EP0769905A1

EP0769905A1 - Fungicidal compositions containing 3-phenyl-pyrazole derivatives for treating propagative plant stock, novel 3-phenyl-pyrazole derivatives, and fungicidal uses thereof

Info

Publication number: EP0769905A1
Application number: EP95925032A
Authority: EP
Inventors: Richard Cantegril; Jacques Mortier; Denis Croisat; Raymond Peignier
Original assignee: Rhone Poulenc Agrochimie SA
Current assignee: Bayer CropScience SA
Priority date: 1994-07-13
Filing date: 1995-07-10
Publication date: 1997-05-02
Also published as: CO4480715A1; WO1996002138A1; CZ9197A3; AU2931295A; JPH10502661A; KR970704349A; BG101207A; PL318161A1; HUT76819A; FR2722369A1; BG62077B1; CN1152853A; SK4697A3; ZA955518B; FR2722369B1; BR9508790A; FI970099A0; FI970099A; MX9700297A; CA2194913A1

Abstract

Fungicidal compositions containing as the active ingredient 3-phenyl-pyrazole derivatives of formula (I), wherein X1 to X5, which are the same or different, are a hydrogen atom, a halogen atom or a nitro or alkyl grouping, etc.; Y is a halogen atom or a nitro group, etc.; and Z is a hydrogen atom or a C(=Z1)Z2 group, phosphoryl, etc. Said compositions are useful in agriculture for protecting propagative plant stock from fungal diseases.

Description

Fungicidal compositions based on 3-phenyl-pyrazole derivatives for the treatment of plant propagating material, new 3-phenyl-pyrazole derivatives and their fungicidal applications

The present invention relates to the use of 3-phenyl-pyrazole derivatives for the protection of plant propagating material against fungal diseases, the compositions containing these derivatives as well as new derivatives of this family, the compositions containing the latter and the fungicidal compositions. containing them as well as a process for the treatment of plants with these derivatives.

Certain 3-phenyl-pyrazole derivatives are described in particular in published applications EP 0538 156 and WO 93/22287 for their advantageous properties against fungal diseases of the leaf parts of plants. By the term "plant propagating material" is meant to designate all the generative parts of the plant that can be used for reproduction and multiplication thereof. Mention may be made, for example, of seeds (seeds in the narrow sense) for crops other than potatoes, roots, fruits, tubers, bulbs, rhizomes, parts of plants or even sprouted plants and young plants. seedlings, which must be transplanted after germination or after emergence from the soil. These young plants can be protected before transplantation by a total or partial treatment by immersion. Among the multiplication products suitable for the treatment process according to the invention, preference will be given to:

- broadleaf seeds: peas, cucumber, melon, soy, cotton, sunflower, rapeseed, beans, flax, beet

- monocot seeds: cereals, corn, rice

- or the potato tubers.

Preferably, the seeds will be coated with 0.1 to 500 g of active material per quintal of seed, preferably 1 to 400 g per quintal. Preferably, in the case of tubers, these are coated with an amount of active material corresponding to the soaking of said product in a composition containing 0.1 g / 1 to 100 g / 1 of active material.

A more specific subject of the invention is, on the one hand, compositions for the treatment of plant propagating material against fungal diseases, characterized in that they contain, as active materials, at least one 3-phenylpyrazole derivative of formula I:

I in which:

X \, X2, X3, X4 and X5, identical or different, are: - a hydrogen or halogen atom, a hydroxy, mercapto, cyano, thiocyanato, nitro, nitroso, amino group optionally substituted by one or two alkyls or phenyls,

- an alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyle.alkylsulfonyl alkylthioalkyle alkylsulfinylalkyle, alkylsulfonylalkyle, benzyle, alényle, alkynyle, cyanoalkyle, alkoxy, alkenoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, formyl, acetyl, alkyl or carbonoxy) di alkylamino (thio) carbonyl, amino (thio) carbonyl, mono- or diarylamino (thio) carbonyl, carboxyl, carboxylate, carbamoyl or benzoyl, - a phenyl, phenyloxy or phenylthio radical

an alkyl- or alkoxy- or mono or di alkylamino-phenyl-sulfenyl or sulfinyl or sulfonyl radical,

- a sulfonic group, its salts, esters and derived amides,

a phosphoryl group, substituted by two groups chosen from the group comprising alkyl, alkoxy, alkylthio and dialkylamino, benzyloxy, phenyloxy or phenyl,

- a trialkyl- or alkylphenyl-silyl group, two of the adjacent Xj, X2, X3, X4 and X5 can also form a bridge comprising from 2 to 4 members, at least one of which can be replaced by an oxygen atom. sulfur or nitrogen, and which may have one or more atoms or groups following C, O, S, N, C = O, C = S, SO, SO2, CH = CH, the carbons of this bridge may or may not be substituted by at least one halogen atom and / or at least one hydroxy, amino, alkyl, alkoxy .alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl or alkoxycarbonyl group, the alkyl part being as defined below, with the proviso that Xjà X5 cannot each be simultaneously a hydrogen atom; Y is a hydrogen, halogen, nitro, cyano, hydroxy, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyloxy, mercapto, carboxyl, carboxylate, formyl, alkyl (thio) carbonyl, arylcarbonyl, alkoxy (thio) carbony, carbamoyl atom , aminoalkyl, thiocyanato or alkyl, alkenyl, alkynyl, alkoxy or alkylthio, alkylsulfinyl or -sulfonyl, the alkyl part of these radicals being optionally mono- or polyhalogenated, an amino optionally substituted by one or two alkyls or phenyls; phenyl, phenoxy, phenylthio, arylsulfinyl or - sulfonyl, Y and XI or X5 can also form a bridge comprising from 1 to 3 members, which can contain one or more atoms or groups following C, O, S, N, C = O, C = S, SO, SO2, CH = CH, the carbons of this bridge can be or not substituted by at least one halogen atom and / or at least one hydroxy, alkoxy, alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl, the alkyl part being as defined below,

Z is:

- a hydrogen, halogen atom, a cyano, nitro, hydroxy group or

- an alkyl, haloalkyl, hydroxyalkyl, formyloxylalkyl, alkyl- or aryl (thio) carbonyloxyalkyle, alkoxy (thio) carbonyloxy alkyl, amino (thio) carbonyloxyalkyle, mono or dialkylamino (thio) - carbonyloxyalkyle, cycloalkyl or cycloalkyl -alkyl, the cycloalkyl part may be substituted by the GR4 group, defined below,

- alkoxy optionally substituted by hydroxy, alkoxy, alkylthio, alkylsulfinyl or -sulfonyl,

-a phenyloxy or phenylthio, phenylsulfinyl or -sulfonyl

- an amino optionally substituted by one or two alkyls

- alkenyl or alkynyl, each containing 3 to 7 carbon atoms, optionally substituted - phenyl or Het, optionally substituted

- a group of formula C (= Zι) Z2 in which:

Z _j is an oxygen or sulfur atom or an alkylamino or alkylimino or arylamino or arylimino group and

- Z2 is: - a hydrogen, halogen atom, a hydroxy, mercapto, cyano, amino group, - alkyl, alkoxy, haloalkoxy, alkylthio, - alkenyl or alkynyl or alkenyloxy, each containing from 3 to 7 carbon atoms,

- phenyl, phenylalkyl, phenoxy, phenalkyloxy, -Het or Het-alkyl, -phenylalkenyl or phenylalkynyl; Het-alkenyl or Het-alkynyl

- mono or di alkylamino, a mono- or diphenyl-amino radical, or alkyl- or arylsulfonylamino,

- a phosphoryl group substituted by two radicals chosen from the group comprising alkyl, alkoxy, alkylthio, dialkylamino, cycloalkyl or cycloalkyl

- alkyl, alkenyl or alkynyl, phenyl, phenylalkyl, Het or Het-alkyl, phenyl or Het, optionally substituted; - or a group S (= Zj) (= Z3) Z2, in which Z \ and Z2 have the same meanings as above and Z3 has the same meanings as without necessarily being equal to Zi,

as well as the tautomeric forms of formula I bis, when Z is a hydrogen atom or isomers when Z is a group of formula C (= Zj) Z ₂ or S (= Zι) (= Z3) Z2,

I bis

as well as the hydracid or perchloric or nitric or sulfuric acid salts or alkyl- or phenyl (optionally substituted) sulfonic acids of the derivatives of formulas I or I bis and their metal complexes, and their N-oxides, it being understood that in all of the above meanings, the linear hydrocarbon part of these groups may comprise from 1 to 7 carbon atoms and may be optionally halogenated (from 1 to 8 halogen atoms),

the cycloalkyl part of these groups can comprise from 3 to 7 carbon atoms and be optionally substituted by at least one substituent chosen from the group GR4 defined below,

the phenyl part denotes the phenyl ring optionally substituted with 1 to 5 substituents chosen from the group comprising a halogen atom, an alkyl or alkoxy of 1 to 3 carbon atoms and nitro, - Het is a heterocyclic radical, mono or bicyclic, containing from 5 to 10 atoms, of which 4 are heteroatoms (oxygen, sulfur, nitrogen, phosphorus); the group GR4 comprises:

- a halogen atom, or a cyano, nitro, mono or dialkylamino group,

- an alkyl, alkoxy, alkylsulfenyl, alkylsulfonyl, alkycarbonyl, alkylthiocarbonyl, alkoxycarbonyl, alkoxythiocarbonyl, mono- or dialkykaminocarbonyl or mono- or dialkykaminothiocarbonyl, mono or dialkylaminosulfonyl, (the alkyl part of all these substituents containing from 1 to 4 carbon atoms and be substituted by 1 to 9 halogen atoms),

Preferably, in formula IY is a chlorine or bromine atom. Other preferred derivatives are such that, in formula I, Z is a hydrogen atom or a group C (= Zι) Z2 _> in which Z \ is an oxygen or sulfur atom. Other preferred derivatives are such that, in formula I, X1-X2 and X4 are a hydrogen or halogen atom or a nitro, amino or alkyl group, optionally halogen, of 1 to 4 carbon atoms.

Other preferred derivatives are such that, in formula I, X3 is a hydrogen or fluorine atom.

Other preferred derivatives are such that, in formula I, XI and / or X5 are a hydrogen atom,.

Other preferred derivatives are such that, in formula I, two adjacent substituents chosen from X \ X2, X3, X4 and X5 form a bridge comprising 3 or 4 links, in particular an optionally halogenated and preferably fluorinated methylenedioxy bridge.

Particularly preferred derivatives are as respectively in the formula

I: a) X \, X3 and X5 are a hydrogen atom and X2, X4 are each a chlorine atom b) X \ is a nitro, X2, X4 are each a chlorine atom X3 is a fluorine atom and X5 is a hydrogen atom c) X \ is a fluorine atom, X2, X4 are each a chlorine atom X3 is a fluorine atom, X3 and X5 are a hydrogen atom

Some of these derivatives are new and such that in formula I: Y is a chlorine atom and Z is a hydrogen atom,

X \ is a hydrogen or halogen atom or a nitro, amino or methyl group X2 is a halogen atom or a nitro, amino or methyl group,

X3 is a hydrogen or halogen atom X4 is a halogen atom or an amino nitro or methyl group, X5 is a hydrogen or halogen atom New preferred derivatives are as in formula I: Y , Z, X \ and X4 are as described above,

X2 is a chlorine or bromine atom, X3 and X5, identical or different, are each a hydrogen or fluorine atom.

The derivatives according to the invention can be prepared according to methods known per se as described in published applications EP 0 538 156 and WO 93/22287. The following examples respectively illustrate the preparation of new derivatives, their physicochemical characteristics (the structures have been verified by NMR analysis), their fungicidal properties in treatment for leaf diseases as well as the fungicidal properties in seed treatment of all of the derivatives according to the invention.

Example 1: Benzoic acids. a) 2,3-Dichloro 5-nitro benzoic acid.

To a solution cooled to 5 ° C. of 100 g (0.52 mol) of 2,3-dichlorobenzoic acid dissolved in 1000 ml of concentrated sulfuric acid, 58 g (0.57 mol) of nitrate of nitrate are added in portions. potassium. After 1 hour, the reaction medium is poured into 8 1 of ice, filtered through sintered glass and then dried (yield 63%; analysis). b) 3-chloro 4-fluoro 5-bromo benzoic acid.

Under an argon atmosphere, 10 g (0.0265 mole) of 3,5-dibromo 4-fluoro benzoic acid are dissolved in 200 ml of dry THF. 37 ml of 1.6 M n-BuLi in solution in hexane are poured, drop by drop, at -70 ° C. After one hour of stirring, 25.1 g

(0.106 mole) of hexachloroethane in solution in 20 ml of dry THF are added.

After 2 hours at -70 ° C, the temperature of the medium is gradually reduced to room. The reaction mixture is hydrolyzed with 50 ml of water and then extracted with ether. The aqueous phase is acidified by addition of IN HCl and then extracted with ether. The organic phase is dried over magnesium sulfate, concentrated under reduced pressure. The solid is recrystallized from a heptane / ether mixture to give 1.2 g of 3-chloro 4-fluoro 5-bromo benzoic acid (yield: 18%; melting point: 184 ° C). c) 3-bromo 4-fluoro 5-bromo benzoic acid.

60.8 g of sodium hydroxide pellets are dissolved in 500 ml of water. 26 ml of bromine are added while maintaining the temperature of the reaction medium below + 10 ° C. 50.0 g (0.169 mol) of 3-bromo 4-fluoro 5-bromo acetophenone dissolved in 50 ml of dioxane are poured in, keeping the temperature of the reaction medium below

+ 10 ° C. The temperature of the reaction mixture is brought back to ambient by controlling the exothermicity so as not to exceed + 35 ° C. Agitation is continued for 1.5 hours at room temperature. The aqueous phase is extracted with ether, acidified to about pH 1 with IN HCl, reextracted with ether. The organic phase is dried over magnesium sulfate, concentrated in vacuo. The solid is triturated in heptane to give 47.5 g of 3-bromo 4-fluoro 5-bromo benzoic acid (yield: 74%; melting point: 201 ° C). d) 3,5-Dichloro 2,4,6-trifluorobenzoic acid.

Under an argon atmosphere and at -70 ° C, 57 ml of a 1.6 M solution of n-BuLi in hexane are added dropwise to a solution of 10.4 g (0.090 mole) of TMEDA in 40 ml of dry THF. At -70 ° C, 15.0 g (0.075 mole) of 3,5-dichloro 2,4,6-trifluorobenzene in 10 ml of dry THF are added dropwise. After 1 hour of stirring at -70 ° C, the reaction mixture is poured onto solid carbon dioxide in 100 ml of dry THF. The reaction medium is stirred, allowing the temperature to rise gradually to ambient, then hydrolysis with water, extracted with ether. The aqueous phase is acidified with IN HCl, extracted with ether. The organic phase is dried over magnesium sulfate, concentrated in vacuo. The solid is recrystallized from a heptane / ether mixture (yield: 54%; melting point 136 ° C). e) 3,5-Dichloro 2,4-difluorobenzoic acid.

Under an argon atmosphere and at -50 ° C, 90 ml of a 1.6 M solution of n-BuLi in hexane are added dropwise to a solution of 14.3 g (0.090 mole) of diisopropyamine in 100 ml of dry THF. After half an hour at -50 ° C, 20.0 g (0.109 mole) of 3,5-dichloro 2,4-difluorobenzene in 70 ml of dry THF are added dropwise. The reaction medium is stirred for 1 hour at -70 ° C., poured onto solid carbon dioxide in 100 ml of dry THF. After returning to ambient temperature, the reaction mixture is hydrolyzed with water, extracted with ether. The aqueous phase is acidified with IN HCl, extracted with ether. The organic phase is dried over magnesium sulfate, concentrated in vacuo. The solid is recrystallized from a heptane / ether mixture (yield: 37%; melting point: 177 ° C). f) 3,5-Dichloro-2,6-difluorobenzoic acid.

9.5 g (0.06 mole) of 2,6-difluorobenzoic acid and 7.8 ml of oxalyl chloride (0.09 mole) are dissolved in 50 ml of 1,2-dichloroethane. 5 drops of DMF are added and the whole is stirred for 1 hour at room temperature. 24 g (0.18 mole) of aluminum chloride are added and the medium is brought to 60-70 ° C. After passing a stream of chlorine for 5 hours, keeping the temperature of the reaction medium between 60 and 70 ° C, the whole is poured into 100 ml of IN HCl. The precipitate is recovered by filtration, washed with water, dried under reduced pressure to give 13 g of a cream solid (Yield: 95.6%; ¹ H & ¹³ C NMR). By operating as above but with the appropriate reagents, the following acids were prepared:

- 3-fluoro 5-bromobenzoic acid (Yield: 78%; melting point: 144 ° C);

- 2-nitro, 3-chloro 5-methylbenzoic acid (Yield: 83%; melting point: 226 ° C);

- 3-fluoro 5-methoxybenzoic acid (Yield: 90%; melting point: 121 ° C)

Example 2: Acetophenones. (see EXAMPLE 4 D of application WO 93/22287)

The acetophenones are obtained from the benzoic acids previously obtained according to the following procedure: a) 2,3-dibromo-5-methyl benzoic acid chloride.

2.1 g (0.00714 mole) of 2,3-dibromo-5-methyl benzoic acid in solution in 20 ml of 1,2-dichloroethane are treated by the addition of 0.78 ml (0.107 mole) of thionyl chloride in solution in 5 ml of 1,2-dichloroethane. The mixture thus obtained is stirred at 60 ° C for about 5 hours then concentrated in vacuo to yield an oil: 2,3-dibromo-5-methyl benzoic acid chloride. b) (2,3-dibromo-5-methylphenyl) ethanone 30 ml of ether is refluxed for 3 hours a mixture of 0.87 g (0.0076 mole) of magnesium ethylate and 1.17 ml (0 0.0076 mol) of ethyl malonate. Then added to this heterogeneous solution 2 g (0.0064 mole) of acid chloride obtained previously diluted in 5 ml of ether. The reaction medium is then stirred at reflux for 3 hours. After cooling, 10 ml of a dilute sulfuric acid solution are added to the reaction medium which is then extracted with ether and washed with water. After drying over MgSO4 and evaporation of the solvent, an oil is obtained which is directly engaged in the decarboxylation step: dilution in a mixture of 5 ml of acetic acid, 5 ml of water and 1 ml of concentrated sulfuric acid then heating to 70 ° C for about 2 hours. The middle The reaction mixture is then extracted with ethyl acetate and neutralized with an aqueous sodium hydroxide solution. After drying over MgSO4 and evaporation of the solvent, an oil is obtained: (2,3-dibromo-5-methylρhenyl) ethanone.

In the same way as above, the following acetophenones are obtained (see table below), from benzoic acids suitably substituted:

B) Preparation of (3.5-dichlorophenvin ethanone from 3.5-dichloroaniline (cf. example 4 F of application WO 93/2228: 300 ml of water and 70 ml of concentrated hydrochloric acid are added to 48.6 g (0.30 mole) of 3,5-dichloroaniline. 30 minutes later, 27.5 g (0.40 mole) of sodium nitrite are poured in dropwise into 32 ml of water while maintaining the temperature between 0 ° and 5 ° C. To the filtered reaction mixture is added 16.2 g (0.2 mole) of sodium acetate. This solution is poured dropwise onto a solution of 28.5 g (0.48 mole) of acetaldoxime, 25.0 g (0.10 mole) of copper sulphate pentahydrate, of 20.5 g (0.018 mole) of anhydrous sodium sulfite and 121 g (1.50 mole) of sodium acetate in 250 ml of water maintained at 15 ° C. After 1 hour of stirring, the medium is acidified by adding concentrated hydrochloric acid. After steam stripping and chromatography of the crude product on a silica column (heptane 90, ethyl acetate 10), 16.6 g (30%) of (3,5-dichlorophenyl) ethanone are recovered, in the form of a colorless liquid.

By operating as above, starting from 3-bromo-5-trifluoromethylaniline, (3-bromo-5-trifluoromethylphenyl) ethanone is obtained (yield: 35%; NMR). b) from 4-acetyl-2,6-dichloroaniline: 814 g (4 moles) of 4-acetyl-2,6-dichloroaniline, prepared according to patent DD 273,435 of 11/15/1989, are recrystallized 1200 ml of concentrated hydrochloric acid and 5200 ml of concentrated acetic acid. After cooling to 0 ° C., a solution of 290 g (4.2 moles) of sodium nitrite in 770 ml of water is run in stream. After 2:30 at this temperature, the solution is poured into a solution at 5 ° C of 2200 ml of 50% hypophosphorous acid in water. At the end of the pouring, the mixture is allowed to return to ambient temperature then 10 l of water are added and the aqueous phase is extracted with dichloromethane. After drying the decanted organic phase, concentrating and distilling the crude product, 591 g are obtained (yield 78%, boiling point: 91-95 ° C. under 1 mm Hg) of (3,5-dichloro) phenyl ethanone in the form of 'a light yellow liquid. By operating as above from 4-acetyl-6-bromo-2-chloroaniline, 89% of (3-bromo-5-chloro) phenyl ethanoneRMN) is obtained.

By operating as above from 3,4,5-trichloroaniline, (3,4,5-trichlorophenyl) -ethanone was obtained (yield: 20%; mp: 75 ° C).

Example 3: 2-chloroacetophenones

(preparation of chloracetophenone by chloracetylation (Friedel-Crafts) of 2-chloro-1- (2-chloro-4-fluoro-5-methylphenyl) ethanone (Example 41 of application WO 93/22287 WO 93/22287)

14.1 g (0.125 mole) of monochloroacetyl chloride are poured in dropwise into a suspension of 16.66 g (0.125 mole) of anhydrous aluminum chloride in 100 ml of dry 1,2-dichlorethane maintained at the temperature of -5 ° C by an ice-acetone bath. 14.46 g (0.1 mol) of 4-chloro-2-fluorotoluene are then poured in dropwise at the same temperature in the solution obtained. The reaction mixture is stirred for 1 hour at - 5 ° C then left to stand overnight, finally brought to 60 ° C until the end of gassing. After cooling in an ice bath, a solution of 5 ml of concentrated hydrochloric acid in 100 ml of water is poured dropwise. After decantation, the organic phase is washed successively with 50 ml of water, 50 ml of saturated NaHCO3 solution and 50 ml of water and then dried over anhydrous magnesium sulfate. After evaporation of the solvent, 22.3 g of pale yellow oil of 2-chloro-1- (2-chloro-4-fluoro-5-methylphenyl) ethanone are obtained, which crystallizes on cooling (melting point: 32 ° C. ; yield: 100%).

Likewise, 2-chloro-1- (3-methyl-4-fluoro-5-methylphenyl) ethanone (melting point 86 ° C., yield 87%) (FG 993) and 2-chloro-1 were obtained. (2-fluoro-3-chloro-4-fluoro-5-chloro phenyl) ethanone (NMR analysis, yield 75%).

Example 4: 3-bromo-4-fluoro-5-bromo acetophenone

133.5 g (1.00 mole) of aluminum chloride are loaded into 400 ml of 1,2-dichloroethane. The whole is cooled to + 10 ° C. and 13.81 g (0.10 mole) of 4-fluoroacetophenone dissolved in 10 ml of 1,2-dichloroethane are added. The reaction medium is heated to + 55 ° C. and 51 ml of bromine are poured in dropwise over approximately 1 hour.

Stirring is continued for 5 hours at + 55 ° C. The reaction medium is brought to ambient temperature, poured into ice-cold acidulated water and extracted with dichloromethane. The organic phases are dried over magnesium sulfate and then concentrated in vacuo.

6.7 g of 3-bromo-4-fluoro-5-bromo acetophenone are obtained (yield: 23%; melting point: 59 ° C).

Example 5: 3-methvl-4-fluoro-5-chloro acetophenone 16.7 g (0.123 mol) of aluminum chloride are loaded into 100 ml of 1,2-dichloroethane. The whole is cooled to + 10 ° C. and 8.2 ml of acetyl chloride are added.

After half an hour at + 10 ° C., 15.0 g (0.104 mole) of 2-fluoro-3chloro toluene dissolved in 10 ml of 1,2-dichloroethane are added. The reaction medium is brought to ambient temperature and then heated for 3 hours at + 50 ° C. After cooling, the mixture is poured into IN HCl and extracted with dichloromethane. The organic phases are dried over magnesium sulfate and then concentrated in vacuo. 11.6 g of 3-methyl-4-fluoro-5-chloro acetophenone are obtained.

Example 6: Enaminones (cf. Examples 5 and 6 of the application WO 93/22287) 1 - (3,5-dichlorophenyl) -3-dimethylaminopropen-2-one- 1:

10 g (0.053 mole) of 3 ', 5'-dicholoroacetophenone are dissolved at room temperature and with stirring in 50 ml of N, N-dimethylformamide dimethylacetal. Stirring is continued and the reaction mixture is heated for 2 h at 90 ° C. The middle is concentrated to dryness under reduced pressure. The residue is taken up with 150 ml of heptane. The orange residue is filtered to give 10.0 g (77% yield, melting point: 100 ° C) of 1- (3,5-dichlorophenyl) -3-dimethylaminopropen-2-one-1.

By operating in an analogous manner, starting from the suitably substituted acetophenone and the second suitable reagent, the enaminone derivatives of formula below were obtained, collated in the following table.

with W = N (CH ₃ ) ₂

Example 7: Chloroenaminones. 1- (3,5-dimethyl-4-fluorophenyl) -2-chloro-3-dimethylamino-2-propene-1-one. A suspension of 6.0 g (0.03 mole) of 2-chloro-3 ', 5'-dimethyl-4'-fluoroacetophenone in a mixture of 7.15 g (0.06 mole) of dimethylformamide dimethylacetal and 100 ml of heptane is brought to 50 ° C. and then stirred at this temperature for 8 h. After cooling, the reaction medium is filtered and the crystals obtained washed with heptane and then dried (3.2 g). By partial evaporation of the filtrate, a new batch of crystals is obtained which are treated in the same way (0.8 g). The two combined batches are then chromatographed on silica gel with elution with a mixture of 70% heptane and 30% ethyl acetate, then 50% heptane and 50% ethyl acetate. 1.84 g of 2-chloro-3 ', 5'-dimethyl-4'-fluoroacetophenone and 1.55 g of 1- (3,5-dimemyl-4-fluorophenyl) -2-chloro-3 are obtained. -dimethylaιnino-2-propene- 1-one, white crystals decomposing at 177.5 ° C (yield: 20%).

By operating in an analogous manner, starting from suitably substituted acetophenone and from the second suitable reagent, there was obtained (3,5-dichloro-2,4-difluorophenyl) -2-chloro-3-dimethylamino-2-propene- l-one (see NMR analysis, yield = 100%).

Example 8: ÎH-Pyrazoles (see Example 7 of application WO 93/22287) 3- (3,5-dichlorophenyl) 1H-pyrazole.

2.4 g (0.05 mole) of hydrazine hydrate are slowly added at room temperature to a solution of 9 g (0.0369 mole) of 1- (3,5-dichlorophenyl) -3-dimethylaminopropen -2- one-1 in 100 ml of ethanol. The reaction mixture is stirred for 2 hours at room temperature and then concentrated to dryness. The residue is triturated in heptane. We obtain

7.1 g (90% yield, melting point 156 ° C) of 3- (3,5-dichlorophenyl) 1H-pyrazole.

By operating in an analogous manner, starting from the appropriately substituted enaminone and the second suitable reagent, the pyrazole derivatives of formula below were obtained, collected in the following table.

EXAMPLE 9: 4-Chloropyrazoles.

A) 3- (3,5-dimethyl-4-fluorophenyl) -4-chloropyrazole (compound no.1).

With stirring and at room temperature, a cold solution of 1.5 g of hydrazine hydrate in 30 ml of glacial acetic acid is quickly added to a suspension of 3.10 g (0.0122 mole) of 1- ( 3,5-dimethyl-4-fluorophenyl) -2-chloro-3-dimethylamino-2-propene-1-one in 20 ml of glacial acetic acid. After 7 h of stirring at room temperature the reaction medium is poured into 200 ml of water. The solid formed is filtered, washed with water and dried under vacuum in the presence of P2O5 and then purified by chromatography on silica gel with elution with a mixture of 70% heptane and 30% ethyl acetate. 2.09 g of 3- (3,5-dimethyl-4-fluorophenyl) -4-chloropyrazole are obtained, a white solid melting at 144 ° C. (yield: 76%).

By operating in an analogous manner, starting from the suitably substituted 1H-pyrazole and the second suitable reagent, 3- (3,5-difluoro-4-fluorophenyl) -4-chloropyrazole was obtained (compound No. 2). B) 4- chloro-3- (3,5-dichorophenyl) 1H-pyrazole (compound n ° 3) :( Example 9a of application WO 93/22287): Halogenation of pyrazoles

2.3 g (0.0152 mole) of 3- (3,5-dichlorophenyl) 1H-pyrazole are dissolved at room temperature and with stirring in 300 ml of dichloromethane. 2.07 g (0.016 mole) of N-chlorosuccinimide is then added, followed by stirring for 4 days at room temperature. The reaction mixture is then concentrated and then chromatographed on a silica column (eluent heptane / ethyl acetate 70/30). 1.4 g (yield: 57%, melting point: 192 ° C.) of 4-chloro-3- (3,5-dichlorophenyl) 1H-pyrazole are obtained.

By operating in an analogous manner, starting from the properly substituted 1H-pyrazole and the second suitable reagent, the 4-chloro pyrazole derivatives of formula below were obtained, collected in the following table.

C) 4-Chloro-pyrazoles (cf. Example 12 (Example 12 of application WO 93/22287). A - Acetylation:

A 11.0 g (0.046 mole) of 4-chloro, 3- (2,2-difluorobenzo-1,3-dioxol-4-yl) pyrazole 1H (prepared as described in French patent application No. 91 12647) dissolved in 100 ml of THF are added 0.25 g (0.005 mole) of 4-dimethylaminopyridine and 4.25 g (0 „042 mole) of triethylamine. A solution of 3.6 g (0.046 mole) of acetyl chloride in 50 ml of THF is poured onto this solution dropwise at 0 ° C. Stirring is continued for 3 h at room temperature. The reaction mixture is poured into 300 ml of water and extracted with ethyl acetate. After drying the organic phase and concentrating under vacuum, the residue is triturated with 50 ml of heptane, filtered and dried. We obtain 12.8 g of l-acetyl-4-chloro-3- (2,2-difluorobenzo-1,3-dioxol-4-yl) pyrazole (compound 14), melting at 131 ° C. b- Nitration:

A 12.8 g of 1- (acetyl), 4-chloro, 3- (2,2-difluorobenzo-1,3, dioxol-4-yl) pyrazole dissolved in 21 ml H2SO4 (96%) and 140 ml CH2Cl2 are added, in small portions and at 0 ° C, 6.3 g (0.063 mole) of KNO3. The reaction medium is stirred for 3 h at 0 ° C. then poured poured over 300 cm 3 of ice. The precipitate is recovered by filtration, washed with water and then with heptane and dried. We obtain 8.05 g of 4-chloro-3- (2,2-difluoro-5-nitrobenzo-l, 3-dioxol-4-yl) pyrazole melting at 180 ° C (yield 63%) (compound 15).

By operating in an analogous manner, starting from the properly substituted 1H-pyrazole and the second suitable reagent, the 4-chloro pyrazole derivatives of formula above were obtained, collected in the following table. Compound Xl, X ₂ , X3, X4, X5. Y Yield (%). F (° C) or n ° Analysis.

16 F, Cl, H, NO2, H. Cl 74,147

17 F, Br, H. NO2, H. Cl 34,154

18 NO2, Cl, H, Cl, H, Cl 55 173

54 F, NO ₂ , H, Cl, H. Cl 46 177

55 Cl, NO2, H, CF}, H. Cl 22 128

56 NO ₂ , OMe, H, F, H. Cl 50 158

Example 10: 3- (2-amino> phenyl-4-chloro pvrazoles (see Example 14 of application WO 93/22287) 3- (2-amino-3,5-dichloro) phenyl-4-chloro pyrazole (compound 19 )

14.6 g (0.05 mole) of 3- (2-nitro-) are introduced into a 500 ml three-necked flask

3,5-dichlorophenyl) 4-chloro pyrazole obtained according to Example 12b, in solution in 200 ml of acetic acid. The solution is brought to 50 ° C. and 8.4 g (0.15 mol) of powdered iron are introduced in portions. The reaction medium is then kept under stirring at 70 ° C for 5 hours. After cooling, the reaction medium is poured into 800 ml of water, filtered through sintered glass, rinsed with water and dried to yield a white solid.

(Yield: 90%, mp: decomposition at 300 ° C) of 3- (2-amino-3,5-dichlorophenyl) 4-chloro pyrazole. By operating in an analogous manner, starting from the suitably substituted 4-chloro-pyrazole, the 4-chloro pyrazole derivatives of formula below were obtained, collected in the following table.

compound Xl, X ₂ , X3, X4, X5. Y Yield (%). F (° C) or n ° Analysis.

20 NH7, Cl, F, Cl, H. Cl 68 160

21 NH, Br, H, Br, H. Cl 47 169

22 Cl, Cl, H, NH, H Cl 69 150

23 F, Cl, H, NH H. Cl 90 145

24 F, Br, H, NH, H. Cl 75 155

57 NH ₂ . Cl, H, Cl, F. Cl 85 150

58 NO ₂ , Cl, H, NH ₂ , H Cl 26 198

Example 11: 4-chloro pvrazoles (Example 15 of application WO 93/22287). 3- (2-methvlthio-3.5-dichloro ') phenvl-4-chloro pyrazole (compound 251

This compound is obtained by diazotization of 3- (2-amino-3,5-dichlorophenyl) -4-chloro pyrazole and reaction with dimethyldisulfide, according to the methods described in the literature: Yield 30%; honey.

From the suitably substituted diazonium salt, and reaction with the appropriate reagent, there are obtained the 3-phenyl-4-choro or bromo pyrazoles compounds of formula above, appearing in the following table, in which the group introduced is marked with an asterisk:

Compound Xl, X ₂ , X3, X4, X5. Y Yield (%). F (° C) or n ° Analysis.

26 F *, Cl, H, Cl, H Cl 75 180

27 F *, Cl, H, Br, H. Cl 74 175 28 F *, Br, H, Br, H. Cl 70 170

29 F *, Br, H, Cl, H Cl 63 176

59 F, Br, H, Cl *, H. Cl 64 176

60 F, Me, H, Cl *, H. Cl 57 136

Example 12: 3- (2-Nitro1phenv1-4-chloro-pvrazoles 3- (2-nitro-3,5-dichloro-4-fluoro phenyl) -4-chloro pyrazole (compound 30). 0.43 ml (0.0104 mole) fuming nitric acid (100%) to a solution cooled to about +5 ° C (ice water bath) of 2.50 g (0.00943 mole) of 3- (3,5-dichloro-4-fluorophenyl) -4-chloro pyrazole (prepared according to the process described in patent WO 9322287, compound 266) in 25 ml of 100% sulfuric acid The reaction medium is stirred cold for 20 minutes then at room temperature for one hour and finally poured over 150 g of ice The precipitate formed is extracted with 150 ml of ethyl acetate The solution obtained is washed with 100 ml of water, 100 ml of a solution saturated with sodium hydrogencarbonate, 100 ml of water, dried over magnesium sulphate and evaporated under vacuum. 2.78 g of 3- (2-nitro-3,5-dicMoro-4-fluorophenyl) -4- are obtained. chloro pyrazole, white solid melting at 196.4 ° C (yield: 95%). n operating in an analogous manner, starting from suitably substituted 4-chloro-pyrazole, the 3- (2-nitro) phenyl-4-chloro pyrazoles derivatives of formula above were obtained, gathered in the following table.

Compos Xl, X ₂ , X3, X4, X5 Y Yield (%) F (° C) oi n ° Analysis

31 NO2, Br, H, Br, H. Cl 25 196

32 NO2, Br, F, Br, H. Cl 73 221

33 NO2, Me, F, Cl, H. Cl 19 214

34 NO2, Cl, F, Me, H. Cl 20 205

61 NO ₂ , Me, H, Br, H. Cl 13,184

Example 13: 3- (5-fluorophenylV4-chloropyrazoles 3- (2,3-dichloro5-fluoro phenyl) 4-chloro pyrazole (compound 35).

3- (5-amino-2,3-dichlorophenyl) -4-chloropyrazole diazonium tetrafluoroborate is obtained by pouring an aqueous solution of sodium nitrite (0.0021 mol) dropwise at 0 ° C on a solution containing 0.002 mol of 3- (5-amino-2,3-dichlorophenyl) -4-chloro-pyrazole and 5 ml of tetrafluoroboric acid in 50% aqueous solution. The reaction medium is thus stirred at 0 ° C for 1 hour then poured into 50 ml of water and of ice. The precipitate obtained is dried quickly under vacuum and then thermally decomposed to dryness at 145 ° C. After cooling, the reaction medium is taken up in dichloromethane and purified by chromatography on silica gel with, as eluent mixture, ethyl acetate / heptane (25/75) (yield: 19%; melting point: 122 ° C). By operating in an analogous manner, starting from suitably substituted 4-chloro-pyrazole, 3- (3-chloro-2,5-difluoro phenyl) -4-chloro pyrazole (compound 36) was obtained (yield: 17%; melting point: 150 ° C).

Example 14: 3- (3-chloro 5-hvdroxv phenvll 4-chloro pyrazole (control derivative Al In a three-necked flask of 1000 ml, 49.5 g (0.2 mole) of 4-chloro-3- (3,5- dichlorophenyl) pyrazole (prepared as described in Example 9 of application WO 9322287) are added to 500 ml of NMP (N-methyl-pyrroidone). 43.2 g (0.8 mole) of sodium methylate are added. and the whole is heated at 140 ° C. for 50 hours. After cooling, the reaction mixture is poured into 500 ml of water, acidified and then extracted with ethyl acetate. After drying of the organic phase and concentration under vacuum, the residue is purified by chromatography on a silica column (eluent: heptane / ethyl acetate 60/40). 28 g (0.12 mol; yield: 61%; melting point: 222 ° C.) of 4- chloro-3- (3-chloro-5-hydroxyphenyl) pyrazole.

Example 15: 3- (3-chloro 5-fluoro phenyll 4-chloro pyrazole (compound 371.

In a 500 ml three-necked flask at 0 ° C., 17.4 g (0.075 mole) of 4-chloro-3- (3-amino-5-chloro phenyl) pyrazole (prepared as described in patent WO 9322287, example 14 ) are added to 150 ml (1.20 mole) of fluoroboric acid (50% in water). 5.7 g (0.826 mole) of sodium nitrite in solution in 10 ml of water are added dropwise while maintaining the temperature between 0 and 5 ° C. Agitation is continued for one hour at room temperature. The solid obtained is filtered through sintered glass, washed with water and then with pentane. Once dry, the solid is decomposed at 150 ° C to give a brown oil taken up in hot isopropanol. After chromatography on a silica column (eluent: heptane / ethyl acetate 70/30), 7.9 g (0.0342 mole; yield: 45.6%; melting point: 150 ° C) of 4- chloro-3- (3-chloro-5-fluoro phenyl) pyrazole.

Example 16: N-SUBSTITUTED PYRAZOLES (Example 19D of application WO 93/22287).

1-acetoxvmethvl-4-chloro-3- (3.5-dichlorophenvnpvrazole (compound 381 0.15 ml of l, 8-diazabicyclo (5.4.0) undecen-7-ene is added, at room temperature, to a solution of 2, 55 g (0.01 mole) of 4-chloro-3- (3,5-dichlorophenyl) pyrazole and 0.90 g

(0.030 mole) of paraformaldehyde in 70 ml of THF. The reaction mixture is stirred for 4 h at room temperature. A solution of 1.20 g (0.015 mole) of acetyl chloride in 10 ml of THF is poured dropwise at 0 ° C. and the stirring is continued for 6 h at room temperature. The reaction medium is concentrated to dryness. The residue is taken up in 15 ml of heptane and then dried. We obtain 3.05 g of l-acetoxymethyl-4-chloro-3- (3,5-dichlorophenyl) pyrazole melting at 95 ° C.

By operating in an analogous manner, starting from the substituted 1-H-4-chloro-pyrazole, the coderivatives of formula I were obtained below

Compound Xl, X ₂ , X3, X4, Y z Yield F (° C) n ° X5. (%). or Analysis.

39 NO2, Cl, F, Cl, H. Cl CH2OA 97 100 c

40 F, Cl, H, Cl, H. Cl CH2OA 95 90 c

Example 17: 4-chloro-3- (5-chloro-3-cyano-2-fluorophenyl1 pyrazole (compound 621.

3- (3-bromo-5-chloro-2-fluorophenyl) -4-chloropyrazole (0.45 g; 0.0014 mole) and copper cyanide (0.14 g; 0.0015 mole) are dissolved in dimethylformamide (DMF) (10 ml) and the whole is heated at 180 ° C for 8 hours. After cooling to room temperature, the mixture is poured into a solution of NH ₄ OH at 14% (50 ml), then extracted with ethyl acetate (2x50 ml), dried over MgSθ4, evaporated under vacuum. The purification of the oily residue on a dry column of silica (elution with 30% ethyl acetate in heptane) produces 0.1 g of a yellow solid (yield: 28%; Melting point: 128 ° C). Example 18: 4-chloro-1- (4-methvlphénvlsulfonvl1pvrazole (compound 631.

Pyrazole (34 g; 0.5 mole) is dissolved in CH2Cl2 (350 ml) at 10 ° C and a solution of sulfuryl chloride (77.6 g; 0.575 mole) is added dropwise in CH ₂ CI (150 ml). When the addition is complete, the mixture is heated at reflux for 18 hours. The dichloromethane is then removed under vacuum, the residue suspended in pyridine (200 ml) and p-toluenesulfonyl chloride (95.33 g; 0.5 mol) is added in portions. This mixture is then heated to reflux and allowed to cool to room temperature. The mixture is cooled in an ice bath and water (800 ml) is added with vigorous stirring. After one hour a solid forms. It is collected by filtration, washed with water and recrystallized from ethanol to give 102 g of 4-chloro-1- (4-methylphenylsulfonyl) pyrazole in the form of a white powder (yield: 80%; Point mp: 96-97 ° C).

Example 19: 4-chloro-5- (3-fluorophenyl1-1- (4-methylphenylsulfonyl1 pyrazole (compound

2.4 g (0.0093 mol) of 4-chloro-1- (methylphenylsulfonyl) pyrazole are dissolved in tetrahydrofuran (THF) (20 ml) and cooled to -78 ° C under argon. 2.5 M n-Butyl lithium (3.92 ml; 0.0098 mol) is added dropwise over 10 minutes and the mixture is stirred at -78 ° C for 1.25 hours. A solution of zinc chloride in THF (10 ml; 0.01 mole) is added dropwise over 10 minutes. The mixture is kept stirring at -78 ° C for 0.5 hour and then at room temperature for 2 hours. Then add tetrakis (triphenylphosphine) palladium (Pd (PPh ₃ ) ₄ (0.35 g; 0.0003 mole) and then a solution of 3-fluoro iodobenzene (1.4 g; 0.0062 mole) in 15 ml of THF The mixture is then brought to reflux for 18 hours, allowed to cool to room temperature, diluted with a solution of EDTA (50 ml) and then subjected to extraction with (3 x 50 ml) of ether. is washed with water, dried over MgSθ ₄ , filtered and evaporated to give a yellow oil (4.1 g). Purification on a dry silica column (elution with 10% ethyl acetate in heptane) gives 1 0.05 g of 4-chloro- 5- (3-fluorophenyl) -1- (4-methylphenylsulfonyl) pyrazole (yield: 48%; Melting point: 110-111 ° C).

By operating as above from 4-chloro-1- (methylphenyl sulfonyl) pyrazole and an appropriate reagent, the compounds of formula below are obtained and indicated in the following table:

The suitable intermediate reagents are obtained according to the following procedures: a) 2-carbomethoxy-4-iodobenzo (b) thiophene:

30.0 g (0.012 mole) of 2-fluoro-6-iodobezaldehyde, at room temperature and under an argon atmosphere, are dissolved in dry dimethyl sulfoxide (150 ml). 14.05 g (0.0119 mole of methyl thioglycolate and then 25.85 g (0.255 mole) of triethylamine are added dropwise over one minute. The whole is heated at 60 ° C. for 2 hours, cooled at room temperature and poured, with stirring, into a mixture of water and ice (1000 ml) The yellow precipitate is recovered by filtration, air dried, suspended in 300 ml of methanol and heated to reflux for 10 minutes The solution is cooled to 0 ° C., the precipitate collected by filtration and dried under vacuum to give 30.2 g of 2-carbomethoxy-4-iodobenzo (b) thiophene, in the form of a cream solid (yield: 79% ; melting point: 123-124 ° C). b) 2-carbomethoxy-4-iodobenzo (b) furan:

4.36 g (0.0109 mole) of sodium hydride (60%, in oil dispersion) is suspended in 100 ml of tetrahydrofuran under an argon atmosphere. The medium is cooled to between + 5 ° C and + 10 ° C using an ice water bath. A solution of 10.3 g (0.115 mole) of methyl thioglycolate in 50 ml of THF is added dropwise over 30 minutes. The whole is stirred for 5 minutes at this temperature. A solution of 21 g (0.084 mole) of 2-fluoro ~ 6-iodobenzadéhyde in 50 ml of THF is added dropwise over 30 minutes. The temperature of the medium spontaneously rises to + 40 ° C. Agitation is continued in one hour at room temperature. The medium is treated with 2 ml of methanol and 50 ml of water then concentrated under reduced pressure. The solid residue is washed with water, cold triturated with methanol and dried under reduced pressure to give 11.3 g of a white solid (yield: 45%; melting point: 141-143 ° C). c) 2-carboxy-4-iodobenzo (b) thiophene: A 10M aqueous solution of sodium hydroxide (5.8 ml) is added to a mixture of 17.0 g (0.053 mole) of 2-carbomethoxy-4-iodobenzo (b) thiophene in 150 ml of ethanol. The whole is heated at reflux for one hour and then concentrated to dryness under reduced pressure. The residue is dissolved in water (300 ml) and washed with ethyl acetate (100 ml). The aqueous phase is acidified to pH = 1 with 36% HCl. The precipitate is recovered by filtration, washed with water and with diisopropyl ether, dried under pressure reduce to 70 ° C to give 15.0 g of a white solid (yield: 93%; melting point: 260 ° C). d) 4-iodobenzo (b) thiophene:

4.3 g of copper chromite doped with barium are suspended in 70 ml of quinoline and the whole is heated to 200 ° C. 13.0 g (0.043 mole) of 2-carboxy-4-iodobenzo (b) thiophene are added in portions. After cessation of the evolution of gas (about 15 minutes), the medium is brought to room temperature, poured into a 36% HCl mixture (100 ml) - ice, filtered through celite. Celite is rinsed with water (200 ml) and ethyl acetate (100 ml). The filtrate is re-extracted with ethyl acetate (2x150 ml), washed with water (400 ml), dried (MgSO4), concentrated under reduced pressure to give 11.65 g of a brown oil. Purification on a silica column (elution with pure heptane) gives 9.6 g of a yellow solid (yield: 86%; melting point: 37-39 ° C).

Example 20: 4-chloro-3- (benzo (b1thien-4-yl1pvrazole (compound 681.

5- (Benzo (b) thien-4-yl) -4-chloro-1- (4-methylphenylsulfonyl) pyrazole (3.3 g; 0.00844 mol) is dissolved in DMF (25 ml) and then heated at 110 ° C for 18 hours. After cooling to room temperature, the mixture is poured into ice with stirring, producing an oily product. This is extracted with ethyl acetate (2x50 ml), washed with water (3x100 ml), dried. Elution on a dry silica column (with 20% ethyl acetate in heptane produces 1.4 g of a yellow solid after trituration (yield: 70%; Melting point: 123 ° C).

By operating as above from an appropriate reagent, 4-chloro-3- (benzo (b) furan-4-yl) pyrazole is obtained (yield: 64%; Melting point: 122 ° C) (compound 69 ).

Example 21 (Metallationl: 4-chloro-3- (5-chloro-2-fluoro-3-phenvlthiophénvl1 pyrazole

(compound 70),

3- (3-Bromo-5-chloro-2-fluorophenyl) pyrazole (1.10 g; 0.0035 mol) is dissolved in tetrahydrofuran (THF) (20 ml) and cooled to -78 ° C under argon. We add, drop dropwise, 1.6 M n-Butyl lithium (5.5 ml; 0.0088 mole) for 10 minutes and the mixture is stirred at -78 ° C for 0.5 hour. Diphenyldisulfide (1.53 g; 0.007 mole) is dissolved in dropwise in THF (10 ml) and the mixture is stirred for 1 hour at -78 ° C and then overnight at room temperature. Then add 100 ml of water. The mixture is extracted with 2x50 ml of ethyl acetate, dried over MgSO4, evaporated in vacuo to give an oily residue. Purification on a dry silica column (elution with 30% ethyl acetate in heptane) gives 0.45 g of 4-chloro-3- (5-chloro-2-fluoro-3-phenylthiophenyl) pyrazole 38 %; 1 H NMR & ¹³ C).

By operating as above from 4-chloro-3- (3-bromo-5-chloro-2-fluorophenyl) pyrazole and an appropriate reagent, the compounds of formula below are obtained and indicated in the following table, in which the group entered is marked with an asterisk:

Example 22: Metal complex of 4-chloro-3- (3.5-dichlorophenvl1pvrazole and copper chloride (compound 74 1.

Copper chloride dihydrate (1.70 g; 0.01 mole) is dissolved in absolute ethanol (10 ml) and triethylorthoformate (1 ml) is added. This mixture is kept stirring for 0.5 hour at room temperature and 4-chloro-3- (3,5-dichlorophenyl) pyrazole (4.95 g; 0.02 mole) dissolved in absolute ethanol ( 10 ml). This mixture is kept stirring for 0.5 hour at room temperature until next day. The precipitate is recovered by filtration, washed with ethyl ether, dried under reduced pressure to give 11.8 g of a light green solid (Yield: quantitative; Melting point: 288 ° C (decomposition).

By operating as above from the appropriate pyrazole and metal salt, the compounds of formula I - L "M ⁺ ~ I and indicated in the following table are obtained, in quantitative yield:

Compound Xi »X2. X3 »4» Xs- M ⁺ L- Color. F (° C). No.

75 H, Cl, H, Cl, H. Cu Br greenish 264 (dec.)

76 H, Cl, H, Cl, H. Cu NO3 blue 190 (dec.)

77 H, Cl, H, Cl, H. Zn Cl white 195 (dec.)

78 H, Cl, H, Cl, H. Zn AcO white> 3O0

79 H, Cl, H, Cl, H. Ni Cl cream> 300

80 NO2, Cl, F, Cl, H. Cu Cl blue 255 (dec.)

81 F, Cl, H, Cl, H. Cu Cl green 287 (dec.)

Other compounds of formula I and known per se from European application 0538 156 are also tested: compound 82: 4-chloro-3- (2'-2 'difluoro-, 3'-benzodioxol) pyrazole (compound n 25) of European application 0538 156) compound 83: 4-chloro-3- (2,3-dichlorophenyl) pyrazole (compound No. 12 of European application 0538 156) compound 84: 4-chloro-3- (2 nitro, 3-chlorophenyl) pyrazole (compound 120 of European application 0538 156)

The present invention also relates to a process for the treatment of cultivated plants affected or liable to be affected by fungal diseases, characterized in that an effective dose of a compound according to the formula ( I). By effective dose is meant an amount sufficient to allow the control and destruction of the fungi present on these cultivated plants. The doses of use can however vary within wide limits according to the fungus to be combated, the type of culture, the climatic conditions, and according to the compound used.

In practice, the compounds are advantageously applied in doses of 0.1 to 500 g of active material per quintal of seed, and preferably 1 to 400 g / quintal.

By fungal diseases is meant diseases caused by phytopathogenic fungi, in particular those of the family of oomycetes, ascomycetes and basidiomycetes. Among the crops which can be the subject of a fungicidal treatment using a compound according to the invention, mention may be made of rice, cereals, in particular wheat and barley, as well as vegetable plants. Rice is a preferred crop for fungicide treatments using a compound according to the invention.

EXAMPLE 23 In Vivo Seed Disinfection Test

Two types of protocol are used depending on whether the seeds are naturally infected (Drechslera gramineal Drechslera teres de la barley) or artificially infected (Cochliobolus sativusl Fusarium culmorum / Fusarium nivale / Septoria nodorum):

30 g of seeds are treated in a HEGE bowl with active ingredients according to the invention in the form of concentrated aqueous suspensions, at a concentration of 1.5 liters per quintal. 30 seeds are sown in pots (7x7x8 cm) on pozzolan peat substrate and 3 pots are produced by treatment. A contaminated untreated control and an uncontaminated control (in the case of artificial contamination) are sown under the same conditions. In the case of artificial contamination, the healthy seeds treated are sown and a suspension of spores is provided at the rate of 10 ml of aqueous suspension per pot. The concentration of the suspension varies depending on the pathogen studied:

Pathogen culture nb of spores

Cochliobolus sativus barley 200,000

Fusarium culmorum / wheat, barley 400000 Fusarium nivale

Septoria nodorum wheat 250000

The pots are placed in a climatic chamber at 5 ° C with saturated humidity, during a period which depends on the test carried out, namely 3 weeks for Drechslera graminea / Drechslera teres and Cochliobolus sativus and 2 weeks for Fusarium culmorum / Fusarium nivale / Septoria nodorum).

The pots are then transferred to a climatic chamber at 10 ° C (photoperiod: 8 a.m. day; 4 p.m. night), relative humidity of 80%, until symptoms are expressed.

The scoring is done visually in comparison with the contaminated untreated control.

Under these conditions, good protection (at least 75% or total) is observed at a dose of 100 g / q:

- on Drechslera graminea: with the following derivatives: 3, 4, 5, 7, 10, 18, 26, 30, 68, 69;

- on Drechslera teres: with the following derivatives: 3, 26, 30, 82, 83, 84; - on Cochliobolus sativus: with the following derivatives: 3, 26, 30;

- on Fusarium culmorum: with the following derivatives: 3, 26, 30, 82, 83, 84;

- on Fusarium nivale: with the following derivatives: 1, 3, 4, 7, 8, 9, 12, 20, 26, 27, 28, 30, 37, 82, 83, 84; - on Septoria nodorum: with the following derivatives: 3, 26, 30, 82, 83, 84;

The present invention also relates to a method of treating cultivated plants affected or likely to be affected by fungal diseases, characterized in that an effective dose of a new compound of formula (I) is applied to the aerial parts of these plants. ) as defined above. By effective dose is meant an amount sufficient to allow the control or destruction of the fungi present on these cultivated plants. The doses of use can however vary within wide limits according to the fungus to be combated, the type of culture, the climatic conditions, and according to the compound used. In practice, the compounds are advantageously applied at doses of 0.002 to 5 kg / ha, and preferably from 0.005 to 1 kg / ha.

Example 24: In vivo test on Botrvtis cinereα on excised tomato leaf: (sensitive strains and strains resistant to benzimidazolesl:

An aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding:

- active ingredient: 60 mg - surfactant Tween 80, oleate of polyoxyethylene derivative of sorbitan) diluted to

10% in water: 0.3 ml

- make up to 60 ml of water.

This aqueous suspension is then diluted with water to obtain the desired concentration of active material. Tomatoes grown in a greenhouse (Marmande variety) 30 days old are treated by spraying with aqueous suspensions as defined above and at various concentrations of the test compound. After 24 hours the leaves are cut and put in a Petri dish (diameter 14 cm), the bottom of which has been previously lined with a disc of wet filter paper (10 leaflets per box).

The inoculum is then brought using a syringe by depositing drops (3 per leaflet) of a suspension of Botrytis cinerea spores, sensitive to benzimidazoles or resistant to benzimidazoles, obtained from 15-day cultures, then suspended at a rate of 150,000 units per cn_3.

The control is made 6 days after the contamination in comparison with an untreated control. Under these conditions, at the dose of 1 g / 1, good (at least 75%) or total protection is observed with the following compounds: 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 19, 20, 21, 26, 27, 28, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 62, 68, 70, 74, 75, 76, 77, 78, 79, 80, 81 on Botrytis sensitive to benzimidazoles.

EXAMPLE 25 In Vivo Test on Pvricularia orv ae Responsible for Piriculariosis of Rice:

- active ingredient: 60 mg

- Tween 80 surfactant, oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- make up to 60 ml of water.

This aqueous suspension is then diluted with water to obtain the desired concentration of active material.

Rice, sown in pots in a 50/50 mixture of enriched peat and pozzolan, is treated at the 10 cm height stage by spraying the above aqueous suspension.

After 24 hours, an aqueous suspension of spores of Pyricularia oryzae, obtained from a 15-day culture, is applied to the leaves, then suspended at the rate of 100,000 units per cm 2.

The rice plants are placed for 24 hours in incubation (25 ° C, 100% relative humidity), then placed in an observation cell, under the same conditions, for 5 days.

Reading is done 6 days after contamination. Under these conditions, at the dose of 1 g / 1, good (at least 75%) or total protection is observed with the following compounds: 1, 5, 6, 8, 9, 10, 12, 13, 17, 19, 20, 21, 23, 24, 26, 27, 28, 30.31, 32, 33, 34, 35, 36, 37, 39, 40, 68, 70, 80, 81. Example 26: In vivo test on Plasmopara viticola:

10% in water: 0.3 ml

- make up to 60 ml of water.

This aqueous suspension is then diluted with water to obtain the desired concentration of active material. Vine cuttings (Vitis vinifera). Chardonnay variety, are grown in pots. When these plants are 2 months old (8 to 10 leaf stage, 10 to 15 cm high), they are treated by spraying with the above aqueous suspension. Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

After drying for 24 hours, each plant is contaminated by spraying with an aqueous suspension of Plasmopara viticola spores obtained from a 7-day culture, then suspended at the rate of 100,000 units per cm 2.

The contaminated plants are then incubated for two days at approximately 18 ° C, in an atmosphere saturated with humidity and then for 5 days at approximately 20-22 ° C under 90-100% relative humidity.

The reading is done 7 days after contamination, in comparison with the control plants.

Under these conditions, at the dose of 1 g / 1, good (at least 75%) or total protection is observed with the following compounds: 1, 2, 3, 4, 5, 6, 8, 9, 11, 13, 16, 20, 21, 23, 24, 26, 27, 30, 31, 35, 33, 36, 37, 39, 40, 62, 68, 70, 72, 73, 74, 77, 78, 79, 80, 81.

Example 27: In Vivo Test on Puccinia Recondita (Blister Rust:

- active ingredient: 60 mg

- Tween 80 surfactant (oleate of polyoxyethylene derivative of sorbitan) diluted to 10% in water: 0.3 ml

- make up to 60 ml of water to obtain a suspension / solution at 1 g / 1. This aqueous suspension is then optionally diluted with water to obtain the desired concentration of active material.

Wheat, in pots, sown on a 50/50 peat soil peat soil substrate, is treated at the 10 cm height stage by spraying the above aqueous suspension. Plants, used as controls are treated with an aqueous solution not containing the active ingredient.

After 24 hours, an aqueous suspension of spores (100,000 sp / cm ^) is sprayed onto the wheat; this suspension was obtained from contaminated plants. The wheat is then placed for 24 hours in an incubation cell at approximately 20 ° C. and at 100% relative humidity, then for 7 to 14 days at 60% relative humidity.

The condition of the plants is checked between the 8th and 15th day after contamination, by comparison with an untreated control.

Under these conditions, at the dose of 1 g / 1, good (at least 75%) or total protection is observed with the following compounds: 1, 2, 3, 4, 5, 6, 7, 8, 9, 10.12, 13, 20, 21, 26, 27, 28, 30, 31, 32, 33, 35, 37, 40.

The present invention also relates to compositions, usable as fungicidal agents, containing as active material (s) one (or more) compound according to formula (I) as described above, in admixture with solid or liquid carriers , acceptable in agriculture and surfactants also acceptable in agriculture. In particular, the inert and usual supports and the usual surfactants can be used.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestrants, etc. More generally the compounds used in the invention can be combined with all the solid or liquid additives corresponding to the usual techniques of formulation.

In general, the compositions according to the invention usually contain from 0.05 to 95% approximately (by weight) of a compound according to the invention (hereinafter called active material), one or more solid or liquid carriers and, optionally, one or more surfactants.

By the term "support", in the present description, is meant an organic or mineral, natural or synthetic material, with which the compound is combined to facilitate its application to the plant, to seeds or to the soil. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, in particular butanol etc.).

The surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (in particular alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (in particular alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters of fatty acids and of polyols, the derivatives containing sulfates, sulfonates and phosphates of the preceding compounds. The presence of at least one surfactant is generally essential when the compound and / or the inert support are not soluble in water and the vector agent for the application is water.

Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 0.05% to 95% (by weight). Their content of surfactant is advantageously between 5% and 40% by weight.

These compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of dusting powders (with compound content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by from a powder (the compound content in these granules being between 0.5 and 80% for the latter cases), the effervescent tablets or tablets.

The compounds of formula (I) can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, powders wettable (or spray powder), pastes, gels. Emulsifiable or soluble concentrates most often include 10 to 80

% of active material, the emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active material.

In addition to the solvent, the emulsifiable concentrates can contain, when necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives previously cited. From these concentrates, emulsions with any desired concentration can be obtained by dilution with water, which are particularly suitable for application to crops.

As an example, here is the composition of some emulsifiable concentrates:

Example CE 1:

- active ingredient 400 g / 1

- alkaline dodecylbenzene sulfonate 24 g / 1

- oxyethylated nonylphenol containing 10 molecules of ethylene oxide 16 g / 1

- cyclohexanone 200 g / 1

- aromatic solvent q.s.p.l liter

According to another formula of emulsifiable concentrate,

Example CE 2

- active ingredient 250 g

- epoxidized vegetable oil 25 g

- mixture of alkylaryl sulfonate and polyglycol ether and fatty alcohols 100 g

- dimethylformamide 50 g

- xylene 575 g

The concentrated suspensions, also applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0 , 1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.

As an example, here is a concentrated suspension composition

Example gÇ 1:

- active ingredient 500 g

- polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g

- sodium polycarboxylate 20 g

- ethylene glycol 50 g

- organopolysiloxane oil (defoamer) i g

- polysaccharide 1.5 g

- water 316.5 g

Wettable powders (or spray powder) are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 30% of a wetting agent, 3 20% of a dispersing agent, and, when necessary, 0.1 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, dyes, etc.

To obtain the sprayable powders or wettable powders, the active ingredients are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders. This gives sprayable powders whose wettability and suspension are advantageous; they can be suspended with 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, pasta can be made. The conditions and methods of making and using these pastes are similar to those of wettable powders or spraying powders.

As an example, here are various compositions of wettable powders (or spraying powders):

Example PM 1

- active ingredient 50%

- ethoxylated fatty alcohol (wetting agent) 2.5% - ethoxylated phenylethylphenol (dispersing agent) 5%

- chalk (inert support) 42.5%

Example PM 2:

- active ingredient 10% - branched type oxo synthetic alcohol,

C13 ethoxylated with 8 to 10 ethylene oxide

(wetting agent) 0.75%

- neutral calcium lignosulfonate (agent dispersant) 12%

- calcium carbonate (inert filler) q.s.p. 100%

Example PM 3: This wettable powder contains the same ingredients as in the previous example, in the following proportions:

- active ingredient 75%

- wetting agent 1.50%

- dispersing agent 8% - calcium carbonate (inert filler) q.s.p. 100%

Example PM 4:

- active ingredient 90%

- ethoxylated fatty alcohol (wetting agent) 4% - ethoxylated phenylethylphenol (dispersing agent) 6%

Example PM 5:

- active ingredient 50%

- mixture of anionic and nonionic surfactants (wetting agent) 2.5%

- sodium lignosulfonate (dispersing agent) 5%

- kaolin clay (inert support) 42.5%

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

The compounds according to the invention can be formulated in the form of water-dispersible granules also included within the scope of the invention.

These dispersible granules, of apparent density generally comprised between approximately 0.3 and 0.6 have a particle size generally comprised between approximately 150 and 2000 and preferably between 300 and 1500 microns.

The active material content of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.

The rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water. These granules can be essentially of two distinct types 30

depending on whether the charge selected is soluble or not in water. When the filler is water-soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants (at a rate of 2 to 20% by weight of the granule), more than half of which is, for example, constituted by at least one dispersing agent, essentially anionic, such as a polynaphthalene alkali or alkaline earth sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as an alkali or alkaline earth alkyl naphthalene sulfonate. Furthermore, although this is not essential, other adjuvants can be added such as anti-foaming agents.

The granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above. Can also be used granules obtained as above and then impregnated with a composition containing the active material.

Preferably, it is obtained by extrusion, operating as indicated in the examples below.

Example GDI: Dispersible granules

In a mixer, 90% by weight of active material and 10% urea pearls are mixed. The mixture is then ground in a pin mill. A powder is obtained which is moistened with approximately 8% by weight of water. The wet powder is extruded in a perforated roller extruder. A granule is obtained which is dried, then crushed and sieved, so as to keep respectively only the granules of a size between 150 and 2000 microns.

Example GD2: Dispersible granules In a mixer, the following constituents are mixed:

- active ingredient 75%

- wetting agent (sodium alkylnaphthalene sulfonate) 2%

- dispersing agent (sodium polynaphthalene sulfonate) 8%

- inert filler insoluble in water (kaolin) 15%

This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.15 and 0.80 mm. These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.

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

Claims

1. Compositions for the treatment of plant propagating material against fungal diseases, characterized in that they contain, as active materials at least one 3-phenylpyrazole derivative of formula I:

in which:

X \, X2, X3, X4 and X5, identical or different, are:

- a hydrogen or halogen atom, a hydroxy, mercapto, cyano, thiocyanato, nitro, nitroso, amino group optionally substituted by one or two alkyls or phenyls,

- an alkyl, hydroxyalkyl, alkoxyalkyl, aminoalky le, alkylsulfonyl alkylthioalkyle alkylsulfinylalkyle, alkylsulfonylalkyle, benzyle, alényle, alkynyle, cyanoalkyle, alkoxy, alkenoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, formyl, acetyl, alkyl or carboxy) mono or di alkylamino (thio) carbonyl, amino (thio) carbonyl, mono- or diarylamino (thio) carbonyl, carboxyl, carboxylate, carbamoyl or benzoyl,

- a phenyl, phenyloxy or phenylthio radical

- a sulfonic group, its salts, esters and derived amides, a phosphoryl group, substituted by two groups chosen from the group comprising alkyl, alkoxy, alkylthio and dialkylamino, benzyloxy, phenyloxy or phenyl,

- a trialkyl- or alkylphenyl-silyl group, two of the adjacent Xι, X2, X3, X4 and X5 can also form a bridge comprising from 2 to 4 members, at least one of which can be replaced by an atom of oxygen.de sulfur or nitrogen, and which may have one or more atoms or groups following C, O, S, N, C = O, C = S, SO, SO2, CH≈CH, the carbons of this bridge may or may not be substituted by at least one halogen atom and / or at least one hydroxy, amino, alkyl, alkoxy, alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl or alkoxycarbonyl group, the alkyl part being as defined below, under provided that X \ X5 cannot each be simultaneously a hydrogen atom;

Y is a hydrogen or halogen atom, a nitro, cyano, hydroxy, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyloxy, mercapto, carboxyl, carboxylate, formyl, alkyl (thio) carbonyl, arylcarbonyl, alkoxy (thio) carbonyl, carbamoyl group, aminoalkyl, thiocyanato or alkyl, alkenyl, alkynyl, alkoxy or alkylthio, alkylsulfinyl or -sulfonyl, the alkyl part of these radicals being optionally mono- or polyhalogenated, an amino optionally substituted by one or two alkyls or phenyls; phenyl, phenoxy, phenylthio, arylsulfinyl or - sulfonyl,

Y and XI or X5 can also form a bridge comprising from 1 to 3 links, which can have one or more atoms or groups following C, O, S, N, C = O, C = S, SO, SO2, CH = CH , the carbons of this bridge may or may not be substituted by at least one halogen atom and / or at least one hydroxy, alkoxy, alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl group, the alkyl part being as defined below below,

Z is:

- a hydrogen, halogen atom, a cyano, nitro, hydroxy or - alkyl, haloalkyl, hydroxyalkyl, formyloxylalkyl, alkyl- or aryl (thio) carbonyloxyalkyl, alkoxy (thio) carbonyloxyalkyl, amino (thio) carbonyloxyalkyl, mono group or dialkylamino (thio) - carbonyloxyalkyl, cycloalkyl or cycloalkyl -alkyl, the cycloalkyl part possibly being substituted by the group GR4, defined below, - alkoxy optionally substituted by hydroxy, alkoxy, alkylthio, alkylsulfinyl or -sulfonyl, - phenyloxy or phenylthio, phenylsulfinyl or -sulfonyl

- an amino optionally substituted by one or two alkyls - alkenyl or alkynyl, each containing 3 to 7 carbon atoms, possibly substituted

- phenyl or Het, possibly substituted

- a group of formula C (= Zι) Z2 in which: - Zj is an oxygen or sulfur atom or an alkylamino or alkylimino or arylamino or arylimino group and - Z2 is:

- a hydrogen or halogen atom, a hydroxy, mercapto, cyano, amino group, - alkyl, alkoxy, haloalkoxy, alkylthio,

- alkenyl or alkynyl or alkenyloxy, each containing from 3 to 7 carbon atoms,

-alkyl, alkenyl or alkynyl, phenyl, phenylalkyl, Het or Het-alkyl, phenyl or Het, optionally substituted; - or a group S (= Zj) (= Z3) Z2, in which Z \ and Z2 have the same meanings as above and Z3 has the same meanings as without necessarily being equal to Z \,

as well as the tautomeric forms of formula I bis, when Z is a hydrogen atom or isomers when Z is a group of formula or S (= Zι) (= Z3) Z2,

I bis

as well as the hydracid or perchloric or nitric or sulfuric acid salts or alkyl- or phenyl (optionally substituted) sulfonic acids of the derivatives of formulas I or I bis and their metal complexes, and their N-oxides, it being understood that in all of the above meanings,

the linear hydrocarbon part of these groups can comprise from 1 to 7 carbon atoms and may be optionally halogenated (from 1 to 8 halogen atoms),

- the cycloalkyl part of these groups can comprise from 3 to 7 carbon atoms and be optionally substituted by at least one substituent chosen from the group GR4 defined below, - the phenyl part denotes the phenyl nucleus optionally substituted by 1 to 5 substituents chosen from the group comprising a halogen atom, an alkyl or alkoxy of 1 to 3 carbon atoms and nitro,

- Het is a heterocyclic radical, mono or bicyclic, containing from 5 to 10 atoms, of which 4 are heteroatoms (oxygen, sulfur, nitrogen, phosphorus) ;.

- the GR4 group includes:

- a halogen atom, or a cyano, nitro, mono or dialkylamino group,

- an alkyl, alkoxy, alkylsulfenyl, alkylsulfonyl, alkycarbonyl, alkylthiocarbonyl, alkoxycarbonyl, alkoxythiocarbonyl, mono- or dialkykaminocarbonyl or mono- or dialkykaminothiocarbonyl, mono or dialkylaminosulfonyl, (the alkyl part of all these substituents containing from there 4 carbon atoms and substituted by 1 to 9 halogen atoms),

2. Compositions according to claim 1, characterized in that, in the formula, Y is a chlorine or bromine atom.

3. Compositions according to either of Claims 1 and 2, characterized in that, in formula I, Z is a hydrogen atom or a group C (= Zi) Z2, in which Z \ is an oxygen atom or sulfur.

4. Compositions according to one of claims 1 to 3, characterized in that, in formula I, Xι, X and X4 are a hydrogen or halogen atom or a nitro, amino or alkyl group, optionally halogen, from 1 to 4 carbon atoms.

5. Compositions according to one of claims 1 to 3, characterized in that, in formula I, X3 is a hydrogen or fluorine atom.

6. Compositions according to one of claims 1 to 3, characterized in that, in formula I, X \ and / or X5 are a hydrogen atom.

7. Compositions according to one of claims 1 to 3, characterized in that, in formula I, two adjacent substituents chosen from X \, X2, X3, X4 and X5 form a bridge comprising 3 or 4 links, in particular a methylenedioxi bridge optionally halogenated and preferably fluorinated.

8. Compositions according to one of claims 1 to 3, characterized in that, in formula I, X \, X3 and X5 are a hydrogen atom and X2, X4 are each a chlorine atom.

9. Compositions according to one of claims 1 to 3, characterized in that, in formula I, X \ is a nitro, X2, X4 are each a chlorine atom X3 is a fluorine atom and X5 is a d atom 'hydrogen.

10. Compositions according to claim 7, characterized in that, in formula I, X \ is a fluorine atom, X2, X4 are each a chlorine atom X3 is a fluorine atom, X3 and X5 are an atom hydrogen.

11. Method for the treatment of plant propagating material against fungal diseases, characterized in that a composition according to one of claims 1 to 8 is used.

12. New compounds of the family of 3-phenyl -pyrazoles, characterized in that they are chosen from the group of formula I:

in which: Y is a chlorine atom and Z is a hydrogen atom,

X \ is a hydrogen or halogen atom or a nitro, amino or methyl group

X2 is a halogen atom or a nitro, amino or methyl group,

X3 is a hydrogen or halogen atom

X4 is a halogen atom or an amino nitro, or methyl group, X5 is a hydrogen or halogen atom.

13. Derivatives according to claim 12, characterized in that, in formula I:

X2 is a chlorine or bromine atom;

X3 and X5, identical or different, are each a hydrogen or fluorine atom.

14. Derivatives according to claim 12, chosen from the group comprising the derivatives of formula I, in which:

Xj = H; X ₂ = CH ₃ ; X ₃ = F; X4 = CH3; and X ₅ = H Xl = NO ₂ ; X2 = Cl; X3 = F; X4 = Cl; and X ₅ = HX _{1 =} NH ₂ ; X2 = Cl; X3 = F; X4 = Cl; and X ₅ = H Xι = F; X ₂ ≈ Cl; X ₃ = F; X4 = Cl; and X ₅ = FX _{1 =} H; X = Cl; X ₃ = H; X4 = F; and X ₅ = H; X _{1 =} F; X ₂ = Cl; X3 = H; X4 = Cl; and X ₅ = HX _{1 =} F; X2 = Br; X3 = H; X4 = Br; and X ₅ ≈ H Xl = CH ₃ ; X ₂ = NO ₂ ; X3 = H; X4 = F; and X ₅ = H;

Xj = F; X ₂ = Cl; X ₃ = F; X4 = Cl; and X ₅ = H;

Xl = F; X ₂ = Cl; X3 = H; Xι = F; X ₂ = Cl; X3 = H;

X _{1 =} H; X ₂ = Cl; X ₃ = F; X4 = Cl; and X5 = H

15. Compositions for the foliar treatment of plants against fungal diseases, characterized in that they contain, as active material, at least one 3-phenylpyrazole derivative according to one of claims 11 to 13.

16. A method for the leaf treatment of plants against fungal diseases, characterized in that at least one 3-phenylpyrazole derivative according to one of claims 11 to 13 is used as active material.