DD260211A5 - FUNGICIDAL AGENT AND ITS USE - Google Patents

Abstract

The invention relates to a fungicidal composition and its use. The fungicidal agent contains as active ingredient 2-cyanobenzimidazole compounds of the formula (I) in which R is a dialkylamino group having 2 to 4 carbon atoms, which have an improved fungicidal action time and are useful for the control of phytopathogenic fungi. The fungicidal agent may also contain other fungicides. Formula (I)

Description

Characteristic of the known solutions

It is known that fungi of the species Oomycetes cause particularly serious diseases. The large number of leaf diseases caused in this way include the mildew diseases of vine, tobacco, tomato, potato and curcurbitaceae.

In EP-A 0087375 2-cyanobenzimidazole compounds are described which are useful in agricultural fungicides, especially as contact fungicides, and have good activity against the pathogens of several mildew species, especially against the pathogens of the herbaceous and blight of the solanaceae (for example, the tomato and the potato), Phytophthora infestans, the blue-leaf of tobacco, Peronospora tabacina and Phytophthora parasitica, the false downy mildew, Plasmopara viticola and the powdery mildew of the Curcurbitaceae, Pseudoperonospora cubensis.

However, it is desirable to continue to expand the spectrum of action and performance of a fungicide.

Object of the invention

The aim of the invention is to provide a fungicidal agent for agriculture, which is effective against various mildews, especially against the late blight of the potato, the (false) mildew of the vine, the late blight of the tomato, the cucumber and the blue mold of the Tobacco and which at the same time has an excellent, immediate onset fungicidal action and improved or persistent fungicidal action and reduced toxicity. It is also desirable that the fungicidal action last longer than that of the compounds described in EP-A 0087 375.

By "sustained fungicidal activity or effect" is meant the period of time during which the fungicidal activity of a compound or drug remains at a satisfactory level after the fungicidal treatment of a culture has been performed.

It is generally assumed that the protection of a culture against fungal diseases remains at a satisfactory level as long as the coefficient of fungicidal activity is at least 80%. The protection is considered absolutely excellent once this coefficient is at least 90%.

In practice, the protection of the crops against the fungal diseases is generally carried out by successive fungicidal treatment at specific intervals throughout the growing season of the vegetation using either a single fungicidal active ingredient or a combination of several fungicidal active substances.

The use of a fungicidally active compound, alone or in combination with other substances whose fungicidal activity lasts longer, is particularly advantageous because it allows a reduction in the individual treatments and, moreover, provides sustained protection to the treated crops or plants for the period between Time of the last fungicide treatment of the row and time of harvest.

Explanation of the essence of the invention

It has been found that with derivatives of 2-cyanobenzimidazole of the general formula (I) Br

(D,

in which R "is a dialkylamino group having 2 to 4 carbon atoms, preferably the dimethylamino group, means that the desired fungicidal effects can be achieved as active ingredient.

It has furthermore been found that the object of the invention can also be achieved with the aid of the combinations of one or more compounds of the formula (I) with at least one fungicide of group (II), i. H. with a fungicide selected from the following subclasses:

1. Chloro or nitro derivatives of benzene, such as quintoene or chlorothalonil,

2. dicarboximide derivatives and cyclic imides such as captan, folpel, captafol, iprodione, procymidone, vinclozolin, fluorimide, chlozolinate and metomeclan,

3. the derivatives which comprise one or more heterocycles, such as the quinoleins (ethoxyquin), morpholines (dodemorph, tridemorph, fenpropimorph), piperidines (fenpropidin) and piperazines (triforin),

4. the derivatives of dithiocarbamic acid, such as maneb, mancozeb, thiram, metiram or zineb or propineb,

5. phenol derivatives such as dinocap or binapacryl,

6. Chinese derivatives such as dithianone and chloranil,

7. the derivatives of carbamic acid and benzimidazoles such as carbendazim, benomyl, methylthiophanate, thiabendazole and fuberidazole,

8. Sulfur compounds such as Dazomet or Etridiazol or sulfur or Fenaminosulf,

9. Diazines or triazines such as quinomethionate, fenarimol, anilazine, nuarimol, bupirimate, ethylrimol, pyrazophos and diclomezine,

10. sulfamides such as dichlofluanid and tolylfluanid,

11. Guanidines like Doguadin,

12. Triazoles, for example those described in British Pat. No. 2,046,260, the contents of which are hereby incorporated by reference, such as diniconazole or other known triazoles, propiconazole, triadimefon, triadimenol, diclobutrazole, bitertanol, penconazole, hexaconazole, flusilazole, myclobutanil, SAN 619F ( Sandoz), ethyltrianol, fluotrimazole, flutriafol, triazoles such as those described in EP-A-0151084, the triazole designated 2- (2,4-dichloro-1-phenyl) -2-methyl- (1,2,4 -triazol-1-yl) -5-trifluoroethoxytetrahydrofuran or its salts. This compound is prepared as follows. According to a process described in EP-A 0151084, 40 ml of trifluoroethanol are mixed with 10.7 g of the compound of the formula (XI) prepared according to Example 2 of EP-A 0151084. HCL gas is bubbled through it, up to a weight increase of 1, 39g. The mixture is then heated for 2 h to 7O ⁰ C. The reaction mixture is poured into 500 ml of water containing 10 g Na ₂ CO ₃ from. It is extracted with ethyl acetate; the organic solution is washed with water, dried, filtered and evaporated. 8 g of crystals are thus obtained, consisting of a mixture of the 2 diastereoisomers of the compound of the formula (I) which begin to melt at 80 ^° C. and show a proton shift at 5.18 and 5.41 ppm in the MNR spectrum.

13. imidazoles such as prochloraz or imazalil and triflumizole,

14. Copper and organic or inorganic copper compounds such as cuprosan.

15. Organotin (IV) compounds such as fentin acetate.

16. Anilazine.

17. Amine phosphites described in BE-PS 890114, the content of which is incorporated herein by reference.

18. Pyridine derivatives such as buthiobate and pyrifenox.

19. 2-aminopyridine derivatives such as fluazinam.

20. Isoxazole and isoxazolone derivatives such as hymexazole and drazoxolone.

21. Phenylcarbamate compounds such as diethofencarb (isopropyl S / I diethoxyphenyl carbamate), methyl N- (3,5-dichlorophenyl) carbamate and the other active compounds against fungi strains resistant to benzimidazoles (e.g. Botrytis cinerea).

The active substances of group (II) are known active substances; most of them are described in works such as "The Pesticidal Manual" edited by "The British Crop Protection Council", 7th edition, 1983. The chemical names of the above enumerated compounds are tabulated in the appendix. If the fungicidal agent according to the invention contains a combination of active ingredients, this is usually a binary combination, i. H. with only one additional active ingredient of group (II); but sometimes ternary combinations, i. H. with two drugs of group (II) or quaternary combinations, d. H. with three active substances of the group (II) or compounds of the formulas (II) to (V) described below

 Preferred active ingredients are those of subclasses 1, 2, 4, 14 and 15.

Among the active substances of group (II), the following active ingredients are also preferred: chlorothalonil, iprodione, fentin acetate, dinocap, maneb, mancozeb, zineb, captan, captafol, folpel, procymidone, copper and copper compounds such as copper oxychloride or copper quinoleate, in binary , ternary or quaternary combination.

It is also possible to combine with the abovementioned combinations one of the following (further) compounds: a) phosphorous acid or its alkali metal salts or the phosphorous acid derivatives, preferably the compounds of the formula (II)

HI

R '- O - P - O

η ¹

M ⁿ ' ⁺ (II)

at them:

R 'is a hydrogen or alkali atom or an alkyl group of 2 to 4 carbon atoms, M is a hydrogen atom or an alkali, alkaline earth or aluminum atom, and n' is an integer of 1 to 3 and the value of M is.

Preferably, M is an alkali metal and n '= 1 when R' is a hydrogen or alkali atom. Preferably that is

Derivative an alkyl-metal phosphite, in particular phosethyl-Al or a Aikalisalz phosphorous acid or the phosphorous acid itself.

b) acetamides, such as those described in US Pat. No. 3,957,847, whose contents are incorporated herein by reference, and which are preferably of the formula (III)

(III)

C - C - NH - C - NHR ² I (1 Il CN O O

in which R ¹ and R ^{2 may be} identical or different and each represents a C ₁ to C ₁₃ alkyl group, preferably a C _{1 to} C ₄ alkyl group and in particular the cymoxanil correspond (R ¹ = CH ₃ , R ² = C ₅ H ₅ ). c) acylanilides as described in the BE-PS (s) 827671 and 827419 or in EP-A-026873, the contents of which are hereby incorporated by reference, and preferably: 1) those of the formula (IV)

^{> 3} CH, OI ³ Il

-C-OCH ₃

(IV)

wherein R ³ and R ^{4 are the} same or different and each represents a hydrogen atom or a C ₁ to C ₄ alkyl group, preferably the methyl group, or a C _{1 to} C ₄ alkoxy group and advantageously R ^{3 is} R ⁴ = methyl;

R ^{5 represents} a -CHH ^ group in which R ^{6 is} a C ₁ to C ₄ alkoxy group, preferably the methoxy group or an aryl group, preferably the phenyl group, or a halogen atom, preferably the chlorine atom, or R ^{5 is} a C ₃ to C ₆ -cycloalkyl group, preferably the cyclopropyl group or a C ₅ - or C ₆ -heterocyclic group, preferably a C ₅ -heterocyclic group having one or two heteroatoms, preferably the 2-furyl, 5-isoxazolyl or 3-oxazolyl group;

R ^{7 is} a hydrogen atom, a halogen atom or a C ₂ -C ₄ -alkyl group, preferably the methyl group, advantageously metalaxyl, furalaxyl, benalaxyl or the compound in which R ³ = R ⁴ = CH ₃ , R ⁷ = H, R ⁵ = 5-isoxazolyl (LAB 149 202 F);

2) those of formula (V)

»5

in the:

R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the same meaning as for the formula (IV), with the same preferred variants and R ⁸ one of the cyclic radicals S-Oxazolidinony ^ S-Butyrolactonyl.S-Thiobutyrolactonyl or 3-Thiooxazolidinonyl, Advantageously Oxadixyl, Cyprofuram, Ofurace or CGA 68099, (RE 26745) wherein R ³ = R ⁴ = methyl, R ⁷ = H, R ⁵ = -CH ₂ OCH ₃ , R ⁸ = 3-butyrolactonyl , RE 26940, in which R ³ = R ⁴ = CH ₃ , R ⁷ = H, R ⁵ = CH ₂ OCH ₃ , R ⁸ = 3-thiobutyrolactonyl or M 12279, in which R ³ = R ⁴ = CH ₃ , R ⁵ = -CH ₂ OCH ₃ , R ⁷ = 3-CI, R ⁸ = 3-oxazolidinonyl.

Some of these compounds are described in DE-PS 884661, which is incorporated herein by reference. The compounds of formula (I) are described in the unpublished French application of February 19, 1986, Serial No. 8602455. These compounds are thus included in group (II). As a combination may be mentioned, for example Mikal (Phosethyl-Al and Folpel), combined with a compound of the invention and Rhodax (Phosethyl-Al + Mancozeb).

The compounds of the formula (I) provided according to the invention as active compounds are prepared by reacting 2-cyano-4-bromo-6-trifluoromethyl-benzimidazole of the formula (VI)

br

F ₃ C

S ₁

CN

or one of its salts, advantageously an alkali metal or alkaline earth metal or ammonium salt, optionally substituted, with a halide of the formula (VII)

X-SO ₂ - R "

in which X represents a halogen atom, preferably a chlorine atom, and R "has the same meaning as in the formula

The reaction of the compound of the formula (VI) with the halide (VII) is advantageously carried out in the presence of an acid acceptor, in anhydrous or non-anhydrous medium, in a solvent which is inert under the reaction conditions, generally at this temperature of the solvent. Suitable acid acceptors are inorganic bases such as sodium hydroxide solution or potassium hydroxide solution, alkali metal or alkaline earth metal carbonates, nitrogen bases such as triethylamine. The solvents used are advantageously aprotic solvents, such as dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, acetonitrile, N-methylpyrrolidone and ethyl acetate. If desired, the reaction can be carried out in the presence of a corresponding catalyst. Useful catalysts include phase transfer catalysts such as quaternary ammonium salts.

In the reaction of the alkali or alkaline earth metal salt or optionally substituted ammonium salt of the compound (VI) with the halide (VII), no acid acceptor needs to be present. This reaction is carried out in anhydrous or non-aqueous medium, in a solvent which is inert under the reaction conditions, generally at the boiling point of the solvent. The abovementioned aprotic polar solvents can be used advantageously in this reaction.

If desired, this reaction may be carried out in the presence of a corresponding catalyst, such as a phase transfer catalyst, for example a quaternary ammonium compound. The alkali or alkaline earth metal salt or optionally substituted ammonium salt of the compound (VI) is prepared in a precursor, optionally in situ by the action of a corresponding base, for example sodium hydroxide, ammonia, baryta or lime or an alkali metal carbonate or an alkali metal alkoxide, for example sodium or sodium or Potassium ethylate on this compound (Vl).

After completion of the reaction, regardless of the method used, the resulting compound is isolated from the reaction medium by conventional methods, for example by distilling the solvent or by crystallizing the compound in the reaction medium or by filtration and then, if necessary, by conventional methods purified, such as recrystallization from an appropriate solvent.

The 2-cyano-4-bromo-6-trifluoromethylbenzimidazole of the formula (VI) can be converted to 2-trichloromethyl-4-bromo-6-trifluoromethylbenzimidazole of the formula (VIII) by the action of ammonia.

(VIII)

are prepared according to the method described in EP-A 87375 (Method A) and US Patent 3576818. To carry out this reaction, the compound (VIII) is advantageously dissolved in a solvent such as dimethylformamide, 1,2-dimethoxyethane, acetonitrile, ethyl acetate and ethyl alcohol, which has no restrictive effect. It can also be prepared according to the procedures and methods B and C described in EP-A 87375.

If desired, then in the same reaction vessel, the preparation of the compound of formula (Vl) can be carried out starting from the compound of formula (VIII) and then the conversion of the compound of formula (Vl) into the compound of formula (I), without the be isolated as an intermediate compound (Vl) or the salt of this compound.

The compound of the formula (VIII) can be prepared by reacting methyl trichloroacetimidate with 1,2-diamino-3-bromo-5-trifluoromethylbenzene of the formula (IX)

br

(IX)

or to a salt of this compound of formula (IX) with a strong acid. Preferably, this salt is prepared by combining one mole of the compound of formula (IX) with one mole of a strong monoacid, such as HCl or HBr, or by mixing two moles of this compound of formula (IX) with one mole of a strong diacid, such as H ₂ SO ₄ , combined. Preferably, this salt is the monochlorohydrate of the compound of formula (IX).

The reaction is advantageously carried out from room temperature in acetic acid medium or in lower alkanols, such as ethanol or methanol. It can also be carried out at the reflux temperature of the solvents used. The compound of the formula (IX) can be prepared from 2-bromo-4-trifluoromethyl-6-nitroaniline of the formula (X)

(X)

be prepared by reduction of the nitro group to the amino group. This reduction may be carried out by any means known to effect the reduction of a nitrobenzene to the corresponding aniline, for example by allowing tin (II) chloride to act in the presence of concentrated hydrochloric acid; with the aid of this latter method, the monochlorohydrate of the compound of the formula (IX) is obtained.

The 2-trichloromethyl-4-bromo-benzimidazole compounds corresponding to the formulas (VI) and (VIII) and the salts of these compounds, especially the alkali metal or ammonium salts which are formed by reacting these compounds with an inorganic or organic base are new compounds, as well as the aniline compounds of the formulas (IX) and (X).

If the fungicidal agent contains an active ingredient combination, the weight ratio of the compound (s) of the group or formula (I) to the compound (s) of the group (II) is between 1: 10,000 and 100, preferably between 1: 1000 and 10 (: 1).

These fungicidal active ingredients are intended for simultaneous, separate or delayed fungicidal treatment of the plants, especially for the fungicidal treatment against pathogens of mildew diseases.

In the case of simultaneous use, it is advantageous to use ready-to-use products containing the combination of active ingredients described above. It is also possible to use products which are obtained by mixing in place of active ingredients or agents containing each of the active ingredients immediately before use, as described below.

The use or application can also be done at intervals.

It is also possible to proceed in such a way that the crops to be protected are treated first with one and then with the other active substance (I) and (II).

The fungicidal agent of the present invention is useful for agriculture. It is particularly useful for the protection of crops of solanaceous, tobacco, vine and cucumbers against the pathogens of (false) powdery mildew of these crops (Phytophthora infestans, Peronospora tabacina, Phytophthora parasitica, Plasmospora viticola, Pseudoperonospora

cubensis).

It is particularly useful for controlling the fungal diseases of solanaceae (tomatoes, potatoes, tobacco), planting cucumbers and vines, and can also be used to regulate plant growth.

The fungicidal composition contains as active ingredient a product according to the invention, as described above, in combination with inert, solid or liquid carriers or diluents which are useful for agriculture and / or with surface-active agents which are compatible with the active substance and also for the Agriculture are acceptable. Above all, the inert and common carriers as well as the common surface active agents are useful.

The agent generally contains 0.5 to 95% active ingredient. Its content of surfactant generally makes 0 to 20% by weight.

The term "carrier" in the sense of the description refers to an organic or inorganic substance of natural or synthetic origin, with which the active ingredient is combined in order to facilitate its application to the plant, to grains (seeds) or to the soil The support may be solid, such as clays, natural or synthetic silicates, silicic acid, resins, waxes, solid fertilizers, etc., or liquid, such as water, alcohols, ketones, Petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, liquid fertilizers and oligoelements, etc.

The surfactant may be an emulsifying agent, a dispersing agent or a wetting agent of ionic or nonionic type. Examples thereof are salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensation products of ethylene oxide and fatty alcohols or fatty acids or fatty amines, substituted phenols, especially Alkylphenols or arylphenols, salts of esters of sulfosuccinic acids, taurine derivatives, especially alkyl taurates, phosphoric acid esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is generally essential if the active ingredient and / or the inert carrier is not water-soluble and water is used as an adjunct to the application.

The fungicidal agent according to the invention can take on very different liquid or solid forms.

Forms for liquid agents or liquid agents for use are solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and wettable powders and pastes.

Molds for solid agents are powders for dusts or for dispersing, the content of which may be up to 100% of the product, and granules, especially those obtained by extrusion, by compression, by impregnation of a granulated support or by granulation of a powder; the active ingredient content in these granules makes up 1 to 80% in the latter cases.

The emulsifiable or soluble concentrates usually contain 10 to 80% active ingredient; the ready-to-use emulsions or solutions in turn contain from 0.001 to 20% active ingredient.

These agents may also contain any other ingredients such as protective colloids, adhesives, thickeners, thixotropic agents, penetrants, stabilizers, scavengers and the like, as well as other known agents having pesticidal, particularly insecticidal or fungicidal activity, or having properties that promote plant growth, such as especially fertilizers, or with properties that regulate the growth of plants. In general, the compounds according to the invention can be combined with any solid or liquid additives which correspond to the usual procedures of preparation or formulation.

For example, in addition to the solvent, the emulsifiable concentrates may contain 2 to 20% additives if required

such as the aforementioned stabilizers, surfactants, penetrants, corrosion inhibitors, dyes or adhesives.

Starting from these concentrates, it is possible by dilution with water to prepare emulsions of any desired concentration, which are particularly suitable for application to the crops or plantings.

The suspension concentrates, which can also be sprayed, are prepared to give a stable flowable product which does not settle; they usually contain 5 to 75% active ingredient, 0.5 to 15% surfactants, 0.1 to 10% thixotropic agents, 0 to 10% additives such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants and adhesives, as well as water or a carrier organic liquid in which the active ingredient is little or not soluble.

Certain organic solids or mineral salts may be dissolved in the carrier to help prevent sedimentation or as antifreeze for the water.

The wettable powders or wettable powders are usually prepared to contain 5 to 95% of active ingredient, and further usually 0 to 5% of a wetting agent, 3 to 10% of a dispersant and, if necessary, 0 to 10% of one or more in addition to the solid carrier several stabilizers and / or other additives such as penetrants, adhesives or anticaking agents, dyes and the like

Starting from the concentrates, emulsions of any desired concentration can be prepared by diluting with water, which are particularly suitable for application to the leaves or foliage.

To produce wettable powders or wettable powders, the active ingredients are intimately mixed in suitable mixers with the additional substances and comminuted or ground in mills or other comminution equipment. In this way, spray powders having advantageous wettability, which can be advantageously suspended, are obtained; you can suspend them with water to any desired concentration, and these suspensions are very beneficial applicable, especially on the foliage of the plants.

Instead of wettable powders you can also make pastes. The conditions and modalities for the preparation and use of these pastes are similar to those of wettable powders or wettable powders.

As already stated, the aqueous dispersions and emulsions, for example the agents obtained by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, are within the general scope of the present invention. The emulsions can be water-in-oil or oil-in-water emulsions and have a thick mayonnaise-like consistency.

The agents according to the invention can be advantageously formulated as water-dispersible granules. These dispersible granules having a bulk density generally from 0.3 to 0.6 have a particle size which is generally about 150 to 2000 μm, preferably 300 to 1500 μm. The active ingredient content of these granules is generally from 1 to 90%, preferably from 25 to 90%.

The remainder of the granules consists essentially of a solid filler and optionally surface-active additives which render the granules dispersible in the water. These granules may be of essentially two distinct types, depending on whether the retained carrier is water-soluble or not water-soluble. If the carrier is water-soluble, it may be of inorganic or preferably organic origin. Excellent results were achieved with urea. In the case of an insoluble carrier, it is preferably inorganic, such as kaolin or bentonite. Advantageously, surfactants are then additionally present in an amount of from 2% to 20% by weight of the granules consisting of more than half of, for example, at least one substantially anionic dispersant, such as an alkali or alkaline earth polynaphthalenesulfonate or alkali or alkaline earth malignofulfonate; the remainder consists of nonionic or anionic wetting agents, such as an alkali or alkaline earth alkyl naphthalene sulfonate.

Furthermore, other additives can be added, such as antifoams, but this is not essential.

The granules can be prepared by mixing the necessary ingredients and then granulating according to several well-known procedures (coating drum, fluidized bed, atomizer, extrusion, etc.). This is generally followed by a comminution process and then screening to the desired particle size within the limits given above.

Preferably, the granules are prepared by extrusion by operating as in Examples 8 and 9.

This mixture was granulated in the fluidized bed in the presence of water and then dried, crushed and sieved to give granules of 0.15 to 0.80 mm in size.

The granules may be used alone (as such) or dissolved or dispersed in water to the desired dose. They may also be used to make combinations with other active ingredients, especially fungicides, the latter being in the form of wettable powders or granules or aqueous suspensions.

The compounds of formula (I) can also be used in the form of dusts. It is also possible to use an agent containing 50 g of active ingredient and 950 g of talc. Furthermore, one can use an agent containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc. These ingredients are mixed and ground, and this mixture is applied by means of dusts.

The liquid, diluted or concentrated preparations, alone or in combination with other pesticides or fertilizers, may advantageously be applied near the plants by irrigation or sprinkling, especially dropwise with a suitable device and by sprinkling.

The storage and transportable agents advantageously contain 0.5 to 95% by weight as active ingredient.

Formulations suitable for agricultural use fungicidal compositions according to the invention can thus contain the active compounds according to the invention provided within very wide limits, ranging from 5 x 10 ^-5 to 95Gew .-% range. Their surfactant level advantageously makes up 5 to 40% by weight.

The application rates can vary within wide limits, which are mainly based on the virulence of the fungi and the climatic conditions.

In general, agents containing from 0.5 to 5,000 ppm of active ingredient are well suited. These values are given for the ready-to-use agents. Ppm means "parts per million". The range of 0.5 to 5,000 ppm corresponds to a range of 5 10 ^-5 to χ

0,5Gew .-%. '

The agent according to the invention is applied to the plants one or more times.

The active ingredient of the formula (I) is advantageously used in an amount of from 2 to 250 g / ha, preferably from 4 to 220 g / ha, depending on the plants to be treated.

Vorteiihafterweise used in the case of Solanacea 2bis200g / ha active ingredient and advantageously 4 to 160g / ha.

Preferably in the case of tobacco in the control of Peronospora tabacina 80 to 220 g / ha and for the control of Phytophthora parasitica 60 to 120g / ha.

In the case of vines, preferably 100 to 250 g / ha are used, and in the case of cucurbitaceae 2 to 50 g / ha.

In the case of combinations, 100 to 3000 g / ha of group (II) active substances are applied individually or in a mixture, depending on the compounds selected.

In practice, doses of 5 to 100 g / hl correspond to doses of about 50 to 1000 g / ha.

embodiments

Example 1: (emulsifiable concentrate) 400 g / l - Active substance 24 g / l - Alkali dodecylbenzenesulfonate - Condensation product of nonylphenol 16g / l and 10 moles of ethylene oxide 200 g / l - Cyclohexanone ad 11 - aromatic solvent Example 2: (emulsifiable concentrate) 250 g - Active substance 25g - epoxidized vegetable oil - Mixture of alkylarylsulfonate and Ether of a polyglycol and fat 100 g alcohols 50 g - dimethylformamide 575 g - xylene Example 3: (Spray Powder) 50% - Active substance 2.5% Ethoxylated fatty alcohol (wetting agent) Ethoxylated phenylethylphenol 5% (Dispersant) 42.5% - Chalk (inert carrier) Example 4: wettable powder) 10% - Active substance - Condensation product from a syntheti branched C ₁₃ oxo alcohol and 8 0.75% up to 10 mol of ethylene oxide (wetting agent) - neutral calcium lignosulphonate 12% (Dispersant) ad 100% Calcium carbonate (inert filler) Example 5: (Spray Powder) This wettable powder contains the same constituents as in the previous example in the following proportions:

- Active substance 75%

Wetting agent 1.50%

Dispersant 8%

Calcium carbonate (inert filler) ad 100% Example 6: (wettable powder)

- active ingredient 90%

- ethoxylated fatty alcohol (wetting agent) 4%

Ethoxylated phenylethylphenol

(Dispersant) 6%

Example 7: (spray powder),

- active ingredient 50%

- Mixture of anionic and nonionic surfactants (wetting agent) 2.5%

Sodium lignosulphonate (dispersing agent) 5%

Kaolin clay (inert support) 42.5% Example 8: (dispersible granules)

In a mixer, 90% by weight of active compound (Compound No. 1) and 10% of urea in pearls were mixed. The mixture was then ground in a spindle mill. A powder was obtained which was moistened with about 8% by weight of water. The wet powder was extruded through a perforated roller extruder. The resulting granules were dried, crushed and sieved; the granules with a size of 150 to 2000 μm were retained.

Example 9: (dispersible granules)

In a mixer, the following components were mixed:

- Active substance (compound no. 1). 75%

Wetting agent (sodium alkyl sulfonate) 2%

- Dispersant

(Sodium polynaphthalenesulfonate) 8%

- water-insoluble inert filler

(Kaolin) 15%

The structure of the compounds described below was confirmed by their NMR or IR spectrum.

Preparation:

, Preparation of i-dimethylsulfamoyl ^ -cyano ^ -bromo-e-trifluoromethyl-benzimidazole To a suspension of 1.5g (0,024mol) potassium hydroxide in scales in 80 ml acetone at room temperature (about 2O ⁰ C) 7.0g (0,024mol) Added 4-bromo-2-cyano-6-trifluoromethyl-benzimidazole. The gradual dissolution of the reactants and a temperature rise to 30 ° C were observed. The resolution was over after an hour. Then, 2.6 ml of dimethylsulfamoyl chloride (0.024 mol) was added to the reaction mixture over 10 minutes, and the reaction mixture was stirred for 18 hours and then poured into 11 liter of distilled water. The resulting precipitate was spun on the filter and then washed with water (4 × 50 ml), then with ethanol (50 ml) and finally with ethyl ether (100 ml). After drying, 4.3 g of i-dimethylsulfamoyl-cyano-bromo-e-trifluoromethylbenzimidazole (Compound A), melting at 198 ° C., were obtained; Yield 45.1%

 The 2-cyano-4-bromo-6-trifluoromethylbenzimidazole was prepared as follows: To 430 ml of 29% ammonia was added, within 45 minutes, 50.8 g (0.13 mol) of 4-bromo-2-trichloromethyl-6-trifluoromethylbenzimidazole , dissolved in 200 ml of ethanol, added.

The temperature of the reaction mixture was maintained at about 25 ° C. After stirring at room temperature for 1 hour, the reaction mixture was filtered. The filtrate was acidified to pH 1 and then decanted. The organic phase was washed with water. This oil crystallized; the solid was washed with water and then dried. There were thus obtained 30.23 g of 2-cyano-4-bromo-6-trifluoromethyl-benzimidazole, which melted at 130 ° C; Yield 78.4%. The 2-trichloromethyl-4-bromo-6-trifluoromethyl-benzimidazole was prepared as follows: To a suspension of 81.1 g (0.28 mol) of i-diamino-S-bromo-6-trifluoromethyl-benzene monochlorohydrate in 600 ml of acetic acid was allowed to run in the course of half an hour 54ml methyltrichloroacetimidate at 21 ⁰ C. The temperature rose up to 40 ° C. After 2 hours, crystallization was observed in the reaction medium, which was stirred at 20 ^° C. for 18 hours. Then the reaction mixture was poured into 21 distilled water. The resulting precipitate was spun off, washed with water (2 × 200 ml) and then completely spun off. After prolonged drying, 101 g of 2-trichloromethyl-4-bromo-6-trifluoromethyl-benzimidazole, which melted at 208 ⁰ C; Yield 95%. The 1,2-diamino-3-bromo-5-trifluoromethylbenzene was prepared in the form of a monochlorohydrate in the following manner: 336 g (1.18 mol) of 2-bromo-4-trifluoromethyl-6 were added in small portions over a period of 1 to 2 hours. Nitroaniline added to a heated to 40 ⁰ C solution of 840g tin (II) chloride dihydrate in 2, oil of concentrated hydrochloric acid. The temperature rose up to 8O ⁰ C. The formation of a larger amount of white precipitate was observed. After completion of the addition, the mixture was heated to 8O ⁰ C for one hour and then cooled to 10 ⁰ C. The resulting precipitate was collected on the filter, washed with concentrated hydrochloric acid (400 ml) and then with dichloromethane (2 x 500 ml), and finally dried in air for 2 days

 This gave 297 g of 1,2-diamino-3-bromo-5-trifluoromethylbenzene in the form of monochlorohydrate, which at a temperature

melted above 270 ° C; Yield 86.3%.

The 2-bromo-4-trifluoromethyl-6-nitroaniline was prepared as follows:

In a cooled flask, 900 ml of water were introduced and then added to 600 ml of concentrated sulfuric acid. Then 150 g (0.73 mol) of 2-nitro-4-trifluoromethylaniline and 117 g (0.73 mol) of bromine were stirred in the course of 1 2 hours, then filtered and washed with water. After drying, 188.5 g of 2-bromo-4-trifluoromethyl-6-nitroaniline, which melted at 70 ° C; Yield 90.6%.

Application Example 1

There are two rows of four plots ä 10 m ² treated with (respectively) on which variety potatoes were planted Sirtema that (Phytophthora infestans) were infected with leaf blight. The plants were treated four times at intervals of 10 days with two fungicidal spray mixtures, as defined below, at a rate of 10 000 l / ha; the spray liquors contained 15 g / hl of active ingredient and had been prepared by diluting a wettable powder of the following composition by weight with water:

- Active ingredient (2-cyano-benzimidazole compound) 50%

Wetting agent ATLOX 4853 B (mixture of anionic and

nonionic surfactant) 2.5%

Dispersant (sodium lignofulfonate) 5%

- kaolin (inert carrier) 42.5%

The experiments were carried out with the compound A described in the preparation example and for comparison with 1-dimethylsulfamoyl-2-cyano-4,6-dibromo-benzimidazole, compound no. 39 of EP-A 87375.

" ' Compound A CONNECTION No.39 Number of stains on the foliage of 10 stems. Measurement 8 days after the 2nd treatment 7 42.3 Number of affected leaves with a total of 10 stems, measurement 11 days after the 3rd treatment 33 234.5 Infestation 1 day after leaf upper 3rd treatment 1.2 7 area% 5 days after the 3rd treatment 2.2 15 4 days after the 4th treatment 2.7 30 10 days after the 4th treatment 4.7 40

Application Example 2:

Two rows of four parcels of 10m ^{2 were} treated, on which tomatoes of the variety Marmande were grown and infested with rot (Phytophthora infestans). These plants were treated four times at 8-day intervals with two spray fungicides, as defined below, at a rate of 1 000 l / ha.

The spray mixtures used differed from those of Example 2 only by the dilution with water, which corresponded to a drug concentration of 5 g / hl

 The active ingredients used were the same as in Application Example 1.

The following results were achieved:

CONNECTION A CONNECTION No. 39 Number of affected leaves at 10 plants 23.3 371.3 Measurement 1 day after the 4th treatment

Infested 1 day after the "3.7 50 leaf upper 4th treatment

area% 9 days after the 10 91

4th treatment

25 days after the 48 97.7

4th treatment

Infested tomatoes (fruits)

16 days after the 9,1 80,9

4th treatment

Application Example 3

Two rows of four parcels of 10m ^{2 were} treated on which wine (grape GÄMAY) was grown and infected with downy mildew (Plasmopara viticöla). The vine plants were treated eight times at intervals of about 11 days with two spray fungicides as defined below at a rate of (each) 1000 l / ha.

The spray mixtures used differ from those of Application Example 1 only by dilution with water, which corresponded to an active compound concentration of 22.5 g / hl.

The following results were achieved:

CONNECTING CONNECTION No. 39 Affected Leaves%

7 days after the 6th treatment 10 66 8 days after the 7th treatment 10 76 30 days after the 8th treatment 12 80.5

60 days after the 12 92

8. Treatment

Application Example 4:

In vivo experiment with combinations of the late tomato blight (Phytophthora infestans) on tomato plants Tomato plants (Lycopersicum esculentum) of the Marmande variety were grown in pots. Once the plants were one month old (5 to 6 leaf stage, height 12 to 15 cm), they were treated with an aqueous suspension or solution containing the test compound at the desired concentration. Each tomato plant received about 5 ml of solution or dispersion. For each concentration of the drug tested, treatment was on two plants.

This suspension was obtained by mechanically comminuting 100 mg of active ingredient in 100 ml of a solution containing 0.05% Tween 80 (condensation product of sorbitan monooleate and 20 moles of ethylene oxide). This gave a suspension containing 1 g / l fungicidal compound. Successive dilutions with distilled water yielded the desired concentrations.

The control plants were treated with the same solution, but without active ingredient content.

After drying for 24 hours, each plant was infected by dusting with an aqueous spore suspension of Phytophthora infestans, which causes the late blight of the tomato, at a rate of about 1 ml / plant (corresponding to about 1 × 10 ⁵ spores per plant).

Then the tomato plants were individually placed in plastic bags to exclude mutual effects of the drugs and then incubated for two days at about 15 ° C in humidity saturated atmosphere and then for five days at about 17 ° C under 70 to 90% relative humidity.

Seven days after infection, the results of the drug-treated plants and control plants were compared.

Cu oxychloride + compound (A)

links concentration effect mg / 1 % Connection (A) 8th 100 4 92 2 58 1 0 Cu oxychloride (B) 4000 0 2000 0 1000 0 500 0 A + B 8 + 4000 100 8 + 2,000 97 4 + 4000 99 4 + 2000 99 4 +1 000 78 4+ 500 83 2 + 1 000 49 2+ 500 92 1 + 1 000 63 1+ 500 92

Mancozeb + compound (A)

links concentration effect mg / l % Connection (A) 8th 100 4 92 2 58 1 0 Mancozeb (B) 1000 100 500 45 250 28 125 0

A + B

8 + 500 8 + 250 4 + 500 4 + 250 4 + 125 2 + 500 2 + 250 2 + 125 1 + 500 1 + 250 1 + 125

100 83 80 93 48 88 56 71 32 76 5

Captan + connection (A)

links concentration effect mg / 1 % Connection (A) 8th 100 4 92 2 58 1 0 Captan (B) 4000 0 2000 0 1000 0 500 0

A + B

8 + 4000 8 + 2000 4 + 4000 4 + 2000 4 +1 000 4+ 500 2 + 1 000 2+ 500 1 + 1 000 1+ 500

97 100 96 92 90 92 85 98 86 9

Nomenclature table

Chlorothalonil tetrachloroisophthalonitrile

Iprodione S-O-Dichlorophenyl O-N-isopropyl-C 1 - dioxoimidazolidine-i-carboxamide

Fenpropimorph (±) -cis-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine

Tridemorph 2,6-dimethyl-4-tridecylmorpholine

Fenpropidinel [3- (p-tert-butylphenyl) 2-methylpropyl] -piperidine

Dinocap "2- (1-methylheptyl) -4,6-dinitrophenyl crotonate

Dithianone 5,10-Dihydro-5,10-dioxonaphtho [2,3-b] -1,4-dithia-anthraquinone

Maneb manganese ethylene bis (dithiocarbamate)

Mancozeb complex of maneb and a zinc salt

Zineb Zinc ethylene bis (dithiocarbamate)

Phosethyl-Al aluminum tris-O-ethylphosphonate

Captan N- (trichloromethylthio) cyclohex-4-ene-1,2-dicarboximide

Carbendazim methyl benzimidazol-2-yl carbamate

Captafol N- (1,1,2,2-tetrachloroethylthio) -cyclohex-4-ene-1,2-dicarboximide

Cymoxanil 2-cyano-N - [(ethylamino) carbonyl] -2- (methoxyimino) acetamide

Nuarimol α- (2-chlorophenyl) -α- (4-fluorophenyl) -5-pyrimidine-methanol

Diniconazole 1- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1,2,4-triazol-1-yl) -1-penten-3-ol.

This latter product is known from the already mentioned GB-PS 2,046,260.

Cymoxanil 1- (2-cyano-2-methoxy-iminoacetyl) -3-ethylurea

Metalaxyl methyl N- (12,6-dimethylphenyl-phenyl) -N- (2-methoxy-acetyl) -DL-alaninate

Furalaxyl Methyl-N- (2,6-dimethylphenyl) -N- (2-furanyl-carbonyl) -DL-alaninate

Benalaxyl methyl-N-phenylacetyl-N-2,6-xylyl-DL-alaninate

Oxadixyl 2-Methoxy-N- (2-oxo-1,3-oxazolidin-3-yl) -2 ', 6'-acetylidylidyne

Phosetyl-Al (see description).

Claims (2)

1. Chloro or nitro derivatives of benzene, such as quintozene or chlorothalonil, 2. dicarboximide derivatives and cyclic imides such as captan, folpel, captafol, iprodione, procymidone, vinclozolin, fluorimide, chlozolinate and metomeclan, 3. the derivatives which comprise one or more heterocycles, such as the quinoleins (ethoxyquin), morpholines (dodemorph, tridemorph, fenpropimorph), piperidines (fenpropidin) and piperazines (triforin), 4. the derivatives or dithiocarbamic acid such as Maneb, Mancozeb, Thiram, Metiram or Zineb or Propineb, 5. phenol derivatives such as dinocap or binapacryl, 6. Chinone derivatives such as Dithianon or Chlpranil, 7. the derivatives of carbamic acid and benzimidazoles such as carbendazim, benomyl, methylthiophanate, thiabendazole and fuberidazole, 8. Sulfur compounds such as Dazomet or Etridiazol or sulfur or Fenaminosulf, 9. Diazines or triazines such as quinomethionate, fenarimol, anilazine, nuarimol, bupirimate, ethylrimol, pyrazophos and diclomezine, 10. sulfamides such as dichlofluanid and tolylfluanid, 11. Guanidines like Doguadin, 12. Triazoles, for example those described in British Pat. No. 2,046,260, such as diniconazole or other known triazoles, propiconazole, triadimenol, diclobutrazole, bitertanol, penconazole, hexaconazole, flusilazole, myclobutanil, SAN 619 F (Sandoz), ethyltrianol, fluorotrimazole, flutriafol, Triazoles such as those described in EP-A 0151084, the triazole designated 2- (2,4-dichloro-1-phenyl) -2-methyl- (1,2,4-triazol-1-yl) -5- trifluoroethoxy-tetrahydrofuran or its salts, 13. imidazoles such as prochloraz or imazalil and triflumizole, 14. copper and organic or inorganic copper compounds such as cuprosan, 15. Organotin (IV) compounds such as fentin acetate. 16. Anilazine, 17. Amine phosphites described in BE-PS 890114, the content of which is hereby incorporated by reference, 18. pyridine derivatives such as buthobiocite and pyrifenox, 19. 2-aminopyridine derivatives such as fluazinam, 20. isoxazole and isoxazolone derivatives such as hymexazole and drazoxolone, 21. Phenylcarbamate compounds such as diethofencarb (isopropyl-3,4-diethoxyphenyl carbamate) and methyl N- (3,5-dichlorophenyl) carbamate, effective against fungi strains resistant to benzimidazoles, such as Botrytis cinerea. 5. Composition according to claim 4, characterized in that it as a further fungicide chlorothalonil, iprodione, fentin acetate, dinocap, maneb, mancozeb, zineb, captan, captafol, folpel, procyidone, copper and copper compounds such as copper oxychloride or copper-quinoleate , contains. 6. Composition according to claim 4 or 5, characterized in that it additionally contains at least one of the following compounds: a) phosphorous acid or alkali metal salts or the phosphorous acid derivatives, preferably the derivatives of the formula (II), R ¹ - O - P - O "
U η ' at them: R 'is a hydrogen or alkali atom or an alkyl group having 2 to 4 carbon atoms means M is a hydrogen atom or an alkali, alkaline earth or aluminum atom, and n 'is an integer of 1 to 3 and corresponds to the value of M; preferably M is an alkali metal and n '= 1 when R' is a hydrogen or alkali atom. Preferably, the derivative is an alkyl-metal phosphite, especially phosethyl-Al or an alkaline salt of phosphorous acid or the phosphorous acid itself; b) acetamides, such as those described in US Pat. No. 3,957,847, preferably of the formula (III) R ¹ _O - N = CC-NH-C-NHR ² I Il Il (»") CN OO in which R ¹ and R ^{2 may be} identical or different and each represents a C _{1 to} C 13 -alkyl group, preferably a C ₁ to C ₄ -alkyl group and in particular correspond to the cymoxanil (R ¹ = CH ₃ , R ² = C ₂ H ₅ ); c) Acylanilides such as those described in the BE-PS (s) 827671 and 827419 or in DE-AO 026873, preferably:
1) those of the formula (IV) CH. OI ³ II .CHC-OCH, ³ (IV) in which R ³ and R ^{4 are} identical or different and are (each) a hydrogen atom or a C _{1 to} C ₄ alkyl group, preferably the methyl group, or a C _{1 to} C ₄ alkoxy group and advantageously R ³ = R ⁴ = methyl; R ^{5 represents} a -CH 2 -R ⁶ group in which R ^{6 is} a C ₁ to C ₄ alkoxy group, preferably the methoxy group or an aryl group, preferably the phenyl group or an aryl group, preferably the phenyl group or a halogen atom, preferably the chlorine atom, or R ^{5 is} a C ₃ to C ₆ cycloalkyl group, preferably the cyclopropyl group or a C ₅ or C ₆ heterocyclic group, preferably a C ₅ heterocyclic group having one or two heteroatoms, preferably the 2-furyl - 5-isoxazolyl-or 3-oxazolyl; R _{7 is} a hydrogen atom, a halogen atom or a C ₂ to C ₄ alkyl group, preferably the methyl group; advantageously, metalaxyl, furalaxyl, benalaxyl or the compound wherein R ³ = R ⁴ = CH ₃ , R ⁷ = H, R ⁵ = 5-isoxazolyl (LAB 149 202 F); 2) those of formula (V) in the: R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the same meaning as for the formula (IV), with the same preferred variants and R ^{8 is} one of the cyclic radicals 3-oxazolidinonyl, 3-butyrolactonyl, 3-thiobutyrolactonyl or 3-thiooxazolidinonyl; advantageously oxadixyl, cyprofuram, ofurace or CGA 68099 (RE 26745) in which R ³ = R ⁴ = methyl, R ⁷ = H, R ⁵ = -CH ₂ OCH ₃ , R ⁸ = 3-butyrolactonyl, RE 26940, in which R ³ = R ⁴ = CH ₃ , R ⁷ = H, R ⁵ = CHaOCH ₃ , R ⁸ = 3-thiobutyrolactonyl or M 12279 in which r ₃ = R ⁴ ₌ CH ₃ , R ⁵ = -CH ₂ OCH ₃ , R ⁷ = 3-CI, R ⁸ = 3-oxazolidinonyl. 7. Composition according to one of claims 4 to 6, characterized in that the weight ratio of the compound (s) of the formula (I) to the additional compound (s) 1: 10000 to 100 (: 1), preferably 1: 1000 to 10 (: 1) corresponds. 8. Use of the agent according to one of claims 1 to 7, characterized in that the compound (s) of the formula (I) in an application rate of 2 to 250g / ha, preferably from 4 to 220g / ha, and the additional ( n) compound (s) at a rate of 100 to 3000g / ha to combat the diseases caused by (false) mildew, especially in solanaceae, tobacco, vines and cucurbitaceae. br R ¹ - O - H
I
PO " _M n '
n ¹ (I) (II) C-C ι ü CN O -NH- Il ο - NHR (III) C _O H _C -NH-C-NH-CC = N-OCH, ^ -> H Il ι J Il
ο cymoxanil CN CH, O I ³ II CH -C-OCH. (IV) C-R- (V) R ' ο S-s V ₁ 3-Oxazolidinonyl Br F ₃ C 3-Butyrolactonyl 3-thiobutyrolactonyl 3-thiooxazolidinonyl (Vl) F ₃ C br
<I ^ \ ^ N Il V-cci V ^ (VIII) br F ₃ C NH. NH. (IX) br F ₃ C NH. NO. (X) (XI) CH-- N - N 1. A fungicidal composition, characterized in that it comprises as active ingredient at least one compound of the formula (I) Br "" (D Wherein R "represents a dialkylamino group having from 2 to 4 carbon atoms, together with an agriculturally applicable inert carrier and / or an agriculturally applicable surfactant. 2. Composition according to claim 1, characterized in that in the formula (I) of the active ingredient R "is the dimethylamino group. 3. Composition according to claim 1 or 2, characterized in that it contains 0.5 to 95 wt .-% of active ingredient and 0 to 20Gew .-% surfactant. 4. Composition according to one of claims 1 to 3, characterized in that it additionally contains at least one of the following fungicides: -1- 260 21Ί Claims: ² II! Field of application of the invention The invention relates to a novel fungicidal composition and its use for the protection of crops against fungal diseases, especially mildew diseases.