DD286100A5 - FUNGICIDAL COMPOSITIONS - Google Patents

Abstract

The invention relates to fungicidal compositions containing as active ingredient compounds of the formula I. The fungicides according to the invention exhibit, in particular, improved properties in the treatment of piriciosis, powdery mildew and rust diseases, in particular in cereals. Formula (I) {Fungicides; fungicidal composition; Triazole and imidazole compounds; Method; combating; Fungal diseases; Mildew; Grain}

Description

Field of application of the invention

The present invention relates to fungicidal compositions containing as active ingredient new compounds with triazole or Imidazolresten.

Characteristic of the known state of the art

Numerous products containing triazole radicals, in particular fungicides, are already known, in particular from European Patent Application EP-A-047594.

Object of the invention

The invention provides compounds which have better properties in the treatment of fungal diseases. In particular, these compounds show improved properties in the treatment of piriciosis, powdery mildew and rust diseases, especially in cereals.

Explanation of the essence of the invention

The invention is based on the object. To provide fungicidal and fungicidal compositions containing as active ingredient new compounds with triazole or Imidazolresten.

These compounds are characterized in that they correspond to the formula I given at the end of the description, in which:

A is the radical (Y) _n Ph- (CH) I _n , in which Ph is a phenyl radical and m = 0 is 1, preferably 0, Y is a halogen atom or a cyano or nitro group or an alkyl or alkoxy radical , Phenyl, phenoxy, benzyl, benzvloxy group, these groups possibly being halogenated,

η is an integer positive number less than 6 or 0, where Y may be the same or different if η is greater than 1,

Tr represents a 1,2,4-triazoH-yl radical,

In the oine, 1,3-imidazole represents 1 -yl radical,

Ri to R _{6 may be} identical or different and each represents a hydrogen atom or a lower alkyl radical, lower cycloalkyl radical, an aryl radical (especially i -lonyl), an aralkyl radical (especially benzyl), a lower alkoxy radical, a lower aikanoyl radical, an aroyl radical (especially benzoyl I), these different radicals each being optionally substituted (for example with one or more atoms or radicals such as halogen atoms and lower alkoxy radicals),

X _{1 represents} a hydrogen atom, a halogen atom, a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), an aralkyl radical (in particular benzyl), these different radicals in each case being optionally substituted in the same way as the radicals Ri to R ₆ ,

a radical QR ₄ , where Q is O or S, and where R _{4 is} a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), an aralkyl radical (especially penzyl), an acyl radical or thioacyl radical (in particular acetyl, Thioacetyl, propionyl.-thiopropionyl), an alkyloxythiolyl, an aryloxythiolyl or aralkyloxythiolyl radical (the term thiolyl corresponds to C = S (S)), where these radicals may be substituted in the same way as the radicals Ri to R ₆ ,

a radical -NR ₄ Rg, wherein R _a and R "may be identical or different and each represents a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (in particular phenyl), an aralkyl radical (in particular benzyl), these being various radicals in each case can be equally optionally substituted as R | to R _6, whereby R ₁ and R ₉ may form a single divalent hydrocarbon radical together containing 3 to 6 carbon atoms, wherein one of these carbon atoms are replaced by an oxygen atom, sulfur atom or a nitrogen atom can be replaced, this one divalent radical in turn optionally being substituted (for example with one or more halogen atoms or lower alkyl radicals, lower alkoxy radicals which are optionally halogenated, or hydroxy),

wherein Hai 1 and Hai 2 are identical or different and represent a halogen atom, preferably selected from chlorine or bromine and wherein preferably Hai 1 and Hai 2 are identical.

The invention further relates to the salts of erfinduigsgemäßen compounds. Suitable salts are those which are tolerated in agriculture by agriculture, it being possible to mention: the chlorohydrates, sulfates, oxalates, nitrates or arylsulfonates and the addition complexes of these compounds with metal salts, in particular iron, chromium, copper, manganese, zinc , Cobalt, tin, magnesium and aluminum salts.

Zinc complexes can be obtained, for example, by reacting a compound of formula I with zinc chloride.

As far as "lower" organic radicals are mentioned in the present text, this means that the radical should contain up to 6 carbon atoms, this radical may be linear or branched.

The Applicant wishes to emphasize that the appended sheets are not to be considered as drawings in the conventional sense, but are an integral part of the description of the present invention.

The compounds of formula I and the compounds optionally useful as intermediates in the processes for their preparation which are defined in the description of the preparation processes may exist in one or more isomeric forms according to the number of asymmetric centers of the molecule. The invention relates

likewise all optical isomers, as well as their racemic mixtures and the corresponding diastereomers. The

Separation of diestereomers and / or optical isomers can be carried out according to one of the known methods. With regard to the fungicidal use found, it has been found that the compounds of the formula I in which Y is a Is halogen and η = 1,2 or 3 are particularly suitable. It has also been found that compounds of the formula I are preferably used in which η = 1 or 2 and Y is a halogen atom which is in the ortho and / or in the P. arastellung. Preferably, η »2 and Y is a halogen atom, preferably chlorine, which is located in the ortho and in the para position. There are those compounds of formula I are preferred in which the radicals R ₁ to R ₆ and Xi is a hydrogen atom, or a

are lower alkyl group and / or Hai 1 and Hai 2 are both a chlorine atom.

More preferably, the radicals R ₁ to Re and X _{1 represent} a hydrogen atom. Those compounds having triazole radicals are

prefers.

The invention likewise relates to the processes for the preparation of the compounds according to the invention.

Step ·)

A haloketone of the formula IIa which is obtainable by a conventional process is obtained, in which formula A and R ₆

the same meaning as in the compounds of the formula and Z represents a halogen atom react with an organometallic compound of formula II b, wherein in the formula II b R ₁ to R ₄ and X _{1 have} the same meaning as above and M, for example, an alkali metal or (Mg Hai) or (Zn Hai), in a solvent which is preferably selected from ethers, e.g. Diethyl ether or tetrahydrofuran, the aliphatic, alicyclic or aromatic

Hydrocarbons, such. As hexane or toluene, at a temperature which is chosen between -50 ° C and the Reflux temperature of the selected solvent and in a molar ratio Il a: II b of preferably between 1.1 and 0.2. The Reaction leads to a compound of formula Il c after neutralization of the reaction medium. This procedure is in the EP-A-0 033 501 described.

Step b)

The compound of the formula III is then allowed to react with an unsubstituted imldazole or triazole in the presence of

react organic base or mineral base. As the base is, for example, pyridine, triethylamine, soda, potassium carbonate or a carbonate or bicarbonate of an alkali metal or alkaline earth metal into consideration. It works in a suitable solvent, such. Example, an alcohol, a ketone, an amide, a nitrile or an aromatic hydrocarbon which is optionally halogenated, at a temperature between 80 ⁰ C and the reflux temperature of the solvent and at a molar ratio

Il cilmidazole or triazole of preferably between 1.1 and 0.2. The reaction leads to a compound of formula Hd. Die Reaction generally proceeds via an epoxide intermediate of the formula IIe, which can optionally be isolated or

netrennt can be prepared by known methods of the prior art. For example, this can be done by reacting the compound of formula IIc with one of the abovementioned bases. In this regard, on the in the

Reference is made to EP-A-0 097425. In any case, the substitution step (grafting step) is advantageously carried out in the presence of an acid acceptor

anhydrous or non-anhydrous medium, in a solvent which is inert under the conditions of the reaction, generally at 50 to 180 ^° C., and preferably at a temperature close to the boiling temperature of the solvent. When

Acid receptors can be called the mineral bases, such as. As soda or potassium carbonate, the alkali metal carbonates or Alkaline earth metal carbonates, the nitrogenous bases such as triethylamine, quaternary amines such as tetrabutylammonium hydroxide or Phosphonium. As the solvent advantageously used aprotic polar solvents such. B. Dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetone, methyl ethyl ketone, acetonitrile, N-methylpyrrolidone or

protic polar solvents, e.g. Methanol or propanol. If desired, this reaction can be carried out in the presence of a suitable catalyst. Suitable catalysts are phase transfer catalysts, for example quaternary ammonium derivatives, such as tetrabutylammonium chloride.

The reaction is preferably in molar excess of triazole or imidazole, preferably between 1.05 and 1.5

carried out. When using a solvent, it is preferable to work in a dilute medium containing 1 to 70% by weight of the

Compounds of formula Hc, He, based on the total solution contains. The acid acceptor is at least in stoichiometric amount with respect to the equivalents of the labile water offsets of the Triazols or l'nidazols present. In general, a ratio of the moral equivalents of 1 to 2.5 is satisfactory. It is obvious that the salt derivative of the triazole or imidazole can be prepared separately, in which case the Presence of an acid acceptor is not required for the grafting. This manufacturing process takes place in

Anhydrous or non-anhydrous medium in a solvent under the same process conditions as described above in the in situ formation of the triazole or imidazole salt derivative.

Step c)

It is added to the compound II d, preferably one mole per mole of this compound, a halogen molecule or a molecule of a

mixed halogen in an inert solvent such. Example, a saturated hydrocarbon or an aromatic, optionally calcined hydrocarbon and receives the compound I. It can perform this addition just as well in mineral acid concentrated environment, which has the advantage, ('' "ß the compound I precipitated as a corresponding salt

The present invention also relates to the use of the compounds of the formula I as fungicides. The compounds according to the invention can be used for the purpose of healing or also as a preventive measure Fungi, in particular of the Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti types,

especially against rust, mildew, blackleg, fusaroses, helminthosporioses, septorioses, rhizoctones

Crops and plants in general, and in particular for cereals such as wheat, barley, rye, oats and their hybrids

and also with rice and corn. The compounds according to the invention are active against fungi, especially those of the

Basidiomycetes, Ascomycetes, Adelomycetes or Fungi imperfecti such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Pirircularia oryzae Cercospora beticola, Puccinia striiformis, Erysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria nodorum, Septoria tritici, Venturia inaequalis, Whetzelinia sclerotiorum, Monilia laxa, Mycosphaerella fijiensis, Marssonina panattoniana, Arternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium

herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzi ep, Phi.tlophora cinerescens, Phoma betae, Phomafoveata, Phoma Hungary, Ustilago maydie, Verticillium dahliae, Ascochyta pis !, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sderotiorum, Sclerotinia minor, Coryneum cardinale , Rhizoctonia soleni.

They are also active against the following fungi: Acrostalagmus koningi, Alternaria, Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron cladosporioides, Lentinus degener ou

tigrinus, Lenzites quercina, Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megeglous, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, read Stereum, Stilbum sp. Trametestrabea, Trichoderma pseudokoningi, Trichothecium roseum.

The compounds of the invention are of particular interest because of their broad spectrum of use against Cereal diseases (rust, mildew) or rice diseases (piriciosis). They are also of great interest to them They work on gray mold (botritis) and cercosporioses and for this reason they can be used in cultures as diverse as

in viticulture, in vegetable cultivation, in arboriculture and in tropical crops, such. Peanuts, banana plants,

Coffee trees, hickory (pecan trees) u.a. be used. These compounds may also be used in the treatment of seeds (cereal grains, cotton, Beets, rapeseed, feed grains), e.g. by wrapping or coating. Such an application form can be found in the U.S. Patent 3,989,501, Col. 7.1, 17-23. Also in FR-A-2588442. It is also possible to wet aqueous solutions

use. In general, the formulations are already known, see Z.3. .Catalogue of the Pesticide Formulation Type of International Coding System * Published by GIFAP Technical Monograph No. 2, pages 12-14, revised in January

In addition to the applications already described above, the products according to the invention also show an outstanding

biocidal activity with respect to numerous other types of microorganisms, including but not limited to. Call fungi of the following species:

- Pullularia, eg the speci 2 P. pullulans

- Chaetomium, z. The species C. globosum

Aspergillus, e.g. B. Aspergillus niger

- Conlophora, z. B. puteana.

Due to their biocidone activity, the products according to the invention allow effective control of microorganisms,

their multiplication creates numerous problems in the agricultural and industrial sectors. They are particularly well suited for the protection of plants or industrial products, such. Wood, leather, paints, paper, ropes,

Plastics bowie industrial water circuits. They are very particularly well suited for the protection of lignocellulosic products, especially wood, z. B. furniture wood, Lumber or wood that is exposed to the elements of the weather, such as the wood of fences, pegs for vines or Railway sleepers. The compounds according to the invention, by themselves or in the form of compositions, as they are described below

be used in the treatment of wood, are generally associated with organic

Solvents may be used and optionally combined with one or more known biocidal products

be such. Pentachlorophenol, metal salts such as salts of copper, manganese, cobalt, chromium or zinc,

Mineral acid or carboxylic acid derivatives (heptanoic acid, octanoic acid, naphthenic acid), organic tin complexes, Mercaptobenzothiazole, and insecticides such. As pyrethroids or chlorinated organic compounds. They point

finally an excellent selectivity towards different cultures.

They are advantageously used in dosages of 0.005 to 5 kg per hectare, in particular in doses of 0.01 to In their practical use, the compounds according to the invention are rarely used on their own. They are mostly Component of compositions. These compositions are suitable for the protection of plants against the Infestations with fungal diseases or plant growth regulating compositions contained as active substance

a compound of the invention as described above in association with solid or liquid carriers which are agriculturally acceptable and / or surface-active agents which are also suitable for agriculture.

In particular, conventional inert carriers and conventional surface-active agents are suitable. The term "carrier" in this text refers to an organic or mineral natural or synthetic substance

with which the active substance is combined to facilitate its application to the plant, to grains or to the soil. This carrier is thus generally inert and must be agriculturally compatible, in particular compatible with the treated plant. The carrier can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied petroleum gas, etc.).

The surface active agent may be an emulsifier, dispersant or wetting agent of ionic or nonionic Type. It is possible to name, for example, the salts of polyacrylic acid, salts of lignosulfonic acids, salts of phenolsulfonic acids

or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or fatty amines, substituted phenols (in particular alkylphenols and arylphenols), the salts of esters of sulfosuccinic acids, derivatives of

Taurine (especially alkyl taurates), phosphoric acid esters of alcohols or polyoxyethylated phenols. The presence

at least one surfactant is generally essential if the active and / or inert carriers are not soluble in water and the solvent required for the application is water. In their application are the

Compounds of formula (I) generally in the form of compositions. Dieso according to the invention Compositions themselves are in quite different forms, in solid or liquid form. As manifestations of solid compositions may be mentioned: powder for atomizing or dispersing (with

a content of a compound of the formula I) which may be up to 100%) and granules, in particular those obtained by extrusion, by contacting, by impregnation of a granulated carrier, by granulation from

of a powder (the content of the compound of formula (I) in these granules may be between 1 and 80% in the latter files).

As manifestations of liquid compositions or those intended to be liquid in their application To form compositions, may be mentioned the solutions, in particular soluble concentrates in water, the

emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders or atomisable powders and pastes.

The emulsifiable or soluble concentrates usually contain 10 to 80% active ingredient, the ready-to-use emulsions or Solutions contain 0.01 to 20% active ingredient. These compositions may also contain all sorts of other ingredients, such as protective colloids,

Adhesive binders, thickeners, thixotropic substances, penetrating agents, stabilizers,

Maskierungsmittel.usw, as well as other known active substances with pesticidal properties (especially insecticides

or fungicides) or with the growth of plants favoring properties (especially fertilizers) or with the

Growth of plant regulating properties. In general, the erfindungegemäßen connections with all

solid or liquid additives known from conventional formulation techniques.

For example, the emulsifiable concentrates may be 2 to 20% suitable in addition to the solvent, if necessary Containing additives such as stabilizers, surface active agents, penetrating agents, corrosion inhibitors, Dyes or the aforesaid binders having adhesive properties. The doses to be used in the use of the compounds according to the invention as fungicides can be used within

Wide ranges vary, depending on the virulence of the fungi and the climatic conditions.

In general, compositions containing from 0.5 to 5,000 ppm active ingredient are well suited. These values are for

specified ready-to-use compositions. Ppm means "parts per million." The range of 0.5 to 5000 ppm is in the range of 5 × 10 ~ ⁶ to 0.5 weight%.

The compositions suitable for storage or transport advantageously contain from 0.5 to 95% by weight.

active ingredient.

Thus, the compositions for use in agriculture according to the invention, the inventive

contain active agents in wide ranges ranging from 5 χ 10 ~ ^e wt .-% to 95Gew .-% range.

By way of example, the composition of some concentrates is reproduced below:

EXAMPLES: Example F (Formulation 1)

- active ingredient 400 g / l - Alkalidodecylbenzenesulfonate 24g / l oxyethyl hard nonylphenol with 10 molecules of ethylene oxide 16g / l - Cyclohexanone 200g / l - aromatic solvent filling up on 1 liter

According to another formulation of an emulsifiable concentrate, Example F 2 is used:

active substance 250 g epoxylated vegetable oil 25 g Mixture of Alkoylarylsulfonat and Polyglycol ethers and fatty alcohols 100 g dimethylformamide 50g xylene 575g

Starting from these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to leaves.

The concentrated suspensions, which can also be applied by sputtering, are prepared so as to obtain a liquid stable product which does not set. They usually contain 10 to 75% active ingredient, from 0.5 to 15% surfactants, from 0.1 to 10% thixotropic agents, from 0 to 10% suitable additives, such as antifoaming agents, corrosion inhibitors, stabilizers, penetrants, adhesives or Binders with adhesive properties and as a carrier water or an 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 prevent sedimentation or to serve as antifreeze for the water. The wettable powders (or powders for atomization) are usually prepared to contain from 5 to 95% active ingredient, and they typically contain from 0 to 5% wetting agent, from 3 to 10% dispersing agent and in addition to the solid support Required 0 to 10% of one or more stabilizers and / or other additives, such as penetrants, binders with adhesive properties or adhesives, anti-caking agents, dyes, etc ..

 By way of example, various compositions of wettable powders are described below:

Example F 3

- Active substance 60% Calcium lignosulfate (deflocculant) 5% - Isopropylnaphthalenesulfonate (anionic Wetting agents) 1% - Silica anti-caking agent 5% - kaolin (filler) 39%

Another 70% composition of a pulverulent powder contains the following ingredients: Example F 4

active substance 700g sodium dibutylnaphthylsulfonate 50g Condensation product in proportion 3: 2: 1 of naphthalenesulfonic acid, Phenolsulfonic acid and formaldehyde 30g kaolin 100 g champagne chalk 120g

Another atomizable pulverulent 40% composition contains the following ingredients: Example F S

- Active ingredient 400g

- Sodium ligno-sulfonate 50g

Sodium dibutylnaphthalenesulfonate 10g

- Silicon dioxide 540g

Another powdery atomizable 25% composition contains the following ingredients: Example F β

- Active substance 250 g - Calclumlignosulfonate 45g - Mixture of equal parts by weight Champagne chalk and hydroxyethylcellulose 19g - Nairium dibutylnaphthalene sulphonate 160 - Silica 195g - champagne chalk 195g - kaolin 261g

Another pulverulent nebulizing 25% composition contains the following ingredients: Example F 7

- active ingredient 250g

Isooctylphenoxy-polyoxyethylene-ethanol 25g

- Mixture of equal parts of champagne chalk and hydroxyethylcellulose 17g

- Sodium aluminosilicate 543g

- Diatomite 165g

Another powdery atomizable 10% composition contains the following ingredients: Example F 8

- active ingredient 100g

- Mixture of sodium salt of sulphates

saturated fatty acids 30g

- Condensation product of naphthalenesulfonic acid and formaldehyde 50g

- kaolin 820g

In order to obtain atomisable or wettable powders, the active ingredients are intimately mixed with the additional substances in suitable mixing equipment and ground in a mill or other suitable milling equipment. This gives atomizable powders whose wettability and suspensibility are good. These can be suspended in water in any desired concentration, these suspensions are particularly well suited for application to Pllanzenblätter or seeds.

Instead of wettable powders one can make pastes, doughs or porridges. The conditions and conditions for the Preparation and use of these pastes (doughs, slices) are comparable to those of wettable or atomizable powders. As already mentioned, the scope of the present invention also includes the dispersions and aqueous emulsions,

for example, those compositions which are obtained when a wettable powder or an emulsifiable

Dilute concentrate according to the invention with the aid of water. The emulsions may be those of the water in oil or oil type

Be water and they can have a thicker texture such as a "mayonnaise". The granules that are applied to the soil are usually made to have grain dimensions

between 0.1 and 2 mm. They can be produced by agglomeration or impregnation. In general, the granules contain 0.5 to 25% active ingredient and 0 to 10% additives such as stabilizers, slow release modifiers, binders and solvents.

For example, in a granular composition, the following ingredients are used:

Example F 9:

- Active ingredient 50g

- Epichlorohydrin 2.5g

Cetyl ether and polyglycol 2.5g

- Polyethylene glycol 35g

- kaolin (grain size 0.3 to 0.8mm) 910g

In this particular case, the active ingredient is mixed with epichlorohydrin and dissolved in 60 g of acetone. You then give that Polyethylene glycol and the cetyl ether and the polyglycol! to. The kaolin is poured into the resulting solution and evaporated

then the acetone in vacuo. It is advantageous to use such microgranules for the control of

Soil fungi. The compounds of formula (I) may also be used in the form of atomizable powders. You can also do one Composition containing 50 g of active ingredient and 950 g of talc use. You can just as well have a composition

containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc. Mix and mill these ingredients and then apply the mixture by nebulization.

Examples I to VII illustrate the various ways of preparing the compounds of the invention and the Compounds themselves. The nomenclature of the compounds has been made in accordance with French standards,

therefore, the numbering of the individual substituents in each case before the substituents themselves.

Example I- Preparation of the H2- (2,4-Dhlchlorophenyl) 2-hydroxy-4,5-dibromophenyl] 1H-1,2,4-triazole

Step a)

Preparation of 1-chloro-2- (2,4-dichlorophenyl) -4-penteno-2-ol: An organomagnesium compound is prepared by adding an allyl bromide solution (180 ml) in tetrahydrofuran (200 ml)

to a suspension of magnesium (126g) in tetrahydrofuran (400ml) at 1O ⁰ C.

At -10 ⁰ C a solution of Trichloralpha, 2,4-acetophenone (232g) in tetrahydrofuran (250ml) is added to and neutralized with Acetic acid. Wash with water, dry and evacuate. A colorless oil is obtained (258g), boiling point

(3 x 10 " ² mmHg) = 140-142" C.

Step b)

Preparation of 1- (2- (2,4-dichlorophenyl) 2-hydroxy-4-pentenyl] 1H-1,2,4-triazole. A mixture of the product obtained in step a) (106g), triazole (55g) and potassium carbonate (160g) is added for four hours

120 * C in dimethylformamide (600 ml) heated. The insoluble matter is filtered off, washed and dimethylformamide and the

Reaction mixture are concentrated in vacuo. The residue dissolved in methylene chloride is washed with water and

then concentrated. The product is obtained by crystallisation in ethyl acetate after dilution with heptane. A pale pink

Solid (97 g) with melting point of 101 ⁰ C is isolated.

Step c)

Preparation of compound no. 1 The compound (35g) obtained in step b) is treated in chloroform (200 ml) at ⁰ ° C. with bromine. After decolorization, the Solvens evaporates. This gives a solid having a melting point of 116 ° C. Example II-Preparation of 1- [2- (2,4-Dlochlorophenyl) 2-hydroxy-4,5-dhlchloropentene] 1H-1,2,4-triaiol. Connection No. 2 The chlorohydrin (113 g) obtained in step a) of Example I dissolved in DMF (100 ml) is poured into a mixture of K ₂ CO ₃ (207 g) and

1,2,4-triazole (35,9g) in DMF (900ml) was poured at 125 ⁰ C. After being quenched to 125 ° C, filter the undissolved and

Evaporation, washing, recrystallization gives the triazole compound Hd (103 g) as a tan solid. This triazole compound dissolved in aqueous concentrated HCL is treated with chlorine until the yellow color persists. The Mixture is then allowed to stand at room temperature and then diluted. The precipitate formed is filtered off

and treated with aqueous sodium bicarbonate. After extraction, drying, evaporation and crystallization, a white solid of melting point 126 ^° C. is obtained.

The compounds H2- (4-chlorophenyl) 2-hydroxy-4,5-dichloropentyl-1H-1,2,4-triazole are obtained in the same way. connection No. 3, melting point 82 ^° C.

1- [2- (2,4-dichlorophenyl) 2-hydroxy-3-methyl-4,5-dibromopentyl] -H1,2,4-triazole. Compound No.4 (oil). 1- (2- (2,4-dichlorophenyl) 2-hydroxy-3-methyl-4,5-dichloropentyl) 1,2,4-triazole. Compound No. 5 (oil).

Examples III to V illustrate the fungicidal applications of the compounds of the invention. In these Examples, the atomization of solutions or suspensions of the active ingredients is carried out under such conditions,

that the atomization of a solution or suspension at a concentration of 1 g / l on average corresponds to an application of approximately 2 micrograms of the active compounds per cm ^{2 of} the plant leaf.

Fine grinding is used to prepare an aqueous emulsion of the active substance to be tested which has the following composition

- active substance to be tested: 60 mg

Tween 80 (surfactant) consisting of an oleate of a polyoxyethylene sorbitan derivative diluted to 10% in water: 0.3 ml

- Make up to 60 ml of water.

This aqueous emulsion is then diluted with water to obtain the desired concentration. In these examples, it is assumed that a product provides total protection against fungal disease when the protection is at least 95%.

Example III In vivo Tett on "Pirlcularia oryzae * Responsible for Pirlculariosis in Rice (Rice Blast) Rei * seeded in small bowls In a mixture of 50:60 from enriched peat pouch pozzolan becomes in the stage of 10cm height

treated by sputtering an aqueous emulsion (slurry, slurry) as defined above. The experiment is repeated twice. After 24 hours, inoculate by applying a suspension of spores obtained from pure culture (600 spores / ml) on the leaves.

The contaminated plants are incubated at 25 ° C and 100% relative humidity for 24 hours before being placed in a Observation cell be brought. The reading takes place 8 days after the contamination. Under these conditions, a complete one is observed at 1 g / L Protection in compounds 1,2,3,4 and 5. B! Play IV- in vivo test on Eryslphe graminls in barley (barley powdery mildew) Starter is sown in trays in a 60:60 mixture of enriched peat and pozzolan and in the stage of 10cm Treated by atomizing an aqueous emulsion (slurry, slurry) at the concentration indicated above. The Trial is repeated twice. After 24 hours sprinkle the barley plants with spores of Eryslphe gramlnis, wherein

the sprinkling is done with the help of sick plants.

The reading takes place 8 to 14 days after the contamination. Under these conditions, the following results are observed: At a dosage of 1 g / l, total protection is obtained

the compounds 1,2,3,4,5.

Example V - In vivo test with "Pucclna recondite" responsible for sclerotherapy Wheat is sown in small bowls In a mixture of 50:50 from enriched peat and pozzolan and in the stage of 10cm Height treated by atomization with an aqueous emulsion (slurry, slurry) as described above. The Trial is repeated twice. After 24 hours, an aqueous suspension of spores (60,000 p / cm ³ ) is applied to the wheat

dusted. This suspension is obtained by means of contaminated plants. Thereafter it stiffens the wheat langin 48 hours incubation cell at approximately a 18 ⁰ C and 100% relative humidity.

After these two days, the wheat is placed in an observation cell in which the relative humidity is 60%. The control of the condition of the plants takes place between the 11th and the 15th day after the contamination by comparison with

an untreated test copy.

At the dosage of 1 g / l gives total protection in the compounds 1,2,3,4 and 5 Example VI - In vitro test for seed fungi and soil fungi The effect of the compounds according to the invention on the following fungi which are responsible for is investigated Diseases of cereals and other plants:

1) Botrvtls cinerea sensitive to carbendazim and cyclic imides

2) Botrytis cinerea resistant to carbendazim and cyclic imides

3) Fusarium oxysporumf.spmelonis

4) Rhizoctonia solani

5) Pseudocercosporella herpotrichoides

6) Septoria nodorum

7) Fusarium culmorum

8) Fusarium nivale

9) Fusarium roseum

10) Helminthosporium gramineum

11) Pyrenophora avenae 12} Helminthosporium teres 13) Rhizoctonia cerealis

The continuous numbers used before the names serve to identify the fungi in the table below. In each experiment one works in the following way: A nutrient medium consisting of potatoes, glucose and agar agar

(Milieu PDA) is introduced with cooling in a series of Petri dishes (20 ml per dish), after they were sterilized in an autoclave at 120 ° C.

During the filling of the shells is injected into the medium under cooling, an acetonic solution of the active ingredient, so that

the desired final concentration is achieved.

Petri dishes such as those described above, in which equal amounts of a nutrient medium are used, are used as test tubes

pours, which contains no active ingredient.

After 24 to 48 hours each shell is inoculated by introducing a fragment of mycelium derived from a culture of the

same fungus emerged.

The shells are preserved for 2 to 10 days (depending on the fungus test) at 22 ⁰ C and dam compares the growth of the fungus in

the trays containing the active substance to be tested with that of the same mushroom in the peel test,

In this way, the degree of inhibition of the growth of the investigated fungus is determined for each compound tested

at a dose of 30ppm.

connection 1 95 2 80 3 10 mushrooms 4 5 12 β 95 13 7 No. 95 80 95 0 90 95 90 100 95 100 100 100 1 90 100 95 100 50 95 80 100 100 95 95 0 2 95 100 95 - 90 95 90 95 100 90 95 100 3 95 100 95 - 90 - 90 90 95 95 95 100 4 95 95 95 - 90 100 100 95 100 5 mushrooms connection 8th 9 11 No. 100 1 100 2 100 3 100 4 100 5

It has also been found that the abovementioned objects can also be achieved by combining one or more compounds of the formula (I) with at least one funigicide of group (II), d. H. a fungicide selected from the following subclasses:

1. the chlorinated or nitrated benzene derivatives, wio z. Quintozen or chlorothalonil,

2. the dicarboximide derivatives, e.g. Captan, Folpel, Captafol, Iprodione, Procymidone,

3. the derivatives comprising one or more Hetsrozyklen such. B. quinolines, morpholine,

4. the phosphorous acid derivatives such as the metal phosphites,

5. the derivatives of dithiocarbamic acid, such as. B. Manebe or Mancozebe,

6. the phenol derivatives, such as. B. dinocap,

7. the quinone derivatives, such as. Dithianon,

8. the derivatives of carbamic acid and benzimidazoles, such as. Carbendazim, benomyl, thiophanate-methyl,

9. the sulfur compounds,

10. the amino and the amides, such as. The dichloran, carboxin, triforin, cymoxanil, taetalaxyl, ofurace,

11. the diazines, such as. The quinomethionate, fenarinol, anilazine,

12. Sulfamides, e.g. dichlofluanid,

13. guanidines, e.g. the Doguadin,

14. Triazoles, such as. Those described in British Patent No. 2046260, the contents of which are intended to be encompassed by this reference from the disclosure of the present application.

The active ingredients of the group (II) are well-known active ingredients, with the majority among them in detail in works such as .The Pesticidal Manual "issued by the" British Crop Protection Council "in the 7th edition, 1983. The combinations according to the invention are usually those of the binary type (a single active ingredient of group II) but you can

in some cases also ternary combinations (2 active substances of the group II) or quaternary combinations (3 active substances of the

Group II) use. Of the active substances of group II, the following active substances are also preferred: chlorothalonil, iprodione, Fenpropimorph, tridemorph, dinocap, dithianone, manebo, mancozebe, phosethyl-al, captan, carbendazim, captafol, sulfur, Diniconazole. The chemical principles of the above mentioned products are given in the attached table according to the

Anglo-Saxon nomenclature. That is, the indication of the substituent position precedes each substituent.

The weight ratio of the compound of the invention to the active ingredients of the group which described obc η

is preferably between 0.0003 and 3000, more preferably between 0.001 and 1000.

It is equally possible with the above-described compounds or combinations insecticides, repellent agent, or Combine germination regulators. Nomenclature belle

Chlorthalonil tprodione

Fenpropimorpho Tridemorph Dinocap

Dithianon Manebe

Mancozebe Phosethyl-Al Captan

Carbendazim Captafol

diniconazole

Tetrachloro-isophtalonitril

S-ß.e-DichlorphenyU-N-isopropyl ^ / l-dioxoimidazolidin-i-carboxamide

( ^t ) -ci8-4- [3- (4-tert-butylphenyl) -2-methylpropyl] -2,6-dimethylmorpholine

2,6-dimethyl-4-tridecylmorpholine

2- (1-methylheptylH.e-dinitrophenyl crotonate

-1,4-dithl8-anthraquinone 5,10-dihydro-5,10-dioxonaphtol- [2,3-b]

Manganese ethylene bis (dithiocarbamate)

Manebe complex with a zinc salt aluminum tris-O-ethylphosphonate

N- {trichloromethylthio) cyclonex-4-en-1,2-dicarboximide

Methyl-benzimidazol-2-yl-cdrbamet

N- <1,1,2,2, -Tetrachlorethylthio) - <; yclohex-4-ene-1,2-dlcQrboximid

1- (2 _> 4-Diuhorphenyl) -4,4-dimethyl'2- (1,2,4-triazol-1-yl) - '- penten-3-ol. The latter product will

already mentioned in the British patent GB 2046260.

28 6 1 OO

\ "3 R ₄ Tr ou Im

Tr ou Im

HqI 2

2861 OO

R ₄ «3

Claims (6)

1. Fungicidal compositions, characterized in that they are active compounds of the formula I, in which A is the group (Y) _n Ph- (CHj) _n where Ph is a phenylene nucleus and m is 0 or 1, preferably 0 is Y is a halogen atom or a cyano or nitro radical, or an alkyl or alkoxy radical Phenyl, phenoxy, benzyloxy group, where these radicals may optionally be halogenated, η is a whole positive number less than 6 or 0, where the radicals Y may be identical or different if η is greater than 1, Tr represents a 1,2,4-triazoM-yl radical,! Represents my 1,3-imidazol-1-yl radical, Ri to R _{6 are} identical or different and each represent a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), aralkyl radical (especially benzyl), a lower alkoxy radical, a lower alkanoyl radical, an aroyl radical (especially benzoyl) these various radicals may each be optionally substituted (eg with one or more atoms or radicals, such as, for example, halogen atoms and lower alkoxy radicals), X _{1 represents} a hydrogen atom, a halogen atom, a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), or aralkyl radical (especially benzyl), these different radicals each optionally in the same way as the radicals R ₁ to R ₅ may be substituted, or represents a radical QR ₆ , wherein Q is O or S, and R _{6 is} a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), an aralkyl radical (in particular benzyl), an acyl or thioacyl radical (in particular acetyl, thioacetyl, propionyl, thiopropionyl), an alkyloxythiolyl, an aryloxythiolyl or aralkyloxythiolyl radical, the term thiolyl corresponds to C = S (S)), where these radicals may each be optionally substituted in the same way as the radicals Ri to R ₆ , or a radical -NR ₈ Rg in which Rs and R _{9 are} identical or different and each represent a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (especially phenyl), an aralkyl radical (in particular benzyl), each of these different radicals may be optionally substituted in the same way as the radicals R ₁ to R ₆ , or wherein Rs and R _{9 may} together form a single divalent hydrocarbon radical having from 3 to 6 carbon atoms, one of these carbon atoms being replaced by an oxygen atom, sulfur atom or Nitrogen atom can be replaced, this single divalent radical itself being optionally substituted (for example with one or more halogen atoms or lower alkyl radicals, lower alkoxy radicals which are optionally halogenated or hydroxy), Hall and Hal 2 are identical or different and each represent a halo atom, preferably selected from chlorine or bromine, w preferably Hall and Hal2 are identical, as well as their salts, this active ingredient being combined with at least one inert agriculturally acceptable carrier. 2. Fungicidal compositions according to claim 1, characterized in that they contain as active ingredient a compound of formula I in which Y is a halogen atom, preferably chlorine, and η = 1,2 or 3. 3. Fungicidal compositions according to claim 2, characterized in that they contain as active ingredient a compound of formula I in which η = 1 or 2 and Y is a halogen atom which is in the ortho and / or in the para position. 4. Fungicidal compositions according to claim 3, characterized in that they contain as active ingredient a compound of formula I in which the radicals R ₁ to R ₆ and X ₁ each represent a hydrogen atom or a lower alkyl radical, preferably a hydrogen atom, and / or Hall and Hal2 both each represent a chlorine atom. 5. Fungicidal compositions according to claims 1 to 4, characterized in that they contain 0.5 to 95% active ingredient. 6. A method for controlling Piizkrankheiten, piricose, powdery mildew or rust on crops, characterized in that applying an effective dose of an active ingredient according to any one of claims 1 to 4, wherein the active ingredient is preferably in an amount of 0.005 to 5 kg / ha, preferably from 0.01 to 0.5 kg / ha. For this 2 pages formulas