JPS59205303A - Fungicidal composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a synergistic fungicidal composition, which contains 3,5-dinitro-4- of the general formula (1) as one of its active ingredients. Other components including the chlorobenzoic acid derivative include dimethyl (N, N"-CI, 2-phenylene-bis(thiocarbamoyl)]-bis(carbamate)), a benzimidazole derivative of formula (II) l II 10 , selected from the group consisting of kyrimidinylmethanol derivatives of (I[) and 1,2,4-)!J azole derivatives of formula (TV)I 6 , wherein the active ingredient of formula (1) and dimethyl-( N,
N'-[1,2-)unilenebis(thiocarbamoyl)4''s(carbamate)) and formula (ff), (I
The weight ratio with other components selected from the group consisting of [) and (IV) is 1:2 to 14:1.

In formula (1), R represents an alkyl group containing 1 to 6 carbon atoms.

R in formula (II) is hydrogen or formula (a) 1 0=C-NH-C4H0(a) represents the group of

In formula (1), R3 and R4 are the same or different and represent a phenyl group optionally substituted with halogen.

In formula (IV), R5 represents hydrogen, a phenyl group, a phenoxy group optionally substituted with a phenyl group or a noryl group, or a benzyl group optionally substituted with a nitrogen group; represents a phenyl group substituted by a fluoromethyl group, R7 is a phenyl group or the following formulas (C), (d) and (e) C-CaH9(C') 1 - C-c, H,, (a) H 2 (in formula (e), R8 represents an alkyl group containing 1 to 4 carbon atoms).

The compositions of the invention are useful in a variety of plant cultivations and are effective against many fungi, depending on the requirements of the method of application (eg dressing seed or treating plant rhizomes).

One of the active ingredients of the fungicide of the invention, namely methyl and isozolobyl 3,5-dinitro-4-chloro-benzoate, and Alternaria cleracea
e and 5clerotinia fructicola
Their activity against U.S. Pat. No. 2,841,52
It is described in the specification of No. 2. Dimethyl (N, N'-
(1゜2-phenylene-bis(thiocarbamoyl)〕-
The bactericidal action of bis(carbamates) is disclosed in Hungarian Patent No. 169,823.

Formula (IT) containing a heterocycle having multiple nitrogen atoms, CM
) and (IV) are also known.

The preparation and fungicidal activity of the systemic fungicide of formula (If) are described in U.S. Pat. No. 3,631,176 and U.S. Pat.
No. 443 and data on the active ingredient of formula (I[) are provided in British Patent No. 1,218,62.
No. 3, and data for the active ingredient of formula (■) are disclosed in US Pat. No. 5,912,752.

Although 3,5-dinitro-4-chlorobenzoate esters that act catalytically on several sites are known compounds, they have not been put to practical use at all. The main reason is that, according to the inventors' observations, these compounds, which are highly effective under practical conditions, are also damaging to the plants to be protected when used in optimal dosages. It means giving. Therefore, a non-negligible risk of phytotoxicity must be taken into account when using these compounds. Problems also arise with the use of systemic fungicides that act on specific sites. Formulas (U), (II) and (IV
), and dimethyl-(N,N'-(1,2-phenylene-
Bis(thiocarbamoyl)-bis(carbamate) was also initially an excellent fungicide.However, in 1960
Since 2010, more and more papers have been published on the resistance of fungi to these compounds that develops after several uses.

The resistance of fungi to benzimidazole derivatives is discussed by George Poules (S, G.

Georpoules: “Antifungal
Compounds J, 5 isler: Deve.
lopment of Fungal Re5ista
nceto fungicides, New Yor
k 1977+ pp, 493-495).

The same document gives 42 references to mutational resistance that occurs as a result of the action of systemic fungicides with several specific sites of action. Considering that the use of systemic fungicides offers several advantages in control methods, despite the possibility of strong resistance, it would not be reasonable to exclude them from practical plant protection. This is supported by the fact that the current and future use of these fungicides is under the constant consideration of experts. Unusual benefits arising from systemic characteristics cannot be excluded. Therefore, research to solve the problem of resistance continues with increasing intensity.

5. Research efforts were developed to discover methods such as: methods to slow the emergence of genes with higher resistance, methods to mitigate changes in strain association in pathogenic populations, and methods to mitigate the increase in resistant strains in actual populations.

Among the possible avenues, the discovery of fungicide combinations based on fungicides with several specific sites of action and their application in plant cultivation techniques is promising. As a result of these efforts, manufacturers of plant protection agents have combined fungicide compositions, such as Rohm and Haas's Epidor (10% by weight).
benomyl and 62% mancozeb by weight) or Eli &Lilly's Trimidal [
F] (containing 8% by weight Nuarimol and 32% by weight Maneb) Still other compositions have been developed. Hungarian Patent No. 158,608 also discloses that 2,3-dihydro-6-methyl-1,4-oxathiin-6-cal has a specific site of action, and that Roxyquinoline.

or composition 6 containing in combination with metal salts thereof. relating to things.

During the inventors' research, first of all the activity of the compounds of formula (1) was investigated and then combinations of active ingredients were tried. These later studies were aimed at determining the usefulness of compounds of formula (T) with known systemic fungicides. The activity of the compound of formula (1) against seven fungi in a liquid medium was determined by the active ingredient (7) from 0.1 to i o o o
Tested within ppm concentration limits.

The results obtained are summarized in Table 1.

Further studies were conducted to determine the optimal weight ratios between the active ingredients of the compositions of the present invention as well as the effective amounts of these compositions to be used. Surprisingly, it has been observed that a synergistic effect appears when the active ingredients are used in certain weight ratios.

The present invention therefore relates to a synergistic fungicide composition, which composition comprises a 3,5-dinitro-4-chlorobenzoic acid derivative of formula (I), in which R is 1 to 6 (1) dimethyl-(N,N'-(1#2-phenylene-
Bis(thiocarbamoyl)-bis(carbamate))
, or (II) a benzimidazole derivative of formula (It) (
(wherein, R1 represents hydrogen or a group of formula (a)), or (Illll pyrimidinyl methanol derivative of formula (1) (wherein R3 and 马 are the same or different, phenyl optionally substituted with halogen) group], or (1v) a 1.2.4-triazole rust conductor of formula (■) (
In the formula, R5 represents hydrogen, a phenyl group, a phenoxy group optionally substituted with a phenyl group or a halogen, or a benzyl group substituted with a halogen, and RI5
represents hydrogen or trifluoromethylphenyl group,
R7 is a phenyl group or groups (C), (d) and (e)
(in which R8 represents an alkyl group having 1 to 4 carbon atoms) and the weight ratio of the active ingredient of formula (1) to any other active ingredient is 1=2 to 14:1.

The 6,5-dinitro-4-chlorobenzoic acid derivative of formula (I) representing one of the active ingredients of the synergistic fungicidal composition according to the invention is an ester, in which R
is an alkyl group containing 1 to 6, preferably 1 to 4 carbon atoms, with methyl or ethyl being most preferred.

In the compound of formula (1), R3 and R4 may be the same or different and represent a phenyl group optionally substituted with one or two halogen atoms.

Preferably R3 and R4 represent a phenyl group substituted by halogen (chlorine and/or fluorine are especially suitable).

In the compound of formula (IV), R5 is hydrogen, a phenyl group, a phenoxy group substituted with a phenyl group or a halogen, or one or two halogen atoms (the halogen is preferably halogen). represents a benzyl group substituted by

R6 represents hydrogen or a trifluoromethylphenyl group, and R7 means a phenyl group or one of groups (c), ((1) and (e). In the group of formula (d),
The butyl group is preferably a tertiary butyl group.

In group (e), 'R8 is 1 to 4, preferably 2 to 4;
means an alkyl group containing 3 carbon atoms.

In the synergistic compositions of the invention, the weight ratio of the active ingredient of formula (I) to any other active ingredient is 1:2.
and 14=1.

Within these limits, the weight ratio of the compound of formula (1) to dimethyl-fN,N'-[1,2-phenylene-bis(thiocarbamoyl)]-bis(carbamate)) is from 1=3 to 3:1. It is desirable that the The weight ratio of the compound of formula (1) to the compound of formula (II) is preferably 1:2 to 6:1. The weight ratio of the compound of formula (1) to the compound of formula (1) is 1:1 to 14:
1 is preferred. The weight ratio of the compound of formula (1) to the compound of formula (■) is preferably 1:2 to 14:1.

The form in which the composition-saving compositions of the invention are applied can be adapted to the given purpose and the requirements of its use. It may be a dressing in the form of a powder or suspension, a solid or liquid spray, an emulsified concentrate, a powder, etc. convenient for treating plant stocks. For the preparation of the compositions, it is possible to use liquid and/or solid carriers, auxiliaries and other additives that are required depending on the formulation and are commonly used in the production of plant protection agents. The content of active ingredient in the composition can vary between 5 and 85%.

Based on the inventors' experiments, against specific bacterial species.

Optimal combinations of compounds, optimal synergistic ratios of active ingredients, average usage amounts relative to total active ingredient content, and specific formulations suitable for particular applications are summarized in Table 2.

(9A) A great advantage of the compositions of the present invention is that the production and application of these compositions reduces their use due to their synergistic action, resulting in new and advanced The aim is to expand the variety of pesticides by providing plant protection agents that are effective against a wide range of microorganisms and have antibiotic effects against a wide range of microorganisms. Further benefits are gained by the fact that farmers should not necessarily abandon known systemic fungicides, which have become increasingly popular as a result of resistance problems.

The composition of the invention and its fungicidal action are illustrated by the following examples without limiting the scope of the invention.

Example 1 A film dressing containing a total of 30 active ingredients in suspension for dressing wheat seeds for autumn sowing was prepared using methyl 3,5-dinitro-4-chlorobenzoate (DNCB-Me) and methyl 1H. -benzimidazolyl-2-carbamate (“cargentasim”) or 1-
(4-chlorophenoxy)-1-(IH-1,2,4-
) riazolyl-1)-3,3-dimethyl-2-butanol ("triadimenol") in the combinations shown in Table 3. The ratios of active ingredients are shown in Tables 4.5 and 6.

Table 3 DCNB-Me + Carpendazim 30%
-DCNB-Me+) riadimenol
-30% ethylene glycol
7q67-cresol-formalde-7r condensation product 6% 6Tymowirit DM-21 type film-forming polymer 16% 16q6 silicone SRE type antifoaming agent 1% 1Tyrodamine
2B4 Dye 2 yen 2% ion exchange water 68% 3
The activity of compositions A and B was studied under laboratory and field conditions against sprout disease of autumn wheat.

Some of the fall/J% wheat seeds of the M2S variety heavily infected with Fusarium spp. were infected with 0.2% by weight of Ti1letia 5porules before dressing.

Fusarj, um spp, or Fusariu
Seeds infected with M spp, and Ti1letia were dressed using the studied compositions shown in Tables 4.5 and 6.

Seeds infected with Fusarium spp. and subjected to hair dressing were tested in the laboratory. In each process,
Two hundred seeds were placed on selective papavide and breeding media and cultured for 10 days at 20-22°C under diffused light. The percentage of germination was determined and then the percentage of infection of Fusarium spp- was evaluated under a microscope.

Eight series of these tests were conducted in parallel, and the average results are summarized in Table 4.

A field experiment was also conducted on seeds infected with 922-Ti1letia in parallel rows in randomly arranged plots of 2 square meters each. The seeds were planted on November 28th with a row spacing of 12C.
IrL was seeded at an amount of 6C1 per plot.

To evaluate phytotoxicity, 150 seeds were sown in the 6th row of each plot using a "seeding reed". This evaluation was made on April 10th of the following year by measuring the number and plant length of plants and determining the condition of the plants based on general impressions. Ti
Activity against Tiletia was assessed by examining each panicle at full maturity and determining the number of healthy panicles and the number of panicles infected with Tiletia. The average test results for 6 parallels are shown in Tables 5 and 6.

1 Based on these experiments, it can be said that in laboratory experiments the activity against Fusarium spp. #/), i.e. by processing the active ingredients in a ratio of 1:2 to 2:1, the synergistic effect in the above case compared to the activity when DNCB-Me or carpendazim were used separately. effective. However, in the case of dressing with DNCB-Me + )riadimenol, 0.3+0.2 and 0.
At a dosage of 4500.15) cy/ also showed high activity. Germination percentage was also improved by these treatments. In plot experiments, treatment with the above amounts and ratios of active ingredients was shown to be the most advantageous in terms of the number of plants developed, plant length, number of panicle infections and their severity.

Example 2 Botrytis cinerea, which harms new shoots,
FusariumGraminearum, Rh1z
octonia 5olari and Tri-chot
A dispersion dressing was prepared for laboratory studies of activity against H. hecium roseum and for the study of activity in the emergence of pea seeds under whirlpool and field conditions, including ethyl 3.5- A total of 30 %
Contains active ingredients. The contents of the composition are shown in Table 7,
Also the ratios of the active ingredients studied and the experimental results are listed in Section 8.9.
．． 1° and Table 11. Seeds of BR-52 peas were gelled in a known manner with the fungicide composition to be tested.

Table 7 Dispersant 1494 10 Ethylene glycol 12Vin
arol ST Poly 2” = Lua A/ Co-/I/
8 Defoamer LO511 Tbod, amin BSA 1150
C], 4 ion exchange water 3
7.1 Activity against fungi was studied by the agar diffusion method under laboratory conditions as follows.

52 ml of potato-agar plates were placed in 15 crIL diameter Hetri dishes and each agar plate was layered with 8 ml of microspore suspension of the fungus under test. The agar medium contained 3 parts by weight of medium and 1 part by weight of microspore suspension.

The concentration of the microspore suspension was adjusted in the field of view by microscopic control to 15-50 microspores/ml. A round hole with a diameter of 10 mm was made on a plate of agar that had been solidified in a dish.

In each hole, 0.2 ml of a mixed aqueous solution of the disinfectant containing the active ingredient under test was pipetted in the amounts and proportions indicated in the evaluation schedule. The culture medium is kept in a thermostat for 25-26 hours.
It was kept at 10°C and its inhibitory effect on inoculated colonies was evaluated by measuring the diameter of its inhibition zone. The results are shown in Table 8.

7 Table 8 Agar diffusion method test 1:3 200 13 9 10 12
1:1 200 14 10 12 1
43:1 200 14 11 11
151:3 300 15 11 10
1611 300 1610 12 17
3:1 300 15 11 13 1
71:3 400 16 9 11 1
61:1 400 17 9 12 1
63:1 400 19 10 14
'181:0 200 12 4 4
81:0 300 14 6 6 1
01:0 400 16 7 7 11
0:1 200 12 7 6 30
:1 300 13 8 7 5 rivers 4D
Dj5978 Based on Table 8, DNCB-Et/Thiophanate-
200. of a composition containing methyl in a ratio of 1=3 to 6:1.
Concentrations of 300 and 400 ppm contain more Fu than expected based on the same usage amounts of those components.
Sarium graminearum, Rh1zoc
toniasolani and Trichotheci
It can be said that it is much more effective against um roseum.

The degree of infection of the dressed seeds was also investigated under laboratory conditions as follows.

Two hundred seeds each were placed on moist filter paper in a sterile vetri dish. After 8 days of incubation at 18°C, the number of seeds infected by the pathogen was determined. The results are shown in Table 9.

From Table 9, it can be seen that the active ingredients DNCB-Et and thiophanate-methyl can well inhibit the growth of pathogens that infect seeds during incubation. It can be observed that the combinations obtained were obtained only when the active ingredients were present in a ratio of 1=1 to 3:1.

The purpose of the greenhouse experiment was to determine the effect of dressings on the germination rate of pea seeds. Therefore, sowing seeds of the BR-52 species were dressed with a composition containing DNCB-Et and thiophanate-methyl in the proportions shown in Table 10, and 100 seeds of each were prepared in propagation tubes containing vegetable soil. The dressed seeds were sown in four parallel rows. Cover the seeds with soil and calculate the number of sprouted plants after sowing.
Measurements were taken on day 1, 14 and 21. The results are shown in Table 10.

However, based on the number of budded plants (although the difference in budding rate is low, the difference in activity between the combination containing the same usage of both active ingredients and those treated separately is surprisingly high.

Combinations containing active ingredients in a ratio of 1=6 to 3:1 have a synergistic effect.

Field Experiments BR-52 dressed pea seeds were tested on 4 nLz plots in a random plot arrangement in four parallel rows. A total of 20 seeds were sown on April 3rd at a depth of 5 crIL with a row width of 40 cIrL and a stem spacing of 5 degrees. Plants that emerged on May 19th were counted with 2 to 4 leaves. The results are shown in Table 11.

During field experiments, the best results were obtained using 1 kg/ton of the DNCB-Et/thiophanate methyl combination containing the active ingredients in a ratio of 1:3 to 3:1.

Example 6 For the study of activity against Plasmopara destru, ctor (onion mildew), 50 t.
Samples of % hygroscopic powder (wp) were prepared according to the compositions shown as A and B in Table 12 of n-propyl 3.5-dinitro-4-chloropene.
It contained both DNCB-Pr and α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinylmethanol (7enarimol J). Random arrays were performed on row-parallel 500 m'' sections. One onion of the "Aroma" variety was sown on April 12th at a rate of 4.5 kg/ha.

Treatment with a budworm agent was carried out at the beginning of the head-heading period (June 21st) and then twice during the head-heading period (June 29th and August 10th) using a "Maruyama" type air vaporizer at 50 DA'/ It was carried out using a combination of active ingredients in which samples A and B shown in Table 12 were mixed according to the usage amounts shown in Table 13 with Hekucool water.

Table 12 Ingredients/Content A BDNCB-
Pr, industrial grade 95% purity 52.63%
-Ultrasil VN5 synthetic silicate
11M 5% kaolin
Section 29.37 Section 35.73 Evaluate 10 x 1 [] plants in each plot for 0 to 2 weeks after the last spraying.
It was conducted using a scoring scale of 6.

5 The scoring scale used to evaluate the degree of infection of the shoots and leaves was as follows.

〇 - No infection 1-5 infection or less 2 = 6-10% infection 3 - 11-25 infection 4 - 26-50% infection 5 = 51-75% infection 6 = 76-100 infection For infection assessment, the number of infected plants was calculated as a percentage of the total number of plants studied (F'%) and the index of the degree of infection (
The infection index) was determined by the following formula.

In the above formula, Fi = infection index al - value of the scoring scale of individual infection fi = number of plants belonging to the scoring scale value of individual infection (frequency) n = total number of plants studied The lower the value of F This means that the effect of objects will be large. The results of this experiment are summarized in Table 16.

From Table 16, it can be said that when DNCB-Pr was used together with Fenarimol, the degree of infection of onions by mildew was reduced to the lowest level. The proportion of the most effective combination showing the best synergistic action at a usage rate of 1 kg/ha is 621-5.7=1.

Example 4 To investigate the activity against Plasmopara viticola (grape mildew), a series of aqueous suspension concentrates containing a total of 40 parts by weight of active ingredient were prepared using isopropyl 6,5-dinitro-4-chlorobenzo-c-
) (DNCB-iPr) and α-(2,4-dichlorophenyl]-α-phenyl-5-pyrimidinylmethanol (r) realarimol”) according to the contents shown in Table 14.

The proportions of active ingredients are shown in Tables 15 and 16 in the Usage column.

Table 14 Component/Content DN ('B-iPr + triarimol
40.0% Ethylene IJ Coal 8
%Ten5iofix XN6 Emulsifier
2% Ten5iofix CD5 emulsifier
1.5% Pluriol PE 10500 Emulsifier 2.5% 5ilicon SRE Antifoam 1.0% Kelzan 8
0-1% ion exchange water
A 44.9% biological experiment was carried out in two parallel lines on a 20-year-old vineyard of Italian Riesling grapes in Renz Mosel. Sixty grapes were planted in several rows in one plot of 180 m2. A total of 8 fungicide applications were applied (20-25 cFrL) at new shoots, during inflorescence elongation, at the beginning of flowering, at the end of flowering, at pea-sized fruits, at 1 inflorescence drop. 0 before, at the time of flower drop of the inflorescence, and at the time of the enlarged growth of fruit grains)
t Fit the D-7 type spray head 7CS'tre
yEtr-Puch-I (performed by spray gun of an aflinger-type atomizer. Together with the composition under test, Kolosul, which is ineffective against grape mildew,
8Q WP sulfur composition 3 to 9/ha and I
1.6117 hectares of Dka 1 ux insecticide were applied to the plants.

The evaluation is 4 x 5 in each plot during the growth period of grape bunches.
This was done by examining 0 bunches and 10 x 5 plants. Untreated controls were evaluated by testing 2 x 10 strains. The degree of infection of leaves and inflorescences and the degree of scorching of leaves and fruits were also measured.

The values of Fl and Fl were calculated by the method, scoring scale and equation set forth in Example 3. The results are shown in Tables 15 and 16.

This experiment revealed that the combination of DNCB-iPr and triarimol in a ratio of 1.25:1 to 421' to 0.7
When used on an area of 197 hectares, it was proven that the effect against grape mildew was greater than expected from the total activity of each active ingredient.

Example 5 Methyl 6,5-dinitro-4-chlorobenzoate (DNCB-Me)'l Methyl 1H-penzimidazolyl-2-carbamate ('carpendasim') for investigating the activity against Fusarium infection of autumn wheat ears.
, 1-(4-chlorophenoxy)-6゜6-dimethyl-
1-(IE-T-1, 2, 4-) Rear door route 1)-
2-butanone (“triazole 2”), 1-[2-(2,
4-dichlorophenyl)-4-propyl-1,6-thioxolani-2]-methyl-IH-1,2,4-triazole (“propiconazole”) and 1-[diphenyl-(3-trifluoromethyl)-phenyl Yomethyl
Table 17: Hygroscopic powder (wp) composition containing 70 wt. Prepared according to. The proportion of each active ingredient is 18
．． 19. Shown in Tables 20 and 21.

Table 17 Ingredients/Amount ABCD (Industrial grade, purity 95%) 73.7--
-DNCB-Me+triadimefon (industrial grade, purity 95%) -73,7--D
NCB-Me+Derobicona ~ Door (industrial grade, purity 95%) --73,7-D
NCE-Me + Fluotrimeter door (industrial grade, purity 95%) ---73,7Cab-0-8i1
Synthetic carrier 10 10 10 10Atlox 48
62 minutes teaching material Ro 3 3 3 Atlox 499
5 Wetting agent 3 3 3 6 PO1yDhOn 0 Dispersing agent 4 4 4 4 Orin carrier 6
．． 3 6.3 6.36,36 Biological experiments on autumn wheat (Jubilejnaja-5
The experiment was carried out in 4 series of 20 plots of 10 plants. Poricide treatment was carried out on 600,137 hectares of water at the end of the harvest. The infectivity of panicles with Fusarium 5pp- was assessed by examining 2×100 panicles in each plot 10 days after spraying.

The crops in each plot were measured after harvest, with an average sample taken from the seed crop and the seed Fusarium spp.
The total degree of infection was determined on the basis of 2×1[]0 seeds by microscopic examination after incubation of the cultures on Papavisa medium for 8 days at 20° C. (Conventional surface disinfection was performed after assessment of internal infection level.) The results of this experiment are summarized in Tables 18.19.20 and 21.

9 60 6,5-dinitro-4-chloro47~do-f--) (DNCB-Me
) and 1-(2-(2,4-1'chlorophenyl)-4-
Ethyl-1,6-thioxolani-2]-methyl-IH
-1,2,4-triazole (“etaconazole”),
1-(4-phenylphenoxy)-3,3-dimethyl-
1-(1a-1,2,4-)Rear door 1)-2-
Butanol (“biteltanol”) and α-(2-
chlorophenyl)-α-(4-chlorophenyl)-5-
A total of 20% by weight and 1t% of active ingredients were added according to Table 22 using birimisonylmeth/-ol ("Fenarimol").
An emulsifiable concentrate containing the following was prepared. The proportions of active ingredients are shown in the Usage column of Table 26.

Table 22 Ingredients/Contents A (Feed B (%l Cf) DNCB-Me + Etacona 1 Household 20--DNC
B-Me+ Bitertanol -20-DNCB-Me+
Fenarimol --20 cyclohexane solvent
20-40 xylene solvent 50 3
8 - AIOX 4858 emulsifier 6 -
-A, 1ox 8916 emulsifier 3.5--A
IOY 4851 Emulsifier 3.5--Isophorone Solvent -3O- Tensiofix D-120 Emulsifier 6.
5-Tensiofix As emulsifier 3
．． 5-Tensiofix B-7425 emulsifier -
5,0-)TAN solvent --30Ar
conal N08Q emulsifier -15. OEmul
sogen EL emulsifier 1.58
anogenate T-180 emulsifier -3,53 Biological experiments were carried out on a 20 year old cultivated land with 7.5x in multiple plots of 0.5 hectares.
It was carried out in two rows grown with 4.5 m fasteners. Fungicide application was carried out 9 times during the growing season with a cycle of 1-2 weeks, depending on the water volume of 1000//ha, using a Kerti sprayer with a Tea-Jet spray head.
Leaf infection was evaluated twice on 10 trees during the first and second budding stages using a tox Na-1Q sprayer. One hundred leaves from each tree were examined. The degree of fruit infection and burn was evaluated on 10 trees before harvest. Fifty fruits from each tree were examined. The results are shown in Table 23.゛From Table 26, the combination of active ingredients tested, namely DNCB-Me and Etacona,
When using 1.15 to 1.35 kg/ha of combination with either Vitertanol or Fenarimol, the proportion of active ingredient is 6.6 to 12.5
When = 1, Venturela 1naequalis
It can be said that there is a synergistic effect on

4 Example 7 Peronosnora mansfluria ()
! Methyl 3,5-dinitro-4-rioo benzoate (DNCB)
-Me) and 1-(2,4-dichloropencyl)-3,3
-dimethyl-1-(1H-1,2,4-triazolyl-
1) -2-Butanol (“Dichobentra 1-ru”)
was used to prepare a composition of hygroscopic powder (wp) containing a total of 70 parts by weight of active ingredients according to Table 24. The proportions of active ingredients are shown in Table 25.

Table 24 DNCB+Me+Diclobentra 1 unit - rule 7
0-linked Cab-0-8i1 synthetic carrier
15% Na, tzer TS wetting agent
6%″Dispergiermittel
ST'' Dispersant 6% Polyp)lon 0 Dispersant 6% 1 Biological experiments were carried out on Ewans type soybeans.

The fungicide treatment using the composition in the first trial was carried out three times (when the soybean plants were 40 cm long, at the early stage of flowering, and at the full flowering stage). Is the spraying 400A? RMJ-1 with water volume of /ha
4--The experiment was carried out using an IQ type field machine. Evaluations were made on 10 x 10 plants 16 days after the final treatment. The results were calculated according to the scoring scale and equation presented in Example 3. The degree of leaf scorch (leaf damage) is also shown in Table 25. When the total amount of active ingredients used is 2.1 kg/ha, the ratio of DNCB-Me to diclopentrazole button is 1:2 to i , 1:i has particularly favorable biological effects. For the same amount of active ingredients used, the activity of the combination of active ingredients exceeds the effect when the same ingredients are measured separately.

B 70 Example 8 To investigate the activity against Ustilago sp.
chlorophenyl)-α-(4-70 chlorophenyl)-5-
Pyrimidinylmethanol (“Nuarimol”) or 1
-(4-chlorophenoxy)-3,3-dimethyl-1-
The 26th
A composition of dressing powder "4r" containing a total of 40% by weight of active ingredients according to the table was prepared. The proportions of active ingredients are shown in Table 27.

Table 26 DNCB-Me+Nuarimol 40-DNC
B-Me+Triadimenol 40Tin
ovetin B wetting agent 2-Di
spergator HG dispersant 5-N
owiol 30/88 polyvinylfurcol-j 4
-Horna Re1nes Milori Bl
au” - dye
1.51 Kaolin 47.
5 40.25Ultrasil VN3 synthetic carrier
5Netzer Is humectant
2.5 Ultrazine Na dispersant 6.0 Rbodoviol 1
4/120 polyvinyl alcohol
-2,5 dextrin
2.5 Rhodamine BSA 11
50 Dye 1.252 G infected with Ustilago sp, (mily mildew)
K-59 barley seeds were dressed with the composition under test and then sown in four parallel rows in 50 m2 plots with a row spacing of 12 CIrL and a depth of 5 crn in a random plot arrangement. Accurately 150 seeds were sown in a 2 m length in the 8th row of each plot. Phytotoxicity was observed when barley was sown to a length of 2 m during the stage of 2-4 leaf development.
Mildew infection was assessed by counting the number of plants sprouting from grain seeds and measuring the length of the sprouted plants. I did it. The same plots were also investigated by microspore germination. The results of this experiment are number 27.
They are summarized in the table.

Table 27 1 +0.5 117.8 8.6II11.2
5+0.25 113.3 8,6 01.4
0+0.10 114.0 8.5 01.4
0 - 110.3 8.2 441.80-
97.5 8.0 15.3- 0.5
114.8 8.5 3.0- 0.7 1
14.5 8.5 1.81 +[1,51
18,58,30 1,25+0.25 119.3 8.7 0
1.40 + 0.1 118.1 8.4
01.40 - 110.3 8.2 441
．． 80 - 97-5 8.0 15.3-
0.5 115.4 8.3 4.3-
0.7 115.0 8.1 0.5 Untreated control 109.0 B, 6 97
．． 5/6 By using the combination of active ingredients at 1.5 kg/ton, the mildew infection of ears was completely eradicated when the ratio of DNCB-Me to Nuarimol or Triazimol was 2:1 to 14:1, respectively. .

Agent: Akira Asamura 4 37/48) 0 Inventor: Marianna Kertész ne Szavo, Budapest, Hungary 6 Mayakovszkyu, 70 0 Inventor: Mihalyi Nagy, Budapest, Hungary 14 Utoya Nagy Lajos Kir 7 Roby 0 Inventors István Magyary Hungarian Gaudro Strömfeld Aulersetany 6 0 Inventors Beta Inkzedy Budapest, Hungary 12 Trnarja Ny 15 0 Inventors Laszlo Wall Budapest, Hungary 1 Suzena Cyr 1 -Ei0 Inventor: Beter Bohus, Budapest, Hungary 9, Napfuenii, Ny 270 Inventor: Gyula Eifert, Dounahara, Hungary・Ny7-A0 Inventor: Jozsev Stanetsk Budapest, Hungary 19 Hikade Aladar Ny 21 0 Inventor Edith Halasz ne Kovacs Budapest, Hungary 10 Gyakol Ny 16 371

Claims (9)

[Claims] (1) A synergistic fungicidal composition having as one of its active ingredients the formula (1), in which R represents an alkyl group containing 1 to 6 carbon atoms. 3,5-dinitro-4-chlorobenzoic acid derivatives and other active ingredients include (1) dimethyl (N
, N'-(1,2-phenylene-bis(thiocarbamoyl)]-bis(carbamate)), (1) Formula (") RI O (wherein, R1 is hydrogen or the following formula (a) ○=c- Benzimidabul derivatives having (li+) formula (I[) H R3-C-R (representing the group NH-c4H9(a)), in which R3 and R4 are the same or different and are optionally substituted by halogen. (representing a substituted phenyl group) and (1v) a pyrimidinyl methanol derivative having the formula (■) represents a phenoxy group or )/lodene-substituted benzyl group, R6 represents '!hydrogen or a trifluoromethylphenyl group, R1 represents a phenyl group or the following formula % () () (wherein R8 is 1 to 4 represents an alkyl group having carbon atoms of
and an active ingredient of formula (1), dimethyl (N,
N”-[1#2-phenylene-bis(thiocarbamoyl)]-♂hisbamate)) and formula (11), (II
) and (IV) in a weight ratio of 1:2 to 14:1. (2) A synergistic fungicidal composition according to claim 1, comprising a total of 5 to 85% by weight of active ingredients. (3) Synergistically acting compound according to claim 1, characterized in that it is a compound of formula (D (R is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an ethyl group). Fungicide composition. (4) Claim 1 characterized by a compound of formula (l[) (R3 and R4 represent a phenyl group substituted with halogen, and the halogen atom is a fluorine and/or chlorine atom) A fungicide composition with synergistic action. (5) A synergistic fungicidal composition according to claim 4, characterized by a compound of formula (1) (R3 and R4 represent a chlorophenyl group). (6) Formula (1) (R3 represents a chlorophenyl group,
and R4 represents a fluorophenyl group. (7) Characterized by a compound of formula (IV) (R5 represents hydrogen, a phenyl group, a phenoxy group optionally substituted with a phenyl group or chlorine, or a benzyl group substituted with 1 or 2 chlorine atoms) A synergistic fungicidal composition according to claim 1. (8) Claim 1 characterized by a compound of the formula (■) (R7 represents a group of the formula (e) C] (in the formula, R8 represents an ethyl group and a zotepyr group) A fungicidal composition having a synergistic action as described in Section 1. (9) Compound of formula (1) and dimethyl (N, N'-(
1,2-phenylene-bis(thiocarbamoyl)-his(carbamate)) in a weight ratio of 1:6 to 3:1. . (IQI) A synergistic fungicide composition according to claim 1, comprising a compound of formula (H) and a compound of formula (It) in a weight ratio of 1:2 to 6:1. (II) A synergistic fungicidal composition according to claim 1, comprising a compound of formula (1) and a compound of formula (1) in a weight ratio of 1:1 to 14:1.02 Formula (1) ) and the compound of formula (IV) in a weight ratio of 1:2 to 14:1. A process for producing a fungicide, in which 3,5-dinitro-4=chloro having 2m C'0O-R C1 (wherein R represents an alkyl group having 1 to 6 carbon atoms) is used as an active ingredient. -benzoic acid derivative and dimethyl (NtN'-1t2-phenylene-bis(thiocarbamoyl)]-bis(carbamate), formula (If) 10 (wherein R1 is hydrogen or formula (a) 0 = C-NH- C, R9 (a) represents a group), as long as it has the formula (I[) in which R3 and R4 are the same or different and are phenyl groups optionally substituted by halogen; midinylmethanol derivatives, and formula (IV) 6 (wherein R5 represents hydrogen, a phenyl group, a phenoxy group optionally substituted with a phenyl group or a halogen, or a halogen-substituted benzyl group, and R6 is hydrogen or trifluoromethylphenyl and R) represents a phenyl group or the following (C), (d) and (e
selected from the group consisting of 1,2.4-)suazole derivatives having a radical of 1 (in which R8 represents an alkyl group containing 1 to 4 carbon atoms); in a weight ratio of 1:2 to 14:1 and further admixing the active ingredient with carriers, dispersion media and other auxiliaries and additives commonly used in the production of plant protection compositions. A method for producing the above composition, characterized by: