.0125 0.0000 0 — — — 0.0250 0.0000 0 — — — 0.0500 0.0000 0 — — — 0.1000 0.0000 2 — — — 0.2000 0.0000 0 — — — 0.0000 0.2500 n/a — 25 — — 0.0000 0.5000 —  1 — — 0.0063 0.2500 1:40 — — 99 33 0.0125 0.5000 — — 99 1 0.0250 0.5000 1:20 — — 100 1 0.0250 0.2500 1:10 — — 100 25 0.0500 0.5000 — — 100 1 0.1000 0.5000 1:5  — — 99 3 0.1000 0.2500 2:5  — — 99 27 0.2000 0.5000 — — 100 1

(40) TABLE-US-00012 TABLE 4 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II)) - in this case wherein R.sup.9 is methyl - against Fusarium culmorum in PDB Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition actvity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0016 0.0000 n/a 7 — — — 0.0031 0.0000 19 — — — 0.0063 0.0000 14 — — — 0.0125 0.0000 20 — — — 0.0250 0.0000 38 — — — 0.0500 0.0000 46 — — — 0.0000 0.0625 n/a — 0 — — 0.0000 0.1250 — 6 — — 0.0016 0.0625 1:40 — — 48 7 0.0031 0.1250 — — 95 23 0.0031 0.0625 1:20 — — 59 19 0.0063 0.1250 — — 95 19 0.0125 0.1250 1:10 — — 100 24 0.0125 0.0625 1:5  — — 50 20 0.0250 0.1250 — — 99 41 0.0250 0.0625 2:5  — — 68 38 0.0500 0.1250 — — 100 49

(41) TABLE-US-00013 TABLE 5 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II)) - in this case wherein R.sup.9 is methyl - against Monographella nivalis (Michmdocium nivale) in PDB Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition activity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0004 0.0000 n/a 0 — — — 0.0008 0.0000 0 — — — 0.0016 0.0000 0 — — — 0.0031 0.0000 0 — — — 0.0000 0.0078 n/a — 42 — — 0.0004 0.0078 1:20 — — 47 42 0.0008 0.0078 1.10 — — 69 42 0.0016 0.0078 1:5  — — 87 42 0.0031 0.0078 2:5  — — 91 42

(42) TABLE-US-00014 TABLE 6 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II)) - in this case wherein R.sup.9 is methyl - against Botryotinia fuckeliana ( Botrytis cinerea) in Vogels Broth Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition actvity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0016 0.0000 n/a 16 — — — 0.0031 0.0000 49 — — — 0.0063 0.0000 61 — — — 0.0125 0.0000 79 — — — 0.0000 0.0156 n/a —  0 — — 0.0000 0.0313 — 12 — — 0.0000 0.0625 — 21 — — 0.0016 0.0625 1:40 — — 80 33 0.0016 0.0313 1:20 — — 47 26 0.0031 0.0625 — — 85 60 0.0063 0.0156 1:10 — — 93 69 0.0063 0.0313 1:5  — — 73 66 0.0063 0.0625 — — 94 83 0.0063 0.0156 2:5  — 68 61

(43) TABLE-US-00015 TABLE 7 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II)) - in this case wherein R.sup.9 is methyl - against Alternaria solani in PDB Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition actvity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0008 0.0000 n/a 36 — — — 0.0016 0.0000 57 — — — 0.0031 0.0000 81 — — — 0.0000 0.0078 n/a — 11  — — 0.0000 0.0156 — 0 — — 0.0000 0.0313 — 0 — — 0.0000 0.0625 — 0 — — 0.0000 0.1250 — 2 — — 0.0008 0.0313 1:40 — — 44 36 0.0016 0.0625 — — 75 57 0.0031 0.1250 — — 90 82 0.0016 0.0313 1:20 — — 70 57 0.0016 0.0156 1:10 — — 65 57 0.0016 0.0078 1:5  — — 71 61

(44) TABLE-US-00016 TABLE 8 Fungicidal activity of compound of formula (I) (compound 1.001) and (B1) the compound of formula (II),) - in this case wherein R.sup.9 is methyl -against Mycosphaerella graminicola (Septoria tritici) in PDB Expected Ratio Compound 1.001 (B1) Combined (additive) Compound 1.001 (B1) compound inhibition Inhibition inhibition actvity (ppm) (ppm) 1.001:(B1) (%) (%) (%) (Colby) 0.0008 0.0000 n/a 15 0.0016 0.0000 34 — — — 0.0031 0.0000 81 0.0000 0.0156 n/a — 15 — — 0.0000 0.0313 15 0.0008 0.0313 1:40 — — 66 28 0.0008 0.0156 1:20 — — 42 28 0.0016 0.0313 88 44 0.0016 0.00156 1:10 — — 50 44 0.0031 0.0313 98 83

(45) TABLE-US-00017 TABLE 9 Fungicidal activity of compound of formula (I) (compound 1.001) and (B2) fenpyrazamine against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B2) compound Compound 1.001 (B2) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B2) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 37 — — — 0.0016 0.0000 64 — — — 0.0000 0.0313 n/a — 0 — — 0.0000 0.0625 — 1 — — 0.0008 0.0313 1:40 — — 42 37 0.0016 0.0625 — — 75 64

(46) TABLE-US-00018 TABLE 10 Fungicidal activity of compound of formula (I) (compound 1.001) and (B4) oxathiapiprolin against Pythium ultimum in PDB Ratio Combined Expected Compound 1.001 (B4) compound Compound 1.001 (B4) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B4) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 0 — — — 0.0031 0.0000 0 — — — 0.0000 0.0625 n/a — 61 — — 0.0016 0.0625 1:40 — — 82 61 0.0016 0.0625 1:20 — — 76 61

(47) TABLE-US-00019 TABLE 11 Fungicidal activity of compound of formula (I) (compound 1.001) and (B4) oxathiapiprolin, against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B4) compound Compound 1.001 (B4) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B4) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 42 — — — 0.0016 0.0000 68 — — — 0.0000 0.0039 n/a — 0 — — 0.0000 0.0078 — 4 — — 0.0000 0.0156 — 0 — — 0.0000 0.0313 — 0 — — 0.0008 0.0039 1:4  — — 55 42 0.0008 0.0078 1:10 — — 49 45 0.0008 0.0156 1:20 — — 50 42 0.0008 0.0313 1:40 — — 64 42 0.0016 0.0625 — — 78 68

(48) TABLE-US-00020 TABLE 12 Fungicidal activity of compound of formula (I) (compound 1.001) and (B4) oxathiapiprolin, against Mycosphaerella graminicola (Septoria tritici) in PDB Ratio Combined Expected Compound 1.001 (B4) compound Compound 1.001 (B4) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B4) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 54 — — — 0.0000 0.0313 n/a — 8 — — 0.0000 0.0625 — 4 — — 0.0016 0.0313 1:20 — — 65 58 0.0016 0.0625 1:40 — — 67 56

(49) TABLE-US-00021 TABLE 13 Fungicidal activity of compound of formula (I) (compound 1.001) and (B5) tolprocarb, against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B5) compound Compound 1.001 (B5) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B5) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 51 — — — 0.0016 0.0000 69 — — — 0.0031 0.0000 82 — — — 0.0000 0.0391 n/a — 0 — — 0.0000 0.0781 — 0 — — 0.0000 0.3125 — 0 — — 0.0008 0.3125 1.40 — — 59 51 0.0016 0.0391 1:25 — — 78 69 0.0031 0.0781 — — 93 82 0.0031 0.3125  1:100 — — 91 82

(50) TABLE-US-00022 TABLE 14 Fungicidal activity of compound of formula (I) (compound 1.001) and (B5) tolprocarb, against Mycosphaerella graminicola (Septoria tritici) in PDB Ratio Combined Expected Compound 1.001 (B5) compound Compound 1.001 (B5) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B5) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 47 — — — 0.0000 0.0391 n/a — 7 — — 0.0000 0.0781 — 1 — — 0.0000 0.1563 — 4 — — 0.0000 0.6250 — 1 — — 0.0016 0.0391 1:25  — — 59 50 0.0016 0.0781 1:50  — — 52 48 0.0016 0.1563 1:100 — — 60 49 0.0016 0.6250 1:400 — — 68 47

(51) TABLE-US-00023 TABLE 15 Fungicidal activity of compound of formula (I) (compound 1.001) and (B6) flufenoxystrobin, against Fusarium culmorum in PDB Ratio Combined Expected Compound 1.001 (B6) compound Compound 1.001 (B6) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B6) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a 24 — — — 0.0500 0.0000 49 — — — 0.1000 0.0000 51 — — — 0.2000 0.0000 55 — — — 0.0000 0.0500 n/a — 5 — — 0.0000 0.1000 — 3 — — 0.0000 0.2000 — 12  — — 0.0250 0.1000 1:4 — — 57 27 0.0500 0.2000 — — 70 55 0.0250 0.0500 1:2 — — 43 28 0.0500 0.1000 — — 63 50 0.1000 0.2000 — — 68 57 0.1000 0.1000 1:1 — — 63 52 0.2000 0.2000 — — 71 60 0.2000 0.1000 2:1 — — 66 56

(52) TABLE-US-00024 TABLE 16 Fungicidal activity of compound of formula (I) (compound 1.001) and (B6) flufenoxystrobin, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B6) compound Compound 1.001 (B6) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B6) inhibition (%) (%) (%) (Colby) 0.0004 0.0000 n/a 0 — — — 0.0008 0.0000 2 — — — 0.0016 0.0000 0 — — — 0.0031 0.0000 4 — — — 0.0000 0.0008 n/a — 23 — — 0.0000 0.0016 — 51 0.0004 0.0016 1:4 — — 83 51 0.0004 0.0008 1:2 — — 41 23 0.0008 0.0016 — — 70 52 0.0016 0.0016 1:1 — — 67 51 0.0031 0.0016 2:1 — — 58 52

(53) TABLE-US-00025 TABLE 17 Fungicidal activity of compound of formula (I) (compound 1.001) and (B6) flufenoxystrobin, against Botryotinia fuckeliana (Botrytis cinerea) in Vogels Broth Ratio Combined Expected Compound 1.001 (B6) compound Compound 1.001 (B6) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B6) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 26 — — — 0.0031 0.0000 44 — — — 0.0063 0.0000 62 — — — 0.0000 0.0063 n/a — 17 — — 0.0000 0.0125 — 23 — — 0.0000 0.0250 — 33 — — 0.0016 0.0063 1:4 — — 44 38 0.0031 0.0125 — — 65 57 0.0063 0.0250 — — 85 75

(54) TABLE-US-00026 TABLE 18 Fungicidal activity of compound of formula (I) (compound 1.001) and (B6) flufenoxystrobin, against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B6) compound Compound 1.001 (B6) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B6) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 65 — — — 0.0000 0.0016 n/a — 6 — — 0.0000 0.0063 — 1 — — 0.0016 0.0016 1:1 — — 74 67 0.0016 0.0063 1:4 — — 72 65

(55) TABLE-US-00027 TABLE 19 Fungicidal activity of compound of formula (I) (compound 1.001) and (B6) flufenoxystrobin, against Mycosphaerella graminicola (Septoria tritici) in PDB Ratio Combined Expected Compound 1.001 (B6) compound Compound 1.001 (B6) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B6) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 33 — — — 0.0031 0.0000 83 — — — 0.0000 0.0031 n/a — 17 — — 0.0000 0.0063 — 23 — — 0.0000 0.0125 — 33 — — 0.0016 0.0031 1:2 — — 43 33 0.0016 0.0063 1:4 — — 48 37 0.0031 0.0125 — — 94 84

(56) TABLE-US-00028 TABLE 20 Fungicidal activity of compound of formula (I) (compound 1.001) and (B9) the compound of formula (III), against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B9) compound Compound 1.001 (B9) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B9) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a  5 — — — 0.0500 0.0000 51 — — — 0.0000 0.1250 n/a — 0 — — 0.0000 0.5000 — 0 — — 0.0000 1.0000 — 10  — — 0.0250 1.0000 1:40 — — 47 14 0.0500 0.1250 2:5  — — 62 51 0.0500 0.5000 1:10 — — 62 51

(57) TABLE-US-00029 TABLE 21 Fungicidal activity of compound of formula (I) (compound 1.001) and (B9) the compound of formula (III), against Botryotinia fuckeliana (Botrytis cinerea) in Vogels Broth Ratio Combined Expected Compound 1.001 (B9) compound Compound 1.001 (B9) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B9) inhibition (%) (%) (%) (Colby) 0.0004 0.0000 n/a  8 — — — 0.0008 0.0000 21 — — — 0.0016 0.0000 33 — — — 0.0000 0.0039 n/a — 14 — — 0.0000 0.0078 — 19 — — 0.0000 0.0156 — 31 — — 0.0000 0.0313 — 52 — — 0.0004 0.0156 1:40 — — 68 37 0.0008 0.0313 — — 71 63 0.0016 0.0625 — — 81 71 0.0004 0.0078 1:20 — — 53 25 0.0008 0.0156 — — 60 46 0.0016 0.0039 2:5  — — 51 42

(58) TABLE-US-00030 TABLE 22 Fungicidal activity of compound of formula (I) (compound 1.001) and (B9) the compound of formula (III), against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B9) compound Compound 1.001 (B9) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B9) inhibition (%) (%) (%) (Colby) 0.0004 0.0000 n/a 21 — — — 0.0008 0.0000 52 — — — 0.0016 0.0000 74 — — — 0.0000 0.0078 n/a —  0 — — 0.0000 0.0156 — 11 — — 0.0000 0.0313 —  5 — — 0.0000 0.0625 — 22 — — 0.0004 0.0156 1:40 — — 62 29 0.0008 0.0313 — — 78 54 0.0016 0.0625 — — 89 80 0.0004 0.0078 1:20 — — 41 21 0.0008 0.0156 — — 72 57 0.0016 0.0313 — — 85 75 0.0008 0.0078 1:10 — — 58 52

(59) TABLE-US-00031 TABLE 23 Fungicidal activity of compound of formula (I) (compound 1.001) and (B9) the compound of formula (III), against Mycosphaerella graminicola (Septoria tritici) in PDB Ratio Combined Expected Compound 1.001 (B9) compound Compound 1.001 (B9) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B9) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 19 — — — 0.0016 0.0000 54 — — — 0.0000 0.0039 n/a — 0 — — 0.0000 0.0156 — 0 — — 0.0313 — 9 — — 0.0625 — 7 — — 0.0008 0.0313 1:40 — — 46 26 0.0016 0.0625 86 57 0.0016 0.0313 1:20 — — 69 58 0.0016 0.00156 1:10 — — 62 54 0.0016 0.0156 2:5  — — 62 54

(60) TABLE-US-00032 TABLE 24 Fungicidal activity of compound of formula (I) (compound 1.001) and (B10) coumoxystrobin, against Fusarium culmorum in PDB Ratio Combined Expected Compound 1.001 (B10) compound Compound 1.001 (B10) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B10) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a 27 — — — 0.0500 0.0000 49 — — — 0.1000 0.0000 55 — — — 0.2000 0.0000 59 — — — 0.0000 0.0500 n/a — 12 — — 0.0000 0.1000 —  8 — — 0.0000 0.2000 — 11 — — 0.0250 0.1000 1:4 — — 54 33 0.0500 0.2000 — — 68 54 0.0250 0.0500 1:2 — — 43 36 0.0500 0.1000 — — 64 53 0.1000 0.2000 — — 70 60 0.2000 0.2000 1:1 — — 70 63

(61) TABLE-US-00033 TABLE 25 Fungicidal activity of compound of formula (I) (compound 1.001) and (B10) coumoxystrobin, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B10) compound Compound 1.001 (B10) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B10) inhibition (%) (%) (%) (Colby) 0.0004 0.0000 n/a 2 — — — 0.0008 0.0000 3 — — — 0.0016 0.0000 0 — — — 0.0031 0.0000 1 — — — 0.0063 0.0000 0 — — — 0.0000 0.0008 n/a — 46 — — 0.0000 0.0016 — 81 — — 0.0004 0.0016 1:4 — — 96 81 0.0004 0.0008 1:2 — — 83 47 0.0008 0.0016 — — 100  82 0.0008 0.0008 1:1 — — 64 48 0.0031 0.0008 4:1 — — 52 46 0.0063 0.0016 — — 98 81

(62) TABLE-US-00034 TABLE 26 Fungicidal activity of compound of formula (I) (compound 1.001) and (B10) coumoxystrobin, against Mycosphaerella graminicola (Septoria tritici) in PDB Ratio Combined Expected Compound 1.001 (B10) compound Compound 1.001 (B10) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B10) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 34 — — — 0.0031 0.0000 82 — — — 0.0000 0.0016 n/a —  5 — — 0.0000 0.0031 — 13 — — 0.0000 0.0063 — 31 — — 0.0016 0.0063 1:4 — — 76 54 0.0016 0.0031 1:2 — — 66 43 0.0031 0.0063 — — 97 87 0.0016 0.0016 1:1 — — 48 37

(63) TABLE-US-00035 TABLE 27 Fungicidal activity of compound of formula (I) (compound 1.001) and (B11) mandestrobin, against Fusarium culmorum in PDB Ratio Combined Expected Compound 1.001 (B11) compound Compound 1.001 (B11) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B11) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a 34 — — — 0.0500 0.0000 54 — — — 0.1000 0.0000 55 — — — 0.2000 0.0000 57 — — — 0.0000 0.1000 n/a —  0 — — 0.0000 0.2000 — 11 — — 0.0250 0.1000 1:4 — — 58 34 0.0500 0.2000 — — 67 59 0.0500 0.1000 1:2 — — 63 54 0.1000 0.2000 — — 68 60 0.2000 0.2000 1:1 — — 68 62 0.2000 0.1000 2:1 — — 64 57

(64) TABLE-US-00036 TABLE 28 Fungicidal activity of compound of formula (I) (compound 1.001) and (B11) mandestrobin, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B11) compound Compound 1.001 (B11) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B11) inhibition (%) (%) (%) (Colby) 0.0063 0.0000 n/a 4 — — — 0.0250 0.0000 5 — — — 0.0500 0.0000 48  — — — 0.0000 0.0250 n/a — 0 — — 0.0063 0.0250 1:4 — — 93 4 0.0500 0.0250 1.2 — — 67 48  0.0250 0.0250 1:1 72 5

(65) TABLE-US-00037 TABLE 29 Fungicidal activity of compound of formula (I) (compound 1.001) and (B11) mandestrobin, against Botryotinia fuckeliana (Botrytis cinerea) in Vogels Broth Ratio Combined Expected Compound 1.001 (B11) compound Compound 1.001 (B11) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B11) inhibition (%) (%) (%) (Colby) 0.0016 0.0000 n/a 29 — — — 0.0063 0.0000 61 — — — 0.0125 0.0000 79 — — — 0.0000 0.0016 n/a — 5 — — 0.0000 0.0250 — 0 — — 0.0000 0.0500 — 8 — — 0.0063 0.0250 1:4 — — 71 61 0.0125 0.0500 — — 90 80 0.0016 0.0016 1:1 — — 42 32

(66) TABLE-US-00038 TABLE 30 Fungicidal activity of compound of formula (I) (compound 1.001) and (B11) mandestrobin, against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B11) compound Compound 1.001 (B11) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B11) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 42 — — — 0.0016 0.0000 68 — — — 0.0000 0.0008 n/a — 0 — — 0.0000 0.0016 — 3 — — 0.0000 0.0031 — 0 — — 0.0000 0.0063 — 12  — — 0.0008 0.0031 1:4 — — 52 42 0.0016 0.0063 — — 86 72 0.0008 0.0016 1:2 — — 54 44 0.0008 0.0008 1:1 — — 54 42

(67) TABLE-US-00039 TABLE 31 Fungicidal activity of compound of formula (I) (compound 1.001) and (B11) mandestrobin, against Gaeumannomyces graminis in PDB Ratio Combined Expected Compound 1.001 (B11) compound Compound 1.001 (B11) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B11) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a 0 — — — 0.0500 0.0000 0 — — — 0.2000 0.0000 0 — — — 0.0000 0.0500 n/a — 17 — — 0.0000 0.1000 — 53 — — 0.0250 0.1000 1:4 — — 59 53 0.0250 0.0500 1:2 — — 48 17 0.0500 0.1000 — — 59 53 0.2000 0.1000 2:1 — — 69 53

(68) TABLE-US-00040 TABLE 32 Fungicidal activity of compound of formula (I) (compound 1.001) and (B12) tebufloquin, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B12) compound Compound 1.001 (B12) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B12) inhibition (%) (%) (%) (Colby) 0.0063 0.0000 n/a 0 — — — 0.0125 0.0000 0 — — — 0.0250 0.0000 0 — — — 0.0000 0.2500 n/a —  7 — — 0.0000 0.5000 — 60 — — 0.0063 0.2500 1:40 — — 45 7 0.0125 0.5000 — — 82 60 0.0125 0.2500 1:20 — — 42 7 0.0250 0.5000 — — 76 60

(69) TABLE-US-00041 TABLE 33 Fungicidal activity of compound of formula (I) (compound 1.001) and (B12) tebufloquin, against Botryotinia fuckeliana (Botrytis cinerea) in Vogels Broth Ratio Combined Expected Compound 1.001 (B12) compound Compound 1.001 (B12) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B12) inhibition (%) (%) (%) (Colby) 0.0063 0.0000 n/a 38 — — — 0.0031 0.0000 54 — — — 0.0000 0.0313 n/a — 5 — — 0.0000 0.1250 — 0 — — 0.0031 0.1250 1:40 — — 60 54 0.0016 0.0313 1:20 — — 46 41

(70) TABLE-US-00042 TABLE 34 Fungicidal activity of compound of formula (I) (compound 1.001) and (B12) tebufloquin, against Alternaria solani in PDB Ratio Combined Expected Compound 1.001 (B12) compound Compound 1.001 (B12) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B12) inhibition (%) (%) (%) (Colby) 0.0008 0.0000 n/a 51 — — — 0.0000 0.0156 n/a — 0 — — 0.0000 0.0313 — 1 — — 0.0008 0.0156 1:20 — — 63 51 0.0008 0.0313 1:40 — — 66 52

(71) TABLE-US-00043 TABLE 35 Fungicidal activity of compound of formula (I) (compound 1.001) and (B13) triclopyricarb, against Fusarium culmorum in PDB Ratio Combined Expected Compound 1.001 (B13) compound Compound 1.001 (B13) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B13) inhibition (%) (%) (%) (Colby) 0.0250 0.0000 n/a 29 — — — 0.0500 0.0000 53 — — — 0.1000 0.0000 57 — — — 0.2000 0.0000 55 — — — 0.0000 0.0500 n/a — 11 — — 0.0000 0.1000 — 10 — — 0.0000 0.2000 — 11 — — 0.0250 0.0500 1:2 — — 49 37 0.0500 0.1000 — — 65 58 0.1000 0.2000 69 62 0.0250 0.1000 1:4 — — 65 37 0.0500 0.2000 — — 71 59 0.2000 0.2000 1:1 — — 73 61 0.2000 0.1000 2:1 — — 69 60

(72) TABLE-US-00044 TABLE 36 Fungicidal activity of compound of formula (I) (compound 1.001) and (B13) triclopyricarb, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B13) compound Compound 1.001 (B13) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B13) inhibition (%) (%) (%) (Colby) 0.0004 0.0000 n/a 4 — — — 0.0008 0.0000 1 — — — 0.0016 0.0000 0 — — — 0.0125 0.0000 0 — — — 0.0000 0.0016 n/a — 23 — — 0.0000 0.0031 — 51 — — 0.0004 0.0016 1:4 — — 40 27 0.0008 0.0031 — — 92 51 0.0016 0.0031 1:2 — — 63 51 0.0125 0.0031 4:1 — — 59 51

(73) TABLE-US-00045 TABLE 37 Fungicidal activity of compound of formula (I) (compound 1.001) and (B13) triclopyricarb, against Botryotinia fuckeliana (Botrytis cinerea) in Vogels Broth Ratio Combined Expected Compound 1.001 (B13) compound Compound 1.001 (B13) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B13) inhibition (%) (%) (%) (Colby) 0.0031 0.0000 n/a 40 — — — 0.0063 0.0000 60 — — — 0.0000 0.0125 n/a —  8 — — 0.0000 0.0250 — 18 — — 0.0031 0.0125 1:4 — — 57 44 0.0063 0.0250 — — 82 67

(74) TABLE-US-00046 TABLE 38 Fungicidal activity of compound of formula (I) (compound 1.001) and (B14) the compound of formula IV, against Monographella nivalis (Michrodocium nivale) in PDB Ratio Combined Expected Compound 1.001 (B14) compound Compound 1.001 (B14) Inhibition inhibition (additive) actvity (ppm) (ppm) 1.001:(B14) inhibition (%) (%) (%) (Colby) 0.0063 0.0000 n/a 0 — — — 0.0125 0.0000 0 — — — 0.0000 0.2500 n/a — 40 — — 0.0063 0.2500 1:40 — — 54 40 0.0125 0.2500 1.20 — — 59 40