DE1620175A1 - Fungicidal agent - Google Patents

Description

Fungicidal Agents The invention relates to fungicides and their use, which is an exceptionally good way of combating fungal diseases obtained from living plants.

It has been found that this Etc feces is obtained by means of a compound of the formula wherein R is methyl or xethyl, contain or are formed from a particle size below 5 microns. It can exist in two tautomeric forms: The outstanding attributes of the invention are 1. to meet the numerous, imperative requirements (including the lack of phytotoxicity) of the practical control of fungal diseases in plants in an excellent manner and to deliver the extremely unique result of the curative treatment of plants that have already been are infected with virulent pungi.

To be useful in combating fungal diseases in plants The means and methods of treatment must first and foremost be appropriate Safety factor for the useful plants. A lot of connections that at Test fungew in artificial media or on other, inanimate documents fungicide Effects can be demonstrated due to an undesirable effect on the host do not use to fight pilsner disease in plants. The means according to the invention is with its broad Area noteworthy of r between the minimum doses that can be used to achieve the desired disease control behavior required, and the amounts that apply without any signs of damage permit. In many cases the greenhouse test shows the lowest Increase the effective dose by a factor of a thousand without damaging the plants. In the Peldeinsats, 60 or more times the required minimum amount are equivalent Dosages safe to use.

Phytotoxicity can take a number of forms, including burning of leaves, decreased or abnormal growth of the upper parts of the plant, abnormal Root growth, reduced fruit set, poor fruit finish, reduced Yield and an undesirable harvest quality (decrease in sugar or protein content, unpleasant tastes and so on). The means according to the invention is of any concomitant phenomena in the form of adverse effects of these or other types free.

It has been shown to be in many pills in certain types metal ions play a role in phytotoxicity. For example, it has been reported that Trace amounts of Kurpfer the appearance of apples can harm. The invention makes it possible to use any Netallions in treatments Fight against fungal diseases to mile.

On further requirements for the practical control of Pils disease in the case of plants include the usability of the available or easy accessible application equipment, comfortable and safe handling, the harmlessness for the consumer of the treated, agricultural products and other, well-known Requirements. The invention results in an astonishing satisfaction of these demands.

An extraordinarily valuable characteristic of the invention lies in effectiveness with the curative treatment already existing in living plants Fungal infections is possible., Plant diseases are becoming quite common these days fought by protective injections, which take place in a specified program. Hielazu It is true that the treatment effort has to be paid before it is known whether a disease is present now actually would occur or not, but the breeder or planter has due the lack of reliable and scattered active curative treatments no other Choice.

In the curative application of the invention, it is unnecessary to use a chemical to be applied before such weather or other circumstances occur are that in fact the initiation of a fungal attack has become possible. The invention makes it possible to eliminate the fungus or fungi from inside the plant (daa means, treat the disease curatively). Which results from the curative effect of the means according to the invention resulting, substantial savings for the grower or grower chemical costs and workload for the application are obvious.

If, as is the case sometimes, during the existence of a useful culture no disease favorable conditions occur can be based on the awareness of having curative treatments available when needed, the costs Avoid chemical treatment entirely.

The active components or substances according to the invention are capable of to enter the living plant and move in it. Such an entry and such systemic movement represent a factor of the above, curative effect. In addition, this occurrence results in And this systemic movement of the effective and lasting debris of the treated plants before a subsequent, new fungal attack. So, treatments meet to remedy one present fungal infection has a dual purpose, that is, they also result in one Protection for the future.

If for any reason this mode of operation is desired, it can the invention can also be used for the conventional, preventive control of fungal diseases use.

According to a preferred embodiment, the compounds according to the formula when preparing with the conventional amount of a Penetrant, e.g., various surfactants, an improved Activity in the fight against fungal diseases of living animals.

Leave the esters of 2-benzimidasolcarbamic acid according to the formula produce by all the conventional methods.

The ester production can, for example, be carried out in a three-stage reaction sequence be carried out, the first reaction being thiourea with dimethyl sulfate mixes to form the 2-methylthiopseudourea sulfate in solution at the second Implementation of the reaction mixture with an altyl chloroformate and a base is then added to form an acylated 2-methylthiopsendourea, and in the last.

Stage a protonic acid and an o-phenylenediamine are added to form the benzimidazoles according to the formula ru.

As mentioned above, the compounds according to the formula result in a Control of a wide variety of fungal diseases in plants without harming them of the host.

To the many fungi against which the active ingredients according to the invention active include Yenturia inaequalis, the causative agent of apple scab, Podosphaera leucotricha, the causative agent of powdery mildew in apples, Urumyces phaseoli, the Bean rust pathogen, Cercospora apii, the causative agent of dry spot disease Celery, Cercospora beticola, the causative agent of leaf spot disease in beetroot, Cercospora musae, the causative agent of sigatoka disease in bananas, Nonolinia (Solerotsnia) lara, the causative agent of brown rot in apricots, Monolinia (Salerotinia) fructicola, the causative agent of brown rot in peaches, botrytis one, the causative agent of gray Mold on fruits, Erysiphe cichoracearxm, the causative agent of powdery mildew in sugar melons and other pumpkin plants, Penicillium digitatum, the pathogen of green soy sky with citrus fruits, Sphaerotheca humuli, the The causative agent of powdery mildew in roses, Diplocarpoa rosae, the causative agent of black spot disease in roses, Uncinula necator. the causative agent of powdery mildew in wine grapes, Coccomyces hienalis, the causative agent of cherry leaf spot disease, Cladosporium carpophilum, the causative agent of scab in peaches, Erysiphe graminis hordei, the causative agent ron Powdery mildew of barley, Piricularia oryzae, the causative agent of retibrand (rice blast), Puccinia reoondita, Puccinia ooronata and Pacclnla glumarum, the pathogens of the leaf rust bsi wheat, oats or grasses, Puccinia graminis trLtioi, the causative agent of Steugelroetea in wheat, Aspergillus niger, the causative agent of cottonseed boll rot and the Paulnis of many plant tissues after injuries and different species of Rhisootonla, Fusarium and Verticillium, dis occur in the soil and the roots or attack other subterranean parts of a variety of plants without dUs this is an exhaustive drawing, the agent according to the invention works curative for and so protects against fungal diseases of living plants, if it is after the The methods described below in the right place and in sufficient quantities is applied to exert the desired effect. It is suitable is particularly suitable for combating diseases in living plants, such as fruit trees, Soot trees, ornamental trees, forest trees, vegetable plants, garden plants (including Ornamental plants, small fruits and berries), fiber plants, cereal and seed plants, Sugar cane, sugar beet, pineapple, fodder and hou plants, beans, peas, soybeans, Peanuts, potatoes, sweet potatoes, tobacco, hops and rese and pasture grass.

Live plants can be cured of fungal disease or from fungal attack Protected are the soil in which the plants grow or in iom them subsequently sown or planted, or of the seeds, tubers, bulbs or other parts of the plant responsible for port planting with an or claims several of the active ingredients.

The application in plants to bring about the initial, curative Effects as well as the formation of secondary protection against fungal diseases takes place on the root part or on the air parts (i.e. stalk, stem and so on, foliage or fruit). For Wurselbehadlung one treats the soil before or after the or during planting or the seeds or parts of plants before pilansening or dew-treated the roots of cuttings before planting. Those above the ground Parts are treated by spraying, dusting, misting or injection. before applications on the root system or on the upper parts of the plants form an important part of the methods according to the invention and are described in more detail below.

Dusts, grains (granules), pellets, slurries are used for soil treatment or solvent used. The soil in which the mushrooms are located is preferred or should grow, with the active ingredients in amounts of 0.01 to 500 parts per million Treats parts by weight of the soil in which the roots exist or are intended to grow. Even better are quantities in the 0.1 to 50 parts per million range; Quantities in the area from 0.25 to 25 parts Jo Million are particularly preferred.

Preferred quantities for the treatment of seeds, tubers, onions or other parts of the plant responsible for reproduction are in the range from 0.03 to 6000 g of active ingredient per 50 kg of treated plant matter. Particularly preferred amounts in the range from 0.1 to 3000 g, in particular 2.5 to 1500 g, of active ingredient are used 50 kg of treated seedlings. The treatment is carried out with dusts, slurries or solutions. Such treatments protect the treated parts themselves against Fungal damage and also lead to a permanent protection of the developing, new plants.

For the treatment of foliage, trunks and the like and fruits living plants, the compounds are suggested in amounts from 0.012 to 60 kg of active ingredient applied per hectare. A range of 0.025 is particularly preferred up to 30 kg / ha, in particular from 0.05 to ir kg / ha. The optimal amount within this Range depends on a number of variables known to those skilled in the art, to which the disease to be combated, the expected weather conditions, the type of the Crops, the stage of development of the crops and the time between belong to the treatments, without this being an exhaustive list. It may be necessary to use treatments with amounts in the specified range in Repeat once or several times at intervals of 1 to 60 days.

The preferred ones are for immersion treatment of the roots of living plants Amounts in the range from 0.5 to 20,000 g of active ingredient per 380 l of water or something else liquid carrier.

A range from 4.5 to 9000 g / 380 l, in particular, is preferred from 45 to 4500 g each 380 1.

As noted above, agents according to the invention are particularly suitable for Until application to living plants.

Treatment of foliage, trunks and the like and the Fruits of plants in the amounts given above is generally done with the help of spray preparations, dusts, or aerosols that contain the appropriate amount of active ingredient abstinence. To combat fungal diseases that are regularly present begins treatment is often given before the problem actually arises, and one continues the treatment continues according to a specific plan. Bine such treatment is called Denotes preventive or protective treatment.

Agents according to the invention also result in successful control when used after the plants are ready for disease. Fungus mycelia within the plant tissue are indeed killed. This kind The treatment is known as Eurativ or Eradication Treatment and allows the significant savings discussed above.

The curative treatment of plant diseases is reinforced, though the treated parts of the plant one or more times each 2 to 12 hours shortly after Application of the agent containing the active ingredient are kept moist. Often this is already done by the long drying after the original spray treatment or obtained naturally through rain, fog or dew. In other circumstances, as in dry spells or in shelters such as greenhouses, the plants must to ensure the best results are kept moist with special oils.

The agents according to the invention contain one or those described above Compounds in an amount sufficient for combating in admixture with a carrier or conditioning agent, usually used as an adjuvant or modifier is applied. Inert solids are generally used as auxiliaries, organic liquid solvents, organic liquid or aqueous diluents and surfactants. For easy, effective application using the Conventional devices are made by making the connections with suitable auxiliaries by mixing, grinding or stirring or by other means, conventional methods can be prepared.

Usually the active ingredient content of the fungicides is 1 to 95% by weight.

Solid agents can be in the form of water-dispersible powders, Dust, pellets and grains are present. Powders dispersible in water are special effective and can either be used as such, with inert solids to form dusts or in grains, or in liquids for spraying or for treating seeds be suspended. The powders usually contain the active ingredient in a mixture various amounts of conditioning agents, surfactants and other ingredients, such as corrosion inhibitors, pigments, adhesives and the like Other suitable extenders for the wettable powders according to the invention are Clays such as kaolin, diatomaceous earth and also synthetic silicon dioxide and silicate. Organic diluents such as walnut shell flour can also be used will.

In the center according to the invention: Ln lies the. Active ingredient in the form of small Particles, e.g. in the form of wettable powders, dusts, suspensions and confirmed Types of granules and pellets; it is desirable to achieve an optimal Activity the connection applications to a fine particle size grind. Preferred grinding devices for obtaining such fine particles include ball mills, sand mills, air mills, pin mills, sizing effective hammer mills, abrasion mills ("Attritors"), air classifier mills (Whizzer mills), Ring roller mills, pin mills (dise mills) and the like.

The active ingredient content of these wettable powders is usually 15 up to 90% by weight. The wettable powders can also be converted into dusts 1 to 25% active ingredient by using pyrophyllite, volcanic ash, ground Phosphate rock or other dense, rapidly settling, inert solids mixes odex grinds. Dust can also be produced by grinding the dust thinner with the active ingredient or in the form of dust concentrates for further dilution getting produced. The dust concentrates can contain 80 to 95% by weight of active ingredient, that with diluents and optionally small amounts of surface-active substances Means can be mixed and ground.

Two types of carriers are most suitable for the granules. The first type of carrier are porous, adsorbent, preformed granules, like deformed and sifted out, granular Clay or heat expanded, granular, sieved vermiculite or granular botanical substances such as corn on the cob. A solution or aqueous suspension of the active ingredient in concentrations can be applied to these granules up to 25%, based on the total weight, can be sprayed on. Except for the active ingredient the solutions or suspensions can be a surface-active agent and also a binder, such as swelling starch, contained to prevent the adherence of small particles of the dispersed product to improve on the dried grains. Such adhesives can also be surface-active Be means; They include products such as polyvinylakotol, sodium, calcium and magnesium lignosulfonate mixed with wood sugars, acrylate and asphalt emulsions, Abietate u 80 on. Oils or other non-volatile liquids such as glycols, can be used to improve adhesion.

The carriers of the second type are powdered kaolinitic clays or betonitic clays in the sodium, calcium or magnesium form. These tones will be mixed with the active ingredients and optionally surface-active agents, and the Mixtures are granulated and dried so that granules are obtained which the active ingredient is evenly distributed through the whole mass. Such grains can be made with 25 to 30 wt .-% active ingredient, but more common is for optimal Distribution a concentration of about 10% by weight is desirable.

Similar agents can be made by using the mixture in Presence of moisture and extruded the extrudates through a suitable Combination of cutting, drying and pounding converted into grains or pellets. The granules according to the invention are most effective in toroidal sizes from 0.25 to 1.5 mm.

Liquid agents that contain one or more of the active disease control compounds Contain according to the invention, are by mixing the active ingredient with a liquid diluent produced. The active ingredient can be in the diluent be in solution or in suspension. Typical liquids for this purpose are water, paraffinic spray oils, alkylated naphthalenes, xylene, alcohols, chlorinated hydrocarbons and concretes. The active ingredient content of these liquid agents is usually around 0.5 to 50%.

In addition, the agents can be surface-active agents,, especially Emulsifiers, included to facilitate suspension or dispersion or the means of emulsifying ila water.

The means according to the invention, especially the liquids and the wettable powders, used as conditioning agents one or multiple surfactants in sufficient quantity to make a given composition easy to make dispersible in water or oil. To the "surface-active agents" These include wetting agents, dispersants, suspending agents and emulsifying agents.

Suitable surface active agents are anionic, cationic and non-ionic agents. In general, the mixtures contain less than 10 wt .- * surfactant; often the level of surfactants is low less than 2% by weight. However, as described below, larger amounts of surfactants in relation to those present in the form of small particles Active ingredient unusual and surprisingly favorable results, such funds give a more effective disease control when looking at the activity of the Components is to be expected when used separately.

Of the nonionic and anionic surfactants are, for the production of the dry, settable products according to the invention solid forms of the compounds known as wetting agents and dispersants best suited. A liquid, non-ionic compound9 which is primarily regarded as an emulsifier, is also used as a wetting agent and The dispersants can be used Preferred wetting agents are alkylbenzene and alkylnaphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long-chain Acid esters of sodium isethionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters, petroleum sulfonates, sulfonated vegetable oils and diter animal acetylenic glycols. Preferred dispersants are methyl cellulose, polyvinyl alcohol, Sodium, calcium and magnesium lignin sulfonate, polymeric alkyl naphthalene sulfonates, Sodium naphthalene sulfonate, polyvinylpyrrolindone derivatives, polymethylene bis-naphthalene sulfonate and sodium N-methyl-N (long chain acid) taurate.

The wetting and dispersing agents in these are preferred, wettable Powders usually contained in concentrations of about 0.5 to 5% by weight. By the inert extender completes the preparation. If necessary, can contain 0.1 to 1% by weight of the extender as a corrosion inhibitor and respectively or replace an anti-foam agent.

The most suitable emulsifiers for the liquid preparations are alkylaryl polyethoxy alcohols, condensation products of ethylene oxide with long-chain Alkyl alcohols, mercaptans or amines, sorbitan fatty acid esters, polyoxyethylene sorbitan -fatty acid esters; Polyethylene glycol fatty acid esters, fatty alkylolamide condensates, amine salts of fatty alcohol sulfates and oil-soluble salts of petroleum sulfonates. Mixtures of emulsifiers are often preferred. Such emulsifiers make up about 2 to 10% by weight of the total preparation.

The control, especially curative control, of fungal diseases with the compounds according to the formula, through the use of certain auxiliary substances, e.g. in the water in which the benzimidazole fungicide is applied, sometimes improved. These auxiliaries, known as penetrants, are surface-active Middle. They improve the behavior on the foliage during immersion treatment from roots of living plants, when liquids are injected into the worms or strains or the like of living plants or in preparations for treatment of fruits, tubers, onions, roots and the like after harvest.

Surface-active agents, the disease control by the invention Reinforce the connections to be used are e.B. sulfonated and resulting amines and amides, diphenyl sulfonate derivatives, ethoxylated alcohols, ethoxylated alkylphenols, ethoxylated fatty acids, ethoxylated fatty acid esters and oils, Polyethylene oxide-polypropylene oxide systems, alkyl sulfonates, surface-active agents based on fluorocarbon compounds, glycerol esters, ethoxylated alcohol sulfates, Glycol esters, isethionates, sulfated thoxylated alkylphenols, lanolin derivatives, Lecithin and lecithin derivatives, alkanolamides, phosphate derivatives, monoglycerides and Derivatives of the same, quaternary ammonium compounds, sorbitan and sorbitol derivatives, Sufosuccinates, alcohol sulfates, sulfated fatty acid esters, sulfated and sulfonated Oils and fatty acids, alkylbenzenesulfonates, imidazolines, taurates, ethoxylated mercaptans, ethoxylated amines and amides, modified phthalic acid-glycerol-alkyd resins and the like Fabrics.

To other surfactants for the purposes of the invention include betaines, alkylnaphthalene sulfonates, condensed naphthalene sulfonates, lignin derivatives, Protein derivatives salicylanilides, sarcosines, petroleum sulfonates and tertiary amine oxides.

The exact mechanism by which these additives behave of the active ingredient, which has an anti-disease effect, is not known; However, the effect is surprising. Perhaps these additives will improve that Penetration of the fungioids into the plant or their change in location in the plant.

Preferred surfactants for enhancing activity the active ingredients are products such as Dioctyluatriumsulfosuccinate ("Aerosol" OT and "Aerosol" OT-B), mixtures of aromatic sulfonates and ethylene oxide derivatives ("Agrimul" GM, "Agrimul" A-100, "Agrimul" N-100, "Emcol" H50A, "Emcol" H53), polyoxyethylene sorbitoleate laurate ("Atlox" 1045A), sodium laurel resultate ("Duponol" ME), polyoxyethylated ptlansliebe Oils ("Emulphor" EL719), lecithin derivatives ("Emultex" R), acid complex phosphoric acid esters ("Gafac" RE-610, "Victawet"), aliphatic amide alkyl sulfonates ("Hyfoamj" Base LL), Oleic acid ester of sodium isethicnate ("Igepon" (AP78), sodium N-methyl-N-oleoyl taurate ("Igepen" T77), the sodium salt of sulfated lauryl and myrimtyl colamide ("In tramine "Y), the oleic acid ester of polyethylene glycol 400 (" Nonisol "210), sodium dodecylbenzenesulfonate ("Sul-Fon-Ate" li 10, "Ultrawet" K), polyoxyethylene ethers of long-chain alcohols ("Sulfonic" LR 30, "Alfonic" 1012-6, "Brij" 30, "Tergitol" TMN), ethylene oxide -Condensation products with condensation products of propylene oxide and ethylenediamine ("Tetronic" 504), Esters of polyhydric alcohols ("Trem" 014), modified phthalic acid-glycerine alkyd resins ("Triton" B1956), quaternary ammonium salts ("Zelec" DP), condensation products from Alkylphenol and ethylene oxide ("Dowfax" 9N4, "Dowfax" 9N10, "Hyonic" 9510, "Tergitols") and the same. The examples in brackets serve for explanation, without to exclude other, more natural commercial products. Examples of other surfactants Agents of the above classes can be found in "Detergents and Emulsifiers", 1965 Annual or 1966 Annual, issued by John W. McGutcheon Incorporated, 236 Mt.

Kemble Avenue, Morristown, New Jersey, V.St.A.

The preferred concentrations of these penetrants in sprays range from 10 to 50,000 parts per million parts of spray liquid. Particularly to be favoured Amounts from 30 to 15,000 parts, in particular from 100 to 5000 parts per million parts.

For dusts, the preferred amounts of penetrant are 1000 up to 300,000 parts per million parts of the material actually applied. Particularly Preferred amounts are from 5000 to 200,000 parts, in particular from 10,000 to 100,000 parts per million.

The means with the content of the present in the form of small particles Active ingredient and surface active agents rarely enhance disease control activity can be produced in several ways. Mar; can s.B. the surface-active Mixing agents with the active ingredient or the active ingredient in a conventional composition, Prepare as described above if spray slurries are to be made. Often it is also possible and convenient to produce preparations in which additives such as active ingredient in a conveniently applicable agent. Know such means Powders, granular te, suspensions or even solutions can be anything from the physical and chemical properties of the manufacturing components.

The surfactant can be used in such mixtures area from 33 to 10,000 parts per 100 parts. Active ingredient. are present. Particularly preferred ratios of 40 to 5000 parts, in particular 50 to 3500 parts, become surface-active Means to 100 parts of active ingredient.

The means with the compound according to the formula also know conventional ones Insectioids, miticides, bacterioids, nematoids, fungioids or others contain agricultural chemicals, such as fear remedies, fruit singulants, , Fertilizers, and the like, so that they have uses other than control from fungal attack can meet. Typical agricultural chemicals or treatment agents, which can be added to the agents according to the invention, or which can also be added to the spray compositions containing one or more compounds according to the invention can be added are explained below: 1,2,3,4,10,10-hexachloro-1,4,4a, 5,8,8a-hexahydro-1,4-endo-exo-5,8-dimethanonaphthalene (Aldrin), 1,2,3,4,5,6-hexachlorocyclohexane (lindane), 2,3,4,5,6,7,8,8-octachloro-4,7-methano-3a, 4.7 , 7a-tetrahydroindane, 1,1,1-trichloro-2,2-bis- (p-chlorophenyl) -ethane (DDT), 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a , 5,6,7,8,8a-octahydro-1,4-endo-exo-5,8-dimethanonaphthalene (Dieldrin), 1,2,3,4,10,10-hexachloro-6,7-epoxy-1,4,4a, 5,6,7,8,8a-octahydro-1,4-endo-endo- 5,6-dimethyanonaphthalene (Endrin), 1 (or 3a), 4,5,6,6,8,8, -Heptachlor-3a, 4,7,7a-tetrahydro-4,7-methanoindene, 1,1,1-trichloro-2,2-bis- (p-methoxyphenyl) -ethane (methoxychlor), 1,1-dichloro-2,2-bis- (p-chlorophenyl) -ethane, chlorinated camphene with a chlorine content of 67 to 69%, 2-nitro-1,1-bis- (p-chlorophenyl) -tutane, 1-Maphthyl-N-methylcarbamate ("Sevin"), methylcarbamic acid ester of 4- (dimethylamino) -3,5-dimethylphenol, Methylcarbamic acid ester of 1,3-dithiolan-2-one oxime, 0,0-diethyl-0- (2-isopropyl) -4-methylpyrimid-6-yl) thiophosphate, 0,0-dimethyl-1-hydroxy-2,2,2-trichloroethylphosphonate, 0,0-dimethyl-S- (1,2-dicarbethoxyethyl) -dithiophosphate (Malathion), 0,0-dimethyl-O-p-nitrophenylthiophosphate (methyl parathion), 0,0-diethyl-O-p-nitrophenylthiophosphate (Parathion), 0, 0-dimethyl -0- (3-chloro-4-nitrophenyl) thiophosphate, di-2-cyclopentenyl-4-hydroxy-3-methyl-2-cyclopenten-1-one chrysanthemate, 0,0-Dimethyl-0- (2,2-dichlorovinyl) phosphate (DDVP), mixture of 53% "Bulan", 26.7 7 "Prolan" and 20.0% related compounds, 0,0-dimethyl-0- (2,4,5-trichlorophenyl) -phosphorothioate, 0,0-dimethyl-S- (4-oxo-1,2,3-benzotriazine-3 (4H) -yl-methyl) -phosphorodithioate ("Guthion"), Bis (dimethylamino) phosphonous anhydride, 0, 0-diithyl-0. (2-keto-4-methyl-7 pyranyl) throphosphate, 0,0-diethyl- (S-ethylmercaptomethyl) -dithiophosphate calcium arsenate, Sodium aluminum fluoride, dibasic lead arsenate, 2'-chloroethyl-1-methyl-2- (p-tert.-butylphenoxy) ethyl sulfite, Azobenzene, 2-hydroxy-2,2-bis- (4-chlorophenyl) -acetic acid ethyl ester, 0,0-diethyl-0- (2- (ethylmercapto) -ethyl) -thiophosphate, 2,4-dinitro-6-sec-butylphenol, toxaphene, 0-ethyl-0-p-nitrophenylbenzenethicphosphonate, 4-chlorophenyl-4-chlorobenzenesulfonate, p-chlorophenyl-phenylsulfone, tetraethyl pyrophosphate, l, l-bis (p-chlorophenyl) -ethanol, 1,1-bis- (chlorophenyl) -2,2,2-trichloroethanol, p-chlorophenyl-p-chlorobenzyl sulfide, Bis- (p-chlorophenoxy) methane, 3- (1-methyl-2-pyrrolidyl) pyridine, mixed esters of pyrethrolone and cinerolone keto alcohols and two chrysanthemum acids, "Cube" - and derris roots, whole powdered, ryanodln, under the name Veratrine known alkaloid mixtures, 2- (o-hydroxyphenyl) -1,3-dithiolane methyl carbamate ester, 2- (o-droxy; henyl) -1, 3-di oxolanmethylcarbamate ester dl-2-allyl-4-hydroxy-3-methyl-2-cyclopenten-1-one, esterified with a mixture of ois- and trans-dl-chrysanthemum monocarboxylic acids, Butoxypolypropylene glycol, p-diolorbenzene, 2-butoxy-2'-thiocyanate diethyl ether, naphthalene, 0-carbamylthiolacetohydroxamic acid methyl ester 1,1-dichloro-2,2-bis (p-ethylphenyl) ethane, O (Mkthylcarbamyl) -thiolacetohydrcxamuremethylester, p-Dimethylaminobenzoldiazosulfonsaures Sodium.

Quinoneoxyaminobenzooxohydrazone, tetraalkylthiuram disulfides, such as T. tramethylthiuram disulfide, or Tetraäthylthiuramidstlfid, metal salts of ethylene-bis-dithicearbamic acid, z. B. the manganese, zinc, iron and sodium salts, pentachloronitrobenzene, n-Dodecylguanidinaaetat (Dodine), N-Trichloromethylthiotetraphydrophthalimide (Captan), Phenylmercury acetate, 2,4-dichloro-6- (o-chloroaniline) -a-triazine (dyrene), N-methylmercury-p-toluenesulfonanilide, Chlorophenol mercury hydroxides, nitrophenol mercury hydroxides, Ethyl mercury acetate, Ethyl mercury 2,3-dihydroxypropyl meroaptide, methyl mercury acetate, methyl mercury 2,3-dihydroxypcopyl mercaptide, 3,3'-ethylene-bis (tetrahydro-4,6-dimethyl-2H-1, 3,5-thiodiazine-2-thione), methylmercury dicyandiamide, N-ethylmercury-p-toluenesulfonanilide, 1,4-dichloro-2,5-dimethoxybenzene, metal salts (e.g. iron, sodium and zinc salts), ammonium and amine salts of dialkyldithiocarbamic acids, Tetrachloronitroanisole, hexachlorobenzene, hexachlorophene, methylmercury nitrile, Tetrachloroquinine, N-trichloromethylthiophthalimide, 1,2-dibromo-3-chloropene, 1,2-dibromo-3-chloroprene, Mixtures of diohloropropane and dichloropropene, ethylene dibromide, chloropicrin, sodium dimethyldithiocarbamate, Tetrachloroisophthalic acid nitrile, 1-Benzimidazoloarbonsäure-2-carboxyaminodimethyleater, Streptomyoin, 2- (2,4,5-trichlorophenoxy) propionic acid, p-chlorophenoxyacetic acid, l-naphthalene acetamide and N- (1-naphthyl) acetamide.

The agricultural chemicals listed above are only valid Examples are, but not limit the scope of the means by which the inventive Active ingredients can be mixed.

The use of the compound according to the invention in a mixture with pesticides, as indicated above, sometimes the activity of the active ingredient appears to be in accordance with of the invention to increase greatly. In other words, it can be surprising high level of effectiveness observed when using a different pesticide is used together with the active ingredient according to the invention The following examples serve to further explain the invention.

B e i s p i e l 1 The ethyl 2-benzimidazole carbamate is as follows: Treat a mixture of 228 parts of thiourea and 110 parts of water over a period of 5 minutes with 244 parts of dimethyl sulfate. The temperature of the reaction mixture is rapidly agitated throughout the work rises to 95 ° C and then begins to cave in. The material is brought in by supplying heat to reflux conditions and kept it for 30 min, then cools to -3 ° C and treated at once with 535 parts of methyl chloroformate. A 25% solution of Aqueous sodium hydroxide is added at a slow rate that the pH of the reaction mixture between 6 and 7 and the Tonperatur kept below 250 ° C When the pH of the mixture reaches 6.9 and the rate of pH change has become negligible, the addition of base will be canceled Alu Base 1005 room parts of the 25% solution required. The telaperture at the end of this addition is 230 C. Immediately after the end of the 13th Bisenzusatnes one gives in the course 360 parts of glacial acetic acid are added for 20 minutes, followed by 324 parts of o-phenylenediamine all at once The resulting mixture is slowly heated to 80 ° C, keep this value for 30 minutes, then cooled to 270 ° C. and the light yellow-brown colored solid product was filtered off isolated, washed well with water and acetone and air-dried. Then a wettable Powder according to the following Recipe made: 2-Benzimidazole carbamic acid methyl ester 15% synthetic, fine silicon dioxide 25% sodium lauryl sulphate 60% Mix the 'benzimidazole with dos silicon dioxide and subjects the mixture to air grinding, until practically all of the particles are less than 5 microns in size, what can be determined microscopically. This mixture is then mixed with the sodium lauryl sulfate mixed and then treated on the hammer mill.

This preparation is added to water in such an amount that that 150 ppm of the active ingredient according to the invention are obtained. This agent is used at a dosage of 10.1 / tree on alternate trees in a Michigan cherry orchard injected using a normal cherry treatment program and Starts early, at the end of summer and more than six weeks after the last treatment the treated trees are healthy and still have all the foliage, while the neighboring, untreated flower on the other hand by the cherry leaf spot disease are severely defoliated.

More trees of the same plantation are added in a dosage of 20 l / tree sprayed with an aqueous suspension containing 6000 ppm of the active ingredient contains according to the invention, whereby you duo the same treatment program as above applies. With this very high Doüierwig (deu 80 times the dosage, that already Protection there) treated trees show no signs for one Chemical damage, which explains the pants safety 5 degrees, the connections According to the invention for useful plants, the ethyl ester is used in a corresponding manner of 2-benzimidazole carbamic acid prepared and used. Corresponding ones are obtained Result.

For example 2 2-Benzimidazole carbuminic acid, 30.0% methyl ester Calcium Magnesium Lignin 15.0% Sulphonate Hydrated Attapulgite 1.4 Anhydrous Sodium Carbonate 2.1 These components are sand milled together until essentially all particles have a fineness below 5 microns Chosen rice field in Louisiana that is heavily contaminated with rice blast fungus infected, ten days after infection, after the fungus has had enough time to to penetrate the rice plants and to settle in them become parcels sprayed with water, which corresponds to the invention with a 300 ppm active ingredient Amount of the above remedy has been added. Four weeks later it is found that the rice plants in the trafficked parcel remain healthy. The the parcels The surrounding, untreated Rois, on the other hand, was seriously ill with the fire There the infection of the rice a good time before the treatment takes place shows this present result the curative effect B e i obtained according to the invention p i e l 3 The agent according to Example 2 is used in a 300 ppm active ingredient according to the amount corresponding to the invention is added to water, since 300 ppm surface-active Agent (a modified phthalic acid glyceral alkyd resin; "Triton" B 1956) contains. The receiving pension is alternated in a j? Oo ierung of 15 1 / tree Spraying trees in a peach garden, starting spraying when the buds open in spring, and sprinkling at intervals until harvest time repeated from 7 to 14 days. The remaining trees in the plantation are left untreated At harvest time the treated trees as well as the fruit turn out to be; esund The fruit of the untreated trees, on the other hand, is thick with peach scab and Brown rot, ex. 4 90 parts attapulgite granules (size range 0.25 to 0.6 mm) are circulated in a rotating mixer and fine with 20 parts the aqueous suspension of Example 2 is sprayed, the circulation is continued, until the suspension is distributed over the surface of the granulate, by drying the Mixture is then obtained a granular mass, the 6 5 des 2-Benzimidazole carbamic acid methyl ester contains.

To form heaped cucumber plants, one brings in on the field In the middle of a 3 m deep hole in the ground, insert three cucumber seeds, taking in some cases 2 g of the above granules are also put into the planting hole, while the other heaps are left untreated, six weeks after ordering the plants in the treated clusters are completely healthy, while the Plants in the untreated piles are severely ill with powdery mildew This explains the disease control with the active ingredient according to the invention taking up from the soil through the roots and systemic transport into the Foliage-In a corresponding manner, instead of the methyl ester, the ethyl and the sec -butyl ester 2-benzimidazole carbamic acid is used Final results for example 5 2-benzimidazole carbamic acid 26% methyl ether Piccolyta resin S-10 38,57 low-boiling isoparaffin oil 26,43 lauryl ether with Polyethylene oxide 9% First dissolve the resin of the above recipe in the isoparaffin oil, then adds the other components and subjects the whole thing to sand molding, btu essentially all particles finer than 5 microns are 4 1 this agent is added to 38 l of water, which immediately produces an excellent The emulsion is obtained from the air on a hectare of banana plantation injected and the treatment repeated at intervals of 21 days. 6 months after the first treatment, the sprayed banana plants are healthy while they are The surrounding, unprayed banana plants were severely damaged by Sigatoka disease are.

Ex. 6 2-Benzimidazole carbamic acid - 70.0% methyl ester Sodium alkylnaphthalene sulfonate 3.0 oleyl ester of sodium 2.0 isethiomat kieselguhr silicon diol 25.0 To achieve a minimal particle size, these Xoponemtes are mixed, Finely ground on the hammer mill (Micronpulverizer) and then air-jet grinding subjected to a particle size below 5 microns as determined by Andreasen pipette sedimentation.

This agent is added to water, ie 300 ppm surface-active Means (ester of polyhydric alcohol "Trem" 014) contains, whereby one it in such Amount sets in that in the aqueous finished preparation 300 ppm of active ingredient according to the Invention can be obtained. This preparation is then applied to alternate trees sprayed on the apple orchard, which is known9 to have been infected with the pathogen a few days earlier of the apple scab was infected at the time of treatment in some trees there are also signs of the onset of powdery mildew growing are present. The medium-sized standard apple trees are sprayed with 4Q l / tree. UM examination three above after treatment reveals the treated trees Completely free of visible signs of scab and not more powdery mildew ale is present at the time of treatment, while the untreated trees have severe scabs and have far more powdery mildew than at the beginning of the experiment present The above agent applied in the above manner thus results in a kill Both the apple scab fungus and the powdery mildew causing Fungus present at the time of treatment and prevents damage by fungal disease Other trees of the same garden are excepted as sprayed above, that the agent is used in such an amount that 21,000 ppm of the active ingredient component (or 70 times the amount for which a curative Disease control is bernnt) be preserved like the prebuilt of these trees The security room is cleared of any signs of chemical damage amazingly big.

Ex. 7 2-Benzimidazole carbamic acid 50% ethyl ester kaolinite clay 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 used in a dosage of 30 kg / ha on an arbitrary basis Selected parcels of a celery field in Florida dusted four days earlier has been infected with the fungus causing celery spot blight. This jTime is sufficient for the fils to penetrate deeply into the tissue of the celery leaf.

Four weeks later, the pollinated color cells only wheat healthy celery plants on9 that grow well. The untreated areas surrounding these parcels, on the other hand are severely ill with celery streak disease and clearly let in recognize less abundant growth.

B e i s p i e l 8 2-Fenzimidazolcarbamic acid methyl ester 70 S Polyethylene oxide adduct des Dcdecylphenols 2.5 5 # methyl cellulose (low viscosity) 0.3% synthetic, fine Silicon dioxide 27.2% These components are mixed together, finely ground on a hammer mill and then subjected to air-jet grinding until to a particle size below 5 microns.

Parcels of a sugar beet field in Minnesota are displayed at intervals sprayed with water for 14 days - that with such an amount of the above remedy has been added so that in the finished suspension 250 ppm of the active ingredient according to of the invention. This suspension is applied at 600 l / ha on each day of treatment upset.

It persisted for 12 weeks after the start of the present experiment The weather was favorable for the growth of the sugar beets and there were frequent intervals, in which an infection with the pathogen that causes leaf spot disease in sugar beet can occur. At the end of the experiment, the R (Ib.n in the treated Pariejlen as healthy and growing well, while the untreated, the treated The areas surrounding the parcels only contained sugar beets, which are seark from the leaf spot disease were sick.

If you treat drug dosages in an appropriate manner, the up to 64fold you applied above. Going to the dosage, no damage occurs of sugar beets inh

Claims (3)

P a t e n t a n s p r ü c h e 1. Fungrcides means that an active ingredient of the general formula N O C-NH-C-OR N, H in which R denotes methyl or ethyl, characterized in that the active ingredient has a particle size below 5 microns owns. 2. Fungicidal agent according to claim 1, characterized in that dasi it is a surfactant, preferably in an amount from 33 to 10,000 Parts per 100 parts of active ingredient. 3. Fungioid agent according to claim 2, characterized in that it as a surface-active agent 50 to 3,500 parts per 100 parts of active ingredient of compounds from the group of dioctyl sodium sulphonates, mixture of aromatic sulphonates and ethylene oxide derivatives, polyethylene sorbitoleate / laurate, sodium lauryl sulfate, polyoxyethylated, vegetable oils, lecithin derivatives, acidic, complene, organic Phosphate ester, aliphatic amide alkyl sulfonates, oleic acid esters des Sodium isethionate, sodium-N-methyl-N-oleoyl-taurate, sodium salt of sulfatitnen Lauryl- and Myristrlcolamides, polyethylene glycol oleic acid esters, sodium dodeoylbenzenesulfonate, Polyoxyethylene ether with long-chain alcohols, ethylene oxide condensates with propylene oxide / ethylene diamine condensates, Polyhydric alcohol esters, modified phthalic acid glycerinalkydharze and A. Contains alkylphenol ethylene oxide condensate.