ACTIVE COMPOUND COMBINATIONS AND FUNGICIDE COMPOSITIONS COMPRISING THOSE

Abstract

The present invention relates to active compound combinations comprising as compound (A) methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, 2-[2-chloro-4-(4-chloro-phenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoic acid or a mixture thereof, at least one fungicide (B) selected from the group of inhibitors of the respiratory chain at complex I or II and at least one further fungicide (C) selected from the group of specified inhibitors of the respiratory chain at complex III, to compositions comprising such compound combination, and to the use thereof as biologically active agents, especially for control of harmful microorganisms in crop protection and in the protection of industrial materials.

Claims

1. An active compound combination comprising (A) as compound (A) methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoic acid or a mixture thereof, (B) as compound (B) at least one compound selected from the group of inhibitors of the respiratory chain at complex I or II, and (C) as compound (C) at least one compound selected from the group of inhibitors of the respiratory chain at complex III consisting of (3.001) ametoctradin, (3.002) amisulbrom, (3.003) azoxystrobin, (3.004) coumethoxystrobin, (3.005) coumoxystrobin, (3.006) cyazofamid, (3.007) dimoxystrobin, (3.008) enoxastrobin, (3.009) famoxadone, (3.010) fenamidone, (3.011) flufenoxystrobin, (3.012) fluoxastrobin, (3.013) kresoxim-methyl, (3.014) metominostrobin, (3.015) orysastrobin, (3.016) picoxystrobin, (3.017) pyraclostrobin, (3.018) pyrametostrobin, (3.019) pyraoxystrobin, (3.020) trifloxystrobin, (3.021) (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}-phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide, (3.022) (2E,3Z)-5-{[1-(4-chlorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.023) (2R)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.024) (2S)-2-{2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide, (3.025) fenpicoxamid, (3.026) mandestrobin, (3.027) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-formamido-2-hydroxybenzamide, (3.028) (2E,3Z)-5-{[1-(4-chloro-2-fluorophenyl)-1H-pyrazol-3-yl]oxy}-2-(methoxyimino)-N,3-dimethylpent-3-enamide, (3.029) methyl {5-[3-(2,4-dimethylphenyl)-1H-pyrazol-1-yl]-2-methylbenzyl}carbamate, (3.030) metyltetraprole and (3.031) florylpicoxamid.

2. The active compound combination according to claim 1, wherein compound (A) is methyl 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-2-hydroxy-3-(1,2,4-triazol-1-yl)propanoate.

3. The active compound combination according to claim 1, wherein compound (B) is selected from the group consisting of (2.001) benzovindiflupyr, (2.002) bixafen, (2.003) boscalid, (2.004) carboxin, (2.005) fluopyram, (2.006) flutolanil, (2.007) fluxapyroxad, (2.008) furametpyr, (2.009) isofetamid, (2.010) isopyrazam (anti-epimeric enantiomer 1R,4S,9S), (2.011) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.012) isopyrazam (anti-epimeric racemate 1RS,4SR,9SR), (2.013) isopyrazam (mixture of syn-epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS,4SR,9SR), (2.014) isopyrazam (syn-epimeric enantiomer 1R,4S,9R), (2.015) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.016) isopyrazam (syn-epimeric racemate 1 RS,4SR,9RS), (2.017) penflufen, (2.018) penthiopyrad, (2.019) pydiflumetofen, (2.020) Pyraziflumid, (2.021) sedaxane, (2.022) 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)-1H-pyrazole-4-carboxamide, (2.023) 1,3-dimethyl-N-[(3R)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.024) 1,3-dimethyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.025) 1-methyl-3-(trifluoromethyl)-N-[2′-(trifluoromethyl)biphenyl-2-yl]-1H-pyrazole-4-carboxamide, (2.026) 2-fluoro-6-(trifluoromethyl)-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)benzamide, (2.027) inpyrfluxam, (2.028) 3-(difluoromethyl)-1-methyl-N-[(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.029) 3-(difluoromethyl)-1-methyl-N-[(3S)-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1H-pyrazole-4-carboxamide, (2.030) fluindapyr, (2.031) 3-(difluoromethyl)-N-[(3R)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.032) 3-(difluoromethyl)-N-[(3S)-7-fluoro-1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl]-1-methyl-1H-pyrazole-4-carboxamide, (2.033) 5,8-difluoro-N-[2-(2-fluoro-4-{[4-(trifluoromethyl)pyridin-2-yl]oxy}phenyl)ethyl]quinazolin-4-amine, (2.034) N-(2-cyclopentyl-5-fluorobenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.035) N-(2-tert-butyl-5-methylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.036) N-(2-tert-butylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.037) N-(5-chloro-2-ethylbenzyl)-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.038) isoflucypram, (2.039) N-[(1R,4S)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.040) N-[(1S,4R)-9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.041) N-[1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.042) N-[2-chloro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.043) N-[3-chloro-2-fluoro-6-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.044) N-[5-chloro-2-(trifluoromethyl)benzyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.045) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[5-methyl-2-(trifluoromethyl)benzyl]-1H-pyrazole-4-carboxamide, (2.046) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-fluoro-6-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.047) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropyl-5-methylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.048) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carbothioamide, (2.049) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.050) N-cyclopropyl-3-(difluoromethyl)-5-fluoro-N-(5-fluoro-2-isopropylbenzyl)-1-methyl-1H-pyrazole-4-carboxamide, (2.051) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-4,5-dimethylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.052) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-fluorobenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.053) N-cyclopropyl-3-(difluoromethyl)-N-(2-ethyl-5-methylbenzyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.054) N-cyclopropyl-N-(2-cyclopropyl-5-fluorobenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.055) N-cyclopropyl-N-(2-cyclopropyl-5-methylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.056) N-cyclopropyl-N-(2-cyclopropylbenzyl)-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide, (2.057) pyrapropoyne, (2.058) N-[rac-(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide, (2.059) N-[(1S,2S)-2-(2,4-dichlorophenyl)cyclobutyl]-2-(trifluoromethyl)nicotinamide and (2.060) cyclobutrifluram.

4. The active compound combination according to claim 1, wherein compound (B) is selected from (2.005) fluopyram, (2.017) penflufen, (2.019) pydiflumetofen, (2.027) inpyrfluxam, (2.038) isoflucypram and (2.060) cyclobutrifluram.

5. The active compound combination according to claim 1, wherein compound (C) is selected from (3.012) fluoxastrobin, (3.020) trifloxystrobin and (3.030) metyltetraprole.

6. The active compound combination according to claim 1, wherein the compound combination is selected from group (T1-B) consisting of the following mixtures: (I)+(2.005)+(3.012), (I)+(2.005)+(3.020), (I)+(2.005)+(3.030), (I)+(2.017)+(3.012), (I)+(2.017)+(3.020), (I)+(2.017)+(3.030), (I)+(2.019)+(3.012), (I)+(2.019)+(3.020), (I)+(2.019)+(3.030), (I)+(2.027)+(3.012), (I)+(2.027)+(3.020), (I)+(2.027)+(3.030), (I)+(2.038)+(3.012), (I)+(2.038)+(3.020), (I)+(2.038)+(3.030), (I)+(2.060)+(3.012), (I)+(2.060)+(3.020), (I)+(2.060)+(3.030).

7. The active compound combination according to claim 1, wherein the weight ratio of compound(s) (A) to compound(s) (B) is from 1000:1 to 1:1000.

8. The active compound combination according to claim 1, wherein the weight ratio of compound(s) (A) to compound(s) (C) is from 1000:1 to 1:1000.

9. The active compound combination according to claim 1 wherein exactly 1 compound (B) is present and exactly 1 compound (C) is present.

10. A composition for controlling one or more harmful microorganisms in crop protection and/or in protection of one or more materials, comprising an active compound combination according to claim 1, in addition to at least one carrier and/or surfactant.

11. A method for controlling one or more harmful microorganisms in crop protection and/or in protection of one or more materials, comprising applying an active compound combination according to claim 1 or a composition thereof to the harmful microorganisms and/or a habitat thereof.

12. A product comprising an active compound combination according to claim 1 or a composition thereof for control of one or more harmful microorganisms in crop protection and/or in protection of one or more materials.

13. A product comprising an active compound combination according to claim 1 or a composition thereof for treatment of a transgenic plant.

14. A product comprising an active compound combination according to claim 1 or a composition thereof for treatment of seed.

15. A seed coated with an active compound combination according to claim 1 or a composition thereof.

Description

EXAMPLES

[0254] The advanced fungicidal activity of the active compound combinations according to the invention is evident from the examples below. While the individual active compounds exhibit weaknesses with regard to the fungicidal activity, the combinations have an activity which exceeds a simple addition of activities.

[0255] A synergistic effect of 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 1967, 15, 20-22):

If

[0256] X is the efficacy when active compound A is applied at an application rate of m ppm (or g/ha),
Y is the efficacy when active compound B is applied at an application rate of n ppm (or g/ha), and
E is the efficacy when the active compounds A and B are applied at application rates of m and n ppm (or g/ha), respectively,
then

[00001]$E=X+Y-\frac{X.Math.Y}{100}$

[0257] For ternary mixtures the following Colby equation results:

If

[0258] X is the efficacy when active compound A is applied at an application rate of m ppm (or g/ha),
Y is the efficacy when active compound B is applied at an application rate of n ppm (or g/ha),
Z is the efficacy when active compound C is applied at an application rate of o ppm (or g/ha), and
E is the efficacy when the active compounds A, B and C are applied at application rates of m, n and o ppm (or g/ha), respectively,
then

[00002]$E=X+Y+Z-\frac{X.Math.Y}{100}-\frac{X.Math.Z}{100}-\frac{Y.Math.Z}{100}+\frac{X.Math.Y.Math.Z}{100.Math.100}$

[0259] The degree of efficacy, expressed in % is denoted. 0% means an efficacy which corresponds to that of the control while an efficacy of 100% means that no disease is observed.

[0260] 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 efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the abovementioned formula.

[0261] A further way of demonstrating a synergistic effect is the method of Tammes (cf. “Isoboles, a graphic representation of synergism in pesticides” in Neth. J. Plant Path., 1964, 70, 73-80).

Example A: In Vitro-Test with Fungal Microorganisms

[0262] Wells of 96-well microtiter plates are filled with 30 μl of a preparation of test compound or compound combination in methanol+emulsifier alkylaryl-polyglycol-ether. Thereafter, the solvent is evaporated in a hood. At the next step, into each well 200 μl of liquid growth medium is given, that has been amended with an appropriate concentration of spores or mycelium suspension of the test fungus.

[0263] With the aid of a photometer the extinction in all wells is measured at the wavelength of 600 nm.

[0264] The microtiter plates are incubated for 3 to 7 days at 20° C. and 85% relative humidity. After the incubation inhibition of growth is determined photometrically. Efficacy is calculated in relation to the untreated control, 0% efficacy means fungal growth as high as in untreated control while 100% efficacy means no fungal growth is measured.

[0265] The tables below clearly show that the observed efficacy of the active compound combination according to the invention is greater than the calculated activity, i.e. a synergistic effect is present.

TABLE-US-00001 TABLE A1 in vitro -Test with Alternaria alternata (2.038) (3.012) (2.005) (3.030) (2.060) (3.020) Colby (I-1) isoflucypram fluoxastrobin fluopyram metyltetraprole cyclobutrifluram trifloxystrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.5 51 0.02 0 0.2 69 0.008 51 10.0 99 2.0 100 0.08 39 0.5 0.2 10.0  1:0.4:20 100 100 0.5 0.2 2.0 1:0.4:4 99 100 0.5 0.2 0.08   1:0.4:0.16 93 91 0.02 0.008 10.0  1:0.4:500 100 100 0.02 0.008 2.0  1:0.4:100 99 100 0.02 0.008 0.08 1:0.4:4 87 70 0.5 56 0.1 28 0.02 0 4.0 95 0.8 73 0.16 72 0.4 92 0.08 70 0.5 4.0 0.4   1:8:0.8 100 100 0.5 4.0 0.08   1:8:0.16 100 99 0.1 0.8 0.4 1:8:4 100 98 0.1 0.8 0.08   1:8:0.8 96 94 0.02 0.16 0.4  1:8:20 100 98 0.02 0.16 0.080 1:8:4 98 91 0.02 0 0.04 97 10.0 97 2.0 100 0.4 97 0.08 64 0.02 10.0 0.04 1:500:2 99 99 0.02 2.0 0.04 1:100:2 100 100 0.02 0.4 0.04 1:20:2 98 99 0.02 0.08 0.04 1:4:2 96 92 0.02 0 0.04 78 1.0 100 0.2 98 0.04 80 0.008 39 0.02 0.04 1.0  1:2:50 100 100 0.02 0.04 0.2  1:2:10 100 100 0.02 0.04 0.04 1:2:2 96 96 0.02 0.04 0.008   1:2:0.4 90 86

TABLE-US-00002 TABLE A2 in vitro -Test with Alternaria alternata (2.017) (3.012) (3.020) (3.030) (2.027) Colby (I-1) penflufen fluoxastrobin trifloxystrobin metyltetraprole inpyrfluxam efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 31 0.2 14 10 100 2.0 100 0.4 97 0.08 48 0.1 0.2 2.0 1:2:20  99 100 0.1 0.2 0.4 1:2:4   98 98 0.1 0.2 0.08 1:2:0.8 87 69 0.1 31 0.2 14 1 100 0.2 95 0.04 75 0.1 0.2 1 1:2:10  100 100 0.1 0.2 0.2 1:2:2   99 97 0.1 0.2 0.04 1:2:0.4 96 85 0.1 31 0.2 14 2 92 0.4 85 0.08 69 0.1 0.2 2 1:2:20  98 95 0.1 0.2 0.4 1:2:4   96 91 0.1 0.2 0.08 1:2:0.8 81 82 0.02 39 10 100 2 100 0.4 85 0.008 0 0.02 10 0.008 1:500:0.4 100 100 0.02 2 0.008 1:100:0.4 99 100 0.02 0.4 0.008 1:20:0.4 95 91 2.5 92 0.1 26 0.02 39 0.2 88 1 86 0.04 41 0.008 0 2.5 0.2 1 1:0.08:0.4 99 100 0.1 0.2 0.04 1:2:0.4 95 95 0.02 0.2 0.008 1:10:0.4 98 93 0.1 39 0.02 18 10 99 2 99 0.4 90 0.08 72 0.04 27 0.008 0 0.1 10 0.04 1:100:0.4 99 100 0.1 2 0.04 1:20:0.4 100 100 0.1 0.4 0.04 1:4:0.4 96 95 0.1 0.08 0.04 1:0.8:0.4 96 88 0.02 10 0.008 1:500:0.4 99 99 0.02 2 0.008 1:100:0.4 100 99 0.02 0.4 0.008 1:0.4:20 98 91 0.02 0.08 0.008 1:4:0.4 81 77

TABLE-US-00003 TABLE B1 in vitro -Test with Botrytis cinerea (2.005) (3.012) (3.020) fluo- fluoxa- trifloxy- Colby (I-1) pyram strobin strobin efficacy expected (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 22 0.8 0 10 86 2 59 0.4 44 0.08 15 0.1 0.8 10  1:8:100 96 89 0.1 0.8 2  1:8:20 85 68 0.1 0.8 0.4 1:8:4 74 56 0.1 0.8 0.08   1:8:0.8 71 34 0.1 22 0.8 0 1  1:8:10 94 89 0.2 1:8:2 91 72 0.04   1:8:0.4 72 29 0.008   1:8:0.08 68 29

TABLE-US-00004 TABLE B2 in vitro -Test with Botrytis cinerea (2.017) (3.030) (2.019) (2.027) (3.012) (3.020) Colby (I-1) penflufen metyltetraprole pydiflumetofen inpyrfluxam fluoxastrobin trifloxystrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 2.5 62 0.5 0 5 7 1 35 10 84 2 49 0.4 30 0.08 18 2.5 5 10 1:2:4   99 94 2.5 5 2 1:2:0.8 93 82 2.5 5 0.4  1:2:0.16 73 75 2.5 5 0.08  1:2:0.032 71 71 0.5 1 10 1:2:20  89 89 0.5 1 2 1:2:4   91 67 0.5 1 0.4 1:2:0.8 65 54 0.5 1 0.08  1:2:0.16 63 47 2.5 63 0.5 3 0.1 0 2 54 1 92 0.2 82 0.04 71 2.5 2 1 1:0.8:0.4 97 99 0.5 2 0.2 1:4:0.4 97 92 0.1 2 0.04 1:20:0.4 87 87 0.5 32 0.2 0 10 83 2 52 0.4 21 0.08 12 0.5 0.2 10 1:0.4:20  90 89 0.5 0.2 2 1:0.4:4   76 67 0.5 0.2 0.4 1:0.4:0.8 65 47 0.5 0.2 0.08  1:0.4:0.16 65 40 0.5 32 0.02 13 0.2 0 0.08 0 1 81 0.2 25 0.04 9 0.008 0 0.5 0.02 1 1:0.4:2   90 87 0.5 0.02 0.2 1:0.4:0.4 78 49 0.5 0.02 0.04  1:0.4:0.08 47 38 0.5 0.02 0.008  1:0.4:0.016 64 32 0.02 0.008 1 1:0.4:50  82 84 0.02 0.008 0.2 1:0.4:10  61 35 0.02 0.008 0.04 1:0.4:2   27 21 0.02 0.008 0.008 1:0.4:0.4 11 13

TABLE-US-00005 TABLE B3 in vitro -Test with Botrytis cinerea (2.027) (3.030) Colby (I-1) inpyrfluxam metyltetraprole efficacy expected (ppm) (ppm) (ppm) ratio % value % 0.5 0 0.1 17 0.02 0 0.2 77 0.04 37 0.008 0 2 15 0.4 25 0.5 0.2 2 1:0.4:4  90 80 0.1 0.04 2 1:0.4:20 81 56 0.1 0.04 0.4 1:0.4:4  67 61 0.02 0.008 2  1:0.4:100 59 15 0.02 0.008 0.4 1:0.4:20 36 25

TABLE-US-00006 TABLE C1 in vitro -Test with Cercospora beticola (2.038) (3.012) Colby (I-1) isoflucypram fluoxastrobin efficacy expected (ppm) (ppm) (ppm) ratio % value % 2.5 99 0.5 74 0.1 36 0.02 50 1 88 0.2 0 0.04 30 0.008 20 2 94 2.5 1 2   1:0.4:0.8 100 100 0.5 0.2 2 1:0.4:4 100 98 0.1 0.04 2  1:0.4:20 100 97 0.02 0.008 2  1:0.4:100 100 98

TABLE-US-00007 TABLE D1 in vitro -Test with Colletotrichum coccodes (2.038) (3.012) (3.020) (3.030) (2.005) (2.060) Colby (I-1) isoflucypram fluoxastrobin trifloxystrobin metyltetraprole fluopyram cyclobutrifluram efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 0 0.04 5 10 96 2 88 0.4 49 0.1 0.04 10  1:0.4:100 96 96 0.1 0.04 2  1:0.4:20 88 89 0.1 0.04 0.4 1:0.4:4 58 52 0.1 0 0.04 9 1 96 0.2 84 0.04 58 0.008 10 0.1 0.04 1  1:0.4:10 96 96 0.1 0.04 0.2 1:0.4:2 87 85 0.1 0.04 0.04   1:0.4:0.4 67 62 0.1 0.04 0.008   1:0.4:0.08 22 18 0.5 3 0.1 0 0.02 0 0.2 14 0.04 9 0.008 23 10 100 2 92 0.4 75 0.008 36 0.5 0.2 10  1:0.4:20 100 100 0.5 0.2 2 1:0.4:4 97 93 0.5 0.2 0.4   1:0.4:0.8 79 79 0.5 0.2 0.008   1:0.4:0.16 56 47 0.1 0.04 10  1:0.4:100 100 100 0.1 0.04 2  1:0.4:20 95 93 0.1 0.04 0.4 1:0.4:4 86 77 0.02 0.008 10  1:0.4:500 100 100 0.02 0.008 2  1:0.4:100 95 94 0.02 0.008 0.4  1:0.4:20 92 80 0.02 0 10 94 2 87 0.4 50 0.08 30 0.16 10 0.02 10 0.16 1:500:8 96 95 0.02 2 0.16 1:100:8 90 89 0.02 0.4 0.16 1:20:8 55 55 0.02 0.08 0.16 1:4:8 55 36 0.1 0 0.02 0 10 100 2 92 0.4 73 0.8 0 0.16 0 0.1 10 0.8 1:100:8 99 100 0.1 2 0.8 1:20:8 96 92 0.1 0.4 0.8 1:4:8 77 72 0.02 10 0.16 1:500:8 100 100 0.02 2 0.16 1:100:8 93 92 0.02 0.4 0.16 1:20:8 75 73 0.5 0 10 95 0.4 51 0.08 15 1 0 0.5 10 1 1:20:2 97 95 0.5 0.4 1 1:0.8:2 62 51 0.5 0.08 1 1:0.16:2 28.15 0.1 0 1 97 0.2 88 0.008 22 0.2 8 0.1 1 0.2 1:10:2 97 97 0.1 0.2 0.2 1:2:2 91 89 0.1 0.008 0.2 1:0.08:2 47 29

TABLE-US-00008 TABLE D2 in vitro -Test with Colletotrichum coccodes (2.060) (3.030) (2.017) (3.020) (2.019) (3.012) Colby (I-1) cyclobutrifluram metyltetraprole penflufen trifloxystrobin pydiflumetofen fluoxastrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.5 11 0.1 19 0.02 8 1 21 0.2 8 0.04 5 10 100 2 94 0.5 1 10 1:2:20  100 100 0.5 1 2 1:2:4  97 95 0.1 0.2 10 1:2:100 100 100 0.1 0.2 2 1:2:20  95 95 0.02 0.04 10 1:2:500 100 100 0.02 0.04 2 1:2:100 94 94 0.1 0 0.02 0 0.2 0 0.04 5 0.04 62 0.008 8 0.1 0.2 0.04 1:2:0.4  67 63 0.1 0.2 0.008  1:2:0.08 38 9 0.02 0.04 0.04 1:2:2  71 64 0.02 0.04 0.008 1:2:0.4  23 13 0.02 3 0.008 8 10 96 2 82 0.02 0.008 10 1:0.4:500 100 96 0.02 0.008 2 1:0.4:100 92 84

TABLE-US-00009 TABLE D3 in vitro -Test with Colletotrichum coccodes (2.019) (3.020) (3.030) (2.027) (3.012) Colby (I-1) pydiflumetofen trifloxystrobin metyltetraprole inpyrfluxam fluoxastrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 0 0.02 3 0.04 0 0.008 9 1 92 0.2 82 0.04 61 0.008 9 0.1 0.04 1  1:0.4:10 96 92 0.1 0.04 0.2 1:0.4:2 91 82 0.1 0.04 0.04   1:0.4:0.4 70 61 0.1 0.04 0.008   1:0.4:0.08 11 8 0.02 0.008 1  1:0.4:50 96 93 0.02 0.008 0.2  1:0.4:10 86 84 0.02 0.008 0.04 1:0.4:2 76 65 0.02 0.008 0.008   1:0.4:0.4 30 18 0.5 0 0.1 0 0.2 19 0.04 9 0.4 72 0.5 0.2 0.4   1:0.4:0.8 81 77 0.1 0.04 0.4 1:0.4:4 80 74 0.5 0 0.02 0 0.2 0 0.008 0 2 83 0.4 50 0.008 0 0.5 0.2 2 1:0.4:4 88 83 0.5 0.2 0.4   1:0.4:0.8 65 50 0.5 0.2 0.008   1:0.4:0.16 5 0 0.02 0.008 2  1:0.4:100 89 83 0.02 0.008 0.4  1:0.4:20 65 50 0.02 0.008 0.008 1:0.4:4 27 0 0.5 16 0.1 0 0.02 4 2 82 0.2 0 0.4 23 0.08 24 0.5 2 0.2 1:4:0.4 90 85 0.1 2 0.4 1:20:0.4 96 85 0.02 2 0.08 1:100:0.4 93 87

TABLE-US-00010 TABLE E1 in vitro -Test with Cordana musae (2.038) (3.012) (3.020) (2.005) (3.030) (2.060) Colby (I-1) isoflucypram fluoxastrobin trifloxystrobin fluopyram metyltetraprole cyclobutrifluram efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 11 0.02 5 0.04 0 0.008 8 10 87 2 77 0.1 0.04 10  1:0.4:100 89 88 0.1 0.04 2 1:0.4:20 82 79 0.02 0.008 10  1:0.4:500 94 88 0.02 0.008 2  1:0.4:100 79 80 0.1 22 0.02 0 0.04 0 0.008 2 1 89 0.2 83 0.04 82 0.008 29 0.1 0.04 1 1:0.4:10 91 91 0.1 0.04 0.2 1:0.4:2  87 87 0.1 0.04 0.04  1:0.4:0.4 87 86 0.1 0.04 0.008   1:0.4:0.08 57 44 0.02 0.008 1 1:0.4:50 91 89 0.02 0.008 0.2 1:0.4:10 84 83 0.02 0.008 0.04 1:0.4:2  84 83 0.02 0.008 0.008  1:0.4:0.4 50 30 0.1 21 0.02 5 1 88 0.2 82 0.8 6 0.16 0 0.1 1 0.8 1:10:8 91 91 0.1 0.2 0.8 1:2:8 92 87 0.02 1 0.16 1:50:8 90 89 0.02 0.2 0.16 1:10:8 87 83 0.1 0 0.8 0 10 96 0.4 77 0.08 65 0.1 0.8 10  1:8:100 97 96 0.1 0.8 0.4 1:8:4 81 77 0.1 0.8 0.08   1:8:0.8 61 54 0.5 21 0.1 10 0.02 30 1 86 1 6 0.2 4 0.04 3 0.5 1 1 1:2:2 92 89 0.1 1 0.2 1:10:2 89 88 0.02 1 0.04 1:50:2 91 90

TABLE-US-00011 TABLE E2 in vitro -Test with Cordana musae (2.017) (3.012) (3.030) (2.019) (3.020) (2.027) Colby (I-1) penflufen fluoxastrobin metyltetraprole pydiflumetofen trifloxystrobin inpyrfluxam efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.5 17 0.02 25 1 0 0.04 0 10 78 0.4 64 0.5 1 10 1:2:20 86 82 0.02 0.04 10  1:2:500 85 83 0.02 0.04 0.4 1:2:20 81 72 0.5 48 0.1 0 0.02 0 1 0 0.2 0 0.04 5 10 89 0.5 1 10 1:2:20 99 94 0.1 0.2 10  1:2:100 90 89 0.02 0.04 10  1:2:500 91 90 0.02 24 0.008 0 1 84 0.2 73 0.02 0.008 1 1:0.4:50 92 87 0.02 0.008 0.2 1:0.4:10 85 79 0.1 0 10 94 2 82 0.4 73 0.08 58 0.04 9 0.1 10 0.04 1:100:0.4 98 94 0.1 2 0.04 1:20:0.4 91 84 0.1 0.4 0.04  1:4:0.4 86 75 0.1 0.08 0.04  1:0.8:0.4 50 62 0.5 24 0.1 12 0.02 4 2 78 0.2 6 0.04 0 0.008 16 0.5 2 0.2  1:4:0.4 85 84 0.1 2 0.04 1:20:0.4 86 80 0.02 2 0.008 1:100:0.4 90 82

TABLE-US-00012 TABLE E3 in vitro -Test with Cordana musae (2.027) (3.020) Colby (I-1) inpyrfluxam trifloxystrobin efficacy expected (ppm) (ppm) (ppm) ratio % value % 0.5 24 0.1 12 0.02 4 0.2 6 0.04 0 0.008 16 1 85 0.5 0.2 1 1:0.4:2  95 89 0.1 0.04 1 1:0.4:10 91 87 0.02 0.008 1 1:0.4:50 87 88

TABLE-US-00013 TABLE F1 in vitro -Test with Diaporthe citri (2.005) (2.019) (3.012) (3.030) (2.060) Colby (I-1) fluopyram pydiflumetofen fluoxastrobin metyltetraprole cyclobutrifluram efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 2.5 99 0.02 5 20 52 0.16 0 2 98 0.4 89 2.5 20 2   1:8:0.8 99 100 2.5 20 0.4   1:8:0.16 99 100 0.02 0.16 2  1:8:100 97 98 0.02 0.16 0.4  1:8:20 94 90 2.5 99 0.02 0 20 31 0.16 0 10 99 0.08 77 2.5 20 10 1:8:4 99 100 2.5 20 0.08    1:8:0.032 96 100 0.02 0.16 10  1:8:500 99 99 0.02 0.16 0.08 1:8:4 82 77 0.02 0 10 99 2 99 0.4 91 0.08 81 0.04 0 0.02 10 0.04 1:500:2 99 99 0.02 2 0.04 1:100:2 98 99 0.02 0.4 0.04 1:20:2 96 91 0.02 0.08 0.04 1:4:2 87 81

TABLE-US-00014 TABLE F2 in vitro -Test with Diaporthe citri (2.017) (3.030) (2.019) (3.012) Colby (I-1) penflufen metyltetraprole pydiflumetofen fluoxastrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.1 18 0.02 2 0.2 0 0.04 0 2 99 0.4 89 0.1 0.2 2 1:2:20 98 99 0.1 0.2 0.4 1:2:4  92 91 0.02 0.04 2  1:2:100 99 99 0.02 0.04 0.4 1:2:20 90 89 2.5 98 0.5 92 0.1 41 1 33 0.2 22 0.04 0 2 66 2.5 1 2 1:0.4:0.8 98 100 0.5 0.2 2 1:0.4:4   100 98 0.1 0.04 2 1:0.4:20  89 80

TABLE-US-00015 TABLE G1 in vitro -Test with Fusarium culmorum (2.038) (2.005) (3.012) (3.020) Colby (I-1) isoflucypram fluopyram fluoxastrobin trifloxystrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.5 0 0.1 0 0.2 11 0.04 0 10 56 0.08 7 0.5 0.2 10 1:0.4:20   53 61 0.5 0.2 0.08 1:0.4:0.16 20 17 0.1 0.04 10 1:0.4:100  64 56 0.1 0.04 0.08 l:0.4:0.8  23 7 0.1 6 0.02 9 0.8 18 0.16 9 0.4 17 0.08 0 0.1 0.8 0.4 1:8:4 42 36 0.02 0.16 0.08  1:8:20 57 31 0.1 6 0.02 9 0.8 18 0.16 9 1 68 0.2 41 0.04 18 0.008 14 0.1 0.8 0.2 1:8:2 66 55 0.1 0.8 0.008   1:8:0.08 40 34 0.02 0.16 1  1:8:50 77 73 0.02 0.16 0.04 1:8:2 34 32

TABLE-US-00016 TABLE H1 in vitro -Test with Parastasonospora nodorum (2.005) (3.012) (3.020) fluo- fluoxa- trifloxy- Colby (I-1) pyram strobin strobin efficacy expected (ppm) (ppm) (ppm) (ppm) ratio % value % 2.5 99 0.02 0 20 100 0.16 14 2 87 0.4 77 2.5 20 2  1:8:0.8 100 100 2.5 20 0.4   1:8:0.16 100 100 0.02 0.16 2  1:8:100 91 88 0.02 0.16 0.4 1:8:20 82 80 2.5 99 0.02 0 20 100 0.16 14 0.2 85 0.04 65 2.5 20 0.2   1:8:0.08 100 100 2.5 20 0.04   1:8:0.016 100 100 0.02 0.16 0.2 1:8:10 89 87 0.02 0.16 0.04 1:8:2  77 71

TABLE-US-00017 TABLE H2 in vitro -Test with Parastasonospora nodorum (2.060) (3.030) (2.017) (3.012) (3.020) Colby (I-1) cyclobutrifluram metyltetraprole penflufen fluoxastrobin trifloxystrobin efficacy expected (ppm) (ppm) (ppm) (ppm) (ppm) (ppm) ratio % value % 0.02 3 0.04 27 10 100 2 100 0.08 80 0.02 0.04 10  1:2:500 100 100 0.02 0.04 2  1:2:100 100 100 0.02 0.04 0.08 1:2:4 90 86 2.5 96 0.02 2 5 22 0.04 11 2 85 0.4 65 0.08 60 2.5 5 2   1:2:0.8 100 100 2.5 5 0.4   1:2:0.16 100 99 2.5 5 0.08    1:2:0.032 100 99 0.02 0.04 2  1:2:100 94 87 0.02 0.04 0.4  1:2:20 86 70 0.02 0.04 0.08 1:2:4 65 65 2.5 96 0.02 2 5 22 0.04 11 0.04 79 0.008 44 2.5 5 0.04    1:2:0.016 100 99 2.5 5 0.008    1:2:0.0032 100 98 0.02 0.04 0.04 1:2:2 84 81 0.02 0.04 0.008   1:2:0.4 46 51 0.02 0 10 100 0.4 92 0.08 76 0.04 0 0.02 10 0.04 1:500:2 100 100 0.02 0.4 0.04 1:20:2 94 92 0.02 0.08 0.04 1:4:2 77 76

TABLE-US-00018 TABLE H3 in vitro -Test with Parastasonospora nodorum (2.027) (3.012) Colby (I-1) inpyrfluxam fluoxastrobin efficacy expected (ppm) (ppm) (ppm) ratio % value % 0.02 9 0.008 20 10 82 2 85 0.08 57 0.02 0.008 10 1:0.4:500 99 87 0.02 0.008 2 1:0.4:100 89 89 0.02 0.008 0.08 1:0.4:4  65 69