Fungicide composition

The present invention relates to a liquid fungicidal composition based on compounds of the triazole and tetrahydrofuran group

Fungicidal compositions based on triazole compounds are known (European Patent No. 151084)

The object of the invention is to broaden the range of compositions with improved properties in the treatment of fungal diseases

The problem solved is solved by the invention consists in the association of compounds in certain proportions to achieve the proposed purpose

The composition according to the invention consists of 25 40% active substance you general formula I ^They\ z^of\ Z ° \ /^e>

in horse% R₅1 A hydrogen atom A represents the phenyl or p-chlorophenyl X atom_x the rabbit exits a hydrogen atom X₂ presents chlorine biom - OH -OC₂H₅ -O-Pi-, -OCH₃ -SCH₃, -S -Pr -s —2ClEt -S -iBu -S iPr —- or X₂ together they represent —O or Cl₂ or N (CH₃)₂ or MeO-N = HO -N = Pr -ΟΝ = Ί represents a group of 12 4 triosol-1-yl 2 5 10% surfactants chosen from alkaline non-phenylenedoxylated alkyl allyl vegetable oil or a mixture of alkyl allyl and alkyl ether sulfates. polyglycol with fatty alcohol 5 20% dispersing agents selected from cycloboxane or dimethylformamide as well as up to 100% aromatic solvents

Following are examples of compositions according to the invention

Example 1 Mix 400g active substance of general formula I 24g alkaline dodecylbenzenesulphonate 16g nonylphenologiethoxylate with 10 molecules of ethylene oxide 200g cyclohexane and aiomatic solvent up to 1 1

Example 2 Mix 250g of substance. active with foimula I 25 g epoxidized vegetable oil lOOg mixture of alkylaryl sulphonate and polyglycol ether with alcohol alcohols 50g dimethylformamide and 575g xylene

Starting from the needle it is concentrated it is possible to obtain full dilution with water a range of emulsions of any concentrated concentration of horses especially suitable for applying it on the fiunze

Concentrated suspensions that are also applicable to powders are sprayed with such mania to obtain a stable fluid product that does not leave sediment, and these suspensions typically contain from 70 to 75% active material from 0 5 to 15% from surfactants from 0.1 to 10% thixotropic agents from 0 10% suitable additives such as, for example, stabilized corrosion inhibiting antifoam agents, penetration agents and additives and as substances supporting water or an organic liquid in which the active matter is slightly soluble or insoluble certain organic solids or mineral salts can be dissolved in the support substance to help prevent sediment. water or as antifreeze for water

The compounds used in the compositions according to the invention are prepared as follows

A Preparation of compound 1 - (4-bromo-2- (2,4-dichlorophenyl) -tethihydro-2-furanylmethyl) -1H- 1,2-4 -triazole (compounds no. 1a 1b and at -j-1b)

Step a) Preparation of 1-chloro-2- (2-4-dichlorophenyl) -4-pentcn-2-ol an organomagnesian derivative is separated by addition of a solution of 110 ml of allyl bromide in 70 ml of ethyl ether with 110 g of magnesium at temperature from 15 to 20 ° C for 3h Heat to reflux temperature for 30 minutes decant and wash the residue with ether Add a trichloride solution to this organic phase at a temperature of 10 to 30 ° C aZ / h 2 4-acetophenone in the amount of 175g in 250g tetialihydrofuran is then neutralized with acetic acid. It is then washed with water, dried over sodium sulfate and then concentrated in distillation under vacuum. A colorless oil is obtained in a quantity of 205g. The melting point is 140 142 ° C at a fraction of 3 10 ~² mm Hg

Step b) Preparation of Compound 1 (2- (2 4 dichlorophenyl) -2 hydroxy 4-pentenyl) -1H - 12 4 triazoles a mixture of the piodus obtained in step a) in the amount of 106 g then 55 g of triazole and 160 g at room temperature. 120 ° C in 600ml of dimethylformamide The insoluble substances are filtered, the dimethylfoimamide is washed and the reaction mixture is then concentrated under vacuum. The dissolved dissolved residue in methylene chloride is washed with water then concentrated. after. dilution with heptane This isolates a solid pituitary pellet of 97g camtotated melt at a temperature of 101 ° C.

Step c) Preparation of compound 1a and 1b The compound obtained in step b) in the amount of 35 g cloform and treated at 0 ° C with bi man After discolouring the solvent is evaporated and the residue is redissolved in methanol

An aqueous solution is then added, potashing until it has obtained a base H After evaporation of the medium under vacuum, the residue is extracted with ethyl acetate washed with water and

93 432 concentrated 40 g of the oily product is obtained which is a mixture of two diastereoisomers in substantially equal proportions. The chromatography on silica is isolated, successively the least polar isomer, the number being in white crystals which melts at 83 ° C and then the isomer. more polar number 1 b in the form, strong white crystals melt at a temperature of 94 ° C after. crystallization is obtained with the melting point at the temperature of 96 ° C, the compound at and then the compound lb with the melting point at the temperature of 104 ° C The mixture at 55% of the compounds at and lb melts at the temperature of 71 ° C in the same is true for both series of the following compounds starting from the corresponding starting materials 1- (4-bromo-2- (4-chlorophenyl) -tetrahydro-2-furanylmethyl) - HH) 1 2 4-triazole-1C mp 74 ° C Ad melting point 78 ° C Ac + d melting point 69 ° C

B Preparation of Compound 1- (2- (2 4-dichlorophenyl) -4-hydroxy-tetrahydro 2-fur anylmethyl) 1H-1 2 4-triazole Compounds Ba and Bb

The lOg of the isomeric compound of Example A is used as the least polar isomer is dissolved in 30 ml of chlorobenzene and then heated to this mixture at reflux tempciatnra for 48 h in the presence of 20 g of sodium benzoate in 30 ml of water and lg of the phase transfer catalyst ADOGEN type 464 methyltrialcliylanionium chloride

After. the dissolution in ether of the organic phase is washed with water and the mixture is removed under vacuum. The residue is then treated at reflux temperature for 3h 100 ml of methanol in 7 g potash. Cool, dilute with water and extract with ethyl acetate. was washed as neutralization and purified by vacuum chromatography Alcohol 2a was isolated as a white powder in the amount of 2 8g with the melting point at 193 * Ό

By proceeding in the same manner and departing from the most polar isomer lb obtained we comply with the example. The obtained 'optically active alcohol Bb horse is presented as white powder with the dc point melting at 162 ° C. The mixture 50 parts of the compound Even 50 parts of compound B b is an oily product

C Preparation of Compound 1- (2- (2 4-dichloro phenyl) -4-ethoxy tetrahydro-2-fur anylmethyl 1H-1 2 4-triazole

Compound No 6a and Compound No 6b An amount of 2 2g of alcohol Ba in solution with 12 ml of dimethylsulfoxide is treated succinctly with 0 43g sodium hydride of 80% concentration then with 1 15ml of ethyl iodide After 15 min the reaction medium is diluted with water. and extracted with ethyl acetate After washing with water. the solvent is evaporated and the residue is purified by chromatography on silica to give a colorless oil which is the Ca isomer which crystallizes by trituration with pentane and melts at 90 ° C in the same manner starting from the compound Bb to obtain the Cb isomer below the shape of a white powder melting at 63 ° C The mixture of 50 parts of compound As 50 wells and of compound Cb is an oily product in the same way were obtained also compounds of formula Viii in the table next appropriate using the appropriate alcohols

<td>No.</td><td>X_x</td><td></td><td>Melting point</td>

<td>4a</td><td>H</td><td>OC-Cl a</td><td> 98°</td>

<td>4b</td><td>OC-Cl 1 a</td><td>H</td><td> 140°</td>

<td>5a</td><td>H</td><td>O —CHj</td><td>oil</td>

<td>5b</td><td>The —CH_S</td><td>H</td><td>oil</td>

<td>6</td><td>H</td><td>O-I-Pr</td><td>oil</td>

<td>6b</td><td>O-n-Pr</td><td>H</td><td>oil</td>

Example D Preparation of Compound 1 (2-2- (2 4-dichlorophenyl) 4-ethylthio tetrahydro-2-fur anylmethyl) -1H-1 2 4-triazole Compound No 7a and Compound No 7b

An amount of 3 8g of bromide as a solution in 38ml of dimethylsulfoxide oxide contains 2 ml and treated with 2 8g of sodium hydrogen sulphide for 2h. Then add 3 3g of potassium in the form of powder and then with 4ml of iodide. ethyl After 10 min of stirring the reaction medium is diluted with water and extracted with ether. After drying and evaporation the isomer 7a is obtained in the amount of 3 9g which is a yellow oil with a melting point at 88 ° C.

By proceeding in the same manner from compound lb, compound 7b is obtained as a pale yellow powder which melts at a temperature of 64 ° C. The mixture of isomers is an oily product in the same way the series of compounds of formula VIII are obtained in the following table using corresponding thiols

<td>No.</td><td>Xi</td><td></td><td>Melting point</td>

<td>8a</td><td>H</td><td>and -CH₃</td><td> 96°</td>

<td>8b</td><td>and -CH₃</td><td>H</td><td>oil</td>

<td>9a</td><td>H</td><td>S —n — Pr</td><td> 110°</td>

<td>9b</td><td>S-n-Pr</td><td>H</td><td>oil</td>

<td>10</td><td>H</td><td>S-2-tongs</td><td> 127°</td>

<td>10b</td><td>S-2-CIET</td><td>H</td><td>oil</td>

<td>1 there</td><td>H</td><td>And Bu</td><td> 68</td>

<td>11b</td><td>And Bu</td><td>H</td><td>oil</td>

<td>, 12a</td><td>H</td><td>And Fr.</td><td> 75</td>

<td>12b</td><td>S —i — Pr</td><td>H</td><td> 65</td>

Example E Preparation of Compound No 13 1- (7- (2 4-dichlorophenyl) -1 4 6-trioxo-spiro (4 4) -7-nonylenylmethyl) -1H-1 2 4-triazole

Step a) Prepare it for the compound 1-chloro-2- (2 ', 4-dichlorfeml) - 3 4 5-pentanetriol

The cloiliidiine obtained in step a) of example 1 in the amount of 91 g is epoxidized in 125 ml of dichloro-1 2-ethane in the presence of 5 g vanadyl ethylacetate and 200 ml of 70% thiothiobutyl peroxide. heating by heating is at the flow temperature for 48b. The reaction medium is cooled and diluted with water and then washed by several sheep with a solution of sodium bisulphite, after which the residue obtained is concentrated and then converted to triol in heating. 200ml water and 200 ml of dioxane in the solution of 5 ml of doric acid for 3 hours. After dilution with water, the reaction medium is extracted with 300 ml of toluene and then concentrated

Step b) Prepare it for compound 2- (2 4-dichlorophenyl ') - 2-chloroethyltetrahydro 4-f uranone

The oily residue obtained in step a) is then heated in 100 ml of toluene and in 200 ml of butanol in the solution of 0 5 g of toluenesulphonic acid in the separation of the water formed. After evaporation and the reaction medium, the residue is but omatographed on silica. a mixture of 40 parts of ethyl acetate 40% beptan pentium to obtain an amount of 14 5 g of colorless oily piodus coitus with a mixture of diastases of the alcohol moiety which is compound 2- (2 4-Dichlophenyl) -4-hydroxy - 2 - two - methyldhydrohydrous This compound is oxidized directly with anhydride _cRomică. in acetic acid to give after full purification chromatography on silica with furanone in the form of white crystals that melt at a temperature of 99 ° C

Step c) Preparation of Compound 7-Chlormyl til-7- (2 4-dichlorophenyl) -1 4 6-trioxide spiro (4 4) nonen

Fuianona obtained in the amount of 4 2g in step b) is dissolved in 500 ml of toluene and heated to reflux temperature in the presence of 6 5 ml of ethylene glycol and 0 lg of 76-toluenesulphonic acid with the separation of the water formed until the disappearance of the initial pipod. The reaction mixture is washed with soda and then diluted with water, extracted with ether and concentrated. Thus, 5 lg of solid white collared piodus is obtained. with the melting point at 99 ° C

Step d) Preparation of compound no. 13

An amount of 5 g of halogen obtained in step c) in 20 ml of dimethylsulfoxide is heated to a temperature of 170 ° C in the presence of 2,75 g of thiazolylsodium for 6 h. The reaction mixture is then washed over extracted water with concentrated ethyl acetate. and chromatographed on silica chromatography. Thus, an amount of 3 6 g of pale yellow crystals is melted at a temperature of 123% thereafter. iccrystallization from a mixture of ethyl acetate and heptane

Example F Preparation of Compound 1 (4-Chloro-2- (2,4-dichloro-phenyl) -tetrahydro-2- furamethyl) -1 Η 1 2 4 inazole Compound m 14a and 14b

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

The hydrochloride obtained in step a) of Example A in 150 ml of dichloromethane solution is stained with 13.4 g of chlorine gas at -15 ° C. The reaction mixture is then stained with a solution of 15 ml of sodium bisulfite. 37% concentration after the horse is washed with water, dried and evaporated. Thus, a crude piodus is obtained under thousands sheets of colorless oil in the amount of 49 7 g. The horse contains about 70% of the desired piodus as a mixture of two eisomeric diastes.

Step b) Preparation of Compound 1- (2,4-Dichlorophenyl) -1- (2,3-dichloro-1-propenyl) -oxirane

Opposed to the method is the addition of 10 3g of crude hydrochloric acid obtained in step a) above in 50 ml of methanol and treated with a 12 ml methanol solution (2 55—10 "³ moles) at ambient temperature Pieeirite is filtered and the methanolic solution is evaporated in vacuo The residue is then purified pine but decorated with silica onions This results in an amount of 7 4 g of toothpaste

A second method consists of bringing the amount of 19 9g of hydrochloride obtained in step a) from example A into 75 ml new meta and to this solution, another compound of 4 9g potash is added. in 20 ml of methanol at ambient temperature. After filtration the insoluble and evaporative substances are obtained 17 1 g of epoxy compound under the starch of a yellow-colored oily piodus. This compound is stained with chlorine to the color of the yellow color 10 Ig, at a temperature of -15 ° C. The reaction mixture is then washed with a solution of sodium bisulphite, then with water. and then it is ev then then in vacuo Thus 20 8 g of clint are obtained, an oily piodus which constitutes a mixture of two of the stars of the eoisome and in a mpit of 45/55

Step c) Prepared as compound 7- (4-chloro-2- (2-4-phenyl) tetrahydro-2-phenylmethyl) - ΊH-7 2-4-triazole The epoxide obtained in step b) in the amount of 61 7g is added in 0 51 butanol-1 and heated at a temperature of 90 ° C for 6 hours at room temperature. of 18 6 g of thiazolylsodium The minor precipitate is filtered and the butanol is evaporated The residue is purified by silica gelation on silica using an eluent starch mixture of 18% ethyl acetate 48% heptane and 4% methanol pentium to obtain successively in the top row of the diadem the zome 14 a with the melting point at the temperature a. of 1 13 ° C then secondly the lithium co-atom 14b with melting point at the temperature of 9 7 ° C The mixture of 50 parts of compound 14a and 50 feet. Compound 14 b melts at the temperature of 90 ° C

Example G Piepaiaiea of ​​compound '15

- (4-oxo 2- (2 4-trichlotdijenyl-teltahidio-2f uianylmethyl) 171 7 2 l triazole

Is it used, an amount of 37 7g of alcohol 2 beads is added to the temperature of - 60 (to a solution of 17ml dimethylsullium &lt;id in 120ml of dichloromethane stained at the temperature of -66 ° C with a starchy solution of 25 4ml of anhydride? in 60 ml of methane diclo After holding for 30 minutes at - 60 ° (leave to return to the temperature of her cam after. st: add. 48ml of tr ιοί ilamine. The reaction mixture is born in water . extended with dichloromethane and eva poiat Plin eti alize from the summits a white powder is isolated caic melts at the temperature of 91 ° C

EXAMPLE H Pt Hepatitis A of Compound UT 20 7 (4 4 diclot-2 (2 4 didotjeml) tetrahydro2 f tyran mehl) -1 II 7 2 4-tnazole

Is it used, a starchy mixture of 3 Ig ketone 15 of 2 3g phosphorus pentadium 30 ml of dichloromethane horse contains 0 25g of clams? Is thiethylammonium stirred? for 2 hours at ambient temperature until the initial compound has disappeared. The reaction mixture is then evaporated diluted with lOOml of water. neutralized with sodium bicarbonate and extracted with ethers After drying and evaporating the oily residue is separated by 2 ews of isopropyl ether. Thus, 0 6g of pod is obtained. white collar with a turning point of 138 ° C

EXAMPLE 1 Splitting of Compound No. 6 7 (4-dime4-ylamydio) 2 (2 L phenyl) tetrahydro 2-Fuylmethyl) -IH-2,4-triazole

Use a starch solution of 0 24g potash and 1 05g clove dimethylamine hydrate. In methanol, add ketone, followed by example ketone, then 0 24g of cyanohydroxy. of sodium After 15b, the mixture is diluted with water extracted with ethyl ether. The dilute peptide is then expanded in the oocene phase. of 3 sheep with 20 ml of hydrochloric acid. Neutralization by extinction and crystallization of the hole on the silica is isolated. 5 (1 6g) as a pale yellow oil (50% mixture of each of two isomers) Example 1 For hepatic compound m 7 7 1- (4-mctoximinol-2- (2 4-dichlorophenyl) tetrahydro-2-fuianylmethylH) 12 4 thiazoi

C) amount of acetone * from example C of 2g in 30 ml of ethanol is heated at the end of the reflux stopper in the methyl methylamine hydrochloride solution (5 8 ml in a 25% solution in water) for 2 hours. it is then diluted with extracted water &lt;u dichloromethane and evaporated. The piodus is isolated but instead a mixture of isopiopilic ethane and heptane under a starch white pudding melts at a temperature of 108Ύ (mixing of two hygrometrics).

Example J and uimă.toaic examples justify. the explanations of the fungicides of the compounds confuse the invention in these examples, the spray solutions and suspensions of active substances are carried out in Asia. The conditions such as pulveiiz.ia a solution or a suspension of concentrations equal to 1 g / l correspond on average to the application. the beak 2 ug / cm² from the subject matter of plant filler.

The compounds present did not illustrate the phytotoxicities cited in these examples, it was considered that a double pyrex requires complete protection. in the reservoir with the fungal disease when the pickling is at least 95% the pickling is considered to be good when it is at least 70% (give inferior. to 80% and as a doctor when it is at least 50% (you give up to 70%) in the present exposure the percentages are outside the indications of counts that weight percentages in case the percentages are expressed in stoichiometric ratio is the mole percentile vo regarding the concentrations of some of these are expressed in millions of cubic feet which corresponds to mg / 1

Example J The test - in vivo - on Botrytis to whom it to tomatoes

A syrupy emulsion of active test material with the following composition is tested by fine marinade, with the following composition: 60 mg active substance Iween, 80 (surfactant) consisting of a polyoxyethylene derivative oil of soibitan diluted to 10% concentration in water 0 3 Me and then make up to 60ml with water This, aqueous emulsion is then diluted with water to obtain the desired concentration

The tomatoes grown in the greenhouse (Marmande variety) in rows of 30 up to 40 days are treated in spray with aqueous emulsions as a porridge as mentioned above and with different concentrations of the test compound, the egg is repeated by 2 sheep. you each have tons of entities

After 24h or after 181i the leaves are cut and put in 2 14 cm diameter Petri dishes, so the round edges were pre-coated with a wet filter disc (5 vials per box)

The inoculation is then carried out using a μ-syringe in the deposition of 3 drops on each loliol from a spore suspension. This spore suspension from Botiytis who she obtained was obtained from a 15-day culture and then brought to a suspension. in a nutritional solution having 100,000 units / cr² the source is performed at 3 and 6 days after contamination compared with the untreated control under these conditions, it is observed at the dose of 1 g / l good or total pickup, with compounds m to lb to + lb 3b 5b 6b 9b 12b Ha Ub 11a 14b 17

Example K staatea m 'ireo - on Etysiphe giamims on oidium at the oiez

It is useful to use the case in. wells in the open ground caic are cut in the stage of lOcm height piin the pulverization of an emulsion of pooses under the starch of pores of the concentration indicated above The analysis is repeated by two. sheep 24h rice plants are powdered with spices of Eiysiphe giamims pu chaiea being made with the help of diseased plants

The lecture is made after 8 to 14 days from contamination, under these conditions the amazing results are obtained at the dose of 1 g / l and good protection is obtained. or total with compounds at lBb at + lb 2a 3a 3b 3a + 3b 4a 4b 5a 5b 6a 6b 7a + 7b io

8a 8b 13 14a, 14b 14a t 14b 15 17 19 20

EXAMPLE I The test runs on Puccinia. iccondiia 1 esponsabild of the mgina giîului

The grains in wells sown in, open nipple are treated in the stage of height cm high spraying with aqueous emulsions' under the shepherd's lime with the same composition as that used in example 11 and at different concentrations of the tesla compound! the balloon is repeated by the sheep with each consciousness

After 24h an aqueous spore suspension (50,000 spores / cm²) is sprayed on wheat this suspension obtained obtained from the 'contaminated plants Then the gray is placed for 481i in &lt;incubation cells of about 18 up to 100% wet dipped

After these two days the relative humidity is brought to 60%. The seedling of the plant stage is made aware that from 1 to 15 days after contamination in comparison with the canopy found at the ig / 1 dome, a good total jump is obtained. you compound to lb to t lb 3a 3b 3a, 3b 5b 6b 7a 7a + 7b 8b 12b 13 14a 14b 14a t-Mb 17 19 20

Example Μ T est -iu alive asupia I'iiiculatiea oiyzae 1 eiponsabHa de pinculo1 ιυζα oieziilin (Rica Blast) The rice in the well is sown in a mixture of 50% peat enriched and each treated at a stage of 10 cm high under the pulp. of porcelain defined above the concentration of the indication The test is repeated for 2 hours. After 48 h, the application on the leaves is treated with a suspension of sprouts obtained in the culture of the lettuce. It is done 8 days after contamination in these conditions we observe the amazing results at the dose cl · '1 g / l a good or total pickup is obtained with the compounds at lb at - | lb la 3b 6a 8a Sb 9a 9b 10b 11a ilb

12a l? B 14a Ub 14a t 14b 15 20

Example N the rest in vitio on seed and soil buds It is studied, the action that the compo- sition con / oim of the present invention on the following eloi the pinch but responsible for the diseases of the crops and the vegetables 1) Ipreuospoiae aveuae 2) Seploiia nodomm V) teelminthospusa) num roseum 5) 1 &lt;usaiiitm culmoiiim

7) Phizoetoniu csreahs 8) Septona tiitici 9) Botiytis cmeiea sensitive, takes the bite of the cimea and the cyclic imidelc 10) Botiytis to the dog it is resistant to the caibendczyme and the cyclic imidtle 11) Pseudoceicospoi ella heipotnehoys 12) Fusanum ox and 13 14) Helminthosporium gi amine-um

The figures shown before the above names will be used as shown by the mushrooms in table 2

For each test, it is operated in such a manic way, in the nutrient medium consisting of potatoes glucose and jellies (PDA medium) it is introduced by fusion on a series of Petri dishes by 20 ml per box after sterilization in autoclave at 120 °. C in which the filling of the box is injected into the medium by means of sui fusion, an acetic acid solution of active substance, to obtain the final concentration, dosed

Petii boxes are used as hammers, similar to the previous ones, in which similar quantities are brought from a nutritious environment that does not contain active matter.

After. 24 or 48h each box is sown by depositing a fragment of the mycelium that comes from a previous culture of the same fungus

The cans are stored for 2 to 10 days (according to the mushroom tested) at 22 ° C and then the growth of the mushroom in these boxes compares to the active raw material, to be tested the same mushroom in the box used as hammer.

Thus, for each tested compound, the percentage inhibition of the fungus considered to be a dose is determined. of 30 parts per million

Compounds of general formula I may be used in the form of an acceptable salt in agriculture, such as hydrochloride sulphates, oxalates, nitral or arylsulfonate, as well as their addition complexes with metal salts and especially with chromium iron salts, magnesium copper, zinc, cobalt, tin, manganese and aluminum.

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

Compounds of formula I and compounds, possibly used as intermediate compounds in the preparation processes may exist in one form or in different forms of isomers according to the number of asymmetric centers of the clin molecule. The inclusion therefore also refers to all optical isomeric forms and to the mixture of compounds and acoustics in the eoisomer diastasis. Suitable separation Separation of the dialysis of the eisomers and / or optical isomers can be performed according to known methods if group X »corresponds to an atom of Halogen (the compound of formula II) a preparation step consists of the following steps

Step a) It is done to. react a halogen ketone of the formula Ha' obtained from the known piocede in which Y n R₅ have the same meanings as those given for com12 wells of formula I and Z corresponding to a halogen atom, with an oiganometallic compound of formula Ilb in which the radicals from Rj to R₄ X_x have the same meanings as those given for compounds of formula I and Z corresponding to a halogen atom with an organomelalic compound of formula Ilb wherein the radicals from R, to R₄ X_t have the same meanings as above and M corresponds to an alkali metal or a magnesium compound (MgHal) in which a zinc compound (ZnHal) is found, for example, in a solvent preferably chosen from ethers, for example, ethyl ether or tetrahydrochloride alicyclic or aromatic aliphatic hydrocarbons such as toluene hexane at a temperature of between -50 ° C and the reflux temperature of the considered solvent and preferably in the ratio of Ha Ilb molar preferably between 1 and 0 2 By reduction, one reaches the compound of the formula lyc after neutralizing the reaction medium

Step &amp;) It is then quenched to react the compound of the liquid formula with unsubstituted triazole in the presence of an organic or mineral base such as pyridine triethylamyrra soda potassium carbonates and bicarbonates of alkaline or alkaline earth metals and in a suitable solvent such as ketone alcohols amide nitrile aromatic hydrocarbons optionally halogenated at a reflux temperature of the solvent and preferably in a molar Hc contribution. triazole between 1 1 and 0.2 which leads to the compound of the formula Ud The reaction usually takes place, with the help of an epoxy intermediate of the formula Ilh, which may be isolated or prepared separately by one of the methods known to those skilled in the art. from the literature

Step c) A halogen or halogen mixture molecule is preferably added to the wet compound, preferably mol, in an inert solvent such as saturated aromatic hydrocarbons and possibly halogenated hydrocarbons, thus reaching compound Ila.

Step d) Compound II is preferably obtained at ambient temperature by cyclization of the compound Ile in the presence of an organic or mineral base indicated in b) in a ratio of inola to compound B of the assumed base. Between 1 1 and 0 66, the reaction can be carried out in an aprotic or piotic solvent medium. Examples of aprotic solvents are water, ketone alcohol, nitiyl ester, saturated or aromatic hydrocarbon, optionally halogenated dimethylsulfoxide amide, such as dimethylfoimamide.

A second process for the preparation of compounds in which the shell X₂ is a halogen consisting of first stage placement

Β7 of triazole nucleus after step d) using the same optional mode for different stages

The compounds according to the present invention can be used for the prevention of fungal disease, so with preventive and curative action mushroom counts, especially of the type basidiomycetes, ascomycetes, adelomycetes or imperfect fungi, especially in the case of the rust of the oldium gray fussus of the helminths of the plant cuttlefish and the cuttlefish. al and especially in cereals such as giîu or? rye, oats, and their hybrids, as well as corn and corn Compound, We confound the present invention are especially active mushroom species, especially for the types of ascomycete adelomycetes or defective fungi such as Botiytis cinerea, Erysiphe graminis, Pucinia iccondita, Piricnlaria oryzae Ceicospora beticola Puccinia Pyreniae avenae, Septoria tritici Venturia insc'qualis, Whetzelinia solrotiorum Monila laxa Mycosphaerclla f ijienis Never panettonian Alternai ia solarii, Aspergillus niger, Cercospora aiachîdicola Cladospoi ium herbarum Helminthosporium oryzae, Penicillium expansum Pestalozzia species Phialophora cine eacens Phoma betae Phoma veata Phoma ling Uslilago myadis Verticillium dahliae scleriorum vitii, Guignardia bidii

The compounds confuse to the piezente invention are especially active against the miners: Balloons gamus Koning Alteinaria Collelotrichum Corticium tolfsii Diplodia natalensis Gaeumennomyces graminis Gibberella fugikutoi Hormodendron classified dospoiioides Lentinus Degen or tigrinus I enzttas quercine Memnoniella echinata Myrothecium verrucana Paecylomyces varioti Pellicularia asasakii, Phellinus megaloporus Polysiictus sanguineus, Poria vaporaria Sclerotimn lolfsii, Stachybotiis ATRA Stereum, Stilbum species Tramctes beam Prichodeima pseudokoningi Trichothecium rosseum

The compounds according to the present invention are, in particular, concerned with their broad spectrum at the level of cereal disease (oidium rustina of the gin belminospo lioze, septoiiosis and fuscriosis) These compounds also have a great interest in the activity of the gray mold (Botrytis) and the cheetah, and for this reason &lt;the compounds can be applied to quite varied crops such as vines and sausage crops and vines. small crops14 such as, for example, the cultivation of banana peanuts, the coffee tree, etc., apart from the waste applications, the products are already present before we confuse the present invention. among others, it presents an excellent biocidal activity with regard to numerous other varieties of mitrooiganisms, among which the mushrooms such as those with the non-limiting fungi such as those of the genus Pullulaiia such as the species P Pullulens Chaetomium such as species C globosum, Aspergillus as for example Aspergillus niger Voniophora as for example species C putana in terms of their biocidal activity &lt;before these fish myths to effectively combat myo-oiganisms of pioliferous pathways create numerous pioblemas in the agricultural field and in the industrial field For this reason is particularly convenient, for the pickling of vegetables or industrial products such as wood, leather, paper, paintings, plastics, water circuits, industrial water circuits

The compounds according to the present invention are particularly well suited to the protection of lignocellulosic pulp and, in particular, the wood pellets &lt;um, for example, furniture such as timber or exposed timber such as * for example, fences, vines, log beams

The compounds confound to the present invention are used alone or under the starvation of compositions as defined above in the treatment of wood and are in the genes put into application as oceanic solvents and may possibly be associated with one or more prodrugs such as for example pentaclox phenol metal salts, especially zinc chromium magnesium zinc, derived from zinc or carboxylic acid mines (acids such as heptanoic acid octanoic acid naphthenic acid etc. organic compounds of tin mercaptobenzothiazole, insecticides such as, for example, piietioids or organotics, finally, the compounds of the present invention have excellent selectivity in relation to the above-mentioned cultures.

These compounds are advantageously applied in doses from 0 005 to 5 kg / ha and more specifically in doses from 0 01 to 0 5 kg / ha

For the practical use of these compounds, they are rarely used as such. Most often these compounds are part of the compositions. These compositions usable for plant pickling against fungal diseases or in the compositions that regulate the growth of plants contain an active compound according to the present invention. as described above in association with solid substances with a role as substrates or with liquid substances acceptable in agriculture and / or with agents surfactants equally acceptable in agriculture Used. especially substances that are as inert and common as usual surfactants

By the term dc substance subjected within the scope of the invention is designated a natural or synthetic organic or mineral matter with which the active matter is associated, thus facilitating its application on plants on seeds or on the soil. This subject is therefore generally inert and it must be to. either acceptable in agriculture especially on the plants to be treated. This subject can be solid (such as natural or synthetic silicate clays, silicate silicates, as well as solid fertilizers, etc.) or liquid substances (water, alcohol ketones, fractions). oil aromatic or paiafinic hydrocarbons hydrochloric chlorinated gases liquefied⁺and etc)

The surfactant may also be an ionic or nonionic scavenging or wetting agent. It may be cited, for example, its polyacrylic acid moiety of its lignosulphonic acid moieties and its moieties. phenolsulfonic acids or naphthalenesulmonic acids of ethylene oxide poles and alcohols, or ι u fatty acids or amialic acids of substituted polyphenols (especially of lymphenolyls or arylphenoloyls) of acylsilic acid sulphide derivatives of taurine (especially allelesinate) estet! phosphorus of alcohol or broad-spectrum phenolilylo The presence of less than one tensile agent in acrylics is essential for active matter and / or storage. so that you do not feel soluble in water and &lt;to the agent \ we all apply is water

As forms of liquid compositions or designed to constitute liquid compositions for application, solutions can be cited, especially water-soluble concentrates. emulsifiable concentrates emulsions concentrated suspensions aerosols wettable powders (or spray powders), pastes

Emulsifiable concentrates or bile solutions most often contain from 10 to 80% in active material emulsions or ready-to-apply solutions also contain from 0 01 to 20% of active material

These compositions may also contain all assortments of other ingredients such as, for example, protective colloids, adhesive substances, thickeners, thixotope agents, penetrating agents, stabilizing agents, sequestering agents, etc., as well as other known active substances with pesticide or insecticidal poppies (especially insecticides). ) or _cu Controlling properties of their plant growth Most generally, the compounds according to the invention described can be combined with any kind of solid or liquid additives that correspond to the usual techniques for drawing the above mentioned compositions.

For example, most often emulsifiable concentrates may contain ι which is required from 2 to 20% of. suitable additives such as, for example, stabilizing surfactants agents feathering agents cohesion inhibitors dyes or adhesives previously mentioned

The doses used in the case of fungicide use of the compounds according to the piezency in the vents can vary within wide limits, especially depending on the virulence of the fungi and the ι

Generally, horse compositions contain from 0 5 up to 5000 ppm of substance. active values ​​are convenient, these values ​​are indicated for ready-to-use ppm compositions, repeating parts per million Zone. from 0 5 up to 5000 ppm corresponds to an area of ​​5 Uri⁵ at 0 5% by weight with regard to the compositions adapted to the stored and at tianspoit they contain more advantageous from 0 5 to 95 by weight of the active substance, the piezant entity has the advantage of obtaining a composition with superior effects iung b ide