ACTIVE COMPOUND COMBINATIONS

Abstract

The present invention relates to active compound combinations comprising Fluopyram, 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 as compound (A) Fluopyram, as compound (B) Prothioconazole and as compound (C) at least one fungicide selected from the group consisting of Trifloxystrobin and Tebuconazole.

2. Active compound combination according to claim 1, wherein compound (C) is Trifloxystrobin.

3. Active compound combination according to claim 1, wherein compound (C) is Tebuconazole.

4. Active compound combination according to claim 1, wherein the weight ratio of compound (A) to compound(s) (B) is from 2:1 to 1:2.

5. Active compound combination according to claim 1, wherein the weight ratio of compound (A) to compound(s) (C) is from 3:1 to 1:3.

6. A Composition for controlling one or more phytopathogenic fungi in crop protection comprising an active compound combination according to claim 1, in addition to at least one carrier and/or surfactant.

7. A Method for controlling one or more phytopathogenic fungi in crop protection, comprising applying an active compound combination according to claim 1 or a composition thereof to a plant, plant part, phytopathogenic fungi and/or a habitat thereof.

8. Method according to claim 7, wherein the phytopathogenic fungi are selected from the group consisting of Cercospora zeae-maydis, Cercospora sojini.

9. Method according to claim 7, wherein the plant is a genetically modified plant.

10. Method according to claim 7, wherein the plant is selected from barley, chickpea, corn, corn grown for seed, cotton, durum, dry peas, field corn, field peas, flax, millet, lentils, oats, soybean, sugar beets, rye, sweet corn, teosinte, triticale, turf grass wheat, and winter wheat.

11. Method according to claim 7, wherein an active compound combination or a composition thereof is applied at a concentration of 50 to 400 g/ha of total active ingredient.

12. Method according to claim 7, wherein an active compound combination or a composition thereof is applied at a concentration of 90 to 175 g/ha of Prothioconazole, 80 to 140 g/ha of Trifloxystrobin or Tebuconazole, 50 to 100 g/ha of Fluopyram.

13. Method according to claim 7, wherein an active compound combination or a composition thereof is applied at one or more growth stages 61 to 69.

14. A product comprising an active compound combination according to claim 1 or a composition thereof for control of one or more phytopathogenic fungi in crop protection.

Description

EXAMPLES

[0294] The advanced fungicidal activity of the active compound combinations comprising as compound (A) Fluopyram, as compound (B) Prothioconazole and as compound (C) at least one fungicide selected from the group consisting of Trifloxystrobin and Tebuconazole is evident from the examples below.

Example A: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0295] The field trials in corn were conducted in Indiana, Minnesota, Iowa, North Carolina, and Illinois of the United States in spring/summer 2015.

[0296] Fertilization and herbicide applications were carried out according to the local agricultural practice. Each trial was conducted with 4 fully randomized replicates. The plot size was approximately 4 meters by 10 meters.

[0297] The following products as shown in Table 1 were sprayed using a backpack sprayer at BBCH—growth stage 63.

[0298] Plots were harvested using a small-plot combine.

TABLE-US-00001 TABLE 1 Active Concentration Application Product Name Ingredients [g/L] Rate [g/ha] STRATEGO YIELD Prothioconazole + 125 36.5 Trifloxystrobin 375 110 PROPULSE + Fluopyram + 200 70 GEM Prothioconazole 200 70 Trifloxystrobin 500 70 PROLINE Prothioconazole 480 200 HEADLINE AMP Pyraclostrobin 146 105 Metconazole  55 40

TABLE-US-00002 TABLE 2 Yield Product Name [bu/acre] Untreated 186 STRATEGO YIELD 196 Fluopyram + 202 Prothioconazole + Trifloxystrobin PROLINE 197 HEADLINE AMP 198

Example B: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0299] The field trials in corn were conducted in Michigan, Ohio, Illinois, Indiana, Iowa, Minnesota, Mississippi, and Florida of the United States in spring/summer 2018.

[0300] Fertilization and herbicide were carried out according to the local agricultural practice. Each trial was conducted with 4 fully randomized replicates. The plot size was approximately 4 meters by 10 meters.

[0301] The following products as shown in Table 3 were sprayed using a backpack sprayer at BBCH—growth stage 63.

[0302] Activity against Cerospora zeae-maydis (CERCZM) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0303] Plots were harvested using a small-plot combine.

TABLE-US-00003 TABLE 3 Concentration Application Product Name Active Ingredients [g/L] Rate [g/ha] DELARO Prothioconazole + 175 105 Trifloxystrobin 150  88 DELARO + Prothioconazole + 175 105 LUNA PRIVILEGE Trifloxystrobin 150  88 Fluopyram 400  75 TRIVIAPRO Azoxystrobin + 110 110 Benzovindiflupyr +  30  30 Propiconazole 125 125 HEADLINE AMP Pyraclostrobin + 146 105 Metconazole  55  40

TABLE-US-00004 TABLE 4 Activity Against CERCZM Product Name [% Abbott] DELARO 58 DELARO + Fluopyram 72 TRIVIAPRo 68 HEADLINE AMP 59

Example C: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0304] The field trial in corn was conducted in Florida in spring/summer 2018.

[0305] Fertilization and herbicide were carried out according to the local agricultural practice. The trial was conducted with 4 fully randomized replicates. The plot size was approximately 4 meters by 10 meters.

[0306] The following products as shown in table 5 were sprayed using a backpack sprayer at BBCH—growth stage 63.

[0307] Activity against Cochiobolus heterostrophus (COCHHE) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0308] Activity against Kabatiella zeae (KABAZE) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

TABLE-US-00005 TABLE 5 Concentration Application Product Name Active Ingredients [g/L] Rate [g/ha] DELARO Prothioconazole + 175 105 Trifloxystrobin 150  88 DELARO + Prothioconazole + 175 105 LUNA PRIVILEGE Trifloxystrobin 150  88 Fluopyram 400  75 TRIVIAPRO Azoxystrobin + 110 110 Benzovindiflupyr +  30  30 Propiconazole 125 125 HEADLINE AMP Pyraclostrobin 146 105 Metconazole  55  40

TABLE-US-00006 TABLE 6 Activity Against COCHHE Product Name [% Abbott] DELARO 50 DELARO + Fluopyram 81 TRIVIAPRO 48 HEADLINE AMP 32

TABLE-US-00007 TABLE 7 Activity Against KABAZE Product Name [% Abbott] DELARO 64 DELARO + Fluopyram 79 TRIVIAPRO 65 HEADLINE AMP 57

Example D: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0309] The field trials in soybean were conducted in Ohio, Indiana, Minnesota, Iowa, Illinois, Kansas, Mississippi, Florida, Arkansas in spring/summer 2018.

[0310] Fertilization and herbicide applications were carried out according to the local agricultural practice. The trial was conducted with twentyfive fully randomized replicates. The plot size was approximately 4 meters by 10 meters.

[0311] The following products as shown in Table 8 were sprayed using a backpack sprayer at BBCH—growth stage 69.

[0312] Activity against Cercospora sojina (CERCSP) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0313] Activity against Septoria glycines (SEPTGL) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0314] Plots were harvested using a small-plot combine.

TABLE-US-00008 TABLE 8 Concen- Application tration Rate Product Name Active Ingredients [g/L] [g/ha] DELARO Prothioconazole + 175 105 Trifloxystrobin 150 88 DELARO + Prothioconazole + 175 105 LUNA PRIVILEGE Trifloxystrobin 150 88 Fluopyram 400 75 QUADRIS TOP SBX Azoxystrobin, + 225 115 Difenconazole 225 115 PRIAXOR Fluxapyroxad + 116.4 49 Pyraclostrobin 333.3 97 TRIVIAPRO Azoxystrobin + 110 110 Benzovindiflupyr + 30 30 Propiconazole 125 125

TABLE-US-00009 TABLE 9 Product Name Yield [bu/ac] Untreated 60.1 DELARO 65.3 DELARO + Fluopyram 67.9 QUADRIS TOP SBX 69.4 PRIAXOR 65.2 TRIVIAPRO 61.7 DELARO 61.9

TABLE-US-00010 TABLE 10 Activity Against CERCSP Product Name [% Abbott] DELARO 58 DELARO + Fluopyram 57 QUADRIS TOP SBX 52 PRIAXOR 51 TRIVIAPRO 55

TABLE-US-00011 TABLE 11 Activity Against SEPTGL Product Name [% Abbott] DELARO 46 DELARO + Fluopyram 55 QUADRIS TOP SBX 48 PRIAXOR 46 TRIVIAPRO 61.7

Example E: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0315] Field trials in corn were conducted in Ohio, Missouri, Minnesota, Iowa, Illinois, Mississippi, Kansas, and Georgia in spring/summer 2019.

[0316] Fertilization and herbicide applications were carried out according to the local agricultural practice. The trial was arranged as a randomized complete block with 4 replications. The plot size was approximately 4 meters by 10 meters.

[0317] The following products as shown in Table 12 were sprayed using a backpack sprayer at BBCH—growth stage 63.

[0318] Activity against Cercospora zeae-maydis (CERCZM) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0319] Plots were harvested using a small-plot combine.

TABLE-US-00012 TABLE 12 Concen- Application tration Rate Product Name Active Ingredients [g/L] [g/ha] DELARO Prothioconazole + 175 102 Trifloxystrobin 150 88 DELARO + Prothioconazole + 175 103 LUNA PRIVILEGE Trifloxystrobin 150 90 Fluopyram 400 75 TRIVAPRO Azoxystrobin, + 110 110 Benzovindiflupyr + 30 30 Propiconazole 125 125 HEADLINE AMP Pyraclostrobin 146 105 Metconazole 55 40

TABLE-US-00013 TABLE 13 Activity Against CERCZM Product Name [% Abbott] DELARO 57 DELARO + Fluopyram 67 TRIVIAPRO 49 HEADLINE AMP 58

Example F: Field Trials with Active Combinations Comprising (A) Fluopyram. (B) Prothioconazole and (C) Trifloxystrobin

[0320] Field trials in soybean were conducted in Ohio, Missouri, Iowa, Illinois, Mississippi, Arkansas, and Georgia in spring/summer 2019.

[0321] Fertilization and herbicide applications were carried out according to the local agricultural practice. The trial was arranged as a randomized complete block with 4 replications. The plot size was approximately 4 meters by 10 meters.

[0322] The following products as shown in Table 14 were sprayed using a backpack sprayer at BBCH—growth stage 69.

[0323] Activity against Cercospora sojina (CERCSP) was calculated according to Abbott (WS Abbott, 1925, J. Econ. Entomol. 18:265-267).

[0324] Plots were harvested using a small-plot combine.

TABLE-US-00014 TABLE 14 Concen- Application tration Rate Product Name Active Ingredients [g/L] [g/ha] DELARO Prothioconazole + 175 102 Trifloxystrobin 150 88 DELARO + Prothioconazole + 175 103 LUNA PRIVILEGE Trifloxystrobin 150 90 Fluopyram 400 75 PRIAXOR Fluxapyroxad + 116.4 49 Pyraclostrobin 333.3 97

TABLE-US-00015 TABLE 15 Activity Against CERCZM Product Name [% Abbott] DELARO 60 DELARO + Fluopyram 65 PRIAXOR 55

Example G: Greenhouse Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0325] The advanced fungicidal activity of the active compound combinations according to the invention is evident from the example 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.

[0326] 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):

[0327] If [0328] X is the efficacy when active compound A is applied at an application rate of m ppm (or g/ha), [0329] Y is the efficacy when active compound B is applied at an application rate of n ppm (or g/ha), [0330] Z is the efficacy when active compound B is applied at an application rate of r ppm (or g/ha), [0331] E.sub.1 is the efficacy when the active compounds A and B are applied at application rates of m and n ppm (or g/ha), respectively, and [0332] E.sub.2 is the efficacy when the active compounds A, B and C are applied at application rates of m, n and r ppm (or g/ha), respectively, and

[0333] then

[00001]$E_1=X+Y-\frac{X.Math.Y}{100}$

[0334] and for a ternary mixture:

[00002]$E_2=X+Y+Z-\left(\frac{X.Math.Y+X.Math.Z+Y.Math.Z}{100}\right)+\frac{X.Math.Y.Math.Z}{10000}$

[0335] 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.

[0336] 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.

[0337] 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).

[0338] The invention is illustrated by the following examples. However the invention is not limited to the examples.

Example G1: In Vivo Preventive Test on Alternaria Test (Tomatoes)

[0339] Solvent: 24.5 parts by weight of acetone [0340] 24.5 parts by weight of dimethyl sulfoxide

[0341] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0342] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0343] To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani. The plants are then placed in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

[0344] The test is evaluated 3 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.

[0345] The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e., a synergistic effect is present.

TABLE-US-00016 TABLE 16 in vivo preventive test on Alternaria test (tomatoes) Ex. 1 trifloxy- prothio- Colby fluopyram strobin conazole Expected ppm ppm ppm Ratio Efficacy % Value % 3 10 1.5 8 0.75 5 3.6 41 1.8 31 0.9 23 4.2 10 2.1 0 1.05 0 3 3.6 4.2 1:1.2:1.4 74 53 1.5 1.8 2.1 1:1.2:1.4 41 36 0.75 0.9 1.05 1:1.2:1.4 36 27

Example G2: In Vivo Preventive Test on Venturia Test (Apples)

[0346] Solvent: 24.5 parts by weight of acetone [0347] 24.5 parts by weight of dimethyl sulfoxide

[0348] Emulsifier: 1 part by weight of alkylaryl polyglycol ether

[0349] To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

[0350] To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 20° C. and a relative atmospheric humidity of 100%.

[0351] The plants are then placed in a greenhouse at approximately 21° C. and a relative atmospheric humidity of approximately 90%.

[0352] The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.

[0353] The table below clearly shows that the observed activity of the active compound combination according to the invention is greater than the calculated activity, i.e., a synergistic effect is present.

TABLE-US-00017 TABLE 17 in vivo preventive test on Venturia test (apples) Ex. 1 trifloxy- prothio- Colby fluopyram strobin conazole Expected ppm ppm ppm Ratio Efficacy % Value % 3 5 1.5 0 0.75 0 3.6 89 1.8 65 0.9 40 4.2 41 2.1 17 1.05 0 3 3.6 4.2 1:1.2:1.4 95 94 1.5 1.8 2.1 1:1.2:1.4 88 71 0.75 0.9 1.05 1:1.2:1.4 40 40

Example H: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0354] Field trials in lentils were conducted in Western Canada in spring/summer 2018. Fertilization and herbicide applications were carried out according to the local agricultural practice.

[0355] Fluopyram was added to Delaro in a final concentration of 50, 75 and 90 g/ha.

[0356] The following products as shown in Table 18 were sprayed using a Backpack hand boom sprayer with air induction flat fan spray nozzles applying 93.5 L/Ha spray solution at crop BBCH—growth stage 62-63.

TABLE-US-00018 TABLE 18 Concen- Application tration Rate Product Name Active Ingredients [g/L] [g/ha] DELARO Prothioconazole + 175 154 Trifloxystrobin 150 132 DELARO 0.88 L/Ha ++ Prothioconazole + 175 154 Fluopyram Trifloxystrobin 150 132 Fluopyram 50, 75 DELARO 0.572 L/ha + Prothioconazole + 175 100 Fluopyram Trifloxystrobin 150 85.8 Fluopyram 90 PRIAXOR + Fluxapyroxad 116.4 49 Pyraclostrobin 333.3 97

TABLE-US-00019 TABLE 19 Yield [% of Priaxor treatment- Product Name Priaxor is 100%] Untreated 92.2 DELARO 99.1 Fluopyram (50 g/ha) 93.8 Fluopyram (75 g/ha) 96.3 DELARO (0.88 L/Ha) + 102.2 Fluopyram (50 g/ha) DELARO (0.88 L/Ha) + 104.2 Fluopyram (75 g/ha) DELARO (0.572 L/Ha) + 101.8 Fluopyram (90 g/ha)

Example I: Field Trials with Active Combinations Comprising (A) Fluopyram, (B) Prothioconazole and (C) Trifloxystrobin

[0357] Field trials in field peas were conducted in Western Canada in spring/summer 2018.

[0358] Fertilization and herbicide applications were carried out according to the local agricultural practice.

[0359] Fluopyram was added to Delaro in a final concentration of 50, 75 and 90 g/ha.

[0360] The following products as shown in Table 20 were sprayed using a Backpack hand boom sprayer with flat fan spray nozzles applying 93.5 L/ha spray solution at crop BBCH growth stage 63.

TABLE-US-00020 TABLE 20 Concen- Application tration Rate Product Name Active Ingredients [g/L] [g/ha] DELARO Prothioconazole + 175 154 Trifloxystrobin 150 132 DELARO 0.88 L/ha + Prothioconazole + 175 154 Fluopyram Trifloxystrobin 150 132 Fluopyram 50, 75 DELARO 0.572 L/ha + Prothioconazole + 175 100 Fluopyram Trifloxystrobin 150 85.8 Fluopyram 90 PRIAXOR Fluxapyroxad + 116.4 49 Pyraclostrobin 333.3 97

TABLE-US-00021 TABLE 21 Yield [% of Priaxor treatment- Product Name Priaxor is 100 % Untreated 98.9 DELARO 103 Fluopyram (50 g/ha) 98.9 Fluopyram (75 g/ha) 99.7 DELARO (0.88 L/ha) + 103.6 Fluopyram (50 g/ha) DELARO (0.88 L/ha) + 106.3 Fluopyram (75 g/ha) DELARO (0.572 L/ha) + 101.6 Fluopyram (90 g/ha)