DD216375A5 - SYNERGISTIC FUNGICIDAL AGENTS - 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

Berlin, 4. 7 · 1984 AP A 01 H / 261 279.2% 518 12

Synergistic fungicidal agents

Field of application of the invention

The invention relates to synergistic fungicides in which a drug component is always a 3,5-dinitro-4-chlorobenzoic acid derivative of general formula (I)

COO-R

(I)

in which R is an alkyl group having 1 to 6 carbon atoms. The second active ingredient component is dimethyl-> H, H * - (1,2-phenylene-bls / thiocarbamoyl /) - biβ / oarbamate / J or a benzimidazole of the general formula ( II)

(II)

-C-OCH ₃

or a pyrimidinyl methanol of the general formula (III)

-9.7.840183970

C-OR A ₄

or a 1,2,4-triazole of the general formula (IV)

(IV)

and the second component behaves by weight in the second, such as 1: 2 to 14: 1. In the general formula (II), R _{1 is} hydrogen or the grouping (a)

QeO - Kfi - CjIq (a)

In the general formula (III), IU and R. have the same or different meaning and represent optionally halogen-substituted phenyl group. In general formula (IV), R _{5 is} hydrogen, phenyl or phenoxy, phenoxy or halo substituted benzyl , halo or phenyl , R 1 is hydrogen or trifluoromethyl substituted phenyl and t is phenyl or a group of formulas (c ), (d) or (e)

- C - O ₄ H ₉ - OH - O ₄ H ₉ 0 OH

(c) (d) (e)

wherein Rq is an alkyl group having 1 to 4 carbon atoms

stands· ' ,

' ^v -'^;'

The fungicidal compositions according to the invention can be used in various crops against numerous types of felt. The application is carried out according to the respective requirements and circumstances, for example by pickling the seed or treating the plants.

Characteristic of the bok ^ v ^ th technical It6 * s ^m '^> p ^ T ^>

Of the one component of the fungicidal composition according to the invention forming 3,5-dinitro-4-chloro-benzoic acid esters of the general formula (I) are the 3,5-dinitro-4-chloro-. benzoic acid methyl and isopropyl ester described in US Pat.: 2,841,522 as fungistatics against Alternaria oleraceae and Sclerotinia fructioola "The fungicidal action of the dimethyl- C N, N ^l - (i, 2-phenylene-bis / thiocarbamoyl /) rbis- (carbamate is * known from HU-PS 169 823.) Also known as the second component, a heteroaromatic ring containing a plurality of nitrogen atoms compounds of the general formulas ClI), (III) and (IV) are known.

The preparation and systemic fungicidal action of the compounds of the general formula (II) are known from US Pat. Nos. 3,631,176 and 3,657,443, relating to the compounds of the

General formula (XXX) reported in British Patent 1,218,623, on the compounds of general formula (XV), U.S. Patent 3,912,752 "the contact-effective, so-called" polyfunctional 3,5-dinitro-4-chlorobenzoic have, although they The main reason for this, as confirmed by our own experiments, is that even under field conditions very effective compounds in the optimal application dose often damage the plants protecting them, their use must be accompanied by danger The use of the so-called "systemic fungicides" which have a specific action (at a certain point) has also given rise to problems. The compounds of the general formulas (XX), (XXX) and (IV) ^e and also belonging to this group Dimethyl- "N ₁ N * - (1,2-phenylene-bis / thioearbamoyl / O-bis / carbamate / J, whose metabolite is the methyl-1H falling under the general formula (XX) -benzimidazol-2-ylcarbamate, were initially fungicidal active ingredients of excellent effect * Since 1960, however, more and more publications have appeared, which report that after repeated use, the fungi were resistant to these compounds · With the resistance of fungi to fungicides of Benzimidazole type is concerned with "G" Georpoules in antifungal compounds (in Development of Fungal Resistance to Fungicides, Sieler, New York, p. 439-495 / 1977 /). In the same publication, 42 other references are given about the mutational resistance caused by the action of the specific systemic fungicides. Since the use of the systemic fungicides, despite the serious disadvantages of resistance, has numerous plant protection advantages, it would be wrong These compounds are no longer available. Experts now expect the use of these fungicides even more for the future, because of their systemic properties

. ''Χ'

Benefits result · For this reason, the research is increasingly focused on the elimination of resistance ·

The topics of this research are: Delaying the formation of genes of greater resistance, slowing down the change in the rootstock of the pathogenic population, methods of delaying the propagation of the resistant strain in the given population. "Among the possible methods seems to be the combination of specific and multi-functional fungicides As a result of this research, the crop protection companies put on the market combined fungicides, for example the agent Epidor (10% by weight of Benomyl and 62% by weight) of the fungicides Wt.% Mancozeb) or the agent Trimidal (8 wt.% Nuarimol and 32 wt.% Maneb).

Combinations of the α-dihydro-S-carboxanilide-o-methyl-1-oxoamine attacking at a specific point and of the polyfunctional 8-hydroxychlnoline or its metal salt are described in HU-PS 158 608.

Object of the invention

The aim of the invention is the provision of new synergistic acting agents with strong fungicidal activity and low phytotoxicity.

Explanation of the essence of the invention

The invention has for its object to produce a combination of known fungicidal compounds, the synergistic

stjsohe has fungicidal activity and can be used to combat even resistant fungal strains «

In some experiments, the effect of the compounds of the general formula (I) was first investigated, then combinations were also carried out. The aim of the latter was to determine whether the compounds of the general formula (I) can be used together with known systemic fungicides Effectiveness of the compounds of the general formula (I) was investigated in liquid nutrient medium in the concentration range from 0.1 to 1000 ppm »The results are shown in Table 1«

Further investigations were carried out with the aim of finding the optimum weight ratio of the active ingredient components of the combination according to the invention. It was surprisingly found that a synergistic effect occurs at a certain weight ratio of the components.

The invention relates to synergistic fungicidal compositions which in addition to a 3t5-dinitro-4-chloro-benzoic acid derivative of general formula (I), wherein R is an alkyl group having 1 to 6 carbon atoms,

  "i"

(i) Dimethyl - ^ "N _# B" - (1,2-phenylene-bis / thiocarbamoyl /) bis-carbamate / J ₉

(ii) a benzimidazole derivative of general formula (II) wherein R _{1 is} hydrogen or group (a)

(iii) a pyrimidinylmethanol derivative of the general formula (III) wherein R and R * are the same or different and are phenyl or halo-substituted phenyl, or. /

Table 1 The colony growth inhibiting thresholds in ppm for 7 species of fungus

Thresholds in ppm 1000 1-0 * 1 Ooletotrichich Lindemudianum Trichothetium roseum Helmintho sporum carbonum 1000 Fusarium gramineum connection Age naria solani Helmetntho- Aspersporium gillus turcicum niger 1-0.1 10-1 10-1 100-10 10-1 3> 5-Dinitro-4-chloro-benzoic acid methyl ester 10-1 10-1 1-0.1 10-1 10-1 100-10 100-10 3,5-dinitro-4-ehlorobenzoic acid ethyl ester 1-0.1 10-1 10-1 10-1 1-0.1 100-10 100-10 3 9 5-dinitro-4-chloro-benzoic acid n-propyl ester 1-0.1 100-10 10-1 100-10 10-1 1000-100 1000-100 3> 5-dinitro-4-chloro-benzoic acid i-propyl ester 10-1 100-10 100-10 1000-100 100-10 1000-100 100-10 3, S-Dinitrö ^ -chloro-benzoic acid tert-butyl ester 100-10 100-10 1000 1000 1000-100 1000 1000 3,5-dinitro-4-chloro-benzoic acid n-amyl ester 1000-100 1000-100 1000 1000 1000 3 »N-octyl S-dinitro-4-chlorobenzoate 1000

Note: Since the octyl ester is not sufficiently effective, it has subsequently been disregarded. "

.- '· - 8th -

(iv) a 1,2,4-triazolene derivative of the general formula (IV) wherein Rc is hydrogen, phenyl or phenoxy, phenoxy or halogen substituted benzyl, or Rg is hydrogen or 5-trifluoromethylphenyl and R 'is phenyl or a phenyl group Grouping of the formulas (c), (d) or (e),

f% 'ft. - "Ft # ^ t on \ λ ^ JTI α-OH - H ⁴ \ O OH

(c) (d)

wherein Rg is an alkyl group having 1 to 4 carbon atoms, ₍

and the weight ratio of the active ingredient of the general formula (I) to the other active ingredients is between 1: 2 and 14: 1.

The one active ingredient of the synergistic fungicidal compositions according to the invention, the 3> 5-dinitro-4-chloro-benzoic acid derivatives of general formula (I) are esters whose formula R is an alkyl group having 1 to 6 carbon atoms Active ingredients of the general formula (I) are advantageous those in which R is an alkyl group having 1 to 4 carbon atoms, and particularly advantageous are those in which R is a methyl or ethyl group ·

In the compounds of the general formula (III), R 1 and R 3 are identical or different and represent a phenyl group or a phenyl group substituted by two halogens.

The compounds in which R and R are a halogen-substituted phenyl group in which halogen is advantageously chlorine and / or fluorine are advantageous.

In general formula (IV), Rc is hydrogen, phenyl, phenoxy substituted by phenoxy, phenyl or halogen, or benzyl substituted by one or two halogens, wherein halogen is preferably chlorine. Rg is hydrogen or trifluoromethylphenyl and R 'is phenyl or a moiety of the formulas (c), (d) or (e). In the grouping of the formula (d) the butyl group is advantageously a tertiary butyl group, in the grouping of the formula (e) Rg is an alkyl group having 1 to 4, advantageously 2 up to 3 carbon atoms ·

In the synergistic fungicidal compositions according to the invention, the weight ratio of the active ingredient of the general formula (I) to the other active ingredients is between 1: 2 and 14: 1.

Below this, the weight ratio of the compounds of general formula (I) to dimethyl- ^ N, N ^f - (1,2-phenylene-bis- / thiocarbamoyl /) - bis / thiocarbamate / J 7 is advantageously between 1: 3 and-3: i ; the weight ratio of the compounds of the general formula (I) to the compounds of the general formula (II) is advantageously between 1: 2 and 6: 1; that of the compounds of general formula (I) to the compounds of general formula (III) preferably between 1: 1 and 14: 1, the weight ratio of the compounds of general formula (I) to the compounds of general formula (IV) is advantageously between 1: 2 and 14: 1 ·

The active compound combinations according to the invention are formulated according to the respective application. The formulations may be dust or emulsion mordants, solid or liquid sprays suitable for treating the plant stock, emulsifiable concentrates, dusts, etc. For the preparation of the formulations, the carriers, diluents and auxiliaries customary in the practice of pesticide preparation are used for the respective purpose. The agents contain a total of 5 to 85% by weight of active compound.

The combinations which are effective for the individual types of fungi, the synergistic ratios of active ingredients, the dosage amounts related to the total active substance content and the characteristic formulation types suitable for the individual purposes are listed in Table 2.

Further investigations were carried out with the aim of finding the optimum weight ratio of the active ingredient components of the combination according to the invention. It was surprisingly found that occurs at a certain weight ratio of the components a synergistic effect.

The lower application rate resulting from the synergism has the advantage that the biosphere is less contaminated. It is also advantageous that agriculture does not need to forego the well-known systemic fungicides, which are, however, pushed into the background because of the resistance problems.

Table 2

fungi

Connection combinations Synergistic range

Total dose of active ingredient

formulation

Pickling against Fusarium, Tilletia etc.

3 »5-dinitro-4-chloro-benzoic acid. methyl ester and methyl-IH-benzimidazol-2-yl-carbamate

3 '5-Dinitro-4-chloro-benzoic acid methyl ester and 1- (4-chlorophenoxy) 3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol

1: 2-2: 1

0.9 kg / t

1.5: 1-3: 1 0.55 kg / t

30 S & Lges

Filmbeiz-

medium

Filmbeiz ·

medium

Pickling against Bo try ti β, Fusarium, Bhizocto · nia, Tricho thecium, etc.

Ethyl 3,5-dinitro-4-chloro-benzoate and dimethyl-1-N, -phenylenebis / thio-carbamoyl /) -bi s / carbamate / 3 1: 1-3: 1

1.0 kg / t

30 & Lges film-remover

Plasmopara destructor

3, S-dinitro ^ -chloro-benzoic acid npropylester and 0L- (2-Ghlorphenyl) - <X X 4-chlorophenyl) -5-pyrimidin-ylmethanol

3: 1-5.7: 1 1.0 kg / ha WP 50

Plasmopara viticola

3,5-dinitro-4-chloro-benzoic acid

propyl ester and ec- (2,4-bichlorophenyl) -1,25: 1-4: 1

6c- phenyl-5-pyrimidinyl-methanol 0.75 kg / ha FW 40

Fusarium spp «

3,5-dinitro-4-chloro-benzoic acid methyl

ester and methyl-IH-benzimidazole-2-3: 1-5.7: 1

yl-carbamate

1.0 kg / ha WP 70

Table 2 (continued)

Mushroom species compound combinations

Synergistic area

0 Total Fonsudo sis lation drug

Fusarium spp «

3 * S-Dinitro ^ -chloro-benzoic acid methyl ester and 1- (4-chlorophenoxy) -3 »3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-5: 1-8 : 1 butanone

3, ^ Dinitro-4-chloro-benzoic acid methyl ester and 1,2 - (/ 2,4-dichlorophenyl / 4-propyl-1,3-dioxolan-2-yl) -methyl-1H-3: 1-4: 1 1,2,4-triazole

Methyl 3,5-dinitro-4-chloro-benzoate and 1- (diphenyl) -3- (trifluoromethyl-phenyl) -methyl-1H-1,2,4-triazole 3: 1-4: 1

0.9 kg / ha WP 70

1.0 kg / ha WP 70

1.0 kg / ha WP 70

Yenturia inaequalis

Methyl 3,5-dinitro-4-chloro-benzoate and 1,2- (/ 2,4-dichlorophenyl / 4-ethyl-1,2-dioxolan-2-yl) -Hiethyl-1H-1,2,4-triazole

6.6: 1-12.5: 1 1.2 kg / ha EC 20

Methyl 3,5-dinitro-4-chloro-benzoate and 1- (4-phenylphenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol 6, 6: 1-12.5: 1

6.6: 1 to 12.5: 1

3,5-dinitro-4-chloro-benzoic acid methyl ester and et- (2-chlorophenyl) -K - (4-chlorophenyl) -5-pyrimidinyl-methanol

1.2 kg / ha EC 20 1.2 kg / ha EO 20

Table 2 (continued)

Types of felt Combination combinations Synergistic Total Fonitoring dose range Active substance

Peronospora 3> S-dinitro ^ -chloro-benzoic acid methylmanshurica ester and 1- (2,4-dichloro-benzyl) -3,3-

dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-

butanol

1: 2-1,1: 1 2.1 kg / ha WP 70

Ustilago spp.

3,5-dinit: ro-4-chloro-benzoic acid ethyl ester and oi- (2-chlorophenyl) -ec- (4-fluorophenyl) -5-pyrimidinyl-methanol 40% dust-2: 1-14: 1 1.5 stain kg / t

40%

ester and 1- (4-chlorophenoxy) -3,3-di-dust

methyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol 2: 1-14: 1 to stain 1.5 kg / t

AueführungsbeiBPiel

The agents according to the invention and their fungicidal action are illustrated in the following examples, but the invention is not limited to the scope of the embodiments.

example 1

For seed dressing of winter wheat are from 3 »5-Dinitro-4-chloro-benzoic acid methyl ester (DHOB-Me) and methyl-1H-benzimidazol-2-yl-carbamate (KARBENDAZIM) or · 1- (4-chlorophenoxy) · 3.3 -dime-thyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol (TRIADIMENOL) the compositions shown in Table 3 prepared * Each agent contains a total of 30 % active ingredient · The respective ratio of the two Active substances to one another are indicated in Tables 4, 5 and 6.

Table 3

Component composition in %

'' '·.' '::>,, - '' A B

DKCB-Me + KARBBHDAZIM 30 -

DNOB-Me + TRIADIMEHOL Ethylene glycol condensate of cresol and pormaldehyde fungicidal agent Mowilit DM-21 antifoam silicone SRE dye rhodamine 2B4 desalted water

In laboratory and field experiments, the effectiveness of agents A and B against the diseases of winter wheat occurring in the epidemic was investigated «

- 30 7 7 6 6 16 16 ¹ 1 2 ' 2 38 38

Winter wheat seed of the species MV 8, which grows strongly with Fusarium spp. was contaminated with 0.2% by weight of the spores of the stone fire before pickling »The control was only with Fusarium spp. · Seed was stained with the doses of the tested compounds given in Tables 4, 5 and 6 »

To investigate the Fusarium spp · infected seeds 200 grain ⁰ C 10 Sage incubated · in diffused light then were placed on selective Papavizas culture medium from each treatment * The culture media were then incubated at 20 to 22 was determined how much percent (based on the The infestation was also examined microscopically by Fusarium spp. The experiments were carried out with 8 repetitions and the average values of the 8 repetitions are given in Table 4.

Field experiments were carried out on 2-meter plots of wheat kernels, which were additionally infected by the spores of the stone fire. · Each attempt was repeated three times in the random block layout. · Sowing was done on the 26 · Novembe.r with a row distance of 12 cm and a seed quantity of 60 g / parcel "In the third row of each parcel, 150 seeds were sown with" seed strips "to assess the phytotoxic effect. · The phytotoxic effect was recorded on the TO · April next year by counting the number of accumulated plants, their condition and their overall condition were assessed · The effectiveness against the stone fire was judged at the time when the grains are still milky in the ears · Each ear was examined and determined how many percent of the fire affected and how many percent were healthy "The average results of the three repetitions are in the table 5 and 6 ·

Table 4

Efficacy against Fusarium

Dose kg / t DNOB-Me + CARBONDAZIM + 0.8 + 0.3 Germination % Infestation with fuaarium %    , ··. 3.5 0.1 + 0.6 + 0.2 102.5 12.5 1.5 0.3 + 0.45 + 0.45 107.7 3.5 1.0 0.45 + 0.3 + 0.1 106.6 3.0 2.2 0.6 + 0.1 + 0.05  107.7 2.5 18.1 0.8 - 105.6 22.1 36.0 0.6 - - 101.7 36.0 25.2 0.9 0.6 0> 3 103.9 25.2 10.5 - '' - ' 0.9 0.4 102.4 18.2 8.5 untreated control untreated control 104.1 15.5 62 Dose kg / t DNCB-Me + TRIADIMENOL 100.0 62 0.1 0 * 3 101.5 0.45 105.2 0.6 107.2 0.8 108.8 0.6 107.5 0.9 101.7 103.9 103.3 103.8 100

Table 5 0.6 0.3 Accumulated in percent of Plant height control 0.9 0.4 97.6 101.5 Investigation of phytotoxicity untreated control untreated control 139.0 103.7 Dose kg / t ONGB-Me + KARHENDAZIM Dose kg / t DNCB-Me + TRIADIMENOL 140.2 106.2 0.1 + 0.8 0.1 + 0.3 105.1 102.2 0.3 + 0.6 0.3 + 0.2 98.3 96.6 0.45 + 0.45 0.45 + 0.45 107.5 98.8 0.6 + 0.3 0.6 + 0.1 98.3 95.2 0.8 +0.1 0.8 + 0.05 100.2 105.2 0.6 0.6 - 109.4 102.2 0.9 0.9 100.0 100.0 ',. . 105.0 100.5 127.4 108.0 145.5 108.6 106.4 1O2i3 99.4, 99.5 107.5 98.8 98.3 95.2 100.2 105.2 111.5 104.5 100.0 100.0

Table 6 healthy ear pieces / parcel sick ear pieces / parcel 912.7 3.7 Efficacy against stone fire 1,247.5 1.3 Dose kg / t DNCB-Me + CARBONDAZIM 1,311.2 1.7 0.1 + 0.8 1,147.8 0.0 0.3 + 0.6 956.3 10.0 0.45 + 0.45 1,024.7 6.3 0.6 +0.3 1,079.7 5.3 0.8 + 0.1 927.4 18.4 0.6 951.9 17.7 0.9 - 804.7 151.7 0.6 933.0 14.0 0.9 Brand-infected control 957.7 10.0 untreated control 1,346.5 4.2 Dose kg / t DNCB-Me + TRIADIMBNOL 1,439.3 0.0 0.1 + 0.3 986.1 3.0 0.3 +0.2 1,012.8 9.6 0.45 + 0.45 1,024.7 6.3 0.6 +0.1 1,079.7 5.3 0.8 + 0.05 901.5 12.0 0.6 - 924.7 12.7 0.9 - 804.7 151.7 - · 0.3 933.0 14.0 0.4 Brand-infected control untreated control

Based on the experiments it can be stated that in the laboratory experiments compared to the separately applied active ingredients DNCB-Me and KARBENDAZIM the combination of both against Fusarium spp · in the application rates 0.3 + 0.6; 0.45 + 0.45; 0.6 + 0.3 kg / t, in the active ingredient ratios of 1: 2 to 2: 1 has a synergistic effect. In the case of stains with DNCB-He and TRIADIMENOL, on the other hand, the effect in the application rates was 0.3 + 0.2; 0.45 + 0.45 kg / t, d. H. in the ranges of 1.5: 1 to 3: 1 greater than the sum of the effects of the individual components · The effect of the treatment also increased the percentage of germination · In the plot experiments were number of accumulated plants, their amount, the number of their and their degree of infection in the case of the stated application rates and active ingredient ratios also best

Example 2

In order to investigate the effect against the germ-damaging fungi Botritis cinerea, Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum in the laboratory and the effect on the emergence of peas under the conditions of the greenhouse and under field conditions were determined using 3f5-Dinitro 4-chloro-benzoic acid ethyl ester (DNCB-Et) and dimethyl- / TΝ, Ν ^ Ο, 2-phenylene-bis / -thiocarbamoyl /) - bis / carbamate / _7 (TIOFANAT-METHYL) containing in total 30% by weight of active compound Mordant prepared on the basis of a plastic dispersion · The composition of the agents is given in Table 7, while the ratios of active ingredients and the results of Tables 8, 9, 10 and 11 emerge. The pea seed of variety BR-52 was pickled by the means in a manner known per se.

Table 7

Proportion in component% by weight »

DNOB-Et + TIOFANATE-METHYL

(96% technical active substance) 31 »5

Dispersant 1494 10

Ethylene glycol 12 Vinarol SIS. X polyvinyl alcohol) 8 Defoamer 1051 1

Rhodamine BSA 1150 0.4

desalinated water 37,1

laboratory tests

Efficacy against fungi was investigated in the laboratory by means of the so-called agar diffusion method. For this purpose, 32 ml of potato agar prepared with water were placed in Petri dishes of 15 cm diameter. A layer of 8 ml of nutrient agar infected with the spores of the test fungus was applied thereon. The nutrient agar consisted of 3 parts by weight of nutrient medium and 1 part by weight of spore suspension. The concentration of the spore suspension was adjusted with the microscope so that the number of spores in the field of view was 15 to 50 spores / ml in the solidified in the Petri dishes Agar plates were fitted with recesses of 5 mm radius. In these, 0.2 ml of aqueous fungicide were introduced with the pipette; the amounts of active compound and ratios go from the table · The cultures were in the thermostat at 25 incubated until 26 ⁰ C · Then, the inhibitory effect was on the growth of colonies by measuring the Hemmz, ones (rings) determined · The results are shown in Table 8 stated ·

From the table it can be seen that the combinations of DNCB-Et and TIOFANAT-METHYL in the ratio of 1: 3 to 3: 1

and in the concentrations of 200, 300 and 400 ppm, in particular against Fuearium graminearum, Rhizoctonia solani and Trichotheoium roseum, were much more effective than would be expected on account of the individual effects of the same doses of the components.

The degree of infection of the pickled seed was also examined under laboratory conditions. 200 μg of this were placed in sterile petri dishes on wet filter paper and incubated at 18 ^° C. for 8 days. The number of infected seeds was then determined. The results are summarized in Table 9 ·

Table 8

Investigation with the agar diffusion method

Drug Ratio DHCB-Et t TIOFANATE-METHYL Total conc. Ppm Radius of the zone of inhibition, Botrytis Fusarium cinerea gramine arum 9 Rhizoc tonia solani 6 Trichotheum roseum 1: 3 200 13 10 10 ₇ 12 1: 1 200 14 11 12 7 14 3: 1 200 14 11 11 15 1: 3 300 15 10 10 16 1: 1 300 16 11 12 17 3: 1 300 15 9 13 17 1: 3 400 16 9 11 16 1: 1 400 17 10 12 16 3: 1 400 19 4 H'" 18 1: 0 200 12 6 4 8th 1: 0 300 14 7 6 10 1: 0 400 16 7 - 7 11 0: 1 200 12 8th 3 0: 1 300 13 9 5 0: 1 400 ¹ 5 8th

Table 9

Dose kg / t DIGB-Et + TIOFAHATE-METHYL 0.9 Infected Grains Alternaria ST) T) » Grains from a total of 200 Ascohyta Pusarium Penicillium SPP · St) T) * ST) T) * - 0.5 0.1 0.75 1.0 -. 0.5 0.25 0.5 - - • - 0.5 0.25 - - 1.0 - 0.75 0.1 3.0 1.5 0.9 -.: · mm - - 3.0 0.75 - 2 2.5 2.5 2.0 1 0.75 1.0 1.0 2.0 3.5 -. 0.1 1.5 1.5 5.0 2.5 - untreated 1.0 1.0 9.0 12.0 8.0

From the table it can be seen that also the components DHCB or TIOPANAT-METHYL ensure a good protection against the propagation of the pathogens, but complete freedom from fungi only in the ratio of 1: 1 to 3: 1 prepared combinations of DHCB-Et and TIOPAHAT- METHYL can be achieved.

Try in the greenhouse

To determine the effect of the mordants on the puffing speed of peas, pea seed of variety BR-52 was dressed with pickling agents of the composition shown in Table 10 and then sown in four repetitions in seed boxes filled with garden soil and then with Earth covered * The accumulated plants were counted on 7, 14 and 21 days after sowing * The results are shown in Table 10 *

Table 10

Dose kg / t DNOB-Et + TIOFANATE-METHYL

from 400 grain accumulated plants, piece, on 7 · 14 · 21 «day

accumulated plants on 21 days, in % of control

0.01 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 0.75 259 316 316 136.8 0.9 o » ¹ 263 361 277 119.9 0.75 - 156 280 280 121.2 1 218 258 281 121.6 - 0.75 138 263 271 117.3 1 162 271 277 119.9 control 102 223 231 100.0

Although the difference in the tempo of casserole is only slight, the big difference between the combinations according to the invention and the effect of similar doses of the individual components is obvious. The combinations in the ratio 10 to 3 have a synergistic effect.

Field trial

Seeded peas of the BR-52 variety were sown on 4 m large plots in the arrangement of the random block on 3 April in a row distance of 40 cm, a plant distance of 5 cm and a sowing depth of 5 cm. each treatment was examined in 4 repetitions. · Aa 19 · May, when the plants had previously unfolded 2 to 4 foliage leaves (true leaves, ie no cotyledons), the plants were counted. The results are summarized in Table 11.

- 24 Table 11

Plots accumulated on a plot, dose kg / t avg. % DNOB-Et + TIOPANAT- Accrued on the on the METHYL plants, piece of seed control

based

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 mm 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 untreated 128.2 64.1 100.0

In the field trial, the best results in a ratio of 1: 3 to 3: 1 prepared combinations of DNCB-Et and TiOFANAT-METHYL in a total application rate of 1 kg / t.

Example 3

To investigate the effect against Plasmopara destructor (peronospora of the onion), 3,5-dinitro-4-chlorobenzoic acid n-propyl ester (DNCB-Pr) and o £ - (2-chlorophenyl) - <* .- (4 -chlorophenyl) -5-pyrimidinyl-methanol (FENARIMOL) 50 wt .-% sprayed powder (WP) prepared, which had the composition A and B indicated in Table 12. The experiments were on randomly arranged outdoor plots of size 500 m ² in 2 repetitions made. On 12 April, onion seed of the variety "Flavor ¹¹ " was sown in an amount of 4.5 kg / ha

Appearance of the flower heads (on 21 July) and then twice (on 29 July and 10 August) sprayed with a portable on the back spray device (Maruyama), the application rate was 500 l / ha and the means of in the Composition used in Table 12 indicated in the doses indicated in Table 13 ·

Table 12

Component, % AB

Technical DWCB-Pr (95%) 52.63 -

PENARIMOL, 98 & Lg -? 1.02

synthetic silicate Ultrasil VN3 10 5

Wetting agent Tensiofix BCZ (alkyl polyglycol ether sulfate) 3 2

anionic dispersant

Dispergator HG 5 -

Dispersant Ultrazine Na

(Lignosulfonate-Ha) - 6.25

Kaolin 29.37 35.73

Two weeks after the last spraying, 10 χ 10 plants were scored on each plot with the aid of a scale 0-6. The value scale used to indicate the level of infestation of the leaves was as follows:

0 no infestation

1 infestation less than 5%

2 infestations between 6 and 10 %

3 infestations between 11 and 25%

4 infestations between 26 and 50 %

5 infestations between 51 and 75 %

6 infestations between 76 and 100 %,

As part of the evaluation, the percentage of infested

Plants (F%) determined as a percentage of the total number of plants and also the so-called infestation index, the latter according to the following formula:

F ₁ infestation index a .. the respective scale value

f. the number of plants belonging to the respective scale value (frequency)

η total number of plants studied

The more effective the agent, the lower the F 1 value. The results are given in Table 13.

Table 13 Number of plants belonging to the scale values 0 1 2 3 4 5 6 34 32 6 10 7 0 F% Λ Dose kg / ha DKCB-Pr + FENARIMOL 11 41 32 9 3 1 0 89 1.91 0.9 0.1 14 38 33 0 0 0 0 86 1.49 0.85 0.15 29 51 14 1 0 0 0 71 1.04 0.8 0.2 34 24 38 19 9 7 0 66 0.82 0.75 0.25 3 31 31 17 3 9 0 97 2.28 0.8 - 9 26 29 18 12 12 2 91 2.01 1,0 - 1 37 31 9 6 8th 0 99 2.60 0.2 , 9 16 31 16 12 18 3 91 1.90 - 0.3 4 96 3.30 control

From the table it can be seen that by applying the

Combination of DNOB-Pr + PENARIMOL infestation by onion · perenospora could be reduced to a minimum value. At an application rate of 1 kg / ha, the most synergistic, most effective combination ratio is between 3: 1 and 5.7: 1 ·

Example 4

To test the efficacy against Plasmopara viticola (peronospora of the wine), 3-dinitro-4-chlorobenzoic acid i-propyl ester (DNCB-iPr) and ot ~ (2,4-dichlorophenyl) -OC-phenyl-5 The frame composition of these compositions is given in Table 14, while the active ingredient ratios are shown in Tables 15 and 16.

Table 14

component Share, % DNCB-iPr + TRIARIMOL 40.0 ethylene glycol 8.0 '/. Tensiofix Xn6, emulsifier 2 Tensiofix CD5, emulsifier 1.5 Pluriol PE 10500, emulsifier 2.5 Silicon SRE, antifoam agent 1.0 Kelzan S. 0.1 desalinated water 44.9

The biological experiments were carried out on 20-year Weinötöcken in Lenz -Moser education (variety: Italian Riesling) in two repetitions. On the 180 m large plots are 60 sticks in rows, with the fungi

ciden is sprayed a total of 8 times (when the shoots are 20 to 25 cm long, when the bud grape stretches, then at the beginning and towards the end of the flower; when the berries are as big as peas, then before the grapes become dense, when they are have been sealed, once again, and finally at the beginning of maturity.) Was used a provided with the spray head Tee-jet D-7 spray system Steyer-Puch-Haflinger with a hand spray gun · The water cost was 1000 l / ha. The sulfur preparation Koiosul 80 WP in an amount of 3 kg / ha, which was inactive against Peronospora, and the insecticide Ekalux in an amount of 1.6 l / ha were also used together with the preparations to be investigated.

The evaluation took place at the time of grape ripeness by examining 4 x 50 grapes and 10 χ 5 sticks from each treated plot. "The untreated control was evaluated on the basis of the examination of 2 χ 10 sticks. · The degree of infestation of foliage and grapes and also to what extent the leaves and grapes are gangrenous. In the manner described in Example 3, the percentage of infected plants (F%) and infestation index (F ₁ ) were calculated. The results are given in Tables 15 and 16.

As can be seen from Tables 15 and 16, the combinations of DNCB-iPr and TRIARIMOL prepared in ratios of active ingredients of between 1.25: 1 and 4: 1 are more effective against Perenospora of the wine at a rate of 0.7 kg / ha than on Because of the sum of the individual effects, that is, there is synergism.

Table 15

0.5 control degree of infestation 26 2 the leaves respective scale value 4 5 6 0 0 56 \ burned % Dose kg / ha DSCB-JLFr + TRIARBÄOL 0.7 Number of belonging 0 1 2 6 0 to the sticks 3 0 0 0 12 0.60 10.3 0.8 +0.1 22 0 0 0 0 0 0 0 0.12 0 0.6 + 0.15 44 0 0 0 0 0 0 0 0 · 0 0.5 +0.2 50 26 4 O 0 0 0 60 0 0 0.4 + 0.3 50 22 3 0 0 0 0 50 0.74 10.5 0.8 19 9 1 1 0 0 0 20 0.56 15.2 1.0 25 8th 0 0 0 0 0 16 0.22 O 40 0 2 0 0 0 0 100 0.16 0 42 0 12 3.5 0 0 6

Table 16

Dose ks / ha 0.5 control Infestation of Grapes 1 2 3 4 Scale- 6 21 0.42 burned 10.1 DHCB-iPr + TRIARIMOL 0.7 8th 25 9 0 5 0 10 0.18 % 0 Number of sticks belonging to the respective value 4 16 0 0 0 0 8th 0.14 0 0.8 + 0.1 0 4 12 0 0 0 0 9 0.1 0 0.6 + 0.15 158 16 2 0 0 0 0 51 1.45 8.3 0.5 +0.2 180 12 20 42 28 0 0 44 1.01 15.7 0.4 +0.3 184 24 29 20 15 0 0 41 0.95 0 0.8 182 23 20 29 10 0 0 23.5 0.46 0 1.0 98 19 14 11 3 0 0 75.5 2.59 0 112 148 58 36 34 0 0 118 0 153 49

example 5

In order to investigate the effect against the Fusarium infestation of the wheat ears, methyl 3-dinitro-4-chlorobenzoate (DNCB-Me) and methyl-IH-benzimidazol-2-ylcarbamate (KARBENDAZIM), 1 - (4-chloro) phenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone (! TRIADiMBPOlT), 1- (2- (2,4-dichlorophenyl) -4-propyl -i, 3-dioxolan-2-yl-methyl-IH-1,2,4-triazole (PEOPIKOITAZOLE) or 1-diphenyl- (3-trifluoromethyl) -phenyl-Htaethyl-1H-1,2,4-triazole (PLtJOTRIMAZOL), the total of 70 wt .-% active ingredient-containing spray powders of the composition indicated in Table 17 were prepared; The ratios of active ingredients are given in Tables 18, 19, 20 and 21.

The tests were carried out in four replicates on plots of 10 m surface with Jubilejnaja 50 winter wheat · The fungicidal treatment was carried out towards the end of the ear emergence with a water consumption of 600 l / ha · The infection of the ears by Pusarium spp · became 10 days after Spraying by examining 2 × 100 ears of each plot

Table 17

component

Proportion in wt .-% A B CD

DNCB-Me + KARBENDAZIM (95 # technical substances)

DNCB-Me + TRIADIMEFON '- (95% technical substances)

DNCB-Me + PROPIKONAZOLE (95 # technical substances)

DNCB-Me + FLUOTRIMAZOLE (95% technical substances)

synthetic carrier Cab-Ö-Sil

Dispersant Atlox 4862 wetting agent Atlox 4995

Dispersant Polifon 0 kaolin as carrier

73.7 -

- 73.7 - ~ -

- - '73,7 -

- - - 73,7

10 10 10 10

3 3 3 3

3 3 3 3

4 4 4 4 6,3 6,3 6,3 6,3

Table 18

Dose kg / ha DNCB-Me + CARBONDAZIM

Infestation by Pusarium spp · %

ears

Grains, insges grains, inner

Yield kg / 10

0.85 π h 0.15 0.20 6.50 4.25 6.55 0.8 H h 0.20 0.50 8.20 6.50 6.42 0.75 H h Ο * 25 1.00 9.50 7.00 6.44 - 0.25 7.30 18.20 15.25 6.11 -; .. 0.50 6.5 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

-33 Table 19

Dose kg / ha infested by Fuearium spp ·, % yield> DNOB-Me + ears grains grains, kg / 10 m 'TRIADIMEPON ineges · inner

0.85 + 0.05 0.9 0.25 5.0 0.9 3.5 6.0 3.5 6.35 0.80 + 0.10 1.8 0.20 3.5 1.8 2.5 4.5 3.0 6.62 0.75 + 0.15 control 0.05 1.0 control 1.5 2.0 1.5 6.67 0.15 Table 20 4.50 7.0 6.5 8.5 6.0 6.15 0.20 4.00 6.5 9.0 8.0 5.0 6.22 5.00 5.0 5.0 13.25 11.5 6.10 4.25 4.25 4.25 11,50 11.5 3.13 11,50 11,50 11,50 38.75 31.25 5.52 Dose kg / ha DNOB-Me + PROPIKONAZOLE Dose kg / ha DNCB-Me + PLUOTRIMAZOLE 0.85 + 0.15 0.85 + 0.15 9.0 5.0 6.45 0.80 + 0.20 0.80 + 0.20 4.5 3.5 6.42 0.75 + 0.25 0.75 + Q, 25 15.5 3.25 6.15 0.25 0.25 14.5 18.5 5.75 - 0.30 0.50 12.5 15.5 5.90 0.9 13.25 11.5 6.10 ^ 1.8 11 * 50 11.5 3.13 control 38.75 31.25 5.52 Table 21 9.5 8.0 5.95 6.0 7.0 6.05 6.5 7.5 6.15 15.5 12.5 5.85 19.0 .. 16.0 5.62 13.25 11.5 6.10 11,50 11,50 3.13 38fI5 31.25 5.52

The data in Tables 18 to 21 were obtained in the following way: "The crop yield of each plot was weighed at harvest. Throughput samples were taken from the wheat grains, from which 2 χ 100 grains were examined for Fusarium infestation. The scale on Papavizas agar cultures were incubated for 8 days at 20 ⁰ C and then examined under the microscope · To investigate the infestation of the inner nuclear clocks were first sterilized superficially from the outside ·

Example 6

To test the efficacy against the apple scab causative agent (Venturia inaequalis), ethyl 3-dinitro-4-chloro-benzoate (DB ^- CB-Me) and 1-2- (2,4-dichlorophenyl) * 4- ethyl-1,3-dioxolan-2-yl) -methyl * 1H-1,2,4-triazole (ETACONAZOLE), 1- (4-phenylphenoxy) -3 # 3-dimethyl-1- (iH-1,2 , 4 * -triazol-1-yl) -2-butanol (BITERTANOL) or · 0C- (2-chlorophenyl) * ⁰ C- (4-chlorophenyl) -5-pyrimidinyl-methanol (FENARIMOL) a total of 20 wt. The composition is shown in Table 22, the active ingredient ratios are shown in Table 23.

-.35 table 22

Component ^ ⁶¹¹ V

From v /

DNCB-Me + ETACONAZOLE 20 DNCB-Me + BITERTANOL - 20

DNCB-Me + PENARIMOL - 20 cyclohexanone as solvent 20-40

Xylene as solvent 50 38 emulsifier Atlox 4858 3 - - · ".

Emulsifier Atlox 8916 3,5 - Emulsifier Atlox 4851 3 »5 - -

Isoforon as solvent -30 emulsifier Tensiofix D-120 -3.5 emulsifier Tensiofix AS - 3,5

Emulsifier Tensiofix B-7425 - 5.0 Solvent (HAN) - - 30

Emulsifier Arkopal N080 - - 5.0 Emulsifier Emuisogen EL - - 1.5 Emulsifier sapogenate T-180 - - 3,5

The biological experiments were carried out on 0.5 hectares of plots of 20-year-old Jonathan apple trees planted at intervals of 7.5 x 4.5 m in two repetitions. The fungicides were applied at intervals of 1 to 2 weeks a total of 9 während during the growing season, for spraying was using a equipped with a tea-jet spray head sprayer Kertitox Na-10 use. The amount of water was 1000 l / ha · The infestation of the leaves was evaluated twice, towards the end of the first and towards the end of the second shoot growth, on 10 trees, 100 leaves of each tree were examined · The infestation of the fruit and the burns were determined on 10 trees before harvest, with 50 apples examined from each tree.

 The results are summarized in Table 23.

From the table it can be seen that at application rates of 1.15 to 1.35 kg / ha, the middle combinations DNCB-Me and ETACONAZOLE, or BITERTANOL or PENARIMOL in the drug ratio range of 6.6: 1 to 12.5 ϊ 1 against Venturia inaequalis show a synergistic effect «

From the table it can be seen that in amounts of between 1.15 and 1.35 kg / ha the investigated combinations in the active ingredient ratio range from 6.6: 1 to 12.5: 1 show a synergistic action against Venturia inaequalis.

- 37th Table 23

Dose kg / ha DNCB-Me + ETACONAZOLE 0.15 Infestation of the 1st evaluation, 0 0 Leaves 2. % Infestation of fruits % burned tests % 1 + 0.15 0.2 0 0 0 7.2 2.2 0 1.25 + 0.1 control 0 5.1 2.3 8.2 2.3 0 1.50 + 0.075 1.4 14.6 14.6 9.8 2.7 10.5 1.50 - 14.6 9.5 9.5 32.3 12.5 10.7 · 2 9.5, 5.3 , 6,8 9.5 10.2 20.4 10.4 5.9 7.2 28.5 5.0 O 9.3 27.4 27.4 26.4 4.7 10.0 27.4 Dose kg / ha DNCB-Me + FENARIMOL 62.6 41.5 ö DNCB-Me + BITERTANOL 1 +0.15 1 +1.5 1.25 + 0.10 5.3 1.9 0 1.25 + 0.1 1.50 + 0.075 8.0 2.2 0 1.50 + 0.075 1.50 - 11.2 2.7 10.0 1.50 - 2.0 - 32.3 12.5 10.7 ² , - 0.15 9.5 10.2 20.4 0.15 0.20 21.5 3.8 0 0.20 control 19.9 2.8 11.1 control 62.6 41.5 0 5.5 2.1 0 6.3 3.2 O 9.5 2.3 10.8 32.3 12.5 10.7 9.5 10.2 20.4 22.4 4.6 0 18.6 3.1 11.3 62.6 41.5 O

- 38 Example 7

To investigate the effect against Peronospora manshurica (the soybean peronospora) were prepared using 3i5-dinitro-4-chloro-benzoic acid methyl ester (DUOB-Me) and 1- (2,4-dichlorobenzyl) -3,3-dimethyl- 1 - (1H-1,2,4-triazol-1-yl) -2-butanol (DIKLOBENTRAZOL) a total of 70% by weight of active ingredient containing wettable powders (WP) of the frame formulation specified in Table 24 prepared · The ratios of the two active ingredients to each other are given in Table 25.

Table 24

Component share, %

DNGB-Me + DIKLOBENTRAZOL 70

synthetic carrier material Cab-o-Sil 15

Wetting agent Netzer IS 3

Dispersant SI 6

Dispersant Polifon 0 6

The experiments were carried out on soybean of the Ewans variety on a parcel of size 1 ha. The plants were treated fungicidally three times: for the first time when they were 40 cm high, then at the beginning of flowering and finally in bloom. For spraying, the device RAH-14-K-1Q was used, the water cost was 400 l / ha. For evaluation, 10 χ ΊΟ plants were scored 16 days after the last treatment. The result was calculated in the manner given in Example 3 Table 25 shows not only the results but also the degree of combustion (leaf damage) ·

Table 25

Dose kg / ha DNCB-He + DiKLOBBNTRAZOL Number of plants belonging to the respective scale value 0 12 3 4 5 6 38 15 12 2 0 0 η A burned % 0.5 + 1.6 33 30 8th 0 0 0 0 67 1.12 0 0.7 + ΐ, 4 62 22 7 0 0 0 0 38 0.46 0 0.9 +1.2 71 25 5 0 0 0 O 29 0.36 0 1.1 + 1.0 70 42 16 11 4 O 0 30 0.35 3.6 1.3 + 0.8 27 38 30 16 10 6 0 73 1.23 10.6 1,3 - 0 33 25. 21 10 0 0 100 2.16 9.8 2.1 - 11 29 21 18 9 1 0 89 1.86 17.6, 1.6 22 26 15 15 7 0 0 78 1.36 0 2.1 37 0 • 40 ^4T 11 8th O 63 1.29 7.9 control 0 100 2.87 , - ·

, , - 40 -

The biological effect is most favorable for a total active ingredient quantity of 2.1 kg / ha in the ratio DNCB-Me: DIKLOBENTRAZOL 1: 2 - 1.1: 1. The effect of the combination exceeds the sum of the individual effects of the components used in the same cans.

Example 8

To test the effectiveness against Ustilago βρ · (dust firing), methyl 3-dinitro-4-chloro-benzoate (DNCB-Me) and <X- (2-chloro-phenyl) -O- (4- fluorophenyl) -5-pyrimidinyl-methanol (UUARIMOL) or · 1 - (4- "chlorophenoxy) -3" 3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol ( TRADIMENOL) a total of 40 wt .-% active ingredient containing dry dressing of the frame composition given in Table 26 · The ratio of the active ingredients to each other is given in Table 27 «

The mordant was stained with GK-59 "barley seed infected with dust fires and then sown 5 cm deep in the random block array at a distance of 12 cm in a row of 5 cm" Sown a section of 2 meters exactly 150 grains. In order to evaluate the phytotoxic effect, in the 2-4-leaf stage, the plants accumulated from the 150 grains were counted and their height was measured. The infection with fire was assessed at flowering time due to the count of gangrenous ears. The result was controlled by germination experiments with the spores. The results are summarized in Table 27.

- 41 table 26

Component share, %

A B

DNOB-Me + NUARIMOL 40 DNCB-Me + TRIADIMENOL - 40.5 Wetting agent Tinovetin Dispersant HG Polyvinyl alcohol Mowiol 30/88 Horna Pure Milori Blue

kaolin

synthetic carrier Ultrasil VN3

Wetting agent Netzer IS Dispersant Ultrazine-NA Polyvinyl alcohol Rhodoviol 14/120

dextrin

Dye rhodamine BSA

2 5 - ul 5 - ' 4 - 1, 47 40,25 5 - 2.5 ml 6.0 - 2.5 - 2.5 - 1.25

Table 27 out of 150 seeds intersected. burnt ears Dose kg / t ran Height, cm piece DNGB-Me + NUARIMOL 117.8 8.6 0 1 + 0.5 113.3 8.6 0 1.25 +0.25 114.0 8.5 0 1.40 + 0.10 110.3 8.2 44 1.40 - 97.5 8.0 15.3 1.80 - 114.8 8.5 3.0 0.5 114.5 8.5 1.8 0.7 109.0 8.6 97.5 control DNCB-Me + TRIADIMENOL 118.5 8.3 O 1 +0.5 119.3 8.7 0 1.25 +0.25 118.1 8.4 0 1.40 + 0.1 110.3 8.2 44 1.40 - 97.5 8.0 15.3 1.80 - 115.4 8.3 4.3 - 0.5 115.0 8.1 0.5 0.7 109.0 8.6 97.5 control

At an application rate of 1.5 kg / t, the combinations with an active ingredient ratio of between 2: 1 and 14: 1 completely inhibited the attack with dust fires.

Claims (13)

Invention claim "·. 1 * Synergistic fungicidal agents »characterized in that they contain as active ingredient a 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula (I) COO-R wherein R is an alkyl group having 1 to 6 carbon atoms, and (i) Dimethyl - ^ "N * N * - (1, a-phenylene-bis / thiooarbamoyl /) - to / oarbamat / J _t (ii) a benzimidazole derivative of the general formula (II) wherein R _{1 is} hydrogen or the group (a), OeC - KH - Q ₄ Hg (a) (lii) a fyrimidinylmethanol derivative of the general formula (III) R ₃ C-OH < ^m > wherein R and R are the same or different and are phenyl or halogen-substituted phenyl, or (iv) a 1,2,4-triazole derivative of the general formula (IV) ; R wherein Rc is hydrogen, phenyl, phenoxy, phenoxy substituted by halogen or phenyl, halo-substituted benzyl, Rg is hydrogen, phenyl group substituted by urifluoromethyl group, Ry represents a phenyl group or a grouping of the formulas (c), (d) or (e), J f 0 OH wherein R _{8 is} an alkyl group having 1 to 4 carbon atoms, contain and the weight ratio of the active substances of the general formula (I) to dimethyl, N '- (1,2-phenylenebis / t-tococarbamoyl) bis-carbamate / _7 or one of the active compounds of the general formulas (II), (III) or (IV) between 1 : 2 lind 14: 1 lies · 2 "synergistic fungicidal composition according to item 1, characterized in that a total of 5 to 85% by weight of active ingredient, are contained 3 · Synergietisch fungicidal composition according to item 1, characterized in that in the general formula (I) R is an alkyl group having 1 to 4 carbon atoms, advantageously a methyl or ethyl group. 4. Synergistic fungicidal composition according to item 1, characterized in that in the general formula (III) Ro and Ri signify a halogen-substituted phenyl group and halogen is fluorine and / or chlorine · The synergistic fungicidal composition according to item 4, characterized in that, in the general formula (III), Ro and R signify an oxy-phenyl group. 6 "synergistic fungicidal composition according to item 4, characterized in that in the general formula (III) R is a chlorophenyl group and R * is a fluorophenyl group 7 · Synergistic fungicidal composition according to item 1, characterized in that in the general formula (IV) R, j is hydrogen, phenyl or phenoxy or phenoxy substituted by phenyl or chloro, or benzyl substituted by one or two halogens. , ι A synergistic fungi aides composition according to item 1, characterized in that in the general formula (IV) R ™ is a group of the formula (e) in which Rq represents an ethyl or propyl group. The synergistic fungicidal composition according to item 1, characterized in that it contains the compound of general formula (I) and dimethyl -> N, N ^f - (1j 2 -phenylene-bis / -thiocarbamoyl) -bis-carbamate / J contains ^f in a weight ratio between 1: 3 and 3: 1 The synergistic fungicidal composition according to item 1, characterized in that it contains the compound of general formula (I) and that of general formula (II) in a weight ratio of between 1: 2 and 6: 1. 11 * synergistic fungicidal composition according to item 1, characterized in that it contains the compounds of the general formulas (I) and (III) in a weight ratio between 1: 1 and 14: 1 « 12 · Synergistic fungicidal agent according to item 1, characterized in that it contains the compounds of the general formulas (I) and (IV) in a weight ratio between 1: 2 and 14: 1 « 13 «A process for the preparation of synergistic fungicidal agents, characterized in that in a weight ratio between 1: 2 and 14: 1, a 3,5-dinitro-4-chloro-benzoic acid derivative of the general formula (I) ,. wherein R is an alkyl group having 1 to 6 carbon atoms, and a dimethyl - ^ * N, N ^f - (1,2-phenylene ^ bis / thiocarbamoyl /) - bis / carbamate / J, a benzyl imidazole derivative of the general formula (II) wherein R represents hydrogen or a group of the formula (a), a pyrimidinyl derivative of the general formula (III) wherein Rj and R * are the same or different and are phenyl or halo substituted Phenyl group, or a 1,2,4-triazole derivative of the general formula (IV) wherein R, - is hydrogen, phenyl or phenoxy group, or phenoxy group substituted by halogen or phenyl group or halogen-substituted benzyl group, Rg is hydrogen or a trifluoromethylphenyl group and Ry is a phenyl group or a group of the formulas (c), (d) or (e) wherein R _{Q is} an alkyl group having 1 to 4 carbon atoms, with carrier, extender and other auxiliary agents customary in the practice of pesticide production - and additives are mixed ·