HU190080B - Fungicide preparations of synergetic effect - Google Patents

Abstract

The invention relates to synergistic fungicidal compositions for the control of numerous types of fungi in different crops. The aim of the invention is to provide new combinations with stronger fungicidal activity and lower phytotoxicity, which are suitable to fight with less application rate and become resistant fungal stems. According to the invention, the new compositions contain 5 to 85% active ingredient in addition to conventional carrier, auxiliary and other additives. An active ingredient component is always a 3,5-dinitro-4-chloro-benzoic acid derivative of the general formula (I), the other active ingredient is dimethyl (N, N '- (1,2-phenylene-bis / thiocarbamate)) bis / carbamate /) or benzimidazole of the formula (II) or pyrimidinylmethanols of the formula III or 1,2,4-triazoles of the general formula (IV). In the formulas, for example: R is an alkyl group with 1 b. 6 carbon atoms; R deep 1 hydrogen or O = C-NH-C deep 4 H deep 9; R deep 3 and R deep 4 are the same or different phenyl group or halogen-substituted phenyl group; R deep 5 hydrogen, phenyl-phenoxy group u. al .; R 6 is hydrogen or substituted phenyl; R deep 7 phenyl group u. a. Formulas I to IV.

Description

FIELD OF THE INVENTION The present invention relates to synergistic fungicidal compositions which contain from 5 to 85% by weight of the total active ingredient, in addition to the usual vehicle, excipient and other additives for pesticides. One component of the active ingredient is in each case a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula (I) in which R 1 is a C 1-6 alkyl group and the other active ingredient is dimethyl {N, N'-. - [1,2-Phenylene-bis (thiocarbamoyl)] - bis (carbamate)} or benzimidazole of formula (II) or pyrimidin-1-yl-ethanol of formula (III) or 1,2,4- of formula (IV) triazole and the weight ratio of the active ingredient of formula I to dimethyl- {N, N '- [1,2-phenylene bis (thiocarbamoyl)] - bis (carbarnate)} is 1: 3-3: 1, The weight ratio of the active ingredient of the formula II to the amount of the active ingredient of the formula II is from 1: 2 to 6: 1 and from 1: 2 to 14: 1 to the amount of the active ingredient of the formula III or IV. In the formula (II), R 2 is the substituent group (a). In the formula (III), R3 and R4 have the same or different meanings and may be phenyl or halogen substituted phenyl. In formula (IV), R5 is hydrogen, phenyl, phenoxy, halo or phenyl substituted phenoxy or halo substituted benzyl, R6 is hydrogen or trifluoromethyl substituted phenyl, and R7 is phenyl or (b), (c), (d). ) and (e). These formulations may be used against a variety of fungal species in various plant cultures, according to the requirements of the particular application technique, e.g. seed dressing or crop management. Methyl and isopropyl ester of 3,5-dinitro-4-chlorobenzoic acid, an active ingredient of the fungicidal compositions of the present invention, is disclosed in U.S. Pat. No. 2,841,522. U.S. Pat. No. 4,198,198, discloses the fungicidal activity of these agents against Alternaria oleraceae and Sclerotinia fructicola. The effect of dimethyl {N, N '- [1,2-phenylene-bis (thiocarbamoyl)] - bis (carbamate)} fungicide is disclosed in U. S. Patent No. 169,823. The compounds of formula (II), (III) and (IV) having a multiple nitrogen heteroaromatic ring are also known.

The preparation of systemic fungicides of formula II and their fungicidal activity are described in U.S. Patent No. 3,631,176. and U.S. Patent No. 3,657,443. U.S. Pat. The active compounds of formula (III) are disclosed in U.S. Patent No. 1,218,623. British Patent No. 3,912,752; U.S. Pat. The so-called contact. multi-action 3,5-dinitro-4-chlorobenzoic acid esters, although known, have not yet been used in practice. The main reason we have found is that these compounds, which are highly effective in the field, often damage the plant to be protected at the optimum application dose, and have a high risk of phytotoxicity when used. There were problems with the so-called. systemic fungicides with specific activity. Dimethyl {N, N'-, which is metabolized to methyl 1 H -benzimidazol-2-ylcarbamate, is a compound of this general formula (II), (III) and (IV). [1,2-Phenylene bis (thiocarbamoyl)] - bis (carbamate)} were initially excellent fungicides.

However, since 1960, there have been increasing reports of fungal resistance to such compounds through repeated use.

Fungal resistance to benzimidazole-type fungicides is dealt with by Geórpoules, S.G .: Antifungal Compounds. In Development of Fungal Resistance to Fungicides. Sisler, New-York, 439-495. pp. (1977).

The same literature discloses an additional 42 sites on mutational resistance to systemic fungicides with other specific activity. Given that the use of systemic fungicides, despite the serious problems of resistance, has many advantages in terms of protection, it would be inappropriate to exclude them from practical plant protection. This is borne out by the fact that those skilled in the art, but more likely to use these fungicides in the future, do not want to give up the extraordinary benefits of systemic properties. Therefore, research into resolving resistance issues is increasingly underway.

Researches include delaying the development of higher resistance genes, modifying the change in pathogen population composition, and reducing resistance growth in a particular population. user in crop production technology. . ·

As a result of this research, combined fungicide formulations of pesticide companies, such as, for example, pesticides, have been produced. Rhom and Haas Epidor (10% benomyl + 62% mancozeb) or Eli Lilly Trimidal (8% nuariniol + 32% maneb) ... etc.

The specific composition of a combination of 2,3-dihydro-5-carboxanilide-6-methyl-3,4-oxathine and the multiple-action 8-hydroxyquinoline or its metal salt is disclosed in U.S. Patent No. 158,608. Hungarian patent specification.

In the first part of our research, we investigated the efficacy of compounds of formula (I) and then carried out experiments with 5 structural combinations. The purpose of the latter studies was to determine the utility of the compounds of formula I with a known systemic fungicide. The efficacy of the compounds of formula (I) was investigated in a liquid medium method at a concentration of 0.1-1000 ppm for 7 fungal species.

The results are summarized in Table 1 below.

Further studies were conducted to determine the optimum weight ratio of the active ingredient components of the compositions of the present invention and the effective dose of the compositions.

It has been surprisingly found in this work that a certain weight ratio of active ingredient components shows a synergistic effect. Based on the experiments, the combinations of compounds effective against particular fungal species, the synergistic drug ratios, the average application doses relative to the total drug content, and the specific serum forms suitable for the purpose are summarized in Table 2.

Table 1 Thresholds for fungal growth inhibition in ppm

Alternaria Helminthosporium Asper- Colletot- Tricho- Helmintho- Fusa- solani Helminthosporium gillus- richum thetium sporu riura turcicum Niger lindemu- roseum carbonum grami- thianum nearum

3,5-dinitro-4-chloro-benzoic acid acid methyl ester 10-1 10-1 1-0.1 10-1 10-1 100-10 10-1 3,5-dinitro-4-chloro-benzoic acid acid ethyl ester 1-0.1 10-1 1-0.1 1Ό-1 10-1 100-10 100-10 N-Propyl ester of 3,5-ditro-nitro-4-chloro-benzoic acid 1-0.1 100-10 1-0.1 10-1 1-0.1 100-10 100-10 I-Propyl ester of 3,5-nitro-4-chloro-nic acid 10-1 100-10 10-1 100-10 10-1 1000-100 1000-100 3,5-dinitro-4-chloro-benzoic acid acid tert-butyl ester 100-10 100-10 10-1 1000-100 100-10 1000-100 100-10 3,5-dinitro-4-chloro-benzoic acid acid n-amyl ester 1000-100 1000-100 100-10 > 1000 1000-100 > 1000 > 1000 3,5-dinitro-4-chloro-benzoic acid acid n-octyl ester > 1000 > 1000 > 1000 > 1000 > 1000 > 1000 > 1000

Table 2

Fungal species; Compound combinations: Synergistic All preparation form agent rates average dose of active ingredient dressing Fusarium, against Tilletia 3,5-Dinitro-4-chlorobenzoic acid methyl ester: methyl 1 H -benzimidazol-2-ylcarbamate 1: 2-2: 1 0.9 kg / t 30% film stripper Csévázés Fusarium, against Tilletia 3,5-Dinitro-4-chlorobenzoic acid methyl ester: 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol 1.5: 1 to 3: 1 0.55 kg / t 30% film dresser dressing Botrytis, Fusariuni Rhizoctonia, Trichothecium, etc. against 3,5-Dinitro-4-chlorobenzoic acid ethyl ester: Dimethyl- (N, N'11,2-Phenylene bis-thiocarb bamoyl)) -Bis (arm brownate)) 1: 1-3: 1 1.0 kg / t 30% film stripper Plasmopara destructor 3,5-dinitro-4-chloro-benzoic acid -n-propyl ester: :-( 2-chloro- 3: 1-5.7 + 1 1.0 kg / ha 50% WP

-phenyl) -C? C- (4-chloro-phenyl) -5-pyrimidin-ylmethanol

Table 2

Fungal species: Compound combinations: Synergistic All preparation form agent rates average dose of active ingredient Plasmopara viticola 3,5-Di nitro-4-chloro-benzoic acid i-propyl ester: c- (2,4-Dichloro-phenyl) -DC-phenyl-5-pyrimidin-yl-methanol 1.25: 1-4: 1 0.75 kg / ha 40 % by weight FW Fusarium spp. 3,5-Dinitro-4-chlorobenzoic acid methyl ester: methyl 1 H -benzimidazol-2-ylcarbamate 3: 1-5.7: 1 1.0 kg / ha 70 t% WP Fusarium spp. 3,5-dinitro-4-chloro-benzoic acid methyl ester: l- (4-chloro-phenoxy) - 3,3-dimethyl-l- (lH-l, 2,4-triamine zol-l-yl) -2-butanone 5: 1-8: 1 0.9 kg / ha 70 % by weight WP Fusarium spp. 3,5-Dinitro-4-chlorobenzoic acid methyl ester: 1,2 - [(2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-yl)] methyl-1H, 2 , 4-triazole 3: 1-4: 1 1.0 kg / ha 70 % by weight WP Fusarium ssp. 3,5-Dinitro-4-chlorobenzoic acid methyl ester: 1- (diphenyl) -3- (trifluoromethyl) phenyl (methyl-1H-1,2,4-triazole) 3: 1-4: 1 1.0 kg / ha 70 % by weight WP Venturia inaoqualis 3,5-Dinitro-4-chlorobenzoic acid methyl ester: 1,2- [2,4-dichlorophenyl) -4-ethyl-1,2-dioxolan-2-yl] methyl-1H-1 , 2,4-triazole 6.6: 1-12.5: 1 1.2 kg / ha 20 % by weight EC Venturia inaoqualis 3,5-Dinitro-4-chloro-benzoic acid methyl ester: 1- (4-phenyl-phenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) - 2-butanol 6.6: 1-12.5: 1 1.2 kg / ha 20 % by weight EC Venturia inaoqualis 3,5-dinitro-4-chloro-benzoic acid methyl ester A mixture of alpha- (2-chlorophenyl) -CC- (4-chlorophenyl) -5-pyrimidin-ylmethanol 6.6: 1-12.5: 1 1.2 kg / ha 20 % by weight EC Peronospora manshurica 3,5-dinitro-4-chloro-benzoic acid methyl ester: l- (2,4-dichloro-benzenesulfonic benzyl) -2,3-dimethyl-l- (lH-k, 2,4- triazol-l-yl) -2-butanol 1: 2-1.1: 1 2.1 kg / ha 70 % by weight WP Ustilago sp 3,5-dinitro-4-chloro-benzoic acid ethyl ester: alpha- (2-chlorophenyl) - -C? C- (4-fluorophenyl) -5-pyrimidine yl-methanol 2: 1-14: 1 1.5 q / t 40% Cartridge Remover Ustilago sp 3,5-dinitro-4-chloro-benzoic acid ethyl ester l- (4-chloro-phenoxy) - 2: 1-14: 1 1.5 q / t 40% Cartridge Remover

-3,3-Dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol was prepared according to the following table in the form of all active suspension film dressers in which the active ingredient ratios were 4, 5 and They are listed in Table 6.

The formulations of the present invention may be formulated for use according to the particular application and its requirements, and may be in the form of a powder or suspension dressing, a solid or liquid spray for crop management, an emulsifiable concentrate, a dusting agent, etc. Liquid and / or solid carriers, adjuvants and other additives, which are customary in the formulation and generally used in the pesticide formulation industry, are used to prepare the composition. The total active ingredient content of the preparation may vary from 5 to 85% by weight. The active ingredient is a compound of formula I wherein R is C 1-6 alkyl and dimethyl- {N, N '- [1,2-phenylene-bis (thiocarbamoyl)] - bis (carbonate)}. 1: 3-3: 1 or benzimidazole derivatives of formula II are used in 1: 2-6: 1 or pyrimidine-ylmethanol derivatives of formula (III) are used in 1: 2-14: 1 or (IV, or a 1,2,4-triazole derivative of the formula (II) in a weight ratio of 1: 2 to 14: 1 relative to one another In the formula (II), R 2 is a substituent (R 3 and R 4 are the same or different). In the formula (IV), R5 is hydrogen, phenyl, phenoxy, halogen or phenyl substituted with phenoxy or halogen, Re is hydrogen. Y is phenyl substituted with trifluoromethyl; and R7 is phenyl or (b) or (c) or (d) or (e).

A particular advantage of the compositions of the present invention is that, when they are manufactured and used, they are enriched with new, high-efficiency and broad-spectrum pesticides that are less contaminated with the biosphere due to their reduced application rate due to synergism. Another benefit is that farmers do not have to give up the use of systemic fungicides, which are well known but are slowly being eliminated due to resistance problems.

The compositions of the present invention and their fungicidal activity are illustrated by the following examples, without limiting the scope of the invention to the embodiments thereof.

Example 1 3,5-Dinitro-4-chlorobenzoic acid methyl ester (DNCB-Me) and methyl 1 H -benzimidazol-2-ylcarbamate (CARBENDAZIM) and 1- (4-) for winter wheat seed dressing using chlorophenoxy) -3,3-dimethyl-1- (111-1,2,4-triazol-1-yl) -2-butanol (TRIADIMENOL) to give 3-dimethyl-1- (111-1,2,4-triazol-1-yl) -2-butanol.

Table 3

Component / Composition THE. B DNCB-Me + carbendazim 30% - DNCB-Me + triadimenol - 30% ethylene glycol 7% 7% Cresolformaldehyde condensate Mowüit DM-21 Vinyl Acetate Vinyl Satate Tip. movie- 6% 6% forming copolymer Silicon SRE tip. silicone 16% 16% cinnamon oil antifoam Rhodamin 2B4 xantham 1% 1% tip. coloring 2% 2% Ion-exchanged water 38% 38%

The efficacy of formulations A and B against germicidal diseases of winter wheat was investigated under laboratory and field conditions.

A portion of MV 8 cultivated winter wheat seed heavily infected with Fusarium spp was infected with 0.2% stonewort spore prior to trimming. Seeds infected with Fusarium spp or Fusarium spp + rock spore were treated with the doses of test formulations shown in Tables 4, 5 and 6.

Laboratory examination with seeded seeds infected with Fusarium spp was performed by placing 200 seeds per treatment on Papvizas selective medium. The seeds were incubated at 20-22 ° C for 10 days in diffused light. Germination% was determined and microscopically assessed for Fusarium spp infection. The test was performed in 8 replicates, the mean results of the 8 replicates are shown in Table 4.

Seeds also infected with gout spore were plotted on 2 m plots in 3 replicates in a random block arrangement. The sowing took place on November 26 at a row spacing of 12 cm with 60 g / parcel seed. All parcels

150-150 seeds were planted in row 3 with a seeding bar to evaluate the phytotoxic effect. The phytotoxic effect was obtained on April 10 of the following year by determining the number, height and overall condition of the emerged plants. Anti-stone efficacy at full maturity was evaluated by examining each curd and determining the number of infected and healthy curds in the stone 611 gel. The average results for the 3 replicates are shown in Tables 5 and 6.

Untreated 100.0 100.0 control

Table 4

Effectiveness test against Fusarium

Dose kg / t DNCB-Me + KAR- BENDAZIM Germination)% % Fusarium spp infection 0.1 + 0.8 102.5 12.0 0.3 0.6 + 107.7 3.5 0:45 & 0:45 106.6 3.0 0.6 0.3 + 107.7 2.5 0.8 + 0.1 105.6 22.1 0.6 - 101.7 36.0 0.9 - 103.9 25.2 - 0.6 102.4 18.2 - 0.9 104.1 15.5 untreated 100 62

control

Dose in kg / t DNCB-triazolo Me + DIMENOL Germination% % Fusarium spp infection 0.1 + 0.3 101.5 3.5 0.3 0.2 + 105.2 1.5 0:45 & 0:15 107.2 1.0 0.6 + 0.1 108.8 2.2 0.8 + 0:05 107.5 18.1 0.6+ - 101.7 36.0 0.9 - 103.9 25.2 - 0.3 103.3 10.5 - 0.4 103.8 8.5 untreated 100 62 control

Table 5

Phytotoxicity test

DNCB-triazolo Me + DIMENCI. Dose in kg / t hatching% 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 95.2 - 0.3 100.2 105.2 - 0.4 111.5 104.5 untreated 100.0. 100.0

control

Table 6 Anti - stone 1 efficiency test DNCB-Me + CARBENDAZIM dose kg / t healthy ears db / plot infected ears db / plot 0.1 + 0.8 912.7 3.7 0.3 0.6 + 1247.5 1.3 0:45 & 0:45 1311.2 1.7 0.6 0.3 + 1147.8 0.0 0.8 + 0.1 956.3 10.0 0.6 - 1024.7 6.3 0.9 - 1079.7 5.3 - 0.6 927.4 18.4 - 0.9 951.9 17.7 Angle fit- 804.7 151.7 steamed con- roll untreated 933.0 14.0 control

DNCB-Me + ARM BENDAZIM Dose in kg / t Rising% Nővényma- 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

DMCB-Me + TRIADIMENOL dose kg / t healthy ears db / plot infected ears db / plot 0.1 + 0.3 957.7 10.0 0.3 0.2 + 1346.5 4.2 0:45 & 0:15 1439.3 0.0 0.6 + 0.1 986.1 3.0 0.8 + 0:05 1012.8 9.6 0.6 - 1024.7 6.3 0.9 - 1079.7 5.3 - 0.3 901.5 12.0 - 0.4 924.7 12.7 Angle infected control 804.7 151.7 untreated control 933.0 14.0

-713

The experiments show that the efficacy against Fusarium spp is 0.3 + 0.6 when compared to the individual DNCB-Me and CARBENDAZIM used in the laboratory; 0.45 + 0.45;

0.6 + 0.3 kg / t, i.e. 1: 2 to 2: 1 by weight. DMCB-Me + TRIADIMENOL screwdrivers, on the other hand, are 0.3 + 0.2; At a dose of 0.45 + 0.15 kg / t, i.e. 1.5: 1 to 3: 1 by weight, the active ingredients were more effective than the components expected. These treatments also improved the germination percentage. The number of plants hatched, the height of the plants, the number of cereals and the infection rates were also the most favorable in the field experiments.

Example 2

We investigated the hatching effect on germinating fungi against Botritis cinerea, Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum under laboratory conditions and under greenhouse and open field conditions of 3,5-dinitro-4-chlorobenzoic acid ethyl ester (DMCB- Et) and dimethyl- {N, N '- [1,2-phenylene bis (thiocarbamol)] - bis (carbamate)} (THIOPHANATE-METHYL) using 30% by weight of total dispersion plastic dispersion dressing agents.

The composition of the formulations is given in Table 7, and the weight ratios of the active ingredient tested are given in Tables 8, 9, 10 and 11, which contain the test results. BR-52 pea seedlings were treated with experimental fungicides in a known manner.

Table 7

Component composition:

DNCB-Et + THIOPHANATE-METHYL 31.5% (96% technical active ingredient)

Table 7

component Composition: The Great Permian Perm 1494 10% sulfonated cresol formal dehid cond. ethylene glycol 12% Vinarol ST poly (vinyl 8% alcohol) Defoamer L051 Fatty Acid- a mixture of diacids and fatty acids 1% Rhodamin BSA 1150 xantham 0.4% tip dye Ion-exchanged water 37.1%

Laboratory tests

The fungal efficacy test was carried out in a laboratory, so called. Agar diffusion was performed by placing 32 ml of aqueous potato agar medium in a 15 cm diameter Petri dish, and then layering 8-8 ml of nutrient agar infected with a test fungus spore suspension. The composition of the nutrient agar is 3 parts by weight of medium + 1 part by weight of a spore suspension. The concentration of the spore suspension was adjusted to 15-50 db / ml spore count per microscopic observation. In a Petri dish frozen agar plates were made into circular wells with a radius of 5 mm and pipetted with 0.2 ml of aqueous fungicide containing the test compounds in the amount and weight ratio of the test compounds. The cultures were incubated in a thermostat at 25-26 ° C and the growth inhibitory effect of the fungal colony was evaluated by measuring the radius of the inhibition zones (rings).

The results are shown in Table 8.

It can be seen from the table that the 1: 3 to 3: 1 weight ratio compositions of DNCB-Et: THIOPHANATE-METHYL at concentrations of 200, 300 and 400 ppm are particularly effective for Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum than for the efficacy of the same doses of each component. would be expected.

-815

Table 8

Greyhound diffusion assay

DNCB-Et: TIO- Total amount of FANAT-methyl active ingredient ratio ppm Inhibition zone radius Imm) Botritis cinerea Fusarium graminearum Rhizoctonia solani Tricho- thecium 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: 1 400 19 10 14 18 1: 0 200 12 4 4 8 1: 0 300 14 6 6 10 1: 0 400 16 7 7 11 0: 1 200 12 7 6 3 0: 1 300 13 8 7 5 0: 1 400 15 9 7 8 We also tested the infectivity of the dressed seeds under laboratory conditions. For this purpose, 200-200 pieces of dressed seeds were placed in a sterile Petri dish on wet filter paper and the seeds were After incubation for 18 days at 18 ° C, the number of pathogens infected was kept. The results of the test are given in Figure 9. Agreement in seeds spreadsheet

Table 9

Dose in kg / t DNCB-Et + Thiophanatemethyl Number of infected seeds based on 200 seeds Alternaria spp Ascohyta spp Fusarium spp Penicillium spp 0.1 0.9 1.0 1.0 - 0.5 0:25 0.75 - - - 0.5 0.5 0.5 - - - - 0.75 0:25 - - - - 0.9 0.1 - - 1.0 1.5 0.75 - 2 2.5 3.0 3.0 1 - 1.0 1.0 - 2.0 - 0.75 1.5 1.5 2.5 3.5 - 1 1.0 1.0 2.0 2.5 treatment 12.0 8.0 5.0 9.0 untreated

-917

From the table it can be seen that although DNCB-Et and thiophanate-methyl components were well inhibited during the incubation of the core infectious pathogens, only a 1: 1-3: 1 weight ratio of DNCB-Et: thiophanate-methyl combined resulted in complete pathogenicity.

Greenhouse test

The purpose of the study was to determine the effect of dressing agents on pea seed10.

blind hatching pace. Therefore, seeded BíÍ-52 pea seeds were seeded with formulations containing the weight ratios of DNCB-Et and thiophanate-methyl as shown in Table 10, and seeded with 100-100 grains of seeded seedlings in 4 seedlings prepared in garden soil.

The seeds were covered with soil and the hatched plants were counted on the 7th, 14th and 21st days after sowing.

The results of this study are shown in Table 10.

Dose in kg / t DNCB-Et + TIOFANÁT- -METHYL Number of plants sprouted from 400 seeds / pc % Of untreated plant hatched Day 21 7 days Day 14 Day 21 0.1 0.9 168 293 299 129.4 0:25 0.75 209 307 308 133.3 0.5 0.5 262 320 320 138.5 0.75 0:25 259 316 316 136.8 0.9 0.1 263 361 277 119.9 0.75 - 156 280 280 121.2 1 - 218 258 281 121.6 - 0.75 138 263 271 7.3 - 1 162 271 277 ' 119.9 treatment - 102 223 231 100.0

untreated

Although there is little difference in hatching rate, there is a surprisingly large difference between the similar doses of DNCB-Et THOPHANATE-METHYL combined and stand alone treatments. Synergistic effect of combinations containing the active ingredient in a weight ratio of 1: 3 to 3: 1.

Field investigation

Random block layout, 4 m ²

11th

plots were seeded with BR-52 seeded pea seed in 4 replicates.

The sowing took place on April 3 with a 40 cm row at 40 and 5 cm seedlings to a depth of 5 cm. A total of 200 seeds were sown. The emerged plants were counted on May 19, in their 2-4 true leaf stage.

The results are shown in Table 11 below.

spreadsheet

Dose in kg / t DNCB-Et + TIOFANÁT- METHYL Average number of plants hatched per piece / parcel Hatched plant% sown seeds quantity compared to relative to the control 0.1 0.9 145.5 72.7 113.5 0:25 0.75 148.2 74.1 115.6 0.5 0.5 151.2 76.6 119.5 0.75 0:25 153.0 76.5 119.0 0.9 0.1 146.5 73.2 114.3 0.75 - 142.5 71.2 111.2 1 '- 144.8 72.4 113.0 - 0.75 139.5 69.7 108.8 - 1 140.2 70.1 109.4 treatment - 128.2 64.1 100.0

untreated

-1019

In the field experiment, the most effective combinations were at 1 kg / L, 1: 3 to 3: 1 by weight combinations of DNCB-El: Thiophanate-Methyl.

Example 3

To test efficacy against Plasmopara destructor (onion mildew), 3,5-dinitro-4-chlorobenzoic acid n-propyl ester (DNCB-Pr) and α- (2-chlorophenyl) -oc- (4-chlorophenyl) -) - 5-Pyrimidin-yl-methanol (FENARIMOL) was prepared with 50% sprayable powder (WP) samples according to composition A and B in Table 12.

The biological experiment was carried out on random 500 m ² open field plots in 2 replicates. On 12 April we planted onions of the Aroma variety with 4.5 kg / ha of seed. The treatments were performed at the beginning of the exfoliation (July 21) and then two more at the exfoliation (July 29 and August 10), using a Maruyama air spray backpack with 500 l / ha water as indicated in Table 12. and B combined with the wind combinations according to Table 13 doses.

Table 12

COMPONENT / Composition THE B ionic dispersant Ultrazine Na lignin 6:25% sulfonate-Na-salt tip. dispersant Kaolin 29.37% 35.73%

Evaluation was carried out two weeks after the last spraying, with 10x10 plants per plot using a scale of 0 to 6.

The scale used to evaluate lonibi infection is as follows:

0 = no infection 20 1 = less than 5% infection

2 = 6-10% infection 3 = 11-25% infection 4 = 26-50% infection 4 = 51-75% infection 6 = 76-100% infection

During the evaluation, the percentage of infected plants (F%) was calculated for _{3Q of} all tested plants and the infectivity index (Fi) was determined using the formula below.

COMPONENT / Composition THE aixFi B 05 Fi = * --- in the formula: 95% technical 52.63% - Fi = infection index DNCB-Pr ai = individual infection scale values 98% Technical - 51.02% fi = for each of the infection scale values fenarimol 40 number of plants (frequency, Ultrasil VN3 10% 5% n = total number of plants tested synthetic silica Tensiofix BCZ alkyl 3% 2% The results of the study are shown in Table 13 polyglycol ether included. sulfate tip. wetting 45 wetting agent Disperser HG an- 5% -

Table 13

Dose in kg / ha Infection class

DNCB-Pr + fenarimol number of plants / pcs 0 1 2 3 4 5 6 F% Fi 0.9 + 0.1 11 34 32 6 10 7 0 89 1.91 0.85 0:15 + 14 41 32 9 3 1 0 86 1:49 0.8 0.2 + 29 38 ' 33 0 0 U 0 71 1:04 0.75 0:25 + 34 51 14 1 0 0 0 66 0.82 0.8 - 3 2 1 38 19 9 7 0 97 2:28 1.0 - 9 31 31 17 3 9 0 91 2:01 0.2 1 26 29 18 12 12 2 99 2.60 0.3 9 37 31 9 6 8 0 91 1.90 untreated 4 16 31 16 12 18 3 96 3:30

control

-1 121

It can be seen from the table that DNCB-Pr + FENARIMOL, taken in combination, minimized the onion peronospora infestation and that the most effective combination ratio for the application rate of 1 kg / ha is between 3: 1 and 5.7: 1.

Example 4

To test efficacy against Plasmopara viticola (grapevine mite), i-propyl ester of 3,5-dinitro-4-chlorobenzoic acid (DNCB-iPr) and α- (2,4-dichlorophenyl) -α-phenyl-5-pi- A series of aqueous suspension concentrates containing 40% by weight of total active ingredients was prepared using rhymidine-ylmethanol (TRIARIMOL) according to the composition shown in Table 14.

The drug weight ratios corresponded to the data in Tables 15 and 16 in the dose column.

Table 14

Coniponent / Composition by weight

DNCB Pr + TRIARIMOL 40.0%

Ethylene glycol 8%

Tensiofix XN 6 Ethoxylated Nonylphenol and Ethoxylated Nonylphenol Phosphate Ester Emulsifier 2%

Tensiofix CDS Ethoxylated Coconut Alcohol Emulsifier 1.5%

Pluriol PE 10 500 propylene oxyethylene oxide cond. emulsifier 2.5%

Silicon SRE Silicone Oil Antifoam 1.0%

Kolzan S xanthan gum tip. thickener 0.1%

Ion exchanged water 44.9%

The biological experiment was performed in a 20-year-old Italian Riesling solo breed of Lenz-Moser in two replicates.

The parcel is 180 ni ² , 60 capital, in series.

Fungicides were applied a total of 8 times (at 20-25 cm shoot development, at the beginning of flowering, at the beginning of flowering, at the end of flowering pea size, before 10 clusters, at the time of cluster closing and at the beginning of growth), Tee-Jet D-7 -Puch Haflinger sprayer with hand spray gun, 1000 l / ha water. Together with the experimental formulations, 3 kg / ha of Kolosul 80 WP sulfur preparation and 1.6 l / ha of Ekalux insecticide were added to the vegetation, which was ineffective against downy mildew.

The evaluation was carried out at the time of grape cluster growth20 on the basis of 4x50 clusters and 10x5 vines on treated plots. The untreated control was evaluated on a 2x10 capital assay. We determined the letter and the cluster infection and the extent of _the leaf and berry perzselödésének well. Using the method, scale and formula of Example 3, F% and Fi were calculated. The results are summarized in Tables 15 and 16.

Table 15

Leaf contamination test

DNCB-iPr- Number of infections class / pc Burn rate%

TRIARIMOL250

dose kg / ha 0 1 2 3 4 5 6 F% Fi 0.8 + 0.1 22 26 2 0 0 0 0 56 0.60 10.3 0.6 + 0:15 44 6 0 0 0 0 0 12 0:12 0 0.5 0.2 + 50 0 0 0 0 0 0 0 0 0 0.4 0.3 + 50 0 0 0 0 0 0 0 0 0 0.8 - 19 26 4 1 0 0 0 60 0.74 10.5 1.0 - 25 22 3 0 0 0 0 50 0.5g 15.2 - 0.5 40 9 1 0 0 0 0 20 0:22 0 0.7 42 8 0 0 0 0 0 16 0:16 0 Kezelet- 0 0 2 6 12 0 0 100 3.5 0

clen control

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Table 16

Cluster infection test

DNCB-Pr + triarimol dose kg / ha Number of clusters in infection class / pcs 6 F% Fi singeing% 0 1 2 3 4 5 0.8 + 0.1 158 8 25 9 0 0 0 21 0:42 10.1 0.6 + 0:15 180 4 16 0 0 0 0 10 0:18 0 0.5 0.2 + 184 4 12 0 0 0 0 8 0:14 0 0.4 0.3 + 182 16 2 0 0 0 0 9 0.1 0 0.8 - 98 12 20 42 28 0 0 51 1:45 8.3 1.0 - 112 24 29 20 15 0 0 44 1:01 15.7 - 0.5 118 23 20 29 10 0 0 41 0.95 0 - 0.7 153 19 14 11 3 0 0 23.5 0:46 0 Kezelet- 49 148 58 36 34 0 0 75.5 2:59 0

clen control

Studies have shown that the DNCB-iPr + TRIARIMOL 1.25: 1 + 4: 1 mass ratio! combinations, against single mite mite, at doses of 0.7 kg / ha at 25 doses were found to be effective beyond the expected total effect of each component.

EXAMPLE 5 Methyl 3,5-Dinitro-4-chlorobenzoic Acid Methyl Ester (DNCB-Me) and Methyl 35-Dinitro Wheat for Efficacy Test

Tab 17

11-Benzimidazol-2-ylcarbamate (CARBENDAZIM), 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone (TRIADIMEephon), 2- (2,4-dichlorophenyl) -4-propyl-1,3-dioxolan-2-ylmethyl-1H-1,2,4-triazole (PPOriOCONAZOLE) and 1- (diphenyl), Using the 3- (trifluoromethyl) (phenyl) methyl-1H-1,2,4-triazole (FLUOTRIMAZOLE), the sprayable powder (WP) compositions containing 70% by weight of the active ingredient were prepared according to Table 17, with They corresponded to the data in Tables 18, 19, 20 and 21.

Component / Composition THE B C D DNCB-Me + CARBENDAZIM (95% technical materials, 73.7 - - DNCB-Me + TRIADIMEFON (95% Technical Materials, - 73.7 - - DNCB-Me + PROPIKONAZOLE (95% Technical Materials) - - 73.7 - DNCB-Me + FLUOTRIMAZOLE (95% Technical Materials) - - - 73.7 Cab-O-Sil synthetic carrier 10 10 10 10 Atlox 4862 Naphthalene Sulfonate + Formaldehyde Con- Densate Na-salt dispersant 3 3 3 3 Atlox 4995 fatty alcohol polyglycol ether wetting agent 3 3 3 3 Polyphone O is a sodium lignin sulfonate dispersant 4 4 4 4 Kaolin carrier 6.3 6.3 6.3 6.3

The biological experiment was carried out on 10 m plots of Jubilee-50 winter wheat in 4 replicates. Fungicide treatment was carried out at the completion of the cereal digestion with 600 l / ha water. Fusarium spp. infections were evaluated 10 days after spraying on the basis of 2x100 ears per plot.

Harvesting yields of plots were determined, and an average of 55 seedlings were taken from the seedlings, from which total Fusarium spp. after incubation for 8 days at 20 ° C in Papavizas medium, the culture was examined with a microscope (pre-surface disinfection was used to assess internal infestation). The results of the test are given in Tables 18, 19, 20 and 21.

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Table 18

Application rate kg / ha DCNB-Ne + KARABENDAZIM % Fusarium spp infection Core (internal) Yield kg / 10 m ² ear Mag (all) 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 11:50 38.75 31.25 5:52

control

Table 19

Dose kg / ha DNCB-Me + TRIADIMEFON % Fusarium spp infection Harvest heaven. kg / 10 m ² ear Mag (all) Core (internal) 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 2.0 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 11:50 38.75 31.25 5:52 control Table 20

Application rate kg / ha DNCB-Me + propiconazole % Fusarium spp infection Harvest heaven. kg / 10 m ² ear Mag (all) Core (internal) 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 11:50 38.75 31.25 5:52 control Table 21 Application rate kg / ha Fusarium spp infection rate% Harvest heaven. DNCB-Me + FLUOTRí MAZOL ear Mag (all) Core (internal) kg / 10 m ² 0.85 0:15 + 3.5 9.5 8.0 5:59 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 11:50 38.75 31.25 5:52 control

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Example 6

Effect against Venturia inaepualis (apple scab) on 3,5-dinylro-4-chlorobenzoic acid methyl ester (DNCB-Me) and 2- (2,4-dichlorophenyl) -4-propyl-1,3 -dioxolan-2-ylmethyl-1H-1,2,4-triazole (PROPIKONAZOLE), 1- (4-phenylphenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole) -1-yl) -2-butanol (BITEROL) or k- (2-chlorophenyl) -oc- (4-chlorophenyl) -5-pyrimidin-ylmethanol (FENARIMOL) , emulsifiable concentrates were prepared according to Table 22, wherein the weight ratios of the active ingredient corresponded to the data in the dose column of Table 23.

Table 22

Component / Composition A B C

DNCB-Me + ETACONAZOLE 20%

DNCB-Me + BITERTANOL -. 20%

DNCB-Me + FENARIMOL - - 20%

Cyclohexanone solvent 20% - 40%

Xylene solvent 50% 38%

Atlox 4858 calcium alkylarylsulfonate and fatty alcohol ethoxylsum, amulge 3%

Atlox 8916 Ethoxylated sorbitan ester of fatty acids and resin acids, emulsifier 3.5%

Altox 4851 Calcium alkylaryl sulfonate and fatty alcohol ethoxylate, emulsifier 3.5%

Isophorone 3,3,5-trimeth-

methyl-cyclohexanone, solvent Tensiofix D-120 ethoxylated castor oil, 30% 5 emulsifier Tensiofix-AS ethoxylated nonylphenol + calcium dodecylbenzene sulfonate blend, 3.5% 10 emulsifier Tensiofix-B-7425 Calcium dodecyl into nolsulfonate + ethoxylated propylated nonylphenol, 3.5% 15 emulsifier HAN solvent, heavy 5.0% 30% aromatic hydrocarbon Arkopal NO80 ethoxylated - 30% 20 nonylphenol, emulsifier Emulsogen EL ethoxylated - 5.0% castor oil, emulsifier Sapogenate T-180 ethoxylated tributyl phenol, 1.5% 25 emulsifier - - 3.5%

The biological experiment was carried out on 0.5 ha plots in a 7.5 x 4.5 m bond with a 20-year-old Jonathan cultivated spindle cultivated in 2 replicates. Fungicide spraying was carried out during the vegetation period, at intervals of 1 to 2 weeks, using a Ker35 titox NA-10 sprayer equipped with a Tee-Jet nozzle at 1000 l / ha water. Evaluation of leaf infestation was performed twice, at the end of the first and second shoot growth, on the basis of determining the infection rate of 100 leaves per tree. Fruit infestation and scorch were evaluated before harvesting on 10 trees with 50 fruits per tree. The results are shown in Table 23.

Table 23

Application rate kg / ha DNCB-Me + etaconazole Levélfertőzöttség % 1. At the 2nd evaluation Fruit contamination% Fruit scorch%

1 +0.15 0 7.2 2.2 0 25.1 + 0.1 0 8.2 2.3 0 1:50 + 0075 1.4 9.8 2.7 10.5 + 1:50 - 14.6 32.3 12.5 10.7 2 9.5 9.5 10.2 20.4 0:15 10.4 28.5 5.0 0 0.2 9.3 26.4 4.7 10.0 untreated control 27.4 62.6 41.5 0

-1 529

Dose kg / ha DNCB-Me + BITERTAN Levélfertözöttség OL% Fruit contamination% Fruit scorch% First when ratings Second 1 +0.15 0 5.3 1.9 0 1:25 & 0:10 0 8.0 2.2 0 1:50 + 0075 5.1 11.2 2.7 10.0 1.50 - 14.6 32.3 12.5 10.7 2 9.5 9.5 10.2 20.4 0:15 5.3 21.5 3.8 0 0:20 5.9 19.9 2.8 11.1 untreated control 27.4 62.6 41.5 0 Application rate kg / ha DNCB-Me + + fenarimol 1 +0.15 0 5.5 2.1 0 1:25 & 0:10 0 6.3 3.2 0 1:50 + 0.75 2.3 9.5 2.3 10.8 1.50 - 14.6 32.3 12.5 10.7 2.0 - 9.5 9.5 10.2 20.4 0:15 6.8 22.4 4.6 0 0:20 7.2 18.6 3.1 11.3 untreated 27.4 62.6 41.5 0 control From the table it can be stated that Cab-o-Sil amorphous silica tested combinations 1.15-1.35 kg / ha dosage sulfur dioxide, synthetic DNCB-Me: ETACONAZOLE or a BI kus carrier 15% Or TERTANOL FENARIMOL 6.6: 1-12.5: 1 if- Netzer IS sulfosuk- for ponds color 35 zinnate, wetting agent 3% nergic effect, Venturia inaequalis. Dispersing with Ski haftalín sulfonate + dispersant 6% Example 7 Polyphone 0 Sodium

-lignin sulfonate, dispersant 6%

Peronospole for testing the efficacy against manshurica (soybean mildew) 3,5-dinitro-4-chlorobenzoic acid methyl ester (DNCB-Me) and 1- (2,4-dichlorobenzyl) -3,3-dimethyl Using a -1- (1H-1,2,4-triazol-1-yl) -2-butanol (DICLO-45 BENTRAZOLE), a sprayable powder (WP) of 70% pure active ingredient was prepared according to the composition shown in Table 24.

The weight ratios of the active ingredient were as in Table 25.

Table 24

Composition / Component

The biological experiment was carried out on a 1 ha plot of Ewans soybean. Fungicides were applied three times with the experimental preparations (at 40 cm height of soy, at the beginning of flowering and then in full bloom). Spraying was carried out with a RAH-14-K-10 50 field machine at 400 l / ha water. Evaluation was performed on the 16th day after the last spraying by boning 10x10 plants.

The result was calculated using the 55 scales and formulas in Example 3. Table 25 also shows the degree of scorch (leaf damage) found.

DNCB-Me + DICLOBENTRAZOLE 70%

-1 631

Table 25

Dose kg / ha DNCB-Me + DICHLOBENTRASE plants of the infection class number (pcs) 5 6 F% Fi singeing% 0 1 2 3 4 0.5 1.6 + 33 38 15 12 2 0 0 67 1:12 0 0.7 1.4 + 62 30 8 0 0 0 0 38 0:46 0 0.9 1.2 + 71 22 7 0 0 0 0 29 0:36 0 1.1 1.0 + 70 25 δ 0 0 0 0 30 0:35 3.6 1.3 0.8 + 27 42 16 11 4 0 0 73 1:23 10.6 1.3 + - 0 38, 30 16 10 6 0 100 2:16 9.0 2.1 - 11 33 25 21 10 0 0 89 1.86 17.6 1.6 22 29 21 18 9 1 0 78 1:36 0 - 2.1 37 26 15 15 7 0 0 63 1:29 7.9 untreated control 0 0 40 41 11 8 0 100 2.87 Bioavailability is 2.1 kg / ha fall- Ultrazino- NA sodium all active ingredients, 1: 2-1 , 1: 1 by weight -lignin sulfonate, ratio DNCB-Me: DICHLOBENTRAZOLE alkalmazó- dispersant - 6.0% soma. THE combination effective 25 Rhodoviol 14/120, poten- stability of outperforms the individual components li (vinyl alcohol) - 2.5% the same doses separately -Separate because effects Dextrin - 2.5%

SAT. Rhodamin BSA 1150

xanthan tip. coloring Example 8 30 components - 1:25%

Ustilago sp. (Powder Angle) for the study of 3,5-Dinitro-4-benzoic acid methyl ester (DNCB-Me) and DC- (2-chlorophenyl) -oc- (4-fluorophenyl) -5-pyrimidine- using 40% by weight of methyl methanol (NUARTIMOL) and 1- (4-chlorophenoxy) -3,3-dimethyl-1 H-1,2,4-triazol-1-yl) -2-butanol (TRIADIMENOL) all active ingredient-containing cartilage dressings were prepared according to Table 26. The weight ratios of active ingredient were as given in Table 27.

Table 26

Kompopens / Composition THE B DNCB-Me + nuarimol 40% - DNCB-Me + triadimenol - 40% Tinovetin B, wetting agent 2% - Disperser HG, Disp. agent 5% - Mowiol 30/88, Poly (vinyl alcohol, 4% - Horna Reines Milori Blau, paint copper phthalocyanine tip. 1.5% Kaolin Ultrasil VN3 Sodium 47.5% 40.25% aluminum silicate, synthetic carrier 5% Netzet IS sulfosuccinate, a wetting agent - 2.5%

GK-59 varieties of barley seed contaminated with experimental preparations were seeded 35 and then seeded in 50 m ² plots at 12 cm row depth and 5 cm deep in a random block arrangement. Exactly 150 seeds were planted on row 2 of each plot on a 2 m section. The total toxicity of fi40 was evaluated at 2-4 leaf stage development of barley by counting and measuring the height of 150-150 seedlings per 2 m section. The angiosperm infection at flowering time was assessed by 45 needles based on counts of gummy ears on the plots, and this was also checked by a spore pre-shaking scarf.

The results of this study are shown in Table 27.

Table 27

55 Dose kg / t hatched plant db Average height cm Infected ear db 60 DNCB-Et + + nuarimol 1 + 0.5 117.8 8.6 0 1:25 & 0:25 113.3 8.6 0 1:40 & 0:10 114.0 8.5 0 1.40 - 110.3 8.2 44 65 1.80 - 97.5 8.0 15.3 0.5 114.8 8.5 3.0 0.7 114.5 8.5 1.8

-1 733

untreated control 109.0 8.6 97.5 DNCB-ET + triadimenol 1 +0.5 118.5 8.3 0 5 1:25 & 0:25 119.3 8.7 0 1:40 + 0.1 118.1 8.4 0 1.40 - 110.3 8.2 44 1.80 - 97.5 8.0 15.3 0.5 115.4 8.3 4.3 10 0.7 115.0 8.1 0.5. untreated 109.0 8.6 97.5 control 15 THE combinations 1.5 kg / t dose.

2: 1-14: 1 DNCB-Et: NUARIMOL or TRIAD IMENOL in weight ratio completely suppressed cereal dust infestation. 20

Claims (3)

Patent Claim Point Synergistic fungicidal compositions comprising biologically active substances and solid or liquid carriers, preferably water, aromatic organic solvents, natural minerals, and surfactants, preferably anionic and / or nonionic wetting and / or dispersing agents, and antifoam, antifreeze and viscosity regulators, characterized in that they contain a total of 5-85% by weight of the active ingredient a) a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula (I) and dimethyl- {N, N '- [1, 1: 3] to 3: 1 by weight; 2-Phenylene bis (thiocarbamoyl)] bis (carbamate) or b) a 3,5-dinitro-4-chlorobenzoic acid derivative of formula (I) and a benzimidazole derivative of formula (II) in a weight ratio of 1: 2 to 6: 1; or c) a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula (I) and a pyrimidin-ylmethanol derivative of the formula (III) in a weight ratio of 1: 2 to 14: 1; or d) a 3,5-dinitro-4-chlorobenzoic acid derivative of formula (I) and a 1,2,4-triazole derivative of formula (IV) in a weight ratio (1: 2) to 14: 1; in formulas (I), (II), (III) and (IV): - R is C 1-6 alkyl, - R 2 is a substituent group (a), - R3 and R4 are the same or different and are phenyl or halogen substituted phenyl, - R5 is hydrogen, phenyl, halo or phenyl substituted phenoxy, halogen substituted benzyl, - Re is hydrogen, phenyl substituted by trifluoromethyl, R 2 is phenyl or (b) or (c) or (d) or (e). 3 drawing formulas