FR2649101A1 - Benzylideneazolylmethylcyclohexane and use as fungicide - Google Patents

Abstract

Benzylideneazolylmethylcyclohexane of formula: in which: R1 to R5 are optionally substituted hydrocarbon residues; X is halogen; n = 1, 2 or 3; W is -CH= or -N. Use as fungicide.

Description

 The present invention relates to novel compounds for phytosanitary use with benzylidene azolylmethylcyclohexane groups. It also relates to the processes for preparing said compounds and the products which may optionally be used as intermediates in the preparation processes. It then relates to the use as fungicides of these compounds, fungicidal compositions based on these compounds and methods for combating fungal diseases of cultures using these compounds. It also relates to a propagating product of cultivated plants which has undergone a protective treatment with a compound of the invention.

 Many products with triazole groups, including fungicides, are already known. In particular, patent applications EP 151084, 246982, 121979 and 89100 disclose tetrahydrofuran triazole fungicides.

By the patent applications EP 272895, 267778, DE 3630840,
BE 867245 triazole fungicides with cyclopentane cycle are known. US Patent 4160838 discloses dioxolane triazole fungicides.

An object of the present invention is to provide other broad-spectrum fungicidal compounds useful in particular in the treatment of foot diseases such as tracheine or leaf borne such as olium, septoria, blastosis, fusariosis, rhinchosporiosis, diseases caused by pathogenic fungi such as Botrytis, Phoma,
Aschochyta, in crops as diverse as cereals, vines, rice, maize, soybeans for example.

 Another aim of the present invention is to propose novel compounds having, in addition to their fungicidal property, a remarkable absence of phytotoxicity with respect to the multiplication products of cultivated plants (in particular monocotyledons or dicotyledons) according to the test mentioned at the end of the description.

 To the applicant's knowledge, these are the first triazole compounds having such a novel function (fungicidal effect in combination with an absence of phytotoxicity on the multiplication products of the cultivated plants).

 These aims are achieved partially or completely by the compounds according to the invention.

These compounds are characterized in that they correspond to formula I below in which

X is a nalogen atom or a cyano group or
nitro, or a C1-C4 alkyl or C 1 -C 4 group
optionally halogenated alkoxy, n is a positive integer or zero, less than 6,
groups X that can be identical or
different when n is greater than 1,
W represents a trivalent group consisting of either a
group = CH-, that is to say a nitrogen atom = N-,
R1, R2, identical or different, represent
the hydrogen atom or a C1-C4 alkyl radical
optionally substituted (for example by one or
several atoms or radicals such as atoms
halogen radicals, C1-C4 alkoxy radicals and
mono or polyhalo C1-C4 alkoxy radicals),
C3-C7 cycloalkyl, C6-C10 aryl (especially
phenyl), C7-C11 alkyl (especially benzyl),
these various radicals possibly being
substituted (for example by one or more atoms
or radicals such as halogen atoms,
C1-C4 alkyl radicals, mono or
polyhalo C1-C4 alkyl, C1-C4 radicals
alkoxy and mono or polyhalo C1-C4 radicals
alkoxy), R1, R2 together can form a
C2-C5 hydrocarbon chain constituting a ring
with the carbon to which R1, R2 are connected,
this chain being possibly substituted as
for C6-C1O aryl radicals previously
cited.

R3 to R5, identical or different, represent
the hydrogen atom or a C1-C4 alkyl radical
optionally substituted (for example by one or
several atoms or radicals such as atoms
halogen radicals, C1-C4 alkoxy radicals and
mono or polyhalo C1-C4 alkoxy radicals),
C3-C7 cycloalkyl, C6-C10 aryl (especially
pnenyl), C7-C11 aralkyl (especially benzyl),
these various radicals possibly being
substituted (for example
by one or more atoms or radicals such as
halogen atoms, C1-C4 alkyl radicals,
mono or polyhalo C1-C4 alkyl radicals,
C1-C4 alkoxy radicals and mono or
polyhalo C1-C4 alkoxy),
The invention also relates to the salified forms of the compounds according to the invention.The salified forms are the agriculturally acceptable forms among which may be mentioned: hydrochloride, sulfate, oxalate, nitrate or arylsulphonate as well as the complexes of adaition of these compounds with metal salts, and in particular salts of iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum.

 By way of example, complexes with zinc can be obtained by reacting the compound of formula I with zinc chloride.

 For the purposes of this text, it is understood that when no precision is given, the radicals concerned may be branched or linear.

 The compounds of formula I and the compounds which may be used as intermediates in the preparation processes and which will be defined on the occasion of the description of these processes may exist in one or more isomeric forms depending on the number of asymmetric centers. of the molecule. The invention thus relates to all optical isomers as well as their racemic mixtures and the corresponding diastereoisomers. The separation of the diastereoisomers and / or the optical isomers can be carried out according to the methods known per se.

 For fungicidal applications it has been found that the invention preferably relates to the compounds of formula I wherein X is halogen and n = 1, 2 or 3.

 It has also been found that it is preferable to use the compounds of formula I in which n = 1 or 2, and X is a halogen atom, preferably chlorine, placed in para if n = 1 and in para , meta if n = 2.

 In view of the above-defined restrictions taken separately or in combination it has been found that it is preferable because of the fungicidal properties of using compounds of formula IA or IS wherein W is -N =.

In view of the above-defined restrictions taken separately or in combination, it has been found that it is preferable because of the fungicidal properties of using the compounds of formula I in which R3 to
R5 are the hydrogen atom.

In view of the above-defined restrictions taken separately or in combination it has been found that it is preferable because of the fungicidal properties of using the compounds of formula I in which R 1 and
R 2 are methyl, ethyl or form a ring of less than 6 members or are the hydrogen atom with the exception of R 1 = R 2 = hydrogen, preferably R 1 is methyl and R 2 is hydrogen or methyl.

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

 In the following description, the substituents described below have the same meaning as those indicated above.

This process involves submitting

selon par exemple A.C. HUITRIC et W.D. KUMLER,
J. Am. Chem.Soc, (1956) 78, 1147, afin d'obtenir des composés de formule

the cyclic ketones of formula (II) with the well-known reaction of aldol condensation by crotonization with a benzaldehyde of formula

according to for example AC HUITRIC and WD KUMLER,
J. Am. Chem. Sac., (1956) 78, 1147, to obtain compounds of formula

Said compounds of formula (IV) are reacted with a sulphonium ylide as described in EJCOREY Michael Chaykovsky J.Am.Soc 87, 1313, (1965) to give oxiranes of formula

 The oxiranes of formula (V) are then reacted with an unsubstituted imidazole or triazole in the presence of organic or inorganic base, for example pyridine, triethylamine, sodium hydroxide, potassium hydroxide, alkali or alkaline earth metal carbonates and bicarbonates. and alkali metal hydrides and in a suitable protic or aprotic solvent, such as, for example, alcohols, ketones, amides, nitriles, DMSO, optionally halogenated aromatic hydrocarbons, at a temperature between 800 and the reflux of solvent and in a molar ratio V: imidazole or triazole preferably between 1.1 and 0.2, which leads to the compounds of formula I.

To obtain a compound of formula I in which
R 1 is an alkyl or aralkyl group as defined above, R 2 different from hydrogen, another process consists of reacting a ketone of formula IV prepared as above, where R 1 is the hydrogen atom and R 2 is different of the hydrogen atom with an alkylating agent
R 1 -Y where R 1 is an alkyl or aralkyl group as defined above, and Y is a leaving group such as halogen, sulphonate or sulphate, for example in the presence of an organic or inorganic base, preferably the hydroxides, alkoxides and alkali hydrides or alkaline earth in a solvent or mixture of protic or aprotic solvents such as saturated, unsaturated or aromatic hydrocarbons, optionally halogenated, alcohols, amides, nitriles, oxygen-derived solvents of sulfides such as
DMSO or sulfolane. Other ketones of formula IV are thus obtained which are converted to oxiranes V as above.

To obtain a compound of formula I in which
R.sub.1, R.sup.2 and R.sup.2 are alkyl or aralkyl as defined above, another process comprises reacting a ketone of formula IV prepared as above, wherein R.sup.1, R.sup.2 is hydrogen with an alkylating agent. R 1 -Y where R 1 is an alkyl or aralkyl group as defined above, and Y is a leaving group such as halogen, sulphonate or sulphate for example in the presence of an organic or inorganic base, preferably the hydroxides, alkoxides and hydrides alkali or alkaline earth in a solvent or mixture of protic or aprotic solvents such as saturated, unsaturated or aromatic hydrocarbons, optionally halogenated, alcohols, amides, nitriles, oxygen-derived solvents of sulfides such as DMSO or sulfolane. other ketones of formula IV which are converted to oxiranes V as above.

In the case where R1, R2 form a chain
C2-C5 hydrocarbon is reacted in the same way as above a compound of formula Y-R6-Y, R6 being an optionally substituted C2-C5 hydrocarbon radical (for example by one or more atoms or radicals such as the atoms of halogens, the radicals
C1-C4 alkyl, mono- or polyhalo C1-C4 alkyl radicals, C1-C4 alkoxy radicals and mono- or polyhalo C1-C4 alkoxy radicals) according to the process indicated above.

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

 The subject of the invention is also the compounds which may optionally be used as intermediates in the preparation processes described above and of formulas IV and V described above.

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

The compounds according to the invention can be used for both preventive and curative control against fungi, in particular of the basidiomycete, ascomycete, adelomycete or fungi-imperfecti type, in particular rust, powdery mildew, trampling, fusarium, helminthosporiosis, septoria, rhizoctonia of plants and plants in general and in particular cereals such as wheat, barley, rye, oats and their hybrids and also rice and corn. The compounds according to the invention are active especially against fungi including basidiomycetes, ascomycetes, adelomycetes or fungi-imperfecti as Botrytis cinerea,
Erysiphe graminis, Puccinia recondita, Piricularia oryzae,
Cercospora beticola, Puccinia striiformis, Erysiphe cichoracearum, Fusarium oxysporum (melonis), Pyrenophora avenae, Septoria tritici, Venturia inaequalis, Whetzelinia sclerotiorum, Monilia laxa, Mycosphaerella fijiensis,
Marssonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum,
Pestalozzia sp, Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma lingam, Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticon rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum,
Sclerotinia minor, Cardinal Coryneum, Rhizoctonia solani.

They are also and still active against the following fungi: Acrostalagmus koningi, the
Alternaria, Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi,
Hormodendron cladosporioides, Lentinus degener or tigrinus,
Lenzites quercina, Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii,
Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra,
Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

 The compounds of the invention are especially interesting for their broad spectrum in terms of cereal diseases (powdery mildew, rust, trampling, helminthosporiosis, septoria and fusariosis). They are also of great interest because of their activity on botrytis and black Sigatoka, and therefore they can be applied to crops as varied as vine, market gardening and arboriculture, and tropical crops such as peanut, banana, coffee, pecan and others.

 Due to their lack of phytotoxicity, the compounds can be used for the protection of plant propagating material against diseases caused by fungi.

 The invention therefore also relates to a multiplication product of cultivated plants which has undergone a protective treatment with a compound of the invention.

 The name "multiplication product" denotes all the generative parts of the plant that can be used for multiplication thereof. Examples include seeds (narrow seeds), roots, fruits, tubers, bulbs, rhizomes, stem parts, plants, (shoots) and other parts of plants. Germinated plants and seedlings that are to be transplanted after germination or after removal from the soil should also be mentioned. These young plants can be protected before transplantation by a total or partial immersion treatment.

 In general, these compounds will be applied at a rate of 0.15 to 5009 per quintal of seeds.

 Thus, these compounds can be used in the treatment of seeds (for example cereals, cotton, beetroot, rapeseed, fodder seeds, vegetable seeds) for example in the form of coating or film coating. US Pat. No. 3,989,501, Col. 7,117-23, may be found in one form of application. Similarly, in FR-A-2 588 442. It will also be possible to use concentrated suspensions.

 In general these formulations are already known see for example "catalog of pesticide formulation types and international coding system" published by GIFAP technical monograph No. 2, pages 12 to 14, revised January 1984.

 In addition to the applications already described above, the products according to the invention also have an excellent biocidal activity with regard to many other varieties of microorganisms among which may be mentioned, without limitation, fungi such as those of the genera - Pullularia as P. pullulans, - Chaetomium as C. globosum, - Aspergillus as Aspergillus niger, - Coniophora as C. puteana.

 Because of their biocidal activity, the products of the invention can effectively combat microorganisms whose proliferation creates many problems in the agricultural and industrial fields. For this purpose, they are particularly suitable for the protection of plants or industrial products such as wood, leather, paints, paper, ropes, plastics, industrial water circuits.

 They are particularly well adapted to the protection of lignocellulosic products and in particular wood, whether it is wood of furniture, frame or wood exposed to the bad weather such as the wood of fence, the stakes of vines, the railway sleepers.

 The compounds according to the invention used alone or in the form of compositions as defined above in the wood treatments, are generally used with organic solvents and may be optionally combined with one or more known biocidal products such as pentachlorophenol, metal salts, especially of copper, manganese, cobalt, chromium, zinc derived from mineral or carboxylic acids (heptanoic acid, octanoic acid, naphthenic acid); organic complexes of tin, mercaptobenzothiazole, insecticides such as pyrethroids or organochlorines.

 The invention also relates to a method for treating cultures affected or susceptible to be affected by fungal diseases, characterized in that it applies to the leaves an effective dose of a compound of the invention.

 The compounds are advantageously applied at doses of 0.002 to 5 kg / ha, and more specifically from 0.005 to 1 kg / ha.

 For their practical use, the compounds according to the invention are rarely used alone. Most often they are part of compositions. These compositions, which can be used for the protection of plants against fungal diseases, or in plant growth regulating compositions, contain as active ingredient a compound according to the invention as described above in association with solid or liquid carriers, which are acceptable in agriculture and / or surfactants also acceptable in agriculture. In particular, the usual inert carriers and surfactants are usable.

 These compositions usually contain between 0.5 and 95% of the compound according to the invention.

 By the term "carrier" in the present specification means an organic or inorganic material, natural or synthetic, with which the active ingredient is associated to facilitate its application on the plant, on seeds or on the ground. This support is therefore generally inert and must be acceptable in agriculture, especially on the treated plant. The support may 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 gases , etc ...).

 The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols. The presence of at least one surfactant is generally indispensable when the active ingredient and / or the inert carrier are not soluble in water and the application carrier agent is water.

 These compositions may also contain any other kind of ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. other known active substances with pesticidal properties (in particular insecticides or fungicides) or with properties promoting the growth of plants (in particular fertilizers) or with properties regulating the growth of plants. More generally, the compounds according to the invention can be combined with any solid additives or liquids corresponding to the usual techniques of formulation.

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

 As forms of solid compositions, mention may be made of dusting or dispersion powders (with a content of compound of formula (I) up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound of formula (I) in these granules being between 1 and 80% for the latter cases).

 The granules intended to be placed on the ground are usually prepared so that they have dimensions of between 0.1 and 2 mm and they can be manufactured by agglomeration or impregnation.-In general, the granules contain 0.5 to 25 % of active material and 0 to 10% of additives such as stabilizers, slow release modifiers, binders and solvents.

According to an example of granule composition, the following constituents are used
Example F 9 - active ingredient 50 g - epichlorohydrin 2.5 g - cetyl polyglycol ether 2.5 g - polyethylene glycol 35 g - kaolin (particle size: 0.3 to 0.8 mm) 910 g.

 In this particular case, the active ingredient is mixed with epichlorohydrin and dissolved with 60 g of acetone; polyethylene glycol and cetyl polyglycol ether are then added. The kaolin is sprinkled with the resulting solution and the acetone is then evaporated under vacuum. Such a microgranule is advantageously used for controlling soil fungi.

 The compounds of formula (I) can still be used in the form of dusting powders; a composition comprising 50 g of active material and 950 g of talc can also be used; it is also possible to use a composition comprising 20% of active material, 10% of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

 As forms of liquid compositions or intended to constitute liquid compositions during the application, mention may be made of the solutions, in particular.

water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or powder for spraying), pastes.

 The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.01 to 20% of active material.

 For example, in addition to the solvent, emulsifiable concentrates may contain, when necessary, 2 to 20% of approved additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives previously mentioned.

As an example, here is the composition of some concentrates
Example F (Formulation) 1 - Active Ingredient 400 g / l - Alkaline Dodecylbenzene Sulfonate 24 g / l - Nonylphenol Oxyethylated to 10 Molecules
of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent qs 1 liter
According to another emulsionnaSle concentrate formula, it is used
Example F 2 - Active Ingredient 250 g - Ecooxidized Vegetable Oil 25 g - Alkylaryl sulfonate mixture
of polyglycol ether and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g
From these concentrates, it is possible to obtain, by dilution with water, emulsions of any desired concentration, which are particularly suitable for application to the leaves.

 The concentrated suspensions, also applicable in spraying, are prepared in such a way as to obtain a stable fluid product which does not settle and usually contain from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0 to 1 to 10% of thixotropic agents, from 0 to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or not soluble: some organic solids or mineral salts may be dissolved in the support to help prevent sedimentation or as antifreezes for water.

 Wettable powders (or spray powder) are usually prepared to contain from 20 to 95% active ingredient, and usually contain, in addition to the solid support, from 0 to 5% of a wetting agent, to 10% of a dispersing agent, and, when necessary, from 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

For example, here are various compositions of wettable powders
Example F 3 - active ingredient 50% - calcium lignosulfonate (deflocculant) 5% - isopropylnaphthalene sulfonate (agent
anionic wetting agent) 1% - Anti-caking silica 5% - Kaolin (filler) 39%
Another composition of 70 D spray powder uses the following constituents
Example F 4 - active ingredient 700 g - sodium dibutylnaphthylsulfonate 50 g - condensate product in proportions
3/2/1 naphthalene sulphonic acid,
of phenolsulfonic acid and
formaldehyde 30 g - kaolin 100 g - chalk of champagne 120 g
Another composition of 40% spraying powder uses the following constituents
Example F 5 - active ingredient 400 g - sodium lignosulfonate 50 9 - sodium dibutylnaphthalene sulphonate 10 g - silica 540 g
Another spray powder composition uses the following constituents
Example F 6 - active ingredient 250 g - calcium lignosulphonate 45 g - equiponderal mixture of chalk of Champagne
and hydroxyethylcellulose 19 g - sodium dibutylnaphthalene sulfonate 15 g - silica 195 g - Champagne chalk 195 g - kaolin 281 g
Another composition of 25% spraying powder uses the following constituents
Example F 7 - Active Ingredient 250 g - isooctylphenoxypolyoxyethylene ethanol 25 g - equiponderal mixture of chalk
Champagne and hydroxyethylcellulose 17 g - sodium aluminosilicate 543 g - kieselguhr 165 g
Another composition of 10% spraying powder uses the following constituents
Example F 8 - active ingredient 100 g - mixture of sodium salts of sulphates
of saturated fatty acids 30 g - condensation product of naphtha acid
sulfonic acid and formaldehyde 50 g - kaolin 820 g
In order to obtain these sprayable powders or wettable powders, the active ingredients are intimately mixed in appropriate mixers with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously especially for application to the leaves of plants.

 In place of the wettable powders, pasta can be made. The conditions and methods of production and use of these pastes are similar to those of wettable powders or powders to be sprayed.

 As already mentioned, the aqueous dispersions and emulsions, for example the compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions may be of the water-in-oil or oil-in-water type and may have a thick consistency such as that of a "mayonnaise".

 The doses of use in the case of use as fungicides of the compounds according to the invention may vary within wide limits, in particular according to the virulence of the fungi and the climatic conditions.

 In general, compositions containing 0.5 to 5000 ppm of active substance are suitable; these values are indicated for ready-to-use compositions. Ppm means "part by million". The zone from 0.5 to 5000 ppm corresponds to a zone of 5x10 5 to 0.5% (weight percentages).

 As regards the compositions suitable for storage and transport, they more preferably contain from 0.5 to 95% (by weight) of active substance.

 Thus, the compositions for agricultural use according to the invention can contain the active ingredients according to the invention within very wide limits, ranging from 5.10 5% to 95% (by weight).

 Examples I to IV illustrate particular modes of preparation of compounds according to the invention as well as the properties of these compounds themselves. The nomenclature of the compounds was indicated according to the French standards except that the numbering of the substituents was put before the substituents themselves.

Example I: Preparation of 2- (4-chlorobenzylidene) 6-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanoides
To a mixture of 22.4 g of 2-methyl cyclohexanone and 28.1 g of para chlorobenzaldehyde in 250 ml of ethanol in OOC is added 100 ml of a 10% aqueous solution of sodium hydroxide. After stirring for 15 hours, the medium is diluted with water and extracted with ethyl acetate. The organic phase dried over Na 2 SO 4 is concentrated and the residue is chromatographed on silica with a 90/10 heptane / ethyl acetate eluent.

A yellow oil is obtained. This is crystallized from pentane to give a pale yellow powder (17.1 g) of 2- (4-chlorobenzylidene) 6-methylcyclohexanone with a melting point of 59 ° C.

3.8 g of this compound in solution in anhydrous THF (33 ml) are added to a reaction medium at -50C prepared in the following manner
0.8 g of sodium hydride (60% dispersion) are heated at 700 ° C. in 26 ml of dry DMSO, then 33 ml of anhydrous THF are added. The mixture cooled to -50 ° C. and treated with trimethylsulfonium iodide (3.9 g) dissolved in dry DMSO (20 ml).

 After 1 hour at -50 the 8- (4-chlorobenzylidene) 4-methyl-oxaspiro [2,5] octane thus formed is treated with triazole (2.2 g) and triazolylsodium (0.28 g). The medium is heated at 930 for 1 h 30 after distilling 30 ml of THF and adding DMF (50 ml).

 After dilution with water (11), the products are extracted with dichloromethane and the residue obtained by evaporation is purified by chromatography (eluent heptane / ethyl acetate 1: 1).

 The major diastereoisomer which has the methyl substituent and the hydroxyl in a cis-relative position and melts at 1390 (Compound No. 1) is obtained first, followed by the minor diastereoisomer which has the methyl substituent and the hydroxyl in the relative trans position in the form of honey (compound 2).

 Stereochemistry is assigned by nuclear magnetic resonance according to techniques well known to those skilled in the art.

Example II: PREPARATION OF 2- (4-Chlorobenzylidene) -6,6-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol
To a reaction medium prepared from toluene (25 ml) of tertamyl alcohol (3.6 ml) and sodium hydride (1.35 g of dispersion in oil at 60%) and heated to 450 ° C., successively added the 2- (4-chlorobenzylidene) 6-methyl cyclohexanone prepared above (7.0 g) and then methyl iodide (5.1 g). The mixture is refluxed (1 h) poured into water and extracted with ethyl acetate. After drying and concentration, the residue is recrystallized from methanol to give 2- (4-chlorobenzylidene) 6,6-dimethylcyclohexanone (4.7 g), m.p.

 The procedure of Example I is then applied to 4 g of this ketone to conduct after chromatography to the expected product melting at 1790C (compound No. 3).

 Examples III to VII illustrate the fungicidal applications of the compounds according to the invention.

 In these examples, the spraying solutions or suspensions of active materials are carried out under conditions such that the spraying of a solution or suspension of concentration equal to 1 g / l corresponds on average to the application of about 2 micrograms of material active per cm2 of leaf of the plant.

 Under the conditions of Examples III to VII, the illustrated compounds did not exhibit phytotoxicity.

 In these examples, it is considered that a product exerts a total protection against a fungal disease when the protection is at least 95%; protection is considered good when it is at least 80% (but less than 95%), good enough when it is at least 70% (but less than 80%), average when it is is at least 50% (but less than 70%).

 In this discussion, the percentages are, unless otherwise indicated and except those relating to yields, percentages by weight. In the case where the percentages are expressed with respect to the stoichiometry, these are molar percentages. Regarding the concentrations, some of them are expressed in ppm (parts per million) which corresponds to mg / l.

Example III In Vivo Test on Botrytis Cinerea on Excised Tomato Leaf
Finely grinding an aqueous suspension of the active ingredient to be tested having the following composition
- active substance to be tested: 60 mg
Tween 80 (surfactant) consisting of an oleate ae
polyoxyethylene derivative of sorbitan) diluted to 10% in
water: 0.3 ml
- complete with 60 ml of water.

 This aqueous suspension is then diluted with water to obtain the desired concentration.

 Tomatoes grown in a greenhouse (variety Marmande) aged 30 to 40 days are sprayed with aqueous suspensions (called slurries) as defined above and at various concentrations of the test compound. The test is repeated twice with each concentration.

 After 24 or 48 hours, the leaves are cut and placed in 2 Petri dishes (diameter 14 cm), the bottom of which has been previously filled with a wet filter paper disk (5 leaflets per box).

The inoculum is then brought with the help of a syringe by depositing drops (3 drops per leaflet) of a suspension of spores. This suspension of spores
Botrytis cinerea was obtained from a 15-day culture, then suspended in a nutrient solution (100,000 units / cm3).

 The control is done at 3 and 6 days after the contamination compared to an untreated control.

 Under these conditions, a good or complete protection with the compounds 1, 2, 3 is observed after 6 days at a dose of 1 g / l.

Example IV - In vivo test on Erysiphe graminis on barley (barley powdery mildew)
Barley, sown on a 50/50 pozzolan peat moss substrate, is treated at a height of 10 cm by spraying an aqueous suspension (called a slurry), as indicated above, with the concentration indicated below. . The test is repeated twice. After 24 hours, the barley plants are dusted with Erysiphe graminis spores, the dusting being done with diseased plants.

 The reading is done 8 to 14 days after the contamination.

 Under these conditions, the following results are observed: at a dose of 1 g / l, good or complete protection with the compounds 1, 2, 3.

Example V - In vivo test on - "Puccina recondita" responsible for wheat rust
Wheat, in pans, sown on a 50/50 pozzolan peat soil substrate is treated at the 10 cm height stage by spraying with aqueous suspensions (called slurries) of the same composition as that described in Example IV and at various concentrations of compound to be tested. The test is repeated twice with each concentration.

 After 24 hours, an aqueous suspension of spores (50000 sp / cm3) is sprayed on the wheat; this suspension was obtained from contaminated plants. The wheat is then placed for 48 hours in an incubation cell at about 180 ° C and 100% relative humidity.

 After 2 days, the relative humidity is reduced to 60%. The control of the condition of the plants is between the 11th and 15th day after the contamination compared to the untreated control.

 At a dose of 1 g / l, good or complete protection with the compounds 1, 2, 3.

Example VI - In Vivo Test on "Puccinia recondita by application in seed treatment
Talent variety wheat seeds are treated with the slurry of the preceding example at doses of 2.5, 5, 10, 25, 50 and 100 g / q, sown in a substrate composed of a 50/50 pozzolan peat moss mixture. 15 days after sowing the seedlings are inoculated with Puccinia recondita, according to the protocol described in Example V. The results are read 30 days and 45 days after sowing.

At the doses indicated with compounds Nos. 1 and 3, the percentage of infection is zero at 30 days after sowing, the seedlings resulting from untreated seeds being 100% contaminated.
EXAMPLE VII In Vivo Test on Fusarium roseun by Application in Seed Treatment
Wheat seeds var. Talent, naturally contaminated with Fusarium roseum are treated with a slurry described above in Example III at a dose of 50 g per 100 kg of seeds. Among 50 g of seeds treated, 200 seeds are deposited on a medium containing gelose and malt in the respective concentrations of 2% and 1%. The seeds are kept for 10 days at 200C.

The control of the condition of the seeds is done by comparison with the untreated control where colonies of Fusarium roseum have developed.

 At the dose of 50 g / 100 kg of seeds, good or complete protection is observed with the compounds 1, 2, 3.

 The example below illustrates the absence of phytotoxicity of compounds according to the invention with respect to seed growth.

Example VIII
Varying wheat grains are treated with a slurry at doses of 2.5, 10, 25, 50, 100, 200, 400 g / q.

The seeds are placed on a filter paper soaked in water. After 15 days of incubation at 250C, the lengths of the coleoptiles and the first leaves are measured for the compounds n0l and 3.

The results are shown in the table below:
dose g / q length (cm)
Coleoptiles and first leaves
0 13
12 13
25 13
50 13
100 12
200 13
400 12
Each value indicated above is the average of forty seedlings.

Claims (13)

1) Compounds with azolylmethylcyclohexane groups  benzilidene of formula in which

R <SEP>, <SEP> / <SEP> / <SEP> (X) n <tb> the <Tb> X is a halogen atom or a cyano group or  nitro, or a C1-C4 alkyl or C1-C4 group  optionally halogenated alkoxy, n is a positive integer or zero, less than 6,  groups X that can be identical or  different when n is greater than 1, W represents a trivalent group consisting of either a  group = CH-, that is to say a nitrogen atom = N-, R1, R2, identical or different, represent  the hydrogen atom or a C1-C4 alkyl radical  optionally substituted (for example by one or  several atoms or radicals such as atoms  halogen radicals, C1-C4 alkoxy radicals and  mono or polyhalo C1-C4 alkoxy radicals),  C3-C7 cycloalkyl, C6-C10 aryl (especially  phenyl), C7-C11 alkyl (especially benzyl),  these various radicals possibly being  substituted (for example by one or more atoms  or radicals such as halogen atoms,  C1-C4 alkyl radicals, mono or  polyhalo C1-C4 alkyl, C1-C4 radicals  alkoxy and mono or polyhalo C1-C4 radicals  alkoxy), R1, R2 together can form a  C2-C5 hydrocarbon chain constituting a ring  with the carbon to which R1, R2 are connected,  this chain being possibly substituted as  for C6-C1O aryl radicals previously  cited.  R3 to R5, identical or different, represent  the hydrogen atom or a C1-C4 alkyl radical  optionally substituted (for example by one or  several atoms or radicals such as atoms  halogen radicals, C1-C4 alkoxy radicals and  mono or polyhalo C1-C4 alkoxy radicals),  C3-C7 cycloalkyl, C6-C10 aryl (especially  phenyl), C7-C11 aralkyl (especially benzyl),  these various radicals possibly being  substituted (for example  by one or more atoms or radicals such as  halogen atoms, C1-C4 alkyl radicals,  mono or polyhalo C1-C4 alkyl radicals,  C1-C4 alkoxy radicals and mono or  polyhalo C1-C4 alkoxy),  and salified forms acceptable in agriculture  of these compounds. 2) Compounds according to claim 1, characterized in that  that X is a halogen atom and n = 1, 2 or 3. 3) Compounds according to claim 2, characterized in that  that n = 1 or 2 and X is a halogen atom,  preferably chlorine, placed in para if n = 1 and para,  meta if n = 2. 4) Compounds according to claim 1, characterized in that  that W is a group -N =. 5) Compounds according to claim 1, characterized in that  that R3-R5 are the hydrogen atom. 6) Compounds according to claim 1, characterized in that  that R1, R2 identical or different are chosen  among the methyl, ethyl or cyclic radicals  of less than 6 links or are the hydrogen atom to  with the exception of R1 R2 = hydrogen, preferably  R1 is methyl and R2 is hydrogen or methyl. 7) Use of the compounds according to one of the claims  1 to 6, as a fungicide, especially in the form of  fungicidal composition comprising 0.5% to 95% of  compounds in combination with solid supports or  acceptable liquids. in agriculture and / or these agents  surfactants also acceptable in agriculture. 8) Process for treating the affected or  likely to be affected by fungal diseases  characterized in that the sheets are applied to  effective amount of a compound according to one of  Claims 1 to 6. 9) Treatment method according to claim 8 in that  a dose of between 0.002 and 5 kg / ha is applied 12) Useful compounds especially as an intermediate in the  preparation of the compounds according to claims 1 to 6,  responding to the formulas.

 in which the substituents R1 to R8, X, n, have  the same meaning as in claims 1 to 6. 13) Propagation product of cultivated plants which has  undergone protective treatment with one of the compounds  according to one of claims 1 to 6 or a composition  according to claim 7, especially a seed. 14) Seed according to claim 13, having undergone a  protective treatment at the rate of 0.1 to 500g per  quintal. 15) Process for preparing the compounds according to  claim 1, characterized in that a reaction is  compound of formula V according to claim 12 with a  imidazole or a triazole in the presence of a base. 16) Process for the preparation of compounds of formula V, according to  claim 12, characterized in that one makes  react a compound of formula IV, according to the claim  12, with a sulfonium ylide.