CH659762A5 - SYNERGISTIC FUNGICIDES. - Google Patents

Description

The invention relates to synergistic fungicides in which an active ingredient is always a 3,5-dinitro-4-chlorobenzoic acid derivative of the general formula (I):

COO-R

wherein R represents an alkyl group of 1-6 carbon atoms. The second active ingredient component is dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /] or a benzimidazole of the general formula (II)

ÏÏ

, JL?

NH-C-OCH,

659 762

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

(IV)

Rr - C - R,

(I)

10th

'6

and the first component is 1: 2 - 14: 1 by weight to the second. In the general formula (II), R represents hydrogen or the grouping (a)

(II)

0 = C - NH -

° 4H9

(a)

R1

or a pyrimidinylmethanol of the general formula (III)

R-

C - CI:

(III)

In the general formula (III), R3 and R4 have the same or different meaning and represent optionally phenyl group substituted by halogen. In the general formula (IV), R5 represents hydrogen, phenyl or phenoxy group, phenoxy group substituted by halogen or phenyl, or halogen-substituted benzyl group. Rô for hydrogen or for phenyl group substituted by trifluoromethyl and R7 for phenyl group or a grouping of the formulas (c), (d) or (e)

c:

o - C4H9 - OH - O4H9

O

(c)

OH (d)

where Rs represents an alkyl group of 1-4 carbon atoms.

The fungicidal compositions according to the invention can be used in various crops against numerous types of fungi. The application takes place according to the respective requirements and circumstances, for example by dressing the seeds or as a treatment of the plants.

Of the 3,5-dinitro-4-chloro-benzoic acid esters of the general formula (I) forming a component of the fungicidal agent according to the invention, the 3,5-dinitro-4-chloro-benzoic acid methyl and isopropyl esters in the US Pat. PS 2 841 522 as fungistatics against Alternaria oleraceae and Sclerotinia fructicola. The fungicidal activity of dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis- (carbamate)] is known from Hungarian Patent No. 169 823. The compounds of the general formulas (II), (III) and (IV) containing a heteroaromatic ring with several nitrogen atoms and which can also be used as the second component are also known.

The preparation and systemic fungicidal activity of the compounds of the general formula (II) are known from US Pat. Nos. 3,631,176 and 3,657,443. British Patent 1,218,623 reports the compounds of the general formula (III) and US Pat. No. 3,912,752 reports the compounds of the general formula (IV). The contact-active, so-called polyfunctional 3,5-dinitro-4-chlorobenzoic acid esters Although they are known, no practical application has been found so far. The main reason for this, as confirmed by our own experiments, is that these compounds, which are very effective even under 45 outdoor conditions, often damage the plants to be protected in the optimal application dose. When used, the risk of considerable phytotoxicity must be expected. Problems also arose when using the so-called specific-acting (systemic fungicides which attack at a certain point) problems. The compounds belonging to this group of the general formulas (II), (III) and (IV) and also the dimethyl- [N, N '- (1,2-phenylene-bis, thiocarbamoyl) bis / carbamate /], the Metabolite, which is methyl IH-benzimidazol-2-yl-carbamate and falls under the general formula (II), were initially fungicidal active substances of excellent activity. Since 1960, however, more and more publications have appeared that report that after repeated use, the fungi became resistant to these compounds 60. S.G. is concerned with the resistance of fungi to benzimidazole-type fungicides. Georpoules in Anti-fungal Compounds (in Development of Fungal Resistance to Fungicides, Sisler, New York, pp. 439 - 495 1977 /). In the same publication, 42 further literature references on 65 indicate the mutation resistance resulting from the action of the specific systemic fungicides. Since the application of systemic fungicides, despite the serious disadvantages due to resistance, with numerous plants

659 762

4th

protection-related advantages, it would be wrong to do without these connections. The experts now, but even more in the future, anticipate the use of these fungicides, since their systemic properties offer extraordinary advantages. For this reason, research is increasingly focused on eliminating resistance.

Topics of this research are: delaying the development of genes of greater resistance, slowing the change in the strain composition of the pathogenic population, methods of delaying the propagation of the resistant strain in the given population. Of the possible methods, the combination of specific and multifunctional fungicides, the production of fungicidal compositions from these combinations and their introduction into agricultural technology appear to be the most promising. As a result of this research, the companies producing pesticides brought combined fungicides onto the market, for example the Epidor agent (10% by weight Benomyl and 62% by weight Mancozeb) from Rhom and Haas, or the agent Trimidal (8% by weight). % Nuarimol and 32 wt .-% Ma-neb) of the company Eli Lilly.

Combinations of the 2,3-dihydro-5-carboxanilide-6-methyl-l, 4-oxatiin and the multifunctional 8-hydroxyquinoline or its metal salt, which attack at a specific point, are described in Hungarian Patent No. 158,608.

The effects of the compounds of the general formula (I) were first investigated in our own experiments, and then experiments with 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. The activity of the compounds of the general formula (I) was investigated in liquid nutrient medium in the concentration range from 0.1-1000 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 agents which, in addition to a 3,5-dinitro-4-chloro-benzoic acid derivative of the general formula (I), in which R represents an alkyl group having 1-6 carbon atoms,

(i) dimethyl- [N, N '(1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /],

25 (ii) a benzimidazole derivative of the general formula (II), in which R] represents hydrogen or group (a),

Table 1

The colony growth inhibiting threshold values in ppm for 7 types of fungus

connection

Threshold values in ppm

Alternaria Helmintho- Aspergillus Colletotrichum Trichothetium Helmintho- Fusarium solani sporium niger lindemuthia-roseum sporum graminearum turcicum num carbonum

3,5-dinitro-4-chloro

methyl benzoate 10-1 10-1 1-0.1 10-1 10-1 100-10 10-1 3,5-dinitro-4-chloro

ethyl benzoate 1-0.1 10-1 1-0.1 10-1 10-1 100-10 100-10

3,5-dinitro-4-chloro

benzoic acid-n-propyl

ester 1-0.1 100-10 1-0.1 10-1 1-0.1 100-10 100-10

3,5-dinitro-4-chloro

benzoic acid i-propyl

ester 10-1 100-10 10-1 100-10 10-1 1000-100 1000-100

3,5-dinitro-4-chloro

benzoic 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 n-amyl ester 1000-100 1000-100 100-10 1000 1000-100 1000 1000 3,5-dinitro-4-chloro

n-octyl benzoate 1000 1000 1000 1000 1000 1000 1000 Note: Since the octyl ester is not sufficiently effective, it was ignored in the following.

(iii) a pyrimidinylmethanol derivative of the general formula (III), in which R3 and R4 are identical or different and stand for phenyl group or halogen-substituted phenyl group, or

(iv) a 1,2,4-triazole derivative of the general formula (IV), wherein Rs is hydrogen, phenyl or phenoxy group, phenoxy group substituted by halogen or phenyl or halogen-substituted benzyl group, R6 for hydrogen or trifluoromethylphenyl and R7 for phenyl group or one

60 grouping of the formulas (c), (d) or (e), in which R8 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 materials between 1: 2 and 14: 1 lies.

65 The one active ingredient of the synergistic fungicidal agents according to the invention, the 3,5-dinitro-4-chloro-benzoic acid derivatives of the general formula (I), are esters in the formula R for an alkyl group with 1-6 carbons.

5

659 762

Substance atoms stands. Of the active compounds of the general formula (I), those in which R is an alkyl group having 1-4 carbon atoms are advantageous, and those in which R is a methyl or ethyl group are particularly advantageous.

In the compounds of the general formula (III), R3 and R4 are identical or different and stand for a phenyl group or a phenyl group substituted by two halogens. The compounds in which R3 and R4 are a halogen-substituted phenyl group in which halogen is advantageously chlorine and / or fluorine are advantageous.

In the general formula (IV), R5 is hydrogen, phenyl, phenoxy group substituted by phenoxy, phenyl or halogen or benzyl group substituted by one or two halogens, where halogen is advantageously chlorine. R6 stands for hydrogen or trifluoromethylphenyl and R7 for phenyl group or a grouping of the formulas (c), (d) or (e). In the grouping of formula (d) the butyl group is advantageously a tertiary butyl group, in the grouping of formula (e) Rg stands for an alkyl group with 1-4, advantageously 2-3 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 the general formula (I) to dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / thiocarbamate /] is advantageously between 1: 3 and 3: 1 ; 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 the general formula (I) to the compounds of the general formula (III) preferably 5 between 1: 1 and 14: 1; the weight ratio of the compounds of the general formula (I) to the compounds of the general formula (IV) is advantageously between 1: 2 and 14: 1.

The active substance combinations according to the invention are formulated in accordance with the particular application. The formulations can be dust or emulsion-like mordants, solid or liquid spray agents suitable for treating the crop, emulsifiable concentrates, dusts, etc. The formulations which are used are the carriers, extenders and auxiliaries which are suitable for the particular purpose and which are customary in the production of crop protection products. The agents contain a total of 5-85% by weight of active ingredient.

The combinations effective for the individual types of fungi, the synergistic active ingredient ratios, the application doses based on the total active ingredient 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 optimal 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.

Table 2

Mushroom species

Connection combinations

Synergi- 0 total formulation of static dose

Active ingredient area

Pickling against Fusa- 3,5-dinitro-4-chloro-benzoic acid methyl ester and methyl-rium, Tilletia etc. 1H-benzimidazol-2-yl-carbamate 1: 2-2: 1

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

1.5: 1-3: 1

Pickling against botrytis, fusarium, rhizoctonia, trichothe-cium etc.

Plasmopara destruc-tor

3,5-Dinitro-4-chloro-benzoic acid ethyl ester and dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /] 1: 1-3: 1

3,5-dinitro-4-chloro-benzoic acid n-propyl ester and cc- (2-

Chlorphenyl) -cc- (4-chlorophenyl) -5-pyrimidin-yl-methanol 3: 1-5.7: 1

Plasmopara viticola 3,5-dinitro-4-chloro-benzoic acid i-propyl ester and a- (2,4-

Dichlorophenyl) -a-phenyl-5-pyrimidinyl-methanol 1.25: 1-4: 1

Fusarium spp. 3,5-Dinitro-4-chloro-benzoic acid methyl ester and methyl

1H-benzimidazol-2-yl carbamate 3: 1-5.7: 1

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

butanone 5: 1-8: 1

3,5-dinitro-4-chloro-benzoic acid methyl ester and 1,2 - (/ 2,4-dichlorophenyl / -4-propyl-1,3-dioxolan-2-yl) methyl-1H-

1,2,4-triazole 3: 1-4: 1

3,5-dinitro-4-chloro-benzoic acid methyl ester and l- (di-

phenyl) -3- (trifluoromethyl-phenyl) methyl-1 H-1,2,4-triazole 3: 1-4: 1

0.9 kg / t 0.55 kg / t

30% film mordant

30% film mordant

1.0 kg / t 30% film mordant

1.0 kg / ha WP 50

0.75 kg / ha FW 40

1.0 kg / ha WP 70

0.9 kg / ha WP 70

1.0 kg / ha WP 70

1.0 kg / ha WP 70

659 762

6

Table 2 (continued)

Mushroom species

Connection combinations

Synergistic area

0 total dose of active ingredient

formulation

Venturia inaequalis 3,5-dinitro-4-chloro-benzoic acid methyl ester and 1,2 - (/ 2,4-dichlorophenyl / -4-ethyl-l, 2-dioxolan-2-yl) -methyl-lH-1,2, 4-triazole

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

6.6: 1-12.5: 1 1.2 kg / ha EC20

6.6: 1-12.5: 1 1.2 kg / ha of 3,5-dinitro-4-chloro-benzoic acid methyl ester and a- (2-

Chlorphenyl) -a- (4-chlorophenyl) -5-pyrimidinyl-methanol 6.6: 1-12.5: 1 1.2 kg / ha

Peronospora mans-3,5-dinitro-4-chloro-benzoic acid methyl ester and l- (2,4-dichlorobenzyl) -3,3-dimethyl-1 - (1 H-1,2,4-triazol-1-yl ) -2-butanol hurica Ustilago spp.

1: 2-1.1: 1

3,5-dinitro-4-chloro-benzoic acid ethyl ester and a- (2-

Chlorphenyl) -a- (4-fluorophenyl) -5-pyrimidinyl-methanol 2: 1-14: 1

3,5-dinitro-4-chloro-benzoic acid ethyl ester and l- (4-chloro

phenoxy) -3,3-dimethyl-1- (1 H-l, 2,4-triazol-1-yl) -2-buta-

nol 2: 1-14: 1

2.1 kg / ha 1.5 kg / t

1.5 kg / t

EC 20 EC 20

WP 70

40% dust stain

40% dust stain

The lower application rate resulting from the synergism has the advantage that the biosphere is less contaminated. Another advantage is that agriculture does not have to do without the well-known systemic fungicides, which are pushed into the background due to the resistance problems.

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 exemplary embodiments.

example 1

For seed dressing of winter wheat, 3,5-dinitro-4-chloro-benzoic acid methyl ester (DNCB-Me) and methyl-lH-benzimidazol-2-yl-carbamate (KARBENDA-ZIM) or l- (4-chloro-phenoxy) - 3,3-dimethyl-l- (lH-l, 2,4-triazol-l-yl) -2-butanol (TRIADIMENOL) prepared the compositions given in Table 3. Each agent contains a total of 30% active ingredient. The respective ratio of the two active ingredients to one another is given in Tables 4, 5 and 6.

Table 3

Composition in

component

% A

B

DNCB-ME + KARBEND AZIM

30th

-

DNCB-Me + TRIADIMENOL

-

30th

Ethylene glycol

7

7

Condensate from cresol and formal

dehyd

6

6

Film-forming agent Mowilit DM-21

16

16

Antifoam agent Silicon SRE

1

1

Rhodamine 2B4 dye

2nd

2nd

desalinated water

38

38

In laboratory and field trials, the efficacy of agents A and B against the diseases of winter wheat occurring in the germ age was examined.

Winter wheat seeds of the type MV 8, which strongly with Fusa-35 rium spp. was contaminated, 0.2% by weight of the spores of the stone fire were infected before pickling. The control was only with Fusarium spp. infected. The seeds were seeded with the doses of the investigated agents given in Tables 4, 5 and 6.

40 To study the Fusarium spp. infected seeds from each treatment were placed 200 seeds on selective Papavizas culture media. The culture media were then incubated at 20-22 ° C in diffused light for 10 days. It was then determined what percentage (based on the control) had germinated. The infestation by Fusarium spp. examined microscopically. The experiments were carried out with 8 repetitions and the average values of the 8 repetitions are given in Table 4.

So field trials were carried out on plots of 2 m2 with the wheat grains additionally infected by the spores of the stone fire. Each attempt was repeated three times in the order of the random block. Sowing was carried out on November 26, with a row 55 distance of 12 cm and a seed quantity of 60 g / parcel. In the third row of each plot, 150 seeds were sown with “seed bars” in order to assess the phytotoxic effects. The phytotoxic effect was assessed the next year on April 10th by evaluating the 60 number of plants that had emerged, their height and their condition based on the overall impression. The effectiveness against the stone fire was assessed at the time when the grains in the ears are still milky. Each individual ear was examined and determined what percentage was affected by the fire and what percentage was healthy. The average results of the three replications are given in Tables 5 and 6.

7

659 762

Table 4 Efficacy against Fusarium

Dose kg / t DNCB-Me +

Germination%

Infest with

CARB DAZIM

Fusarium%

0.1 +0.8

102.5

12.5

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 control

100.0

62

Dose kg / t DNCB-Me +

TRIADIMENOL

0.1 + 0.3

101.5

3.5

0.3 +0.2

105.2

1.5

0.45 + 0.45

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 control

100

62

Table 5

Investigation of phytotoxicity

Dose kg / t DNCB-Me +

Accumulated

Plant height

CARB DAZIM

as a percentage of control

0.1 +0.8

97.6

101.5

0.3 +0.6

139.0

103.7

0.45 + 0.45

140.2

106.2

0.6 + 0.3

105.1

102.2

0.8 + 0.1

98.3

96, '6

0.6

107.5

98.8

0.9

98.3

95.2

- 0.6

100.2

105.2

- 0.9

109.4.

102.2

untreated control

100.0

100.0

Dose kg / t DNCB-Me +

TRIADIMENOL

0.1 + 0.3

105.0

100.5

0.3 +0.2

127.4

108.0

0.45 + 0.45

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 control

100.0

100.0

Table 6 Effectiveness against stone fire

Dose kg / t DNCB-Me +

Healthy sick

CARB DAZIM

Ears of corn

Ears of corn

Piece / parcel

Piece of parcel

0.1 + 0.8

912.7

3.7

0.3 + 0.6

1247.5

1.3

0.45 + 0.45

1311.1

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

control infected with fire

804.7

151.7

untreated control

933.0

14.0

Dose kg / t DNCB-Me +

TRIADIMENOL

0.1 +0.3

957.7

10.0

0.3 + 0.2

1346.5

4.2

0.45 + 0.45

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

control infected with fire

804.7

151.7

untreated control

933.0

14.0

Based on the tests, it can be established that in the laboratory tests compared to the separately

active substances DNCB - Me and KARBENDAZIM used the combination of both against Fusarium spp. in the application quantities 0.3 + 0.6; 0.45 + 0.45; 0.6 + 0.3 kg / t, i.e. H. has a synergistic effect in the active ingredient ratios of 1: 2 to 2: 1. With pickling with DNCB - Me and TRIADIMENOL, however, the effect was 0.3 + 0.2; 0.45 + 0.45 kg / t, i.e. in the ranges from 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. The number of plants that had emerged, their height, the number of ears and their degree of infection were also the best in the case of the plot tests in the case of the application rates and active ingredient ratios mentioned.

Example 2

In order to investigate the activity against the germ-damaging fungi Bo-tritis cinerea, Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum in the laboratory or the effect on the emergence of peas (pods) under the conditions of the greenhouse and outdoors, using 3, 5-Dinitro-4-chloro-benzoic acid ethyl ester (DNCB -Et) and dimethyl- [N, N '- (1,2-phenylene bis thio-carbamoyl /) - bis / carbamate /] (TIOFANAT-METHYL) in total Pickling agent containing 30 wt. The composition of the agents is given in Table 7, while the drug ratios and the results are shown in Tables 8,9, 10 and 11. The BR-52 pea seed was sown with the agents in a manner known per se.

659 762

Table 7

component

Share in% by weight

DNCBl-Et + TIOFANAT-METHYL

(96% technical active ingredient) 31.5

Dispersant 1494 10

Ethyl englycol 12

Vinarol ST (polyvinyl alcohol) 8

Defoamer 1051 1

Rhodamine BSA 1150 0.4

desalinated water 37.1

Laboratory tests The effectiveness against fungi was investigated in the laboratory using the so-called agar diffusion method. For this purpose, 32 ml of potato agar prepared with water were poured into Petri dishes of 15 cm diameter. A layer of 8 ml nutrient agar, which was infected with the spores of the test fungus, was applied. 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 visual field was 15-50 spores / ml. Wells of 5 5 mm radius were made in the agar plates solidified in the petri dishes. 0.2 ml of aqueous fungicide were introduced into each with the pipette; the amounts and ratios of active ingredients are shown in the table. The cultures were incubated in the thermostat at 25-26 ° C. The inhibitory effect on the growth of the colonies was then determined by measuring the zones of inhibition (rings). The results are shown in Table 8.

From the table it can be seen that the combinations of DNCB - Et and TIOFANAT-METHYL in a ratio of 1: 3 to 3: 1 and in concentrations of 200,300 and i5 400 ppm were particularly more effective than against Fusarium graminearum, Rhizoctonia solani and Trichothecium roseum this was to be expected due to the individual effects of the same doses of the components.

The degree of infection of the seed was also examined under laboratory conditions. For this purpose, 200 seeds each 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

Examination with the agar diffusion method

Drug ratio

Total conc.

Inhibition zone radius, mm

DNCB-Et: TIOFA-

ppm

Botrytis

Fusarium

Rhizoctonia

Trichothecium

NAT METHYL

cinerea graminearum solani roseum

1: 3

200

13

9

10th

12

1: 1

200

14

10th

12

14

3: 1

200

14

11

11

15

1: 3

300

15

11

10th

16

1: 1

300

16

10th

12

17th

3: 1

300

15

11

13

17th

1: 3

400

16

9

11

16

1: 1

400

17th

9

12

16

3: 1

400

19th

10th

14

18th

1: 0

200

12

4th

4th

8th

1: 0

300

14

6

6

10th

1: 0

400

16

7

7

11

0: 1

200

12

7

6

3rd

0: 1

300

13

8th

7

5

0: 1

400

15

9

7

8th

Table 9

Dose kg / t DNCB-Et +

Infected grains from a total of 200 grains

TIOFANATE METHYL

Alternaria spp. Ascohyta spp.

Fusarium spp.

Pénicillium 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

-

2nd

2.5

3.0

3.0

1

-

1.0

1.0

-

2.0

-

0.75

1.5

1.5

2.5

3.5

-

0.1

1.0

1.0

2.0

2.5

untreated

12.0

8.0

5.0

9.0

9

659 762

The table shows that the components DNCB and TIOFANAT-METHYL also ensure good protection against the multiplication of pathogens, but complete freedom from fungi only with combinations of DNCB-Et and TIOFANAT-METHYL prepared in a ratio of 1: 1 to 3: 1 can be reached.

Try in the greenhouse

In order to determine what influence the dressing agents have on the peas' pace of growth, pea seed of the BR-52 variety was dressed with dressing agents of the composition given in Table 10 and then sown in 100 repetitions in four repetitions in seed boxes filled with garden soil and then with soil covered. On the 7th, 14th and 21st day after sowing, the emerged plants were counted. The results are summarized in Table 10.

Table 10

Dose kg / t DNCB-Et + TIOFANAT-METHYL

plants grown from 400 grain, piece, on the accrued plants on the 21st day, in

7.

14.

21st day

% of control

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

0.75

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

-

(1.75

138

263

271

117.3

1

162

271

277

119.9

control

102

223

231

100.0

Although the difference in the speed of emergence is only slight, the great difference between the combinations according to the invention and the effect of similar doses of the individual components is striking. The combinations in a ratio of 1: 3 to 3: 1 work synergistically.

Field trial On 4 m2 plots arranged in a random block, pickled peas of the BR-52 variety were sown on April 3 at a row distance of 40 cm, a plant distance of 5 cm and a seed depth of 5 cm. There were 200 grains on each plot, each treatment was examined in 4 replicates. The plants were counted on May 19, when the plants had already developed 2-4 subsequent leaves (real leaves, i.e. no cotyledons). The results are summarized in Table 11.

Table 11

Dose kg / t DNCB-Et +

plants grown on a par,

TIOFANATE METHYL

cell through

%

average on

run on that on the

Plants,

Seeds

control

Covered in pieces

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

untreated

128.2

64.1

100.0

In the field test, the best results were obtained in a ratio of 1: 3 to 3: 1 prepared combinations of DNCB-Et and TIOFANAT-METHYL in a total amount of 1 kg / t.

35

Example 3

To investigate the action against Plasmopara de-structor (onion peronospora), n-propyl 3,5-dinitro-4-chloro-benzoate (DNCB - Br) and a- (2-40 chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidinyl-methanol (FENARIMOL) 50% by weight wettable powder (WP), which had the composition A and B given in Table 12. The tests were carried out on randomly arranged outdoor plots of 500 m2 in 2 repetitions. On April 12, onion seeds of the "Aroma" variety were sown at a rate of 4.5 kg / ha. The fungicidal agents were sprayed when the flower heads appeared (on July 21) and then twice (on July 29 and August 10) with a spray device (Maruyama) which was portable on the back, the application rate being 500 l / ha and the agents of the composition given in Table 12 were used in the doses given in Table 13.

55 Table 12

Component,% A B

technical DNCB-Pr (95%) see FENARIMOL, 98% synthetic silicate Ultrasil VN3 surfactant Tensiofix BCZ (alkyl polyglycol ether sulfate)

anionic dispersant 65 dispersant HG

Dispersant Ultrazine Na (Ligninsul-

fonat-Na)

kaolin

52.63

10th

51.02 5

6.25

29.37 35.73

659762

10th

Two weeks after the last spraying, 10 × 10 plants were scored on each plot using a 0–6 grade scale. The scale of values used to indicate the degree of infestation of the leaves was as follows:

0 no infection

1 infestation less than 5%

2 infestations between 6 and 10%

3 infestation between 11 and 25%

4 infestation between 26 and 50%

5 infestations between 51 and 75%

6 Infestation between 76 and 100%.

As part of the evaluation, the percentage of infected plants (F%) as a percentage of the total number of plants and also the so-called infestation index were determined, the latter using the following formula:

10th

Fi fi n

x fi)

in

Infestation index the number of plants belonging to the respective scale value (frequency)

worth the respective scale Total number of plants examined The more effective the remedy, the lower the F; value. The results are shown in Table 13.

Table 13

Dose kg / ha

DNCB-Pr + FENARIMOL

Number of plants belonging to the scale values 0 12 3 4

5

6

F%

Fi

0.9

0.1

11

34

32

6

10th

7

0

89

1.91

0.85

0.15

14

41

32

9

3rd

1

0

86

1.49

0.8

0.2

29

38

33

0

0

0

0

71

1.04

0.75

0.25

34

51

14

1

0

0

0

66

0.82

0.8

-

3rd

24th

38

19th

9

7

0

97

2.28

1.0

-

9

31

31

17th

3rd

9

0

91

2.01

0.2

1

26

29

18th

12

12

2nd

99

2.60

-

0.3

9

37

31

9

6

8th

0

91

1.90

control

4th

16

31

16

12

18th

3rd

96

3.30

From the table it can be seen that by using the combination of DNCB-Pr + FENARIMOL the onion perenospora infestation could be reduced to a minimum value. With an application rate of 1 kg / ha, the best synergism, the most effective combination ratio is between 3: 1 and 5.7: 1.

Example 4

In order to investigate the activity against Plasmopara viticola (Perono-spora of the wine), i-propyl ester (DNCB-iPr) and a- (2,4-dichlorophenyl) -a from 3,5-dinitro-4-chloro-benzoate were used -phenyl-5-pyrimidinyl-methanol (TRIARI-MOL) a total of 40% by weight of active ingredient-containing aqueous suspension concentrates. The framework composition of these agents 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 1.0

KelzanS 0.1

desalinated water 44.9

35 The biological tests were carried out in duplicate on 20-year-old vines in the Lenz-Moser grape variety (variety: Italian Riesling). There are 60 floors in rows on the 180 m2 plots. The fungicides are sprayed a total of 8 times (if the 40 shoots are 20-25 cm long, if the bud is stretching, then at the beginning and towards the end of flowering; if the berries are as large as peas, then before the grapes become dense when they have become tight, again, and finally at the beginning of maturity). A spraying system from Steyer-Puch-Haflinger with a spray head 45 Tee-Jet D-7 was used with a hand spray gun. The water consumption was 10001 / ha. Together with the preparations to be examined, the sulfur preparation Kolosul 80 WP, which is ineffective against Peronospo-ra, was applied in an amount of 3 kg / ha and the insecticide Ekalux in an amount of 1.61 / ha.

The evaluation was carried out at the time of grape ripening by examining 4 x 50 grapes and 10 x 5 sticks from each treated plot. The untreated control 55 was evaluated on the basis of the examination of 2x10 sticks. The degree of infestation of foliage and grapes and also to what extent the leaves and grapes are burnt. In the manner described in Example 3, the percentage of infected plants (F%) and the infested 60 dex (Fi) was calculated. The results are shown in Tables 15 and 16.

As can be seen from Tables 15 and 16, the combinations of 65 DNCB-iPr and TRIARIMOL prepared in the active ingredient ratios between 1.25: 1 and 4: 1 are more effective than can be assumed on the basis of the sum of the individual effects, ie there is synergism.

11

659 762

Table 15 Degree of infestation of the leaves

Dose kg / ha Number of sticks F% F belonging to the respective scale value, burned

DNCB-iPr + TRIARIMOL 0 1 2 3 4 5 6%

0.8 +

0.1

22

26

2nd

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

-

19th

26

4th

1

0

0

0

60

0.74

10.5

1.0

-

25th

22

3rd

0

0

0

0

50

0.56

15.2

-

0.5

40

9

1

0

0

0

0

20th

0.22

0

0.7

42

8th

0

0

0

0

0

16

0.16

0

control

0

0

2nd

6

12

0

0

100

3.5

0

Table 16 Infestation of the grapes

DNC-iPr + TRIARIMOL dose kg / ha

Number of sticks belonging to the respective scale value 0 1 2 3 4 5

6

F%

F.

burned%.

0.8 +

0.1

158

8th

25th

9

0

0

0

21st

0.42

10.1

0.6 +

0.15

180

4th

16

0

0

0

0

10th

0.18

0

0.5 +

0.2

184

4th

12

0

0

0

0

8th

0.14

0

0.4 +

0.3

182

16

2nd

0

0

0

0

9

0.1

0

0.8

-

98

12

20th

42

28

0

0

51

1.45

8.3

1.0

-

112

24th

29

20th

15

0

0

44

1.01

15.7

-

0.5

118

23

20th

29

10th

0

0

41

0.95

0

0.7

153

19th

14

11

3rd

0

0

23.5

0.46

0

control

49

148

58

36

34

0

0

75.5

2.59

0

Example 5

In order to investigate the action against the Fusarium infection of the wheat ears, methyl 3,5-dinitro-4-chloro-benzoate (DNCB - Me)

and

Methyl 1 H-benzimidazol-2-yl-carbamate (KARBENDAZIM), 40 l- (4-chlorophenoxy) -3,3-dimethyl-l- (lH-l, 2,4-triazole-

l-yl) -2-butanone (TRIADIMEFON), 1- 2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-yl-

methyl-1 H-1,2,4-triazole (PROPIKON AZOL) or 45

1-diphenyl- (3-trifluoromethyl) -phenyl-methyl-1 H-1,2,4-

triazole (FLUOTRIMAZOLE)

the wettable powders containing a total of 70 wt. the drug ratios are given in Tables 50, 18, 19, 20 and 21.

The tests were carried out in four replicates on plots of 10 m2 with Jubilejnaja 50 winter wheat. The fungicidal treatment was carried out towards the end of the ear shifting with a water consumption of 55 6001 / ha. Fusarium spp. was determined 10 days after spraying by examining 2 x 100 ears of each plot.

Table 17 (continued)

Table 17

component

Proportion in% by weight ABC

D

DNCB-Me + KARBEN-DAZIN (95% technical substances)

component

Proportion in% by weight ABC

D

DNCB-Me + TRIADIMEFON (95% technical substances)

DNCB-Me + PROPIKON-AZOL (95% technical substances)

DNCB-Me + FLUOTRIMAZOLE (95% technical substances)

synthetic carrier Cab-O-Sil

Dispersant Atlox 4862 wetting agent Atlox 4995 dispersant Polifon 0 kaolin as carrier

73.7

73.7

-

-

-

73.7

10th

10th

10th

10th

3rd

3rd

3rd

3rd

3rd

3rd

3rd

3rd

4th

4th

4th

4th

6.3

6.3

6.3

6.3

Table 18

73.7 -

Dose kg / ha

Infestation by Fusarium spp. %

Yield

DNCB-Me +

Ears of corn

Grains

Grains,

kg 10 m2

CARB DAZIM

overall inner

0.85 + 0.15

0.20

6.50

4.25

6.55

0.8 + 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

6.5

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

659 762

12

Table 19

Dose kg / ha DNCB-Me + TRIADIMEFON

Infestation by Fusarium spp.,% Yield ears of grain, grain, kg / 10 m2 total inner

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

control

11.50

38.75

31.25

5.52

Table 20

Dose kg / ha DNCB-Me + PROPIKONAZOLE

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

control

11.50

38.75

31.25

5.52

Table 21

Dose kg / ha

DNCB-Me +

FLUOTRIMAZOLE

0.85 + 0.15

3.5

9.5

8.0

5.95

0.80 + 0.20

2.5

6.0

7.0

6.05

0.75 + 0.25

1.5

6.5

7.5

6.15

0.25

6.5

15.5

12.5

5.85

0.50

9.0

19.0

16.0

5.62

0.9

5.0

13.25

11.5

6.10

1.8

4.25

11.50

11.50

3.13

control

11.50

38.75

31.25

5.52

The data in Tables 18-21 were obtained in the following way. The yield of each parcel was weighed at harvest. Average samples were taken from the wheat kernels, from which 2 x 100 kernels were examined for fusarium attack. The cultures applied to the Papavizas culture medium were incubated at 20 C for 8 days and then examined with a microscope. To examine the infestation of the inner grains, the ears were first sterilized on the surface from the outside.

Example 6

To study the effectiveness against the pathogen of apple scab (Venturia inaequalis), 3,5-dinitro-4-chloro-benzoic acid methyl ester (DNCB - Me) and

1- 2- (2,4-dichlorophenyl) -4-ethyl-l, 3-dioxolan-2-yl) -

methyl-1 H-l, 2,4-triazole (ETAKONAZOLE), 1 - (4-phenylphenoxy) -3,3-dimethyl-1 - (1 H-2,4-triazole-

l-yl) -2-butanol (BITERTANOL) or a- (2-chlorophenyl) -a- (4-chlorophenyl) -5-pyrimidinyl-

methanol (FENARIMOL)

emulsifiable concentrates containing a total of 20% by weight of active ingredient. The composition is shown in Table 22, the active ingredient ratios are shown in Table 23.

10th

Table 22

component

Proportion, wt% A B

20th

20 50 3

3.5 3.5

20th

38

30th

20 40

3.5

-

3.5

-

5.0

-

30th

5.0

1.5

3.5

, 5 DNCB-Me + ETAKONAZOL DNCB-Me + BITERTANOL) DNCB-Me + FENARIMOL Cyclohexanone as solvent Xylene as solvent 20 Emulsifier Atlox 4858 Emulsifier Atlox 8916 Emulsifier Atlox 4851 Isoforon as solvent Emulsifier Tensiofix D-120 2s Emulsifier Bios 7425 solvent (HAN) emulsifier Arkopal N080 emulsifier Emuisogen EL 30 emulsifier SapogenatT-180

The biological tests were carried out in duplicate on plots of 0.5 ha on 35 x 20-year-old Jonathan apple trees planted at 7.5 x 4.5 m intervals. The fungicides were applied a total of 9 times at 1-2 week intervals during the growing season, and a Kertitox 40 Na-10 spray device equipped with a tea jet spray head was used for spraying. The amount of water was 10001 / ha. The infestation of the leaves was evaluated twice, namely towards the end of the first and towards the end of the second shoot growth, on 10 trees, 100 leaves from each tree being examined. The infestation of the fruit and the burns were determined on 10 trees before harvesting, 50 apples from each tree being examined. The results are summarized in Table 23.

From the table it can be seen that the medium combinations DNCB-Me and ETAKONAZOL, or BITERTANOL or FENARIMOL in the active ingredient ratio range from 6.6: 1 to 12.5: 1 against Venturia in application rates of 1.15-1.35 kg / ha show a synergistic effect inaequalis.

55

65

Table 23

Dose kg / ha

Infestation of the leaves

Infestation of the burned

DNCB-Me +

1.

2nd

fruit

Fruit,

ETAKONAZOLE

Evaluation,%

%

%

1 + 0.15

0

7.2

2.2

0

1.25 + 0.1

0

8.2

2.3

0

1.50 + 0.075

1.4

9.8

2.7

10.5

1.50 -

14.6

32.3

12.5

10.7

2nd

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

control

27.4

62.6

41.5

0

13

659 762

Table 23 (continued)

Dose ka / ha infestation of leaves infestation of burned

DNCB-Me +

BITERTANOL

1 + 1.5 0

1.25 + 0.1 0

1.50 + 0.075 5.1

1.50 + - 14.6

2 - 9.5

0.15 5.3

0.20 5.9

Control 27.4

Dose 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 + 0.075

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

control

27.4

62.6

41.5

0

It can be seen from the table that, in the application rates 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 effect against Venturia inaequalis.

Example 7

To study the action against Peronospora manshurica (the Peronospora of soy), using 3,5-dinitro-4-chloro-benzoic acid methyl ester (DCNB - Me) and

1 - (2,4-dichlorobenzyl) -3,3-dimethyl-1 - (1 H-1,2.4-triazole-

l-yl) -2-butanol (DIKLOBENTRAZOL)

A total of 70% by weight of active ingredient-containing wettable powder io (WP) of the framework recipe given in table 24 was produced. The ratios of the two active ingredients to one another are given in Table 25.

Table 24

Component share. ° o

DNCB-Me + DIKLOBENTRAZOL 70

synthetic carrier material Cab-o-Sil 15

20 wetting agents Netzer IS 3

Dispersant SI 6

Dispersant Polifon 0 6

25 The experiments were carried out on soy of the Ewans variety on a plot of 1 ha. The plants were treated with fungicide three times: first when they were 40 cm high, then at the beginning of flowering and finally in full bloom. The device RAH-30 14-K-10 was used for spraying, the water consumption was 400 l / ha. For evaluation, 10x10 plants were rated 16 days after the last treatment. The result was calculated in the manner given in Example 3. In addition to the results, Table 25 also shows the degree of burn 35 (leaf damage).

5.3

1.9

0

8.0

2.2

0

11.2

2.7

10.0

32.3

12.5

10.7

9.5

10.2

20.4

21.5

3.8

0

19.9

2.8

11.1

62.6

41.5

0

Table 25

Dose kg / ha Number of plants F% F belonging to the respective scale value, burned

DNCB-Me + DIK-%

LOBENTRAZOL 0 12 3 4 5 6

0.5 + 1.6

33

38

15

12

2nd

0

0

67

1.12

0

0.7 + 1.4

62

30th

8th

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

25th

5

0

0

0

0

30th

0.35

3.6

1.3 + 0.8

27th

42

16

11

4th

0

0

73

1.23

10.6

1.3 -

0

38

30th

16

10th

6

0

100

2.16

9.8

2.1 -

11

33

25th

21st

10th

0

0

89

1.86

17.6

- 1.6 -

22

29

21st

18th

9

1

0

78

1.36

0

2.1

37

26

15

15

7

0

0

63

1.29

7.9

control

0

0

40

41

11

8th

0

100

2.87

-

The biological effect is most favorable with a total amount of active ingredient of 2.1 kg / ha in the ratio range 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 doses.

Example 8

To investigate the effectiveness against Ustilago sp. (Dust burns) using methyl 3,5-dinitro-4-chloro-benzoate (DNCB - Me) and a- (2-chlorophenyl) -a- (4-fluorophenyl) -5-pyrimidinyl-

methanol (NUARIMOL)

or 60 1 - (4-chlorophenoxy) -3,3-dimethyl-1 - (1 H-1,2,4-triazol-1-yl) -butanol (TRIADIMENOL)

a total of 40% by weight of active ingredient containing dry mordants of the frame composition given in Table 26. The ratio of the active substances to one another 65 is given in Table 27.

Barley seed of the GK-59 variety, which was infected with dust fire, was dressed with the dressing agents and then on 50 m2 plots in the arrangement of the Zu

659 762

14

If blocks are sown 5 cm deep at a distance of 12 cm. In the 8th row of each plot, exactly 150 seeds were sown over a section of 2 m. To assess the phytotoxic effect, the plants which had emerged from the 150 seeds were counted in the 2-4 leaf stage and their height was measured. The infection with fire was assessed at the time of flowering based on the count of the burnt ears. The result was checked by germ experiments with the spores. The results are summarized in Table 27.

Table 26

Component share,%

A B

DNCB-Me + NUARIMOL 40

DNCB-Me + TRIADIMENOL - 40.5

Wetting agent Tinovetin B 2 -

, Disperser HG 5 -

Polyvinyl alcohol Mowiol 30/88 4 -

Horna Pure Milori Blue 1.5 -

Kaolin 47.5 40.25

synthetic carrier UltrasilVN3 - 5

Wetting agent Netzer IS - 2.5

Dispersant Ultrazine-NA - 6.0

Polyvinyl alcohol Rhodoviol 14/120 - 2.5

Dextrin - 2.5

Rhodamine BS A dye - 1.25

Table 27

Average dose kg / t from 150 seeds. burned spikes accumulated height, cm pieces

DNCB-Me + NUARIMOL

1 + 0.5

117.8 l

?, 6

0

1.25 + 0.25

113.3 *

5.6

0

1.40 + 0.10

114.0 l

?, 5

0

1.40 -

110.3 i

5.2

44

1.80 -

97.5 i

3.0

15.3

0.5

114.8 i

3.5

3.0

0.7

114.5 i

3.5

1.8

control

109.0 i

3.6

97.5

DNCB-Me + TRIADIMENOL

1 +0.5

118.5 i

3.3

0

1.25 + 0.25

119.3!

3.7

0

1.40 + 0.1

118.1 <

3.4

0

1.40 -

110.3:

3.2

44

1.80 -

97.5:

8.0

15.3

0.5

115.4 1

8.3

4.3

0.7

115.0:

8.1

0.5

control

109.0:

8.6

97.5

At a rate of 1.5 kg / t, the combinations with an active ingredient ratio between 2: 1 and 14: 1 completely suppressed the dust fire.

5

10th

15

20th

25th

30th

35

40

45

50

55

60

65

S

Claims (9)

659 762 2. Synergistic fungicidal agent according to claim 1, characterized in that a total of 5-85% by weight of active ingredient is contained. 2nd PATENT CLAIMS 1. Synergistic fungicidal agents, characterized in that they contain a 3,5-dinitro-4-chloro-benzoic acid derivative of the general formula I as active ingredient Ç00-R c) a pyrimidinylmethanol derivative of the general formula 111 R- wherein R represents an alkyl group with 1-6 carbon atoms, and a) dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /], b) a benzimidazole derivative of the general formula II , N r ~ i ° ^? 2TH-C- OCH, (II) j R-, (III), wherein R3 and R4 are identical or different and represent phenyl group or halogen-substituted phenyl group, or d) a 1,2,4-triazole derivative of the general formula IV R, 20th (IV) 5 wherein R] is hydrogen or group a, 0 = C - NH - C / Hq | 4 9 - C - C4H9 25th 0 (c) (a) - CH - I. OH (d) R5 is hydrogen, phenyl or phenoxy group, phenoxy group substituted by halogen or phenyl group, halogen-substituted benzyl group, Rg for hydrogen, phenyl group substituted by trifluoromethyl group, R7 represents phenyl group or a grouping of the formulas (c), (d) or (e), U X. Y / w ° 4H9 wherein R8 represents an alkyl group with 1-4 carbon atoms, contain and the weight ratio of the active ingredients of the general formula (I) to dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /] or one of the active ingredients of the general formulas (II), (III) or (IV) is between 1: 2 and 14: 1. 3. Synergistic fungicidal agent according to claim 1, characterized in that in the general formula (I) R represents an alkyl group having 1-4 carbon atoms, advantageously a methyl or ethyl group, in the general formula (III) R3 and R4 one halogen-substituted phenyl group and halogen is fluorine and / or chlorine, in the general formula (IV) R5 represents hydrogen, phenyl or phenoxy group or phenoxy group substituted by phenyl or chlorine or by one or two halogens benzyl group, in the general formula (IV ) R7 is a group of the formula (e), Cl (e) wherein R8 represents an ethyl or propyl group. 4. Synergistic fungicidal agent according to claim 3, characterized in that in the general formula (III) R3 and R4 represent a chlorophenyl group. 5. Synergistic fungicidal agent according to claim 3, characterized in that in the general formula (III) R3 is a chlorophenyl group and R4 is a 45 mean fluorophenyl group. 6. Synergistic fungicidal agent according to claim 1, characterized in that it is the compound of general formula (I) and dimethyl- [N, N '- (1,2-phenylene-bis / thiocarbamoyl /) - bis / carbamate /] in a weight so Ratio between 1: 3 and 3: 1 contains. 7. Synergistic fungicidal agent according to claim 1, characterized in that it is the compound of general formula (I) and that of the general formula 55 (II) in a weight ratio between 1: 2 and 6: 1. 8. Synergistic fungicidal composition according to claim 1, characterized in that it contains the compounds of general formulas (I) and (III) in a weight ratio. 6o ratio between 1: 1 and 14: 1 contains. 9. Synergistic fungicidal composition according to claim 1, characterized in that it contains the compounds of general formulas (I) and (IV) in a weight ratio between 1: 2 and 14: 1. -R-