NO865112L - RELATIONSHIPS WITH FUNGICIDE EFFECT, THEIR PREPARATION AND USE IN FUNGICIDE PREPARATIONS. - Google Patents

Description

The present invention relates to a new compound for use in connection with plant protection, containing triazole and oligoether groups and fungicidal preparations of this product. The invention also relates to a method for producing the above-mentioned compound and use in plant protection,

especially when it comes to the fight against parasitic fungi. but also

in the growth regulation of plants, using the same compound and the above-mentioned preparations.

Many compounds, especially fungicides, containing a triazole group are previously known, especially from EPO patent application 151,084.

One purpose of the present invention is to provide compounds and preparations with improved activity and/or selectivity.

Another purpose of the present invention is to provide compounds and preparations which can not only be used against fungal attacks on various types of grain, but also against fungal

attack on vines, on crops intended for market sale and more especially in the cultivation of fruit trees and against rust attack on grain.'

Another purpose of the present invention is to provide compounds and preparations with reduced toxic effects compared to certain previously known products.

It has now been found that these objectives can be achieved with the help of

of the compound according to the invention, with general

shape 1

and likewise with agriculturally tolerable salts of this nature.

The compound according to the invention can occur in two diastereoisomeric forms. The invention therefore relates to both a mixture of the two di a stereoisomeric forms and the two diastereoisomeric forms separately. Separation of the diastereoisomers can be carried out using methods which are known per se.

The invention also relates to the salts of the compound according to the invention, and more particularly hydrochloride, sulphate, oxalate, nitrate or ary 1 su 1 phonate, as well as the addition complexes of this compound with metal salts, in particular iron, chromium, copper, manganese, zinc, cobalt, tin, magnesium and aluminum salts. The product group comprising products of general formula (I), its diastereoisomers and its derivatives, is referred to hereafter in the plural form: The compounds according to the invention.

It has also been found that the above-mentioned purposes can be achieved by virtue of the combination of one or more of the compounds of formula (I) with at least one fungicide from group (II), i.e. that the fungicide is chosen from the following subgroups: 1. Chlorinated or nitrated benzene derivatives such as kintozene. one or more heterocycles in spoon rings, such as quinoline (ethoxyquin), morpholines (dodemorph,

tridemorph, fenpropi morph), and piperidines (fenpropidine),

4. Phosphoric acids in water such as metal phosphites, such as fosetyl-Al and phosphoric acid itself, 5. Dithiocarbamic acid derivatives such as maneb, mancozeb or z i neb,

6. Phenols in spirit levels such as dinocap or binapacryl,

7. Quinonderi vates such as dithianone or chloranil,

8. Carbamic acid and benzimidazole derivatives such as carbendazim, benomyl and ti ofanathmethyl1, 9. Sulfur there in vats such as dazomet or etridiazole or sulphur, 10. Amines and amides such as dichloran, carboxin, triforin, cymoxanil, metalaxyl and ofuras, 11. Diazines such as quinomethionate. fenarimol, anilazine, nuarimol, bupirimate, ethylrimol and pyrazofos,

12. Sulfamides such as diclofluanid and two 1y1 f 1uanide,

13. Guanidines such as doguadine,

14. Triazoles such as those described in British patent 2,046,260, which include diniconazole or other k/girl triazoles, propiconazole, triadimefon, triadimenol,

di clobutrazol, bitertanol. penconazole and f 1u t r i a f o1,

15. Tmidazoles such as procloraz or i rn a z a 1 i 1 ,

16. Cyanobenzi midazoles such as those described in French patent 2,521,141, and 17. Copper or organic or inorganic copper derivatives.

The active compounds of group (II) are known active compounds and most of them are described in detail in works such as "The Pesticide Manual", published by The British Grop Protection Council, 7th edition from 1983.

The preparations in accordance with the invention are in most cases of the binary type (a single active compound from group II), but sometimes ternary preparations (two active compounds from group II) or quaternary preparations (three active compounds from group II).

Among the active compounds, those selected from subgroups 1, 2, 3, 4, 5, 6, 7, 8, 9 and 17 are preferred.

Among the active compounds from group II, the following active compounds are preferred: Chlorthalonil, iprodione, fenpropimorph, tridemorph, fenpropidine, dinocap, dithianone, maneb, mancozeb, zineb, fosetyl-Al, cymoxanil, nuarimol, captan, carbendiazim, captafol, sulphur, copper and copper deri-

vats such as copper oxychlorid or copper quinoleate.

The chemical names for the products listed above are indicated in the attached table according to English nomenclature.

The weight ratio between the compound according to the present invention and the active compounds from group II described above is preferably between 0.0003 and 3000 and advantageously between 0.001 and 1000.

The present invention also relates to a method for producing the compounds according to the invention, as several of these compounds are described in EPO patent application 151,084, and to which reference is made in the present application.

According to a first method, a compound is reacted

with formula

in which Z is a chlorine or a bromine atom, with an alkali metal derivative (for example a sodium or potassium salt), or an ammonium or phosphonium derivative (quaternary) of triazole.

The reaction is usually carried out in a polar aprotic solvent and can also be catalysed, i.e. by addition of a 1 ka 1 i met a 11iod id, the temperature is generally between 50 and 250°C, preferably between 70 and 230°C. For economic reasons, the most commonly used concentrations of the reactants are between 1 and 50%.

The compound with formula (II) can be prepared by reacting the alcohol CF3-CH2OH (trifluoroethanol) with a compound of

shape 1

in the presence of an acid catalyst, Z having the above meaning and R being an organic radical, preferably a lower (C1 4 ) a 1ky1 r ad i ka 1, since it is possible for two R 3 radicals together to form a divalent organic radical, preferably a lower a 1ky1enrad in ka 1.

The acid catalyst used in this reaction can be a protic or an aprotic acid. Examples of protic acids include hydrochloric acid, sulfuric acid, trifluoroacetic acid, perchloric acid, benzenesulfonic acid, toluenesulfonic acid and methanesulfonic acid. Lewis acids such as BF^, A1C1^ °9 SnC14 can be mentioned as aprotic acids. When hydrochloric acid is used as a catalyst, it can be produced in situ, i.e. by means of an acyl chloride, and especially acetyl chloride, which reacts with the alcohol present to give HC1.

The reaction is usually carried out by only heating the indicated reactants. The temperature is generally within the ternary temperature range from 50°C to the boiling point temperature of the reaction mixture. Trifluoroethanol usually acts as a solvent in the reaction mixture. An inert coalescing agent can also be added, in particular an aliphatic, alicyclic or aromatic hydrocarbon, which is halogenated, or otherwise an ether.

The compounds of formula (III) are prepared in accordance with methods known per se.

According to another method for producing the compounds according to the invention, trifluoroethanol (CF3-CH20H) is reacted with a compound of the formula

in the presence of an acid catalyst. The different symbols indicated in the formula for both these reactants are as indicated above. It is also possible to use an acid catalyst such as those indicated above, in connection with the preparation of the compounds of formula (II). The reaction conditions will always be similar to those defined above for the preparation of the compounds of formula (II).

The compounds of formula (IV) can also be obtained according to methods which are known per se.

The preparations are made by simply mixing the required products and compounds.

The present invention also relates to the compounds of formula (II) in which Z is a chlorine or bromine atom. These compounds can, if desired, be used as intermediates for the preparation of the compounds of formula (I).

The present invention also relates to the use of the compounds of formula (I) and fungicidal preparations as indicated above.

The compounds and preparations according to the invention can therefore be used both in the preventive and curative fight against fungi, in particular against bas idiomycetes, ascomycetes, adelomycetes or incomplete fungi, in particular rust fungi, oidium, root rot, fusarioses, helminthsporioses, septorioses, rhizoctons for vegetation and plants in general, and in particular for various types of grain such as wheat, barley, rye, oats and their hybrids, but also rice and maize.

The compounds according to the invention are particularly active against the fungi mentioned in EPO patent application 151,084. They are also active against the following fungi: Acrosta1agmus koningi, Alternaria, Colletotrichum, Corticium rolfsii, Diplodia natalensis, Gaeumannomyces graminis, Gibberella fujikuroi, Hormodendron c1adospori oi des, Lentinus degener or tigrinus, Lenzites quercina, Memnoniella echinata, Myrothecium verrucaria, Paecylomyces varioti, Pel 1icularia sasakii, Phellinus megaloporus, Polystictus sanguineus, Poria vaporaria, Sclerotium rolfsii, Stachybotris atra, Stereum, Stilbum sp. Trametes trabea, Trichoderma pseudokoningi and Trichothecium roseum.

The compounds and preparations according to the invention are of particular interest due to their wide range of applications

with regard to diseases in various types of cereals (oidium, rust fungus, root rot, whole mint sporosis, septorioses and especially fusarioses which are difficult to combat). They are also of great interest due to their activity against gray mold (Botrytis) and cercosporioses, and they can therefore be used for a number of different plants, such as vines, cultivated crops and crops from fruit trees and tropical plants, such as peanuts, banana palms, coffee bushes, palm, coconut palm, pecan and others.

Finally, it should be mentioned that they develop an excellent selectivity towards the crops.

In addition to the applications described above, the products according to the invention can also have an excellent biocidal activity against many other types of microorganisms, among which one should mention fungi, such as those of the genus:

Pu 11u1 ar i a , like the species P. pullulans,

Chaetomium, like the species C. globosum,

Aspergillus, such as the species Aspergillus niger, and

Coniophora, such as the species C. puteana.

As a result of their biocidal activity, the compounds according to the invention make it possible to combat effectively those microorganisms whose rapid multiplication causes a number of problems in agriculture and industry. So far, they are particularly suitable for the protection of plants or industrial products such as wood, leather, paints, paper, rope, plastic and water systems within industry.

In particular, they are well suited for the protection of 1 ignoce11u1ose products, and in particular wood used in furniture, timber or wood used in constructions which are particularly exposed to harsh weather conditions, such as timber used as fencing material, supporting vines or railways - sleeps.

The compounds or preparations according to the invention, which are used either alone or in the form of mixtures for the treatment of wood as indicated above, can, if desired, be combined with one or more known biocidal products such as pentachlorphenone, metal salts, especially copper, manganese, cobalt, chromium or zinc, derived from inorganic acids or carboxylic acids (heptanoic, octanoic or naphthenic), organotin compounds and mer-captobenzoate in azole.

They are generally used in amounts of from 0.005 to 5 kg/ha, advantageously in amounts of from 0.01 to 5 kg/ha, preferably 0.05 and more particularly from 0.1 to 2 kg/ha.

The use of at least one of the compounds of formula (I) in combination with iprodione is of particular interest in the treatment of diseases that occur in the various types of cereals and sprouts, such as leaf diseases.

The use of at least one of the compounds of formula (I) in combination with fenpropidine is of particular interest in the treatment of diseases in various types of grain and sprouts, such as leaf diseases.

The use of at least one of the compounds of formula (I) in combination with fenpropimorph is of particular interest in the treatment of diseases in various cereals and beets.

The use of at least one of the compounds of formula (I) in combination with tridemorph is of particular interest in the treatment of diseases in various types of grain.

It is obviously possible to use ternary or quaternary mixtures with the above-mentioned compounds in the treatments indicated above.

Thus, the use of a ternary mixture based on fenpropimorph, iprodione and a compound according to the invention, or a mixture based on tridemorph, iprodione and a compound according to the invention, is of particular interest.

The use of at least one of the compounds of formula (I) in combination with maneb is of particular interest in the treatment of diseases on vegetables, fruit trees, fruit and vines.

The use of at least one of the compounds of formula (I) in combination with mancozeb is of particular interest in the treatment of diseases in vegetables, fruit trees, fruit and vines.

The use of at least one of the compounds of formula (I) in combination with sulfur is of particular interest in the treatment of diseases in vegetable crops, fruit trees, fruit and vines. The use of at least one of the compounds of formula (I) in combination with dinocap is of particular interest in the treatment of diseases on vegetable crops, fruit trees, fruit and vines.

It is clearly possible to use ternary or quaternary mixtures with the above compounds with respect to the above treatments.

The use of at least one of the compounds of formula (I) in combination with carbendazim is of particular interest in the treatment of diseases on fruit trees and fruit, or on vegetables and various types of grain.

The use of at least one of the compounds of formula (1) in combination with captafol is of particular interest in the treatment of diseases on various cereals, fruit trees, fruit and potatoes.

The use of at least one of the compounds of formula (I) in combination with captan is of particular interest in the treatment of diseases on various cereals, fruit trees and fruit.

The use of at least one of the compounds of formula (I) in combination with dithianone is of particular interest in the treatment of diseases on fruit trees and fruit.

The use of at least one of the compounds of formula (I) in combination with mancozeb is of particular interest in the treatment of diseases on fruit trees and fruit.

The use of at least one of the compounds of formula (I) in combination with copper is of particular interest in the treatment of diseases on fruit trees and fruit.

It is clearly possible to use ternary or quaternary mixtures of the above compounds in the treatment indicated above.

The use of at least one of the compounds of formula (I) in combination with chlorthalonil is of particular interest in the treatment of diseases on vegetable crops. various cereals, beets and potatoes.

The use of at least one of the compounds of formula (T) in combination with diniconazole is of particular interest in the treatment of soot attacks on the various types of grain, especially onion soot on barley and wheat (Ustilago nuda).

In practice, the compounds and preparations according to the invention are rarely used alone. In most cases, they are parts of mixtures. These mixtures which can be used to protect plants against fungal attacks, or mixtures which regulate plant growth, contain, as an active substance, a compound according to the invention as described above, in combination with solid or liquid agriculturally tolerable carriers and/or surfactants ve means which are also tolerable in terms of use. In particular, the usual inert carriers and the usual surfactants in the means can be used.

In the present description, the term "carrier" denotes an organic or inorganic, natural or synthetic substance with which the active substance is combined to facilitate application to the plant, to the sprouts or to the soil. This carrier is therefore generally inert, and it must be tolerable in terms of use, particularly with regard to the plant being treated. The carrier can be in solid form (clay, natural or synthetic silicates, say 1 isium oxide, resins, waxes, fertilizers in solid form, etc.), or in liquid form (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, gases in liquid form etc.).

The surface-active agent can be an emulsifying, spraying or wetting agent of ionic or non-ionic type. Examples include salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or naphthalene sulfonic acids, polycondensates of ethylene oxide with fatty acids or fatty acids or with fatty amines, substituted phenols (especially alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, taurine derivatives (especially alkyltaurates) and phosphorous, esters of alcohols or condensates of ethylene oxide with phenols. The presence of at least one surface-active agent is generally necessary when the active substance and/or the inert carrier is insoluble in water and when the transfer agent for application is water.

When applied, the compounds of formula (I) and the mixtures are therefore generally in the form of preparations, as these preparations according to the invention can be in various liquid or solid forms.

As solid forms of the preparations, mention can be made of the powder for sprinkling or spreading out (with a content of up to 100% of the compound of formula (!)), and granules, especially those produced by extrusion, compression, impregnation of a carrier for granules or by granulation starting from a powder (the content of the compound of formula (1) in these granules is between 1 and 80% in the latter cases).

As liquid forms of the preparations or those that constitute liquid preparations when applied, mention can be made of solutions, especially water-soluble concentrates, emulsifying concentrates, emulsions, flow agents, aerosols, powders that can be soaked (or powders used in spraying) and pastes.

These preparations may also contain a number of other settling agents, such as, for example, protective colloids, adhesives, thickening agents, thixotropic agents, penetrating agents, stabilizers, deposition agents, etc., as well as other known active substances with disinfectant properties (especially insecticides or fungicides), or with properties that promote plant growth (especially fertilisers), or properties for regulating plant growth. More generally, the compounds according to the invention can be combined with any thickening agent in solid or liquid form in accordance with usual design methods.

As regards the area of application of the compounds and preparations according to the invention in the form of fungicides, these can vary within wide limits, especially depending on the virulence of the fungi and the climatic conditions.

As a general rule, preparations containing 0.5 to 5000 ppm active substance are very suitable. These values concern preparations that are ready for use. Ppm means "parts per million". The range from 0.5 to 5000 ppm corresponds to a range from 5•10~5 to 0.5% (weight percent).

When it comes to preparations that are suitable for storage and transport, these more advantageously contain from 0.5 to 95% by weight of active substance.

Thus, therefore, the preparations according to the invention used in agriculture can contain active substances according to the invention that lie within a range that extends from 5-10"5 to 95 weight*.

As a general rule, the preparations according to the invention usually contain from approximately 0.05 to 95% by weight of active substances (formula I and group II) according to the invention, approximately from 1 to 95% by weight of one or more carriers in solid or liquid form, and, if desired, from 0.1 to 50% by weight, preferably from about 5 to 40% by weight, of one or more surfactants.

The emulsifying or soluble concentrates in most cases contain from 10 to 80% by weight of active substances, while the emulsions or solutions that are ready for use contain from 0.01 to 20% by weight of active substance. In addition to the solution, the emulsifying concentrates may, if necessary, contain from 2 to 20% by weight of suitable additives, such as the above-mentioned stabilizers, surfactants, penetrating agents, corrosion inhibitors, coloring agents and adhesives.

The following examples show the composition of some of the concentrates:

Example F 1.

According to another composition of emulsifying concentrate, used:

Example F 2.

By using these concentrates, it is possible to prepare, by diluting with water, emulsions of any desired concentration which are particularly suitable for application to foliage.

Liquids, which can also be applied by spraying, are manufactured in such a way as to produce a stable liquid product that does not settle, and they usually contain from 10 to 75% by weight of active substance, from 0.5 to 15% surfactants, from 0.1 to 10% by weight of thixotropic agents, and from 0 to 10% by weight of suitable setting agents such as antifoams, corrosion inhibitors, stabilizers, penetrants and adhesives, and, as a carrier, water or an organic liquid wherein the active substance is sparingly soluble or not soluble at all, some of the organic substances in solid form or the inorganic salts can be dissolved in the carrier to help prevent sedimentation or in the form of antifreeze is for water.

The wettable powders (such as powders for spraying) are usually prepared so that they contain from 20 to 95% by weight of active substance and that they usually contain, in addition to the solid carrier, from 0 to 5% by weight of a wetting agent, from 3 to 10% by weight of a dispersant, and. if necessary, from 0 to 10% by weight of one or more stabilizers and/or other thickening agents such as penetrating agents, adhesives or anti-caking agents. coloring agents etc. 1 the following example shows different compositions of the powder that can be soaked:

Example F 3.

Another composition of a powder intended for spraying with a strength of 70% includes the following ingredients:

Example F 4.

Another composition of a powder used for spraying with a strength of 40% has the following composition:

Example F 5.

Another composition of a powder used for spraying with a strength of 25% has the following composition:

Example F 6.

Another composition of a powder used for spraying and with a strength of 25% has the following composition:

Example F 7.

Another composition of the powder used for spraying

and with a strength of 10% has the following composition:

Example F 8.

To produce these powders that are used by spraying or the powders that can be soaked, the active substances are mixed well with the setting agents in suitable mixing devices, and ground using mills or other suitable grinding devices. Powders are obtained which can be used for spraying and whose ability to soak and form suspensions is advantageous, as they can be dissolved by using water in any desired concentration, as these suspensions can be particularly advantageously used when applied to plant foliage.

You can make pastes instead of powders that can be soaked. The conditions and methods for making and using these pastes are the same as for soakable powders or sprayable powders.

As previously established, aqueous dispersions and emulsions, for example preparations which are prepared by diluting a wettable powder or an emulsifying concentrate according to the invention with water, are covered by the present invention. The emulsions can be of the water-in-oil or oil-in-water type, and can have a thick consistency such as mayonnaise.

The granules to be placed on top of the soil are usually produced so that they have a size between 0.1 and 2 mm and they can be produced by agglomeration or impregnation. In general, the granules contain from 0.5 to 25% by weight of active substance and from 0 to 10% by weight of 1 setting agent such as stabilizers, modifying agents for extended duration of action, binders and solvents.

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

Example F 9.

In this particular case, the active substance is mixed with epichlorohydrin and dissolved in acetone (60 g), after which polyethylene glycol and polyoxycoethyl ether are added. The kaolin is sprayed with the solution obtained and the acetone is then evaporated under vacuum. Microgranules of this type are particularly beneficial in combating soil fungi.

The compounds of formula (I) and the preparations can also be used

in the form of loose powders, it is also possible to use a mixture comprising 50 g of active substance and 950 g of talc, it is also possible to use a mixture comprising 20 g of active substance, 10 g of finely divided silica 1 in sium oxide and 970 g of talc , as these ingredients are mixed and ground, after which the mixture is then applied by sprinkling it outwards.

The following examples illustrate the invention and show how it can be used.

Examples 1 to 3 illustrate special methods for producing the compounds according to the invention, as well as the compounds themselves. Among the physical properties given for these compounds, the proton NMR shift (delta) values for the -0-CH-O- (acetal) group are indicated. These

shift is measured in ppm and determined in relation to a reference compound which is tetramethylsi 1 an. NMR is carried out at 100 MHz in deuterochloroform.

Examples 4 to 10 illustrate the fungicidal properties of the compounds according to the invention and their use.

Example 1:

A compound with formula

foremost in lies.

According to the method described in EPO patent application 151,084, trifluoroethanol (40 ml) is mixed with the compound of formula (V) (10.7 g). HCl gas is bubbled through to obtain a weight gain of 1.39 g. The mixture is heated to 70°C for two hours. It is poured into water (500 ml) containing Na 2 CO 3 (10 g). It is extracted with ethyl acetate,

the organic solution is washed with water, dried, filtered and evaporated. In this way, crystals (8 g) are obtained which comprise a mixture of two diastereoisomers of the compound of formula (I) which melt at 80°C and whose NMR shows a proton shift (delta) at 5.18 and 5.41 ppm.

Example 2:

The compound obtained in Example 1 is treated using liquid chromatography on a silica column at a pressure of 0.3 bar (above atmospheric pressure) with an eluent comprising a mixture of ethyl acetate and heptane in the volume ratio 80/20.

A first fraction A (3 g) and a second fraction B (3.6 g) were collected.

Each of these fractions forms a precipitate which crystallizes out. The crystals A prepared from fraction A are consistent with one of the diastereoisomers. They melt at 84°G and have a proton shift (delta) of 5.41 ppm in NMR. The diastereoisomer A is characterized by the fact that the triazolyl methyl group and the trifluoroethoxy group sit on the same side of the plane of the tetrahydrofuran ring.

The crystals B prepared by fraction B correspond to the second diastereoisomer. They melt at 1670C and have a proton shift (delta) of 5.18 ppm in NMR.

Example 3.

Trifluoroethanol (40 ml) is mixed with the compound of formula

(10.8 g), which is prepared as shown in EPO patent application 151,084.

HCl gas is bubbled through the solution until the weight has increased by 1.5 g. The mixture is heated to 70°C for four hours and then poured into water (500 ml) containing Na 2 CO 3 (10 g). Extraction with CHCl3 is carried out, the organic phase is washed with water, dried and evaporated. A compound of formula (I) (12.7 g) is obtained in the form of a mixture of two diastereoisomers.

Example 4:

Treatment was carried out on four plots, each plot having four apple trees of a type known by the name "Calville", which is very sensitive to fruit scab (a disease with the Latin name Venturia inaequalis and whose French name is La travelure). The treatments took place at intervals of 12 days from fruit bud rotation until the middle of fruit growth. These treatments included the application of a spray mixture, i.e. a diluted aqueous emulsion of the active substance described in example 1. This spray mixture was applied in an amount of 10 hl/ha and was prepared by diluting an emulsifying concentrate, this concentrate itself containing 62 g/ l of the active substance, 203 g/l of cyclohexanone, 609 g/l of acetophenone, 50 g/l of calcium chloride and 100 g/l of a condensate of ethylene oxide with castor oil, the concentration of the active substance in spray bl and in none was 2.5 g/hl.

The results have been compared with a corresponding product whose known chemical formula is closest, i.e. the formula for the compound in example 42 in EP0 patent application 151,084, this product being referred to hereafter as the reference product. The product used for comparison in this way includes, like the product in example 1 according to the invention, all possible diastereoisomeric forms.

The results were measured as follows:

Phytotoxicity: measured one day after the third treatment and expressed as a percentage according to a visual assessment of the general condition of the leaves and fruit, a value of 15% being the maximum acceptable value,

Leaf activity: measured one day after the fifth treatment and expressed as a percentage of the number of leaves attacked by scab,

Fruit activity: measured at the end of the treatment and expressed as a percentage of the number of fruits attacked.

The results are as follows:

Example 5:

The method used is as in example 4, but apple trees of the Golden type are treated with a spray mixture in which the concentration of active substance is 5 g/hl.

The results are as follows:

Example 6:'

Four plots were treated, each plot having

15 vines of the type known under the name Carignan, which is very sensitive to powdery mildew (a disease with the Latin name Uncinula necator, whose French name is Oidium). The treatments were carried out at 14-day intervals from bud-shooting to ripening (a period until the bunches of grapes change colour).

These treatments comprise the application of a spray b1 and ing of the same type as in example 4 and in a ratio of 1.5 g/hl.

The obtained results compared as in Example 4 were as follows:

Examples 7 to 10:

Four plots (10 m ) with wheat crops were subjected to treatment. One or two treatments were carried out at the time when the first sign of disease appeared.

The spray mixture was of the same type as in example 4, and was applied in such a quantity that the amount of active substance was 90, 120 or 150 g/ha, depending on the tests.

No phytotoxicity was observed in any of the tests.

In Example 7, a Nebraska-type wheat crop was treated, which was attacked by yellow rust (Puccinia stri in form is), the results being checked ten days after the second treatment, on the highest leaf just below the axil.

In Example 8, a wheat crop of the type Vai 11 ant was treated, which was attacked by brown rust (Puccinia recondita), the results being checked 19 days after the first treatment, on the highest leaf just below the axil.

In Example 9, a wheat crop of the Longbow type was treated, which was attacked by ray spot (Septoria tritici), the results being checked 46 days after the only treatment, on the highest leaf just below the axil.

In Example 10, a Roazon wheat crop was treated, the results being checked 44 days after the only treatment on the second leaf below the axis (the first leaf, or uppermost leaf, was not affected by the disease). This last measurement shows the good sustained effect of the products.

The results are measured and expressed in terms of:

Leaf activity: percentage of the number of leaves attacked by

the disease,

Leaf surface activity: percentage of leaf surface that is

attacked by the disease.

The results were as follows:

Example 1 1 :

In vivo test on Erysiphe graminis f.sp.hordei on barley (powdery mildew: barley).

Fine paint is used to produce an aqueous emulsion of the active substance to be examined, which has the following composition:

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

■-Plants, in pots, which were sown in clay soil, are treated when they are 10 cm high by spraying them with an aqueous emulsion (called spray mix) of the concentrate given below. The test is repeated twice. After 24 hours, the building plates are sprinkled with spores of Erysiphe graminis, as the sprinkler is carried out with the help of diseased plants.

The reading is carried out eight to twelve days after the contamination.

Under these conditions, the following results were observed:

When using the compounds of example 1 and compound A of example 2, in an amount of 0.1 g/l, complete protection greater than or equal to 95%.

Example 12:

In vivo test on "Puccinia recondiata" which causes brown rust in wheat.

Wheat plants in pots, which are sown in clay soil, are treated when they are 10 cm high by spraying them with aqueous emulsions (known as spray mixtures) of the same compound as that described in Example 11 with different concentrations of test compound 1 sen . The test is repeated twice with each concentration.

After 24 hours, an aqueous suspension of spores (50,000 sp/cc) is sprayed onto the wheat plants, this suspension having been prepared using contaminated plants. The wheat plants are then placed for 48 hours in an incubation cell at approximately 18°C and at 100% relative humidity.

After these two days, the relative humidity is reduced to

60%. Control of the condition of the plants is carried out between the 11th and the 15th day after the contamination, by comparison with an untreated control.

With these conditions, the following results are achieved:

At a dose of 0.1 g/l, complete protection is achieved with the compounds in examples 1 and 2 (compound A).

Example 13:

In vitro tests on seed fungi and soil fungi.

An investigation is carried out which relates to the effect of the compounds according to the invention on the following fungi, which are responsible for secondary diseases in cereals:

The abbreviations given in brackets are used as abbreviations for the fungus in question in table (II).

The following procedure is carried out in each test:

A nutrient medium containing potatoes, glucose and agar (PDA medium) is added, subcooled, to a series of Petri dishes (20 ml per dish) after sterilization in an autoclave at 120°C.

While the bowls are being filled, an acetone solution of the active substance is introduced into the subcooled medium to produce the final desired concentration.

Petri dishes identical to the above are used as controls, as equal quantities of a nutrient medium, which does not contain active substance, are added to these.

After 24 or 48 hours, each dish is seeded by depositing a mycelium fragment from a previous culture of the same fungus.

The dishes are stored at 22°C for two to ten days (depending on the fungus to be examined), and then the fungal growth in the dishes containing the active substance is compared with the growth of the same fungus in the dishes used as a control.

In this way, the lowest possible dose is determined

inhibit the development of the fungus in question to an extent of 80 - 100% for each test compound. This dose is called the "minimum inhibitory concentration".

These minimum inhibitory concentrations, which are expressed in ppm, are indicated in the following table, in which the abbreviations have the meaning indicated previously.

The concentrations of the suspensions of the active substance used in the above-mentioned examples are given in g/l and essentially agree with the application amounts with the same numbers, but expressed in g/ha.

The following examples illustrate the properties of the preparations

according to the invention.

Example 14 - in vitro test on Septoria nodorum (compound

iprodione).

A culture medium that is supercooled is introduced into a series of sterile Petri dishes.

During the filling, an acetone solution of the active substance is introduced into the subcooled medium, which comprises the preparation of the compound obtained in accordance with example 1. with iprodione in different ratios to produce the desired concentration of the active substance.

Petri dishes identical to the above are used as controls and filled as indicated above, with the exception that the nutrient medium contains no active substance.

After 24 hours, each dish is seeded by depositing a mycelium fragment from a previous culture of the same fungus on the dish.

The dishes are stored at 22 - 2°C for 15 days and the fungal growth on the dishes containing the active substance(s) to be examined is compared with the growth of the same fungus in the control dishes.

Under these conditions, percent inhibition is calculated using the following formula:

in which:

I is percent inhibition,

T is the average diameter, in mm, of the development of

mycelium in the control1 dish,

TT is the average diameter, in mm, of the development of

mycelium in the treated dish, and

d is the diameter of the mycelium fragment deposited at

the beginning of the test.

The results obtained under these conditions are given below, in terms of actual inhibitory percentage I .

% inhibition on Septoria nodorum

Example 15 - in vitro test on Septoria nodorum

(compound/fenpropimorph).

The operating conditions are the same as in the previous example. The results are shown below:

Example 16 - in vitro test on Septoria nodorum (compound/tr in demorph).

Dr i ft conditions are the same as in the previous example. The results are shown below;

Example 17 - in vitro test on Septoria tritici

(connection/captafol).

The operating conditions are the same as in the previous example. The results are as shown below:

Example 18 - in vitro test on Botrytis cincerea

(connect1 see / ka rbendazim).

The conditions are the same as in the previous example. The results are shown below:

Example 19 - in vitro test on Botrytis cinerea

(commander/captain).

The operating conditions are the same as in the previous example. The results are as shown below:

Example 20 - in vitro test on Botrytis cinerea VE 35

f f o r b i n d e 1 s e / i p r o d i o n ).

(= resistant to iprodione and to carbendazim), same operating conditions as in the previous example.

The results are as shown below:

Example 21 - in vitro test on Alternaria tenuis

(compound/iprodione).

The operating conditions are the same as in the previous example. The results are as shown below:

Example 22 - in vitro test on Mon i 1 i a lasca

(compound/carbendazim).

The operating conditions are the same as in the previous example. The results are as shown below.

Example 23 - in vitro test on Helminthosporum gramineum

(compound/fenpropimorph).

The operating conditions are the same as in the previous example. The results are as shown below:

Example 24 - in vitro test on Fusarium roseum

(compound/chlorothalonil ).

The operating conditions are the same as in the previous example. The results are as below:

Example 25 - in vitro test on Fusarium roseum

(connection/maneb).

Dr i ftsbet inge1 sene are the same as in the previous example. The results are as shown below:

Example 26 - in vitro test on Venturia pirina

(connection/captain).

The operating conditions are the same as in the previous example. The results are as shown below: Example 27 - in vitro test on Pseudocercosporel1 a herpo-trichoides (compound/tridemorph). The conditions are the same as in the previous example. The results are as shown below:

Example 28 - in vitro test on Erysiphe graminis f.sp. hordei

on barley (me 1 dew/barley).

The procedure is the same as in example 11, the active substance being a combination of the compound obtained according to example 1 with tridemorph in a weight ratio of 1:1.

At a dose of 0.06 g/1, protection is complete (greater than 95%).

Example 29 - in vivo test for Botrytis cinerea on tomatoes.

An aqueous emulsion is prepared in the same way as shown in example 11 in that a preparation comprising the compound obtained according to example 1 and iprodione in a weight ratio equal to 1 is used as the active substance.

Tomato plants grown under glass (type Marmande^ and which are from 30 to 40 days old are treated by spraying them with an aqueous emulsion.

After 24 to 48 hours, the leaves are cut off and placed in two Petri dishes (11 cm diameter), the bottom of which is previously covered with a thin, moist filter paper (five leaves per dish).

The inoculum is then introduced using a syringe, with drops of a spore suspension deposited (three drops per leaf). This spore suspension of 3otrytis cinerea is obtained from a 15-day-old culture which was dissolved in a close-up solution (80,000 units/cc).

The measurement is carried out six days after the contamination, by comparing with an untreated control.

Protection was complete (greater than 95%) at a dose of 0.66 g/l of the active substance.

Example 30 - in vivo test on Erysiphe graminis f.sp. hordei

on wheat (mildew: wheat).

The procedure is the same as in example 11, the active substance being a combination of the compound obtained according to example 1, with tridemorph and fenpropimorph, in a weight ratio:

Compound from example 1: tridemorph or fenpropimorph =

11 1 .

Wheat plants in pots, which are sown in clay soil, are treated when they are 10 cm high by spraying them with an aqueous emulsion (called spray mixture), the concentration of active substance of which is shown below. The test is repeated twice. After 24 hours, the wheat fields are sprinkled with spores of Erysiphe graminis, the scattering being carried out using diseased plants.

The reading is carried out eight to twelve days after contamination.

Under these conditions, the following results were observed: Complete protection (greater than or equal to 95%) at a dose of 0.063 g/l of active substance.

Example 31 - in vivo test on Septoria nodorum mite1 of

wheat septoriosis.

The procedure is the same as in example 11, the active substance being a combination of the compound obtained according to example 1 with ipridion in the following weight ratio:

Compound from Example 1: iprodione = 1.

Wheat plants in pots that have been sown in clay soil are treated when they are 10 cm high by spraying them with an aqueous emulsion (called a spray mixture), the concentration of active substance of which is as indicated below. The test is repeated twice.

After 24 hours, an aqueous suspension of spores (150,000 sp/cc) is sprayed onto the wheat plants. this suspension is obtained from in vitro cultures of fungi. The wheat plants are then placed for eight days in an incubator in an incubator at approximately 20°C and 100% relative humidity. Measurement of the condition of the plants is carried out between the eighth and the fifteenth day after contamination, by comparison with an untreated control.

Under these conditions, a protection greater than 90% is observed at a dose of 0.25 g/l of active substance.

Example 32 - preventive in vivo test on Monilia sp. and Penicillium sp., fruit remedies, especially for

apples. rot.

Although they are independent of each other, these two tests are brought together under the same example because the procedures carried out are similar. The procedure carried out is the same as in example 11, in that the active substance is a combination of the compound according to example 1 with iprodione, in a weight ratio = 1.

The apples are treated by spraying them with an aqueous suspension (called spraying agent) whose concentration of active substance is as indicated below. The test is repeated twice.

After 24 hours, an aqueous suspension of spores is sprayed

(50,000 sp/cc in the case of Mon i 1 i a sp. and 250,000 sp/cc in the case of Pen i c i 11 i um sp.) on the apples, this suspension being obtained from contaminated fruit. The apples are then placed in an incubation cell at approximately 20°C and at 90-100% relative humidity. Measurement of the condition of the fruit is carried out between the fifth and the tenth day after contamination in the field, by comparison with the untreated control11.

Under these conditions, a protection of 49% was observed in the case of Monilia sp., and 21% in the case of Penicillium sp. at a dose of 0.66 g/l.

Example 33 - in vivo test on Erysi<p>he graminis f.sp. hordei

on barley (mildew: barley).

The method carried out is the same as in example 11, the active substance being a combination of the compound obtained according to example 1 with tridemorph, in a weight ratio:

Compound from example 1: tridemorph = 0.033.

Barley in pots sown in clay soil is treated when they are 10 cm high by spraying them with an aqueous emulsion (called spray compound) whose concentration is as shown below. The test is repeated twice. After 24 hours, the barley plants are sprinkled with spores of Erysiphe graminis, as the sprinkling is carried out using diseased plants.

Readings are carried out eight to twelve days after contamination.

Under these conditions, the following results were obtained:

50% protection at a dose of 0.1 g/l.

Example 34 - in vivo test on grape fungus (Plasmopora viticola).

The procedure followed is the same as in Example 11 to prepare an aqueous emulsion of an active substance comprising a compound obtained according to Example 1 with fosetyl-Al in a weight ratio of 0.5.

Cuttings of vines (Vitis vinifera) of the Chardonnay type are grown in pots. When these plants are two months old (eight to ten leaf stages, 20 to 30 cm high), they are treated by spraying them with an aqueous suspension or solution of the test substance. Each vine plant receives approximately 5 ml of the solution or dispersion.

After drying for 24 hours, each plant is contaminated by spraying it with an aqueous suspension of spores of Plasmopora viticola, which is responsible for grape blight, at a ratio of approximately 1 ml/plant (i.e. approximately 10 spores per plant).

After this contamination, the vine plants are placed in an incubation device for two days at approximately 18°C, in an atmosphere saturated with moisture, and then for five days at approximately 20 - 22°C at 90 - 100% relative humidity.

The reading is carried out seven days after the contamination. Under these conditions, the following results are observed:

Complete protection at 3 g/l.

Nomenclature table1.

Claims (1)

1. Compound which can especially be used as a fungicide, characterized by the formula as well as commercially acceptable salts of this compound. 2. Connection as stated in claim 1, characterized by it being in the form of a mixture of diastereoisomers. 3. Connection as stated in claim 1, characterized in that it is in the form of a diastereoisomer in which the triazolylmethyl and trifluoroethoxy groups are located on the same side of the plane of the tetrahydrofuran ring. 4. Process for producing a compound as claimed, characterized in that a connection with general1 formula wherein Z is a chlorine or bromine atom, is reacted with an alkali metal derivative of an imidazole or triazole. 5. Method as stated in claim 4, characterized in that the temperature used is between 50 and 250°C, and/or that the mixture contains an aprotic polar solvent, and/or the total concentration of the reactants is between 1 and 50%. 5. Process for producing the compound specified in claim 1, characterized in that tr i f 1uorethanol (CF^ Ch^OH) is reacted in the presence of an acidic catalyst with a compound of formula in which R 3 is an organic radical, preferably alkyl, as it is possible for two R 3 radicals together to form a single divalent radical such as the alkylene. 7. Fungicidal preparation which, as active substance, contains a compound according to one or more of claims 1 - 3, characterized in that the active substance is combined with at least one inert carrier that is acceptable for use, the preparation preferably comprising from 0.5 to 95% active substance, the preparation possibly comprising from 1 to 95% carrier and from 0.1 to 20% surfactant. 8. Procedure for combating fungal diseases on a v 1 i ngers, characterized in that an effective dose of an active substance according to one or more of claims 1 - 3 is applied, or that a preparation in accordance with claim 7 is applied, the active substance being applied in an amount of from 0.005 to 5 kg/ha , preferably from 0.01 to 0.5 kg/ha. 12. Connection by formula characterized in that Z is chlorine or bromine. 10. A preparation which can especially be used as a fungicide, characterized in that it comprises one or more of the compounds according to one or more of claims 1 - 3, and one or more of the compounds selected from group (II) which comprises the following subgroups : 1. Chlorinated or nitrated benzenes such as quintozene or chlorthalonium1, 2. Dicarboximide derivatives such as captan, folpel, captafol, iprodione and procymidone, 3. Derivatives containing one or more heterocyclic rings such as quinolenes (ethoxyquin), morpholines (dodemorph, tridemorph, fenpropimorph) and piperidines (fenpropidine), 4. Phosphoric acid derivatives such as meta11 phosphites, such as fosetyl-Al and phosphoric acid itself, 5. Diti ocarbamic acid derivatives such as maneb, mancozeb or z i neb, 6. Fenolderi water such as dinocap or binapacryl, 7. Quinonderi vates such as dithianone or chloranil, 8. Carbamic acid and benzi midazo1 there in waters such as carbendazim, benomyl and thiophanate methyl, 9. Sulfur there in water such as dazomet or etridiazole or sulphur 10. Amines and amides such as dichloran, carboxin, triforin, cymoxanil, metalaxyl and ofuras, 11. Diazines such as quinomethionate. fenarimol, anilazine, nuarimol, bupirimate, ethylrimol and pyrazofos, 12. Sulfamides such as dichlorfluanid and tolylfluanid, 13. Guanidines such as doguadine, 14. Triazoles such as those described in British Patent 2,046,260 (to which reference is made) such as diniconazole or other known triazoles, propiconazole, triadimefon, triadimenol, diclobutrazol, bitertanol, penconazole and flutriafol, 15. Imidazoles such as prochlorate or imaza 1 in 1, 16. Cyanobenzi midazo1 are like those described in French patent 2,521,141, and 17. Copper or copper derivatives, especially selected from the following active substances: Chlorthalonil, iprodione, fenpropi morph, tridemorph, fenpropidine, dinocap, dithianone, maneb, mancozeb, zineb, fosetyl-Al, cymoxanil, captan, carbendazim, captafol , sulphur, copper and copper derivatives such as copper oxychlorid , the weight ratio between the compound of formula (I) and the active substance(s) from group (II) being between 0.0003 and 3000, in particular between 0.001 and 3000. 11. Fungicidal preparation, characterized in that it comprises as an active substance a combination according to claim 10, and at least one inert carrier tolerable in terms of use, the preparation preferably comprising from 0.5 to 95% active substance. 12. Procedure for combating fungal diseases on crops, characterized in that an effective dose of a preparation according to claim 10 is applied, the preparation being applied in an amount from 0.005 to 5 kg/ha, preferably from 0.01 to 0.5 kg/ha. 13. Use of the preparations as stated in claim 10, as a fungicide; respectively of at least one compound according to one or more of claims 1 - 3, with one or more compounds selected from fenpropidine, fenpropimorph, tridemorph or iprodione, for the treatment of diseases in cereal crops; respectively with one or more compounds selected from maneb, zineb, mancozeb, sulfur or dinocap for treating vines; respectively with one or more compounds selected from carbendazim, captafol, captan, dithianone, mancozeb, maneb and copper for the treatment of trees.