IE61234B1 - Compounds containing triazole or imidazole groups and tetrahydrofuran, use of these as fungicides and processes for the preparation thereof - Google Patents

Abstract

Compounds of formula: Y is a halogen atom or a cyano or nitro group or an optionally halogenated alkyl or alkoxy group, n is a positive integer lower than 6 or zero, Tr denotes a 1,2,4-triazol-1-yl group and Im a 1,3-imidazol-1-yl group, R1 to R5 denote the halogen atom or a lower alkyl radical, X1 and X2 denote a halogen atom or a hydrocarbyl radical. Use of these compounds as fungicides especially against the disease of cereals and in arboriculture.

Description

The present invention relates to new compounds, containing triawle or imidasole and tetrahydro furan groups, for use in plant protection. It also relates to the processes for the preparation of the said compounds and products which can bs used, if desired, as intermediates in the processes of preparation. It further relates to the use of these compounds as fungicides, to the fungicidal compositions based on these compounds and to the processes, using these compounds, for the control of fungal diseases of crops.

Numerous products, especially fungicides, containing triaxole groups are already known, in particular, from European Patent Application No. 151,084. In fact, this patent application describes the compounds the formula of which is given at the end of the description and their use as fungicides.

One object of the present invention is to provide compounds which have improved properties in the treatment of fungal diseases.

Another object of the present invention is to provide compounds which also have an improved spectrum of use in th® field of fungal diseases.

It has now been found that these objects could be achieved by means of the products of the invention. The latter are characterised in that they correspond to the formula (I) in which A is a group (Y)n Ph-(CH2)m, where Ph is a phenylene ring and m = 0 or 1» preferably 0» Y is a halogen atom or a cyano or nitro group, or an optionally halogenated alkyl or alkoxy group, n is rero or a positive integer less than 6, if being possible for the groups Y to be identical or different when n is greater than 1» Tr represents a l»2,4-triazol~l-yl group and Im a 1»3-imidazol"l~yl group, to R3, which may be identical or different, represent a hydrogen atom or a (linear or branched) alkyl radical containing at most six carbon atoms. a eycloalkyl radical containing at most six carbon atoms, a phenyl or benzyl radical or an alkoxy radical containing at most six carbon atoms, it being possible for these various radicals to be optionally substituted (for example with one or more atoms or radicals such as halogen atoms, and alkoxy radicals containing at most six carbon atoms, X, and X2, which may be identical or different, represent a hydrogen atom, a halogen atom, an alkyl radical containing at most six carbon atoms, a eycloalkyl radical containing at most six carbon atoms or a phenyl or benzyl radical, it being possible for these various radicals to be optionally substituted, in a manner similar to the groups R, to a group Q-R5, in which Q represents 0 or S, and R6 represents a hydrogen atom or an alkyl radical containing at most six carbon atoms, a eycloalkyl radical containing at most six carbon atoms or a phenyl, benzyl, acyl or benzoyl radical, It being possible for these radicals' to be substituted in a manner similar to the groups R, to Rs and to have identical or different meanings when Xx and X2 each correspond to OR@ or SRs, a group of formula -Q-R7-Q-, where Q has the same meaning as above and in which R7 is a divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, it being possible for one of these carbon atoms to be replaced by an oxygen or nitrogen atom, the said single divalent radical Itself being optionally substituted (for example with one or more halogen atoms ; ' or - alkyl radicals containing at most six carbon atoms, alkoxy radicals containing at most six carbon atoms, or hydroxyl’ radicals), a group -N ReRg, In which R@ and Rg, which may be identical or different, represent a hydrogen atom or an alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms or a phenyl radical, it being possible for these various radicals to be optionally substituted in a manner similar to the groups R, to Rs, or alternatively Re and Re together can form a single divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, it being possible for one of these carbon atoms to be replaced by an oxygen, sulphur or nitrogen atom, the said single divalent radical itself being optionally substituted (for example with one or more halogen atoms, or alkyl radicals containing at most six carbon atoms, optionally halogenated alkoxy radicals containing at most six carbon atoms, or hydroxyl radicals), a group - N-Rlo, in which R10 corresponds to an alkyl radical containing at most six carbon atoms, or a cycloalkyl radical containing at most six carbon atoms, or to a group of formula ORXX in which Rxx is an alkyl, it being possible for these radicals to be substituted in a manner similar to the groups R, to R3, or a hydroxyl group, a group N3, on condition that Σ, is other than N3, Xx or X, can constitute together ~O or ~S, on the general conditions that X, and X3 cannot simultaneously correspond to a hydrogen atom or to an alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing af most six carbon atoms, a phenyl radical or a benzyl radical, and if Xx and X2 are different and either one of them is ORg, then, in this case only, Rs can be only a benzoyl or acyl group.

The invention also relates to the salified forms of the compounds according to the invention. The salified forms ar® the forms which are acceptable in agriculture among which there may be mentioned the hydrochloride, sulphate, oxalate, nitrate or arylsulphonate and the addition complexes of these compounds with metal salts, and especially iron, chromium, copper, manganese, zinc, ' cobalt, tin, magnesium and aluminium salts.

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

It should be noted that the compounds claimed are not described in European Patent Application No. 151,084.

Within the meaning of the present text, it is understood that the adjective lower, when it qualifies an organic radical, means that this radical contains at most six carbon atoms. This radical may be linear or branched.

The applicant wishes to emphasize that the plates appended should In no way be considered as drawings, but as forming an integral part of the description of the invention.

The compounds of formula I and the compounds which may, If appropriate, be used as intermediates in the preparation processes, and which will be defined at the time of describing these processes, may exist in one or more Isomeric forms depending on the number of asymmetric centres In the molecule. Therefore, the invention relates to all the optical isomers as well as to their racemic mixtures and to the corresponding diastereoisomers . The separation of the diastereoisomers and/or the optical isomers may be carried out according to methods known per se.

For the purpose of fungicidal applications, it has been found that the invention related preferably to the compounds of formula I In which Y is a halogen and n ~ 1, 2 or 3.

It has also been found that it was preferable to use the compounds of formula I in which n - 1 or 2, and Y is a halogen atom placed in the ortho and/or para position.

More preferably, n-2 and Y is a halogen atom, advantageously chlorine, placed In th® ortho- and the para-positions.

Taking into account the restrictions defined above, considered separately or In combination, it has been found that, by virtue of the fungicidal properties, It was preferable to use the triazole compounds of formula II In which Rx to R5 correspond to a hydrogen atom or to a lower cycloalkyl or alkyl group, Y, n and m have the same meaning as in formula I with the preferred variants listed above, and Hal corresponds to a halogen atom, preferably chlorine or bromine, and Xx is a halogen atom, preferably chloride or bromine, or a hydrogen atom, and advantageously a hydrogen atom.

Taking into account the restrictions defined above, considered separately or in combination, it has been found, that, by virtue of the fungicidal properties. It was preferable to us© th© triazol© compounds ox formula, III in which to R3 correspond to a hydrogen atom or to a lower cycloalkyl or alkyl group, Y, n and m have th® same meaning as in formula I, with the preferred variants listed above, X, corresponds to a hydrogen atom or to a lower cycloalkyl or alkyl group, Q has the same meaning as In formula I and R° corresponds to a hydrogen atom or to a lower cycloalkyl or alkyl group.

The preferred triazole compounds of formula II are those in which the Rj to R3 groups correspond to a hydrogen atom.

The preferred triazole compounds of formula III are those of which the Rx to R3 groups correspond to a hydrogen atom, where corresponds to a hydrogen atom or lower cycloalkyl or alkyl, and where Rg corresponds to a lower cycloalkyl or alkyl group and preferably Q ~ 0.

Th® present invention also relates to processes for the preparation of th® compounds according to the invention.

In the case where the X2 group corresponds to a halogen atom (compound of formula II), a preparation process consists of the following stages: Stage .a.) A haloketone of formula Ila obtained by a known process, in -which Y, n and R3 have the same meaning as that given for the compounds of formula I and 2 corresponds to a halogen atom, is reacted with an organometallic compound of formula lib, in which R, to R,% and X, have the same meaning as above and M. corresponds to an alkali metal or a magnesiumcontaining group (Mg Hal) or a zinc-containing group (Zn Hal) for example, in a solvent, preferably chosen from ethers such as diethyl ether or tetraS hydrofuran, aliphatic, alicyclic or aromatic hydrocarbons such as hexane or toluene at a temperature chosen between -50 °C and the reflux temperature of the solvent in question and in a molar ratio of IIa;IIb which is preferably of between 1.1 and 0-2.

The reaction leads to th® compound of formula lie after neutralisation of the reaction medium.

Stage ta) The compound of formula lie is then reacted with an unsubstituted triazole or imidazole in the presence of an organic or inorganic base, for example pyridine, triethylamine, sodium hydroxide, potassium hydroxide, carbonates and bicarbonates of alkali or alkaline earth metals, and in a suitable solvent such as, for example, alcohols, ketones, amides, nitriles or optionally halogenated aromatic hydrocarbons, at a temperature of between 80® and the reflux temperature of the solvent and in a molar ratio of He:imidazole or triazole which is preferably of between 1.1 and 0.2, which leads to the compound of formula lid. The reaction generally passes through an epoxide intermediate or formula Uh which may, if appropriate, be isolated or prepared separately by methods known to the man skilled in the art.

Stage c) A molecule ox halogen or of mixed halogen is added, preferably mole for mole, to the compound lid in an inert solvent such as saturated or optionally halogenated aromatic hydrocarbons, which leads to the compound lie.

Stage d) The compound II is preferably obtained at ambient temperature by the cyclisation of the compound lie in the presence of an organic or inorganic base indicated in b in a molar ratio of compound Ilsbase which is preferably of between 1.1 ~ 7 ~ and Ο , δ ο The reaction may be carried out in a protic or aprotic solvent (water, alcohol, ketone, nitrile, ester, saturated or optionally halogenated aromatic hydrocarbon, dimethyl sulphoxide or amide such as dimethylformamide).

A second process for the preparation of the compounds where the X2 group Is a halogen consists in placing stage b) of grafting the imidazole or triazole ring after stage d), using the same procedure for the different stages. Thus, a halogen or halogen halide (mixed halogen) molecule is added to the compound lie to give the compound Ilf, the latter than being cyclised to give the compound Ilg, which is then provided with a triazole or imidazole group to give th® compound II.

Other preparation processes may, of course, also be suitable.

In the case where the X2 group corresponds to QR6, and Xx is other than Hal (compounds of formula III), one preparation process consists in reacting a compound of formula II with a heteroatomic nucleophile of formula Rg-Q-E, in which Rs and Q have the same meaning as in formula I and E Is a cation, for example an alkali or alkaline earth metal or a quaternary ammonium. The reaction is carried out in a suitable solvent in the presence of a base and, if appropriate, a phase transfer catalyst and at reaction temperatures which are generally of between -30 C and the reflux temperature of the solvent used and in a molar ration II:RSQ E which is preferably of between 1.2 and 0.1.

Another process consists in reacting the compound Ilg under the same conditions with the same heteroatomic nucleophile to obtain ε compound Ilia to which the . triazole or imidazole ring is then attached as described previously.

It is also possible to obtain the compounds in the formula of which Rg Is an optionally mono- or polyhalogenated lower alkyl group, by reacting the·· compounds III or Ilia in the formula of which Rg cor8 responds to the hydrogen atom with an alkyl halide (monoor polyhalogenated, is appropriate) in a molar ratio of III or liashalide which is preferably of between 1.1 and 0.2» in the presence of an organic or inorganic base. If the starting compound was Ilia» a triasole or imidazole ring is then attached.

In the case where X, corresponds to a hydroxyl group (compounds of formula III in which Q corresponds to the oxygen atom and Rg to the hydrogen atom)» compounds of formula Ug or II may also be reacted, if appropriate, in the presence of an inert organic solvent, at a temperature of between -30 s and the reflux temperature of the solvent, with a hydroperoxide, hydroxide, oxide or superoxide of an alkali metal, alkaline earth metal or other metal, in a molar ratio which is preferably of between 1.1 and 0.2, and, in the case where compound Ilg is the starting compound, an imidazole or triazole ring may then be attached.

In the case where Z2 corresponds to J?3, the compounds Ilg or II are reacted with an alkali metal or ammonium azide in a molar ratio which is preferably of between 1.1 and 0.2» preferably in an aprotic solvent, at a temperature of between -30° and ths reflux temperature of the solvent, and, if Ilg was the starting compound, the azide compound is then reacted with an imidazole or triazole ring.

In the case where Z2 corresponds to a hydroxyl group, th© compounds lie or lid may also be reacted with a peroxide in order to obtain the epoxide compounds of formula Illb for lie, and IIIc for the compound lid. These epoxides may then b® hydrated to triols Hid and I He respectively in a way which is well known. The cyclisation is carried out in the presence of a dehydrating agent such as hydrochloric, hydrobromic, sulphuric or sulphonic acids, if appropriate in a protic or aprotic solvent. This leads to compound Ilia in which QRg corresponds to OH to which a triazole or imidazole ring is then attached, or to compound HI in the case of the β compound, me. Optionally, if necessary, the alcohol group may be protected in a manner known per se for compounds IIId and Ills.

Tbe compounds of formula, II or Ilg may also be 5 reacted with an alkali metal or alkaline earth metal carboxylate (acyclic, cyclic, saturated, unsaturated or aromatic) (especially sodium benzoate) in the presence of a phase transfer catalyst and optionally in the presence of an aprotic polar or inert solvent, If reauired in the presence of water, and at temperatures of between 0® and the reflux temperature of the solvent in question.

In the case where Xx and x2 together correspond to an oxygen atom which is doubly bonded to tetrahydro furan (compounds of formula IV where 1, corresponds to the oxygen atom), one process of preparation consists In operating from a compound of formula Ilia or III in which QR3 corresponds to hydroxyl and Xx to hydrogen, with a well-known oxidising agent in order to obtain a compound IV or IVa onto which an imidazole -or triazole ring Is grafted.

Th® gem-halogenated compounds (Xx = X2 ~ Hal) are prepared by reacting phosphorus pentachloride with the ketone (compound of formula IV in which Xx corresponds to an oxygen atom), if required In the presence of an aprotic inert solvent and if required in th® presence of a quaternary ammonium halide, preferably at ambient temperature.

In order to obtain the thioketone group (compound of formula IV < where Xx corresponds to the sulphur atom) thionation of the ketone group is carried out by reacting the compounds IV or IVa, for example, with H,S or P2S5 in a molar ratio which Is preferably of between 1.. 1 and 0.2, in the presence of an inert organic solvent (pyridine or hydrocarbon, for example) at a temperature of between 20* and the reflux temperature.

In the case where X, and X2 simultaneously correspond to 0¾ (compound of formula V) the compounds of' formula (IV) or (IVa) in which Xx (or X2) corresponds to an oxygen or sulphur atom which is doubly bonded to tetrahydrofuran are reacted with a compound of formula KQRg where Q corresponds to Q or S in a molar ratio which is preferably of between 1.1 and 0.2, in the presence of an acid catalyst and in a suitable solvent, which may be the alcohol or thiol itself, or an inert solvent such as hydrocarbons or alcohols. If the starting compound was that of formula IVa, th© compound of formula Va is obtained and an imidazole or triazole ring is then grafted onto the compound of formula Va.

In the case where and X2 correspond to Q-Ry-Q and R7 constitutes a single divalent radical as defined previously, the compounds of formula (IV) or (IVa) are reacted with a compound HQ-Ry-QH under the same conditions as for the monohydric alcohols or the monothiols. If IVa was the starting compound, th® compound Vb is obtained, to which an imidazole or triazole is attached under the same conditions as before.

In the case where X2 corresponds to N-R8R9, a preparation process consists in reacting a compound of formula II or of formula IXg with an amine of formula Π-N R8Rg in a molar ratio of between 1.1 and 0.2, if appropriate In the presence of another organic or inorganic base. This leads to the compound of formula VI In the case where the starting compound was that of formula II and to compound via to which an imidazole or triazol® ring is subsequently attached In the case where the starting compound was that of formula Ilg.

In the case where Σ, (or X2) corresponds to the = N-R10 group (compound of formula VII), a compound of formula IV or IVa Is reacted with an amine of formula R10-NH, or with one of its salts in a molar ratio which is preferably of between 1.1 and 0.2, in an inert organic solvent. In the case of the compound IVa, the compound Vila is obtained, to which an imidazole or. triazole ring is then attached.

The compound of formula VII in which R10 corresponds to a hydroxyl may also be reacted with an alkylating agent of formula Ru .0 in which Ru is an optionally substituted lower alkyl and in which D corresponds to a sulphonium, ammonium, sulphonate or sulphate group, in the presence of an organic or inorganic base, in order to obtain the oxime substituted on the oxygen.

The subject of the invention is also the compounds which can be used, if appropriate, as intermediates in the preparation processes described above and of formula II, lie, lid, He, Ilf, Hg, Ilh, III, Ilia, mb, me, Hid, Hie, IV, iva, v, va, vb, vi, via, vii and Vila in which Rx to Y, Tr, Im, m, η, X,, X,, Q, Hal and Z have any one of th© meanings mentioned in the preceding description.

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

Th© compounds according to the invention may be used for the preventive as well as curative control of fungi, especially of the basidiomycetes, ascomycetes, adelomycetes or fungi imperfect! type, in particular the rusts, mildew, eyespot, fusarium diseases, helminth©sporium diseases, septoria diseases and rhizoctonia diseases of crops and of plants in general and, in particular, of cereals such as wheat, barley, rye, oats and their hybrids and also rice and maize. Th® compounds according to the invention are active, in particular, against fungi, especially of the basidiomycetes, ascomycetes , adelomycetes or fungi imperfect! type such as Botrytis cinerea, Erysiphe graminis, Puccinis recondita, Piricularia oryzae, Cercospora beticola, Puccinia striiformis, Erysiphe cichoraceaxum, Eusarium oxysporum (melonis), Pyrenophora avenae, Septoria tritici, Venturia in&egrualis, Whetzelinia sclerotiorum, Manilla laxa, Mycosphaerella fijiensis, Marssonina panettoniana, Alternaria. solani, Aspergillus niger, Cercospora arachidicola, Cladosporium herbarum, Helminthosporium oryzae, Penicillium expansum, Pestaloszia so.., Phialophora cinerescens, Phoma betas, Phoma foveata, Phoma lingam, Ustilago 'maydis, Verticillium dahlia®.

Ascochyta pisi, Guignardia bidwellii, Corticium rolfsii, Phomopsis viticola, Sclerotinia scXerotiorum, Scleratinia minor, Coryneum cardinals and Rhizoctonia solani.

They are also and continue to be active against the following fungi: Acrostalagmus koningi, the Alternaria, the Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hoxmodendron cladosporioides, Lentinus degener or tigrinus, Lenzites guercina, Msmnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pellicularia sasakii, Phellinus megaloporust Polystictus sanguineus,,, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, the Stereum, Stilbraa sp., Trametes trabea, Trichoderma pseudokoningi and Trichothecium roseraa.

The compounds of the invention ar© of special interest because of their broad spectrum as regards cereal diseases (mildew, rust, eyespot, net blotch, leaf spot and fusarium diseases). They are also of special interest because of their effectiveness against grey mould (Botrytis) and cercospora diseases and, because of this, they may be applied on crops as varied as grape vine, market-garden crops and tree crops and tropical crops such as peanut, banana, coffee, pecan nut and others.

In addition to the applications already described above, the products according to the invention additionally have an excellent biocidal activity with respect to many other kinds of microorganisms, among which there may be mentioned in a non-limiting way fungi such as those belonging to the genera: - Pullularia such as the species P. pullulans, - Chaetomium such as the species C. globosum, - Aspergillus such as the species Aspergillus niger, - Conxophora such as the species C. puteana.

Owing to their biocidal activity, the products of the invention make it possible to control effectively microorganisms whose proliferation gives rise to numerous problems in the agricultural and industrial fields. To this end, they are particularly well suited for the protection of plants or of industrial products such as wood, leather, paints, paper, ropes, plastics and industrial water circuits.

They are particularly well suited for the protection of lignocellulos© products and especially of wood, whether it is timber for furniture or construction, or timber which is exposed to bad weather such as timber for fencing, vine stakes or railway sleepers.

The compounds according to the invention, used on their own or in the form of compositions as defined above in the treatments of wood, are generally employed with organic solvents and may, if appropriate, be used in combination with one or xaore known biocidal products such as pentachlorophenol, metal salts, especially copper, manganese, cobalt, chromium or sine salts derived from inorganic or carboxylic acids (heptanoic, octanoic or naphthenic acids); organic complexes of fin, mercaptobenzothiazole, insecticides such as pyrethroids or organochlorine compounds.

Finally, they have an excellent selectivity with respect to crops.

They are advantageously applied at doses of 0.005 to 5 kg/ha, and more specifically 0.01 to 0.5 kg/ha.

In practical use, the compounds according to the invention are rarely used alone. Most often they form 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 the active substance a compound according to the invention as described previously, in association with solid or liquid carriers which are acceptable in agriculture, and/or surfactants, also acceptable in agriculture. Conventional inert carriers and conventional surfactants can especially be used.

The term carrier, in the present description, denotes a natural or synthetic organic or inorganic material, with which the active substance is combined In order to facilitate its application on the plant, on seeds or on th® soil. Therefore, this carrier is generally inert and it must be acceptable in agriculture, especially on the treated plant. The carrier 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.).

Th® surfactant may be an emulsifier, dispersant or wetting agent of Ionic or non-ionic type. For example, ι there may be mentioned polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), sulphosuccinic acid ester salts, taurine derivatives (especially alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols. The presence of at least one surfactant is generally indispensable when the active substance and/or the inert carrier are insoluble in water and the vector agent for the application Is water.

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

As solid forms of compositions, there may be mentioned powders for dusting or scattering (with a content of the compound of formula (1) reaching up to 100 %) and granules, especially those obtained by extrusion, by compacting, by impregnation of a granulated carrier, or by granulation starting from a powder (the content of the compound of formula (I) in these granules being between 1 and 80 % In these latter cases).

As liquid forms of compositions, or forms intended to constitute liquid compositions when applied, there may be mentioned solutions, especially water-soluble concentrates, emulsifiable concentrates» emulsions» flowables» aerosols» wettable powders (or powder for spraying) and pastes.

The emulsifiable or soluble concentrates most 5 frequently contain 10 to 80 % of active substance» whereas the emulsions or solutions ready for application contain» for their part, 0.01 to 20 % of active substance.

These compositions may also contain any other 10 type of ingredients such as» for example» protective colloids» adhesives» thickeners, thixotropic agents, penetrants» stabilisers, sequestering agents and th© like, as well as other known active substances with pesticidal properties (especially insecticidal or fungi15 cidal properties) or properties which promote plant growth (especially fertilizers) or plant growth regulating properties. More generally, the compounds according to the invention may be combined with all those solid or liquid additives which correspond to th® usual techniques of formulation.

For example, in addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20 % of suitable additives such as the stabilisers, surfactants, penetrants, corrosion inhibitors, colouring agents or adhesives mentioned above.

In the case where the compounds according to the invention are used as fungicides,, the doses to be used may vary within broad limits according, in particular, to the virulence of the fungi and the climatic conditions.

In general, compositions containing 0.5 to ,000 ppm of active substance are very suitable; these values apply to the compositions ready for application. Ppm denotes parts per million". The range from 0.5 to 5,000 ppm corresponds to a range from 5 x 10'3 to 0.5 % (percentages by weight).

As regards compositions which are suitable for storage and transportation, they more advantageously contain from 0.5 to 95 % (by weight) of active substance.

Thus, the compositions for agricultural use according to the invention may contain the active substances according to the invention within very broad limits, ranging from 5,10"5 % to 55 % (by weight).

By way of example, the compositions of some concentrates are given below: Example F (formulation) 1 Active substance Alkali metal dodecyl benzenesulphonate Oxyethylated nonylphenol containing 10 molecules of ethylene oxide Cyclohexanone Aromatic solvent q.s.

According to another formula for an emulsifiable concentrate, th® following are used: Example F 2s Active substance Epoxide-treated vegetable oil Mixture of alkylarylsulphonate, polyglycol ether and fatty alcohols Dimethylformamide Xylene 400 g/litre g/litre g/litre 200 g/litre 1 litre 250 g 25 g 100 g 50 g 575 g From these concentrates, by dilution with water, it is possible to obtain emulsions of any desired concentration , which are especially suitable for application on leaves.

Flowables, which can also be applied by spraying, are prepared so as to obtain a stable fluid product which does not settle > they usually contain from 10 to 75 % of active substance, from 0.5 to 15 % of surfactants, from 0.1 to 10 % of thixotropic agents and from 0 to 10 % of suitable additives such as antifoams, corrosion inhibitors, stabilisers, penetrants and adhesives, and, as a carrier, water or an organic liquid in which the active substance is of low solubility or insoluble: some solid organic substances or inorganic salts may be dissolved In the carrier to assist in preventing sedimentation, or as anti-freezes for the water.

The wettable powders (or powder for spraying) are usually prepared so as to contain 20 to 95 % of active substance, and they usually contain, in addition to the solid carrier, from 0 to 5 % of a wetting agent, from 3 to 10 % of a dispersant, and, when necessary, from 0 to 10 % of one or more stabilisers and/or other additives such as penetrants, adhesives, or anti-caking agents, colouring agents etc.

By way of example, various compositions of wettable powders are given below: Example F 3= 1 Active substance 50 % Calcium ligno,sulphonate (deflocculant) 5 % Isopropyl naphthalenesulphonate (anionic wetting agent) 1 % Anti-caking silica 5 % Kaolin (filler) 39 % Another composition of powder for spraying, at 70 % strength, uses the following constituents: Example F 4: Active substance 700 g Sodium dibutylnaphthalenesulphonate 50 g Condensation product of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde in proportions 3:2:1 30 g Kaolin 100 g Whitener 120 g Another composition of powder for spraying, at 40 % strength, uses the following constituents; Example. JL 5.» Active substance 400 Sodium lignosulphonate 50 Sodium dibutylnaphthalenesulphonate 10 Silica 540 Another composition of powder for. spraying, at 2S % strength, uses the following constituents: Example F._ 6: Active substance 250 g Calcium lignosulphonate 45 g Mixture of whitener and hydroxyethylcellulose in equal parts by weight 19 g Sodium dibutylnaphthalenesulphonate 15 g Silica 195 g Whitener 195 g Kaolin 281 g Another composition of powder for spraying, at 25 % strength, uses the following constituents: Examole F 7; Active substance 250 g Isooctylphenoxy-polvoxyethylene-ethanol 25 g Mixture of whitener and hydroxyethylcellulose in equal parts by weight 17 g 15 Sodium aluminosilicate 543 g Kieselguhr 165 g Another composition of powder for spraying, at 10 % strength, uses the following constituents: Example F 8; Active substance 100 g Mixture of sodium salts of sulphates of saturated fatty acids 30 g Condensation product of naphthalenesulphonic acid and formaldehyde 50 g Kaolin 820 g To obtain these powders for spraying or wettable powders, the active substances are intimately mixed In suitable mixers with the additional substances, and the mixtures are ground in mills or other suitable grinders.

Powders for spraying are thereby obtained, the wettability and suspendability of which are advantageous; they may be suspended In water at any desired concentration and these suspensions may be very advantageously used, especially for application on plant leaves.

Instead of the wettable powders, pastes can be produced. The conditions and means of production and use of these pastes are similar to those for wettable powders' or powders for spraying.

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

Granules intended for placing on the soil ar® 10 usually prepared so as to be between 0.1 and 2 mm in size, and they may be manufactured by agglomeration or impregnation. In general, the pellets contain 0.5 to 25 % of active substance and 0 to 10 % of additives such as stabilisers, slow-release modification agents, binders and solvents.

According to an example of granule composition, the following constituents are used: Example F 9s Active substance 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 ease, the active substance is mixed with epichlorohydrin and dissolved in 50 g of acetone; polyethylene glycol and cetyl polyglvcol ether are then added. The kaolin is wetted with the solution obtained and the acetone is then evaporated under vacuum.

A microgranule of this type is advantageously used to control soil fungi.

The compounds of formula (I) may also be used in the form of powders for dusting; a composition containing 50 g of active substance and 950 g of talc can also be used; a composition containing 20 g of active substance, g of finely divided silica and 970 g of'talc may also be used; these constituents axe mixed and ground, and the mixture is applied by dusting.

Examples I to VII illUcStrate particular ways of preparing the compounds according to the invention as well as these compounds themselves. Ths nomenclature of the compounds has been given according to French standards, except that the numbering of the substituents has been placed before the substituents themselves.

Example I: Preparation of l-r4-bromo-2-(2,4-diehloro~ phenyl 1 tetrahydrof ux-an-2_-ylmethyl Ί - IH-1 ,.2^4^ r iazole..

Compounds Nos, la. lb and la + lb Stage a) Preparation of l-chloro-2-(2»4-dichlorophenyl) 4-penten~2-ol; An organomagnesium derivative is prepared by adding a solution of allyl bromide (110 ml) in ethyl ether (700 ml) and tetrahydro furan (200 ml) with magnesium (110 g)» between 15 and 20°C» over three hours. The mixture is refluxed for 30 min and decanted, and the residue is washed with ether.

A solution of alpha»2»4-trichloroacetophenone (175 g) in tetrahydrofuran (250 g) at -30°C is added to this organic phase and the mixture is neutralised with acetic acid. This is washed with water, dried over sodium sulphate, concentrated and then distilled under vacuum. A colourless oil is obtained (205 g). B.p. (3 10'2 mm Hg) = 140-142°C.

Stage b) Preparation of l-[2-(2»4-dichlorophenyl)~ 2-hydroxypenten-4-yl]-1H-1»2»4-triasole A mixture of the product obtained in stage a) (106 g), triazole (55 g) and potassium carbonate (160 g) is heated in dimethylformamide (600 ml) at 120e for four hours. The insoluble materials are filtered and washed with dimethylformamide, and the reaction mixture is concentrated under vacuum. The residue, dissolved in methylene chloride. Is washed with water and then concentrated. The product Is obtained by crystallisation in ethyl acetate after dilution with heptane. A pale pink solid, m.p. 101% Is isolated (97 g).

Stage c) Preparation of the compounds No. la and So. lb The compound obtained in stage b (35 g) in chloroform (200 ml) is treated with bromine at 0°. After decolorising, the solvent is evaporated and the residue redissolved in methanol. An aqueous solution of potassium hydroxide is then added until a basic pH is obtained. After evaporating the medium under vacuum, the residue is extracted with ethyl acetate, washed with water and concentrated. Th© oil obtained (40 g) consists of a mixture of two diasfereoisomers in substantially equal proportions. Using silica column chromatography, th© least polar isomer No. las white crystals m.p. 83 e, and then the most polar isomer No. lb: white crystals m,p. 94°, are isolated In sequence. After recxystallisafcion, la, m.p. 96s and lb, m.p. 104°, ar© obtained. The 50:50 mixture of la and lb has a melting point of 74°.

The following compounds were prepared in the same way, using the appropriate raw materials: l-[4-bromo~ 2- ( 4-chlorophenyl)tetrahydrofuran-2-ylmethyl) 1H-1,2,4-triazole: 1C: m.p. 74e; Id: m.p. 78® and Ic+d: m.p. 69°.

Example, II - Preparation of 1-f 2- f 2,4-dichlorophenyl)4 ^hydroxytetrahydrofuran^a-y Imethyl) -1H-3^.2.,, 4ttr.iazole.._ Compounds No..2a and No. 2b. g of the isomer la of Example I, which is the least polar isomer, dissolved In 30 ml of chlorobenzene, Is refluxed for 48 h, in the presence of 20 g of sodium benzoate in 30 ml of water, and 1 g of the phase transfer catalyst ADOGSN 464 methyltrialkylammonlum. chloride. The 4-benzoate compound, that is to say the compound 4a (X, - H and S2 = OC@) of melting point 98 aC, or the II o compound 4b (2^ = OC0 and Z, ~ H) of melting point 140°C, II o Is then obtained as an intermediate.

After diluting with ether, the organic phase is.. •washed with water and reduced under vacuum. The residue is then treated with methanol (100 ml) in the presence of potassium hydroxide (7 g) at reflux temperature for 3 hours. The mixture is cooled, diluted with water and extracted with ethyl acetate, and the product washed to neutrality and. purified by chromatography, the crude product being obtained after concentration under vacuum. The alcohol 2a is isolated In tha form of a white powder (2.8 g), aa.p. 193.

Operating In the same way, starting from the most polar isomer lb obtained according to Example I, th® optically active alcohol 2b is obtained in the form of a white powder, m.p. 162°C. The 50:50 mixture of 2a and 2b is an oil.

Example III - Preparation of 1-(2-(2,4-dichlorophenyl)4-ethoxyt.etrahydgofuran-2-ylmethyl)-1K~1,2,4-triazole.

Comoounds No. 3a and No. .3b.

The alcohol 2a (2., 2 g) dissolved in dimethylsulphoxide (12 ml) is treated, in sequence, with 80 % strength sodium hydride (0.42 g) and then with ethyl iodide (1.15 ml). After 15 minutes, the medium is diluted with water and extracted with ethyl acetate. After washing with water, the solvent Is evaporated and the residue is purified by silica column chromatography to obtain a colourless oil which Is the isomer 3a which crystallises on trituration with pentane m.p. 90; in the same way, starting with 2b, the isomer 3b, which is a whit® powder, m.p. 63, is obtained. The 50:50 mixture of 3a + 3b is an oil. The compounds of formula VIII listed in the following table were obtained in the same way, using the appropriate alcohols: __________ _ _ No. Melting point 5a H o-ch3 oil 5b o-ch3 H oil 6a H O-n-Pr oil 6b O-n-Pr 3 oil Example IV - Preparation of l-r2-L2,4-dichlorophenvll4-ethylthiotetrahydrofuran-2-ylmethyl 1-1H-1,2,4-triazole.

Compounds No. 7a and No. 7b The bromide la (3.8 g) dissolved in dimethyl sulphoxide (38 ml) containing water (2 ml) is treated with sodium hydrogen sulphide (2.8 g) for 2 hours. Powdered potassium hydroxide (3.3 g) is then added, followed by ethyl iodide (< ml). After 10 minutes of stirring, the medium Is diluted with water and extracted with ether. After drying and evaporation, the isomer 7a, which is a yellow oil (3-9 g), m.p. 88", is obtained.

Operating in the same way, starting with lb, 7b is obtained In the form of a pale yellow powder, m.p. 64°. The mixture of isomers is an oil. The compounds of formula VIII listed in the following table were obtained in the same way, using the appropriate thiols: No. Xx X, Melting point 8 8. H s-ch3 96 8b s-ch3 H oil 9a H S-n-Pr 110 9b S-n-Pr H oil 10a H S-2-ClEt 127 10b S-2-ClEt Ά oil Ila H S-i-Bu 68 11b 5-i-Bu H oil 12 a H S-i-Pr 75 12b S-i-Pr H 65 Example V - Preparation of 1-(7-(2,4-dichlorophenyl) 1., 4 ,6_-tr ioxospiroj4_._4] nonan-7-ylmethyll-1H-1 „2,4triasole.

Compound No. 13 Stage, a) Preparation of l-chloro-2-(2,4-dichlorophenyl) 3 f4,5-pentanetriol.

The chlorohydrin obtained in stage a) of Example 1 (91 g) is epoxidised in 1,2-dichloroethane (125 ml) in the presence of vanadyl acetylacetonate (5 g) and 70 % strength tert-butyl peroxide (200 ml) by heating at tine reflux temperature for 48 hours. The cooled medium is diluted with water, washed several times with a sodium bisulphite solution and then concentrated. The residue is then converted to triol by heating in water (200 ml) and dioxan© (200 ml) in the presence of perchloric acid (5 ml) for 3 hours. After dilution with water, the medium is extracted with toluene (300 ml) and then concentrated. Stace hl Preparation of 2-(2,4-dichlorophenyl) -2-chloromethyltetrahydrofuran-4-one The oily residue obtained In stage a) is then heated, in toluene (100 ml) and butanol (200 ml) in the presence of paratoluenesulphonic acid (0.5 g), with the separation of the water formed. After evaporating the reaction medium, the residue is chromatographed on a silica column (40sSO ethyl acetate/heptane eluent) to obtain a colourless oil (14.5 g) corresponding to a mixture of alcohol diastereoisomers, namely 2-(2,4-dichlorophenyl) -4-hydroxy-2-chloromethyltetrahydrofuran. This product is directly oxidised with chromic anhydride In acetic acid to obtain, after purification by silica column chromatography, furanone In the form of white crystals, m.p. 99°C.

Stage cl Preparation of 7-chloromethyl-7-(2,4-dichlorophenyl )-1,4,6-trioxaspiro [4.4] nonane.

The furanone obtained in stags b.) (4.2 g), In toluene (50 ml). Is heated at reflux temperature in th© presence of ethylene glycol (S. 5 ml) and p-toluenesnlphonic acid (0.1 g), with the separation of the water formed, until the disappearance of the starting product.

The medium is washed with sodium hydroxide and then diluted with water, extracted with ether and concentrated. A white solid (5.1 g), m.p. 99 9, is obtained. Stage d) Preparation of compound 13 The halide of stage c) (5 g) in dimethyl sulphoxide (20 ml) is heated to 170° in the presence of triazolyl sodium (2.75 g) for 6 hours. The medium is poured into water, extracted with ethyl acetate, concentrated and purified by silica column chromatography. After recrystallisation in an ethyl acetate/heptane mixture, pale yellow crystals (3.S g), m.p. 123°, are isolated.

Example VI - Preparation of 1- Γ 4-chloro-2-(2 ,_4-dichlorophenyl ) Ttetrahydrof uran-2-ylmethylJ -IK-KJb 4-triazole. Compounds No. 14a and No. 14b Stage al Preparation of 2-(2,4-dichlorophenyl)1 , 4 , 5-trichloro-pentanol.

The chlorohydrin obtained in stage a) of Example I dissolved in dichloromethane (150 ml) is treated with gaseous chlorine (13.4 g) at -159. The medium Is than treated with a 37 S strength sodium bisulphite solution (15 ml), washed with water, dried and then evaporated. A crude product In the form of a colourless oil (49.7 g) containing approximately 70 % of the desired product in the form of a mixture of two diastereoisomers Is obtained.

Stage b) Preparation of l-(2,4-dichlorophenyl)-l-(2,3dichloro-l-propanyl)oxirane A first method consists in dissolving the crude chlorohydrin (10.3 g) obtained in stage a) above in methanol (30 ml) and treating It with a solution of methanolic potassium hydroxide (12 ml) at a concentration of 2.55 - 10*3[sic] moles/litre, at ambient temperature. The precipitate is filtered and the methanolic solution is evaporated under vacuum. The residue is purified by silica column chromatography. A colourless oil is obtained (7.4 g).

(. A second method consists in dissolving the chlorohydrin (19.9 g) obtained in stage a of Example I in methanol (75 ml), and treating it with a potassium hydroxide (4.9 g) solution in methanol (20 ml) at ambient temperature. After the filtration of the insoluble material and evaporation, epoxide (17.1 g) is obtained in the form of a yellow oil. This epoxide is treated with chlorine until the yellow colour (10.1 g) persists at -15°C. The medium is then washed with a sodium bisulphite solution followed by water, and then evaporated under vacuum. A, yellow oil (20.8 g) consisting of a mixture of two diastereoisomers in a ratio of 45;55 is obtained. Stage c) Preparation of l-(4-chloro-2-(2,4-dichlorophenyl )tetrahydrofuran-2-yImethy1]-1H-1,2,4triasole The epoxide obtained in stage b) (61.7 g) in 1-butanol (0.5 litre) is heated at 90° for 6 hours in the presence of triazolyl sodium (18.6 g). Th® inorganic precipitate is filtered and the butanol is evaporated. The residue is purified by silica column chromatography (48 % ethyl acetate:48 % heptane: 4 % methanol eluent) to obtain, in sequence, the first diastereoisomer 14a, m.p. 113s’, and then the second diestereoisomer 14b, m.p. 97®. The 50:50 mixture of 14a + 14b has a melting point of 90s.

Example VII Preparation of 1- Γ 4-oxo-2- (2,4-dichlorophenyi) tetrahydrofuran-2-vlmethvlJ-lH-l, 2., 4-triazole. Compound .15 The alcohol 2a (37.7 g) is added at -60" to a solution of dimethyl sulphoxide (17 ml), in dichloromethane (120 ml), treated at -60* with a solution of trifluoroacetic anhydride (25.4 ml) in dichloromethane (SO ml). After maintaining at -60s for half an hour, the temperature is allowed to rise to ambient temperature and triethylamine (48 ml) is then added. The medium is poured into water, extracted with dichloromethane and evaporated. A white powder (m.p- 91*) is isolated by crystallisation in ether. ( 10 ( Example viii Preparation of .l~f4.4-dichloro-2~r_2r4-diehlorophenyrL·: tetrahv,drofuran-2-vlmethvl 1-1H-1., 2,4-triazole.

Compound No.. 20 A mixture of ketone 15 (3.1 g), phosphorus pentachloride (2.3 g) and dichloromethane (30 al) containing triethylbenzyl&mmoniura chloride (0.25 g) is stirred for 2 hours at ambient temperature until the starting material disappears. Th® medium is evaporated, diluted with water (100 ml), neutralised with sodium bicarbonate and extracted with ether. After drying and evaporation, th® oily residue is recrystallised in isopropyl ether (twice). A white powder (Q.S g), m.p. 138°, is obtained.

Example II - Preparation of 1- Γ4-dixaethylamino-2- (2., 4dichlorophenyl) tetrahvdrof uran-2-ylmethyn -1H-1,2., 4triazole. Compound 16 The ketone of Example III and then sodium cyanoborohydride (0.24 g) are successively added to a solution of potassium hydroxide (0.24 g) and dimethylaraine hydrochloride (1.05 g) in methanol. After 15 hours, th® medium is diluted with water and extracted with ether. The desired product is then extracted from the organic phase with 6N hydrochloric acid (3 x 20 ml). After neutralisation, extraction and silica column chromatography, compound No. 5 (1.6 g) is isolated in the form of a pale yellow oil (50:50 mixture of 2 isomers).

Example X - Preparation of 1 - Γ 4-met hcxylming-2-(2,4dichlorophenyl)tetrahydrofuran~2-vlmethyl1-1H-1,2,4triazole. Compound 17.

The ketone of Example III (2 g) in ethanol (30 ml) is heated under reflux in the presence of methoxylamine hydrochloride (5.8 ml of a 25 % solution in water) for 2 hours. The medium is diluted with water, extracted with dichloramethane and evaporated. The product is isolated by crystallisation in a mixture of diisopropyl ether and heptane, in the form of a white.. powder, m.p. 108* (mixture of the two geometric isomers). ( 10 IS C The compounds in which Ru - H (4-hydroxyimino) m.p. " 195° 18 Ru ~ (4-isopropoxyimino) oil 19 were prepared in the same manner.

Example KI and those which follow illustrate the fungicidal applications of the compounds according to ths invention.

In these examples, the sprayings of solutions or suspensions of active substances are carried out under conditions such that the spraying of a solution or suspension of concentration equal to 1 g/litre corresponds on average to the application of approximately 2 micrograms of active substance per cm3 of leaf area of the plant.

Under the conditions of Example KI and those which follow, the compounds Illustrated showed no phytotoxicity.

In these examples, a product Is regarded as providing complete protection against a fungal disease when th© protection is at least 95 %? th® protection is regarded as good when it is at least 80 % (but less than 95 %)» as fairly good when it Is at least 70 % (but less than 80 %) and as average when it is at least 50 % (but less than 70 %).

In the present account, the percentages are, except where otherwise indicated and except those relating to yields,. percentages by weight. In the case where ths percentages are expressed relative to the stoichiometry, these are molar percentages. As regards concentrations, some of these ar© expressed in ppm (part per million) which corresponds to mg/litre.

Example XI - In vivo test. pq_Botrytis einerea on tomato An aqueous emulsion of the active substance to be tested, having the following composition, is prepared by fine grinding: - active substance under tests 60 mg - Tween 80 (surfactant consisting of an oleate of a polyoxyethylated sorbitan derivative) ( 10 ( diluted, to 10 % strength in water: 0.3 ml the volume is made up to 60 ml with water.

This aqueous emulsion is than diluted with water to obtain th® desired concentration. - to 40-day-old, greenhouse-cultivated tomatoes (variety Marmande) are treated by spraying with aqueous emulsions (called slurries) as defined above and at various concentrations of the compound to be tested. The trial is replicated twice with each concentration.

After 24 or 48 hours, the leaves ar® cut and placed in 2 Petri dishes (diameter 14 cm) the base of which has previously been provided with a disc of moist filter paper (5 leaflets per dish).

The Inoculum is then applied by means of a syringe by depositing drops (3 drops per leaflet) of a spore suspension. This suspension of Botrytis cinerea spores was obtained from a 15-day-old culture, which was then suspended in a nutrient solution (100,000 units/cm3).

Verification is carried out 3 and S days after the contamination by comparison with an untreated control.

Under these conditions, at a dose of 1 g/litre, a good or total protection is observed with compounds la, lb, la + lb, 3b, 5b, 6b, 8b, 9b, 12b, 14a, 14b, 14a + 14b and 17.

Example XII - In vivo test on Ervsiphe graminis on barley fbarley mildew) Barley, In pots, sown In plain soil. Is treated at the 10 cm height stage by spraying with an aqueous emulsion (called slurry) at the concentration indicated below. Th® trial is replicated twice. After 24 hours, the barley plants are dusted with Ervsiphe graminis spores, the dusting being carried out using diseased plants.

Readings are taken 8 to 14 days after contamination.

Under these conditions, the following results ar© observed: at a dose of 1 g/litre, good or total protection with compounds la, lb, la + lb, 2a, 2b, 3a, 3b, 3a + 3b, 4a, 4b, 5a, 5b, 6a, 6b, 7a + 7b, 8a, 8b, 13, 14a, 14b, 14a + 14b, 15, 17, 19 and 20.

Example XIII - In vivo test on Puccina [sicl recondita responsible for wheat rust Wheat, in pots, sown in plain soil, is treated at the 10 cm height stage by spraying with aqueous emulsions (called slurries) of the same composition as that described in Example VIII and at various concentrations of the comoound to be tested. The trial is replicated twice at each concentration.

After 24 hours, an aqueous suspension of spores (50,000 sp/cm3) is sprayed onto the wheat; this suspension was obtained from contaminated plants. The wheat Is then placed for 48 hours in an incubation cell at approximately 18 BC and at 100 % relative humidity.

After these 2 days, th® relative humidity is lowered to 60 %. The condition of the plants is verified between the 11th and the 15th days, after contamination, by comparison with the untreated control.

At a dose of 1 g/litre, good or total protection with compounds la, lb, la + lb, 3a, 3b, 3a + 3b, 5b, 6b, 7a, 7a + 7b, 8b, 12b, 13, 14a, 14b, 14a + 14b, 17, 19 and 20.

Example XIV - In vivo test on Piricularia orvzae responsible for rice blast Rice, in pots, sown in a 50::50 mixture of enriched peat and possolana, is treated at the 10 cm height stage by spraying with an aqueous emulsion (called slurry) defined above at the concentration indicated below. The trial Is repeated twice. After 48 hours, treatment is carried out by applying on the leaves a suspension of spores obtained In pure culture.

The reading Is carried out 8 days after contamination. under these conditions, the following results are observed: at a dose of 1 g/litre, good or total protection with compounds la, lb, la + lb, 3a, 3b, 6a, 8a, 8b, 9a, 9b, 10b, Ila, lib, 12a, 12b, 14a, 14b, 14a + 14b, 15 and 20.

Examole XV - In vitro test on seed funci and soil fund The action ox the compounds according to the invention is studied on the following fungi responsible for diseases of cereals and other plants s 1) Pyrenophorae avenae 2) Septoria nodorum 3) Helminthosporium teres 4) Fusarium rossua 5) Fusarium nivale 6) Fusarium culmorum 7) Rhisoctonia cerealis 8) Septoria tritici 9) Botrytis cinerea sensitive to carbendazime and to cyclic imides 10) Botrytis cinerea resistant to carbendazime and to cyclic imides 11) Pseudocercosporella herpotrichoides 12) Fusarium oxysporum F. sp. raelonis 13) Rhizoctonia solani 14) Helminthosporium gramineum The numbers which appear before the names will be used to represent these fungi in Table (II).

For each trial, the procedure is as follows; a nutrient medium consisting of potato, glucose and agar (PDA medium) is introduced supercooled into a series of Petri dishes (20 ml per dish) after sterilising in an autoclave at 120°C.

In the course of filling the dishes, an acetone solution of the active substance Is injected into the supercooled medium, to obtain the desired final concentration.

Petri dishes similar to the above, Into which are poured similar quantities of a nutrient medium which does not contain the active substance, are taken as control.

After 24 or 48 h each dish Is seeded by depositing a fragment of mycelium originating from a previous culture of the same fungus.

The dishes are stored for 2 to 10 days (depending on the fungus being tested) at 22 °C, and the growth of the fungus in the dishes containing the active substance to be tested is compared with that of the same fungus in the dish used as the control.

For each compound tested, the degree of inhibition of the fungus considered, at a dose of 30 ppm, is thus determined. The results are given in the following fable.

Compound No. 1 2 Fungi 6 7 3 4 5 la 100 100 100 95 100 100 95 lb 100 90 100 100 100 100 90 la + lb 100 95 100 95 100 100 90 2a 50 95 80 50 80 100 80 2b 80 110 80 50 90 90 80 3a 95 90 100 50 80 80 90 3b 95 95 100 80 90 100 90 3a + 3b 80 0 80 0 80 80 80 4a 90 0 90 80 80 90 90 4b 95 80 95 80 80 100 90 5a 50 90 50 50 50 50 50 5b 100 100 100 90 95 100 95 5 a 50 90 50 50 50 50 50 6b 100 95 95 80 90 90 90 7a 95 95 95 0 0 0 50 7b 95 90 95 0 0 0 50 7a + 7b 50 95 50 0 0 0 50 8a 95 80 95 80 50 100 80 8b 100 90 95 80 80 90 80 9a 95 90 95 80 80 90 80 9b 80 95 95 0 0 80 80 10a 80 0 80 50 90 95 80 10b 90 80 90 0 0 50 80 Ila 90 50 95 0 0 0 80 11b 90 80 95 0 0 0 80 Compound No. 1 2 3 Fungi 6 7 4 5 Ι2δ. 90 30 95 0 80 30 30 12b 95 90 95 80 80 90 80 13a — 90 <=-*— —- — -- 14a 95 95 100 ος a# *v 100 100 90 14b 95 90 100 90 95 100 90 14a + 14b 100 95 100 100 100 100 95 15 Λ» rvf 0 og 80 0 0 50 0 16 80 0 80 0 0 50 0 17 80 0 30 80 OS sf «w 80 30 18 19 90 0 80 80 90 50 80 20 90 80 95 90 95 90 90 Compound No. 8 0 10 Fungi 13 •a /9 1 w 11 12 la 100 100 100 100 100 80 100 lb - CJ« 95 100 100 80 100 la + lb 100 95 e# ¢3 100 100 90 OS 25 2 a 0 95 05 100 0 0 80 2b 0 80 50 100 80 0 80 3a o •A 90 90 95 0 0 90 3b 100 95 100 80 80 95 3a + 3b 0 80 95 0 0 0 80 30 4a 0 qs ας 0 0 0 90 4b 0 95 Ql« *4 90 95 0 95 5a 0 0 0 100 0 0 50 5b 0 ssg e/ «Si 90 100 95 90 90 i* . 3d 0 50 50 100 0 0 50 35 6b 50 ας 95 100 80 80 95 7a Q 95 95 OS 0 80 80 7b 0 ί 90 95 90 0 50 50 Compound No. 8 G 10 Fung. 11 12 13 14 7a + 7b 95 95 100 50 80 50 8a 0 80 80 80 80 80 95 8b 0 95 95 90 80 80 95 Q S3 0 90 SO 90 80 80 G5 rf QiJ 9b 0 ag rf 90 100 80 80 50 10a 50 80 0 0 0 0 0 10b 0 90 05 rf 190 80 50 50 9 0 Ila 0 0 80 50 50 50 95 11b 0 80 80 80 80 80 @5 12a 0 50 80 80 0 80 90 12b 0 95 95 90 80 80 100 13a - 0 0 100 50 0 - 14 a - 100 100 100 100 80 100 14b 0 95 05 100 80 80 100 14a*Hl4b 50 05 rf 05 rf 0& 100 100 80 95 15 - 0 0 95 0 0 0 16 0 0 0 0 0 0 80 17 0 80 80 0 0 0 80 18 19 0 0 0 0 0 0 90 20 0 80 90 100 50 80 90

Claims (28)

1. Compounds containing triazole ox imidazole, tetrahydrofuran and phenyl groups, characterised in that they correspond to the general formula (I) 5 in which A is a group (Y) a «-Ph~(CH 2 ) a ~, where Ph is a phenylene ring and at « 0 or 1, Y is a halogen atom or a cyano or nitro group, or an optionally halogenated alkyl or alkoxy group, 10 n is zero or a positive integer less than 6, It being possible for the groups Y to be identical or different when n is greater than 1, Tr represents a 1,2,4-triazol-l-yl group and Im a 1,3-imidazol-l-yl group, 15 R x to R 5 , which may be identical or different, represent a hydrogen atom or a linear or branched alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms, a phenyl or benzyl radical or an alkoxy radical containing at most 20 six carbon atoms, it being possible for these various radicals to be optionally substituted with one or more halogen atoms or alkoxy radicals containing at most six carbon atoms; X x and 2 2 , which may be identical or different, 25 represent a hydrogen atom, a halogen atom, an alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms or a phenyl or benzyl radical, it being possible for these various radicals to be optionally substituted in a manner similar 30 to the groups a, to R 3 , a group Q-R 6 , in which Q represents 0 or S, and R 6 represents a hydrogen atom or an alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms or a phenyl, benzyl, benzoyl or 5 acyl radical, it being possible for these radicals to be substituted in a manner similar to the groups R x to R s and to have identical or different meanings when and X, each correspond to OR 6 or SR 6 , a group of formula -Q-R 7 ~Q~, where Q has the same 10 meaning as above and in which R 7 is a divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, it being possible for one of these carbon atoms to be replaced by an oxygen or nitrogen atom, the said single divalent radical itself being optionally substituted with one or IS more halogen atoms or hydroxyl groups, . alkyl radicals containing at most six carbon atoms or alkoxy radicals containing at most six carbon atoms, a group -N-R e Rg, in which R 8 and Rg, which may be identical or different, represent a hydrogen atom or an 20 alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms or a phenyl radical, it being possible for these various radicals to be optionally substituted in a manner similar to the groups R x to R 3 , or alternatively R 8 and R g together 25 can form a single divalent hydrocarbon radical comprising from 2 to 6 carbon atoms, It being possible for on® of these carbon atoms to be replaced by an oxygen, sulphur or nitrogen atom, the said single divalent radical itself being optionally substituted with one or more halogen 30 atoms,, hydroxyl groups, alkyl radicals containing at most six carbon atoms or optionally halogenated alkoxy radicals containing at most six carbon atoms, a group =N-R 10 , in which R 10 corresponds to an alkyl radical containing at most six carbon atoms, or a 35 cycloalkyl radical containing at most Is carbon atoms, or to a group of formula 0R u in which R u is an alkyl, it being possible for these radicals to be substituted in a' manner similar to the groups R x to or a hydroxyl group, a. group N 3 , on condition that X 2 is other than Kt 3 , X x or X 2 can correspond to -0 or =S, the other group being eliminated, on the general conditions that X x and X 2 cannot simultaneously correspond to a hydrogen atom or to an alkyl radical containing at most six carbon atoms, a cycloalkyl radical containing at most six carbon atoms, a phenyl radical or a benzyl radical, and if X x and X 2 are different and either one of them is 0R 6 , then, in this case only, Rg can be only a benzoyl or acyl groups and their salified forms.

2. Compounds according to Claim 1, characterised in that m = 0, n = 1, 2 or 3 and Y is a halogen atom.

3. Compounds according to Claims 1 and 2, characterised in that n = 1 or 2 and Y Is a halogen atom in the ortho and/or para position.

4. Compounds according to Claim 3, characterised in that Y is a chlorine or bromine atom.

5. Triazole compounds according to one of Claims 1 to 4, characterised in that they correspond to the formula II in which Y, m and n have one of the meanings indicated in the compound of formula I, R, to R 3 correspond to a hydrogen atom or to an alkyl or cycloalkyl group containing at most six carbon atoms, Hal corresponds to a halogen atom and X, Is a halogen or hydrogen atom.

6. Compounds according to Claim 5, characterised in that Hal is chlorine or bromine and X x is chlorine or bromine.

7. Triazole compounds according to one of Claims 1 to 4, characterised in that they correspond to the formula ill in which Y, n and m have one of the meanings indicated in the compound of the formula I, R x to R 3 correspond to a hydrogen atom or to an alkyl or cycloalkvl group containing at most six carbon atoms, H, corresponds to a hydrogen atom or to an alkyl or cycloalkyl group containing at most six carbon atoms, Q has the same meaning as in the formula I and Rg corresponds to a hydrogen atom or to an alkyl or cycloalkyl group containing at most six carbon atoms.

8. - Compounds according to Claim 7, characterised in that the groups R x to R 3 correspond to a hydrogen atom or to an alkyl or cycloalkyl group containing at most six carbon atoms, and R e corresponds to an alkyl or cycloalkyl group containing at most six carbon atoms and optionally substituted In a manner similar to the groups Rl to R5 ·

9. Process for the preparation of the compounds of formula II, In which R x to R 5 , A, Y, n and X x have the same meaning as in Claim 1 and Hal corresponds to a halogen atom, characterised in that it consists of the following steps; Step, a.). A halo ketone of formula Ila, Ila in which Y# n and R 3 have th® same meaning as that given for the compounds of formula I and Z corresponds to a halogen atom, is reacted with an organometallic compound of formula lib, Ί* & 5 Κ»<» I—to ( ( to obtain the compound of formula lie. lie Step b) The compound of formula lie is then reacted with an unsubstituted imidazole or triazole in the presence of 10. An organic or inorganic base and in a suitable solvent, Step c) A halogen molecule or mixed halogen molecule is added to the compound IId lid in an Inert solvent# leading to the compound lie, He Step d) The compound II is obtained by cyclisation of the compound He in the presence of an organic or inorganic base.

10. Process for the preparation of the compounds of formula II, in which Rj to R s , y, n, A and X, have the same meaning as in Claim 1 and Hal corresponds to a halogen atom, characterised in that a halogen molecule or mixed halogen molecule Is added in an inert solvent to the compound lie according to Claim 9, to obtain the compound Ilf, the latter being cyclised in the presence of an organic or inorganic base to lead to the compound Ug, 15 to which an unsubstituted triazole or imidazole group is attached in the presence of an organic or inorganic base and In a suitable solvent.

11. Process for the preparation of the compounds of formula III or V, in which R x to R s , Y, n, A and X x have the same meaning as in Claim 1 and Q corresponds to an oxygen or sulphur atom, characterised in that a compound of formula II or Ilg is reacted with a nucleophile containing a hetero atom, of formula R 5 -Q-B in which R 6 and Q have the same meaning as in the compound of formula I and E is a cation, in the presence of a base and optionally of a phase transfer catalyst, and in the case where the starting material is the compound Ilg, an unsubstituted imidazole or triazole is attached.

12. Process for the preparation of the compounds of formula III in which Rg is an optionally mono- or polyhalogenated alkyl group containing at most six carbon atoms, characterised in that a compound of formula III or Ilia in which Rg corresponds to a hydrogen atom is reacted with an alkyl halide (where appropriate mono- or polyhalogenated) in the presence of an organic or inorganic base, and In that an imidazole or triazole ring is then attached If the starting material is the compound Ilia Ilia

13. Process for formula IV the preparation of the compounds of IV in which R, to η, Y and A have th© seas meaning as In Claim 1 in which X x and Σ, together correspond to an oxygen atom, characterised in that a compound of formula III or ' Ilia in which Y, a and to R 3 have the same meaning as in Claim· 1 and 1 is a halogen atom, and in IVa IV - 46 which QR S corresponds to a hydroxyl group and K x to a hydrogen atom, is oxidised, and in that, when the starting material is the compound Ilia, an unsubstituted imidazole or triasole ring is then attached. 5

14. Process for the preparation of compounds of formula IV in which X x and X 2 together correspond to a sulphur atom and ¥, n and to R 3 have the same meaning as in Claim 1, characterised in that the compound of the formula IV in which Χχ and X 2 together correspond to an 10 oxygen atom is subjected to a thionation.

15. Process for the preparation of the compounds of formula V, characterised in that the compounds of formula IV or A 15 IVa in which Χχ and X 2 together correspond to an oxygen or sulphur atom doubly bonded to the tetrahydrofuran ar® reacted with a compound of formula HQSLg, where Q corresponds to Q or S, in the presence of an acid cat20 alyst and in a suitable solvent, which can be the alcohol or thiol itself or an inert solvent; if th® starting materiel is the compound of formula iva, the compound of formula Va is obtained, and an imidazole or triasole ring is then grafted onto the compound of formula Va. 25 IS. Process for the preparation of the compounds of formula II In which to R Sf η, Y and A have the same meaning as in Claim 1 where X, and X 2 correspond to a halogen atom, preferably chlorine or bromine, characterised In that a compound of formula III or Ilia in 30 which Y, η, Ηχ to R s and A have the same meaning as in Claim 1' and Z is a halogen atom, and in which 0¾ corresponds to a hydroxyl group and X, to a hydrogen atom. Is oxidised and in that phosphorous pentachloride is then added to the ketone (compound of formula IV in which X, corresponds to an oxygen atom), optionally in the presence of an aprotic polar solvent and optionally of a quaternary ammonium halide, preferably at room temperature.

16. 17. Compounds which can be used, where appropriate, as intermediates in the preparation processes of Claims 9 to 16» characterised in that they correspond to th® formulae IIIc and I He IIIc Hie in which to y, A, m, n, X x and X 2 have any one of the meanings stated In Claim 1 or 8.

17. 18. Use of the compounds according to one of Claims 1 to 8 as a fungicide. In particular in the form of fungicidal compositions containing as active substance a compound according to one of Claims 1 to 8» preferably 0.5 to 95 % by weight, this active substance being In combination with at least one agriculturally acceptable inert carrier.

18. 19. Process for the control of fungal diseases of crops, characterised in that an effective dose of an active substance according to one or Claims 1 to 8 is applied, preferably at a rate of 0.005 to 5 kg/ha, and advantageously 0.01 to 0.5 kg/ha. -4820. A compound as claimed in Claim 1, substantially as hereinbefore described and exemplified.

19. 21. A process for the preparation of a compound as claimed in Claim 1 , substantially as hereinbefore described and exemplified.

20. 22. A compound as claimed in Claim 1, whenever prepared by a process claimed in a preceding claim.

21. 23. A process according to Claim 10 or 15 for the preparation of a compound of formula II given and defined, therein, substantially as hereinbefore described and exemplified.

22. 24. A compound of formula II given and defined in Claim 10 or 16, whenever prepared by a process claimed in any one of Claims 10, 16 or 23.

23. 25. A process according to Claim 11 for the preparation of a compound of the formula III or V given and defined therein, substantially as hereinbefore described and exemplified.

24. 26. A compound of the formula III or V given and defined In Claim 11 whenever prepared by a process claimed in any one of Claims 11 or 25.

25. 27. A process according to Claim 12 for the preparation of a compound of the formula III given and defined therein, substantially as hereinbefore described and exemplified.

26. 28. A compound of the formula III given and defined la Claims 12 whenever prepared by a process claimed In Claim 12 or 27. -4929. A process according to Claim 13 or-14 for th® preparation of a compound of the formula IV. given and defined therein, substantially as hereinbefore described and exemplified. j . 5 30. A compound of the formula IV given and defined in Claim 13 or 14, whenever prepared by a process claimed in Claim 13, 14 or 29.

27. 31. A process according to Claim 15 for the preparation of a compound of formula V given and defined therein, 10 substantially as hereinbefore described and exemplified.

28. 32. A compound of formula V given and defined in Claim 15, whenever prepared by a process claimed in Claim 15 or 31.