CS244842B2 - Synergically acting fungicidal agent - Google Patents

Abstract

Synergistically acting fungicidal agent containing 5 to 85% by weight of its total weight of active substances consisting of a derivative of 3,5-dinitro-4-chlorobenzoic acid of the general formula where R represents an alkyl group of 1 to 6 carbon atoms and of dimenthyl-ΓΝ,Ν'-/1,2-ίβnylene-bis/thiocarbamoyl/ /bis/carbaroateU/J in a weight ratio of 1:2 to 14:1. The agent enriches the range of pesticides with a new, highly effective agent protecting a wide range of plants and polluting the biosphere less than known agents, since it can be used in smaller quantities due to the synergistic action of the components.

Description

The invention relates to a fungicidal composition containing a 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula X

/1/ where R represents an alkyl group with 1 to 6 carbon atoms, as one active substance and as another active substance which forms a synergistic mixture with the active substance of general formula I, dimethyl·'· [n,n'-/ i,2-phenylene-bis/thiocarbanoyl/ /bis/carbamate/J .

The composition according to the invention is suitable for treating various plant cultures against numerous fungal diseases, for example for treating seed sets or for treating plant parts.

One type of active ingredient 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 cleraceae and Sclerotinia fructicola are known from US patent specification number 2,841,522. The fungicidal activity of dimethyl-£n,n'-/1,2-phenylene-bis/thiocarbamoyl/ /carbamate/J is described in Hungarian patent specification number 169,823.

The contact action of 3,5-dinitro-4-chlorobenzoic acid esters on various sites is not used in practice at all, 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 significant risk of phytotoxicity must be taken into account.

There are also problems with the use of systemic fungicides that have specific sites of action. Dimethyl-[N,N--/ 1,2-phenylene-bis/thiocarbamoyl/ /-bis/carbamate/] metabolizing methyl-/1H/-benzimidazol-2-yl-carbamate, has had excellent fungicidal activity from the beginning. However, after 1960, the literature increasingly points to the resistance of fungi to this compound, which develops after repeated use.

The development of mutational resistance to the action of systemic fungicides having certain specific actions is known from the literature. For example, in the publication S. G. Georpoules: Antifungal Compounds and in the publication Sislfer: Development of Fungal Resistance to Fungicides /Vývoj odností hub proti fungicidem/, New York 1977, various literature on this problem is referred to.

If it is considered, regardless of the possibility of some resistance, that the use of systemic fungicides has some advantages in combating fungi, it would not be reasonable to exclude them from plant protection practice.

This supports the fact that the use of these fungicides at present and in the future is under constant control of experts. The extraordinary advantages resulting from the systemic properties cannot be neglected.' Therefore, research into solving the problems of resistance against these fungicides is increasingly intensive.

This research effort is focused on the following problems: 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, the identification and adaptation of fungicide mixtures based on fungicides with certain specific modes of action for plant cultivation technology seems promising.

The result of this effort is the combined fungicide products of manufacturers for the protection of gratings3 244842 β

lin, for example Epidor from Rhom and Haas Co. ./containing 10% by weight of benomyl o

and 62% mandozeb/ or Trimldal from Eli and Lilly Co. /containing 8% by weight of nuarimol and 32S maneb/ and other similar compositions.

Hungarian Patent No. 158,608 also relates to a composition containing 2,3-dihydro-6-methyl-1,4-oxathiin-6-carboxanilide, which has a specific action in a mixture with 8-hydroxychloroquine or its metal salt. This composition has various specific actions.

In the course of the research in connection with the present invention, the efficacy of the compounds of formula X and then of mixtures of active ingredients was first investigated. The aim of this research was to determine the utility of the compound of formula X together with known systemic fungicides.

The efficacy of the compounds of general formula X was investigated in liquid media with respect to seven species of fungi at a concentration of 0.1 to 1000 ppm of active ingredient. The results obtained are shown in Table 1.

Table 1

Altemaria solani Helminthosporiumturcicum Aspergillus- niger Colleto- trichome cute- thianum Methyl 3,5-dinitro-4-chloro benzoate 10-1 10-1 1-0.1 10-1 Ethyl 3,5-dinitro-4- -chloro benzoate 1-0.1 10-1 1-0.1 10-1 n-Propyl-3,5-dinitro-4- -chloro benzoate 1-0.1 100-10 1-0.1 10-1 Isopropyl-J,5-dinitro- -4-chlorobenzoate 10-1 100-10 10-1 100-1 tert-Butyl-3,5-dinitro- -4-chloro benzoate 100-10 100-10 10-1 1,000-100 n-Amyl-3,5-dinitro-4- -chloro benzoate 1,000-100 1,000-100 . 100-10 > 1,000 n-O-octyl-3,5-dinitro-4- -chloro benzoate + > 1,000 > 1,000 > 1,000 > 1,000

continued table 1 Tricho- Helminth- Fusarium thecium sporium graminea- roseum carbon rum 10-1 100-10 10-1 10-1 100-10 100-10 1-0.1 100-10 100-10 10-1 1,000-100 1,000-100 100-10 1,000-100 100-10 1,000-100 > 1,000 > 1,000 > 1,000 > 1,000 > 1,000

+ Note: Octyl ester was not studied further as its efficacy was insufficient

Further research was carried out to determine the optimum weight average of the active ingredients in the fungicidal composition according to the invention in order 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 synergically acting fungicidal composition which contains, in addition to the 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula I, where R represents an alkyl group with 1 to 6 carbon atoms, dimethyl-[1,11'-[1,2-phenylene-bis(thiocarbamoyl)]-[bis(carbamate)] in a weight ratio of 1:2 to 14:1.

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

The preferred weight ratio of the compound of general formula I to dimethyl-[n,N'-[1,2-phenylene-bis]thiocarbamoyl]-bis]carbamate is 1:3 to 3:1.

The application form of the composition according to the invention can be adjusted depending on the substrate to which the fungicidal composition according to the invention is applied and according to the requirement 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, powder and similar forms.

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.

and

AND

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 compositions known from the prior art, since it can be used in smaller quantities due to the aynergic action of the components.

Another advantage is that farmers do not have to give up well-known systemic fungicides, which they would slowly have to abandon due to the slow development of fungal resistance to these agents.

The fungicidal composition according to the invention and its fungicidal action are illustrated by the following practical example, which does not, however, limit the invention in any way. The percentages are always by weight.

Example 1

For research on the effectiveness in the laboratory against damage to pea shoots by the fungi Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum, as well as for research on the influence on pea emergence in greenhouse conditions and in field conditions, a dispersion stain containing a total of 30% by weight of active ingredients is prepared using ethyl-3,5-dinitro-4· -chloro-benzoate /DNCB-Et/ together with dimethyl-N,N'- £/ 1,2-phenylene-bis-(thiocarbamoyl) /-bis/carhamate/J /thiophanate-methyl/.

The content of the components is given in Table 2, the weight ratios of the studied active substances are given in Tables 3, 4, 5 and 6. BR-52 peas are treated with fungicidal agents in a known manner.

Table 2

Content /%/

Components

DNCB-Et + thiophanate-methyl /technical, 96% by weight/ Dispersant 1494 Ethylene glycol

Polyvinyl alcohol Vinarol ST Antifoaming agent L051 Thodamine BSA 1150 Demineralized water

31.5

10.0

12.0

8.0

1.0

0.4

37.1

Antifungal efficacy studied in laboratory conditions by the agar diffusion method:

32 ml of aqueous potato agar medium and 8 ml of agar medium with a suspension of spores of the tested fungus are added to Petri dishes with a diameter of 15 cm. The agar medium contains three parts by weight of the culture medium with one part by weight of the spore suspension.

The concentration of the spore suspension is adjusted to 15 to 50 spores/ml in the field for microscopic inspection. Circular holes of 10 μm diameter are made on agar plates solidified on the plates.

0.2 ml of an aqueous mixture of a fungicidal agent is introduced into each hole by pipetting, the fungicidal agent containing the tested active substances in the amount and ratio according to the table. The cultures are incubated in a thermostat at a temperature of 25 to 26 °C and then the inhibitory effect on the fungal columns is evaluated by measuring the diameter of the inhibition zone. The results are shown in table 3.

244942

From Table 8 it is clear that at a concentration of 200, 300 and 400 ppm of a fungicidal composition containing DNCB-Et/thiophanate-methyl in a weight ratio of 1:3 to 3:1, much greater efficacy is achieved, especially against Fusarium graminearum, Rhizoctonia solanum and Trichothecium soreum, than could be expected with regard to the efficacy of the same doses of the active ingredients alone.

Table 3

Agar diffusion test Diameter of the inhibition zone in mm Ratio of active ingredients DNCB-Et : thio- phanate-methyl Total amount of active ingredients ppm Botrytis cinerea Fusarium graminearum Rhizoctonia solani Trichothecium roseum 1 : 3 200 13 9 10 12 1 : 1 200 14 10 12 14 3 : 1 200 14 11 11' 15 1 : 3 300 15 11 10 16 1 ; 1 300 16 10 12 17 3 : 1 300 15 11 13 17 1 : 3 400 16 9 11 16 1 : 1 400 17 9 12 16 3 : and 400 19 10 14 18 l ; 0 200 12 4 4 8 1 : 0 300 14 6 6 10 i : 0 400 16 7 7 11 0 ; 1 200 12 7 6 3 0:1 300 13 8 7 5 0 : i 400 15 9 7 8

The degree of infection of the stained seeds is also examined. under laboratory conditions: 200 seeds are placed in a sterile Petri dish on filter paper. After incubation at 18 °C for eight days, the number of seeds infected with pathogenic fungi and germs is determined.

The results are shown in Table 4, from which it is clear that the active ingredients DNCB-Et and thiophanate-methyl can inhibit the growth of pathogenic infection on seeds during incubation, while completely pathogenic germs in a free state are achieved only in the case of a mixture of DNCB-Et/thiophanate-methyl with a ratio of active ingredients of 1:1 to 3:1.

Table 4

Dose kg/t number of infected seeds out of 200 seeds

DNCB-Et + nat-methy: thiopha- L Alternaria spp. Ascochyta spp. Fusarium spp. Penicillium spp. 0.10 0.90 1.0 1.0 - 0.5 0.25 0.75 - - - 0.5 0.50 0.50. - - - - 0.75 0.25 - - - - 0.90 0.10 - - 1.0 1.5 0.75 - 2.0 2.5 3.0 3.0 1.00 - 1.0 1.0 - 2.0 - 0.75 1.5 1.5 2.5 3.5 - 1.00 1.0 1.0 2.0 2.5 not rubbed 12.0 8.0 5.0 9.0

The effect of dressings on the germination rate of peas is tested in a greenhouse. For this purpose, seeds of the pea variety BR-52 are treated with preparations containing DNCB-Et together with thiophanate-methyl in the weight ratios given in Table 5, and 100 of the treated seeds are sown in growing boxes filled with soil, each test being carried out four times. The seeds are covered with soil and the number of emerged plants is determined 7, 14 and 21 days after sowing. The results are given in Table 5.

Table 5

Dose kg/t Number of plants grown from 400 seeds Number of plants sprouted DNCB-Et + thlo- in the case of untreated phanate-methyl Day 7 Day 14 Day 21. checks, % 0.10 0.90 168 293 299 129.4 0.25 0.75 209 307 308 133.3 0.50 0.50 262 320 320 138.5 0.75 0.25 259 316 316 136.8 0.90 0.10 263 361 277 119.9 0.75 156 280 280 121.2 1.00 218 258 281 121.6 0.75 138 263 271 117.3 1.00 162 271 277 119.9 rteotreated 102 223 231 100.0 Although the differences in the number of plants from sown seeds are small, they are surprising differences when using the same doses of agents in a mixture and when using them individually. Mixtures containing active ingredients in 1:3 weight ratio up to 3:1 show clear synergistic the effect of the elements. For field test with pickling peas type BR-52 sows 2 for plots of land measuring 4 m and pro- There are always four parallel tests . A total of 200 peas are sown on April 3rd with a spacing of row 40 cm, with plant spacing 5 < cm and to a depth of 5 cm. The emerged plants are counted in in stage two up to four leaves 19. May. Exam results are listed in Table 6. Table 6 Dose kg/t Medium number - Percentage of plants that emerged DNCB-Et + emerged plants- with regard to number of sown thiophanate- lin seed control methyl piece/plot 0.10 0.90 145.5 72.7 113.5 0.25 0.75 148.2 74.1 115.6 0.50 0.50 151.2 76.6 119.5 0.75 0.25 153.0 76.5 119.0 0.90 0.10 146.5 73.2 114.3 0.75 - 142.5 71.2 111.2 1.00 - 144.8 72.4 113.0 0.75 139.5 69.7 108.8 1.00 140.2 70.1 109.4 untreated 128.2 64.1 100.0 Field trials achieved best results at a dose of 1 kg/t DNCB-Et/thiopha- nat-methyl in by weight ratio both components 1 : 3 to 3 : 1.

Claims (3)

Synergistic fungicidal composition, characterized in that it contains, by weight, from 5 to 85% by weight, of an active ingredient consisting of a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula I (1): R is C1 -C6 alkyl and dimethyl 1, N- (1,2-phenylene-bis) thiocarbamoyl (bis) carbamate) in a weight ratio of 1: 2 to 14: 1. 2. A synergistic fungicidal composition according to claim 1 comprising a compound of formula (I) wherein R is C1-C4alkyl, especially methyl or ethyl. 3. A synergistic fungicidal composition according to claim 1 comprising a compound of formula I wherein R is as defined in claim 1 and dimethyl 1, 1,2-phenylenebis / thiocarbamoyl / bis / carbamate / j in a weight ratio of 1: 3 to 3: 1.