DE1620175C3 - Fighting fungi on living plants - Google Patents

Description

From US-PS 30 10 968 fungicidally active alkyl esters of 2-benzimidazole carbamic acid with fewer than 7 carbon atoms in the alkyl radical are known. A fungicidal effect on living plants is not described there; Nor is noted that the particle size of the active ingredients for the 2 ^r> fungicidal activity plays a role. Neither is it indicated that the methyl 2-benzimidazole carbamate described in US Pat. Next jo are known from US-PS 29 33 502 fungicidal chelates of esters of 2-aminobenzimidazoIcarboxylic acids, which can also be used as fungicides for living plants. Fungicidal 2-benzimidazole-carbamic acid compounds are also described in US Pat. No. 2,933,504, including dialkyl esters of 2-carboxyamino-1-benzimidazole-carboxylic acid. To combat fungal diseases, the compounds described there can be sprayed onto the plants without damaging the plants.

The object of the invention is to prevent fungal attack on living plants and their parts to combat prophylactically and curatively while avoiding damage to the plants.

The invention is defined in the claim. 4 ^r >

The compounds used according to the invention show a surprisingly better fungicidal action and / or a lower phytotoxicity on living plants than numerous other compounds covered by the disclosure of US Pat. No. 3,010,968. In addition, the fungicidal action of the compounds used according to the invention is considerably better when used in a particle size of essentially below 5 μm than when used in a particle size above this. γ,

The active ingredients used according to the invention have the advantage of a very wide range of application between the minimum dose which is required to achieve the desired effect and the amount which can be used without any signs of damage. In many cases, in the greenhouse test, the lowest effective dose can be increased by a factor of a thousand without damaging the plants. In the field, dosages corresponding to 60 times the required minimum amount are safe to use. 6 ^r )

Another advantage of the compounds used according to the invention is their low phytotoxicity. the often necessary for a fungicidal effect use of metal ions, but which have a phytotoxic effect is not necessary when using the compounds used according to the invention.

A particular advantage of the use according to the invention results in the curative treatment of living plants that are infected schotuvpn fungi. Plant diseases are becoming ■> very general nowadays fought by protective spraying, which takes place in a fixed program. Here the Treatment should be given before it is known whether a condition will actually occur, but the The grower or grower generally has none due to the lack of reliable curative treatments another choice.

When using the invention, it is unnecessary to apply the fungicide before conditions have occurred that make a fungal attack appear possible. The invention enables the Fighting fungal diseases inside the plant, that is to say curatively. This results in a Saving of fungicides.

The entry of the compounds used according to the invention into the living plant also results in a sustained protection of the treated plants from new fungal infestation, d. that is, those used according to the invention Connections also have a preventive effect.

The esters used according to the invention can be prepared by conventional methods. The ester production can e.g. B. be carried out in a three-stage reaction sequence, with one in the first stage Mixing thiourea with dimethyl sulfate, the resulting 2-methylthiopseudourea sulfate in the second stage mixed with methyl or ethyl chloroformate and then a base and in the last stage to the acylated Adds 2-methylthiopseudourea a protonic acid and o-phenylenediamine. The ester obtained is then formulated and μπι with conventional mills to a particle size of essentially below 5 to marry.

Venturia inaequalis, the The causative agent of apple scab, Podosphaera leucotricha, the causative agent of powdery powdery mildew on apples, Uromyces phaseoli, the causative agent of bean rust, Cercospora apii, the causative agent of dry spot disease in celery, Cercospora beticola, the causative agent of leaf spot disease in sugar beet, Cercospora musae, the causative agent Sigatoka disease in bananas, Monolinia (ScIerotinia) laxa, the causative agent of brown rot in apricots, Monolinia (Sclerotinia) fructicola, the causative agent of brown rot in peaches, Botrytis cinerea, the causative agent of gray mold on fruits, Erysiphe cichoracearum, the causative agent of powdery mildew Sugar melons and other pumpkin plants, Penicillium digitatum, the causative agent of green mold Citrus fruits, Sphaerotheca humuli, the causative agent of powdery mildew in roses, Diplocarpon rosae, the The causative agent of black spot disease in roses, Uncinula necator, the causative agent of powdery mildew in grapes, Coccomyces hiemalis, the causative agent of cherry leaf spot disease, Cladosporium carpophilum, the causative agent of scab in peaches, Erysiphe graminis hordei, the causative agent of powdery mildew Barley, Piricularia oryzae, the causative agent of rice blight, Puccinia recondita, Puccinia coronata and Puccinia glumarum, the causative agent of leaf rust in wheat, oats or grasses, Puccinia graminis tritici, the causative agent of stalk rust in wheat,

Aspergillus niger, the causative agent of cottonseed boll rot and the putrefaction of many plant tissues after injuries and various species of Rhizoctonia, Fusarium and Verticillium, found in the soil and the roots or other subterranean parts attack a variety of plants.

The compounds used in the present invention can be used particularly for combating fungi in the following Plants are used: fruit trees, nut trees, ornamental trees, forest trees, vegetable plants, garden plants (including ornamental plants, small fruits and berries), fiber plants, cereals and seeds, Sugar cane, sugar beet, pineapple, fodder plants, beans, peas, soybeans, peanuts, potatoes, Tobacco, hops, turf and pasture grass.

For root treatment, the soil is treated before, after or during planting or the Sow seeds or parts of plants before planting or dip the roots of cuttings before Set. The parts above the ground are sprayed, dusted, misted or injected treated. Such applications on the root system or on the upper parts of the plants form one important part of the methods according to the invention and are described in more detail below.

For the immersion treatment of the roots of living plants, the preferred amounts are in the range from 0.5 to 20,000 g of active ingredient per 3801 of water or one other liquid carrier. A range from 4.5 to 9000 g / 3801, in particular from 45, is particularly preferred up to 4500 g each 3801.

Dusts, grains (granules), pellets or slurries are used for soil treatment. Preferably, the soil is used with the active ingredients in amounts of 0.01 to 500 parts per million parts by weight of the soil treated. Quantities from 0.1 to 50 parts, quantities from 0.25 to 25 parts per million are even better are particularly preferred.

Preferred amounts for the treatment of seeds, tubers, bipods and similar parts of plants are in the range from 0.03 to 6000 g of active ingredient per 50 kg of treated seedlings. Are particularly preferred Quantities from 0.3 to 3000 g, in particular 2.5 to 1500 g Active ingredient per 50 kg of treated seedlings. The treatment is carried out with dusts or slurries.

For the treatment of foliage, stems and fruits of living plants, the compounds are preferred used in amounts of 0.012 to 60 kg of active ingredient per hectare. A range of is particularly preferred 0.025 to 30 kg / ha, in particular from 0.05 to 15 kg / ha.

The curative treatment of plant diseases is intensified when the treated parts of the plant or several times each 2 to 12 hours shortly after the application of the agent containing the active ingredient kept moist. Often this is already caused by the slow drying after the original spray treatment or obtained naturally through rain, fog or dew.

The active ingredients used according to the invention are usually mixed with an excipient, such as a carrier or conditioning agent. The auxiliaries used are generally used inert solids, organic, liquid or aqueous diluents and surface-active agents. Suitable Agents are produced by combining the compounds used according to the invention with the auxiliaries by mixing, grinding or stirring, or by other conventional methods. Normally the active ingredient content of the fungicides is 1 to 95% by weight.

Solid agents can be in the form of water-dispersible powders, dusts, pellets or grains are present. Water dispersible powders are particularly effective and can either be used as such used, diluted with inert solids to form dusts or in liquids for spraying or for seed treatment be suspended. Usually the powders contain the active ingredient in admixture with various Amounts of conditioning agents, surfactants and other ingredients such as corrosion inhibitors, Pigments, adhesives or common extenders. The active ingredient content of the wettable powder is usually 15 to 90% by weight. The wettable powders can also be converted into dusts, which 1 contain up to 25% active ingredient by using pyrophyllite, * volcanic ash, ground phosphate rock or other, dense, rapidly settling, inert solids mixes or wedges dusts can also get through Grinding the dust thinners with the active ingredient or in the form of dust concentrates for the further dilution can be made. The dust concentrates can contain 80 to 95% by weight of active ingredient, mixed with diluents and optionally small amounts of surface-active agents and can be married.

Two types of carriers are most suitable for the granules. The first type of carriers are preformed granules. An aqueous suspension of the active ingredient in concentrations can be applied to these grains up to 25%, based on the total weight, can be sprayed on. In addition to the active ingredient, the Suspensions a surfactant and binding agent

3 ^r ) contain agents to improve the adherence of the small particles of the dispersed active ingredient to the grains.

The carriers of the second type are powdered kaolinitic or bentonitic clays in the sodium, Calcium or magnesium form. These clays are made with the small particles of the active ingredient and optionally surfactants are mixed, and the mixtures are granulated and dried to form a Granulate is obtained in which the active ingredient particles are evenly distributed throughout the mass. Such Granules can be made with 25 to 30% by weight active ingredient, but a concentration is more common of about 10% by weight is desirable. Similar agents can be made by turning the mixture in

TO the presence of moisture and extrude the extrudates through an appropriate combination of Cutting, drying and crushing converted into grains or pellets. The granules are in grain sizes from 0.25 to 1.5 mm most effective.

Liquid agents are created by mixing the active ingredient with a liquid diluent manufactured. The active ingredient is in suspension in the diluent. Typical liquids for this Purpose are water, paraffinic spray oils, alkylated naphthalenes, xylene, alcohols, chlorinated hydrocarbons and ketones. The active ingredient in part of these liquid agents is usually about 0.5 to 50%. Also can the agents contain surface-active agents, especially emulsifiers, to make the suspension or To facilitate dispersion or to emulsify the agent in water.

The fungicidal agents made from the active ingredients, especially the liquids and wettable ones

Powders contain a or as a conditioning agent several surfactants in sufficient quantity to easily incorporate into a given composition To make water or oil dispersible. The surface-active agents here include wetting agents, Dispersants, suspending agents and emulsifying agents.

Suitable surfactants are anionic, cationic and nonionic agents. In general the mixtures contain less than 10% by weight surfactant; often the salary is due surfactants below 2% by weight. However, larger amounts of the surfactant result By means of a more effective fungus control than one with knowledge of the effectiveness of the individual components can expect.

Surface-active agents which fight fungus by the compounds used according to the invention reinforce are z. B. Dioctyl sodium sulfosuccinate, mixtures of aromatic sulfonates and ethylene oxide derivatives, Polyoxyethylene sorbitol acid laurate, sodium lauryl sulphate, polyoxyethylated vegetable oils, lecithin derivatives, acidic complex organic phosphoric acid esters, aliphatic amide alkyl sulfonates, oleic acid esters of sodium isethionate, sodium N-methyl-N-oleoyl taurate, the sodium salt of sulfated lauric acid and myristic acid ethanolamine salt, the oleic acid ester of polyethylene glycol with a molecular weight of 400, sodium dodecylbenzenesulfonate, polyoxyethylene ether of long-chain alcohols, ethylene oxide condensation products with propylene oxide / ethylene diamine condensates, Esters of polyhydric alcohols, modified phthalic acid-glycerol-alkyd resins, quaternary Ammonium salts and condensation products from alkylphenol and ethylene oxide.

Favorable concentrations of surfactant in sprays range from 10 to 50,000 parts per million parts of spray liquid Quantities of 30 to 15,000 parts are particularly favorable, especially from 100 to 5000 parts per million parts.

For dusts, the preferred amounts of surfactant are 1,000 to 300,000 parts each Million parts of the material actually applied. Amounts from 5000 to are particularly preferred 200,000 parts, especially from 10,000 to 100,000 parts per million.

The amount of the surface active agent can be 33 to 10,000, particularly 50 to 3,500 parts per 100 parts Active ingredient.

example 1

A wettable powder is produced according to the following recipe:

2-benzimidazole carbamic acid

methyl ester 15

Synthetic fine silica 25

Sodium Lauryl Sulphate 60

The benzimidazole is mixed with the silicon dioxide and the mixture is subjected to air milling until virtually all of the particles are less than 5 microns in size, as can be seen microscopically. This mixture is then mixed with the sodium lauryl sulfate and then treated on the hammer mill.

This preparation is added to water in such an amount that 150 ppm of the active ingredient are obtained receives. This remedy is applied at a dosage of 10 L / tree on every other tree in a Michigan cherry orchard injected, being a normal

Example 2 _O 2-benzimidazole carbamic acid methyl ester 30.0 Calcium Magnesium Lignin Sulphonate 15.0 Hydrated attapulgite 1.4 Sodium carbonate anhydrous 2.1 water 51.5

Applies treatment program for cherries and starts early in the year. At the end of summer and more than six weeks after the last treatment, the treated trees are healthy and still have that entire foliage, while the neighboring, untreated trees are affected by cherry leaf spot disease are severely defoliated.

Additional trees in the same plantation are added at a dosage of 20 l / tree with an aqueous Injected suspension that contains 6000 ppm of the active ingredient, using the same treatment program as above apply those with this very high dosage (80 times the dosage that already Protection there) treated trees show no signs of chemical damage, which is the high The degree of security that the compound used has for useful plants

The ethyl ester of 2-benzimidazole carbamic acid is used in a corresponding manner corresponding results.

These components are sand milled together until essentially all of the particles are less than 5 microns fineness.
A rice field in Louisiana that is heavily infected with Piricularia oryzae is chosen to use the agent. Ten days after infection, after the fungus has had enough time to penetrate the rice plants and settle in them, the plots are sprayed with water to which an amount of the above agent corresponding to 300 ppm of active ingredient has been added. Four weeks later it can be seen that the rice plants in the treated plots remain healthy. The untreated rice surrounding the plots, on the other hand, is seriously ill from the fire.

Since the rice is infected well before the treatment, the result is curative Effect.

Example 3

The agent according to Example 2 is added to water in an amount corresponding to 300 ppm of active ingredient, the 300 ppm modified phthalic acid glycerol-. alkyd resin as a surfactant contains Die The suspension obtained is applied at a dosage of 15 l / tree on every other tree in a peach garden sprayed, starting with the spraying when the buds open in spring, and that Spraying repeated at intervals of 7 to 14 days until harvest time. The remaining trees of the planting remain untreated

At harvest time, the treated trees and the fruit turn out to be healthy. The fruit of the untreated trees, on the other hand, are severely affected by peach scab and brown rot.

Example 4

90 parts of attapulgite granules (size range 0.25 to 0.6 mm) are placed in a rotating mixer

circulated and finely sprayed with 20 parts of the aqueous suspension from Example 2. The overturning continues until the suspension is distributed over the surface of the granulate. By drying the mixture a granular mass is then obtained which contains 6% of the 2-benzimidazole carbamic acid methyl ester.

In a field, three cucumber seeds are placed in 3 cm deep holes at center-to-center distances of 3 m, whereby you also put 2 g of the above granules into some planting holes.

Six weeks after ordering, the plants in the treated planting holes are completely healthy, while the plants in the untreated planting holes are severely affected by powdery mildew. this explains the disease control with the active ingredient used according to the invention with inclusion from the soil through the roots and systemic transport into the foliage.

In a corresponding manner, the ethyl ester of 2-benzimidazole carbamic acid is used instead of the methyl ester used. Corresponding results are obtained.

Example 5

2-Benzimidazole carbamic acid methyl ester

j3-pinene polymer with a
Softening point of 10 ° C
Low boiling isoparaffin oil
Lauryl ether with polyethylene oxide

26th

38.57
26.43
9

First you dissolve the resin of the above formulation in the isoparaffin oil, then add the other components and sand mill until essentially all of the particles are finer than 5 microns.

4 1 of this agent are added to 381 of water, an excellent emulsion results immediately. The emulsion obtained is taken up from the air one hectare of banana plantations was sprayed and the treatment repeated at intervals of 21 days. 6th Months after the first treatment, the sprayed banana plants are healthy, while the surrounding, unsprayed banana plants are severely damaged by Sigatoka disease.

Example 6

2- benzimidazole carbamic acid

methyl ester 70.0

Sodium alkyl naphthalene sulfonate 3.0

Sodium isethionate 2.0 oleic acid ester

Diatomaceous earth silica 25.0

There are growing powdery mildew. The medium-sized standard apple trees are sprayed with 40 l / tree. An examination three weeks after the treatment shows that the treated trees of visible signs of scab are completely free and no more powdery mildew than at the time of Treatment is available while the untreated trees are severely affected by scab and far more show powdery mildew than at the beginning of the

ίο There was an attempt. The above, in the above way The agent applied thus kills both the apple scab fungus and the powdery one Powdery mildew fungus.

Other trees in the same garden are sprayed as above with the exception that the Agent used in such an amount that 21,000 ppm of active ingredient (or 70 times the amount with which one curative fungus control is achieved). Like keeping these trees free from anything If the signs of chemical damage are explained, the safety margin is astonishingly large.

Example 7

2-benzimidazole carbamic acid

ethyl ester
Kaolinite clay

50
50

The ingredients are mixed and air-jet milled until the active ingredient has a particle size of less than 5 microns. Mixing the product with talc creates a 20% dust.
This agent is dusted at a dosage of 30 kg / ha on randomly selected plots of a celery field in Florida that had been infected four days previously with the fungus causing celery spot disease. This period is sufficient for the fungus to penetrate deeply into the tissue of the celery leaf.

Four weeks later, the pollinated plots show only healthy celery plants that are growing well. the Untreated areas surrounding these plots, on the other hand, are strongly affected by celery spot disease become ill and clearly show a less lush growth.

Example 8

The components are mixed, finely ground on a hammer mill and then air-jet grinding subjected to particle size below 5 microns as determined by Andreasen pipette sedimentation.

This agent is added to water containing 300 ppm of an ester of a polyhydric alcohol as a surface-active agent Contains agent, it being used in such an amount that in the aqueous Finished preparation 300 ppm of active ingredient can be obtained. This preparation is then put on every other tree of an apple orchard known to have been infected with the apple scab pathogen three days earlier infected, with some trees showing signs of the onset at the time of treatment 2-Benzimidazole carbamic acid methyl ester

Polyethylene oxide adduct of
Dodecylphenols
Methyl cellulose (low viscosity)
Synthetic fine silica

70

2.5
0.3

27.2

These components are mixed together, finely ground on the hammer mill and then the Subjected to air jet milling to a particle size below 5 microns.

Plots of sugar beet fields in Minnesota are watered at 14-day intervals injected, which has been mixed with such an amount of the above agent that in the finished suspension 250 ppm of the active ingredient are present. This suspension is applied at 600 l / ha on each day of treatment.

For 12 weeks after the start of the experiment, there was one favorable for the growth of the sugar beets

909 628/8

Weather and revealed frequent intervals in which an infection with the pathogen fungus causing leaf spot disease could occur with sugar beets. At the end of the experiment, the beets turned out to be in the treated plots as healthy and growing well, while the untreated, the treated plots

surrounding areas only had sugar beets, which were severely affected by leaf spot disease.

If treated appropriately at drug doses up to 64 times the above applied dosage, there is no damage to the sugar beet.

Claims (1)

Claim: Use of a compound of the general formula C-NH-C-OR ίο wherein R is methyl or ethyl, in a particle size of essentially below 5 μΐη in the fight against fungal attack on living plants and their parts. ι ^r >