CS241543B2 - Fungicide - Google Patents

Abstract

The invention relates to synergistically active fungicide compositions containing, as one active ingredient a 3,5-dinitro-4-chloro-benzoic acid derivative of the formula (I> <IMAGE> wherein R stands for an alkyl group containing 1 to 6 carbon atoms, while the other active ingredient is one of the group consisting of dimethyl N,N'-[1,2-phenylene-bis-(thiocarbamoyl)]-bis(carbamate), a benzimidazole derivative of the formula (II), <IMAGE> wherein R1 stands for hydrogen or a group of the formula (a), <IMAGE> a pyrimidinylmethanol derivative of the formula (III), <IMAGE> wherein R3 and R4 are the same or different and stand for a phenyl group optionally substituted by halogen, and a 1,2,4-triazole derivative of the formula (IV), <IMAGE> wherein R5 stands for hydrogen, a phenyl group, a phenoxy group optionally substituted by phenyl or a halogen; R6 stands for hydrogen or a trifluoromethylphenyl group and R7 stand for phenyl or for one of the groups (c) to (e> <IMAGE> wherein R8 represents an alkyl group containing 1 to 4 carbon atoms.

Description

(54) Fungicidal product

2

BACKGROUND OF THE INVENTION The present invention relates to a synergistic fungicidal composition containing, by weight, from 5% to 85% by weight of the active compound consisting of an alkyl ester of -3,5-dinitro-4-chlorobenzoic acid wherein the alkyl has 1 to 6 carbon atoms and a pyrimidinylmethanol derivative

OH

.7 (II!) Where

R ₃ and R 4 have the same or different meanings and represent a phenyl group optionally substituted by halogen atoms, in a weight ratio of 1: 2 to 14: 1.

The composition enriches the pesticide range with a new, highly effective composition protecting a broad spectrum of plants and polluting the biosphere less than known compositions, as it can be used in a small amount due to the synergistic action of the ingredients ^; -amount.

The present invention relates to a synergistic fungicidal composition comprising a 3,5-dinitro-4- (chlorobenzic acid) derivative of the formula I

where

R represents an alkyl group having 1 to 6 carbon atoms as one active ingredient, the other active ingredient forming a synergistically active mixture with the active ingredient of the formula I is a pyrimidinylmethanol derivative of the formula III

Cli) where

R ₃ and R 4 have the same or different meanings and are a phenyl group optionally substituted by halogen atoms.

The composition according to the invention is suitable for the treatment of various plant cultures against numerous fungi, for example for seed dressing or for the treatment of plant parts.

One type of active ingredient of the fungicidal composition of the invention, methyl 3,5-dimtro-4-chlorobenzoate and isopropyl 3,5-dinitro-4-chlorobenzoate, and their activity against Alternaria fungi. cleracsae-and Sclerotinia fructicola are known from U.S. Patent 2,841,522. The fungicidal action of dimethylthiyl {N, N * - [1,2-phenylene-bis (thiocarbamoyl)] -bis (carbamate.) is described in Hungarian · U.S. Patent No. 169,823; The compounds of the formulas II, III and IV containing a heteroaromatic ring - having several nitrogen atoms - are also known.

The process for the preparation and the fungicidal action of systemic fungicides of the general formula II are known from U.S. Pat. Nos. 3,631,176 and 3,657,443, while the characteristics of the active compounds of the formula III are described in British Patent Specification 1,218,623. The characteristics of the active compounds of the general formula IV are described in U.S. Pat. No. 3,912,752.

The simultaneous action of 3,5-dinitro-4-chlorobenzoic acid esters at various sites is not practiced at all, although they are known compounds. The main reason is probably the fact that although these compounds are very effective in field conditions, they damage the protected plant when used in optimal doses. Therefore, a considerable risk of phytotoxicity must be taken into account in their use. Problems are also with the use of systemic fungicides having specific sites of action. The compounds of formula (II) metabolizing methyl (1H) benzimidazol-2-ylcarbamate have an excellent fungicidal action, but after 1960, the literature has increasingly pointed to the resistance of fungi to these compounds, which develop after repeated use.

Fungus resistance to benziimidazoles is reported in SG Georpoules: Antifungal Cornpounds in Sisler: Developiment of Fungal Resistance -to Fungicides, New York 1977, pp. 493-495. In this publication, 42 references to the development of mutational resistance to systemic fungicides having certain specific treatments. - Considering, irrespective of the possibility of some resistance, that the use of systemic fungicides has some advantages in combating fungi, it would be unreasonable to exclude them from the practice of plant protection. This is supported by the fact that the use of these fungicides at present and in the future is under constant control by experts. The extraordinary advantages of system properties cannot be overlooked.

Therefore, research into resolving the problems of resistance to these fungicides has become more and more intensive.

This research effort focuses on the following tasks: to prevent the development of genes with higher resistance; mitigating changes in the combination of strains -with a pathogenic population -and mitigating the increase in resistance of strains of the current population. From the possible paths, it seems promising - to detect and adapt to plant growing technology based on fungicide-based mixtures - with fungicides with certain specific modes of action. These efforts have resulted in a combination of fungicidal agents from plant protection product manufacturers, such as Ephorn® from Rhorn and Haas-Co.. (containing 10% benoimyl by weight and 62% mancozeb) or Trimiidal® from Eli and Lilly Co. (containing -8% nuarrine and 3'2% -maneb), and other similar compositions. Hungarian Patent Specification No. 158,608 also relates to a composition comprising 2,3-dihydro-6-methyl-1,4-oixathiin-6-carboxanilide which has specific actions in admixture with 8-hydroxy-xychiimolamine. or- with him

6 metal salt; this composition has various specific effects.

In the course of the research in connection with the present invention, the activity of the compounds of the formula I was first examined and then the active compound mixtures. The aim of this research was to determine the usefulness of a compound of formula I together with known systemic fungicides. Activity of the compounds of the formula. It has been investigated in a liquid medium with respect to 7 species of fungi at a concentration of 0.1 to 1,000 ppm of active ingredient. The results obtained are shown in Table 1.

T a b u 1 к а 1

Mushroom column growth values, ppm

Alternaria solani Helmmtho- Aspergillus- Colletotrichum Trichothecium Helmintho- Fusarium sparium niger lindomuthia- roseum sporium graminearum turcicum num carbonum

O O O O O O O Ή 1 rd I Ή I r-i AND tH AND o o G 1 o 1 o 1 o 1 o 1 ó O O O O O O O rd г — 1 rd rd 1 — t o rH o rH Λ AND

rH O O o rd rd θ ' rd rd rd O F | AND AND | 1 O O O rd O O O O rd rd rd O O тЧ r4 O AND rd

Further investigations were carried out to determine the optimal weight ratio of the active ingredients in the fungicidal composition of the invention and to determine the useful dose of the fungicidal composition. Surprisingly, it has been found that the synergistic action is manifested at a clearly defined weight ratio of the active ingredients.

Accordingly, the present invention provides a synergistic fungicidal composition comprising, in addition to a 3,5-dinitro-4-chloro-benzoic acid derivative of the formula I wherein R is C 1-6 alkyl, a pyrimidinylmethanol derivative of the formula III, wherein R ₃ and R4 have the same or different meanings and represent a phenyl group optionally substituted by a halogen atom, wherein the weight ratio of the active compound of the formula I to the active compound of the formula III is 1: 2 to 14: 1.

The 3,5-dimethyl-4-chlorobenzoic acid derivatives of formula I, one of the components of the synergistic fungicidal composition of the invention, are esters in which R is an alkyl group having 1 to 6 carbon atoms, preferably having 1 to 4 - carbon atoms and in particular a methyl group or an ethyl group.

In compounds of formula III, R 3 and R 4 may have the same or different meanings and are a phenyl group optionally substituted by one or two halogen atoms. Preferably R 3 and R 4 are each a phenyl group substituted with a halogen atom, which is preferably a chlorine atom and / or a fluorine atom.

Preferably, the weight ratio of the compound of formula I to the compound of formula III is 1: 1 to 14: 1.

The dosage form of the composition of the invention may be adapted to the substrate to which the fungicidal composition of the invention is applied and the requirements of use. It may be a mordant in powder form <n = eib‘o suspension; a solid or liquid spray application to the plant; emulsifiable concentrate, powder - and similar forms. Liquid and / or solid carriers, adjuvants and other ingredients according to the formulation requirements and used generally in the preparation of plant protection products may be used to prepare the fungicidal composition of the invention. The total active ingredient content of the composition may be 5 to 85% by weight.

Table 2 shows the results obtained on the basis of the tests on the most advantageous mixtures of compounds - given fungal species, the most advantageous synergistic ratios of the components of the effective, medium application doses with respect to. the total content of active ingredients and the characteristics of the compositions for the intended use.

Table 1k and 2

Type Mixture mushrooms The ratio of synergistically active substances Medium dose of active substances Formulation Plasmopa-n-propyl-3,5-dimtro-4-yl-10-oxo ^; t: ailfara de- - (2-chlorophenyl) -ial.fa- ^(4-Chloro, r phenyl) -5- 5Q% WP structor -pyrimidinylniethanol Plasmoisopropyl-3,5-dinitro-4-chlorobenzoate: para: alpha- (2,4-dichlorophenyl) -alpha-phenyl-5- 3: 1- to 5.7 -: 1 1.0 kg / ha vitioolapyrimidinylmethanol Venturia methyl-3,5-dihydro-4-dihydro-4-chlorophenyl-alpha- (4-chlorophenyl) - ^, benzoate: alphainaequalis- (2-chlorophenyl) - alpha - (4-chlorophenyl) - 5- 1.25-: 1- to 4: 1 0.75 kg / ha 40% -FW -pyrimidinylmethanol Ustilago ethyl-4,5-diniro-4-chloobenzoate: alphasp. - (2-chlorophenyl) -alpha- (4-fluorophenyl) - 6.6: 1 to 12.5: 1 1.2 kg / ha 20% EC -S-pyrimidinylmethanol 2: 1 to 14: 1 1.50 kg / t 40% motel powder

WP = wettable powder

EC - emulsifiable concentrate

A particular advantage of the composition according to the invention is that it enriches the range of pesticides with a new, highly effective plant protection agent that protects a wide spectrum of plants, polluting the biosphere less than the prior art, since it can be used in smaller quantities due to the synergistic action of the ingredients. . Another advantage is that farmers do not have to give up the well-known systemic fungicides that they would have to slowly. . leave for a gradually evolving resistance of fungi - to these agents.

The following practical examples illustrate the composition of the invention and its fungicidal action. however, the invention is not limited thereto. The percentages are always by weight.

Example 1

A wettable powder (WP) of 5% by weight (1% containing n-propyl-3,5-diniroi-4-chloro ⁱⁿ benzoate (DNCE-Pr) and alpha-) was prepared to study the activity against Plasmopara. 2-chlorophenyl] -alpha- (4-chlorophenyl) -5-pyrimidinylmethanol (PHENARIMOL) in the composition as given for mixture A and B in Table 3. Biological compounds were performed. on 500-m ² plots in two parallel trials The onion species "Aroma" was planted on 3 April at a rate of 4.5 kg / ha Fungicide treatment was carried out at the beginning of head formation (21 July). twice when creating warheads (July 29 -a

[August 10]] - a "Maruyama" machine and 500 l / ha of water and a mixture of the active ingredients in a ratio according to Table 4 were used, using compositions A and B according to Table 10.

3.

Table 3

Folder / Contents

Technical DNCB-Pr with 95% purity

Technical PHENARIMOL - with a purity of 98% Ultnasil VN3 Synthetic Silicate VN3 Tensiofix BCZ alkylpolyglycolethe sulfate sulphate

Anionic dispersant Dispergatar HG

Sodium lignsulfonate type dispersant Ultrazine Na Kaolin

The evaluation is carried out two weeks - after the last - by spraying on a scale of 0 to 6 for 10 x 10 plants from each plot.

Scale used to assess the rate of leaf infection:

simple infection less than 5 '% infection - 6 to 10'% infection- 11 to 25% infection 26 - to 50% infection- 51 to 75% infection 76 to 100%

For evaluation, the number of infected plants is calculated as a percentage (F%) of the total number of plants examined and the -infection rate index is determined according to this equation

AND (B) 52,63% - 51,02% 10.50-% 5,00% 3,00% 2,00% 5,00% - 6.21% 29, 37% 35,73%

• a ·, x fj where is

Fj index of the infection rate, a, individual scale assessment values, i, number of plants subjected to individual assessment scale (frequency), n total number of plants examined.

Thus, the lower the F value, the more effective the fungicidal composition is. The results of these tests are shown in Table 4. From Table 4, it is apparent that DNCB-Pr, when used in conjunction with PHENARIMOL, reduces the extent of fungal infection onions to a minimum. At a dose of 1 kg / ha, a mixture at a ratio of 3: 1 to 5.7: 1 is most effective, with a synergistic effect.

12

Example 2

To investigate efficacy against Plasmopara viticola (non-falling mold). an aqueous suspension concentrate containing 40% by weight of the active compounds is prepared using isopropyl 3,5-dinitro-4-chlorobenzoate (DNCB-iPr) with alpha-4-dichlorophenyl-alpha-phenyl-5-pyrimidinylmothanol (TRIARIMOL) according to Table 5. The active compound ratio is shown in the dose column in Tables 6 and 7.

Table 5

Slcžka / obsah

DNCB-iPr + TRIARIMOL 40.0%

Ethylenglykojl 8,0%

Tensiofix emulsifier

XN6 2,0

Tensiofix emulsifier

CD5 1.5 ‘% o

Plurlol emulsifier

PE 10 500 2.5%

Anti-foaming agent Silicon SRE 1,0%

Kelzain S 0.1%

Demineralized water 44.9%

The biological test is carried out with 20 years old wine planting. species Italian rizling in two parallel cultivations according to Lenz

-Moser. Sixty vine plants are in rows on a plot of 180 m2. Spraying by fungicide is carried out 8 times (in shoots of 20 to 25 cm, in the extension of the grapes, at the beginning of flowering, at the end of flowering, in the state of grains of pea size, before closing the grapes, after closing the grapes and in blooming) at 1000 l / ha and Steyer-Puch-Hafllnger hand syringes equipped with a Tee-Jet D-7 spray head. 3 kg / ha of Colosulum 80 WP, which is a sulphurous agent, is applied with the test product, and

1.6 l / ha of Ekalux insecticide per plant, these agents do not affect the mold caused by Pilaspopara viticola.

Evaluation is performed at the beginning of flowering of vine plants by testing 4 x 50 grapes and 10 x 5 plants from each plot. The untreated control is assessed by evaluating 2 x 10 plants. The rate of leaf and grape infection is determined. as well as the degree of damage to the leaves and grains. In the manner described in Example 1, the F ° / o value and the F 1 value were calculated. The results are shown in Tables 6 and 7.

Tests have shown that a dose of 0.7 kg / ha of a composition comprising DNCB-iPr and TRIARIMOL in a weight ratio of 1.25: 1 to 4: 1 is much more effective against a wine-attacking mold than would be expected from the overall efficacy of the fungicidal active ingredients. means.

Assessment of leaf infection rate

Dose kg / ha Number of plants with respect to scale rating numbers F% Fj PoDNo-iPr -} - TRIARIMOL 0 1 2 3 4 5 Plant (θ / ο)

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Example 3

To investigate efficacy against Venturia inaequalis (causing apple stinginess), a formulation was prepared using methyl 3,5-dinitro-4-chlorobenzoate (DNCB-Me) and 1- [2-2,4-dichlorophenyl] -4-ethyl-1,3-dioixolan-2-yl] methyl-1H-1,2,4-trlazole (ETACONAZOLE}, 1- (4-phenylphenoix) -3,3-dimethyl-1

- (1H-1,2,4-triazol-1-yl) -2-butanol (BITERTANOL) and alpha- (2-chlorophenyl) -alpha- (4-chlorophenyl) -5-pyrimidinylmethanol (PHENARIMOL) in in the form of an emulsifiable concentrate containing a total of 20% by weight of the active ingredients according to Table 8. The active ingredient ratio is in the dose column of Table 9.

Ta b u1k a 8

The folder / content A (%) B (%) C (%) DNCB-Me + ETACONAZOLE 20 May - - DNCB-Me + BITERTANOL - 20 May - DNCB-Me + PHENARIMOL - -— 20 May Cyclohexanone as solvent ¹ 20 May - 40 Xylene as solvent ¹ 50 38 - Atlox Emulsifier 4,858 3 - - Emulsifier Atlox 8,916 3.5 - - Emulsifier Atlox 4,851 3.5 -. . - Isofoiron as solvent - 30 - Tensiofix D-120 emulsifier - 3.5 - Tensiofix AS emulsifier - 3.5 - Tensiofix B-7 425 emulsifier - 5.0 - Solvent HAN —— . - 30 Arcopal N 080 emulsifier -  - 5.0 Emulsogen EL - - 1.5 Sapogenate T-180 emulsifier - - 3.5

Biological tests shall be carried out in two rows in the case of a twenty-year culture of Joinatan, grown on plots of 0.5 hectares, at intervals of 7.5 x 4.5 m.

The fungicidal composition is used nine times during the marketing period of 1 to 2 weeks using a water volume of 1000 liters per hectare using a Karti tox Na · 10 syringe equipped with a Tee-Jet spray head. The leaf infection rate is assessed twice in ten trees at the end of the first and second stages of shoot growth. 100 leaves from each tree are examined. The rate of fetal infection and the degree of infestation are evaluated at. ten trees before harvest. Examine 50 fruits from each tree; the results are shown in Table 9.

Rate kg / ha

DNCB-Me + ETACONAZOLE

Table 9

Leaf infection rate

1. 2.

rating%

Infection rate Fetal damage (%)

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 '2 - 9.5 9.5 10.2 20.4 - 0,15 10.4 28.5 5.0 0 - 0,2 9.3 26.4 4.7 10.0 Untreated control 27.4 62.6 41.5 0

Leaf infection rate

1. 2.

rating%

Table 9 (continued)

Dose kg / ha DNCB-Me + BITERTANOL

Fetal infection rate (% Fetal damage (%)

1 + 0.15 0 5.3 1.9 0 1.25 + 0.10 0 8.0 2.2 0 1.50 + 0.075 5.1 11.2 2.7 10.0 1.50 - 14.6 32.3 12.5 10.7 2 - 9.5 9.5 10.2 20.4 - 0,15 5.3 21.5 3.8 0 - 0.20 5.9 19.9 2.8 11.1 Untreated control 27.4 62.6 41.5 0 Rate kg / ha Leaf infection rate Infection rate Evaluation DNCB-Me. + PHENARIMOL 1. 2. fruits% fruits%

rating,%

1.00 + 0.150 0 5.5 2.1 0 1,25 + 0.100 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 2.00 - 9.5 9.5 10.2 20.4 - 0.150 6.8 22.4 4.6 0 - 0.200 7.2 18.6 3.1 11.3 neošetře financial control 27.4 62.6 41.5 0

It can be seen from Table 9 that a dose of 1.15 to 1.35 kg / ha of a formulation containing a mixture of investigational active substances, i.e. DNCB-Me together with either ETACONAZOLE or BITERTANOL or PHENARIMOL, exhibits a synergistic action with respect to Venturia sponge inaequalis when the weight ratio of the active substances is 6.6: 1 to 2.5: 1.

Example 4 sp. a formulation was prepared using methyl 3,5-dinitro-4-clilorbenzoate (DNCB-Me) and alpha- (11-chlorophenyl) -. alpha.-4-fluorophore (? 1? 5? 1) -5; -pyrimidinylmethylene-4- (4-chlorophenoxy) -3- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2- buitanol · (TRIADIMENOL) in the form of a dressing powder containing 40% by weight of the active substances according to Table 10. The weight ratio of the active substances is given in Table 11.

For research on efficacy against Ustilago

Table 10

Items / content A (%) B (%) DNCB-Me + NUARIMOL 40.00 _ DNCB-Me · TRIADIMENOL - 40.00 Wetting agent Tinovetin B 2.00 - Dispergator HG 5.00 - Polyvinyl alcohol Nowiol 30/88 4.00 - "Upper · Reines Milori Blau" dye 1.50 - Kaolin 47.50 40.25 Synthetic carrier Ultrasil-VN3 - 5.00 Wetting agent Netzer IS 2.50 Ultrazine Na Dispersant 6.00 Polyvinyl alcohol RIOCIOVOL 14/120 2.50 Dextrin 2.50 Rhodamin BSA dye . 1,25

Seeds. barley of GK-59 species infected with Usitiia-go sp., is pickled with test means, then sown on plots of 50 m ² with a row spacing of 12 cm to a depth of 5 cm; four plots are always sown in the same way. Exactly 150 seeds are sown in the eighth row of each plot at a length of 2 m. Phytotoxicity is evaluated at the developmental stage of two to four barley leaves by counting the plants resulting from 150 seeds sown in the eighth row at a length of 2 m and measuring the height of the mature plants. Mold infestation is evaluated during flowering by counting the ears affected by anthrax. sperm germination is also evaluated. The test results are shown in Table 11.

Table 11 shows that at a dose of 1.5 kg of active ingredient mixture per ton of seed, the fungal ear infection is completely suppressed at a DNCB-Me to NUARIMOL or TRIADIMENOL ratio of 2: 1 to ‘14: 1 by weight.

Claims (6)

the object of the invention Synergistic fungicidal composition, characterized in that it contains, by weight, from 5 to 85% by weight of active compound consisting of a 3,5-dinitro-4-chlorobenzoic acid derivative of the formula I OH Rc-Rh Λ Where COOR means R is C 1 -C 6 alkyl, and from the pyrimidinylnylmethanol derivative. of formula III wherein R3 and R4 are the same or different. a phenyl group optionally substituted by a halogen atom, in a weight ratio of 1: 2 to 14: 1. 2. A synergistic fungicidal composition as claimed in claim 1 comprising a compound of the general formula (I). of formula (I) wherein R is C1-C4alkyl, in particular methyl-methyl-ethyl. Third píisobícLíftingMdiB Synergistic composition according to claim 1, levered that it contains a compound obehného vzoorce III, R ₃ .and R ₄ is phenyl substituted by halogen, wherein the halogen is fluorine and / Neto chlorine. Fourth synergistically active fungicide composition according to claim 3, characterized in that it comprises a compound of formula III wherein R ₃ and R ₄ each represents a chlorophenyl group. 5. A synergistic fungicidal composition according to claim 3 comprising a compound of formula (III) wherein R &lt; _{4 &gt}; is fluorophenyl, R &lt; ₃ & gt _; is chlorophenyl. Sixth synergistically active fungicide composition according to claim 1, characterized in that it comprises a compound of formula I wherein R is as in paragraph 1 above, and a compound of formula III wherein R ₃ and R ₄ in claim 1 has the meaning given in weight ratio of 1: 1 to 14: 1.