Synergistic fungicidal active substance combinations

Abstract

Novel active compound combinations comprising a carboxamide of the general formula (I) (group 1) ##STR00001##
in which
A, R.sup.1, R.sup.2 and R.sup.3 are as defined in the description,
and the active compound groups (2) to (23) listed in the description have very good fungicidal properties.

Claims

1. A composition comprising (1-1) N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and at least one fungicidal compound selected from the group consisting of: (19-2) chlorothalonil; (19-10) spiroxamine; and (19-13) fenamidone wherein the weight ratio of (1-1) to (19-2), (19-10) or (19-13) is from 1:1 to 1:20, and wherein if the fungicidal compound is spiroxamine, then spiroxamine and N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide are the only fungicidal compounds in the composition.

2. A method for controlling unwanted phytopathogenic fungi, comprising applying a composition according to claim 1 to the unwanted phytopathogenic fungi, their habitat, or a combination thereof.

3. A process for preparing a fungicidal composition, comprising mixing a composition according to claim 1 with an extender, a surfactant, or a combination thereof.

4. The composition of claim 1 wherein the active compound is spiroxamine.

5. The composition of claim 1, which comprises (1-1) N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and (19-2) chlorothalonil.

6. The composition of claim 1, which comprises (1-1) N-(3′,4′-dichloro-5-fluoro-1,1′-biphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide and (19-13) fenamidone.

Description

USE EXAMPLES

(1) In the use examples shown below, in each case mixtures of the carboxamides of the general formula (I) (group 1) below with the mixing partners given in each case (structural formulae see above) were tested.

(2) Carboxamides of the formula (I) used:

(3) ##STR00188##

Example A

(4) Pyrenophora teres Test (Barley)/Curative

(5) Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(6) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(7) To test for curative activity, young plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain in an incubation cabinet at 20° C. and 100% relative atmospheric humidity for 48 hours. The plants are then sprayed with the preparation of active compound at the stated application rate.

(8) The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80%.

(9) Evaluation is carried out 12 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(10) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(11) TABLE-US-00022 TABLE A Pyrenophora teres test (barley)/curative Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 25 43 (2-2) fluoxastrobin 25 0 (3-17) tebuconazole 25 29 (1-1) + (2-2) fluoxastrobin (1:1) 25 + 25 71 43 (1-1) + (3-17) tebuconazole (1:1) 25 + 25 71 60 *found = activity found **calc. = activity calculated using Colby's formula

Example B

(12) Erysiphe Test (Barley)/Protective

(13) Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(14) To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.

(15) To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are dusted with spores of Erysiphe graminis f.sp. hordei.

(16) Plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80% to promote the development of mildew pustules.

(17) Evaluation is carried out 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(18) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(19) TABLE-US-00023 TABLE B Erysiphe test (barley)/protective Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 12.5 0 (2-4) trifloxystrobin 12.5 78 (3-15) prothioconazole 12.5 67 (1-1) + (2-4) trifloxystrobin (1:1) 12.5 + 12.5 94 78 (1-1) + (3-15) prothioconazole (1:1) 12.5 + 12.5 89 67 *found = activity found **calc. = activity calculated using Colby's formula

Example C

(20) Puccinia Test (Wheat)/Curative

(21) Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(22) 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.

(23) To test for curative activity, young plants are sprayed with a conidia suspension of Puccinia recondita. The plants remain in an incubation cabinet at 20° C. and 100% relative atmospheric humidity for 48 hours.

(24) The plants are then sprayed with the preparation of active compound at the stated application rate.

(25) The plants are placed in a greenhouse at a temperature of about 20° C. and a relative atmospheric humidity of about 80% to promote the development of rust pustules.

(26) Evaluation is carried out 8 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(27) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(28) TABLE-US-00024 TABLE C Puccinia test (wheat)/curative Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 62.5 22 (19-10) spiroxamine 62.5 0 (6-14) 62.5 44 (6-11) 62.5 0 (2-11) picoxystrobin 62.5 78 (1-1) + (19-10) spiroxamine (1:1) 62.5 + 62.5 100 22 (1-1) + (6-14) (1:1) 62.5 + 62.5 67 57 (1-1) + (6-11) (1:1) 62.5 + 62.5 44 22 (1-1) + (2-11) picoxystrobin (1:1) 62.5 + 62.5 89 83 *found = activity found **calc. = activity calculated using Colby's formula

Example D

(29) Gibberella zeae Test (Barley)/Curative

(30) Solvent: 50 parts by weight of N,N-dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(31) 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.

(32) To test for curative activity, young plants are sprayed with a conidia suspension of Gibberella zeae. The plants remain in an incubation cabinet at 22° C. and 100% relative atmospheric humidity for 24 hours. The plants are then sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants remain in a greenhouse under translucent incubation hoods at a temperature of about 22° C. and a relative atmospheric humidity of about 100%.

(33) Evaluation is carried out 6 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(34) The table below shows clearly that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(35) TABLE-US-00025 TABLE D Gibberella zeae test (barley)/curative Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 62.5 40 (2-12) pyraclostrobin 62.5 80 (3-12) epoxyconazole 62.5 0 (1-1) + (2-12) pyraclostrobin (1:1) 62.5 + 62.5 90 88 (1-1) + (3-12) epoxyconazole (1:1) 62.5 + 62.5 60 40 *found = activity found **calc. = activity calculated using Colby's formula

Example E

(36) Sphaerotheca fuliginea Test (Cucumber)/Protective

(37) Solvents: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(38) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.

(39) To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea.

(40) The plants are then placed in a greenhouse at about 23° C. and a relative atmospheric humidity of about 70%.

(41) Evaluation is carried out 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(42) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(43) TABLE-US-00026 TABLE E Sphaerotheca fuliginea test (cucumber)/protective Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1)  4 30  2 36  1 16  0.5 0 (1-7)  2 0  1 0  0.5 0 (2-1) azoxystrobin  0.5 20 (2-2) fluoxastrobin  1 0 (2-4) trifloxystrobin  2 10 (2-12) pyraclostrobin  2 0 (3-15) prothioconazole  1 43 (3-17) tebuconazole  1 10 (3-21) bitertanol  1 0 (4-2) tolylfluanid 20 0 (6-6) fenhexamid 20 0 (6-14) penthiopyrad  4 0 (7-1) mancozeb 20 0 (7-4) propineb 20 11 (9-3) pyrimethanil 20 0 (12-4) iprodione 20 0 (19-2) chlorothalonil 20 0 (19-10) spiroxamine 20 0 (22-1)  2 11 (22-2)  1 22 (1-1) + (2-1) azoxystrobin (1:1) 0.5 + 0.5 87 20 (1-7) + (2-1) azoxystrobin (1:1) 0.5 + 0.5 63 20 (1-1) + (2-2) fluoxastrobin (1:1)   1 + 1 95 16 (1-7) + (2-2) fluoxastrobin (1:1)   1 + 1 92 0 (1-1) + (2-4) trifloxystrobin (1:1)   2 + 2 57 42 (1-7) + (2-4) trifloxystrobin (1:1)   2 + 2 93 10 (1-1) + (2-12) pyraclostrobin (1:1)   2 + 2 53 36 (1-1) + (3-15) prothioconazole (1:1)   1 + 1 70 52 (1-1) + (3-17) tebuconazole (1:1)   1 + 1 90 24 (1-1) + (3-21) bitertanol (1:1)   1 + 1 50 16 (1-1) + (4-2) tolylfluanid (1:10)   2 + 20 98 36 (1-1) + (6-6) fenhexamid (1:10)   2 + 20 85 36 (1-1) + (6-14) penthiopyrad (1:1)   4 + 4 82 30 (1-1) + (7-1) mancozeb (1:10)   2 + 20 93 36 (1-1) + (7-4) propineb (1:10)   2 + 20 65 43 (1-1) + (9-3) pyrimethanil (1:10)   2 + 20 96 36 (1-1) + (12-4) iprodione (1:10)   2 + 20 74 36 (1-1) + (19-2) chlorothalonil (1:10)   2 + 20 91 36 (1-1) + (19-10) spiroxamine (1:10)   2 + 20 100 36 (1-1) + (22-1) (1:1)   2 + 2 67 43 (1-1) + (22-2) (1:1)   1 + 1 94 34 *found = activity found **calc. = activity calculated using Colby's formula

Example F

(44) Alternaria solani Test (Tomato)/Protective

(45) Solvents: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(46) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.

(47) To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Alternaria solani.

(48) The plants are then placed in an incubation cabinet at about 20° C. and 100% relative atmospheric humidity.

(49) Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(50) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(51) TABLE-US-00027 TABLE F Alternaria solani test (tomato)/protective Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 1 61 0.5 42 (1-7) 1 63 0.5 28 (2-3) 0.5 22 (3-3) propiconazole 0.5 3 (5-3) benthiavalicarb 1 5 (8-4) metalaxyl-M 0.5 7 (8-5) benalaxyl-M 0.5 14 (1-7) + (2-3) (1:1) 0.5 + 0.5 67 44 (1-7) + (3-3) propiconazole (1:1) 0.5 + 0.5 56 30 (1-1) + (5-3) benthiavalicarb (1:1)   1 + 1   77 63 (1-1) + (8-4) metalaxyl-M (1:1) 0.5 + 0.5 62 46 (1-1) + (8-5) benalaxyl-M (1:1) 0.5 + 0.5 67 50 *found = activity found **calc. = activity calculated using Colby's formula

Example G

(52) Phytophthora infestans Test (Tomato)/Protective

(53) Solvents: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(54) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.

(55) To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabinet at about 20° C. and 100% relative atmospheric humidity.

(56) Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(57) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(58) TABLE-US-00028 TABLE G Phytophthora infestans test (tomato)/protective Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 10 0 5 0 1 0 0.5 0 (4-2) tolylfluanid 10 0 (5-1) iprovalicarb 10 64 5 61 (5-3) benthiavalicarb 0.5 56 (19-13) fenamidone 0.5 41 (1-1) + (4-2) tolylfluanid (1:10)   1 + 10  51 0 (1-1) + (5-1) iprovalicarb (1:1)  10 + 10  88 64   5 + 5   77 61 (1-1) + (5-3) benthiavalicarb (1:1) 0.5 + 0.5 73 56 (1-1) + (19-13) fenamidone (1:1) 0.5 + 0.5 51 41 *found = activity found **calc. = activity calculated using Colby's formula

Example H

(59) Botrytis cinerea Test (Bean)/Protective

(60) Solvents: 24.5 parts by weight of acetone 24.5 parts by weight of dimethylacetamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

(61) To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvents and emulsifier, and the concentrate is diluted with water to the desired concentration.

(62) To test for protective activity, young plants are sprayed with the preparation of active compound at the stated application rate. After the spray coating has dried on, 2 small pieces of agar colonized by Botrytis cinerea are placed onto each leaf. The inoculated plants are placed in a darkened chamber at about 20° C. and 100% relative atmospheric humidity.

(63) The size of the infected areas on the leaves is evaluated 2 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(64) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(65) TABLE-US-00029 TABLE H Botrytis cinerea test (bean)/protective Application rate of active compound Efficacy in % Active compounds in g/ha found* calc.** (1-1) 5 54 (9-3) pyrimethanil 5 4 (12-4) iprodione 5 13 (1-1) + (9-3) pyrimethanil (1:1) 5 + 5 92 56 (1-1) + (12-4) iprodione (1:1) 5 + 5 100 60 *found = activity found **calc. = activity calculated using Colby's formula

Example I

(66) Alternaria mali Test (In Vitro)/Microtitre Plates

(67) The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.

(68) For inoculation, a spore suspension of Alternaria mali is used. After 5 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.

(69) 0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.

(70) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(71) TABLE-US-00030 TABLE I Alternaria mali test (in vitro)/microtitre plates Application rate of active compound Efficacy in % Active compounds in ppm found* calc.** (1-1) 0.03 51 0.003 25 (10-3) carbendazim 0.03 15 (19-3) fenamidone 0.003 2 (20-1) pencycuron 0.003 11 (1-1) + (10-3) carbendazim (1:1)  0.03 + 0.03  79 59 (1-1) + (19-3) fenamidone (1:1) 0.003 + 0.003 35 27 (1-1) + (20-1) pencycuron (1:1) 0.003 + 0.003 67 33 *found = activity found **calc. = activity calculated using Colby's formula

Example J

(72) Rhizoctonia solani Test (In Vitro)/Microtitre Plates

(73) The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.

(74) For inoculation, a mycelium suspension of Rhizoctonia solani is used. After 5 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.

(75) 0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.

(76) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(77) TABLE-US-00031 TABLE J Rhizoctonia solani test (in vitro)/microtitre plates Application rate of active compound Efficacy in % Active compounds in ppm found* calc.** (1-1) 0.3 80 0.1 40 (17-1) fosetyl-A1 0.3 24 (11-2) propamocarb 0.1 25 (1-1) + (17-1) fosetyl-A1 (1:1) 0.3 + 0.3 98 85 (1-1) + (11-2) propamocarb (1:1) 0.1 + 0.1 88 55 *found = activity found **calc. = activity calculated using Colby's formula

Example K

(78) Septoria tritici Test (In Vitro)/Microtitre Plates

(79) The microtest is carried out in microtitre plates using potato dextrose broth (PDB) as liquid test medium. The active compounds are used as technical grade a.i., dissolved in acetone.

(80) For inoculation, a spore suspension of Septoria tritici is used. After 7 days of incubation in the dark and with shaking (10 Hz), for each filled cavity of the microtitre plates, the light transmittance is determined with the aid of a spectrophotometer.

(81) 0% means an efficacy which corresponds to the growth in the controls, whereas an efficacy of 100% means that no fungal growth is observed.

(82) The table below clearly shows that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(83) TABLE-US-00032 TABLE K Septoria tritici test (in vitro)/microtitre plates Application rate of active compound Efficacy in % Active compounds in ppm found* calc.** (1-1) 0.01 15 (14-3) triazoxide 0.01 29 (1-1) + (14-3) triazoxide (1:1) 0.01 + 0.01 69 40 *found = activity found **calc. = activity calculated using Colby's formula

Example L

(84) Sphaerotheca fuliginea Test (Gherkin)/Protective

(85) To produce a suitable preparation of active compound, the substance to be tested is homogenized in a mixture of acetone/Tween/water. The suspension is then diluted with water to the desired concentration.

(86) Gherkin plants (Vert petit de Paris cultivar) are sown in starter cups on 50/50 peat soil/pozzolana soil substrate and cultivated at 20° C./23° C. At the 2-leaf stage, the plants are sprayed with the preparation of active compound at the stated application rate.

(87) To test for protective activity, the plants are, after 24 h, sprayed with an aqueous spore suspension of Sphaerotheca fuliginea (100 000 spores/ml). The plants then remain at 20° C./25° C. and 60/70% relative atmospheric humidity.

(88) Evaluation is carried out 21 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.

(89) The table below shows clearly that the activity found for the active compound combination according to the invention is higher than the calculated activity, i.e. that a synergistic effect is present.

(90) TABLE-US-00033 TABLE L Sphaerotheca fuliginea test (gherkin)/protective Application rate of active compound Efficacy in % Active compounds in ppm found* calc.** (1-1) 8 60 (6-2) boscalid 8 50 (1-1) + (6-2) boscalid (1:1) 8 + 8 98 80 *found = activity found **calc. = activity calculated using Colby's formula