CS244843B2 - Synergeticaly effective fungicide agent - Google Patents

Abstract

The invention relates to a synergistically active fungicidal composition comprising a derivative 3,5-dinitro-4-chlorobenzoic acid of formula I COOR / 1 / wherein R is C 1 -C 6 alkyl as one active ingredient and as such another active compound which forms a synergistic mixture with the active compound of formula X, a derivative benzimidazole of formula XI / 11 / r ", where it means R 1 is a hydrogen atom or a group of formula (a) The composition of the invention is useful for treating a variety of plant cultures against multiple fungi, for example for pickling seedlings or for treating parts of plants.

Description

One type of active ingredient of the fungicidal composition of the invention, methyl 3,5-dinitro-4'-chlorobenzoate and isopropyl 3,5-dinitro-4-chlorobenzoate and their activity against fungi Alternaria clearaceae and Scleritinia frueticola are known from U.S. Pat. The compounds of formula (II) are also known processes for the preparation and the fungicidal action of systemic fungicides of formula (II) is known from U.S. Pat. Nos. 3,631,176 and 3,657,443.

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

Therefore, a considerable risk of phytotoxicity must be taken into account in their use. There are also problems with the use of systemic fungicides having specific sites of action. The compounds of formula II metabolizing methyl (1H) benzimidazol-2-yl-carbamate, which are within the scope of the compounds of formula II, have excellent fungicidal activity from the outset.

However, after 1960, there is increasing reference in the literature to the resistance of fungi to these compounds, which develop after repeated use.

Fungus resistance to benzimidazoles is reported in S. G. Georpoules: Antifungal compounds in Sisler: Development of Fungal Resistance to Fungicides, New York 1977, pp. 493-494.

There are 42 references in this publication to the development of mutational resistance to the action of systemic fungicides having certain specific actions. Taking into account, notwithstanding the possibilities of certain resistance, that the use of systemic fungicides has some advantages in combating fungi, it would be unreasonable to exclude the use of these compounds from plant protection practice.

This is supported by the fact that the use of these fungicides now and in the future is under constant control by experts. The extraordinary advantages resulting from the system properties cannot be overlooked. Therefore, research into resolving the problems of resistance to these fungicides has become increasingly sophisticated.

These research efforts focus on the following tasks: to prevent the development of genes with higher resistance; mitigating changes in the combination of strains with a pathogenic population and mitigating the increase in resistance of strains of the current population.

From the possible pathways, a mixture of fungicide-based fungicides with certain specific modes of action seems to be a promising discovery and adaptation for plant growing technology. These efforts have resulted in combined fungicidal agents from manufacturers of plant protection products such as Epidor ^R from Rohm and Haas co. (containing by weight 10 4 benomyl and 62 4 mancozeb) or Trimidal ^R from Eli ar.d Lilly Co. (containing 8 4 nuarimol and 32 4 maneb) and other similar compositions. Hungarian Patent Specification No. 158,608 also relates to a composition comprising 2,3-dihydro-6-methyl-1,4-oxathiine-6-carboxanilide having specific actions in admixture with 8-hydroxyquinoline or a metal salt thereof; this composition has various specific actions.

In the course of the investigations related to the present invention, the efficacy of the compounds of the formula I and then of the active compound mixtures was first examined in order to determine the usefulness of the compounds of the formula I together with known systemic fungicides.

The activity of the compound of the formula I was examined in a liquid medium with respect to 7 days of fungi at a concentration of 0.1 to 1000 ppm of active substance, the results obtained are given in Table 1.

Further investigations were conducted to determine the optimal weight ratio of the active ingredients in the fungicidal composition of the invention and to determine the useful dose of the fungicidal composition. Surprisingly, it has been found that the synergistic action is manifested at a clearly defined weight ratio of the active ingredients.

The invention thus relates to a synergistic fungicidal composition comprising, in addition to a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula I wherein R is as defined above, a benzimidazole derivative of the formula IX, wherein R 6 is as defined above, by weight ratio of 1: 2 to 14: 1.

The derivatives of 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 formula (I) represents an alkyl group having 1 to 6 carbon atoms, preferably C 1 -C 4 and in particular methyl or ethyl.

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

The dosage form of the composition may be adapted depending on the substrate to which the fungicidal composition of the invention is applied and the requirements of use. It may be a stain in the form of a powder or a suspension; solid or liquid spray applied to a plant) emulsifiable concentrate, powder and the like.

Liquid and / or solid carriers, auxiliaries and other additives may be used to prepare the fungicidal compositions of the present invention according to formulation requirements and used generally in the manufacture of plant protection products. The total active ingredient content of the composition may be 5 to 85% by weight.

Table 2 shows the results obtained from the tests on the most advantageous mixtures of compounds against a given fungal species, the most advantageous synergistic ratios of the components of the effective, medium application rates with respect to the total active substance content and the characteristics of the compositions for the intended use.

Table 1

Mushroom column growth values, ppm Alternaria solani Helmintho- sporium turcicum Asper- gillus- Niger Colleto- trichum lidomu- thianum Tricho- thecium roseum Methyl-3,5-dinitro-4- chlor benjjoát 10-1 10-1 1-0,1 10-1 10-1 Ethyl-3,5-dinitro-4- chloro benzoate 1-0,1 10-1 1-0,1 10-1 10-1 n-Propyl-3,5-dinitro-4- chloro 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

n-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> 1 000-100> 1 000> 1 000> 1 000

Methyl 3,5-dinitro-4-chloro benzoate

Ethyl 3,5-dinitro-4-chloro benzoate n-Propyl-3,5-dinitro-4-chloro benzoate

Isopropyl 3,5-dinitro-4-chloro benzoate tert-Butyl-3,5-dinitro-4-chloro benzoate n-Amyl-3,5-dinitro-4-chloro benzoate n-Otyl-3,5-dinitro -4-chloro benzoate +

Helminthosporium carbonum

100-10

100-10 ·

100-10

000-100

000-100> 1,000> 1,000

Fusarluai graminearum

AND

10-1

100-10

100-10

000-100

100-10> 1 ooo> 1,000 + Note:

The octyl ester was not further studied as its efficacy was insufficient

Table 2

Kind of mushroom Mixture The ratio of synergistically active substances Medium dose of active substances Formulation Mordant against methyl-3,5-dinitro-4-chloro- Fusarium, Tille- benzoate: methyl-1H-benzoate tia etc. imidazol-2-yl-carbamate 1: 2 to 2: 1 0.9 kg / t 30% pickling powder Fusarium spp. methyl 3,5-dinitro-4-chlorobenzoate: methyl 1H-benzimidazol-2-ylcarbamate 3: 1 to 5.7: 1 1.0 kg / ha 70% WP ⁺

⁺ WP means wettable powder

A particular advantage of the composition according to the invention is that it enriches the pesticide range with a new, highly effective plant protection agent that protects a broad spectrum of plants, polluting the biosphere less than known agents, 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 have to leave slowly because of the resistance of fungi to these slowly evolving agents.

The composition according to the invention and its fungicidal action are illustrated by the following examples, which are not to be construed as limiting the invention. Parts and percentages are by weight unless otherwise indicated.

Example 1

For the dressing of winter wheat seed, a mordant containing a total of 30% active ingredients in suspension is prepared using methyl 3,5-dinitro-4-chlorobenzoate (DNCB-Me) together with methyl 1H-benzimldazol-2-ylcarbamate (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 active ingredient ratio is given 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% Cresolfoxmaldehyde condensation product 6% 6 S Film-forming polymer Mowilit DM-21 16% 16 »Anti-foaming Silicon SRB 1% 1% Dye Shodamin 2B4 2% 2% Demineralized water 38% 38 %

The efficacy of mixtures A and B is studied under laboratory and field conditions with regard to the disease of autumn wheat shoots.

part of the autumn wheat seed MV 8 is largely infected with Fusarium spp. and 0.2% by weight Tllletia sporúles prior to pickling. Grains infected with Fusarium spp. or Fusarium Sp. and Tllletia are pickled with doses of the studied mixtures as shown in Tables 4, 5 and 6.

Seeds infected with Fusarium spp and stained shall be subjected to a laboratory test. For each treatment, 200 seeds are placed in Papaviza selective broth and incubated under diffuse illumination at 20-22 ° C for 10 days.

The percentage of germination, then the percentage of infection by Fusarium spp. is evaluated under a microscope. 8 parallel tests are always performed and the results are shown in Table 4.

Table 4

Effectiveness against Fusarium

dose kg / t Germination Infection rate of Fusarium spp 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 such Tilletia shall be tested in a field on m plots of land in three randomly arranged parallels. The seeds are sown on November 28 in rows of 12 cm at a rate of 60 g per plot »150 seeds are sown with a 7 seed drill in the third row of each plot to evaluate phytotoxicity.

This evaluation was carried out on 10 April of the following year to determine the number and height of the resulting plants and to assess the general impression of the plants. Efficacy against Tilletia is evaluated at harvest time by testing each ear and determining the number of mature ears and ears infected with Tilletia. The mean values of the three plots are given in Tables 5 and 6

Table 5

Phytotoxicity studies

Dose kg / t DNCB-Me + CARBENDAZIM Vzejití /% / 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 Vzejití /% / 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

Effectiveness against Tilletia

Dose kg / t Healthy ears Infected ears

DNCB-Me + CARBENDAZIM piece / land piece / land 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 a fungus Tilletia 804.7 151.7 Untreated control 933.0 14.0 Example 1 ad 2

To investigate the efficacy against Fusarium fungus attacking the wheat of late wheat, a formulation was prepared according to Table 7 using methyl 3,5-dinitro-4-chlorobenzoate (DNCB-Me) and methyl 1H-benzimidazol-2-ylcarbamate (CARBENDAZIM). 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone / TRIADIMEFON, 1f 2- (2,4-dichlorophenyl) - 4-propyl-1,3-dioxolan-2-yl-4-methyl-1H-1,2,4-triazole (PROPICONAZOLE) and 1- (4-diphenyl-5-trifluoromethyl) phenyl] 1-methyl-1H-1,2 4-triazole (FLDOTRIMEZOLE) in the form of a wettable powder (WP) containing

70% by weight of the active substances. Ratio of active substances is given in Tables 8, 9, 10 and 11 Table 7 Folder / Contents A /% / B /% / C /% / D /% / DNCB-Me + CARBENDAZIM / technical, purity 95% / DNCB-Me + TRIADIMEFON 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 Atlox 4862 dispersant 3 3 3 3 Wetting agent Atlox 4995 3 3 3 3 Polyphon 0 dispersant 4 4 4 4 Kaolin carrier 6.3 6.3 6.3 6.3

Biological tests shall be carried out in the case of winter wheat of the species Jubilejnaja-5O on plots of 10 m @ 3, the tests being carried out on four plots each. The fungicidal treatment is carried out at a volume of 600 l / ha at the end of the cob formation. Fusarium spp. ears are evaluated by examining 2 x 100 ears of each plot 10 days after spraying.

The yield of the plots is determined after harvesting, a sample is taken from the harvested grain and the total grain infection rate of Fusarium spp. by examining 2,000,000 grains of the culture to be examined microscopically after incubation in a Papaviza medium at 20 ° C for 8 days.

Preliminary surface disinfection is performed in conjunction with the assessment of the rate of internal infection. The results of these tests are shown in Tables 8, 9, 10 and 11.

Table 8

Rate kg / ha DNCB-Me + + CARBENDAZIM Fusarium spp. /% / Harvest weight kg / 10 m ² Ear grain /overall/ 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 Untreated control 11.50 38.75 31.25 5,52

Table 9 Rate kg / ha Sponge infection rate Fusarium spp. /% / Mass DNCB-Me + Ear Grain 'Grain harvest + TRIADXMEFON /overall/ /internally/ kg / 10 m ² 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. /% / Mass DNCB-Me + Ear Grain Grain harvest + PROPICONAZOLE /overall/ /internally/ kg / 10 m ² 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

Rate kg / ha DNCB-Me + Fusarium spp. /%/ Mass Grain · /overall/ Grain /internally/ Harvest kg / ¹⁰ M + PLUOTRIMEZOLE Ear 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 SUBJECT OF THE INVENTION 1. Synergically acting a fungicidal composition characterized by: that its total weight contains by weight 5 to 85% effective substances consisting of from 3,5-dinitro-

-chlorobenzoic acids of the formula I

Claims (3)

Table 11 Rate kg / ha DNCB-Me + Fusarium spp. /%/ Mass Grain · /overall/ Grain /internally/ Harvest kg / ¹⁰ M + PLUOTRIMEZOLE Ear 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 SUBJECT OF THE INVENTION 1. Synergically acting a fungicidal composition characterized by: that its total weight contains by weight 5 to 85% effective substances consisting of from 3,5-dinitro- - chlorobenzoic acids of the formula I wherein R represents a C 1 -C 6 alkyl group and a benzimidazole derivative of the formula II (II) where R R represents a hydrogen atom or a group of the formula (a) and in a weight ratio of 1: 2 to 14: 1. 2. A synergistically acting fungicidal composition according to claim 1, characterized in that. It comprises a compound of the formula I in which R represents a C1-C4 alkyl group, in particular a methyl or ethyl group. 3. A synergistic fungicidal composition according to claim 1, wherein the compound comprises a compound of formula I wherein R is as defined in point 1 and a compound of formula II wherein Rj is as defined in point 1 in a weight ratio of 1: 2 to 2. 6: 1.