CS244842B2 - Synergicaly effective fungicide agent - Google Patents

Abstract

A synergistic fungicidal agent containing on its total weight 5 to 85% by weight of active ingredient from a 3,5-dinitro-4-chlorobenzoic acid derivative acids of the formula wherein R is an alkyl group of 1 to 6 carbon atoms and dimentyl-ΓΝ, Ν '- / 1,2-benzylene-bis / thiocarbamoyl / / bis / carbaroateU / J in a weight ratio of 1: 2 to 14: 1. The product enriches the assortment of pestir ’ a new, highly effective means of protecting wide range of plants and polluting less than the known means, since it may be due to synergistic action use the ingredients in smaller quantities.

Description

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

(1) wherein R represents a C 1 -C 6 alkyl group as one active ingredient and as another active ingredient which forms a synergistic mixture with the active ingredient of formula (I), dimethyl, n, n ' phenylene bis (thiocarbanoyl) bis (carbamate) J.

The composition according to the invention is suitable for the treatment of various plant cultures against a number of fungal diseases, for example for seed dressing or for the treatment of plant parts.

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 cleraceae and Sclerotinia fructicola are known from U.S. Pat. No. 2 The fungicidal action of dimethyl-n, n '- [1,2-phenylene-bis (thiocarbamoyl)] (carbamate) J is described in Hungarian patent specification 169 823.

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 phytotoxioity must be taken into account when using them.

There are also problems with the use of systemic fungicides having specific sites of action. Methyl (N, N - [1,2-phenylene-bis (thiocarbamoyl) [(bis) carbamate]] metabolizing methyl (1H) -benzimidazol-2-ylcarbamate, has from the outset an excellent fungicidal action. However, after 1960, there is an increasing reference in the literature 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 in the literature. For example, G. Georpoules: Antifungal Compounds and Sislfer: Development of Fungal Resistance to Fungicides, New York 1977, refer to various literature on this problem.

Taking into account, notwithstanding the possibility of some resistance, that the use of systemic fungicides systemic has some advantages in combating fungi, it would not be wise to exclude them 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 merits of systemic properties cannot be overlooked. ' Therefore, research into resolving the problems of resistance to these fungicides has become increasingly intensive.

This research effort is focused on the following problems: to prevent the development of genes with higher resistance; to mitigate changes in the combination of strains with the pathogenic population and to mitigate the increase in resistance of the strains of the current population. Among possible routes, it seems promising to find and adapt for plant growing technology with fungicide-based mixtures with certain specific modes of action.

These efforts have resulted in manufacturers' combined fungicidal agents for the protection of grates 244842 β

Lin, such as Rhidor and Haas Co. Epidor containing 10% by weight of benomyl

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

Hungarian Patent No. 158,608 also relates to a composition comprising 2,3-dihydro-6-methyl-1,4-oxathiine-6-carboxanilide having a specific action in admixture with 8-hydroxyquinoline or a metal salt thereof. Various specific actions.

In the course of the research in the context of the present invention, the efficacy of the compounds of formula (X) was first examined and then the active compound mixtures. The aim of this research was to determine the usefulness of the compound of formula X together with known systemic fungicides.

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

Table 1

Altemaria solani Helmintho- sporium turcicum Asper- gillus- Niger Colleto- trichum lindomu- 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-chloro benzoate 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-Octyl-3,5-dinitro-4- -chloro benzoate + > 1,000 > 1,000 > 1,000 > 1,000

continuation of Table 1 Tricho- Helmintho- Fusarium thecium sporium graminea- roseum oarbonum 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: The octyl ester has not been further studied since its efficacy was insufficient

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

Accordingly, the present invention relates to a synergistic fungicidal composition comprising, in addition to the 3,5-dinitro-4-chlorobenzoic acid derivative of the formula I, wherein R is C1-C6 alkyl, dimethyl-1,1'-l, 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 formula (I), one of the active ingredients of the synergistic-acting fungioid according to the invention, are esters in which R represents an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. and in particular methyl or ethyl.

Preferred is the weight ratio of the compound of formula (I) to 'dimethyl-N, N' - (1,2-phenylene-bis) thiocarbamyl (1-bis) carbamate (Q 1: 3 to 3: 1).

The dosage form of the composition of the invention may be adapted to the substrate to which the fungicidal composition of the invention is applied and to the requirement of use, such as a mordant in powder or suspension form; a solid or liquid spray applied to the plant; emulsifiable concentrate, powder and the like.

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

and

AND

A particular advantage of the composition according to the invention is that it enriches the range of pesticides with a new, highly effective composition protecting a wide range of plants, polluting the biosphere less than those known in the art because of the aynergic action of the components .

Another advantage is the fact that farmers do not have to give up well-known systemic fungicidal agents which they would have to leave slowly because of the fungus's resistance to slow-growing agents.

The fungicidal composition according to the invention and its fungicidal action are illustrated by the following non-limiting example. Percentages are meant by weight.

Example 1

In order to investigate efficacy in the laboratory against damage to pea shoots by Botrytis cinerea, Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum, as well as to investigate the effect on pea emergence under greenhouse and field conditions, a dispersant stain containing a total of 30 wt. % of active ingredients 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 active substances studied are given in Tables 3, 4, 5 and 6. BR-52 peas are pickled with fungicidal agents in a manner known per se.

Table 2

Content /%/

Folders

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

Polyvinyl alcohol Vinarol ST Antifoam L051 Thodamine BSA 1150 Demineralized water

31.5

10.0

12.0

8.0

1.0

0.4

37.1

Efficacy against fungi studied in laboratory conditions by diffusion method on agar:

In a 15 cm diameter Petri dish, 32 ml of an aqueous potato agar medium is added and 8 ml of agar medium with a spore suspension of the test fungus is introduced. The agar medium contains three parts by weight of the culture medium with one part by weight of the spore suspension.

The spore suspension concentration is adjusted to 15 to 50 spores / ml in the field for microscopic control. Round holes with a diameter of 10 mra are formed on agar plates solidified on plates.

0.2 ml of an aqueous mixture of the fungicidal composition is introduced into each opening by pipetting, the fungicidal composition containing the active compounds to be tested in the amounts and proportions indicated in the table. The cultures are incubated in a thermostat at 25-26 ° C and then the inhibitory action on fungal columns is measured by measuring the diameter of the inhibition zone. The results are shown in Table 3.

244942

It can be seen from Table 8 that at a concentration of 200, 300 and 400 ppm of a fungal composition comprising DNCB-Et / thiophanate-methyl in a weight ratio of 1: 3 to 3: 1, much greater efficacy is achieved especially against Fusarium gramlnearum, Rhizoctonia solanl and Trichothecium soreum than would be expected with respect to the efficacy of the same doses of the active ingredients themselves.

Table 3

Diffusion test on agar Diameter of inhibition zone in mm Active ingredient ratio DNCB-Et: thlo- phanate-methyl Overall amount of active substances ppm Botrytis cinerea Fusarium gramlnearum Rhizoctonia solani Trichothecium roseum 13 200 13 9 10 12 1 - 1 200 14 10 12 14 3 - 1 200 14 11 11 ' 15 Dec 13 300 15 Dec 11 10 16 1; 1 300 16 10 12 17 3 - 1 300 15 Dec 11 13 17 13 400 16 9 11 16 1 - 1 400 17 9 12 16 3: a 400 19 Dec 10 14 18 l; 0 200 12 4 4 8 It was 1 - 0 at the break 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 Dec 9 7 8

The degree of infestation of pickled seeds under laboratory conditions is also investigated: 200 seeds are each placed in a sterile petri filter paper tray. 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, and it is clear from Table 4 that the active ingredients DNCB-Et and thiophanate-methyl can inhibit the growth of a pathogenic seed infection during incubation, while perfectly pathogen-free germs are only achieved with the DNCB- Et / thiophanate-methyl with an active ingredient ratio of 1: 1 to 3: 1.

Table 4

Dose kg / t number of infected seeds from 200 seeds

DNCB-Et + nat-methy: thiopha- L Alternaria spp. Ascohyta 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 neoěe třeno 12.0 8.0 5.0 9.0

The greenhouse tests the effect of stains on the rate of emergence of peas. For this purpose, pea seeds of BR-52 species are pickled with preparations containing DNCB-Et together with thiophanate-methyl in the proportions given in Table 5, and 100 pickled seeds are each seeded in soil-cultivated flower boxes and tested four times. The seeds are covered with soil and the number of emerging plants determined 7, 14 and 21 days after sowing. The results are shown in Table 5.

Table 5

Dose kg / t Number of plants from 400 seeds Number of plants emerged DNCB-Et + thlo- in the case of untreated phanate-methyl 7th day Day 14 Day 21. controls,% 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 rteošetřeno 102 223 231 100.0 Any differences in the number of emerged Plants of sown seeds are small, they are surprising differences in the use of the same dosage of compositions in the composition and in their individual use. Mixtures containing active substances in weight ratio 1: 3 to 3: 1 show clearly synergistic effect of eložek. For field The test is stained pea type BR-52 seed 2 land with an area of 4 m and Four parallel tests are always performed . A total of 200 peas are sown on 3 April with a distance row 40 cm, with a plant distance of 5 < cm and to a depth of 5 cm. The outgrowth plants are counted in in stage two up to four sheets 19. May. Test results are given in Table 6. Table 6 Dose kg / t Medium count - Percentage of emerging plants DNCB-Et + emerging plants- with regard to number of sowed thiophanate- tench seeds control methyl piece / land 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 The field tests were achieved best results at a dose of 1 kg / t DNCB-Et / thiopha- nat-methyl ve 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.