CS244843B2 - Act synergistically! fungicidal agent - Google Patents

Abstract

The invention relates to a synergistic fungicidal composition containing a 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula I COOR /1/ where R represents an alkyl group with 1 to 6 carbon atoms, as one active ingredient and, as another active ingredient which forms a synergistic mixture with the active ingredient of the general formula X, a benzimidazole derivative of the general formula XI /11/ r ", where Rj represents a hydrogen atom or a group of the general formula /a/ The composition according to the invention is suitable for treating various plant cultures against numerous fungi, for example for treating seed sets or for treating plant parts.

Description

One type of active ingredients of the fungicidal composition according to the invention, methyl 3,5-dinitro-4·-chlorobenzoate and isopropyl 3,5-dinitro-4-chlorobenzoate and their activity against the fungi Alternaria clearaceae and Scleritinia frueticola are known from US patent specification number 2,841,522. Compounds of general formula II are also known, the method of preparation and fungicidal action of systemic fungicides of general formula II are known from US patent specification numbers 3,631,176 and 3,657,443.

The contact action of 3,5-dinitro-4-chlorobenzoic acid esters on various sites is not used at all in practice, although these compounds are known. The main reason is probably the fact that although these compounds are very effective in field conditions, they damage the protected plant if used in optimal doses.

Therefore, when using them, the considerable risk of phytotoxicity must be taken into account. There are also problems with the use of systemic fungicides that have specific sites of action. Compounds of the general formula II, metabolizing methyl-/1H/benzimidazol-2-yl-carbamate, which falls within the scope of compounds of the general formula II, have excellent fungicidal activity from the outset.

However, after 1960, the literature increasingly points to fungal resistance to these compounds, which develops after repeated use.

The resistance of fungi to the action of benzimidazoles is reported in the publication S. G. Georpoulés: Antifungal compounds in the publication Sisler: Development of Fungal Resistance to Fungicides, New York 1977, pp. 493 to 494.

There are 42 references in this publication to the development of mutational resistance to systemic fungicides with specific actions. If it is considered, regardless of the possibility of specific resistance, that the use of systemic fungicides has some advantages in controlling fungi, it would not be reasonable to exclude the use of these compounds from plant protection practice.

This is supported by the fact that the use of these fungicides, both now and in the future, is under constant control of experts. The extraordinary advantages resulting from the systemic properties cannot be overlooked. Therefore, research into solving the problems of resistance against these fungicides is becoming increasingly intensive.

This research effort is focused on the following tasks: preventing the development of genes with higher resistance; mitigating changes in the combination of strains with the pathogenic population; and mitigating the increase in resistance of strains in the current population.

Among the possible paths, it seems promising to identify and adapt to the technology of plant cultivation fungicide mixtures based on fungicides with certain specific modes of action. The result of this effort are combined fungicidal compositions of plant protection product manufacturers, for example Epidor ^R of Rohm and Haas Co. (containing by weight 10 4 benomyl and 62 4 mancozeb) or Trimidal ^R of Eli ar.d Lilly Co. (containing by weight 8 4 nuarimol and 32 4 maneb) and other similar compositions. Hungarian Patent No. 158 608 also relates to a composition containing 2,3-dihydroxy-6-methyl-1,4-oxathiin-6-carboxanilide, which has specific actions in a mixture with 8-hydroxyquinoline or its metal salt; this composition has various specific actions.

In the course of the research related to the present invention, the efficacy of the compounds of general formula I and then of mixtures of active ingredients was first investigated, with the aim of determining the utility of the compound of general formula I together with known systemic fungicides.

The efficacy of the compound of general formula I was investigated in a liquid medium with respect to 7 days of fungi at a concentration of 0.1 to 1,000 ppm of active substance, the results obtained are in Table 1.

Further research was carried out to determine the optimum weight ratio of the active ingredients in the fungicidal composition according to the invention and to determine the useful dose of this fungicidal composition. Surprisingly, it was found that the synergistic effect is manifested at a clearly defined weight ratio of the active ingredients.

The invention therefore relates to a synergistically acting fungicidal composition which contains, in addition to a 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula I, where R has the above-mentioned meaning, a benzimidazole derivative of the general formula IX, where R^ has the above-mentioned meaning, in a weight ratio of 1:2 to 14:1.

The derivatives of general formula I, one of the active ingredients of the synergistic fungicidal composition according to the invention, are esters of 3,5-dinitro-4-chlorobenzoic acid, whereby R in general formula I represents an alkyl group with 1 to 6 carbon atoms, preferably with 1 to 4 carbon atoms and especially a methyl or ethyl group.

A particularly preferred weight ratio of the compound of general formula I to the compound of general formula II is 1:2 to 6:1.

The application form of the composition can be adjusted depending on the substrate to which the fungicidal composition according to the invention is applied and the requirements of use. It can be a dressing in the form of a powder or suspension; a solid or liquid composition applied by spraying on the plant), an emulsifiable concentrate, a powder and the like.

For the preparation of the fungicidal composition according to the invention, liquid and/or solid carriers, auxiliaries and other additives may be used according to the formulation requirements and generally used in the production of plant protection compositions. The total active substance content in the composition may be 5 to 85% by weight.

Table 2 shows the results obtained on the basis of tests and concerning the most advantageous mixtures of compounds against given fungal species, the most advantageous synergistic ratios of active ingredients, average application doses with regard to the total content of active substances and the characteristics of the compositions for a given purpose of use.

Table 1

Fungal column growth values, ppm Alternaria solani Helminthosporiumturcicum Aspergillus- niger Colleto- trichome to the people- thianum Trichothecium roseum Methyl-3,.'5-dinitro-4- chloro benzoate 10-1 10-1 1-0.1 10-1 10-1 Ethyl 3,5-dinitro-4- Chlorobenzoate 1-0.1 10-1 1-0.1 10-1 10-1 n-Propyl-3,5-dinitro-4- chlor benaoate 1-0.1 100-10 1-0.1 10-1 1-0.1 Isopropyl-3,5-dinitro- -4-chloro benzoate 10-1 100-10 10-1 100-1 10-i tert-Butyl-3,5-dinitro- -4-chloro benzoate 100-10 100-10 10-1 1,000-100 100-10

ji-Amyl-3,5-dinitro-4-chloro benzoate n-Octyl-3,5-dinitro-4-chloro benzoate + continuation of table 1

000-100 1,000-100 >1,000 >1,000

100-10 >1 Ρθθ 1,000-100 >1,000 >1,000 >1,000

Methyl 3,5-dinitro-4chlorobenzoate

Ethyl 3,5-dinitro-4chlorobenzoate n-Propyl 3,5-dinitro-4chlorobenzoate

Isopropyl-3,5-dinitro-4-chlorobenzoate tert-Butyl-3,5-dinitro-4-chlorobenzoate n-Amyl-3,5-dinitro-4-chlorobenzoate n-Octyl-3,5-dinitro-4-chlorobenzoate +

Helminthosporium carbonum

100-10

100-10·

100-10

000-100

000-100 > 1,000 > 1,000

Fusarium graminearum

AND

10-1

100-10

100-10

000-100

100-10 >1000 >1000 + Note:

Octyl ester was not studied further because its efficacy was insufficient.

Table 2

Type of mushroom Mixture Ratio of synergistically active substances Medium dose of active ingredients Formulation Anti-stain methyl-3,5-dinitro-4-chloro- Fusarium, Tillet- benzoate : methyl-1H-benz- those etc. imidazol-2-ylcarbamate 1:2 to 2:1 0.9 kg/t 30% pickling powder Fusarium spp. Methyl 3,5-dinitro-4-chlorobenzoate : methyl 1H-benzimidazol-2-yl-carbamate 3:1 to 5.7:1 1.0 kg/ha 70% WP ⁺

⁺ WP means wettable powder

An exceptional advantage of the composition according to the invention is that, during production and use, it enriches the range of pesticides with a new, highly effective composition, protecting a wide range of plants, polluting the biosphere less than known compositions, since it can be used in smaller quantities due to the synergistic action of the components. Another advantage is the fact that farmers do not have to give up well-known systemic fungicides, which they would slowly have to abandon due to the slowly developing resistance of fungi to these compositions.

The composition according to the invention and its fungicidal action are illustrated by the following practical examples, which, however, do not limit the invention in any way. Parts and percentages are always by weight unless otherwise stated.

Example 1

For the treatment of winter wheat seeds, a dressing containing a total of 30% of active ingredients in suspension is prepared using methyl-3,5-dinitro-4-chlorobenzoate /DNCB-Me/ together with methyl-1H'benzimidazol-2-yl-carbamate /CARBENDAZIM/ or 1-(4-chlorophenoxy)-1-(1H-1,2,4-triazol-1-yl)3,3-trimethyl-2-butanol /TRIADIMENOL/ in the mixtures shown in Table 3. The ratio of active ingredients is shown in Tables 4, 5 and 6.

Table 3

Active substance/mixture A B DCNB-Me 4- CARBENDAZIM 30%

DCNB-Me + TRIADIMENOL - 30% Ethylene glycol 7% 7% Cresulfoxmaldehyde condensation product 6% 6 S Film-forming polymer Mowilit DM-21 16% 16 » Antifoam agent Silicon SRB 1% 1% Dye Shodamin 2B4 2% 2% Demineralized water 38% 38%

The effectiveness of mixtures A and B is studied under laboratory and field conditions with regard to shoot diseases of winter wheat.

A portion of the seed of winter wheat MV 8 is heavily infected with Fusarium spp. and 0.2% by weight of Tillletia sporules before pickling. Grains infected with Fusarium spp. or Fusarium Sp. and Tillletia are picked with doses of the studied mixtures as shown in Tables 4, 5 and 6.

Seeds infected with Fusarium spp and stained are subjected to laboratory testing. For each treatment, 200 seeds are placed in Papaviza selective nutrient medium and incubated under diffuse lighting at 20 to 22 °C for 10 days.

The germination percentage is determined, then the percentage of infection with the fungus Fusarium spp. is evaluated under a microscope. 8 parallel tests are carried out and the results are shown in Table 4.

Table 4

Effectiveness against Fusarium

dose kg/t Germination Fusarium spp infection rate DNCB-Me + CARBENDAZIM % % 0.10 + 0.80 102.5 12.0 0.30 + 0.60 107.7 3.5 0.45 + 0.45 106.6 3.0 0.60 + 0.30 107.7 2.5 0.80 + 0.10 105.6 22.1 0.60 - 101.7 36.0

0.90 - 103.9 25.2 - 0.60 102.4 18.2 - 0.90 104.1 15.5 Untreated control 100.0 62.0 0.10 + 0.30 101.5 3.5 0.30 + 0.20 105.2 1.5 0.45 + 0.15 107.2 1.0 0.60 + 0.10 108.8 2.2 0.80 + 0.05 107.5 18.1 0.60 + - 101.7 36.0 0.90 - 103.9 25.2 - 0.30 103.3 10.5 - 0.40 103.8 8.5

untreated control 100.0 62.0

Seeds, infected with Tilletia, are tested in the field in plots measuring m in three parallels arranged randomly. Seeds are sown on 28 November in rows 12 cm apart at a rate of 60 g per plot» 150 seeds are sown with a 7-row drill in the third row of each plot for phytotoxicity evaluation.

This evaluation was carried out on 10 April of the following year to determine the number and height of the plants that had emerged and to assess the general impression that the plants made. The efficacy against Tilletia was assessed at harvest by examining each ear and determining the number of mature ears and ears infected with Tilletia. The mean values from the three plots are given in Tables 5 and 6.

Table 5

Phytotoxicity studies

Dose kg/t DNCB-Me + CARBENDAZIM Received /%/ Plant height 0.1 + 0.8 97.6 101.5 0.3 + 0.6 139.0 103.7 0.45 + 0.45 140.2 106.2 0.6 + 0.3 105.1 102.2 0.8 + 0.1 98.3 96.6 0.6 107.5 98.8 0.9. - 98.3 95.2 0.6 100.2 105.2 0.9 109.4 102.2 Untreated control 100.0 100.0

Dose kg/t DNCB-Me + TRIADIMENOL Received /%/ Plant height 0.1 + 0.3 105.0 100.5 0.3 + 0.2 127.4 108.0 0.45 + 0.15 145.5 108.6 0.6 + 0.1 106.4 102.3 0.8 + 0.05 99.4 99.5 0.6 107.5 98.8 0.9 - 98.3 Λ 95.2 0.3 100.2 105.2 0.4 111.5 104.5 Untreated control 100.0 100.0

244849

Table 6

Efficacy against Tilletia

Dose kg/t Healthy ears Infected ears

DNCB-Me + CARBENDAZIM piece/plot piece/plot 0.1 + 0.8 912.7 3.7 0.3 + 0.6 1 247.5 1.3 0.45 · t 0.45 1 311.2 1.7 0.6 + 0.3 1 147.8 .0.0 0.8 + 0.1 956.3 10.0 0.6 - 1 024.7 6.3 0.9 - 1 079.7 5.3 - 0.6 927.4 18.4 - 0.9 951.9 17.7 Check : infected with fungus Tilletia 804.7 151.7 Untreated control 933.0 14.0 Appendix 1 ad 2

To investigate the effectiveness against infection by the Fusarium fungus attacking winter wheat ears, a preparation is prepared according to Table 7 using methyl-3,5-dinitro-4-chlorobenzoate /DNCB-Me/ and methyl-1H-benzimidazol-2-yl-carbamate /CARBENDAZIM/, 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1H~ -1,2,4-triazol-1-yl)-2-butanone /TRIADIMEFON, 1-(2-/2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl^/-methyl-1H-1,2,4-triazole /PROPICONAZOLE/ and 1-(diphenyl-ys-trifluoromethyl/phenyl J-methyl-1H-1,2,4-triazole /FLDOTRIMEZOLE/ in the form of a wettable powder /WP/ containing

by weight 70 S active ingredients. Ratio active ingredients are listed in tables 8, 9, 10 and 11 Table 7 Component/content And /%/ B /%/ C /%/ D /%/ DNCB-Me + CARBENDAZIM /technical, purity 95%/ DNCB-Me + TRIADIMEPHONE 73.7 - - - /technical, purity 95%/ - 73.7 - - DNCB-Me + PROPICONAZOLE /technical, purity 95%/ DNCB-Me + FLUTRIMEZOLE - - 73.7 - /technical, purity 95%/ - - ' 73.7 Cab-O-Sil Synthetic Carrier 10 10 10 10 Dispersant Atlox 4862 3 3 3 3 Atlox 4995 Wetting Agent 3 3 3 3 Dispersant Polyphon 0 4 4 4 4 Kaolin carrier 6.3 6.3 6.3 6.3

Biological tests are carried out for winter wheat of the variety Jubilejnaya-5O on plots of 10 m^, with tests carried out on four plots each. Fungicidal treatment is carried out at a volume of 600 l/ha at the end of ear formation. The degree of infection with the fungus Fusarium spp. of the ears is assessed by examining 2 x 100 ears from each plot 10 days after spraying.

The yield of the plots is determined after harvest, a sample of the harvested grain is taken and the total level of infection of the grain with the fungus Fusarium spp. is assessed by examining 2 x 100 grains of the test crop microscopically after incubation in Papaviza medium at 20 °C for 8 days.

Preliminary surface disinfection is carried out in connection with the assessment of the level of internal infection. The results of these tests are presented in Tables 8, 9, 10 and li.

Table 8

Dose kg/ha DNCB-Me + + CARBENDAZIM Fusarium spp. infection rate /%/ Harvest weight kg/10 m ² Crow grain /total/ Grain /internally/ 0.85 + 0.15 0.20 6.50 4.25 6.55 0.80 + 0.20 0.50 8.20 6.50 6.42 0.75 + 0.25 1.00 9.50 7.00 6.44 - 0.25 7.30 18.20 15.25 6.11 - 0.50 6.50 16.00 11.75 6.01 0.9 5.00 13.25 11.50 6.10 1.8 4.25 11.50 11.50 3.13 Unseen control 11.50 38.75 31.25 5.52

Table 9 Rate kg/ha Fungal infection rate Fusarium spp. /%/ Weight DNCB-Me + Crow Grain ' Grain harvests + TRIADXMEFON /total/ /internally/ kg/10 ^m2 0.85 + 0.05 0.25 6.0 3.5 6.35 0.80 + 0.10 0.20 4.5 3.0 6.62 0.75 + 0.15 0.05 2 3 1.5 6.67 0.15 4.50 8.5 6.0 6.15 0.20 4.00 8.0 5.0 6.22 0.9. 5.00 13.25 11.5 6.10 1.8 4.25 11.50 11.5 3 13 Untreated control 11.50 38.75 31.25 5.52

Table 1 0 Rate kg/ha Rate fungal infection Fusarium spp. /%/ Weight DNCB-Me + Crow Grain Grain harvests + PROPICONAZOLE /total/ /internally/ kg/10 ^m2 0.85 + 0.15 5.0 9.0 5.0 6.45 0.80 + 0.20 3.5 4.5 3.5 6.42 0.75 + 0.25 1.0 15.5 3.25 6.15 0.25 7.0 14.5 18.5 5.75 0.30 6.5 12.5 15.5 5.90 0.9 5.0 13.25 11.5 6.10 1.8 4.25 11.50 11.5 3.13 Untreated control 11.50 38.75 31.25 5.52

Table 11

Dose kg/ha DNCB-Me + Fusarium spp. infection rate /%/ Weight Grain · /total/ Grain /internally/ harvest kg/10 m ^Z + PLUOTRIMEZOLE Crow 0.85 +0.15 3.5 9.5 8.0 5.95 0.80 + 0.20 2.5 6.0 7.0 6.05 0.75 + 0.25 1.5 6.5 7.5 6.15 0.25 6.5 15.5 12.5 5.85 0.50 9.0 19.0 16.0 5.62 0.9 5.0 13.25 11.5 6.10 1.8 4.25 11.50 11.50 3.13 Untreated control 11.50 38.75 31.25 5.52 OBJECT INVENTION 1. Synergistically acting a fungicide characterized by that on its total weight contains by weight 5 to 85% effective substances consisting of from a derivative of 3,5-dinitro-

-chlorobenzoic acids of general formula I

Claims (3)

Table 11 Dose kg/ha DNCB-Me + Fusarium spp. infection rate /%/ Weight Grain · /total/ Grain /internally/ harvest kg/10 m ^Z + PLUOTRIMEZOLE Crow 0.85 +0.15 3.5 9.5 8.0 5.95 0.80 + 0.20 2.5 6.0 7.0 6.05 0.75 + 0.25 1.5 6.5 7.5 6.15 0.25 6.5 15.5 12.5 5.85 0.50 9.0 19.0 16.0 5.62 0.9 5.0 13.25 11.5 6.10 1.8 4.25 11.50 11.50 3.13 Untreated control 11.50 38.75 31.25 5.52 OBJECT INVENTION 1. Synergistically acting a fungicide characterized by that on its total weight contains by weight 5 to 85% effective substances consisting of from a derivative of 3,5-dinitro- -chlorobenzoic acids of the general formula I where R represents an alkyl group with 1 to 6 carbon atoms and from a benzimidazole derivative of the general formula II /11/ «1 ° where R^ represents a hydrogen atom or a group of the general formula /a/ /a/ in a weight ratio of 1:2 to 14:1. 2. A synergistically acting fungicidal composition according to item 1, characterized in that it contains a compound of the general formula I, where R represents an alkyl group with 1 to 4 carbon atoms, especially a methyl or ethyl group. 3. A synergistic fungicidal composition according to item 1, characterized in that it contains a compound of general formula I, where R has the meaning given in item 1, and a compound of general formula II, where Rj has the meaning given in item 1, in a weight ratio of 1:2 to 6:1.