BG60841B1 - Compounds containing triazole or imidazole tetrahydrofuran and pehnyl group and methods for their preparation and application - Google Patents

Abstract

The invention relates to triazole, imidazole and tetrahydrofuran derivatives of the general formula in which the substituents are as defined in the description. The derivatives have fungicidal activity and are used in agriculture to combat fungal diseases of crop plants.

Description

The invention relates to novel compounds For the control of plant diseases in the groups of triazolo, imidazole and tetrahydrofuran. It also relates to the methods of preparation of the above derivatives and, optionally, the intermediates used in their preparation. The invention also relates to the application of these compounds as fungicides, to fungicidal compositions based on these compounds, and to methods of combating fungal diseases in cultivated plants.

Known as fungicides, they are many derivatives of triazole (I). This patent describes compounds whose formula is given at the end of the description and their use as fungicidal agents.

It is an object of the present invention to provide compounds having better properties in the control of fungal diseases in cultivated plants.

«It. - ^ ---., .. lA ^, - and \ ^: ^ -. », ^ ihaaAiV ^ No.Ch * · - ·, -:,

Another object of the present invention is to provide compounds exhibiting an improved range of uses in the field of fungicidal diseases.

It has been found that these objectives can be achieved by the products of the invention. They are characterized in that they correspond to formula (1), in which:

A is the group P / v- (¾ where P ^ is a phenyl nucleus and ig = 0 or 1, preferably 0,

Y is a halogen atom or a cyano group or a nitro group or an alkyl group or an alkoxy group optionally halogenated; 1}

T ₂ represents a 1,2,4-ariazol 1-yl group and 1 1, 1,3-imidazol 1-yl group _; to the same or different, represent a hydrogen atom or a lower alkyl radical, a lower cycloalkyl, aryl (predominantly phenyl), aralkyl (predominantly benzyl), lower alkoxy, lower alkanoyl, aroyl (predominantly benzoid), these different radicals, optionally substituted (for example by one or more atoms or radicals, such as halogen atoms or lower alkoxy radicals),

X1, identical or different represent a hydrogen atom, a halogen atom, a lower alkyl radical, a lower cycloalkyl radical, an aryl radical (preferably phenyl) or aralkyl b.

/ mainly benzyl, these various radicals being optionally similarly substituted on the groups p ^ _and

- 3 group Q, - Eg, in which Q represents 0 or 5, and Eg represents a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, aryl (predominantly phenyl), aralkyl (predominantly benzyl), acyl, aroyl or thioacyl (mainly benzoyl) , acetyl, thioacetyl, propionyl, thiopropionyl), alkyloxythionyl, aryloxythionyl or aralkyloxythionyl (thionyl term) corresponds to C = 5fS ?, these radicals may be substituted in a manner similar to the groups to E ^ and may have identical or different meanings each such as X, and X ₂ correspond to OR ₆ or SR ₆ > group of formula -Q-E7-Q - »if Q has the pure meaning as above, and in which E? is a divalent hydrocarbon radical having from two to six carbon atoms, one of its carbon atoms being optionally substituted by an oxygen or nitrogen atom, the aforementioned divalent radical itself being substituted by one or more halogen atoms or lower alkyl radicals, lower alkoxy, hydroxy radicals / - ^ EgRg group in which Εθ and Eg-identical or different represent a hydrogen atom or a lower alkyl radical, a lower cycloalkyl radical, aryl (predominantly phenyl), aralkyl (predominantly benzyl), such as benzyl). these differences and radicals can btdat optionally substituted _in a manner similar to that of the groups E ^ to Eg, and also Εθ and Eg can together form one common divalent hydrocarbon radical having two to six carbon atoms, one of these carbon atoms being substituted by an oxygen atom, sulfur or nitrogen, and as above, a divalent common radical may itself be substituted (for example by one or more halogen atoms or radicals: lower alkyl, lower alkoxy optionally halogenated, hydroxy),

- 4 = V- £ | q group in which the lower alkyl radical, lower cycloalkyl radical, aryl (predominantly phenyl), aralkyl (predominantly benzyl), corresponds to a group of the formula Οξ-c in which alkyl or aralkyl is aryloxy Such radicals may be substituted in a similar manner to the hydroxy groups.

Ί a group, provided that X>> is different from Λβ,

X | and Xg may form together = O or = S, provided that, if X1 is selected from: hydrogen, lower alkyl radical, lower cycloalkyl radical, aryl radical or aralkyl radical, Xg may not satisfy any of the following in this list ·

The invention also relates to the salt forms of the compounds according to the invention. The salt forms are the forms acceptable in agriculture, among which may be cited: chlorhydrates, sulfates, oxalates, niarates or arylsulfonates, as well as the attachment complexes of these compounds with metal ools and specifically, salts of iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum ·

As an example, zinc complexes can be prepared by reacting the compound of formula (I) with zinc chloride

It should be noted that the compounds claimed are not described in the fl] ·

For the purposes of this text, it is understood that the adjective lower, when characterized by an organic radical, means that this radical contains up to six carbon atoms. This radical may be linear or branched.

The Applicant wishes to emphasize that the tables added should by no means be regarded as illustrations but as forming a general part of the description of the invention.

The compounds of formula (I) and the compounds used as intermediates in the preparation, which will be described and defined in the process of exposition of these methods, may exist in one or more isomeric forms, depending on the number of asymmetric centers of The molecule The invention also relates to all optical isomers, as well as their racemic mixtures and the corresponding diastereoisomers. Separation of diastereoisomers and / or optical isomers can be accomplished by known methods.

In view of the fungicidal applications, it has been found that the invention relates mainly to compounds of formula (I) in which Y is halogen and Τ /, - 1 »2 or 3.

It has also been found that it is preferable to use compounds of formula (I) in which b) = 1 or 2 and Y is a halogen atom of the p-mo and / or para-inst.

Preferably, £ = 2 and Y is a halogen atom, preferably chlorine at ortho or para-site.

Considering the above definitions, taken alone or together, it has been found to be preferable, - in the light of fungicidal properties, to use triazole compounds of formula II in which E2d corresponds to a hydrogen atom, alkyl a group or a lower cycloalkyl group, Y, tq. have the same meaning as in formula I with the above preferred options, Na! corresponds to a halogen atom, preferably chlorine or bromine, X 1 is a halogen atom, preferably chlorine

-6or bromine or a hydrogen atom and preferably a hydrogen atom *

Taking into account the limitations described above, taken alone or together, that in connection with the fungicidal properties, it is preferable to use the triazole compounds of formula III in which R 5 to 5 correspond to a hydrogen atom, an alkyl group or lower cycloalkyl, Y, Z2, ζτζ have the same meaning as in formula I, with the above preferred options, corresponding to a hydrogen atom, an alkyl group or a lower cycloalkyl group

Q has the same meaning as in formula 1, R ^O corresponds to a hydrogen atom, to a lower alkyl or cycloalkyl group ·

And

The triazole compounds of formula II which are preferred are those whose groups R 1 to Rg correspond to a hydrogen atom · Preferred triazole compounds of formula III are those to which the groups R1 to correspond to a hydrogen atom, wherein X1 corresponds to a hydrogen atom or alkyl or lower cycloalkyl, and where Rg corresponds to an alkyl group, lower cycloalkyl and preferably 4 = 0 ·

The present invention also relates to methods of preparing the compounds of the invention.

® When the group Xg corresponds to a halogen atom / compound of formula II / the preparation method consists of the following steps:

Step a / The reaction of a halogen ketone of formula Pa is obtained by any known method in which Y, t, Rg have the same meaning as that given for the compounds of formula I and Z corresponds to a halogen atom with an organometallic compound with formula IIb »in which R1 to X2 have the same meaning as above, and M corresponds to an alkali metal or to a magnesium (N, N, N) or zinc 7 Z (iHab) compound, for example, in a solvent preferably selected from ethers such as diethyl ether or tetrahydrofuran, aliphatic

-7 hydrocarbons, alicyclic or aromatic, such as hexane, toluene, at a temperature between -50 ° C and the reflux temperature of the selected solvent and in a molar ratio of Pa: II ', preferably between 1.1 and 0.2 _g

The reaction results in a compound of formula IIc after neutralization of the reaction medium »

Step b / The reaction of the compound of formula Ps with imidazole or triazole - unsubstituted - in an organic or mineral base, for example pyridine, triethylamine, sodium base, potassium base, carbonates and bicarbonates of the alkali and alkaline earth metals and in 'is then carried out: solvent, such as alcohols, ketones, amides, nitriles, aromatic hydrocarbons, optionally halogenated, at a temperature between 80 ° and the solvent boils and in a molar ratio of Ps: imidazole or triazole, preferably between 1.1 and 0.2, resulting in eat Hot formula · The reaction usually goes through an intermediate epoxy of formula PA, which can be isolated or prepared separately by methods known to the person skilled in the art »

The step in / Ktm compound of formula II d is added, mole per mole, mole-

tower halogen or mixed halide in an inert solvent such as hydrocarbons substituted or aromatic - optionally halogenated and this gives compound IIe »

Step d / Compound II is preferably obtained at room temperature by cyclisation of compound II in the presence of an organic or mineral base given in step $ 7 at a molar ratio of compound II: base preferably between 1.1 and 0.66. " can be carried out in a medium of aprotic or aprotic solvent / water, alcohol, ketone, nitrile, ester, hydrocarbon substituted or aromatic - optionally halogenated, dimethylsulfoxide, amide as dimethylformamed e

-8E ^ zinc A second way of preparing the compounds in which Xg is halogen is to place in step b) the grafting of the imidazole or triazole nucleus, after step d), which is done in the same way in the individual steps. Thus a compound halogen or halogen halide (mixed halogen) is attached to compound IIc to give compound 11 ^ and the latter cyclizes and to compound 11 ^ to which thiazole or imidazole is then attached to give the compound II.

Of course, other methods of preparation may also be appropriate.

In the case where the group Xg corresponds to Q5g and X1 is different from Hal, (compounds of formula III), the method of preparation consists in reacting a compound of formula II with a heteroatom nucleophile of formula Eg-Q2-E , in which Eg and ξ have the same meanings as in formula I, and E is a cation, for example alkali or alkaline earth metal or quaternary ammonium. The reaction is carried out in a suitable manner

solvent in the presence of a base and optionally a phase transfer catalyst, and at reaction temperatures generally between -30 ° C and the reflux temperature of the solvent used, and at a molar ratio of III: RgQE preferably between 1.2 and 01, B & y another method consists of reacting compound 11- under the same conditions with the same heteroatom nucleophile to obtain compound IIIa, to which the triazole or imidazole nucleus is then fixed, as described above. The preparation of the compounds in the formula of which Eg is a lower alkyl group, optionally mono- or polyhalogenated, is also ----- - - _ - - - - - - Λ possible by reacting the compounds Ιΐί or Sha in the formula to which Eg corresponds to a hydrogen atom, with an alkyl halide (optionally mono- or polyhalogenated) in a molar ratio

III or Illa: a halide, preferably between 1.1 and 0.2, in the presence of an organic or mineral base · If left from the compound, we will subsequently fixate on the triazole or imidazole nucleus ·

When X ₂ is a hydroxyl group (the compounds of formula III in which it is an oxygen atom and is a hydrogen atom), it can also be reacted in the presence of an inert organic solvent at a temperature between -30 ° and the boiling point of the solvent, of the compounds of formula or II with hydrocress, hydroxide, oxide or peroxide - alkali, alkaline earth or metal-

preferably in a molar ratio of between 1.1 and 0.2 and then fixed, provided that the compound IL · / is the parent compound, imidazole or triazole nucleus ·

When X ₂ corresponds to Λ / θ, οβ reacts compounds 11 ^. or II with an alkali metal or ammonium azide in a molar ratio of preferably between 1.1 and 0.2, * preferably in an aprotic solvent and at a temperature between -30 ° and the reflux temperature of the solvent, and then the reaction is carried out compound, if we came out of compound 11 ^, with imidazole or triazole. When X ₂ is an alkoxy or aryloxy or aralkyloxythioyl group, the compounds of 11 or II are reacted with an alkali metal or ammonium xanthate.

When X ₂ is a hydroxyl group, an interaction * can take place? of compounds IIc and ΙΙ / Ζ- with peroxide to obtain epoxidized compounds of formula III6 for Hc and IIIc for ΙΙέΖ · These epoxides can then be hydrated with a triol or IIIΛ, respectively, by a known method. cyclization in the presence of a dehydrating agent such as hydrochloric, hydrobromic, sulfuric or sulfonic acid, if necessary in a flow or apo-

This produces a compound IIIa, in which <j) Pg corresponds to OH, which then joins the triazole or imidazole nucleus, or to compound III in the case of compound IIIa. If necessary, the alcohol group may be protected by any of the known methods for the III cL and III compounds.

The compounds of formula II or IIj may be reacted with a carboxylate (acyl, cyclic, substituted, unsubstituted or aromatic) of an alkali metal or alkaline earth metal (preferably sodium benzoate) in the presence of a phase transfer catalyst and, if necessary, * in the presence of an inert or polar aprotic solvent, optionally in the presence of water and at temperatures between 0 ° and the boiling point of the solvent.

When and Xg correspond together to an oxygen atom ^ double bonded with tetrahydrofuran / compounds of formula IV, X1 is a oxygen atom ^ the method of preparation consists in reacting a compound of formula IIIa or III in which ξΡθ corresponds to hydroxyl. and X1 is hydrogen, with some known: an oxidant to give compound IV or IVa, which is grafted with imidazole or triazolio dcro.

Halogen is obtained (X ^ = Xr> = Hal) by reacting phosphorus pentachloride with a ketone (the compound of formula IV: wherein X1 corresponds to an oxygen atom) in the presence of an inert aprotic solvent and optionally a quaternary ammonium halide, preferably room temperature.

In order to obtain a thioketone group / compound of formula IV, wherein X 1 is a sulfur atom, thionation of the ketone group is carried out by reacting compounds IV or IVa, for example with or p ₂ S 5j ^B molar ratio preferably between 1.1 and 0 , 2 in the presence of an inert organic solvent (pyridine or hydrocarbon)

-11 at a temperature between 20 ° C and boiling point.

When X ^ and Xg correspond simultaneously to (a compound of formula V), the compounds of formula IV or IVa are reacted in which X ^ (or Xg) is an oxygen atom or a sulfur atom double bonded with tetrahydrofuran to a compound with formula HQRg, which corresponds to 0 or S _t in a molar ratio, preferably between 1.1 and 0.2 in the presence of an acid catalyst and in a suitable solvent, which may be the alcohol or the thiol itself or an inert solvent, such as hydrocarbons or alcohols If left from the compound of formula IVa, a compound of formula IV is obtained eels Va, then the compound of formula Va is grafted an imidazole or a triazole ring.

When and Xg correspond to ξφ - ф, such as fy? is a single divalent radical _} as defined, the compounds of formula IV or IVa are reacted with the compound under the same conditions as for monoalcohols or monothiols. Leaving compound IVa yields compound V, which is coupled to imidazole or triazole under the same conditions as 1fedi.

^X 2 reacting a compound of formula II or 11 with an amine of formula H-A / EdE in a molar ratio between 1.1 and 0.2, if necessary in the presence of another organic or mineral base. This leads to a compound of formula VI when exiting a compound of formula II and to compound Pa, which subsequently joins an imidazole or ariazole core when leaving a compound of formula II · ν

When χ ^ / or χ ^ / correspond to the carcass = 010 (compound VII)

When m -Ρθί ^ is answered, the method of obtaining consists in

-12 is reacted with a compound of formula IV or iVa with an amine of formula Ij ^ Q- // ¾ or any of its salts in a molar ratio preferably between 1.1 and 0.2 in an inert organic solvent. In the case of compound IVa, the compound VlIa is obtained, KiM which then joins an imidazole or triazole nucleus.

A compound of formula VII may also be reacted, in which it is substituted with an agent of the formula in which it is substituted and in which D is a halogen, hydroxyl group, with alkyl being lower alkyl or aralkyl optionally sulfonium, ammonium, sulfonate

or a sulfate group, in the presence of an organic or mineral base, to form an oxygen-substituted oxime.

It is also an object of the present invention to use as intermediates in the preparation process the intermediates described above and are Formulas 11, Po, I /, Pe, II /, ΙΙΙ, ΙΙΙβ, ΙΠέ, IIIo, IIb /, IIIe, IV , IVa, V, Va, V6, VI, Via, VII, Vila, in which to Εθ, B, Tr.Iw.W, »,, Χ _χ , Χ ₂ , <£, Hal, ί have any of the following -up values ·

The present invention also relates to the use of the compounds of formula I as fungicides.

The compounds of the invention can be used to combat, both preventative and current, against fungi, in particular of the types of basidiomycetes, ascomycetes, adelomycetes or fungi-imperfections. in particular comb, oidium, bed, fusariosis, helminthosporiosis, septoriosis, plant and plant rhizomes, mainly cereals such as wheat (wheat), barley, rye, oats and hybrids, and rice. The compounds of the invention are active in particular against the basidiomycetes, ascomycetes, adelomycetes or fungi-imperfections such as fungi, such as

-13 Botrytis cinerea, Erysiphe graminls, Pucclnla recondite, Piricularia oryzae, Cercospora beticola, Pucclnla striiformls, Erysiphe c 1 ch or acearu tn, Fusarium oxysporum (uelonis), Pyrenophora avenaea, Septoria triticiel erynaaisliurnis, Venturia eurisia eluniais, ,, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzia sp. bidwellii, Corticium rolfsii, Photnopsis vltlcola, Sclerotinla sclerot ioruro, Sclerotinia minor, Coryneun cardinale, Rhizoct onia solani.

They are also as active as the following mushrooms:

: Acrostalagmus koningi, les Alternaria, les Col1etotr1chum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminls, Gibberella fujikuroi, Hormodendron cladosporioides, Lentlnus degener ou tigrinus, Lenzites quercina, Memnonlella echinata, Myrotheclum verrucaria, Paecy lotnyces varloti, Pellicularia sasakli, Phelllnus megaloporus, Polystlctus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, les Stereuro, Stllbum sp. Trametes trabea, Trichoderma pseudoconingl, Trichotheclum roseum.

- 14 The compounds of the invention are of particular interest with their broad spectrum with respect to cereal diseases (oidium, rust, bed, hemintosporiosis, septoriosis and fusariosis). · They are also of great interest ^ due to their activity against gray rot / & /. sercosporiosis, and because of this fact, they can be applied to a variety of crops, such as vines, vegetables, vegetables and 1ropical crops such as peanuts, bananas, coffee, walnuts, etc. ·

In addition to the applications described above, the products according to the invention also exhibited excellent biocidal activity against many other types of microorganisms, among which fungi such as those of the following types may be cited, without limitation:

- Ri, iSu ΙκζΡ seeing R. ri CSu;

- CliFbiioFifUFi _t as vca C <

as a species as a species

Because of their biocidal activity, the products of the invention make it possible to efficiently destroy micro-organisms whose reproduction creates numerous problems in agriculture and the economy. Therefore, they are particularly suitable for protecting plants or industrial products, such as wood, leather, paints, paper, plastics, industrial circulation water ·

In particular, they are well suited for protecting lignocellulosic products, and especially timber, as far as wood for furniture, scaffolding, or wood exposed to the weather, such as fence wood, vines, railway sleepers ·

- 15 The compounds of the invention used alone or in the form of compositions such as those defined above for woodworking? usually applied with organic solvents and may optionally be mixed with one or more known biocidal products, such as pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium, zinc, mineral or carboxylic acid / heptanoic, octane, naphthenic derivatives acid /, the organic complexes of tin, mercaptobenzothiazole, insect ticides, such tato perotroids or organochlorine compounds ·

Finally, they show excellent crop selectivity ·

They are mainly applied at doses of 0.005 to 5kg / ha and usually from 0.01 to 0.5kg / ha ·

For their practical application, the compounds of the invention are rarely used alone. Most often, they are part of compositions. · These compositions, useful for protecting plants from fungicidal disease or in plant growth regulating compositions, contain as an active substance a compound of the invention, such as those described above, in admixture with solid or liquid a carrier acceptable in agriculture and / or surfactants also acceptable in agriculture. In particular, inert and conventional carriers and conventional surfactants are usable.

The term 'carrier' in this statement means an organic or mineral substance, natural or synthetic, with which the active substance is mixed to facilitate its application to plants, seeds and soil. This carrier is usually inert and must be acceptable to agriculture, in particular the crops to which it is applied. The carrier can be solid / clay, naturally- 16 -

or synthetic silicates, silicon, resins, waxes, solid fertilizers, etc. · / or liquid / water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc. · / ·

The surfactant may be an emulsifying agent, dispersing or wetting of the ionic or non-ionic type. fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, kaolin derivatives (especially alkylturates), phosphorus eu · The presence of at least one surfactant is usually inconceivable when the active substance and / or the inert carrier are insoluble in water and when the carrier is water.

For their administration, the compounds of formula (I) are generally in the form of compositions; these compositions according to the invention are themselves in various forms, solid or liquid.

Dust or dispersion powders (containing the compound of formula (I)) may be cited as solid compositions _. up to 100% / and granules especially those obtained by extrusion, by tabletting, by impregnation of a granular carrier, by granulation * leaving the powder / with the content of a compound of formula (I) in these granules being between 1 and 80% in the latter cases / · /

Solution solutions may be cited as a form of liquid formulations or intended to form liquid formulations in use.

these, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or spray powders), pastes.

Emulsifiable or soluble concentrates usually contain from 10 to 80% of the active substance, while emulsions and solutions ready for use contain from 0.01 to 20% of the active substance.

These compositions may also contain any other types of ingredients' such as protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, complexing agents, etc., as well as other active substances with pesticidal properties / mainly insecticides and fungicides / or with plant growth-enhancing properties (mainly fertilizers) or with plant growth-regulating properties · Most commonly, the compounds according to the invention can be mixed with liquid or solid additives that are in love. their application techniques.

For example, emulsifiable concentrates may, when necessary, contain from 2 to 20% suitable additives, such as stabilizers, surfactants, penetration agents, corrosion inhibitors, colorants or adhesives, already cited.

The doses for use of the compounds of the invention, in the case of use as fungicides, can vary widely depending on fungal infections and climatic conditions.

Generally formulations containing from 0.5 to 100% of the active substance are appropriate ^ these values are indicated for the ready-to-use compositions. Pprrt means parts per million · The range from 0.5 to 5000 ppm corresponds to an area of 5 · 10 ⁵ to 0.5% (weight percent).

- 18 In the case of formulations adapted for storage and transport, they usually contain from 0,5 to 95% / weight / active substance.

Thus, the compositions for agricultural use according to the invention can contain the active substances of the invention within a very wide range from 5.10 ° to 95% (w / w).

As an example, we present the composition of several horses

teshgrata.

Example ₽ 1 / formulation / active substance 400g / l alkaline dodecylbenzenesulfonate 24g / l • oxyethylated with 10 molecules ethylene oxide nonylphenol 16g / l cyclohexanone 200g / l aromatic solvent o. s.p. 1l

According to another recipe, an emulsifiable concentrate is used

Example P 2:

active ingredient250g epoxidized vegetable oil25g

- mixture of alkoylaryl sulfonate and polyglycol ether and fatty alcohols 100g dimethylformamide50g xylene575g

Leaving these concentrations by dilution with water, emulsions of any desired concentration can be obtained, which are particularly suitable for application to the leaves · _Λ

Concentrated suspensions, also applicable by spraying, are obtained in such a way as to obtain a liquid stable product which does not precipitate and generally contains from 10 to

75% active substance, 0.5 to 15% surfactants, 0.1 to 10% xyotropic agents, 0 to 10% suitable additives such as antifoams, corrosion inhibitors, stabilizers, penetration agents and adhesives, and as a carrier -water or organic liquid in which the active substance is low or insoluble: certain solids or mineral salts may be dissolved in the carrier to prevent precipitation or as antifreeze to water ·

The wettable powders / spray powders / are usually prepared in such a way that they contain from 20 to 95% of the active substance and usually contain in addition a solid carrier, from 0 to 5% of a wetting agent, from 3 to 10% of a dispersing agent and, where necessary from 0 to 10% of one or more stabilizers and / or additives, such as penetration agents, adhesives or anti-caking agents, colorants and the like.

As an example, we present different wetting compositions

powders.

Example P 3;

active substance 50% calcium lignosulfonate / deflocculant / 5% isopropylnaphthalene sulfonate / anionic wetting agent / 1% silicon antimonate 5% kaolin / filler / 39%

Another 70% spray powder composition contains the following ingredients: ^k

Example P 4.

active substance 700g

sodium dibutylnaphthylsulfonate50g condensation product in ratios 3/2/1 naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde 3Og kaolin100g champagne harm120g

Another 40% spray composition contains the following ingredients.

Example P 5.

active substance 400g sodium lignosulfonate 50g sodium dibutylnaphthalene sulfonate South silicon 540g

Another 25% spray powder composition contains the following ingredients.

Example P 6 i

active substance 250g calcium lignosulfonate 45g an equivalence mixture of champagne harm and hydroxyethyl cellulose 19 years sodium dibutylnaphthalene sulfonate 15g silicon 195g champagne damage 195g kaolin 281g

Another 25% spray powder composition contains the following ingredients. >

Example P 7.

active substance

250g

- 21 isooctylphenoxy - polyoxyethylene - ethanol 25 g equivalence mixture of champagne chalk and hydroxyethyl cellulose 17 g sodium aluminosilicate 543 g acid 165 g

Another 10% spray powder composition shakes off the following ingredients.

Example $ 8.

active substance 100g mixture of sodium salts of sulfates of substituted fatty acids 30g product of the condensation of naphthalenesulfonic acid and formaldehyde 50g kaolin 820g

In order to obtain these nebulisers or powders, mix them in suitable mixers, the active substances with additional substances, and grind in ball or other suitable mills. Thus, pulverizer powders are obtained, whose wettability and slurry are preferable. be suspended in water at any desired concentration and these suspensions are very conveniently applicable in particular for use on plant leaves.

Pastes can be created in place of blasting powders · The conditions and specifics of creating and applying these pastes are similar to those of blasting or spray powders ·

As already stated, aqueous dispersions and emulsions, for example, the compositions obtained by diluting with water a ^ wet powder or an emulsifiable concentrate according to the invention, are within the scope of-.

- 22 of the present invention »Emulsions may be of the type water-in-oil or oil-in-water and may have a thick texture such as that of mayonnaise» »>

Granules intended for use on soil are generally prepared in such a way that they have a size between 0.1 and 2 mm and can be produced by agglomeration or impregnation. Typically, the granules contain 0.5 to 25% active substance and 0 to 10% additives, such as stabilizers, slow release modifiers, binders and solvents.

According to one example of a granular composition, the following ingredients are used.

Example F 9:

active ingredient50g epichlorohydrin2.5g cetyls and polyglycols ether2.5g polyethylene glycol35g kaolin / granulometry: 0.3 to 0.8mm / 910g

In this particular case, the active substance was mixed with epichlorohydrin and dissolved with 60 g of acetone; then polyethylene glycol, cetyl and polyglycol ether are added »The wetted kaolin · - 'with the resulting solution and then the acetone is evaporated in vacuo» One such microgranulate is mainly used to fight fungi in soil »

The compounds of formula (I) may also be used in the form of powders to be dusted; may also be used with a composition containing 50g of active ingredient and 950g of talc; · a composition may also be used containing 20g of active substance, Southern finely silicon and 970g of talc; these ingredients are mixed

·. * «·· ^f A *

- 23 and is ground and the mixture is applied by crushing ·

Examples 1 to 7 illustrate conventional methods of preparing the compounds of the invention as well as the compounds themselves. The nomenclature of the compounds is given in accordance with the French requirements, taking into account the fact that the numbering of the compounds is

the names are the names of the substitutes themselves.

EXAMPLE I Preparation of 1- [4-bromo 2- (2,4-dichlorophenyl) tetrahydro 2-furanylmethyl] 1H 1,2,4r-triazole. Compounds Nos. 1a, 1 / and 1a + 16.

Step a) Preparation of 1-chloro 2- ^ 2,4-dichlorophenyl} 4-pent 2-ol;

An organomagnesium derivative is prepared by adding a solution of allyl bromide (110 ml) in ethyl ether (10 ml) and tegrahedrofuran (200 ml) with magnesium (II 2 g) at a temperature between 15 and 20 ° C for three hours. It was heated to reflux Zomin, decanted and the precipitate washed with ether.

To this organic phase and at -30 ° C, a solution of water was added, dried over vacuum in vacuo. Half (205g). Boiling _trichloro-a, 2,4 acetophenone / 175g / in THF / 250g / and neutralized with acetic acid. Wash sulphate was washed, concentrated, and then a colorless oily liquid (3.10-¾^) = 140 - 142 ° C.

Step b / Preparation of 1- (2- (2,4-dichlorophenyl) 2-hydroxy 4-pentyl)

H, 1,2,4-triazole

A mixture of the product obtained in step a) (106 g), triazole (55 g) and potassium carbonate (160 g) was heated for 4 hours at 120 ° C in dimethylformamide (600 ml). The insoluble constituents were filtered, washed with dimethylformamide and the reaction mixture was concentrated in vacuo. · The precipitate dissolved in methylene chloride.

- 24 washes with water and then concentrated. The product was obtained by crystallization in ethyl acetate after dilution with heptane. A pale pink precipitate (97 g) was melted at 101 ° C.

Step c / Preparation of compounds # 1a and # 1

The compound in step b (compound 35g) was treated with bromine at 0 ^O in chloroform (200 ml). After discoloration, the solvent was evaporated and the residue redissolved in methanol. Then get to

slow the aqueous solution of potassium to give an alkaline pH. After evaporation of the medium, the precipitate was extracted with ethyl acetate, washed with water and concentrated. The resulting oily liquid (40 g) is composed of a mixture of two diastereoisomers in approximately equal amounts. Silicon chromatography sequentially isolates at least the polarisomer No. 1a: white tristals * melting at 83 °, then the most polar No. li: white crystals * melting at 94 °. Recrystallization results in 1a * melting at 96 θ and melting at 104 °. The 50: 50 mixture of 1a and 1 $ melts at 74 °.

In the same way, the following compounds were prepared starting from the appropriate starting materials: 1- ^ 4-bromo 2- ^ 4-chlorophenyl} tetrahydro 2-furanylmethyl] 1H 1,2,4-triazole 1c = 74 ⁰ 1 / Mg = 78 ⁰ Ic + Id Tm = 69 °.

Example II: Preparation of 1- (2- (2,4-dichlorostrophenyl) 4-hydroxy tetrahydro 2-furanylmethyl] 1H, 1,2,4-triazole. Compounds 2a and 2D

Sub-isomer Ia of Example I, which is at least the polar titer, dissolved in 30ml of chlorobenzene ^ is refluxed for 48 hours in the presence of 20g of sodium benzoate, in 30ml of water and 1g of phase transfer catalyst JlDOQEl / 464 Kilomonium chloride.

After dilution with ether, the organic phase is washed with water and recovered in vacuo.

refluxed in methanol (100 mL) in the presence of potassium (7 g) · Cooled, diluted with water, extracted with ethyl acetate, washed to neutrality and purified by chromatography the whole product _f obtained aded concentrating under vacuum · Alcohol 2a is isolated as a white powder (2.8g), melting at 193 °.

I-Sato proceeds in the same way _; starting from the most polar isomer 11 obtained according to Example 1, the optically active alcohol 2 ^, which is a white powder, is obtained _; melting at 162 ° C. The 50/50 mixture of 2a and 2έ is oily »Example III: Preparation of 1- {2- ^ 2,4-dichlorophenyl} 4-ethoxy tetrahydro 2-furanylmethyl] 1H 1,2,4-triazole. Compounds # 3 and # 3b ·

Alcohol 2a (2, 2g) _; dissolved in dimethylsulfoxide (12ml) _? was treated sequentially with sodium hydride - 80% (0.42 g) and then with ethyl iodide (1.15 ml). · After 15 minutes the medium was diluted with water and extracted with ethyl acetate. · After washing with water >> the solvent was evaporated and the precipitate was evaporated. is purified by silica chromatography to give a colorless oily liquid, which is the isomer 3a, which is crystallized upon trituration in pentane, melting at 90 ° C; also, leaving 2 ^, the isomer 3b is obtained, which is a white powder melting at 63 ° C. The 50/50 mixture of 3a + 3έ is an oil. The same are obtained compounds of formula VIII / combined in the lower table when using appropriate alcohols ·

Melting point

4a -------- H

4 ^ p>

Fr.

5a N

5i 0-CH ₃ '0 $ in —98' ⁰ H 140

Ο-ΟΗθ oil

H oil

- 26 6a Η

6b 0- / 7. -Pv

oil butter

Example IV. Preparation of 1- [2- (2,4-dichlorophenyl) 4-ethylthio tetrahydro 2-furanylmethyl-1H 1,2,4-triazole Compounds No. 7a and No. 7 ^

Bromide 1a (3.8g) dissolved in dimethylsulfoxide (38ml) containing water (2ml) was treated with sodium bisulfite (2.8g) for two hours. Powdered potassium base (3.3g) was added and then this ethyl iodide (4ml) · After 10 minutes of stirring, the medium was diluted with water and extracted with ether · After drying and evaporation, the isomer 7a was obtained, which is a yellow oily liquid (3.9g), melting at 88 ° C.

Proceeding in the same way, starting from 1l, 7 ^ is obtained in the form of a pale yellow powder, melting at 64 ° C. · The mixture of isomers is oily. · In the same way compounds of formula (VIII) were obtained, combined in the following table using appropriate thiols.

......... ^X 1 · ...... * 2 ............. Tbc ^ wG melting ' ^ 8a -------- and ......... 'S-'CHg ------------ --------- _g6 ------------- 8 ^ S-dream ₃ Η butter 9a n S-n- Rg 110 94 ζ -YL · - Ru Η butter 10a Η 5-2-ClEi 127 ιοί S-a-ciE Η butter 11a Η 68 ' 114 S-i -Bt /> Η butter 124 $ - v -Pr Η 65 12a Η $ -ί -Rg 75

- 27 Example V. Preparation of 1- [7- ^ 2,4-dichlorophenyl) 1,4, 6-trioxospiro (4,4-nonayl methyl) 1H 1,2,4-triazole. Compound No. 13.

Step a / Preparation of 1-chloro 2- (2,4-dichlorophenyl) 3,4,5-pentaneriol.

The chloroshydrin (91 g) obtained in step a) of Example I (91 g) was epoxidized in dichloro-1,2 ethane (125 ml) in the presence of vanadiracetyl acetonate (5 g) and 70% tertiary butyl stress (200 ml) by heating for 48 hours. refrigerator. The cooled medium was diluted with water, washed several times with sodium bisulfite solution, and then concentrated. The precipitate was then transformed into a triol by heating in water (200 ml) and dioxane (200 ml) in the presence of perchloric acid (5 ml) for 3 hours. After dilution with water, the medium was extracted with toluene (30ml) and then concentrated.

Step b / Preparation 2 - (^ 2,4-Dichlorophenyl) 2-chloromethyl tetrahydro

4-furanone.

The oily precipitate obtained in step a) was heated in toluene (100 mL) and butanol (200 mL) in the presence of paratoluenesulfonic acid (0.5 g) by separating the resulting water. After evaporation of the reaction medium, the precipitate was chromatographed on silica (eluent ethyl acetate / heptane 40 (60) to give a colorless oily liquid (14.5 g) corresponding to the diastereoisomers of the alcohol, 2- (2,4edichlorophenyl) 4-hydroxy 2-chloromethyl tetrahydrofuran. This product is directly oxidized by chromic anhydrite in acetic acid to obtain after purification by silica furanone on white silicone, melting at 99 ° C.

The resulting step (furanone) (4.2 g) was heated in toluene (50 ml) at reflux in the presence of ethylene glycol (6.5 ml) and toluenesulfonic acid (0.1 g), separating the resulting water until the starting material disappeared. · product·

The medium was washed with sodium hydroxide, then diluted with water, extracted with ether and concentrated. A white solid (5.1g) was obtained, melting at 99 ° C.

I. Step d / Preparation of Compound 13 *

The halide of step c (5g) was heated at 170 ° C in dimethyl sulfoxide (20ml) in the presence of triazole sodium (2.75g) for 6 hours. The medium was poured into water, extracted with ethyl acetate, concentrated and is purified by silica chromatography · Isolated pale yellow crystals (3.6 g), which were evaporated at 123 after recrystallization in ethyl acetate / heptane Example e-

and No. 14 ^ ·

The chlorhydrin obtained in step a) of Example I dissolved in dichloromethane (150 ml) was treated with chlorine gas (13.4 g) at -15 °. The medium is then treated with a 37% sodium bisulfite solution (15 ml), washed with water and dried, then evaporated. A colorless oily product (49.7 g) containing approximately 70% of the desired is obtained. product in the form of two diastereoisomers ·

Step b / Preparation of 1- (2,4-dichlorophenyl) 1- (2,3-dichloro 1-propanyl)

- 29 oxiran.

One method of preparation consists in dissolving the resultant step (a) of crude chloroquine (10, 3r) in methanol (3ml) and treatment with a methanol solution of potassium containing 2.55-10 mol / l (12ml) at room temperature · The precipitate was filtered off and the methanol solution was evaporated in vacuo · The precipitate was purified by silica chromatography · Colorless oily liquid was obtained / 7.4g / ·

Another method consists in dissolving in methanol (75 ml) of the chlorinated chloroxtrin obtained in step a) of Example I (19.9 g) and treating it with a solution of potassium (4.9 g) in methanol 20 ml at room temperature · After filtration of the insoluble and evaporation gave the epoxy (17.1 g) as a yellow oil. This epoxide is treated with chlorine to a yellow color consistency (10.1 g) at -15 °. The medium was then washed with sodium bisulfite solution, then the water was evaporated in vacuo. A yellow oily liquid (20.8 g) was obtained containing a mixture of the two diastereoisomers in a ratio of 45/55 · Step c) Preparation of 1- [4-chloro 2 - (^ 2,4-dichlorophenyl) tetrahydro 2-furanylmethyl] 1H 1 , 2,4-arias ol ·

The epoxide obtained in step 6 ( _f (61.7r) in butanol-1 (0.5l) was soaked at 90 ⁰ for 6 hours in the presence of triazolyl sodium (18.6 g). The mineral precipitate was filtered off and the butanode evaporated. · The residue was purified by silica chromatography (eluent 48% ethyl acetate 48% heptane 4% methanol) to give successively the first diastereoisomer 14a, melting at 113 ° and then the second diastereoisomer 14 ^ melting at 97 °. 50/50 at 14a and 146 melts at 90 °

- 30 Example VII; Preparation of 1- ^ 4-oxo 2- ^ 2,4-dichlorophenyl) tetrahydro 2-furanylmethyl ^ 1H 1,2,4-triazole Compound 15 · Alcohol 2a (37.7 g) was added at -60 ⁰ in a solution of dimethyl sulfoxide (17ml) in dichloromethane (120ml), treated at -60 ⁰ with trifluoroacetic anhydride solution (25.4ml) in dichloromethane (60ml) · After half an hour at -60 ° C, the temperature was allowed to reach room temperature and triethylamine (48 ml) was added ·

The medium is poured into water, extracted with dichloromethane and boiled. · A white, melting three 91 ⁰ powder is isolated, after crystallization in ether ·

Example VIII; Preparation of 1- [4,4-dichloro 2 - {^ 2,4-dichlorophenyl) tetrahydro 2-furanylmethyl] 1 H 1,2,4-triazole, compound No. 20 ·

Mixture of ketone 15 (3.1g), phosphorous pentachloride (2.3g), dichloromethane (3ml) containing triethylbenzylammonium chloride (0j25r) _? is stirred for two hours at room temperature until the starting material disappears · The medium is evaporated, diluted with water (100 ml), neutralized with sodium bicarbonate and extracted with ether · After drying and evaporation the oily precipitate is recrystallized in isopropyl ether (twice) · Obtained a white powder (0.6 g), melting at 138 ° C. Example IX: Preparation of 1- [4- (4-dimethylamino) 2- (2,4-dichlorophenyl) tetrahydro-2-furanylmethyl] -NH. 2,4-piazole, compound16

To the solution of potassium base (0.24 g) and dimethylamine hydrochloride (1.05 g) in methanol was added successively the ketone of Example III and then sodium cyanoborohydride (0.24 g) · After 15 minutes, the medium was diluted with water and extracted with ether. · then the desired product was extracted from the organic phase with hydrochloric acid 6Λ // 3 x 20ml / after neutralization, extraction and silica chromatography were isolated 5 bg / ^iN D as a pale yellow oily

- 31 liquid / 50/50 mixture of both isomers / ·

Example X. Preparation of 1- (4-methoxyimino 2- (2,4-dichloropheyl) tetrahydro 2-furanylmethyl) 1 H 1,2,4-triazole, compound 17.

The ketone of Example III (2d) dissolved in ethanol (30ml) was refluxed in the presence of methoxylamine hydrochloride (5.8ml 25% solution in water) for two hours · The medium was diluted with water, extracted with dichloromethane and evaporated · The product was isolated by crystallization in a mixture of diisopropyl ether and heptane as a white powder, melting at 108 ° C (mixture of two geometric isomers) ·

In the same manner, compounds were obtained for which = H (4-hydroxyamino) T _m = 195 ^O 18 = 4-isopropoxyimino [19]

Examples ΪΙ, and following illustrate fungshttststsnite uses of the compounds according to the invention · In these examples, the atomization of solutions or suspensions of the active compounds is carried out under such conditions that the spray solution or suspension with a concentration _/ equal to 1 g / l to satisfy the average of applying two micrograms of active substance per cm leaf of plant ·

Under the conditions of Examples X and the following, the compounds shown do not have phytotoxicity ·

In these examples, a product is considered to have a complete protective effect against fungicidal disease when the protection is not less than 95%; protection is considered very good ^ when it is at least 80% / but less than 95% /, very good when it ^ is at least 70% / but lower than 80% /, as average ^ when it is at most -almost 50% / but less than 70% / ·

In this statement the percentages are / are off

- 32 we ^ when the opposite is given? and exceptionally _; when it comes to yields / weights · Where? percentages are expressed in terms of stoichiometry? they refer to molar percentages · In terms of concentrations, some of them are expressed in ppm ^ / parts per million /, which corresponds to mg / l ·

Example XI ϊ Nest t'k 1 // on δοίζγί; 6 ounces of tomato ·

Fine grinding results in an aqueous emulsion of the active ingredient for testing, having the following composition: active substance for testing 'omg, g-'

Sfc · tu / euz 80 / surfactant consisting of. oleate of polyethoxylated sorbitan derivative / diluted to 10% in water 0, 3ml, supplemented to boMl with water.

This aqueous emulsion is then diluted with water to obtain the desired concentration ·

Tomatoes? sown in a greenhouse (of the Marmand species) are treated for 30-40 days by spraying with water emulsions (called pulps), as described above, and at different concentrations of the test compound. The experiment is repeated twice with each concentration.

After 24 or 48 hours * the leaves are cut and placed in two petri dishes (14 cm in diameter), the bottom of which has been previously covered with moistened filter paper / 5 leaves in petri dishes / · The infection is introduced by means _{of a} syringe, drip drops / 3 drops per leaf / of spore suspension · This spore suspension of

was obtained starting from a 15-day culture, then suspended in nutrient solution (100,000 units / cm).

Control is performed on the third and sixth day after infection by comparison with an untreated witness.

Under these conditions, complete protection is afforded at a dose of

- 33 l / l with compounds 1a, 1 ^, 1a + 1έ>, 34, 5 ^, 6 ^, 8 ^, 9 ^, 12 ^

14a, 14 /, 14a + 14έ, 17.

Example XII; Test ICs νι ΐ / ο on #faming _p0 barley / barley powdery mildew /.

Planted in plant soil in pots of barley was triturated at the Yummy stage by spraying an aqueous emulsion (called sludge) and the concentrations given below. The experiment was repeated twice. 34 th hour barley plants are dusted with spores of / ^ & ^ JV nuiu4> »ka ^T0 dusting is carried out using diseased plants. Reporting is made from the eighth to the fourteenth day after infection.

Under these conditions, the following results are observed: at a dose of 1 g / l good or complete protection with compounds: la, lb _t la + 1 /, 2a, 2 /, 3a, 3l, 3a + 3 /, 4a, 4 ^, 5 a , 5 /, 6a, b /, 7a + 7 ^, 8a, 8 /, 13, 14a, 14 /, 14a + 14 /, 15, 17, 19, 20.

EXAMPLE XIII: Test for cerebral cortex.

The cereals planted in plant pots were treated at Height stage by spraying with an aqueous emulsion (called a pulp) with the same composition as that described in Example VIII and at different concentrations of the test compound. The experiment is repeated twice at each concentration.

iHa aqueous spore suspension (50000 sp / cm) was sprayed on the grain for 24 hours; as this suspension was obtained by coming out of infected plants. The wheat is then transferred for 48 hours in an incubation cell at about 18 ° C and 100% relative humidity.

At the end of the second day, the relative humidity is increased to 60%. Control of the condition of the plants was carried out between the 11th and 15th day after infection by comparison with an untreated witness.

- 34 At doses of 1g / l the protection is good or complete with compounds:

1a, 14, 1a + 14, Za, 34, Za + 3 ^, 54, 6-4, 7a, 7a + 7 ^, 8 /, k »13, 14a, 14 4, 14a + 144, 17, 19. 20 ·

Example XIV: Test in, on pin'cuFla / KZ, causing

Pi by rice / & c £ β & ΖΛ, 'έ / ·

Rice planted in pots in a 50/50 mixture, enriched peat and red soil, was treated at the Icm height by spraying an aqueous emulsion (called a pulp) and described above at the concentrations given below. times · At the end of the 48th hour, it is treated by applying a slurry of pure culture spores on the leaves ·

Reading is done on the 8th day after infection · Under these conditions, the following results are approaching: at a dose of 1 g / l good or complete protection with compounds 1a, 14, | 1a + 1 ^, Za, 3 ^, 6a, 8a1 8 ^, 9a, 9 4, 1θέ, 11a, 114, 12a, 12 fe, 14a, 140, 14a + $ 14, 15, 20 ·

Example XV; Test / k riifo on embryos and soil mushrooms ·

The effect of the compounds according to the invention on the following fungi causing diseases in cereals and other plants are investigated: l.Py

with.

4 · Fusarium 5 · FuSCUlUW

8. itiiici

- ,. 'ΤτίΧ

9. sensitive to carbendazim and cyclic imides

VO * dottc {t / ib tiwtfb resistant to carbendazim and cyclic imides 11 · Piutdpozsws ^ rit / a,

12> ROML 1b F <sp

13 · Mi ^ ΟοΙοπμΟ, $ & (! O / 1m

The figures appearing before the names will be used to represent the mushrooms in Table II.

In each experiment, proceed as follows: a culture medium consisting of potato, glucose and agar (PPA medium) was introduced, cooled in a series of plates (20 ml / petri), after sterilization in an autoclave at 120 ° C.

In the process of refilling the plates, acetone solution of the active substance is introduced into the cooled medium to obtain the desired final concentration.

Similar plates are used as a witness, pouring similar amounts of nutrient-free medium.

After 24 or 48 hours, each plate was infected with a micellar fragment of culture from the same sponge.

The plates were placed for two to ten days (depending on the sponge tested) at 22 ° C and then the development of the sponge in the plate containing the substance tested with the same sponge in the plate used as a witness was compared.

Thus, for each compound tested, the amount of mushroom inhibition estimated at the 3Orde dose is determined. The results are given in the following tables.

-36Composition I Mushrooms

η ° 1 ι 1 1 2! 1 3 1 1 4 | 1 5 1 6 I 7 la 1 100 1 1 100 1 100 1 1 95 | I 100 1 100 ι 95 lb 1 100 i 1 90 | 1 100 1 100 | 1 100 1 100 1 90 la + lb I 100 1 95 1 100 I 1 95 | I 100 1 100 I 90 2 a 1 50 | 1 95 1 1 80 I 50 | ! 80! 1 100 1 80 2b 1 80 I 110 1 80 I I 50 | 1 90 1 90 ι 80 3a 1 95 1 1 90 | 1 100 1 ! 50 | 1 80 i 1 80 1 90 3b 1 95 1 1 95 | 1 100 | ! 80 | 1 90 1 100 I 90 3a + 3b I 80 1 1 o | 1 80 I o | 1 80 i 1 80 1 80 4a 1 90 1 1 0 1 1 90 I 1 80 | 1 80 | 1 90 I 90 4b 1 95 | 1 80 | 1 95 | 80 | 80 | 1 loo ι 90 5a 1 50 | 1 90 | 1 50 | 1 50 | 1 50 ί 1 50 ι 50 5b 1 100 I 1 100 I 1 100 1 90 | 95 I 1 100 ι 95 6a 1 50 1 1 90 | 1 50 | 50 | 1 50 1 1 50 ι 50 6b 1 100 | 1 95 | 1 95 | 80 | [90 I 1 90 I 90 7a 1 95 | 1 95 | 1 95 1 ο ι ί ο! 1 ο 1 50 7b 1 95 | 1 90 | 1 95 | 0 | ι ο ι 1 0 1 50 7a + 7b | 50 | 1 95! 1 50 | ο ι ! 0 1 ^{1 0 1} 50 8a 1 95 1 1 80 | 1 95 | 80 | 50 1 1 100 I 80 8b 1 100 I 1 90 | 1 95 1 80 | 80 1 1 90 1 80 9a 1 95 1 : 9o ι 95 | 80 | 80 1 ! 90 I 80 9b 1 80 1 1 95 | [95 | 0 1 1 0 I 1 80 I 80 10a 1 80 | 0 | 1 80 | 50 | 90 1 95 1 80 10b 1 90 1 80 | 1 90 | 0 1 0 ι 1 50 ι 80 11a 1 90 I 50 | 95 | 0 1 0 1 l ο ι 80 lib 1 90 1 and 80 | 95 1 0 1 0 1 1 θ.Ι 80 12a 1 90 | 80 | 95 I 0 1 80 1 [80 I 80 12b 1 95 1 90 | 1 95 I 80 | 80 1 1 90 I 80

37 ·

Composition 1 η ° 1 ί 1 2 1 Mushrooms 1 of 1 4 1 1 5 1 1 6 1 1 7 1 13a 1 - 1 90 1 1 - 1 - 1 1 -! 1 - 1 - 1 14 a 1 95 1 95 1 1 100 1 95 1 1 100 1 1 100 1 90 1 14b 1 95 1 90 1 1 100 I 90 1 1 95 1 1 100 1 90 1 14a + 14b] 100 1 95 1 1 100 1 150 1 100 1 1 100 1 1 95 1 15 1 0 1 95 1 1 80 1 0 1 1 0 i 1 50 1 0 1 16 1 80 1 0 1 1 80 1 ο 1 1 ο 1 1 50 1 1 0 I 17 1 80 1 0 1 1 80 1 80 1 1 95 1 1 80 1 1 80 1 18 1 1 1 1 1 1 [1 1 1 1 1 19 1 90 1 ο 1 1 80 1 80 1 1 90 1 1 50 1 1 80 1 20 1 90 1 80 1 1 95 1 90 1 1 95 1 1 90 1 1 90 1

38Composition I Mushrooms

η ° 1 8 1 9 1 10 1 1 11 1 1 12 1 13 1 14 | la 1 100 1 100 | I 100 1 100 | 1 100 1 80 1 100 1 lb 1. . - 1 95 | 1 95 1 1 loo | 1 100 1 80 | 1 1001 la + ib 1 100 1 95 | 1 95 1 1 loo I 1 100 1 ! 90 | 1 95 | 2 a 1 ο 1 95 | 1 95 1 1 loo | 1 0 1 0 1 1 80 | 2b 1 o 1 80 | I 50 1 1 loo | 1 80 | 0 1 1 801 3a 1 95 I 90 | ! 90 I 1 95 | 1 0 1 0 1 1 90 | 3b 1 100 1 95 | 1 100! 1 95 | 1 80 I 80 | 1 951 3a + 3 b | 0 1 80 | ! 95 1 1 0 | 1 0 1 0 1 I 80 | 4a 1 0 1 1 95 I 1 95 1 1 0 | 1 0 1 0 1 1 90 | 4b 1 ο I 95 | 1 95 | 1 90 | 1 95 I ο 1 1 951 5a 1 ο 1 1 o 1 1 0 | 1 100 1 1 0 1 0 | 1 50 | 5b 1 ο 1 95 I [90 I 1 loo | 1 95 1 90 | 1 901 6a 1 ο 1 1 50 I 1 .50 I 1 loo I 1 0 1 ο 1 1 50 | 6b 1 50 I 95 | 1 95 I 1 loo | 1 80 1 80 I 95 | 7a 1 0 1 1 95 I 1 95 1 1 95 I 1 0 1 80 | 1 80 | 7b 1 ο 1 90 | 95 I 1 90 | 1 o 1 50 | 1 50 | 7a + 7b | - 1 1 95 | 1 95 1 1 100 I 1 50 1 80 I 1 50 | 8a 1 o 1 80 | and 80 | 1 80 | 80 I 80 | 951 8b 1 0 1 95 | 1 95 1 1 90 | 1 80 I 80 | 1 951 9a 1 0 1 90 I 90 1 1 90 | 80 1 80 | ! 95 | 9b 1 0 1 95 | 1 90 1 1 100 I 1 80 1 80 Ί ! 50 | 10a 1 50 I 80 | 0 I 1. 0 1 ! 0 1 0 1 01 10b 1 0 1 1 90 1 1 95 1 1 80 | and 50 | 50 | 90 | 11a 1 0 1 0 1 80 I 1 50 | 50 I 50 | 95 | lib 1 0 1 80 | ! 80 | 1 80 I 1 80 | 80 | 95 | 12a 1 0 1 50 | ; so i 1 80 | 0 I 80 | 90 | 12b 1 0 1 95 | 95 1 1 90 | ! 80 I 80 | 100 | 13a 1 - 1 0 1 1 0 1 1 100 I 50 | 0 1 - 1

..mH-h-39-

Composition ' N ° 1 8 I 1 9 1 10 Mushrooms 1 ii 1 12 | 1 13 1 1 14 I 14a I - 1 1 100 1 100 1 loo 1 100 | 80 1 100 1 14b | . o | 1 95 | 95 1 loo 1 80 | 80 i 1 1001 14a + 14b | 50 | 1 95 | 1 95 1 loo 1 100 | 80 1 95 | 15 1 - 1 ! 0 I 0 1 95 I 0 1 ο 1 1 01 16 I 0 1 1 0 I 1 0 1 0 1 0 1 0 1 80 | 17 | ο 1 1 80 | 80 1 0 | o I 0 1 1 80 | 18 | 1 1 1 1 1 1 1 1 19 | 0 1 o | 1 o 1 o 1 0 1 0 1 1 90 | 20 | 0 1 1 80 1 1 90 1 loo 1 50 | 80 | 1 901

Claims (16)

1. Compounds containing a triazole or imidazole tetrahydrofuran and phenyl group of the general formula wherein A represents the group (Y) _n - Ph (CH ₂ ) _w - in which Ph denotes a phenyl nucleus and m has a value of 0 or 1, Y denotes halogen atom or cyano or nitro, alkyl or alkoxy radicals, optionally halogenated, η denotes an integer positive or 0 less than 6, where the groups Y may be the same or different when η is greater than 1, Tr is 1, 2,4-triazol-1-yl, and Im represents imidazol-1-yl group, _R] to R, may be the same or different, and znachavat hydrogen atom, a lower alkyl, lower cycloalkyl, phenyl or benzyl, or benzoyl lower alkoxy, X] and _X2 may be the same or different and represent hydrogen, halogen, lower alkyl, lower cycloalkyl, phenyl, benzyl, a group QR ₆ , in which Q is oxygen or sulfur and R ₆ is hydrogen, lower alkyl, lower cycloalkyl, aryl, aralkyl, acyl or thioacyl, alkyloxythiol, aryloxythiol or aralkyloxythiol, a group of formula -QR ₇ -Q- in which Q has the meanings, mentioned above, and in which R is a divalent hydrocarbon radical containing two to six atoms in glerod, as one of its carbon atoms may be replaced by an oxygen or nitrogen atom, and the bivalent radical may optionally also be substituted, for example by one or more halogen atoms or lower alkyl groups, lower alkoxy radical or hydroxy; a group of the formula -NR _g R ₉ in which R ₍ and R _g are the same or different and denote hydrogen or lower alkyl, lower cycloalkyl, aryl, aralkyl, these radicals being optionally substituted in a manner similar to that for the groups R 1 to R J ₅ and also R 1 and R 5 can together form a divalent hydrocarbon radical containing 2 to 6 carbon atoms, one of these carbons being replaced by one oxygen, sulfur or nitrogen atom, and the divalent radical may is optionally substituted by the group = N - R _10, wherein R ₁₀ represents lower alkyl, lower cyclic Oalkyl, aryl, aralkyl, a group of formula OR _n, where R _n is alkyl, aralkyl, aryloxy, hydroxy, N ₃ group, provided that X ₂ is different from N _3, X _t and X ₂ may represent oxygen, or sulfur or other leaving group, provided that X, and X ₂ cannot simultaneously represent hydrogen, lower alkyl, lower cycloalkyl, aryl or aralkyl, and salts thereof. Compounds according to claim 1, wherein η has a value of 1 or 2 and Y represents halogen placed in the ortho- and / or position, preferably chlorine or bromine. Compounds according to claims 1 or 2 having the formula in which Y, m, η have the meanings given in formula I, R, to R ₅ denote a hydrogen atom, alkyl or lower cycloalkyl, Hal means a halogen atom, preferably chlorine or bromine, X! means halogen, preferably chlorine or bromine or hydrogen. Compounds according to claims 1 or 2 of the general formula wherein Y, n, m have the meanings indicated in formula I, R 1 to R ₅ denote hydrogen, alkyl or lower cycloalkyl; X ₁ is hydrogen, alkyl or lower cycloalkyl, O, Q has the meanings given in formula 1, R ₆ represents hydrogen, alkyl or lower cycloalkyl. 5. Compounds according to claim 4, in which R] to R _s are hydrogen, alkyl or lower cycloalkyl and R ₆ is lower alkyl, lower cycloalkyl, optionally substituted. A process for the preparation of compounds of Formula II, wherein R 1; to R _s , A, Y, and, X ₍ having the same meanings as claimed in claim 1 and Hal means a halogen atom, characterized in that it consists of the following steps: Step a) A halogen ketone of formula Pa, in which Y, n, R _s have the meanings given in formula I, and Z represents halogen, is reacted with an organometallic compound of formula IIb to obtain the compound of formula IIc; Step b) The compound of formula Ps is reacted with unsubstituted imidazole or triazole in the presence of an organic or inorganic base and in a suitable solvent; Step c) The compound hal is attached to a halogen molecule in an inert solvent environment to give compound Pe; Step d) Compound II is prepared by cyclization of compound Pe in the presence of an organic or inorganic base. A process for the preparation of compounds of formula II, wherein R 1 to R _s , Y, n, A, X ₎ have the meanings given in claim 1, and Hal represents a halogen atom, characterized in that to the compound Pc according to claim 9 is added a halogen or halogen molecule mixed in an inert solvent to give the compound Ilf, which cycles in the presence of an organic or inorganic base to give the compound Ilg to which an unsubstituted triazole or imidazole group is attached in the presence on an organic or inorganic basis in the environment of n a suitable solvent. A process for the preparation of compounds of formulas III or IV, in which R _f to R ₆ , Y, n, A, X ₍ have the meanings given in claim 1, and Q denotes an oxygen or sulfur atom, characterized in that that a compound of formula II or Ilg is reacted with a nucleophilic heteroatom compound of formula R ₆ -QE in which R ₆ and Q have the meanings given above in formula I, and E is a cation in the presence of a base and optionally a catalyst for interfacial transfer, and when using the Ilg compound as the starting product, an unsubstituted imidazole or triase is added l. A process for the preparation of compounds of formula II wherein R ₆ represents a lower alkyl group optionally mono- or polysubstituted by halogen according to claim II, characterized in that a compound of formula III or III wherein R ₆ represents hydrogen is reacted with an alkyl halide (optionally mono- or polysubstituted by halogen) in the presence of an organic or inorganic base and then, if exited from a compound of formula IIIa, an imidazole or triazole nucleus is attached. A process for the preparation of compounds of formula IV, wherein R 1 to R ₅ , η, Y, A have the meanings given in claim 1, and X _x and X ₂ together represent an oxygen atom, characterized in that the compound of formula III or IIIa in which Y, n, R ₍ to R _s have the meanings given in claim 1, Z is halogen and in which QR ₆ is a hydroxyl group and X ₍ is hydrogen, is oxidized and if the compound IIIa is used) , then an unsubstituted imidazole or triazole nucleus is attached. A process for the preparation of compounds of formula IV, in which Xj and X ₂ together represent sulfur and Y, n, R ₍ to R _s have the meanings given in claim 1, characterized in that a compound of formula IV, c wherein X] and X ₂ together represent oxygen, is subjected to a thionation. 12. A process for preparing compounds of formula V, characterized in that compounds of the formula IV or IVa, wherein X] and X ₂ together represent oxygen or sulfur, linked via a double bond with tetrahydrofuran, is reacted with a compound of formula HQR ₆ , in which Q is oxygen or sulfur, in the presence of an acid catalyst in an environment of a suitable solvent, which may be alcohol or thiol, or inert solvent, if left from a compound of formula IVa, a compound of formula Va is obtained and then to the compound of formula Va is bonded tears triazole or imidazole nucleus. 13. Process for the preparation of compounds of formula I in which R _J to R _fi, η, Y, A are as defined in claim 1, wherein X | and X ₂ denotes halogen, preferably 5 chlorine or bromine, characterized in that a compound of formula III or III in which Y, n, R 1 to R _s and A have the meanings given in claim 1, Z represents halogen and QR ₆ means a hydroxyl group, and Xj represents hydrogen, 10 is oxidized by the addition of phosphorus pentachloride to the ketone (compound of formula IV, in which X ₍ means oxygen), optionally in the presence of a polar aprotic solvent and optionally in the presence of a 15 quaternary ammonium halide preferably at room temperature. Compounds optionally obtainable by the methods of claims 9 to 15 having the formulas 20 He, Ilh, Sha to P1e, IVa, Va, Vb, Via, Vila, in which Rj to R ₆ , Y, A, m, η, X _p X ₂ , Q, Z have the meanings given in claims 1 or 5 . Use of the compounds according to one of claims 1 to 5 as fungicides, preferably in the form of fungicidal compositions containing as active substance a compound according to claims 1 to 5, preferably in an amount of from 0.5 to 95% by weight. , the active substance being in a mixture of at least one inert carrier acceptable to agriculture. 16. A method for combating fungal diseases of cultivated plants, characterized in that an effective amount of the active substance according to claims 1 to 5 is applied, preferably 0.005 to 5 kg / ha, preferably 0.01 to 0.5 kg / ha.