DD298875A5 - BENZYLIDEN-AZOLYLMETHYLCYCLOALKANES OR ALKENES AND THEIR USE AS FUNGICIDES - Google Patents

Abstract

The invention relates to benzylidene-azolylmethylcycloalkanes or alkenes of the formulas in which: A and Al are hydrocarbon chains having from 1 to 3 carbon atoms, R 1, R 2, R 3, R 4 and R 5 are hydrocarbon radicals, X is a halogen, n is 1, 2 or 3, W is CH or N, as well as their use as fungicides. Formula IA and IB {Benzylideneazolylmethylcycloalkanes; Benzylidenazolylmethyl-cycloalkenes; fungicides; Schaedlingsbekaempfungsmittel; Seed treatment; Pilzbekaempfung; Basidiomycetes; Ascomycetes; adelomycetes; Fungi imperfecti; Powdery mildew; Cereal rust; gray mold}

Description

The present invention relates to novel compounds for plant hygiene use with Benzylidenazolylmethylcycloalkan or -alkene residues. The invention further relates to processes for the preparation of these compounds and to the products which may optionally be used as intermediates in these preparation processes. Finally, the invention relates to the use of these compounds as fungicides, fungicidal compositions based on these compounds and ancestors for combating fungicidal diseases on crops using these compounds. The invention also relates to a propagation product of crop plants which has undergone protective treatment with a compound of the invention.

There are already numerous substances with triazole groups, in particular fungicides known. In particular from the European patent applications EP1Ü1084,246982,121979,89100 known fungicidal triazoles with a tetrahydrofuran ring. European patent applications EP 272895.267778, German patent application DE 3630840 and Belgian patent application BE 867 245 disclose fungicidal triazoles having a cylopentane ring. From the European patent application EP 324646 and the US! ^J atent 4684396 fungicidal triazoles with cycloalkane radicals are known. US Pat. No. 4,160,038 discloses fungicidal triazoles having a dioxolane ring.

In view of this prior art, which is known to the Applicant and can be considered as state of the art within the meaning of rule 27-1, paragraph C, an object of the present invention is to provide other fungicidal compounds with a broad spectrum, in particular in diseases of the forehead such as blackleg or leaf diseases such as mildew, Septoriose, Pyrikulariosis, Fusariosen, Rhynchosporiose and by pathogenic fungi such. B. Botrytis, Phoma, Aschochyta caused diseases are applicable to different cultures such. As cereals, grapevines, rice, corn or soybeans

 These compounds are characterized by the following formulas IA or IB:

IA

* Vs ^

in which

A -CR ₀ R ₇ - OdBr-CR ₆ R ₇ CR ₈ R ₉ OdCr-CR ₆ R ₇ CR ₈ R ₉ CR ₁₀ R ₁ , -

A1 CR ₇ = ^ CR ₆ R ₇ -CR ₉ = OdBr-CReR ₇ -CRsRr-CRn =.

That is, the cycloalkane may be a cyclopentane, cyclohexane or cycloheptane or a cyclopentene, cyclohexene or cycloheptene.

X is a halogen atom, preferably fluorine, bromine or chlorine or a cyano or nitro group or a C | -C ₄ -Aikylrest or C ₁ -C ₄ -AIkOXYrCSt, which is optionally halogenisiert,

η is a positive integer or zero and less than 6, the radicals X could be identical or different if η is greater than 1,

W is a trivalent group consisting of either a = CH group or a nitrogen atom = N, R ₁ , R _{2 are} identical or different and each represents a hydrogen atom or a C ₁ -C ₄ -alkyl radical which is optionally substituted ( z. B. with one or more atoms or radicals such as. for example, halogen atoms, C, -C ₄ alkoxy, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, Cz-C ₄ alkenyl, C ₂ -C ₄ Alkinyl, mono- or polyhalogenated'C ₂ -C ₄ alkenyl, mono- or polyhalogenated C ₂ -C ₄ -AIkInVl) a C ₁ -C ₄ - alkoxy, which may optionally be substituted, (eg with one or more atoms or Radicals such as, for example, halogen atoms, C ₁ -C ₄ -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₁ -C ₄ -alkynyl, mono- or polyhalogenated C ₁ -C ₄ -alkenyl, mono- or polyhalogenated C ₁ -C ₄ -alkynyl) a C ₃ -C ₇ -cycloalkyl radical, a C 9 -C ₁₀ -aryl radical (in particular phenyl), a CH 2 n-aralkyl radical (in particular benzyl), where d These different radicals may optionally be substituted (z. B. with one or more atoms or radicals such. B. halogen atoms, CHV alkyl radicals, CC ^ alkoxy and mono- or polyhalogenated C ^ C ^ alkoxy radicals, where R ₁ and R ₂ together can form a Cj-CV hydrocarbon chain, which are bonded together with the carbon to the R ₁ and R ₂ , represents a ring, which chain may optionally be substituted as indicated by the aforementioned C ₆ -C ₁₀ radicals, or R ₁ and R ₂ together are a C ₁ -C 4 -hydrocarbon dioxolane chain with the carbon bonded to R ₁ and R ₂ , which chain is optionally substituted as indicated in the abovementioned Ce-Cio-aryl radicals,

R ₃ and R ₆ to R _{11 are} identical or different and represent a hydrogen atom or a CHV alkyl radical which is optionally substituted (for example with one or more atoms or radicals such as, for example, halogen atoms, C 1-4 -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy), or C ₃ -C ₇ cycloalkyl radical, Ce-do-aryl radicals (in particular phenyl) a C ₇ -C ₁ , -Aralkylreste (in particular benzyl), these different radicals may each be optionally substituted

(For example, with one or more atoms or radicals such as halogen atoms, C ₁ -C ₄ - alkyl radicals, mono- or polyhalogenated C ₁ -C ₄ -AlkYl, C ₁ -C ₄ alkoxy radicals and mono- or polyhalogenated C ₁ -C ₄ alkoxy), or two adjacent residues of chain A together with the atoms of A to which they are attached, form a fused phenyl or cycloalkane ring, R _{5 represents} a hydrogen atom, an optionally substituted C, -C ₄ alkyl (for example substituted with "one or more atoms or radicals such as. for example, halogen atoms, C ₁ -C ₄ alkoxy, mono- or polyhalogenated C, -C ₄ alkoxy, C ₂ -C ₄ -alkenyl, Cr -C ₄ alkynyl, mono- or polyhalogenated Cr-C ₄ alkenyl, mono- or polyhalogenated C ₂ -C ₄ alkynyl), a Cy-CrCycloalkylrest, C6-C ₁₀ aryl (especially phenyl), C ₇ -C Aralkyl radical, in particular benzyl), where these various radicals may optionally be substituted (for example with one or more atoms or radicals, such as, for example,

Halogen atoms, C, -C ₄ alkyl, mono- or polyhalogenated C, -C ₄ alkyl, C, -C ₄ alkoxy and mono- or polyhalogenated C ₁ -C ₄ -alkoxy), or R _{5 is} a radical C ( = O) -R ₁₃ , where R _{13 is} a

C 1 -C ₄ -alkyl radical is substituted or unsubstituted or substituted (eg with one or more atoms or radicals such as, for example,

Halogen atoms, Ci-C ^ AIkoxyresten mono- or polyhalogenated C, -C ₄ alkoxy, C ^ Cr-AIkenyl, C ₂ -C ₄ -AIWnVl, mono- or polyhalogenated Cj-CvAlkenyl, mono or polyhalogenated C2-C · ₄ Alkynyl) is a C 1 -C 6 cycloalkyl radical, C 9 -C 10 aryl radical (especially phenyl), C 1 -C 6 aralkyl radical (in particular benzyl), these various radicals being optionally substituted (for example with one or more atoms or radicals, such as ., for example, halogen atoms, Ci-C ₄ alkyl, mono- or polyhalogenated C | -C ₄ alkyl, C ₁ -C ₄ alkoxy and or polyhalogenated Ci-C ₄ alkoxy), a Cj-C ₄ -Ethinylrest or mono- or polyhalogenated C 1 -C 4 ethynyl

Ri _{2 has} one of the meanings given for R ₅ , with the exception of C f = O) -R ₁₃ , R _{4 represents} a hydrogen atom, a halogen atom, in particular a chlorine or bromine atom, a C ₁ -C ₄ -AlkYIrCSt which optionally substituted is (for example, with one or more atoms or radicals such as, for example, halogen atoms, _C..) -C ₄ alkoxy, mono- or polyhalogenated _Ci-C4 -alkoxy, C ₂ -C ₄ - alkenyl, Cj-C AIkinyl, mono- or polyhalogenated Cj-CvAlkenyl, mono- or polyhalogenated Cj-C ^ AIkinyl) a Cr-C ₇ - cycloalkyl radical, Cj-Cio-aryl (especially phenyl), C ^ -Cu-aralkyl (especially benzyl), wherein these various radicals may optionally be substituted UB having one or more atoms or radicals such as halogen atoms, C 1 -C ₄ -alkyl radicals, mono- or polyhalogenated C 1 -C ₄ -alkyl radicals, C 1 -C ₄ -alkoxy radicals and mono- or polyhalogenated C 1 -C ₄ -alkoxy).

The invention also relates to the salt forms of the compounds of the invention. Salt forms include agriculturally acceptable salts, e.g. may call: the chlorohydrates, sulfates, oxalates, nitrates or arylsulfonates such. As the addition complexes of these compounds with metal salts and in particular salts of iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum.

So z. B. the complexes are obtained with zinc by reacting the compound of formula I with zinc chloride.

Unless specified otherwise, the radicals mentioned can each be branched or linear in the present text. The term "optionally halogenated" means optionally mono- or polyhalogenated.

In the formula I wire Id, the symbol paves the symbol

that the stereochemistry of the double bond can be indiscriminately either E or Z or a mixture of these two.

In view of the steric hindrance, the predominant form will be that where R _{) 2} is in the Z position with respect to R ₃ , R ₄ .

The compounds of formulas I and the substances which may optionally be used as intermediates in the preparation processes of these compounds, which are defined as appropriate in the description in the preparation processes, may exist in one or more isomeric forms corresponding to the number of asymmetric centers of the molecule. The invention relates equally well to all optical isomers and their racemic mixtures and the corresponding diastereomers of these compounds. The separation of the diastereomers and / or the optical isomers can be carried out by means of methods known per se.

With regard to the fungicidal applications, it has been found that those compounds are preferred according to the invention in which in the formula IA or IBn = 1,2 or 3 and preferably X is a halogen selected from chlorine, bromine or fluorine.

It has furthermore been found that it is preferable to use compounds of the formula IA or IB in which η = 1 or 2 and X is a halogen atom which is in the para position when η = 1 and in meta-para or ortho-para position when η = 2, where preferably η = 1 and X is in the para position. The position E is practically obtained as the only form when Ri ₂ H

It has proved to be very advantageous if X is a chlorine atom.

In view of the above-mentioned limitations taken alone or in combination, it has been found that it is preferable, in view of the fungicidal properties, to use compounds of formula I in which W-N =.

If appropriate, taking into account the aforementioned limitations taken alone or in combination, it has further been found that, in view of the fungicidal properties of the compounds, it is preferable to employ compounds of the formulas IA and IB in which R ₃ , Re, Re and R _t0 each represent a hydrogen atom, and preferably R _4, R _7, Rg and Rn represent a hydrogen atom or a Ci-C ^ AIkylrest.

With or without the aforementioned limitations taken alone or in combination, it has further been found that it is preferable, in view of the fungicidone properties, to use compounds of the formula IA or IB in which Ri and R _{2 are} selected from the radicals methyl and ethyl or are a hydrogen atom.

With or without the aforesaid limitations taken alone or in combination, it has further been found that, in view of the fungicidal properties, compounds in which R _{6 is} a hydrogen atom or a C 1 -C ₄ -alkyl radical, more preferably R, are preferably used _{5 is} a hydrogen atom.

With or without consideration of the aforementioned limitations, alone or in combination, it has further been found that, in view of the fungicidal properties, compounds in which R] _{2 is} a hydrogen atom are preferably used.

With or without consideration of the aforementioned limitations per se or in combination, it has been found that more preferably with respect to the fungicidal properties, compounds of the formulas IA are used, in which preferably A CR ₈ R ₇ or CR ₆ R _{7 is} CRsR ₉ .

Preferably, in view of the activity when applied to leaves (especially against botrytis) as well as lacking phytotoxicity, which allows application in the treatment of seeds, triazoles of the formula IA in which A CR ₆ R? R j, R _{2 are} selected from methyl or ethyl radicals, R ₃ , R ₆ to R ₇ and R ₁₂ are hydrogen, R _{4 is} methyl, ethyl, n-propyl, i-propyl or a hydrogen atom, or A is CReR ₇ CR ₈ Rg is wherein R) and R _{2 are} selected from the groups methyl, ethyl or hydrogen, R ₃ , R ₆ to R ₉ and R ₁₂ are hydrogen and R _{4 is} methyl, ethyl, i-propyl, n-propyl or a hydrogen atom

 The following compounds are preferred:

2- (4-chlorobenzylidene) -5-methyl-5-ethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol

2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol

2- (4-chlorobenzylidene) -6-methyl 1- (1H-1,2,4-triazol-1-ylmethyl) 1-cyclohexanol

2- (4-chlorobenzylidene) -6,6-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohoxanol

2- (4-chlorobenzylidene) -1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol

The invention also includes the processes for the preparation of the compounds of the invention.

In the following description, the substituents have the same meaning as given above unless otherwise stated.

A - Compounds of Formol IA

The method consists of the chloride of an omega-alkenoic acid of the formula

CO Cl

react to leave, in which R ₁ and R _{2 is} a C | can represent -C ₄ alkyl, the mono- or with one or more C ₂ -C ₄ alkenyl radicals, _C2-C4 alkynyl radicals polyhalogenated Cr-C ₄ Alkenylresten, mono- or polyhalogenated Cr-C ^ Alkinylresten or a C, -C ₄ alkoxy substituted in the presence of aluminum chloride in an inert solvent such as. For example, dichloromethane or carbon disulfide or nitromethane as described in the literature by KR KOPECKY et al in Can. J. Chem. 59, 3273 (1981) and W. CAGOSTA et al in J. Am. Soc 93,5513 (1971) is described, so that a mixture of cycloalkanol! and cycloalkenone of the formula:

III IV

is obtained.

In the compound of formula IV or-CR corresponds to residues A1H -CR ₇ H, ₆ Rt-CR ₉ H, or CR ₆ R ₇ -CR ₈ Rg CRi ₁ H and that is only obtained when A is A1H.

In the event that one wishes to obtain a compound V in which R _{4 is} a hydrogen atom, the compound of formula III is subsequently subjected to a catalytic hydrogenation to give the compound,

to obtain.

In the event that one wishes to prepare a compound of formula V above in which R _{4 is} not a halogen atom or hydrogen atom, reacting a magnesium compound of the formula R ₄ M (M = MgHaI), which is obtainable in a conventional manner, z. By reacting the compound of formula R ₈ J with magnesium in the presence of ether with a cycloalkenone of formula III in the presence of a catalytic amount of copper iodide at low temperature in a polar solvent. Water is then added to the mixture to isolate the compound of formula V. The cycloalkanone of the formula V thus obtained in which R ₁ and R _{2 have} the same meaning as in the general formula, with the exception that they can not represent a C) -C ₄ -alkyl radical, the mi 'sin or more C ^ C. ^ Alkenyl, C ₂ -C ₄ -AIkInVl, mono- or polyhalogenated CHVAIkenyl, mono- or polyhalogenated C ₂ -C ₄ -AIkInVIrBSt or a C ^ C ^ alkoxy substituted, wherein R _{4 has} the same meaning as in the general formula except that it can not represent a halogen atom, wherein R ₃ , R ₆ and R _{7 have} the same meaning as in the general formula, the well-known aldolization Crotonisierungsreaktion is subjected, by condensation with a benzaldehyde of the formula

Vl

to give compounds of formula VII in which Ru is a hydrogen atom: O

To obtain a compound of the formula VII in which R _{12 is} different from hydrogen, a silyl ether of the formula XI is allowed:

xl

with a ketal of formula XII

XII

react in which R _{16 represents} a C, -C ₄ -Alky! rest, wherein first the ketal of the formula XII with a titanium tetrachloride in a halogenated solvent such as. B. Dichloromethane at about ^{0 0} C and then the silyl ether of formula Xl at about 0 ^c C and then added and hydrolyzed with HCl as described in T. NUKAIYANA et al J. Am. Chem. Soc. 1974,96,7503 is described.

In order to obtain a compound of formula VII in which R _{1 is} an alkyl or aralkyl group which is optionally substituted according to the definition given in the general formula wherein R _{2 is} not hydrogen and is not substituted by one or more C ₂ -C 4 Alkenyl, C ₁ -C ₄ alkynyl, C ₂ -C ₄ alkynyl mono- or polyhalogenated C ₁ -C ₄ alkyl, another method is to prepare one of the ketones of formulas III, V, VII prepared as described above in which Ri is a hydrogen atom and R _{2 is} not hydrogen and not a C) -C ₄ - optionally substituted by one or more C 1 -C ₄ -alkenyl, C 1 -C 6 -alkynyl, mono- or polyhalogenated C 1 -C ₄ -alkynyl, Alkyl radical is to react with an alkylating agent R | -Y: in which R _{1 represents} an alkyl or aralkyl group which is optionally substituted as defined above in the general formula, and in which Y is an leaving group such as. As halogen, sulfonate or sulfate, z. Example, in the presence of an organic or mineral base, preferably a hydroxide, alkoxide or alkali or alkaline earth metal hydride in a protic or aprotic solvent or solvent mixture such as a saturated, unsaturated or aromatic hydrocarbon which is optionally halogenated, an alcohol, an amide, a nitrile , or a solvent in which an oxygen-bound sulfur is present, such as. DMSO or sulfolane. In this way, ketones of the formulas III, V or VII are obtained. In the event that ketones of the formula III or V have been obtained, which is possible in the case of one of the abovementioned routes, the conversion process indicated above is then carried out To obtain ketones of formula VII.

In order to obtain a compound of formula VII wherein Ri and R _{2 are} identical and each represents an alkyl or aralkyl group as defined by the general formula, another method is to use a ketone of formula III, V or VII as indicated above in which R ₁ and R _{2 represent} a hydrogen atom, reacting with an alkylating reagent R ₁ -Y in which R _{1 represents} an alkyl or aralkyl group as defined by the general formula and Y represents a leaving group such as halogen, sulfonate or sulfate, in the presence of an organic or mineral base, preferably a hydroxide, alkoxide or alkali or alkaline earth hydride, in a protic or aprotic solvent or solvent mixture, such as. In a saturated, unsaturated or aromatic hydrocarbon, the

optionally halogenated, in an alcohol, an amide, a nitrile or a solvent with sulfur-bonded oxygen such as DMSO or sulfolane. Sometimes it is possible to isolate an intermediate in which only one of R ₁ , R _{2 represents} an alkyl or aralkyl group as defined above. These compounds VII are also suitable for obtaining the compounds I according to the methods described herein. In the case where a ketone of the formulas III or V has been obtained, which is possible in one of the abovementioned ways, the subsequent conversion process is then carried out to obtain ketones of the formula VII.

In the event that Ri and R] form a C ₂ -C ₆ hydrocarbon chain, a compound of the formula YR ₃ -Y in which R ₉ represents a C ₁ -C hydrocarbon radical, which is optionally substituted, is left in the same way as before (For example, with one or more atoms or radicals such as halogen atoms, Ci-Cn-alkyl radicals, mono- or polyhalogenated Ci-C ₄ -alkyl radicals, C) -C4-alkoxy and mono- or polyhalogenated Ci-C ^ alkoxy) with a ketone of Reacting formula III, V, VII, wherein R ₁ and R _{2 represent} hydrogen atoms, while maintaining the above-mentioned method.

In the case where Ri and / or R _{2 represent} an allyl group, another method is to use a ketone of the formula V in which R ₁ and R _{2 represent} hydrogen atoms with 2 moles of allyl alcohol and 1 mole of 2,2-dimethoxypropane react in the presence of a catalytic amount of paratoluene sulfonic acid and in an inert solvent such as toluene to obtain the corresponding monoallylated ketone, as described by WL Howard and NB Lorette in Org. Synth. 42, 34 (1964).

This ketone is then reacted with the compound of formula VI as indicated above, and another allyl radical is introduced by alkylation by the method given above.

In the event that R ₁ and / or R _{2 are} C 1 -C ₄ -alkoxy radicals, it is advantageous to start from a cycloalkanone of the formula V in which the alkoxy radical (s) have already been introduced beforehand, by means of the prior art known methods (eg by reaction of the a-brominated ketones with Aikalialkoholaten).

Another general method for preparing ketones VII in which at least one of R ₁ , R _{2 is} hydrogen is to prepare an enamine starting from a cycloalkanone V in which at least one of R ₁ and R _{2 is} hydrogen, by the method of BC McKUSICK, FE NURFORD Org. Synth. Coil. Vol. V, 808 and then the latter with a benzaldehyde VI according to L.BIRKOFFER, SMKIM, HDENGELSChem. Ber. (1962), 95, 1495. According to this article, the acidic hydrolysis then leads to the ketones VII, in which at least one of the radicals R ₁ , P _{2 is} hydrogen.

The said compound of formula (VII) is reacted with a sulfurylidene as described by EJ. COREY M. CHAYKOVSKY in J. Am. Chem. Soc. 87,1313 (1965) to the oxiranes of the formula:

IX

to obtain. The oxirane of the formula (IX) is then allowed to react with an imidazole or a triazole which is unsubstituted in the presence of an organic or mineral base, for example pyridine, triethylamine, soda, potash, a carbonate or a bicarbonate of an alkali or alkaline earth metal or a hydride reacting an alkali metal in a suitable solvent such. Example, an alcohol, ketone, amide, nitrile or an optionally halogenated aromatic hydrocarbon at a temperature between 80 ° C and the reflux temperature of the solvent and in a molar ratio IX: imidazole or triazole, which is preferably between 1.1 and 0.2 which eventually leads to compounds of the formula I in which Rs is a hydrogen atom and R ₄ is other than halogen, the other substituents having the same meaning as indicated in the general formula.

The compounds of the formula I in which R _{4 is} a halogen atom and R _{5 is} a hydrogen atom are obtained by allylic halogenation of the compounds of the formula I in which R ₄ and R _{5 are} hydrogen atoms with the aid of NBS (N-bromosuccinimide) , NCS (N-chlorosuccinimide), t-BuOCl in CC 14 in the presence of peroxides or UV light according to the method of L. HORNER, EHWINKELMANN, in Angew. Chem. 71, 349, (1959).

The compound of formula I in which R ₅ is other than hydrogen and R _{4 is} other than halogen is obtained by etherification or esterification of the compounds of formula I in which R _{5 is} hydrogen and R _{4 is} other than halogen Using conventional methods known in the art: The ethers can be obtained by treating an alkali metal salt of an alcohol of formula I (e.g., a lithium salt or sodium salt) with a suitable halide of formula R ₅ Hal. The esters can be obtained by conventional methods by treating an alkali metal salt of formula (I) with the appropriate acid chloride of formula R ₆ C = OCI or the corresponding anhydride of formula (R ₈ I ₂ O ₂ C = O.

The compounds of formula (I) wherein R _{4 is} halogen and R _{5 is} other than hydrogen are obtained in a first esterification or etherification step as described above from a compound of formula (I) wherein R s and R ₄ Are hydrogen atoms and subsequent halogenation of the resulting compound of formula (I), as described above, for example with NBS.

The compounds of the formulas XI and XII are obtained by methods known per se from the prior art. For example, one can acetalize the corresponding benzophenone in an acidic medium with an alcohol R ₁₀ OH, if it is the compound of formula XII. To the corresponding cyclopentanone can be given trimethylsilyl chloride in the presence of dimethylformamide and triethylamine, if it is the compound of formula XII.

B Compounds of the formula IB in which A1 represents CR ₇

The cyclic ketone of the formula IiV) is subjected to the well-known aldolization / crotonization reaction by condensation with a benzaldehyde of the formula VI to obtain the compound of the formula VIII:

VIII

Said compound of formol (VIII) is reacted with a sulfonium ylide as described in E.J. COREY Michael CHAYKOWSKY J. Am. Chem. Soc. 87,1313, (1965) to form an oxirane of the formula:

to obtain.

The oxirane of the formula (X) is allowed to react with an imidazole or triazole which is unsubstituted in the presence of an organic or mineral base such as e.g. As pyridine, triethylamine, soda, potash, a carbonate or bicarbonate of an alkali metal ir sinem suitable solvent such. An alcohol, a ketone, an amide, a nitrile or an aromatic optionally halogenated hydrocarbon, at a temperature of between 80 ° C and the reflux temperature of the solvent and in a molar ratio IX to imidazole or triazole of preferably between 1.1 and 0, 2, whereby compounds of formula IB are obtained:

IB

in the R ₅ = Hist.

The same methods to alkylate or allylate the α-position to the hydroxy group (R ₁ , R ₂ ) as described above are also applicable to prepare a compound in which R _{6 is} different from H. Of course, other manufacturing processes can equally well be used. The invention also relates to the compounds which may optionally be used as intermediates in the preparation processes described above and correspond to the formulas III, IV, V, VII, VIII, IX and X which are described oban, in which the substituents A A1, X, n, R) to Rs and R _{) 2 have} the same meaning as in claim 1. The present invention also relates to the use of compounds of formula I as fungicides. The compounds according to the invention can be employed either for preventive or curative purposes for the control of fungi, in particular against fungi of the type Basidiomycetes, Ascomycetes, Adelomycetes or fungi-imperfecti, in particular rust, mildew, blackleg, fusaroses, fusarium roseum, fusarium nivale, helminthosphorioses, Rhynchosporiosen, Septorioses, rhizoctones on vegetables and plants in general and especially in cereals such. Weizon, barley, rye, oats and their hybrids as well as rice and corn. The compounds of the invention are particularly effective against fungi, in particular of the type Basidiomycetes, Ascomycetes, Adelomyceten or fungiimperfecti 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, Moniiia laxa, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria soiani, Aspergiiius niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestalozzia sp. Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma Hungary, Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia sclerotiorum, Sclerotinia minor, Coryneum cardinale, Rhiuoctonia soiani.

They are also and additionally effective against the following fungi: Acrostalagmus koningi, 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 sanguineu3, Poria vaporaria, Sclerotiurn rolfsii, Stachybotris atra, Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

The compounds according to the invention are of particular interest because of their broad spectrum of action against cereal diseases (mildew, rust, blackleg, helminthosporiosis, septorioses and fusarioses). They are also of interest for their effectiveness against gray mold (Botrytis) and cercosporioses and for this reason can be applied to crops as diverse as vines, vegetables, tree crops and also tropical crops such as e.g. Peanuts, bananas, coffee plants, pecans and others.

In view of the lack of phytotoxicity of these compounds, these can be used for the protection of the propagation products of plants for the control of fungal diseases.

The invention thus also relates to a propagation product of crop plants which has been subjected to a protective treatment with a compound according to the invention.

"Propagation product" refers to all generative parts of the plant that can be used for their reproduction, such as the seeds (seeds in the strict sense), roots, fruits, tubers, onions, rhizomes, parts of the stem, the plants ( Shoots, shoots) and other parts of the plants, as well as the sprouted plants and the young plants that have to be transplanted after they have germinated or left the soil.These young plants can be completely or partially transplanted before transplanting Treatment to be protected by watering.

In general, these compounds are used in an amount of 0.1 g to 500 g per pound of grains.

In this way, these compounds can be used in the treatment of seeds (for example of cereals, cotton, beets, oilseed rape, forage crops or vegetables), e.g. B. by wrapping or with a film. In US-PS 3989501, column 7, lines 17-23 can be found such an application form. Also in FR-A-2588442. Concentrated suspensions can be used with equal difficulty.

In general, these formulations are already known, they are found z. In the "catalog of pesticide formulation types and international coding system" published by GIFAP technical monograph No. 2, pages 12-14, revised in January 1984.

Besides the applications already described above, the products according to the invention also show an excellent biocidal activity with regard to numerous other varieties of microorganisms, of which one may cite examples without mentioning the fungi, such as those of the species:

- Pullularia, z. ß. the species P. pullulans,

- Chaetomium, z. The species C. globosum,

Aspergillus, e.g. The species Aspergillus niger,

- Coniophora, z. For example, the species Coniophora puteana.

Because of their biocidal efficacy, the products of the present invention are effective in controlling microorganisms whose rapid multiplication leads to numerous agricultural and industrial problems. Because of this, these are particularly well suited for the protection of plants or industrial products, such. As wood, leather, paints, paper, rope, plastics and industrial Wa jserkreisläufen.

They are particularly well suited for the protection of lignocellulosic products and especially wood, both for furniture wood, timber and wood, which is exposed to the weather, such. As fence posts, pegs for grapevines or railway sleepers.

The compounds of the present invention, either taken alone or in the form of compositions of the type defined above, are generally used together with organic solvents and may optionally be combined with one or more known biocidal substances, such as e.g. As pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium, zinc derivatives of mineral acids or carboxylic acids (heptanoic acid, octanoic acid, naphthenic acids, organic complexes of tin, mercaptobenzothiazole and insecticides such as.

the pyrothroids and organochlorine compounds are combined. '

The invention also relates to a process for the treatment of fungal diseases or crops which are to be reckoned with such infestation, characterized in that an effective dose of a compound according to the invention is applied to the leaves.

The compounds are preferably used in dosages of 0.002 to 5 kg / ha and in particular from 0.005 to 1 kg / ha.

In practice, the compounds according to the invention are rarely used on their own. Mostly they are part of compositions. These compositions, which are suitable for the protection of plants against fungal diseases or compositions which regulate plant growth, contain as active ingredient a compound of the invention as described above in association with solid or liquid carriers which are agriculturally and / or also suitable for agriculture surface active agents, in particular inert conventional carriers and conventional surface-active agents are suitable.

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

The term "carrier" in this application refers to an organic or mineral, natural or synthetic substance with which the active ingredient is combined in order to facilitate its application to the plant, to seeds or to the soil The carrier may be solid (clays, natural silicates or synthetic silicates, silicic acid, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied petroleum gas, etc.).

The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type. For example, the polyacrylic acid salts, SaUo of lignosulfonic acids, salts of phenolsulfonic acids or naphthalenesulfonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acids or fatty amines, substituted phenols (in particular alkylphenols or arylphenol), salts of the esters of sulfosuccinic acids, derivatives of taurine (especially alkyl taurates), Phosphoric acid esters of alcohols or polyoxyethylated phenols. The presence of at least one surface active agent is generally essential if the active ingredient and / or the inert carrier are not soluble in water and the applying agent is water.

These compositions may also contain any kind of other ingredients, such as. As protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestering agents, etc., as well as other known active substances having pesticidal properties (especially insecticides or fungicides) or with properties that promote plant growth (in particular fertilizers) or with properties that regulate plant growth.

More generally, the compounds of this invention can be combined with any type of solid or liquid additive that conforms to conventional formulation techniques.

When used, the compounds of the formula (I) according to the invention are therefore generally present in the form of compositions. According to the invention, these compositions can be present in very different forms, solid or liquid.

As forms of solid compositions may be mentioned powder for the dusting or dispersions (containing up to 100% of the compound of formula (I) and also granules, especially those obtained by extrusion, compaction, impregnation of a granulated carrier or granulation from a powder (the content of the compound of the formula (I) in these granules may be between 1 and 80% in the latter cases).

As an example of a granule composition, the following components may be used:

Example P 9 50 g active substance 2.5 g Eplchlorhydrin 2.5 g Cetyl and polyglycol ethers 35 g polyethylene glycol 910g Kaolin (grain size 0.3 to 0.8 mm)

In this particular case, the active ingredient is mixed with epichlorohydrin and dissolved in 60 g of acetone. Then, the polyethylene glycol and the cetyl and polyglycol ether are added. The kaolin is poured into the resulting solution and the acetone is evaporated in vacuo. It is advantageous to use such microgranules for controlling soil fungi.

The compounds of formula (I) may also be used in the form of powders for pollination. It is also possible to use a composition containing 50 g of active ingredient and 950 g of talc. It is equally possible to use a composition containing 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc. Mix and mill these ingredients and then apply the mixture by atomization.

As forms of liquid compositions or compositions which are liquid in use, there may be mentioned solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or atomisable powders) or plastics.

The emulsifiable or soluble concentrates usually contain 10 to 80% active ingredient, the ready-to-use emulsions or solutions, however, contain 0.01 to 20% active ingredient.

In addition to the solvent, the emulsifiable concentrates z. If necessary, contain from 2 to 20% of suitable additives such as stabilizers, surface active agents, penetrants, corrosion inhibitors, dyes or adhesives as described above.

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

Example F (formulation) 1

Active ingredient 400 g / l

Alkalidodecylbenzenesulfonate 24 g / l

oxethylated nonylphenol with 10 molecules of ethylene oxide 16 g / l

Cyclohexanone 200 g / l

aromatic solvent up to 1 liter

As another formulation of an emulsifiable concentrate one can use: Example F ?.

Active ingredient 250 g

epoxidized vegetable oil 25 g mixture of Alkoylarylsulfonat and

Polyglycol ethers and fatty alcohols 100 g

Dimethylformamide 50g

Xylene 575 g

Starting from these concentrates, it is possible, by dilution with water, to obtain emulsions of any desired concentration, which are particularly well suited for application to leaves.

The concentrated suspensions, which may also be applied by sputtering, are prepared to give a liquid stable product which does not set and generally contain from 10 to 75% active ingredient, 0.5 to 15% surface active agents, 0, 1 to 10% thixotropic agents, 0 to 10% suitable additives such as Antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives and as carriers they contain water or an organic liquid in which the active ingredient is little or not soluble. Certain organic solids or mineral salts may be dissolved in the carrier to prevent sedimentation or as antifreeze for the water.

The wettable powders (or atomisable powders) are usually prepared to contain from 20 to 95% active ingredient and generally contain, in addition to the solid carrier, 0 to 5% wetting agent, 3 to 10% dispersant and, if necessary, 0 to 10%. one or more stabilizers and / or other additives such as penetrants, adhesives, anti-caking agents, dyes, etc.

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

Example F 3

Active ingredient 50%

Calcium lignosulfonate deflocculant) 5%

Isopropylnaphthalenesulfonate (anionic wetting agent) 1%

Silica anti-caking agent 5%

Kaolin (filler) 39%

Another composition of atomizable powder with 70% active ingredient consists of the following constituents: Example F 4

Active ingredient 700 g

Sodium dibutylnaphthylsulfonate 50 g of condensation product in the ratio 3: 2: 1

from naphthalenesulfonic acid, phenolsulfonic acid and formaldehyde 30g

Kaolin 100g

Champagne chalk 120 g

Another composition of atomizable powder with 40% active ingredient contains the following ingredients: Example F 5

active substance 400 g sodium lignosulfonate 50 g sodium dibutylnaphthalenesulfonate 10g silica 540 g

Another composition of a nebulizable powder with 25% active ingredient contains the following constituents: Example F 6

active substance 250 g calcium lignosulfonate 45 g Mixture of equal parts by weight Champagne chalk and hydroxyethylcellulose 19g sodium dibutylnaphthalenesulfonate 15g silica 195g champagne chalk 195g kaolin 281g

Another composition of a nebulizable powder with 25% active ingredient contains the following ingredients: Example F 7

active substance 250 g Isooctylphenoxy-polyoxyethylene ethanol 25 g Mixture of equal parts by weight of champagne chalk and hydroxyethyl cellulose 17g sodium aluminosilicate 543 g diatomaceous 165g

Another composition of a nebulizable powder with 10% active ingredient contains the following ingredients:

Active ingredient 100 g

Mixture of the sodium salts of sulfates of saturated fatty acids 30 g

Condensation product of naphthalenesulfonic acid and formaldehyde 50 g

Kaolin 820g

In order to obtain wettable or atomisable powders, the active ingredients are thoroughly mixed with the additional substances in suitable mixing devices and ground in mills or other suitable grinding devices. This gives atomizable powders whose wettability and suspendability is favorable. It can be brought into suspension with the aid of water in any desired concentration, and these suspensions are very suitable in particular for application to the leaves of plants.

Instead of wettable powders one can also make pastes or doughs. The conditions and modalities of preparation and use of these pastes are similar to those of wettable or atomizable powders.

As already stated, the aqueous dispersions and emulsions, e.g. those compositions obtainable by diluting a wettable powder or an emulsifiable concentrate according to the invention with water, of the general scope of the present invention. The emulsions may be of the water-in-oil type

or oil-in-water type, and they can have a thick consistency such as B. have a "mayonnaise".

The application doses are variable in the case of application of the compounds of the invention as fungicides within wide ranges, in particular in dependence on the virulence of the fungi and on the climatic conditions.

In general, compositions containing 0.5 to 5000 ppm of active ingredient are well suited. These values are given for ready-to-use compositions. Ppm means "part per million parts". The range of 0.5 to 5000 ppm corresponds to a range of 5 × 10 ^-6 to 0.5% (weight percent).

Dio storable and transportable compositions contain advantageously 0.5 to 95 wt .-% of active ingredient.

Thus, the compositions of the invention suitable for agricultural use can contain the active compounds according to the invention in very wide ranges, from 5 10 " ⁵ % to 95% (wt .-%).

The following examples illustrate the particular production methods of the compounds according to the invention and these compounds themselves.

Example I

Preparation of 2- (4-chlorobenzyllene) -5,5-dimethyl-1- (1H-1,2,4-triazole-1-7-methyl) -cyclopentanol To a mixture of 10 g of 2,2-dimethylcyclopentanone and 13.8 g of 4-chloro-benzaldehyde in 100 ml Ethanol is added at 0 ° C 100ml of an aqueous 10% sodium carbonate solution. After 30 minutes, a thick slurry is filtered and the washed solid is then dried. This gives 12.5 g of 2 2-dimethyl 5- (4-chlorobenzylidene) 1-cyclopentanone having a melting point of 120 ° C. This compound was dissolved in 50 ml of THF added to a solution formed in the following manner: 1.9 g of sodium hydride (80% dispersion in mineral oil) in 50ml anhydrous DMSO is heated to 80 ⁰ C until complete solution of the solid. Then the solution is diluted with 100 ml of THF and then cooled to -10 ° C. Are added to the mixture within 10 minutes a solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethylsulfoxide added and the mixture is stirred 15m; nAn -1O ⁰ C. A solution of 11.8 g 2,2-dimethyl-4 Chlor5- (4-chlorobenzylidene ) 1-cyclopentanone is then added in 100 ml of THF.

The mixture thus prepared is allowed to stand at room temperature, then poured into the water and extracted with ether, washed with water, dried and distilled. This gives 7- (4-chlorobenzylidene) 4,4-dimethyl-1-oxaspiro (2,4) heptane, which is used directly for the next step.

A mixture of 5 g of the product with 2.8 g of 1,2,4-triazole and 11 g of potassium carbonate is heated in 40 ml of N, N-dimethylformide for 4 hours. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the expected product having a melting point of 154 ^° C. (Compound No. 1).

In the same way, the following compounds were obtained:

2- (4-fluorobenzylidene) 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 147 ⁰ C) Compound No. 2.

2- (2,4-dichlorobenzylidene) -5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl-1-cyclopentanol (m.p .: 13O ⁰ C) Compound No. 3.

2- (4-trifluoromethylbenzylidene) -5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (m.p. 132 ⁰ C) Compound

2- (4-Chlorobenzylidene) 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil) Compound No. 5.

2-Benzylidene-1- (1H-V, 4-triazol-1-ylmethyl) -1-cyclopentanol (oil) Compound No.6.

2- (4-bromobenzylidene) -5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl-1-cyclopentanol (m.p. 152 ⁰ C) Compound No.7.

2-benzylidene 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 137 ⁰ C) Compound No. 8.

2- (3,4-dichlorobenzylidene) 5,5-dimethyl 1 - (1H-1,2,4-triazol-1-ylmethyl-1 -cyclopentanol (m.p. 157 ⁰ C) Compound No.9.

2- (4-Chlorobutylidene) 5-methyl-1- (1H-1,2,4-triazol-1-ylmethyl-1-cyclopentanol (oil) Compound No. 10.

2- (2-chlorobenzylidene) -5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentaiol (oil) Compound No. 11.

2- (4-Phenylbenzyüden) 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 167 ⁰ C) Compound No.12.

2- (4-chlorobenzylidene) 5-methyl5-ethyl1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 144 ⁰ C) compound no.. 13

2- (4-chlorobenzylidene) 5,5-dimethyl 1- (1 H-1,2,4-triazol-1-ylmethyl) -1-methoxy-cyclopentane (melting point 84 ⁰ C) compound

2- (4-chlorobenzylidene) 4,5,5-trimethyl1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 148 ⁰ C) compound no. 15 °.

2- (4-chlorobenzylidene) of 5-mothyl 5-methoxymethyl 1- (iH-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 109 ⁰ C) Compound No.. 16,.

a ^ -Chlorbenzylidenlö.S-din-propyli-dH-i ^^ - triazol-i-ylmethyD-i-cyclopijntanol (melting point 123 ⁰ C) Compound no. 17.

2- (4-chlorobenzylidene) 5,5-diethyl. 1 - (1 H-1,2,4-triazol-1-cyclopentanol -ylmethylM (melting point 171 ⁰ C) of compound # 18.

2- (4-fluorobenzylidene) 5,5-diethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 166 ⁰ C) prebinding No.19.

2- (4-fluorobenzylidene) 5,5-din-propyl1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 127 ⁰ C) of Compound No. 20.

2- (4-cyanobenzylidene) 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl-1-cyclopentanol (melting point 137 ⁰ C) Compound No.21.

2- (4-chlorobenzylidene) 5,5-dimethyl 3-ethyl 1 - (1H-1,2,4-triazol-1-ylmethyl) -1 cyclopentanol (melting point 58 ⁰ C) compound

2- (4-Parachlorphenoxybenzyliden) 5,5-dimethyl 1- {iH-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (melting point 112 ⁰ C) Compound No.23.

2- (4-Chloro-benzylidene) -3-isopropyl-5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol (oil) Compound No.24.

Example Il

Preparation of 2- (4-chlorobenzyllene) 5,5-dimethyl-OH-imidazolylmethyl-1-cyclopentanol A mixture of 5 g of 7- (4-chlorobenzylidene) 4,4-dimethyl-1-oxaspiro (2,4) heptane, prepared according to In the previous example, 2.8 g of imidazole and 11 g of potassium carbonate are heated in 40 ml of N, N-dimethylformamide for 4 hours. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the expected product whose melting point is 174 ^° C., compound no. 25.

In the same way, the following compounds were obtained:

2- (4-fluorobenzylidene) 5,5-dimethyl 1- (1H-imidazolylmethyl) -1-cyclopentanol (m.p. 16O ⁰ C) Compound No. 26. 2- (2,4-dichlorobenzylidene) -5,5-dimethyl 1- (1H-imidazolylmethyl) -1-cyclopentanol (mp 134 ^° C.) Compound No. 27. 2- (4-trifluoromethylbenzylidene) -5,5-dimethyl 1- (1H-imidazolylmethyl) -1-cyclopentanol (m.p. 171 "C) Compound No. 28.

Example III

Preparation of 2- (4-fluorobenzyllene) 5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxy-3-cyclopentene To a mixture of 10 g of 2,2-dimethyl-4 -chloro-1-cyclopentanone and 8.4 g of 4-fluorobenzaldehyde in 100 ml of ethanol are added to 50 ml of an aqueous 10% strength sodium carbonate solution. After 30 minutes, a viscous slurry was filtered and the solid was washed and dried. This gives 11.8 g of 2,2-dimethyl-4-chloro-5 (4-fluorobenzylidene) -cyclopentanone 1 having a melting point of 69 ⁰ C. 3.1 g of sodium hydride (80% dispersion in mineral oil) in 50 ml of anhydrous DMSO are heated to 80 ° C until the solid has completely dissolved. Thereafter, the solution is diluted with 100 ml of THF and then cooled to -1O ⁰ C. Is added to the mixture within 10 minutes a solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethylsulfoxide added and the mixture is stirred 15 min at -1O ⁰ C. A solution of 11.8 g 2,2-dimethyl-4-chloro-5- ( 4-FluorobenzylideneM-cyclopentanone was then added in 100 mL of THF The resulting mixture was allowed to stand at room temperature and then poured into water and extracted with ether, washed with water, dried and distilled to give 7- (4-fluorobenzylidene ) 4,4-dimethyl-1-oxaspiro (2,4) 5-heptene, which is used directly for the subsequent step.

A mixture of 5.5 g of the product obtained with 2 g of 1,2,4-triazole and 6.6 g of potassium carbonate is heated in 50 ml of N ₁ N-dimethylformamide for 4 hours. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized, to obtain 2.4 g of the expected product with a melting point of 168 ⁰ C (compound no. 29).

In the same way, the following compounds were obtained:

2- (4-chlorobenzylidene) 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxy-3-cyclopentene (melting point 203 ⁰ C) compound

2- (2,4-dichlorobenzylidene) 5,5-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-hydroxy-3-cyclopentene (melting point 182 ⁰ C) Compound No.31.

Example IV

Preparation of 2- (4-fluorobenzylidene) 5,5-dimethyl-1- (1H-imidazolylmethyl) -1-hydroxy-3-cyclopentene A mixture of 5.5 g of 7- (4-fluorobenzylidene) 4,4-dimethyl-1-oxaspiro ( 2.4) 5-heptene prepared according to the previous example with 2 g imidazole and 6.6 g potassium carbonate is heated in 50 ml N, N-dimethylformamide for 4 hours. The mixture is poured into water and extracted with ethyl acetate. The organic phase is washed, dried and recrystallized to give the expected product which has a melting point of 172 ^° C. (Compound No. 32).

Example V

Preparation of 2- (4-chlorobenzylidene) -3,5,5-trimethyl 1- (1H-1,2,4-triazoi-1-ylmethyl) -1-cyclopentanol A mixture of 2.3 g of sodium hydride and 120 ml of DMSO is added to 75 ⁰ C heated until the solid has dissolved. 120 ml THF is added and d <e solution is cooled to -5 ⁰ C. 16 g of trimethylsulfonium iodide in 50 ml of DMSO are added, keeping the temperature below ⁰ ° C. 15.8 g of 2- (4-chlorobenzylidene) 3,5,5-trimethylcyclopentanone dissolved in 20 ml of THF are added and the solution is allowed to stand at room temperature.

A solution of sodium triazolyl is prepared starting from 5.3 g of 1H-1,2,4-triazole. 2.3 g of sodium hydride are added in 100 ml of DMSO and then the mixture is heated to 13O ⁰ C for a period of 2 hours. The solution is washed with water, extracted with ethyl acetate, dried and purified on silica. This gives 2.4 g of a yellow solid.

Melting point 148 ⁰ C.

The 2- (4-chlorobenzylidene) 3,5,5-trimethylcyclopentanone is obtained in the following manner:

To 2,7g of magnesium in 50ml of ether are added 7ml of methyl iodide. When the organomagnesium compound is formed, the solution is cooled to -5 ⁰ C, and 1 g of copper iodide are added. 10 g of 5,5-dimethyl-2-cyclopentenone in 30 ml are added keeping the temperature below ⁰ ° C. 10 g of chlorobenzaldehyde in ether are then added. Finally, 50 ml of concentrated hydrochloric acid are added and then 50 ml of water. The aqueous phase is then extracted with ether. The organic phase is washed, dried and purified on a silica column. 15.8 g of an oily product are obtained. The 5,5-dimethyl-2-cyclopentenone is obtained in a manner known per se.

Example VI

Preparation of 2- (4-chlorobenzyllene) -5,5-diallyl-1- (1H-1,2,4-trla-7-ol-1-ylmethyl) -1-cyclopentanol A mixture of 2.7 g of sodium hydride and 120 ml of DMSO is allowed to dissolve Heated to 75 ⁰ C. Add 12OmI THF and cool the solution to -5 ° C. The temperature being kept below 0 ⁰ C 12.6g of trimethylsulfonium iodide in 50 ml of DMSO are added. 16.5 g of 2- (4-chlorobenzylidene) SS-diallylcyclopentanone in 20 ml of THF are added and the solution allowed to stand at room temperature.

A solution of Natriumtriazolyl, which was prepared from 8.3 g 1 H-1,2,4-triazole, 4.8 g of sodium hydride in 100 ml DMSO is added and then the mixture is heated to 80 ⁰ C for 2 hours. The solution is washed with water, extracted with ethyl acetate, dried and purified on a silica column. This gives 6.2 g of a yellow solid (mp 128 ° C) Compound Nr.33.

The 2- (4-chlorobenzylidene) -5,5-diallylcyclopentanone is obtained in the following manner:

2.5 g of sodium hydride are washed with 50 ml of heptane. 100 ml of toluene and 6.7 ml of t-amyl alcohol are added and warmed to 50 ° C. When hydrogen evolution is complete, 15 g of 2- (4-chlorobenzylidene) -5-allylcyclopentanone and 8.1 ml of allyl chloride are added. The solution is heated to reflux, cooled and washed with water. The organic phase is dried. 16.5 g of a liquid product are obtained after evaporation. The 5-allylcyclopentanone is prepared by the method of W.L. Howard N.B. Lorette Org. Synth. 42.34 received.

In the same way, 2- (4-fluorobenzylidene) -5,5-diallyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol was obtained.

(Mp 112 ⁰ C). Connection no.34.

Example VII

Preparation of 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazomo-1-methyl) -1-methoxycyclopentanol 4.2 g Powdered Potash and 5.2 g 2- (4-chlorobenzylidene) 5, 5-Dimethyl 1- (1H-1,2,4-triazolemethycyclopentane-i-oil in 32 ml of DMSO are stirred at room temperature, 2 ml of methyl iodide are added and the mixture is stirred, the solution is poured into water and extracted with ethyl acetate. the organic phase is washed again with water and dried. After purification on a silica column 4.9 g of pure product are obtained. Melted point 84 ⁰ C.

The 2- (4-chlorobenzylidene) -5,5-dimethyl-1- (1H-1,2,4-triazolemethyl) cyclopentan-1-ol is obtained in the following manner:

100 ml of an aqueous 10% strength sodium carbonate solution are added at ⁰ ° C. to a mixture of 10 g of 2,2-dimethylcyclopentanone and 13.8 g of 4-chlorobenzaldehyde in 100 ml of ethanol. After 10 minutes, a viscous slurry is filtered and the solid is washed and then dried. This gives 12.5 g of 2,2-dimethyl-5- (4-chlorobenzylidene) 1-cyclopentanone with a melting point of 12O ⁰ C.

This compound was dissolved in 50 ml of THF added to a solution formed in the following manner: 1.9 g of sodium hydride (80% dispersion in mineral oil) in 50 ml of anhydrous DMSO are heated to 8O ⁰ C until complete dissolution of the solid. The solution is then diluted with 100 ml of THF and then cooled to -10.degree. Are added to the mixture within 10 minutes a solution of 11.5 g of trimethylsulfonium iodide in 80 ml of dimethylsulfoxide added and the mixture is stirred 15 min at -10 ⁰ C. A solution of 11,8g2,2-dimethyl-4-chlor5- (4-chlorobenzylidene) 1-cyclopentanone was then added in 100 ml of THF. The resulting mixture is allowed to stand at room temperature and then poured into water and extracted with ether, washed with water, dried and distilled. This gives the 7- (4-chlorobenzylidene) 4,4-dimethyl 1-oxaspiro (2,4] heptane, which is used directly for the subsequent step. A mixture of 5 g of the product with 2.8 g of 1,2,4 Triazole and 11 g potassium carbonate are heated in 40 ml Ν, Ν-dimethylformamide for 4 hours.

The mixture is poured into water and extracted with ethyl acetate. The organic phase wherein the expected product is obtained having a melting point of 154 ⁰ C is washed, dried and recrystallized. (Compound No. 1).

Melting points for the following compounds for information given below: 2,2-dimethyl-4 chloro 5- (4-fluorobenzylidene) -cyclopentanone 1 having a melting point of 69 ⁰ C. 2,2-dimethyl-4 chloro 5- (4-chlorobenzylidene) 1 -cyclopentanone having a melting point of 68 ⁰ C. 2,2-dimethyl-4 chloro 5- (2,4-dichlorobenzylidene) 1-cyclopentanone having a melting point of 68 ⁰ C. '

2,2-Dimethyl5- (4-fluorobenzylidene) 1-cyclopentanone having a melting point of 69 ⁰ C. 2,2-dimethyl-4 chloro 5- (4-chlorobenzylidene) cyclopentanone 1 having a melting point of 12O ⁰ C. 2.2 -Dimethyl5- (4-trifluormethylbenzyliden) cyclopentanone 1-1-cyclopentanone having a melting point of 107 ⁰ C. 2,2-Dimethyl5- (2,4-dichlorobenzylidene) is obtained as an oil

2,2-dimethyl-4 chlor5- (4-chlorobenzylidene) 1-cyclopentanone with a melting point of 6O ⁰ C. 2- (4-chlorobenzylidene) cyclopentanone 1 having a melting point of 63 ⁰ C

 2-Benzyl-1-cyclopentanone is obtained as an oil.

2- (4-bromobenzylidene) 1-cyclopentanone with a melting point of 97 ⁰ C.

 2,2-dimethyl-5-benzylidene-1-cyclopentanone is obtained as an oil

 2,2-Dimethyl 5 - (3,4-dichlorobenzylidene) 1-cyclopentanone is obtained as an oil

 2- (3,4-dichlorobenzylidene) 1-cyclopentanone is obtained as an oil

2-Methyl5- (4-chlorobenzylidene) 1-cyclopentanone having a melting point of 107 ⁰ C. 2-methyl 5- (2-chlorobenzylidene) cyclopentanone-1 is obtained as an oil

 2,2-Dimethyl 5- (2-chlorobenzylidene) 1-cyclopentanone is obtained as an oil

2-phenylbenzylidene 1-cyclopentanone with a melting point of 146 ^° C.

2,2-Dimethyl-5 phenylbenzyliden 1 -cyclopentanone having a melting point of 120 ⁰ C. 2-ethyl 2-melhyl5- (4-chlorobenzylidene) 1-cyclopentanone having a melting point of 85 ⁰ C. 2-Allyl5- (4-chlorobenzylidene) 1-cyclopentanone having a melting point of 60 ⁰ C. 2,2-Diallyl5- (4-chlorobenzylidene) 1-cyclopentanone as an oil

 2,2,4-trimethyl-5- (4-chlorobenzylidene) 1-cyclopentanone is obtained as an oil

2-Methyl-2-methoxymethyl-5- (4-chlorobenzylidene) -1-cyclopentanone is obtained as an oil. 2-Allyl5- (4-fluorobenzylidene) 1-cyclopentanone cyclopentanone-1 having a melting point of 111 ⁰ C. 2,2-Diallyl5- (4-fluorobenzylidene) is obtained as an oil.

2,2-diethyl-5- (4-chlorobenzylidene) -cyclopentanone is obtained as an oil

 2,2-Diethyl 5- (4-fluorobenzylidene) 1-cyclopentanone is obtained as an oil

 2- (4-cyanobenzylidene) 1-cyclopentanone is obtained as an oil

 2,2-Dimethyl 5 - (4-cyano-benzylidene) 1-cyclopentanone is obtained as an oil

2,2-dimethyl-4-ethyl-5- (4-chlorobenzylidene)-1-cyclopentanone is obtained as an oil. 2- (4-p-Chlorphenoxybenzyliden) -cyclopentanone 1 having a melting point of 92 ^C C. 2.2-Dimethyl5- (4-p-chlorphenoxybenzyliden) 1-cyclopentanone as an oil. 2,2-dimethyl-4-isopropyl-5- (4-chlorobenzylidene) -1-cyclopentanone is obtained as an oil. 2,2-dimethyl-5- (4-chlorobenzylidene) 1-cyclopentanone having a melting point of 60 ° C. 2,2-Dimethyl5- (2,4-dichlorobenzylidene) 1-cyclopentanone having a melting point of 68 ⁰ C. 2,2-Dimethyl5- (4-fluorobenzylidene) 1-cyclopentanone having a melting point of 69 ° C.

Example VIII

Preparation of 2- (4-chlorobenzylidene) 6-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanols To a mixture of 22.4 g of 2-methylcyclohexanone and 28.1 g of parachlorobenzaldehyde in 250 ml of ethanol is added at ⁰ ° C. 100 ml of an aqueous 10% strength sodium carbonate solution. After stirring for 1 h, the medium is diluted with water and extracted with ethyl acetate.

The dried organic phase over Na? SO4 is concentrated and the residue is chromatographed on silica with

an eluent / heptane / ethyl acetate 90/10. A yellow oil is obtained. This is crystallized in pentane to give a pale yellow powder (17.1 g): 2- (4-chlorobenzylidene) 6-methylcyclohexanone with a melting point of 59 ^° C.

3.8 g of this compound was dissolved in 33 mL of anhydrous THF is added to a reaction medium at -5 ⁰ C was added, which was prepared in the following manner:

0.8 g of sodium hydride (60% dispersion) are heated at 70 ° C. in 26 ml of dry DMSO and then 33 ml of anhydrous THF are added. The cooled to -5 ⁰ C mixture is mitTrimethylsulfoniumjodid (3.9g) dissolved in 20 ml of dry DMSO treated.

After 1 hour at ⁰ -5 C 8- (4-chlorobenzylidene) 4-methyl1 -oxaspiro [2,5] octane is prepared as treated with 2.2 g of triazole, and 0.28 g Natriumtriazolyl.

The reaction medium is heated to 93 ° C for 1 hour and 30 minutes after distillation of 30 ml of THF and addition of b0 ml

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

One first obtains the main diastereoisomer having the methyl substituent and the hydroxyl group in the cis position relative and melts at 139 ⁰ C (compound No.35) as well as less in which the methyl substituent and the Hyderoxylgruppe project from the relatively diastereoisomers in trans position to each other, which is obtained in the form of a honey-like mass (compound no. 36).

Stereochemistry is determined by nuclear magnetic resonance using methods well known in the art.

Example IX

Preparation of 2- (4-chbrbenzylidene) -6,6-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol. To a reaction medium consisting of (25 ml) toluene, (3 , 6 ml) of tert.-amyl alcohol and sodium hydride (1.35 g as a 60% dispersion in oil) and was heated to 45 ⁰ C, are gradually added the above-prepared 2- (4-chlorobenzylidene) 6-methylcyclohexanone (7 , 0g) and then (5.1 g) of methyl iodide. The mixture is brought to the reflux temperature, kept at this temperature for 1 hour, poured into water and extracted with ethyl acetate. After drying and concentration, the residue is recrystallized from methanol to give 4.7 g of 2- (4-chlorobenzylidene) -6,6-dimethylcyclohexanone

be obtained, melting point at 92 ⁰ C.>

The procedure described in Example I is then applied to 4 g of this ketone, so that after chromatography, the expected product is obtained, which melts at 179 ⁰ C (Compound No. 37).

In the same way, the following compounds were obtained:

2- (4-fluorobenzylidene) -6,6-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, isomer A, Compound No. 38, m.p.

2- (4-Chlorobenzylidene) 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, Isomer A, Compound No. 39, mp 117 ° C.

2- (4-Chlorobenzylidene) -6-cyclohexyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, Isomer A, Compound No.40, mp

2- (4-chlorobenzylidene) -6-cyclohexyl-1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, isomer B, compound no. 41, m.p.

2- (4-Chlorobenzylidene) -6-t-butyl 1 - (1H-1,2,4-triazole-1-ylmethyl) -1-cyclohexanol, Isomer A, Compound No. 42, m.p.

2- (4-chlorobenzylidene) -6-sec-butyl 1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, isomers A + B.Verbindung No.43, melting point 171 ⁰ C.

2- (4-Chlorobenzylidene) -6-sec-butyl-1- (1H-1,2,4-triazol-1-ylmethyl-1-cyclohexanol, isomer C + D. Compound No.44,148 ⁰ C.

2- (4-Chlorobenzylidene) -6-methyl, -6-phenyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, Isomer A, Compound No.45, m.p. 177 ⁰ C.

2- (4-Chlorobenzylidene) -6-methyl, -6-phenyl 1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, Isomer B, Compound No. 46, mp 133 ⁰ C.

2- (4-chlorobenzylidene) -6-methyl, -6-ethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, isomers A + B compound # 47, Melting point 175 ^° C.

2- (4-Chlorobenzylidene) -6-methyl, -6-isopropylm- (iH-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, Isomer A, Compound No.48, mp 154 ° C.

2- (4-chlorobenzylidene) -e-methyl _/ -6-isobutyl1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, Isomer A, Compound No. 49, melting point 163 ⁰ C.

2- (4-Chlorobenzylidene) -6-m (t-butyl, -6-isobutyl 1- (1H-1,2,4-triazol-1-yl-methyl) -1-cyclohexanol, isomer B, Compound No. 50, m.p. 184 ^0C .

2- (4-chlorobenzylidene) 1- (1H-1,2,4-triazol-1-yl-methyl) -1-cycloheptanol. Compound No. 54, mp 104 ° C.

2- (4-Chlorobenzylidene) -7,7-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cycloheptanol, Compound No.54, m.p.

2- (4-fluorobenzylidene) -1- (1H-1,2,4-tirazol-1-ylmethyl) -1-cycloheptanol. Compound No. 56, mp 91 ^° C.

2- (4-Chlorobenzylidene) -7-methyl 1- (1H-1,2,4-triazol-1-yl-methyl) -1-cycloheptanol, Compound No.56, m.p. 166 ° C.

For information, the features of some starting cycloalkanones are given below. The reader will note that the literature provides general methods for preparing these compounds. One can e.g. Reference to the following documents:

DE-OS 2245518

THERE. WHITTING J., Chem. Soc. (1971), 3396.

G. Le GUILLANTON (1969), Bull. Soc. Chim. 2,871th

PAL PERJESI et al. Chem. Ber. (1987), 120, 1449.

J.M. CONIA et al. Soc. Soc. Chim. (1970), 2972.

2- (4-fluorobenzylidene) 1-cyclohexanone with a boiling point of 14O ⁰ C at 0.02 mm Hg.

2- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 54 ° C.

2-Methyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 59 ^° C.

2,2-dimethyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 92 ^° C.

2,2-dimethyl 6- (4-fluorobenzylidene) 1-cyclohexanone with a melting point of 51 ^° C.

2-Cyclohexyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 97 ° C.

2-t-Butyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a boiling point of 18O ⁰ C at 0.06 mm Hg.

2-sec-Butyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 46 ^° C.

2-phenyl 6- (4-chlorobenzylidene) -cyclohexanone with a 1 Melted point 121 ⁰ C.

2-Methyl 2-phenyl 6- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 77 ^° C.

1,1-Dimethyl 3- (4-chlorobenzylidene) -2-tetralone is present as an oil.

2-methyl 2-ethyl 6- (4-chlorobenzylidene) 1-cyclohexanone with melting point 7O ⁰ C.

2-Methyl 2-isobutyl 6- (4-chlorobenzylidene) 1-cyclohexanone is present as an oil.

2-Methyl 2-isopropyl 6- (4-chlorobenzylidene) 1-cyclohexanone is present as an oil.

6- (4-chlorobenzylidene) spiro [4,5] decan-5-one is present as an oil.

2- (4-fluorobenzylidene) 1-cycloheptanone of melting point 62 ^° C.

2- (4-chlorobenzylidene) 1-cycloheptanone with melting point of 75 ° C.

2-methyl-7- (4-chlorobenzylidene) 1-cycloheptanone with a melting point of 74 ^° C.

2,2-Dimethyl 7- (4-chlorobenzylidene) 1-cycloheptanone with a melting point of 63 ° C.

2,2-dimethyl 7- (4-chlorobenzylidene) 1-cyclohexanone with a melting point of 63 ° C.

The following examples illustrate the fungicidal uses of the compounds of the invention.

In these examples, the sputtering of the solutions or suspensions of the active ingredients is carried out under such conditions that the sputtering of a solution or suspension at a concentration of 1 g / l corresponds on average to an application of about 2 micrograms of the active ingredient per cm ^{2 of} the leaf of the plant ,

In the conditions of Examples X to XVI, the illustrated compounds have shown no phytotoxicity.

In these examples, if the protection given to a product by a fungal disease is at least 95%, this is considered complete protection. Protection is considered to be good if it is at least 80% (but less than 95%), satisfying if it is at least 70% (but below 80%) and average if it is at least 50% (but below 70%).

In the present application, percentages are percentages by weight unless otherwise specified and unless they are statements of yields. In the case that the percentages are expressed in relation to the stoichiometry are mole percentages. Concerning the concentrations, some figures are expressed in ppm (parts per million), which corresponds to an indication in mg / l.

The experiments were carried out with doses of 1 g / l or 0.3 g / l, without this anticipating the value of the products themselves.

Example X - In vivo test on Botrytis cineroa on the excised leaf of a tomato. Fine grinding is used to prepare an aqueous emulsion of the active substance to be tested, which has the following composition:

- active substance: 60mg

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

- you fill up on 60ml of water.

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

In the greenhouse grown tomatoes (variety Marmande), which were 30 to 40 days old you were treated ¹ ch dusting with aqueous emulsions (called slurries) as defined above, with different concentrations of the compound to be tested. The experiment is repeated twice at each concentration.

After 24 or 48 hours, the leaves are cut and placed in 2 petri dishes (14 cm in diameter), the soil of which was previously covered with a piece of wet filter paper (5 leaflets per dish).

The inoculum is then introduced by means of a syringe by applying drops (3 drops per leaflet) of a spore suspension. This spore suspension of Botrytis cinerea was obtained from a 15-day culture, which was subsequently suspended in a nutrient solution (100,000 units per cm ³ ).

The control examination is carried out 3 and β days after the contamination by comparison with an untreated comparative assay.

Under these conditions, at a dose of 1 g per / i after 6 days, good or complete protection can be observed for compounds 1 and 3, and at a dose of 0.3 g / l good or complete protection for the compounds 2,15 , 16,35,38 and 39.

Example XI - In vivo test with Erysiphe graminis on barley (barley powdery mildew) Barley seeded in wells in a substrate of peat-pozzolan soil 50/50 is treated at the 10 cm height by sputtering an aqueous emulsion (slurry) in which previously described and with the concentration given below. The experiment is repeated twice. After 24 hours sprinkle the barley plants with spores of Erysiphe graminis, wherein this sprinkling is done with the help of sick plants.

The reading takes place 8 to 14 days after the contamination. Under these conditions, the following results are observed:

At a dose of 1 g / l, good or complete protection is obtained for compounds 1,2,3,14,26 and 0,3 g / l for compounds 4,11,38,53,55.

At a dose of 1 g / L, satisfactory or average protection is obtained for the compounds 10,25,33 and 0,3 g / L for the compounds 8,15,22,29 and 39.

Example XII - In vivo test with "Puccina recondita", pathogen of wheat rust disease Wheat seeded in wells in a peat-pozzolan soil 50/50 substrate becomes 10 cm high by sputtering with aqueous emulsions (slurries) of the same composition treated in different concentrations of the compound to be tested as described in Example IV The experiment is repeated twice at the same concentration.

After 24 hours, an aqueous spore suspension (50,000 spores pn / cm ³ ) is spotted on the wheat. This suspension was obtained from contaminated plants. The wheat is then brought for 48 hours into an incubation cell at about 18 ^° C. and a 100% relative humidity.

After 2 days, the relative humidity is reduced to 60%. The control of the condition of the plants takes place between the 11th and 15th day after the contamination by comparison with an untreated comparative experiment.

At the dose of 1 g / l, good or complete protection was obtained for the compounds 1,2,3,10,14,25,26,27 and 33 and at a dose of 0,3g / l for the compounds 4, 7,9,13,14,15,18,19,28,34,35,37,38,43,47 and 53.

At a dose of 2 g / l, a satisfactory or average protection was obtained for compound 5 and 0.3 g / l for compounds 8, 10, 11, 20, 22, 42, 44 and 49.

Example XIII - "Piricularia oryzae" In Vivo Test Pirice Rice Rice (Rice Blast) Rice seeded in wells into a mixture of enriched peat pouch Pozzolan (50/50) is grown at a 10 cm height by sputtering an aqueous emulsion ( The experiment is repeated twice, and after 48 hours, the leaves are treated by application of a spore suspension obtained in pure culture.

The reading takes place 8 days after the contamination. Under these conditions, the following results are observed:

At a dose of 1 g / l, a good or total protection is obtained for the compounds 1,2,4,25,28 and at dose of 0.3 g / l ^be: the compounds 7, 9,11,12,13, 14, 22, 29, 30, 33, 34, 38, 39, 43, 44, 47.

At a dose of 1 g / l, satisfactory or average protection is obtained with the compounds 5,26,27 and at 0,3 g / l with the compounds 15,16,18,23,31,32,42,48 and 49 ,

Example XIV - "Puccinia recondita" In Vivo Test Using Seed Treatment Wheat grains of the variety Talent are treated with the slurry of the previous example at a dose of 70 μg / pound and seeded in a substrate composed of a mixture from peat and pozzolan soil 50 / 50.15 days after sowing, the plantlets are inoculated with Puccinia recondita according to the procedure given in Example XII, reading the results 30 days and 45 days after sowing.

At the indicated doses, in the compounds 1,2,3,4,13,28,29,30,31,32,35 and 37, the percentage of infection 30 days after sowing is equal to zero, resulting from the untreated seeds Plantlets are 100% contaminated.

Example XV - In vivo test with Fusarium roseum using seed treatment Wheat grains of the variety "Talent" which were naturally contaminated with Fusarium roseum were treated with a slurry according to the definition described above under Example X, with doses of 10 , 25,50 and 100g per 100kg grains.

From 50g of treated seeds, 200 seeds were placed in a medium containing agar-agar (gelose) and malt at respective concentrations of 2% and 1%. The seeds were kept at 20 ° C for 10 days. The control of the condition of the seeds was made by comparison with the untreated control experiment where colonies of Fusarium roseum developed.

At the indicated doses, good or complete protection is observed for the compounds 1,2,3,4,13,15,28, 29,30,31,32,35,37, 52 and 54.

The example reproduced below illustrates the lacking phytotoxicity of the compounds according to the invention with regard to the growth of the seed grains.

Example XVI

Seeds of the variety "Talent" were treated with a slurry in the cans 2,5,10,25,50,100,200 and 400g / double centner.

The seeds were placed on a water-soaked filter paper. After 15 days of incubation at 25 ⁰ C, the lengths of the first and coleoptiles leaves with the compounds no. Were measured 1,13,15,35 and 37.

The results are included in the table below:

oppelz Entner Length (cm) Coleoptile and first leaves 0 13 12 13 25 13 50 13 100 12 200 13 400 12

Each of the above values represents an average for 40 pills.

Claims (28)

claims: 1. Benzylideneazolylmethylcycloalkanes or alkenes of the formulas: in which A is -CR ₆ R ₇ - or CR ₆ R ₇ CR ₈ R ₉ - or -CR ₆ R ₇ CR ₈ R ₉ CR ₁₀ R ₁₁ -AlStCR ₇ = ^ CH ₆ R ₇ -CR ₉ = CR ₆ R ₇ -CR ₈ R ₉ -CR ₁₁ or a cyano or nitro group which is a C ₁ -C ₄ alkyl radical or C ₁ -C ₄ alkoxy radical which is optionally halogenated, η is a very positive number or zero which is less than 6, where the radicals X may be identical or different if η is greater than 1, W represents a trivalent group consisting of either a = CH group or a nitrogen atom = N- R ₁ , R _{2 are} identical or different and represent a hydrogen atom or a C ₁ -C ₄ -alkyl radical which is optionally substituted (eg with one or more atoms or radicals such as, for example, halogen atoms, C ₁ -C ₄ ) Alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, mono- or polyhalogenated C ₁ -C -alkenyl, mono- or polyhalogenated C ₂ -C ₄ - AIkINYI), a C ₁ -C ₄ -alkoxy radical, which is optionally substituted (eg. with one or more atoms or radicals such as halogen atoms, C ₁ -C ₄ -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkyl, C ₂ -C ₄ -alkyl, mono- or polyhalogenated C ₂ -C ₄ -AlkBnYl, mono- or polyhalogenated C ₂ -C ₄ -AlkInYl) a C ₃ -C ₇ -CyClOaIkyIrest, a C ₆ -C ₁₀ -ArYlrest (especially phenyl), a C ^ Cn-aralkyl radical (especially benzyl), wherein these various radicals may optionally be substituted (for example with one or more atoms or radicals such as halogen atoms, C ₁ -C ₄ -alkyl radicals, mono- or polyhalogenated C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy radicals and mono- or polyhalogenated C ₁ C ₄ alkoxy), wherein R ₁ and R _{2 may} together form a C ₂ -C ₆ hydrocarbon chain which forms a ring with the carbon to which R 1 and R _{2 are} attached, this chain being optionally substituted as in the case of the aforementioned Ce-C ^ aryl radicals or Ri and R ₂ together may form a Cjr-Cg hydrocarbon dioxolane chain are bonded to the carbon to the R ₁ and R ₂ , said chain may optionally be substituted as described in the aforementioned Ce-C ₁₀ aryl radicals; Ra, R ₆ to Rn are identical or different and each represents a hydrogen atom or a C ₁ -C ₄ -alkyl radical which is optionally substituted (for example with one or more atoms or radicals, such as halogen atoms, C 1-10 -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy), or a C ₃ -C ₇ -cycloalkyl radical or a C ₆ -C ₁₀ -aryl radical (especially phenyl) a Cy-Cn-aralkyl radical (in particular benzyl), these various radicals being optionally substituted may be (for example, with one or more atoms or radicals such as halogen atoms, C ₁ -C ₄ -AlkYlTeStOn, mono- or polyhalogenated C ^ Cj-alkyl radicals, C ₁ -C ₄ alkoxy radicals and mono- or polyhalogenated C ^ C. ^ Alkoxy radicals), or two adjacent radicals of the chain A together with the atoms of A which they are attached form a fused phenyl ring or cycloalkane ring, R _{5 represents} a hydrogen atom, a C ₁ -C ₄ -alkyl radical, which is optionally substituted (eg. by one or more atoms or radicals such as halogen atoms, C ₁ -C ₄ -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, C ₁ -C -alkenyl, C ₂ -C ₄ -alkyl, mono- or polyhalogenated C ₂ -C ₄ -AlkOnYl-, mono- or polyhalogenated C ₂ -C ₄ -AlkInYl), a C ₃ -C ₇ - cycloalkyl, C ₆ -C ₁₀ -ArYlrest (especially phenyl), Cr-C ^ -Aralkylrost (especially benzyl ), wherein these various radicals may optionally be substituted (eg with one or more atoms or radicals such as halogen atoms, C 1 -C -alkyl radicals, mono- or polyhalogenated C 1 -C ₄ -C ₄ -alkoxy radicals and mono- or polyhalogenated C 1 -C ₄ -alkoxy), or R _{5 represents} a radical CJ = O) -R ₁₃ , where Ri _{3 represents} a C 1 -C ₄ -alkyl radical which is optionally substituted (for example with one or more atoms or radicals such as, for example, halogen atoms, C 1 -C -alkoxy radicals, mono- or polyhalogenated C ₁ -C ₄ -alkoxy, C ₁ -C -alkenyl, C ₂ -C ₄ -alkyl, mono- or polyhalogenated C ₂ -C ₄ -alkenyl, mono- or polyhalogenated C ₂ -C ₄ -alkynyl) a C ₃ - C _{7 is} cycloalkyl, C 1 -C ₁₀ -aryl (in particular phenyl), C 1 -C 3 -aryl (in particular benzyl), where these various radicals may optionally be substituted (eg with one or more atoms or radicals, such as, for example, . halogen atoms, ^ -C ^ alkyl, mono- or polyhalogenated C ₁ -C ₄ -alkyl, Ci-C ₄ -Alkoxyre ^r: th and or polyhalogenated Ci-C ₄ -alkoxy), or C ₂ -C ₄ -EtIiJnYl- ReSt, or mono- or polyhalogenated C ₂ -C ₄ ethynyl, R _{12 has} one of the meanings given for R ₆ , with the exception of C (OO) -R ₁₃ , R _{4 represents} a hydrogen atom, a halogen atom, in particular a chlorine atom or bromine atom, a C 1 -C ₄ -alkyl radical which is optionally substituted ( z. B. with one or more atoms or radicals such as halogen atoms, Ci-C-alkoxy, mono- or polyhalogenated _Ci-C4 -alkoxy, C ₂ -C ₄ alkenyl, C ₂ -C ₄ -AIkInYl mono-, or polyhalogenated C ^ C ^ alkenyl, mono- or polyhaloated C ₂ -C ₄ -AlkJnYl,) a C3-C ₇ -cycloalkyl, Cg-Cio-aryl (especially phenyl), Cy-Cn-aralkyl (especially benzyl), these various radicals may optionally be substituted (eg with one or more atoms or radicals such as halogen atoms, ^ -Q-alkyl radicals, mono- or polyhalogenated C ^ Cj-alkyl radicals, C ₁ -C ₄ - alkoxy radicals and mono- or polyhalogenated C ^ C-alkoxy radicals) and the agriculturally acceptable salt forms of these compounds. 2. Compounds according to claim 1, characterized in that η = 1,2 or 3. 3. Compounds according to claim 2, characterized in that X is a halogen atom selected from chlorine, bromine and fluorine. 4. Compounds according to claim 3, characterized in that η = 1 or 2 and X is in the para position when η = 1 and in meta-para or ortho-para position when η = 2. 5. Compounds according to claim 4, characterized in that η = 1. 6. Compounds according to claim 3,4 or 5, characterized in that X is a chlorine atom. 7. Compounds according to claim 1, characterized in that W is a nitrogen atom. 8. Compounds according to claim 1, characterized in that R ₃ , Re, Rg and R _{10 represent} hydrogen atoms. 9. Compounds according to claim 8, characterized in that R ₄ , R ₇ , Rg and R _{11 represent} a hydrogen atom or a CT-C ₄ alkyl radical. 10. Compounds according to claim 1, characterized in that R ₁ and R _{2 are} selected from the radicals represent methyl or ethyl or a hydrogen atom. 11. Compounds according to claim 1, characterized in that R _{5 is} a hydrogen atom. 12. Compounds according to claim 1, characterized in that Ri _{2 is} a hydrogen atom. 13. Compounds according to claim 1, characterized in that they correspond to the formula IA. 14. Compounds according to claim 13, characterized in that when A is CR ₆ R ₇ , R ₁ and R _{2 are} selected from the radicals methyl or ethyl, R ₃ and R ₅ to R ₇ and R _{12 represent} a hydrogen atom and R ₄ Represents methyl, ethyl, i-propyl, n-propyl or a hydrogen atom. A compound according to claim 14 which is the 2- (4-chlorobenzylidene) 5,5-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) 1-cyclopentanol or the 2- (4-chlorobenzylidene) - 5-methyl-5-methyl-1H-1,2,4-triazol-1-ylmethyl) -1-cyclopentanol. 16. A compound according to claim 13, characterized in that when ACReR ₇ CReRgISt, R ₁ and R _{2 are} selected from the radicals methyl, ethyl or a hydrogen atom, R ₃ and R ₅ to Rg and R _{12 are} a hydrogen atom and R ₄ is a methyl radical, ethyl radical, i-propyl radical, n-propyl radical or a hydrogen atom. A compound according to claim 13 which is the 2- (4-chlorobenzylidene) -6-methyl-1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol or the -2- (4-chlorobenzylidene ) -6,6-dimethyl 1- (1H-1,2,4-triazol-1-ylmethyl) -1-cyclohexanol, or the 2- (4-chlorobenzylidene) -1- (1H-1,2,4- triazol-1-ylmethyl) -1-cyclohexanol. 18. Use of compounds according to any one of claims 1 to 17 as fungicides, in particular in the form of fungicidal compositions, the 0.5% to 95% of the compounds in combination with solid or liquid agriculturally acceptable carriers and / or surface-active also for agriculture compatible agents. 19. A process for the treatment of cultures which are infected with fungal diseases or threatens the infestation, characterized in that applying to the leaves an effective amount of a compound according to any one of claims 1 to 17 or a composition according to claim 18. Treatment method according to claim 19, characterized in that a dose of between C, 002 and 5 kg / ha is used. A propagation product of crops which has been subjected to a protective treatment with one of the compounds according to any one of claims 1 to 17 or a composition according to claim 18. 22. Seed according to claim 21, which has been subjected to a protective treatment in an amount of 0.1 to 500 g / quintal. 23. Compounds which can be used as intermediates in the preparation of compounds according to claims 1 to 17, which correspond to the formulas in which the substituents n, R ₁ , R ₂ , A ₁ , A, R ₃ , R ₄ , R _{12 have} the same meaning as in claim 1. 24. A process for the preparation of compounds of the formula IA in which R ₁ , R ₂ , R ₃ , R ₂ , X, n, W and A have the same meaning as in claim 1, R ₄ is different from a hydrogen atom, R ₅ is a hydrogen atom, characterized in that a compound of formula VII is reacted with a sulfonium ylide to obtain oxiranes of formula IX, and then reacted with an unsubstituted imidazole or triazole in the presence of a base. 25. A process for the preparation of compounds of the formula IA, in which R ₁ , R ₂ , R ₃ , R ₁₂ , X, n, W and A have the same meaning as in claim 1, R _{4 is} a halogen atom, R _{5 is} a hydrogen atom by allylic halogenation of the compounds of formula (I) wherein R ₄ and R ₅ are hydrogen. 26. A process for the preparation of compounds of the formula IA in which R 1, R ₂ , R ₃ , R ₁₂ , X, n, W and A have the same meaning as in claim 1, R _{4 is} different from halogen and R _{5 is} from Hydrogen is different, by esterification or etherification of compounds of formula IA which were obtained according to claim 24. 27. A process for the preparation of compounds of the formula IA in which R ₁ , R ₂ , R ₃ , R ₁₂ , X, n, W and A have the same meaning as in claim 1, R _{4 is} a halogen atom, R ₅ of Hydrogen, which are obtained in a first step by esterification or etherification according to claim 26 of a compound of formula I in which R ₄ and R _{5 represent} a hydrogen atom followed by an allylic halogenation. 28. A process for preparing compounds of the formula IB in which R ₁ , R ₂ , A, n, X have the same meaning as in claim 1, R _{5 is} a halogen atom, characterized in that a compound of the formula VIII reacting a sulfonium ylide to obtain an oxirane of the formula X, followed by reaction with an imidazole or triazole in the presence of a base, optionally followed by esterification or etherification, to obtain a compound in which R _{5 is} a hydrogen atom.