FI91866B - Compounds containing a triazole or tetrahydrofuran group, their use as fungicides, processes for their preparation and intermediates - Google Patents

Description

91866

The present invention relates to novel compounds for use in plant protection which contain a triazole and tetrahydrofuran group. The invention also relates to processes for the preparation of said compounds and to compounds which can optionally be used as intermediates in the preparation processes. The invention also relates to the use of said compounds as fungicides and to methods for controlling fungal diseases in cultures using these compounds.

Several compounds containing a triazole group, in particular fungicides, are already known, in particular from EP-A-151 084, which describes compounds of the formula or2 O Rj A-- - Tr wherein Tr is 1,2,4-triazol-1-yl, A is preferably phenyl substituted by one or two halogens,

R 1 is hydrogen or alkyl and R 2 is hydrogen or an optionally substituted hydrocarbon.

It is an object of the present invention to provide compounds with improved properties in the treatment of fungal diseases.

Another object of the present invention is to provide compounds whose spectrum of use in the field of fungal diseases has also been improved.

91866 2

It has now been found that these objects can be achieved by means of the compounds according to the invention, which are characterized by their general formula I.

/ X.

0 A -— X2 (I) A-- -Tr in A is a group (Y) n-Ph-, wherein Ph is phenyl, Y is halogen and n is 1 or 2,

Tr is 1,2,4-triazol-1-yl and one of X and X2 is hydrogen and the other is halogen, hydroxy, lower alkoxy, lower alkylthio, chloroalkylalkylthio or benzoyloxy, or X, and X2 together represent an oxo group or iminoryh-methoxy-system

The invention also relates to salts of the compounds of formula I. Compounds in the form of a salt are those which are suitable for use in agriculture and may be mentioned as hydrochloride, sulphate, oxalate, nitrate or arylsulphonate as well as addition complexes of these compounds with metal salts, and in particular iron, chromium, copper, manganese , with zinc, cobalt, tin, magnesium and: aluminum salts.

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

It should be noted that the claimed compounds are not described in EP-A-151 084.

In this context, lower, when it defines an organic radical, means a radical containing up to six carbon atoms. This radical can be straightforward. or branched.

3,91866

The compounds of formula I and those compounds which may optionally be used as intermediates in the preparation methods and which are further defined in the description of these methods may exist in the form of one or more isomers depending on the number of asymmetric centers in the molecule. The invention therefore relates to all optical isomers as well as to their racemic mixtures and corresponding diastereoisomers. Separation of diastereoisomers and / or optical isomers can be carried out by methods known in the art.

With regard to the use as fungicides, it has been found that the invention preferably relates to those compounds of the formula I in which Y is a halogen atom in the ortho and / or para position.

Preferably n = 2 and Y is preferably in the chloro ortho and para positions.

It has been found that it is most advantageous to use triazole compounds of formula II in relation to their fungicidal properties.

/ Xl 0 f — Hal (II) A-- -Tr; where A and Tr have the same meaning as above,

Hai is halogen, preferably chlorine or bromine, and X! is hydrogen.

It has been found that it is most advantageous to use triazole compounds of formula III in relation to their fungicidal properties.

.QR «o -X, (III) A-- -Tr wherein A and Tr are as defined above, X 1 is hydrogen, Q is oxygen or sulfur and 91866 4 R 6 is hydrogen or lower alkyl. Q is preferably oxygen and R 6 is preferably lower alkyl.

The invention also relates to processes for the preparation of compounds of formula I. For these production methods, reference is made to the appended claims 5-9.

In the case where the group X2 is a halogen atom (a compound of formula II), the production method comprises the following steps:

Step a) A haloacetone of formula IIa obtained by a known method, wherein A is as defined above and Z is halogen, is reacted with an organometallic compound of formula Hb wherein X 1 is as defined above and M is an alkali metal and a magnesium-containing group (Mg Hai), or for example a zinc-containing group (Zn Hai), in a solvent selected from, for example, ethers such as diethyl ether or tetrahydrofuran, aliphatic, alicyclic or aromatic hydrocarbons such as hexane, toluene, and at a temperature selected from -50 ° C and between the reflux temperature of the solvent in question, and in a molar ratio of IIa: IIb, preferably between 1.1 and 0.2. The reaction provides a compound of formula IIe when the reaction medium is neutralized.

4

Step b) The compound of formula IIe is then reacted with an unsubstituted triazole in the presence of an organic or inorganic base such as pyridine, triethylamine, sodium hydroxide, potassium hydroxide, and alkali metal or alkaline earth metal carbonates and bicarbonates such as solvents. for example: alcohols, ketones, amides, nitriles, aromatic, optionally halogenated hydrocarbons, at a temperature between 80 ° C - solvent reflux temperature and in a molar ratio of Ile: triazole, preferably between 1.1 and 0.2, to give a compound of formula Ild. The reaction takes place κ 91666 5 usually via an epoxide intermediate of formula Uh

B

The compound of formula Uh may optionally be isolated or prepared separately by methods known to those skilled in the art.

Step c) One molecule of halogen or mixed halogen in an inert solvent such as a saturated or optionally halogenated aromatic hydrocarbon is added to compound IId, preferably in a molar per molar ratio, to give a compound of formula IIe.

Step d) The compound of formula II is preferably obtained at ambient temperature by cyclizing the compound of formula Ile in the presence of an organic or inorganic base as indicated in b) in a molar ratio of compound II: base, preferably between 1.1 and 0.66.

The reaction may take place in a protic or aprotic medium (water, alcohol, ketone, nitrile, ester, saturated or optionally halogenated aromatic hydrocarbon, dimethyl sulfoxide, amide such as dimethylformamide).

Another method for preparing compounds in which the group X2 is halogen is such that step b), in which a triazole ring is attached as a side chain, is placed after step d) using the same procedure in different steps. Thus, one molecule of halogen or halogen halide (mixed halogen) is added to compound Ile to give compound IIf, and this is then cyclized to compound Ilg, to which a triazole group is then introduced to give compound II.

Other manufacturing methods are, of course, also suitable.

91866 6

In the case where X 2 is a group QR 1 and X 1 is hydrogen (compounds of formula III), a process for the preparation of a compound of formula II is reacted with a heteroatomic nucleophile of formula I 1 -QE wherein R 6 and Q are as defined above and E is a cation, for example alkali or earth metal or quaternary ammonium. The reaction takes place in a suitable solvent in the presence of a base and optionally a phase transfer catalyst, at a reaction temperature which is usually between -30 ° C and the reflux temperature of the solvent and in a molar ratio of II: R 60 E of between 1.2 and 0.1.

In another method, compound Ilg is reacted under the same conditions with the same heteroatomic nucleophile to give compound lila, to which a triazole ring is then attached, as described above.

It is also possible to obtain compounds of the formula R6 is lower alkyl or chloro-lower alkyl by reacting a compound III or lila in which R * is a hydrogen atom with an alkyl halide or chloroalkyl halide in a molar ratio of III or lila: a halide which is preferably between 1.1 and 0.2 , and an organic or inorganic base is included. If starting from the compound purple, a triazole ring is then attached.

In the case where X2 is a hydroxyl group (compounds of formula IIi wherein Q is an oxygen atom and R8 is a hydrogen atom), a compound of formula II or IIg may also be reacted in the presence of an optionally inert organic solvent at a temperature between -30 ° C the reflux temperature of the solvent, with an alkali, alkaline earth or other metal hydroperoxide, hydroxide, oxide or superoxide, in a molar ratio of preferably 1.1 to 0.2, and can then be fixed in the case where the compound Ilg is starting material, triazole ring.

91866 7

In the case where X2 is a hydroxyl group, the compounds of formula Ile or Ild can also be reacted with a peroxide to give epoxide compounds IIIb in the case of Ile and IIIc in the case of Ild.

OH X, OH Xj Z Tr mb me These epoxides can then be hydrated to the triol IId and IIIe, respectively, by a well-known method.

Z Tr

Illd Ille

The cyclization takes place in the presence of a dehydrating agent, such as hydrochloric, hydrobromic, sulfuric or sulfonic acid, optionally in a protic or aprotic solvent.

This gives compound lila, where 0¾ is an OH group, to which the triazole ring is then attached, or compound III, in the case of compound IIle. If necessary, the alcohol group can optionally be protected in a known manner in the compounds IIld and IIIe.

The compounds of formula II or IIg may also be reacted with an alkali metal or alkaline earth metal carboxylate, in particular sodium benzoate, in the presence of a phase transfer catalyst and optionally in an inert or polar aprotic solvent, optionally in the presence of water and at a temperature of between 0 ° C and the reflux temperature of the solvent in question.

8 91866

In the case where X 1 and X 2 together represent an oxygen atom double bonded to tetrahydrofuran (compounds of formula IV), the preparation process starts from a compound of formula IIIa and III wherein QR * is hydroxyl and X is hydrogen and a well known oxidizing agent to give compound IV or compound IVa, 0 '(iva) A--

--z

to which a triazole ring is attached as a side chain.

In the case where X 1 and X 2 together represent the group = N-R 10, where R 10 is methoxy, the compound of formula IV or IVa is reacted with an amine of formula R 10 -NH 2 or a salt thereof in a molar ratio of preferably 1.1- 0.2, in an inert organic solvent. In the case where compound IVa is used, a triazole ring is finally attached to the obtained compound.

It is also possible to react a compound in which R, O is hydroxyl with an alkylating agent of the formula RnD in which Ru is methyl and D is halogen, a sulphonium, ammonium, sulphonate or sulphate group, together with an organic or inorganic base to obtain an oxime having a methyl substituent on the oxygen atom.

The invention also relates to compounds which can optionally be used as intermediates in the preparation processes described above and which have the formula IIIc or IIIa OH X! OH OH X, A ^ Ov <IIIC) * ^ 0 ^, IIIe>: Tr Tr 9 9 '| 566 in which formulas A, Tr and Xj have the same meaning as above.

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

The compounds according to the invention can be used for controlling fungi, in particular fungi of the basidiomycetes, ascomycetes, adelomycetes or fungi-imperfecti type, which can be both prophylactic and curative in various plant diseases, such as barley in plants and seedlings in general and cereals in particular wheat. , rye, oats and their hybrids and also rice and maize, rust, mold, root rot, fusariosis, helminthosporiosis, septoriose and rhizocton.

The compounds according to the invention are particularly active against fungi which are of the type Basidiomycetes, ascomycetes, adelomycetes or fungi-imperfecti, such as Botrytis cinerea, Erysiphe graminis, Puccinia recondita, Piricularia oryzae, Cercospora beticola, Puccinia striheformis, Eucci Pyrenophora avenae, Septoria tritici, Venturis inaequalis, Whetzelinia sclerotiorum, Monilla laxa, Mycosphaerella fijiensis, Marsonina panettoniana, Alternaria solani, Aspergillus niger, Cercospora arachidicola, Cladosporium Herbarum, Helmintho. sporium oryzae, Penicillium expansum, Pestalozzia sp., Phialophora cinerescens, Phoma betae, Phoma foveata, Phoma Iin-gam, Ustilago maydis, Verticillium dahliae, Ascochyta pisi, Guignardia bidwellii, Corticium rolfici, Phomopsi car-dinale, Rhizoctonia solani.

They are also active against the following fungi: Acrostalagmus koingi, Alternaria, Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujiku-roi, Hormodendron cladosporioides, Lentinus Degener or tig-Rinus, Lenzites quenzine , Paecylomyces varioti, Pellicularia sasakii, 91866 10

Phellinus megaloporus, Polystictus sanguineus, Poria vapor-ria, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi, Trichothecium roseum.

The compounds and combinations according to the invention are particularly advantageous due to their wide spectrum for cereal diseases (rust, mold, root rot, helminthosporiosis, Septoriosis and especially fusariosis). They are particularly advantageous because they are effective against Botry-tis and cercosporiosis and allow them to be well applied to a wide variety of crops such as vines, vegetable and fruit gardens, tropical crops such as peanut, banana, coffee bush, pecan.

In addition to the uses described above, the substances according to the invention also have excellent biocidal activity against a number of other variants of microorganisms, including but not limited to fungi belonging to the following genera: - Pullularia, such as P. pullulans, - Chaetomium, such as C. globosum, Aspergillus, such as Aspergillus niger, - Coniophora, such as C. puteana.

Due to their biocidal action, the substances according to the invention can be used to effectively control microorganisms, the proliferation of which poses a number of problems in agriculture and industry. Therefore, they are particularly well suited for the protection of plants and industrial products such as wood, leather, paints, paper, ropes, plastics, industrial water systems.

They are particularly well suited for the protection of lignocellulosic products and in particular wood, be it furniture or construction wood or wood exposed to weathering, such as wooden fences, vine support poles, track sleepers.

The compounds of the invention used alone or in the form of compositions as defined above for the treatment of wood are usually used in organic solvents and may optionally be combined with one or more known biocides, for example: pentachlorophenol, inorganic or carboxylic acids (heptanoic, octanoic, naphthenic) metal salts, especially copper, manganese, cobalt, chromium, zinc salts, organotin complexes, mercaptobenzothiazole, insecticides such as pyrethroids or organochlorine compounds.

Finally, they still have excellent selectivity for cultures.

They are usually applied at doses of 0.005 to 5 kg / ha, preferably at doses of 0.01 to 0.5 kg / ha.

The compounds of the invention are rarely used alone. Most often they are part of the compositions. These compositions, which are suitable for the protection of plants against fungal diseases or compositions which regulate the growth of seedlings, contain as active ingredient a compound according to the invention as described above in combination with solid or liquid agriculturally acceptable carriers and / or surfactants which are also acceptable in agriculture. Particularly suitable are inert and conventional carriers and conventional surfactants.

The term "carrier" as used herein means an organic or inorganic substance, whether of natural or synthetic origin, to which the active substance is incorporated in order to facilitate its application to a plant, seed or soil. This carrier is therefore normally inert and must be acceptable in agriculture, in particular for the crop in question. The carrier can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases, etc.).

The surfactant may be an emulsifying, dispersing or wetting agent, of the ionic or non-ionic type. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulphonic acids, salts of phenol sulphonic acids or salts of naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or fatty acid or fatty amine ester salts, substituted phenols (especially alkylphenols), substituted phenols (especially alkylphenols), especially alkyl taurates), phosphoric acid esters of alcohols or polyethoxylated phenols. The presence of at least one surfactant is usually necessary because the active substance and / or the inert carrier are insoluble in water and water is used as a vector in the application.

Thus, the compounds of formula I are usually in the form of compositions for application; the compositions of the invention themselves are in very different forms, either solid or liquid.

Solid forms of the compositions include powders for spraying or dispersing (up to 100% of the compound of the formula I) and granules, in particular those obtained by impregnation, compression or impregnation of a carrier in the form of granules or granulation of a powder (the concentration of the compound of formula I in these granules is between 1-80% in the latter cases).

Liquid forms of the compositions or intended to be liquefied during application may be 13

Ci Λ C £ c s 1 O O O

mention solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, wettable powders (or sprayable powders), pastes.

Emulsifiable or soluble concentrates usually contain 10-80% of active ingredient, while ready-to-use emulsions or solutions contain 0.01-20% of active ingredient.

These compositions may also contain all kinds of other ingredients, such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, plant penetration enhancers, stabilizers, sequestering agents, etc., as well as other active ingredients known for their pesticidal properties (especially in-insecticides or insecticides). fungicides) or properties that promote seedling growth (specifically fertilizers) or seedling growth regulating properties. The compounds of the invention can usually be combined with any solid or liquid excipient corresponding to conventional formulation techniques.

In addition to the solvent, the emulsifiable concentrates may contain, if necessary, 2-20% of suitable additives, such as stabilizers, surfactants, plant penetration enhancers, corrosion inhibitors, paints, adhesives, as already mentioned above.

The dosage amounts of the compounds and combinations according to the invention, when used as fungicides, can vary within wide limits, in particular according to the viability of the fungi and the weather conditions.

Compositions containing 0.5-5000 ppm of active ingredient are generally well suited; these values are given for ready-to-use compositions, ppm means "parts per million". The range of 0.5-5000 ppm corresponds to 5 x 10'5 to 0.5% (w / w).

91866 14

The compositions to be stored and transported, on the other hand, more preferably contain 0.5 to 95% by weight of active ingredient.

Thus, the compositions according to the invention for use in agriculture may contain the active ingredients according to the invention in a very wide range, from 5.10-5% to 95% (by weight) -

The following are examples of the composition of some concentrations.

Example F (formulation) 1 - active ingredient 400 g / l - alkalidodecylbenzenesulfonate 24 g / l - nonylphenol condensed with 10 molecules of ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent q.s.p. 1 liter

According to another emulsifiable concentrate formula:

Example F 2 - active ingredient 250 g - epoxidized vegetable oil 25 g - a mixture of alkylaryl sulfonate and polyglycol ether and fatty alcohols 100 g - dimethylformamide 50 g - xylene 575 g These concentrates are obtained by diluting emulsions with water of any desired concentration, and which are particularly suitable for application to leaves.

Concentrated suspensions, which can also be applied by killing, are prepared to give a stable, non-settling fluid product and usually contain 10-75% of active ingredient, 0.5-15% of surfactants, 1-10% thixotropic agents, 0-10% suitable additives such as antifoams, anti-corrosion agents, stabilizers, plant penetration enhancers and adhesives and as a carrier water or an organic liquid in which the active ingredient is sparingly or not at all soluble; some solid organic substances or inorganic salts may be dissolved in the carrier, which helps to prevent sedimentation or freezing of the water.

Wettable powders (or fusible powders) are usually prepared in such a way that they contain 20-95% of active ingredient and usually contain, in addition to a solid carrier, 0-5% of wetting agent, 3-10% of dispersant and when it is if necessary, 0-10% of one or more stabilizers and / or other additives, such as plant penetration enhancers, adhesives or anti-clumping agents, dyes, etc.

The following are examples of different wettable powder compositions:

Example F 3 - active ingredient 50% - calcium lignosulfonate (flocculant) 5% - isopropylnaphthalene sulfonate (anionic wetting agent) 1% - silica (lump disintegrant) 5% - kaolin (filler) 39%

Another 70% spray powder composition uses the following ingredients:

Example F 4 - active substance 700 g - sodium dibutyl naphthyl sulfonate 50 g ---- · 1 ..

91866 16 - Condensation product of naphthalenesulphonic acid, phenolsulphonic acid and formaldehyde in a ratio of 3/2/1 30 g - Kaolin 100 g - Champagne chalk 120 g

The second 40% spray powder composition uses the following ingredients:

Example F 5 - active ingredient 400 g - sodium lignosulfonate 50 g - sodium dibutylnaphthalenesulfonate 10 g - silica 540 g

The second 25% spray powder composition uses the following ingredients:

Example F 6 - active substance 250 g - calcium lignosulfonate 45 g - mixture of equal amounts by weight

Champagne chalk and hydroxyethylcellulose 19 g - sodium dibutylnaphthalene sulphonate 15 g - silica 195 g - Champagne chalk 195 g - kaolin 281 g

Another 25% spray powder composition uses the following ingredients:

Example F 7 - active substance 250 g - isooctylphenoxypolyoxyethylene ethanol 25 g - mixture with equal weights

Champagne chalk and hydroxyethylcellulose 17 g - sodium aluminosilicate 543 g - diatomaceous earth 165 g 91 866 17

The following ingredients are used in a 10% composition of the powder to be incorporated:

Example F 8 - active ingredient 100 g - a mixture of sodium salts of saturated fatty acids 30 g - a condensation product of naphthalenesulfonic acid and formaldehyde 50 g - kaolin 820 g These -teissa. In this way, sprayable powders are obtained which have advantageous wetting and suspending properties, can be suspended in water at any desired concentration and these suspensions can be used very advantageously, in particular for application to the leaves of plants.

Instead of wettable powders, pastes can be prepared. The conditions and uses of these pastes are similar to those of wettable powders or blendable powders.

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

Granules to be placed in the ground are usually made to have dimensions of 0.1-2 mm and can be made by agglomeration or impregnation. The granules usually contain 0.5-25% of active,. 9, S66 and 0-10% additives such as stabilizers, sustained release agents, binders and solvents.

According to an example of a granular composition, the following ingredients are used:

Example F 9 - active substance 50 g - epichlorohydrin 2.5 g - polyglycol ethyl acetate 2.5 g - polyethylene glycol 35 g - kaolin (particle size: 0.3-0.8 mm) 910 g In this special case, the active substance is mixed with epi-chlorohydrin and is dissolved in 60 g of acetone, and then polyethylene glycol and polyglycol ketyl ether are added. The kaolin is irrigated with the solution obtained and then the acetone is evaporated off under vacuum. Such microgranules are preferably used to control soil fungi.

The compounds of formula I can be used in the form of further sprayable powders; a composition containing 50 g of active ingredient and 950 g of talc may also be used; a composition containing 20 g of butter can also be used; itching agent, 10 g of finely divided silica and 970 g of talc; these ingredients are mixed and ground and the mixture is applied by spraying.

Examples I-VII show specific methods for preparing the compounds of the invention as well as these compounds themselves. The nomenclature of the compounds is given according to French norms, except that the numbering of the substituents is placed in front of the substituents themselves.

91 866 19

Example I

Preparation of 1- [4-bromo-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -β-1,2,4-triazole. Compounds No. la,

Ib ia la + Ib_

Step a) Preparation of 1-chloro-2- (2,4-dichlorophenyl) -4-penten-2-ol:

An organomagnesium derivative is prepared by adding magnesium (110 g) to a solution of allyl bromide (110 ml) in ethyl ether (700 ml) and tetrahydrofuran (200 ml) at 15-22 ° C over 3 hours. Heat at reflux for 30 min, decant and wash the residue with ether.

To this organic phase is added at -30 ° C a solution of trichloro-alpha-2,4-acetophenone (175 g) in tetrahydrofuran (250 g) is neutralized with acetic acid. Wash with water, dry over sodium sulfate, concentrate and then distill in vacuo. A colorless oil (205 g) is obtained. Boiling point (3 · 102 mmHg) = 140-142 ° C.

Step b) Preparation of 1- [2- (2,4-dichlorophenyl) -2-hydroxy-4-pentenyl] -1H-1,2,4-triazole

A mixture of the material obtained in step a) (106 g), triazole (55 g) and potassium carbonate (160 g) is heated for four hours at 120 ° C in dimethylformamide (600 ml). The insoluble material is filtered off, washed with dimethylformamide and the reaction mixture is concentrated in vacuo. The residue is dissolved in methylene chloride and washed with water and concentrated. The compound is obtained by crystallization from ethyl acetate after dissolution in heptane. A light red solid (97 g) melting at 101 ° C is isolated.

Step c) Preparation of Compounds No. Ia and Ib The compound obtained in Step b) (35 g) in chloroform (200 ml) is treated at 0 ° C with bromine. When it has become colorless, the solvent is evaporated off and the residue is redissolved in methanol. An aqueous solution of potassium hydroxide is then added until the pH is basic. After evaporation of the medium in vacuo, the residue is extracted into ethyl acetate, washed. with water and concentrated. The oil obtained (40 g) consists of a mixture of two diastereoisomers almost equal to Sara. Silica column chromatography sequentially isolates less polar isomer No. 1a: white crystals melting at 83 ° C, followed by more polar isomer No. Ib: white crystals melting at 94 ° C. After recrystallization, isomer Ia is obtained, melting at 96 ° C and Ib, melting at 104 ° C. A 50/50 mixture of Ia and Ib melts at 74 ° C.

In a similar manner the following compounds were prepared starting from the appropriate starting materials: 1- [4-bromo-2- (4-chlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole, m.p. = 74 ° C, Id m.p. = 78 ° C, lc + d, m.p. = 69 ° C.

Example II

Preparation of 1- [2- (2,4-dichlorophenyl) -4-hydroxy-tetrahydro-2-furanyl-methyl] -1H-1,2,4-triazole. Compounds No. 2a and No. 2b__ 10 g of the isomer of Example I, which is the less polar isomer dissolved in 30 ml of chlorobenzene, are heated at reflux for 48 h in the presence of 20 g of sodium benzoate in 30 ml of water containing 1 g of phase transfer catalyst "ADOGEN 464", methyltrialkylammonium chloride.

After diluting the organic phase with ether, it is washed with • water and evaporated to a smaller volume in vacuo. The residue is then treated at reflux for 3 h in methanol (100 ml) with potassium hydroxide (7 g). Cool, dilute with water, extract with ethyl acetate, wash until neutral and purify by chromatography after concentration in vacuo. Alcohol 2a is isolated in the form of a white powder (2.8 g) melting at 193 ° C.

Following the Selma procedure starting from the more polar isomer obtained in Example Ib), the optically active alcohol 2b is obtained in the form of a white powder 91866 21 and melts at 162 ° C. The 50/50 mixture 2a and 2b is oil.

Example III

Preparation of 1- [2- (2,4-dichlorophenyl) -4-ethoxy-tetrahydro-2-furanylmethyl] -1h-1,2,4-triazole.

Compounds No. 3a and No. 3b_

Alcohol 2a (2.2 g) dissolved in dimethyl sulfoxide (12 mL) is treated sequentially with 80% sodium hydride (0.42 g), then ethyl iodide (1.15 mL). After 15 min, the medium is diluted with water and extracted with ethyl acetate. Wash with water and evaporate the solvent and purify the residue by chromatography on a silica column to give a colorless oil which is isomer 3a which crystallizes on trituration with pentane and melts at 90 ° C; likewise, starting from 2b, isomer 3b is obtained as a white powder melting at 63 ° C. The 50/50 mixture 3a + 3b is an oil. In a similar manner, the compounds of formula VIII, summarized in the following table, are obtained using the appropriate alcohols: No. X, X2 Melting point 4a H QC-φ 98

II

o 4b OC-φ H 140 n o 5a H 0-CH3 oil 5b O-CHj H oil 6a H O-n-Pr oil 6b O-n-Pr H oil

Example IV

Preparation of 1- [2- (2,4-dichlorophenyl) -4-ethylthio-tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole

Compounds No. 7a and No. 7b_

Bromide Ia (3.8 g) dissolved in dimethyl sulfoxide 91,866 ------ 12 (38 ml) containing water (2 ml) is treated with sodium hydrogen sulphide (2.8 g) for 2 h. Potassium hydroxide is then added as a powder (3.3 g) followed by ethyl iodide (4 ml). Stir for 10 min and dilute the medium with water and extract with ether. Dry and evaporate to give isomer 7a as a yellow oil (3.9 g), melting at 88 ° C.

Following the same procedure and starting from 1b, 7b is obtained in the form of a pale yellow powder melting at 64 ° C. The mixture of isomers is an oil. Similarly, compounds of formula VIII summarized in the following table are obtained using the appropriate thiols: No. Xi X2 Melting point 8a H S-CH3 96 8b S-CHj H oil 9a H Sn-Pr 110 9b Sn-Pr H oil 10a H S-2-ClEt 127 10b S-2-ClEt H oil 11a H Si-Bu 68 11b Si-Bu H oil 12a H Si-Pr 75 12b Si-Pr H 65

Example V

Preparation of 1- [7- (2,4-dichlorophenyl) -1,4,6-trioxospiro [4,4] -7-nonanylmethyl] -1H-1,2,4-triazole

Compound No. 13_

Step a) Preparation of 1-chloro-2- (2,4-dichlorophenyl) -3,4,5-penta-triol

The chlorohydrin (91 g) obtained in step a) of Example I is epoxidized in dichloro-1,2-ethane (125 ml) with vanadyl acetylacetonate (5 g) and tert-butyl peroxide at 70% (200 ml). heating at reflux for 48 h. The medium is cooled and diluted with water, washed several times with sodium bisulfite solution and then concentrated to 91866-23. The residue is converted to the triol by heating in water (200 ml) and dioxane (200 ml) with perchloric acid (5 ml) for 3 h. Dilute with water and extract the medium with toluene (300 ml) and then concentrate.

Step b) Preparation of 2- (2,4-dichlorophenyl) -2-chloromethyl-tetrahydro-4-furanone

The oily residue obtained in step a) is then heated in toluene (100 ml) and butanol (200 ml) with para-toluenesulphonic acid (0.5 g) and the water formed is separated off. After evaporation of the reaction medium, the residue is chromatographed on a column of silica (eluent: ethyl acetate / heptane, 40:60) to give a colorless oil (14.5 g) corresponding to a mixture of diastereoisomeric alcohols which is 2- (2,4-dichlorophenyl). ) -4-hydroxy-2-chloromethyl-tetrahydrofuran. This compound is oxidized directly with chromium anhydride in acetic acid to give, after chromatography on a silica column, furanone in the form of white crystals melting at 99 ° C.

Step c) Preparation of 7-chloromethyl-7- (2,4-dichlorophenyl) -1,4,6-trioxaspiro [4,4] nonane The furanone (4.2 g) obtained in step b) in toluene (50 ml) is heated refluxing with ethylene glycol (6.5 ml) and para-toluenesulfonic acid (0.1 g) and separating the water formed until the starting material disappears.

The medium is washed with sodium hydroxide and then diluted with water and extracted with ether and concentrated.

A white solid (5.1 g) is obtained which melts at 99 ° C.

Step d) Preparation of compound 13

The halide of step c) (5 g) in dimethyl sulfoxide (20 ml) is heated at 170 ° C in the presence of triazolyl sodium (2.75 g) for 6 h. The medium is poured onto water, extracted with ethyl ether, concentrated and purified by chromatography on a column of silica. Light yellow crystals (3.6 g) are isolated, melting at 123 ° C after recrystallization from ethyl acetate / heptane.

Example VI

Preparation of 1- [4-chloro-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole

Compounds No. 14a and No. 14 b_

Step a) Preparation of 2- (2,4-dichlorophenyl) -1,4,5-trichloro-2-pentanol

The chlorohydrin obtained in step a) of Example I dissolved in dichloromethane (150 ml) is treated with chlorine gas (13.4 g) at -15 ° C. The medium is then treated with 37% sodium sulfite solution (15 ml), washed with water and dried and evaporated. The crude product is obtained in the form of a colorless oil (49.7 g) containing about 70% of the desired compound in the form of a mixture of two diastereoisomers.

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

In the first method, the crude chlorohydrin (10.3 g) obtained in step a) above is dissolved in methanol (30 ml) and treated with a methanolic solution of potassium hydroxide which titrates from 2.55 to 103 mol / l (12 ml) at ambient temperature. The precipitate is filtered off and the methanol solution is evaporated in vacuo. The residue is purified by chromatography on a column of silica. A colorless oil (7.4 g) is obtained.

In another method, the chlorohydrin (19.9 g) obtained in step a) of Example I is dissolved in methanol (75 ml) and treated with a solution of potassium hydroxide (4.9 g) in methanol (20 ml) at ambient temperature. The insoluble material is filtered off and evaporated to give the epoxide (17.1 g) as a yellow oil. This epoxide is treated with chlorine until a yellow color persists (10.1 g) at -15 ° C *. The medium is then washed with aqueous sodium bisulfite solution and then evaporated in vacuo. A yellow oil (20.8 g) is obtained which is a 45/55 mixture of two diastereoisomers.

Step c) Preparation of 1- [4-chloro-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole The epoxide obtained in step b) (61.7 g) was 1 (0.5 L) is heated at 90 ° C for 6 h in the presence of triazolyl sodium (18.6 g). The inorganic precipitate is filtered off and the butanol is evaporated. The residue is purified by chromatography on a silica column (eluent: 48% ethyl acetate, 48% heptane and 4% methanol) to give successively the first diastereoisomer 14a, melting at 113 ° C, then the second diastereoisomer 14b, melting at 97 ° C. The mixture 50/50 14a + 14b melts at 90 ° C.

Example VII

1- [4-oxo-2- (2,4-dichlorophenyl) tetrahydro-2-furanyl-methyl-1H-1,2,4-triazole. Compound 15. Preparation Alcohol 2a (37.7 g) is added at -60 ° C to a solution of dimethyl sulfoxide (17 ml) in dichloromethane (120 ml) and treated at -60 ° C with a solution of trifluoroacetic anhydride (25, 4 ml) in dichloromethane (60 ml). Half an hour later at -60 ° C, allowed to return to ambient temperature and then triethylamine (48 mL).

: Pour the medium into water, extract with dichloromethane and evaporate. A white powder is isolated which melts at 91 ° C by crystallization from ether.

Example VIII

Preparation of 1- [4,4-dichloro-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole, Compound No. 20

A mixture of ketone 15 (3.1 g), phosphorus pentachloride (2.3 g), dichloromethane (30 ml) containing triethylbenzylammonium chloride (0.25 g) is stirred for 2 h at ambient temperature until the starting material disappears. . The medium is evaporated, diluted with water (100 ml), neutralized with 26 91 866 sodium bicarbonate and extracted with ether. Dry and evaporate and crystallize the oily residue from isopropyl ether (2 times). A white powder (0.6 g) is obtained, melting at 138 ° C.

Example IX

Preparation of 1- [4-dimethylamino-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole, Compound 16

To a solution of potassium hydroxide (0.24 g) and dimethylamine hydrochloride (1.05 g) in methanol is added sequentially the ketone of Example III, followed by sodium cyanoborohydride (0.24 g). After 15 h, dilute the medium with water, extract with ether. The desired compound is then extracted from the organic phase with 6 N hydrochloric acid (3 x 20 ml). Make neutral, extract and chromatograph on a column of silica and isolate compound 5 in the form of a pale yellow oil (a mixture of 50/50 two isomers).

Example X

Preparation of 1- [4-methoxyimino-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole, compound 17__

The ketone from Example III (2 g) in ethanol (30 ml) is heated at reflux in the presence of methoxylamine hydrochloride (5.8 ml of a 25% solution in water) for 2 h. The medium is diluted with water, extracted with dichloromethane and evaporated. The compound is isolated by crystallization from a mixture of diisopropyl ether-heptane in the form of a white powder melting at 108 ° C (mixture of two geometric isomers).

In a similar manner, compounds with Ru = H (4-hydroxyamino), m.p. = 195 ° 18

Ru = - <(4-isopropoxyimino), oil 19.

Example XI et seq. Illustrates the use of the compounds of the invention as fungicides.

91866 27 In these examples, sprays of solutions or suspensions of the active substances are carried out under conditions such that the spraying of a solution or suspension at a concentration of 1 g / l corresponds to an average application of about 2 μg of active substance per cm2 to the leaf of the plant.

Under the conditions of Example X et seq., The compounds described have not been phytotoxic.

In these examples, it is considered that the product provides complete protection against fungal disease when the protection is at least 95%; protection is considered good when it is at least 80% (but less than 95%), fairly good when it is at least 70% (but less than 80%), mediocre when it is at least 50% (but less than 70%).

In the following presentation, percentages are by weight unless otherwise indicated, except for those relating to yields. In the case where the percentages are expressed in stoichiometric proportions, they are molar percentages. In terms of concentrations, some of them are expressed in ppm (parts per million), which corresponds to mg / l.

Example XI

In vivo test for Botrytis cinerea in tomatoes: Prepared by finely grinding an aqueous emulsion of the active substance to be tested with the following composition: - active substance 60 mg - Tween 80 (surfactant oleate of ethylene oxide and sorbitan condensate) diluted to 10% strength in water 0.3 ml - water to 60 ml This aqueous emulsion is then diluted with water to obtain the desired concentration.

91866 28

Greenhouse grown tomatoes (from the Marmande variant) that are 3-40 d old are treated by spraying with aqueous emulsions as defined above and at various concentrations of the test compound. The experiment is repeated twice at each concentration.

After 24 or 48 h, the leaves are cut and placed in 2 petri dishes (diameter 14 cm) with a damp filter paper plate (5 small leaves per dish) previously placed on the bottom.

Drops (3 drops per leaf) of spore suspension are then inoculated with a syringe. This spore suspension of Botrytis cinerea is obtained from a 15 d old culture, then suspended in a nutrient mixture (100,000 units / cm3).

The reading is performed 3-6 d after contamination by comparison with an untreated control plant.

Under these conditions, at a dose of 1 g / l, good or complete protection is observed with compounds Ia, Ib, Ia + Ib, 3b, 5b, 6b, 8b, 9b, 12b, 14a, 14b, 14a + 14b, 17.

Example XII

In vivo test for Erysiphe graminis in barley (barley-Härmä) _: Barley sown in pots with loose clay soil is treated to a height of 10 cm by spraying with an aqueous emulsion, the concentration of which is given below. The experiment is repeated twice. After 24 h, the barley seedlings are sprayed with the spores of Erysiphe graminis and the spraying is carried out on diseased plants.

Reading is performed 8-14 d after contamination.

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

Ib, 2a, 2b, 3a, 3b, 3a + 3b, 4a, 4b, 5a, 5b, 6a, 6b, 7a + i 7b, 8a, 8b, 13, 14a, 14b, 14a + 14b, 15, 17, 19 , 20.

29 91 866

Example XIII

In vivo test for "Puccinia recondita" causing brown rust in wheat_

Wheat sown in small pots with a fluffy clay soil is treated to a height of 10 cm by spraying with aqueous emulsions of the same composition as in Example VIII and at different concentrations of the test compound. The experiment is repeated twice with each concentration.

After 24 h, an aqueous spore suspension (50,000 / cm3) is sprayed onto the wheat; this suspension has been obtained from contaminated plants. The wheat is then placed in an incubation chamber for 48 h at a temperature of about 18 ° C and 100% relative humidity.

After these two days, the humidity is reduced to 60%. The condition of the plants is controlled between days 11 and 15 from the time of infection by comparison with a control plant that has not been treated.

At a dose of 1 g / l, good or complete protection with compounds la,

Ib, la + Ib, 3a, 3b, 3a + 3b, 5b, 6b, 7a, 7a + 7b, 8b, 12b, 13, 14a, 14b, 14a + 14b, 17, 19, 20.

Example XIV

j In vivo test for "Piricularia oryzae" causing rice piriculariosis (rice plague) _

Rice sown in pots in a 50/50 mixture of enriched peat and pozzolan is treated at a height of 10 cm by spraying with an aqueous emulsion of the concentration defined above. The experiment is repeated twice. After 48 h, the plants are treated by applying to their leaves a suspension of spores obtained from pure cultivation.

The reading is performed 8 d after contamination. Under these conditions, the following results are observed: at a dose of 1 g / l good: or complete protection with Ia, Ib, Ia + Ib, 3a, 3b, 91866 30 6a, 8a, 8b, 9a, 9b, 10b, 11a, lib, 12a, 12b, 14a, 14b, 14a + 14b, 15, 20.

Example XV

In vitro test for seeds and soil fungi The effect of the compounds according to the invention on the following fungi causing diseases in cereals and other plants is investigated: 1) Pyrenophorae avenae 2) Septoria nodorum 3) Helminthosporium teres 4) Fusarium roseum 5) Fusarium nivale 6) Fusarium culmorum 7) Rhizoctonia cerealis 8) Septoria tritici 9) Botrytis cinerea sensitive to carbendazim and cyclic imides 10) Botrytis cinerea resistant to carbendazim and cyclic imides 11) Pseudocercosporella herpotrichoides 13) Fusarium oxpotysys 12) Fusarium oxum solani 14) Helminthosporium gramineum: The figures associated with the names will be used for these fungi are shown in Table II.

Each experiment is performed as follows: a nutrient quadrant solution consisting of potato, glucose, and agar (PDA medium) is placed subcooled in a series of petri dishes (20 ml per dish) in an autoclave after sterilization at 120 ° C.

During the filling of the plates, an acetone solution of the active substance is injected into the subcooled medium to obtain the desired final concentration.

31 91866

For comparison, petri dishes analogous to the above are taken, into which the same amounts of nutrient solution containing the active substance are drained.

After 24 or 48 h, each dish is inoculated with a layer of mysee pieces from a previous culture of the same fungus.

The plates are stored for 2-10 d (depending on the fungus tested) at 22 ° C and then the growth of the fungus in the plates containing the active substance to be tested is compared with the growth of the same fungus in the plate used as a reference.

In this way, for each test compound, the degree of fungal inhibition at a dose of 30 ppm. The results are reported in the table below.

«32 9 1 6 6 6

Compound Mushrooms No._1_2_3 4_5_6 7 Sat 100 100 100 95 100 100 95

Ib 100 90 100 100 100 100 90 la + Ib 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 6a 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 11a 90 50 95 0 0 0 80 11b 90 80 95 0 0 0 80 12a 90 80 95 0 80 80 80 12b 95 90 95 80 80 90 80 33 9 '! 866

Compound Mushrooms No._1 2_3_4_5_6 7 13a - 90 14a 95 95 100 95 100 100 90 14b 95 90 100 90 95 100 90 14a + 14b 100 95 100 150 100 100 95 15 0 95 80 0 0 50 0 16 80 0 80 0 0 50 0 17 80 0 80 80 95 80 80 18 19 90 0 80 80 90 50 80 20 90 80 95 90 95 90 90 «« «34 91866

Compound Mushrooms No._8 9 10 11 12_13 14 Sat 100 100 100 100 100 80 100

Ib - 95 95 100 100 80 100 la + Ib 100 95 95 100 100 90 95 2a 0 95 95 100 0 0 80 2b 0 80 50 100 80 0 80 3a 95 90 90 95 0 0 90 3b 100 95 100 95 80 80 95 3a + 3b 0 80 95 0 0 0 80 4a 0 95 95 0 0 0 90 4b 0 95 95 90 95 0 95 5a 0 0 0 100 0 0 50 5b 0 95 90 100 95 90 90 6a 0 50 50 100 0 0 50 6b 50 95 95 100 80 80 95 7a 0 95 95 95 0 80 80 7b 0 90 95 90 0 50 50 7a + 7b - 95 95 100 50 80 50 8a 0 80 80 80 80 80 95 8b 0 95 95 90 80 80 95 9a 0 90 90 90 80 80 95 9b 0 95 90 100 80 80 50, 10a 50 80 0 0 0 0 0 '10b 0 90 95 80 50 50 90 11a 0 0 80 50 50 50 95 11b 0 80 80 80 80 80 95 12a 0 50 80 80 0 80 90 12b 0 95 95 90 80 80 100 13a - 0 0 100 50 0 «91866

Compound Mushrooms No._8 9 10 11 12_13 14 14a - 100 100 100 100 80 100 14b 0 95 95 100 80 80 100 14a + 14b 50 95 95 100 100 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

Results of comparative tests (greenhouse tests) cl ci c \ * ci \ Br ^ "v.

U — J O

Compound I (compound of the invention) and compound C (compound known from EP-A-89 100) were tested in the same manner for 5 diseases: • Botrytis cinerea (BOCI) in tomatoes (cf. Example XI) - Erysiphe graminis f. Sp. hordei (barley fungus) (cf.

Example XII) - Erysiphe graminis f. sp. tritici (wheat fungal disease) (as in Example XII) - Puccinia recondita (PURE) in wheat (brown green mold) (cf. Example XIII) - Piricularia oryzae (PIOR) in rice (cf. Example XIV) 36 91 566

The results presented in the table below show the inhibitory ratio of the disease-causing fungus. It is found that the cow compound I of the invention is more effective compared to compound C, which is completely ineffective against two of the five fungi.

Compound Dose BOCI E.g. E.g. PURE PIOR

(ppm) (barley) (wheat) I 111 90 98 95 90 90 C 111 50 98 50 0 0

Claims (12)

A compound containing a triazole, tetrahydrofuran and phenyl group, characterized in that it has the general formula I ο // Λ> ΝΝ ^ -χ2 (I) A-- -Tr 91866 where A is a group (Y) n -Ph-, where Ph is phenyl, Y is halogen and n is 1 or 2, Tr is 1,2,4-triazol-1-yl and one of the groups X, and X2 is hydrogen and the other is halogen, hydroxy , lower alkoxy, lower alkoxy, chloro alkoxy or benzoyl oxy, or X, and x 2 together represent an oxo group or methoxyimony group, and salts thereof. A compound according to claim 1, characterized in that Y is in ortho and / or para position. Compound according to claim 2, characterized in that Y is a chlorine or bromine atom. A compound according to claim 1, characterized in that it is 1- [4-bromo-2- (2,4-dichlorophenyl) -tetrahydro-2-furanylmethyl] -1H-1,2,4-triazole. A process for the preparation of a compound of formula II A. /. Hal (II) A-- -Tr where A and Tr are the same as in claim 1, X, is hydrogen and Hai is halogen, characterized in that it comprises the following steps: step a): a halogen acetone, of the formula Ha (IIa) ) «_ 91866 where A is as defined above and Z is halogen, is reacted with an organometallic compound of formula lib lib / II (IIb) HH to obtain a compound of formula Il Z step b): then the compound of formula Ile is reacted with unsubstituted triazole in the presence of an organic or inorganic base in a suitable solvent, step c): the compound of the formula (ll OH, HA <3 K <1) Tr. a halogen or mixed halogen molecule is added to an inert solvent to give a compound of formula He OH X! Hal Tr step d): the compound of formula II is obtained by cycling the compound of formula Ile in the presence of an organic or inorganic base. 91866 6. A process for preparing a compound of formula II XnN 2 -Hai (II) A-- -Tr where A and Tr denote the same species in claim 1, X, is hydrogen and Hai is halogen, characterized in that a compound of formula Ile OH X, H z where A and Xj are as defined above and Z is halogen, a halogen or mixed halogen molecule is added to an inert solvent to give a compound of formula IIf OH X, Hai atO and this is cyclized in the presence of an organic or inorganic base to give a compound of formula Ilg 91866 (Ilg) A-- -z where an unsubstituted triazole group is joined in the presence of an organic or inorganic base in a suitable solvent. 7. A process for preparing a compound of formula III yQR6 and X, (III) A-- -Tr where A and Tr are the same as those of claims 1, X, are hydrogen and QR , characterized in that a compound of formula II or Ilg 0 Hai 0 Hai A - 1 A-- -Tr -Z (ID (Ilg) wherein A, Tr and X are as defined above, Hai is halogen and Z is halogen, reacted with a heteroatom-containing nucleophile of formula R R -QE, wherein R6Q is as defined above and E is a cation, in the presence of a base and possibly in the presence of a phase transfer catalyst, and if added from the compound Ilg, an unsubstituted triazole group is added. A process for the preparation of a compound of formula III / O * 6 ox, (III) A - -Tr + S1S66 where A and Tr are the same as in claims 1, x, are hydrogen and QR6 is lower alkoxy, lower alkoxy or chloro -alkylthio, characterized in that a compound of formula III, or a compound of formula purple (purple) A-- -Z where A, Tr and X, are as defined above, Z is halogen and QRe is -OH or -SH, is reacted with an alkyl halide which is possibly substituted by chlorine, in the presence of an organic or inorganic base, and if taken from the compound of the formula purple, then a triazole group is joined therein. A process for preparing a compound of formula IV o (iv) A - 1 -Tr where A and Tr denote the same as in claim 1, characterized by oxidizing a compound of formula III or Ula / QRi / N. / X, oy-χι 0 qr6 A-- A-- -Tr -Z (III) (purple) wherein A and Tr are as defined above, X is hydrogen, Z is halogen and QRe is hydroxy, and if all poured from the compound of the formula purple, an unsubstituted triazole group is joined therein. 91 866 Compounds which may be used as intermediates in the preparation processes of claims 5-9, characterized in that they have the formula IIIc or Hie OH X, OH OH X, Tr Tr being A, Tr and X, denote the same as in Claim 1 . Use of a compound according to any one of claims 1-4 as a fungicide, especially in the form of fungicide compositions which contain as an active substance a compound according to any of claims 1-4, preferably 0.5-95% by weight, which active substance is associated with at least one inert, acceptable carrier in agriculture. A method for controlling fungal diseases in crops, characterized in that an effective dose of 0.005-5 kg / ha, preferably 0.01-0.5 kg / ha, of an active substance according to any of claims 1-4 is applied.