HU188180B - Phitopathogen fungicide and antivirus preparatives - Google Patents

Abstract

The invention relates to compositions for the chemical control of phytopathogenic fungi and bacteria in cereal, potato, fruit, vegetable and ornamental plants, consisting of a synergistic mixture of the antimicrobial active ingredient 2-chloro-6-methyl-4-benzylphenol with fungicides in the mixing ratio from 100: 1 to 1: 100, preferably when used against fungal and bacterial mixed infections with a mixing ratio of 5: 1 to 1:50.

Description

FIELD OF THE INVENTION The present invention relates to a phytopathogenic fungus and a bacterial agent which comprises a synergistic combination of an antimicrobial agent, a mixture of 2-chloro-6-methyl-4-benzylphenol (CMB) and carbendazim, maneb or cineb.

Fungi and bacteria attacking crop plants cause damage to crops and stored crops estimated at over $ 20 billion a year. In addition to growing needs, the use of pesticides is of great importance in increasing crop yields and protecting stored crops. Many plant diseases have not yet found a product that can be used with sufficient efficiency and economy (rotting of stored crops, bark disease of fruit trees), especially bacteria, with the exception of potato dressing. Losses caused by crop rot during storage, especially potatoes, are a worldwide problem. Chemical agents for controlling fungal and bacterial pests of potato tubers are described in the literature. Among the many agents used, benzimidazoles (thiabendazole, fuberidazole, benomyl, carbendazim) are the most effective against dry rotting of tubers (Fusarium spp. And Phoma spp.) (See German Patent Nos. 130,427 and 110,423, U.S. Pat. No. 1,209). German Patent Publication Nos. 799 and 1 237 731, incorporated herein by reference

German Patent Publication No. 745,784; U.S. Patent Nos. 3,631,176; and 3,657,443; and German Patent Publication No. 107,204). For example, benomil's outstanding efficacy is explained, inter alia, by its maturation control effect, where 10-20% of the applied amount penetrates the potato tuber about 3 mm deep (Murdoch, Wood, 1972; Burth, Müller, Jahn, 1979).

Dithiocarbamates can also be used to prevent dry rot of the tuber. Pentachloronitrobenzene, manet and mancoceb are used primarily against Rhizoctonis. To date, only the antibiotic chlorinephenicol has been used to effectively control bacterial wet rot of the tuber (Erminia spp.) (See German Patent No. 78,423). It is advantageous to use a mixture of benzimidazole and chloramphenicol to control the pest complex (see German Patent Specification 110 423). This blend allows potato diseases to be effectively combated and can be stored.

The use of chloramphenicol, the first broad-spectrum and first synthetic antibiotic, is not harmless for dressing the stored crop. When used as a medicament in human antimicrobial therapy, there are three major side effects, allergy, gastrointestinal incompatibility, and damage to hematopoiesis (WHO; IARC, 1975, MAYR, 1977).

The WHO has recommended that antibiotics used in human medicine should not be used for purposes other than medicine. On this basis, chloramphenicol is not used worldwide as a plant protection product. It is very important that the continuous use of chloramphenicol as a pesticide would cause environmental contamination and therefore a reduction in bacterial susceptibility should be expected (Rosenthal et al., 1977). Lower sensitivity is often associated with resistance factors (R plasmids), which can be conjugated or transduced in bacteria between species, genera, families, or even orders, with potentially fatal consequences for therapy (WHO, 1973, Rische, 1975).

CMB (2-Chloro-6-methyl-4-benzylphenol) is a new active ingredient from known phenol-type antimicrobial compounds, which must be synthesized from a by-product of herbicide synthesis (4-chloro-2-methylphenol). (see German Patent Publication No. 131,748). CMB is distinguished by its good antimicrobial activity and can therefore be used in human and veterinary medicine.

The object of the present invention is to provide an agent which is suitable for controlling phytopathogenic fungi and bacteria and for treating shoots, as well as for dressing and protecting stored crops in agriculture and horticulture and which is particularly suitable for avoiding rot in stored potato tubers. has a fungicidal and bactericidal action and does not have the disadvantages described above, particularly in the treatment of stored potatoes, and which also allows the treatment of plant diseases which have not been sufficiently controlled (e.g. mixed rot of stored crops, bark disease of fruit trees) .

SUMMARY OF THE INVENTION It is an object of the present invention to provide an agent for controlling phytopathogenic fungi and bacteria for the treatment of sprouts and the treatment of stored potato tubers. In doing so, chloramphenicol, which has many dangers when used, should be replaced with more potent compounds, while reducing stored rot potato yield by 60-80%, increasing potato yield by 5-10% and improving tuber quality and at least 50 The incidence of black-stalked and rhizocotonic plants should be reduced by.

Surprisingly, it has been found that mixtures of antimicrobial CMB and carbendazim, maneb or cineb are excellent against fungal and bacterial pests, both in single and mixed infections, and exhibit an increase in activity beyond that known for each compound. Thus, for the first time, CMB can be used in plant protection.

The synergistic effect of the mixture is achieved when the ratio of the CMB / fungicide in the delay is 100: 1-1. It is between 100. When treating stored potatoes, the optimal effect is 1: 50-1; A CMB / fungicide ratio of 5 is achieved.

When treating potato tubers with rot pathogens and bark disease in fruit trees, Carbendazim is preferred. The active compound combination of the present invention is formulated with customary carriers and excipients to form a composition for use.

It has been found that various types of formulations (spray, powder, suspension, emulsion), preferably liquid serum forms, can be used with good results. The effect is achieved by the addition of suitable formulation auxiliaries, such as solvents (dimethylsulfoxide, dimethylformamide, HM FT, triacetin), also known as penetration aids, and positively influenced by the addition of oils (mineral and triglycerides). In addition, insecticides, bactericides, viricides, ferrets, minerals, trace elements, and biological process control agents may be added to the compositions of the present invention to extend the field of application to plant hygiene and plant care. Preferably, the aqueous spray can be applied to the plant shoot, or to the agricultural or horticultural crop by a number of known methods.

Examples

Composition of test preparations: Preparation I

30 weight / CMB 44 weight / xylene 6 weight / n-butanol 8 weight / propylene glycol 12 weight / ethoxylated alkylphenyl polyglycol ether II. preparation 1 weight / CMB 50 weight / carbendazim 4 weight / propylene glycol 35 weight / synthetic silica 4 weight / sulfite szennylúgpor 6 weight / ethoxylated alkylphenyl polyglycol ether III. preparation 4 weight / CMB 50 weight / carbendazim 5 weight / propylene glycol 35 weight / synthetic silica 3 weight / sulfite szennylúgpor 3 weight / ethoxylated alkylphenyl polyglycol ether ARC. preparation 6.00 weight / CMB 31.25 weight / carbendazim 8.00 weight / propylene glycol 41.00 weight / synthetic silica 6.75 weight / nátriumligninszulfonát 7.00 weight / ethoxylated alkylphenyl polyglycol ether Preparation V. 30.0 weight / CMB 0.5 weight / carbendazim 57.5 weight / Calcium carbonate 6.0 weight / nátriumligninszulfonát 6.0 weight / ethoxylated alkylphenyl polyglycol ether VI. preparation 30 weight / CMB 3 sviy% carbendazim 6 weight / sulfite waste liquor 55 weight / Calcium carbonate 6 weight / ethoxylated alkylphenyl polyglycol ether

VII. preparation 30 weight / - CMB 6 weight / carbendazim 52 weight / kaolin 6 weight / Ca dodecylbenzene sulphonate 6 weight / ethoxylated alkylphenyl polyglycol ether Vili. preparation 32 weight / CMB 4 weight / carbendazim 52 weight / kaolin 6 weight / Ca dodecylbenzene sulphonate 6 weight / ethoxylated alkylphenyl polyglycol ether IX. preparation 20 weights / CMB 40 weight / carbendazim 32 weight / synthetic silica 4 weight / sulphite waste liquors. 4 weight / ethoxylated alkylphenyl polyglycol ether Preparation X. 15 weight / CMB 15 weight ⁰ / carbendazim 20 weights / propylene glycol 28 weight ⁰ / kaolin 6 weight / sulfite waste liquor 6 weight / ethoxylated alkylphenyl polyglycol ether XI. preparation 9.1 Weight / CMB 30.0 weight ⁰ / maneb 10.9 weight / propylene glycol 40.0 weight / synthetic silica 5.0 weight / sulfite waste liquor 5.0 weight / ethoxylated alkylphenyl polyglycol ether XII. preparation 19.8 weight / CMB 6.0 weight / zineb 20.2 weight ⁰ / propylene glycol 44.0 weight / synthetic silica 5.0 weight / sulfite waste liquor 5.0 weight / ethoxylated alkylphenyl polyglycol ether

Example 1 Laboratory study of potato tubers

To prepare the composition of the present invention, CMB and carbendazim benzimidazole fungicide are mixed in a ratio of 1:50 (formulation I) to 1: 12.5 (formulation II) and formulated with the usual excipients (tebids, solvent, water) to form a liquid. This preparation was tested in laboratory tests on Fretarium dry rot (Fusarium spp.), Bacterial wet rot (Erwina spp.) And mixed rot (Fusarium spp. + Erwinia spp.) By artificial infection of Adrette potato. The fungicidal efficacy of the preparation is given in Table A. Fungicidal efficacy was calculated from the degree of infection. The efficacy of formulations I and II against the three types of rot is significantly higher than the individual efficacy of each of the fungicidal components. They have a particularly remarkable excellent effect against bacterial wet rot and mixed rot, which are very difficult to combat.

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The table

Quantity Active substance (active ingredient _Fusarium . Efficiency wet rot mixed rot pro ton) rot CMB + Carbendazim 2.5g + 125g 83 100 95 (Preparation I) CMB + Carbendazim l0g + 125g 92 100 96 (Preparation II) CMB 2.5 g 28 7 CMB 10 g 37 40 10 carbenda- _inc 125 g zim ^e 70 IQ. 10

Example 2 Testing of potato tubers under practical conditions

Libelle potato tubers were investigated under storage conditions with Preparation III containing 1: 10 mixture of CMB / carbendazim and CMB / carbendazim. 5 kg of the sample was artificially infected (5 replicates in a laboratory dressing drum), treated with the test composition and stored under normal conditions. Bercema-Demex, a commercial preparation containing chloramphenicol as a bactericidal component, was used for the comparative study. The efficacy found is shown in Table B. Formulations I and II of the present invention exhibit the same fungicidal activity as chloramphenicol-containing reference substance, Formulation III exhibiting improved fungicidal activity against mixed rot.

Table B

Infection (%)

agent Quantity (tonne of active substance) Fusa- lium- rotha- Das wet mixed all rotha- rotha- rotha- Das Das Das untreated control - 10.3 0 5.7 15.0 CMB + carbendazim (Preparation I) 2.5g + 125g 6.5 0 0.8 7.3 CMB + carbendazim (Preparation II) 10g + 125g 7.1 0 0.9 8.0 CMB + carbendazim (Preparation III) 24g & 125g 6.0 0 0.4 6.4 carbendazim + + chloramphenicol 115g + 2.6g 5.4 0 0.8 7.2

and CMB and carbendazim were applied to agar agar for fungi. It is then infected with various pathogens of fruit tree bark disease (Nectris spp., Phomopsis spp., Pezicula spp., Phytophthora spp., Glososporium spp.).

The assay is evaluated by measuring mycelial growth and expressed as fungicidal efficacy. The test results are shown in Table C. According to the invention, the efficacy of Formulation V is substantially high, against individual pathogens, compared to the individual active ingredient components.

Table C

Pathogen agent Quantity (Ppm) Effective- pany (° C / h) CMB + carbendazim 300 100 Nectris spp. CMB 300 30 carbendazim 1 60 Phomopsis spp. CM B + Carbendazim 300 100 CMB 300 85 carbendazim 5 70 Pezicula spp. CMB + carbendazim 300 100 CMB 300 30 Phytophthora carbendazim CM B + Carbendazim 1 300 45 55 spp. CMB 300 40 Glososporium carbendazim CM B + Carbendazim 5 300 0 100 spp. CMB 300 25 carbendazim 1 40

Example 4: Seed treatment against wheat germ (Tilletia spp.)

To prepare the composition of the present invention, CMB and carbendazim benzimidazole fungicide are mixed in a ratio of 10: 1 (Formulation V) to 5: 1 (Formulation VI) and formulated with standard excipients and assayed by the GaBner method. The fungicidal activity of the tested formulations was determined by dressing wheat seeds (Alcedo variety) artificially contaminated with Tilletia spores and incubating in a foam bath. During the evaluation, spore formation was measured. The efficacy of the compositions of the present invention compared to a commercial formulation (Falisan-Universal Dry Dresser 69) is given in Table D. The antimicrobial agent inhibits spore formation well, but the compositions of the present invention are significantly better. The efficacy of the comparator formulation is achieved only by formulation V.

Example 3 Investigation of bark disease of fruit trees in a petri dish

To prepare the composition of the invention, CMB and carbendazim benzimidazole fungicide are mixed in a ratio of 60: 1 and formulated with conventional excipients (Formulation IV). This picture 4

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Table D

Table F " _t . ,,,. sporulation

Active ingredient (ai / 100 kg ^r "stands _mag) _ ^b untreated control - 1

CMB + Carbazazim -> n '+ i (formulation V) ⁸ ' ^g

CMB + Carbendazim in "+?" (Preparation VI) SS

CMB 20 g 2

CMB 10 g 2

Falisan-Universal- 4 88 o 3

- dry dresser 69 ' ^e

Rating: 0 = spore formation above 50% = spore formation 15-50% = spore formation 3-15% = spore formation 0-3%

EXAMPLE 5 Testing for a primary apple powdery mildew infection

Jonathan apple trees were treated with the composition of the invention (composition VII, CMB carbendazim 8: 1) during the rest period (January). In spring, the fungicidal activity of the test composition was measured by counting the developed powdery mildew candles. The results are shown in Table E. The effect of the composition of the invention is greater than that of the individual components and thus reduces the infection.

Table E

agent Infection (%) Efficiency (%) untreated control 70 CM B + Carbendazim RDI (Preparation VII) CMB 30 57 carbendazim 67 4

EXAMPLE 6 Investigation of corn flour

Two formulations of the invention are prepared in which CMB is mixed with carbendazim, a benzimidazole fungicide in a ratio of 2: 1 (formulation VIII) to 1: 1 (formulation IX) and formulated with conventional excipients. Single-leaf wheat plants for the test are Erysiphe graminis DC f. sp. trididi Marchal and after 24 hours sprayed with the composition of the invention (formulations VIII and IX) with CMB and the carbendazim active ingredient Thicoper. The fungicidal efficacy of the tested formulations is shown in Table F. The fungicidal efficacy was obtained from the degree of infection of the infection.

The compositions of the invention show a clear synergistic effect; while each of the active ingredient components can produce only an inadequate effect, the composition of the invention is well suited for combating powdery mildew under laboratory conditions.

agent Active ingredient concentration (%) Efficiency (%) CM B + carbendazim (preparation VIII) 0.1 1 0.05 99 CM B + Carbendazim (Preparation IX) 0.05 + 0.05 97 CMB 0.1 33 CMB 0.05 31 carbendazim 0.05 45

Example 7

Study of the effect against Erwina amylovora Burr

To prepare the composition of the invention, CMB was mixed with mann in a ratio of 1: 3.3 (Formulation X) and used for in vitro testing. To test for bactericidal activity, bacterial growth was assayed in a Petri dish on agar medium using appropriate values. The test result is given in Table G. The composition according to the invention exhibits a significantly better effect than the individual active ingredient components.

Table G

agent Active ingredient concentration (%) Bacterium- development Untreated control 0 CMB + maneb (Preparation X) 0.03 + 0.1 3 maneb 0.1 2 CMB 0.03 2

See Table D for the Ni assessment.

Example 8

Phythophthora spp. testing of effect

To formulate the composition of the present invention, CMB was mixed with cinee (composition XI) and Maneb (composition XII) at a ratio of 3.3: 1 and formulated in a liquid formulation with the usual excipients. The preparation was tested on tomato leaves in the Catalog of Methods for Pesticide Testing published in the GDR 6-2.1.3. method.

The fungicidal activity of the test composition was measured in a number of infections (see Table H). The compositions of the present invention exhibit a significantly better effect than non-systemic cineb and maneb alone.

Table H.

Active ingredient Effectiveness (%)

CM B + cineb 0 1 + 0 03 69 (Preparation XI) CMB + maneb 0 1 + 0 03 80 (Preparation XII) 90s 0.03 23 maneb 80 0.03 38 CMB 0.1 23

Claims (2)

Patent claims CLAIMS 1. A phytopathogenic antifungal agent comprising a synergistic combination of 2-chloro-6-methyl-4-benzylphenol and carbendazim or maneb or cineb in a 100: 1 to 1: 100 weight ratio as active ingredient. -65% by weight of solid carriers, preferably natural or artificial stone flours, and / or liquid diluents, preferably polar or apolar solvents, and optionally surfactants, preferably anionic or nonionic emulsifying and / or dispersing agents 5 next. 2. An agent according to claim 1, wherein the ratio of 2-chloro-6-methylbenzylphenol to carbendazim in the active compound combination is between 1:50 and 1: 5.