CA2194913A1 - Fungicidal compositions containing 3-phenyl-pyrazole derivatives for treating propagative plant stock, novel 3-phenyl-pyrazole derivatives, and fungicidal uses thereof - Google Patents

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

WO 96/02138 PCT / FTt95 / 00921 Fungicidal compositions based on 3-phenyl-pyrazole derivatives for the treatment propagating plant material, new 3-phenyl-pyrazole derivatives and their fungicide applications The present invention relates to the use of 3-phenyl-pyrazole derivatives for the protection of propagating plant material against diseases fungal compositions containing these derivatives as well as new derivatives of this family the compositions containing these and fungicidal compositions the thus containing than a process for the treatment of plants with these derivatives.
Certain 3-phenyl-pyrazole derivatives are described in particular in the applications published EP 0 538 156 and WO 93/22287 for their advantageous properties against the fungal diseases of the leaf parts of plants.
By the term "propagating plant material" is meant to denote all the generative parts of the plant that can be used for reproduction and the multiplication of it. We can cite for example seeds (seeds in the narrow sense) for crops other than potato, roots, fruit, tubers, bulbs, rhizomes, parts of plants or sprouted plants and young plants, which have to be transplanted after germination or after emergence from the soil. These young plants can be protected before transplantation by a total or partial treatment with immersion.
Among the multiplication products suitable for the treatment process according to the invention is preferred:
- broadleaf seeds: peas, cucumber, melon, soy, cotton, sunflower, rapeseed, bean, 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 hundredweight of seed, preferably 1 to 400 g per quintal.
Preferably, in the case of tubers, these are coated with a quantity of matter active corresponding to the soaking of said product in a composition containing 0.1g / l to 100 g / 1 of active ingredient.

The invention more particularly relates on the one hand to compositions for treatment of plant propagating material against diseases fungal, characterized in that they contain, as active ingredients at least one derivative 3-phenylpyrazole of formula I:

Xi N \
NOT
in which:
X1, X2, X3, X4 and X5, identical or different, are:
- a hydrogen or halogen atom, a hydroxy, mercapto, cyano group, thiocyanato, nitro, nitroso, amino optionally substituted with one or two alkyls or phenyls, - an alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylsulfonyl radical alkylthioalkyle alkylsulfinylalkyle, alkylsulfonylalkyle, benzyle, alényle, alkynyl, cyanoalkyl, alkoxy, alkenoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, formyl, acetyl, alkyl- or alkoxy (thio) carbonyl, 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 - an alkyl- or alkoxy- or mono or di alkylamino-phenyl-sulfenyl radical or sulfinyl or sulfonyl, - a sulfonic group, its salts, esters and derived amides, - a phosphoryl group, substituted by two groups chosen from the group including alkyl, alkoxy, alkylthio and dialkylamino, benzyloxy, phenyloxy or phenyl, - a trialkyl- or alkylphenyl-silyl group, two of the adjacent X1, X2, X3, X4 and X5 can also form a bridge comprising from 2 to 4 links, at least one of which may be replaced by one atom oxygen, sulfur or nitrogen, and which may have one or more atoms or groups following C, O, S, N, C = O, C = S, SO, S02, CH = CH, the carbons of this bridge can to be or not substituted by at least one halogen atom and / or at least one group hydroxy, amino, alkyl, alkoxy alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl or alkoxycarbonyl, the alkyl part being as defined below, provided that Xlà X5 cannot each be at the same time a hydrogen atom;
Y is a hydrogen atom, a halogen atom, a nitro, cyano, hydroxy group, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyloxy, mercapto, carboxyl, carboxylate, formyl, alkyl (thio) carbonyl, arylcarbonyl, alkoxy (thio) carbonyl, carbamoyl, 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 Xl 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 being able to be or not substituted by to minus one halogen atom and / or at least one hydroxy, alkoxy, alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl, the alkyl part being such that defined below, Z is:
- a hydrogen, halogen atom, a cyano, nitro group, hydroxy or -an alkyl, haloalkyl, hydroxyalkyl, formyloxylalkyl, alkyl- or aryl (thio) carbonyloxyalkyle, alkoxy (thio) carbonyloxyalkyle, amino (thio) carbonyloxyalkyl, mono or dialkylamino (thio) -carbonyloxyalkyl, cycloalkyl or cycloalkyl -alkyl, the cycloalkyl part may be substituted by the GR4 group, defined below, - alkoxy optionally substituted by hydroxy, alkoxy, an 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 from 3 to 7 atoms of carbon, possibly stolen - phenyl or Het, possibly subtitled - a group of formula C (= Z1) Z2 in which:
- Z1 is an oxygen or sulfur atom or a group alkylamino or alkylimino or arylamino or arylimino and - Z2 is:
- a hydrogen atom, a halogen atom, a group hydroxy, mercapto, cyano, amino, - alkyl, alkoxy, haloalkoxy, alkylthio, - alkenyl or alkynyl or alkenyloxy, each containing 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 radical diphenyl-amino, or alkyl- or arylsulfonylamino, - a phosphoryl group substituted by two selected radicals from the group comprising alkyl, alkoxy, alkylthio, dialkylamino, cycloalkyl or cycloalkyl - alkyl, alkenyl or alkynyl, phenyl, phenylalkyl, Het or Het-alkyl, phenyl or Het, possibly subtitled;
- or a group S (= Z1) (= Z3) Z2, in which Zl and Z2 have the same meanings as above and Z3 has the same meanings as without being necessarily equal to Z1, as well as the tautomeric forms of formula I bis, when Z is an atom hydrogen or isomers when Z is a group of formula C (= Z1) Z2. or S (= Z1) (= Z3) Z2, X2 I, X

Z / N \ N
I bis as well as the hydracid or perchloric or nitric acid salts or sulfuric or alkyl- or phenyl (optionally substituted) sulfonic acids of the derivatives deformules I
or I bis and their metal complexes, and their N-oxides, it being understood that in all of the above meanings, 21 ~ 49: I ~

- the linear hydrocarbon part of these groups can comprise from 1 to 7 carbon atoms and possibly be halogenated (from 1 to 8 atoms halogen), the cycloalkyl part of these groups can comprise from 3 to 7 atoms carbon and be optionally substituted with at least one substituent chosen from the GR4 group 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 GR4 group includes:
- a halogen atom, or a cyano, nitro, mono or dialkylamino, 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 1 with 4 carbon atoms and can be substituted by 1 to 9 atoms halogen), Preferably, in formula IY is a chlorine or bromine atom.
Other preferred derivatives are such that, in formula I, Z is an atom of hydrogen or a group C (= Z1) Z2, in which Zl is an oxygen atom or sulfur.
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, eventually halogenated, from 1 to 4 carbon atoms.
Other preferred derivatives are such that, in formula I, X3 is an atom hydrogen or fluorine.
Other preferred derivatives are such that, in formula I, X1 and / or X5 are a hydrogen atom,.
Other preferred derivatives are such that in formula I, two substituents adjacent chosen from Xl, X2, X3, X4 and X5 form a bridge comprising 3 or 4 links, in particular an optionally halogenated methylenedioxy bridge and preference fluorinated.
Particularly preferred derivatives are as respectively in the formula I:

WO 96/02138 6 PCT / FR95 / 00921 ~
a) X1, X3 and X5 are a hydrogen atom and X2, X4 are each an atom of chlorine b) X 1 is a nitro, X2, X4 are each a chlorine atom X3 is an atom of fluorine and X5 is a hydrogen atom c) X 1 is a fluorine atom, X2, X4 are each a chlorine atom X3 is a fluorine atom, X3 and X5 are a atom hydrogen Some of these derivatives are new and such as in formula I:
Y is a chlorine atom and Z is a hydrogen atom, X1 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 group nitro, or methyl, X5 is a hydrogen or halogen atom New preferred derivatives are such as in formula I:
Y, Z, X1 and X4 are as described above, X2 is a chlorine or bromine atom, X3 and, X5, identical or different, are each a hydrogen atom or fluorine.
The derivatives according to the invention can be prepared according to methods per se known as described in published applications EP 0 538 156 and WO
93/22287.
The following examples respectively illustrate the preparation of derivatives new, their physico-chemical characteristics (the structures have been verified by NMR analysis), their fungicidal properties in treatment of diseases foliar as well that the fungicidal properties in seed treatment of all 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- acid dichlorobenzoic dissolved in 1000 ml of concentrated sulfuric acid, are added in portions 58 g (0.57 mol) of potassium nitrate. After 1 hour, the reaction medium is poured in 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 acid benzoic are dissolved in 200 ml of dry THF. 37 ml of 1.6 M n-BuLi solution in the hexane are poured, drop by drop, at -70 C. After one hour shaking, 25.1 g (0.106 mole) of hexachloroethane in solution in 20 ml of dry THF are added up.
After 2 hours at -70 ° C., the temperature of the medium is gradually reduced to the ambient. The reaction mixture is hydrolyzed with 50 ml of water and then extracted 1 ether. The the aqueous phase is acidified by addition of 1N HCl and then extracted with ether.
The sentence organic is dried over magnesium sulfate, concentrated under pressure scaled down. The solid is recrystallized from a heptane / ether mixture to give 1.2 g of 3- acid chloro 4-fluoro 5-benzoic bromo (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 bromine are added while keeping the temperature of the reaction medium below +
10 C. 50.0 g (0.169 mole) of 3-bromo 4-fluoro 5-bromo acetophenone in solution in 50 ml of 1o dioxane are poured in while maintaining the temperature of the reaction medium lower than + 10 C. The temperature of the reaction mixture is brought back to ambient in controlling the exothermicity so as not to exceed +35 C. Stirring is continued 1.5 hours to the ambient. The aqueous phase is extracted with ether, acidified to pH 1 approximately.
with 1N HCl, reextracted with ether. The organic phase is dried over magnesium sulfate, concentrated under vacuum. The solid is triturated in heptane to give 47.5 g of acid 3-bromo 4-fluoro 5-benzoic bromo (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 the hexane are added dropwise to a solution of 10.4 g (0.090 mole) from TMEDA
in 40 ml of dry THF. A-70 C, 15.0 g (0.075 mole) 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 carbon dioxide solid carbon in 100 ml of dry THF. The reaction medium is stirred, letting it rise gradually the ambient temperature, then hydrolyzed with water, extracted with ether. The aqueous phase is acidified with 1N HCl, extracted with ether. The sentence organic is dried on magnesium sulfate, concentrated in vacuo. The solid is recrystallized in a mixture heptane / ether (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 L' 3o hexane are added, dropwise, to a solution of 14.3 g (0.090 mole) of diisopropylamine 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 to drip. The reaction medium is stirred for 1 hour at -70 ° C., poured onto dioxide solid carbon in 100 ml of dry THF. After returning to room temperature, the mixed reaction is hydrolyzed with water, extracted with ether. The aqueous phase is acidified with HCl 1N, extracted with ether. The organic phase is dried over sulphate magnesium, concentrated under vacuum. 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 chloride of oxalyl (0.09 mole) in 50 ml of 1,2-dichloroethane. 5 drops of DMF and the whole is stirred for 1 hour at room temperature. 24 g (0.18) are added mole) of aluminum chloride and the medium is brought to 60-70 C. After passing a current of chlorine for 5 hours, maintaining the temperature of the reaction medium between 60 and 70 C, the whole is poured into 100 ml of 1N HCl. The precipitate is recovered by filtration, washed with water, dried under reduced pressure to give 13 g of a creamy solid (Yield:
95.6%; 1H NMR & 13C).
By operating as above but with the appropriate reagents, we prepared the following acids:
- 3-fluoro 5-bromobenzoic acid (Yield: 78%; melting point:
144 C);
- 2-nitro, 3-chloro 5-methylbenzoic acid (Yield: 83%;
fusion:
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) Acetophenones are obtained from benzoic acids previously obtained according to the following procedure:
a) 2,3-Dibromo-5-methyl benzoic acid chloride.

2.1 g (0.00714 mole) 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 chloride thionyle in solution in 5 ml of 1,2-dichloroethane. The mixture thus obtained is restless at 60 C for approximately 5 hours then concentrated in vacuo to lead to obtaining a oil: 2,3 dibromo-5-methyl benzoic acid chloride.
b) (2,3-dibromo-5-methylphenyl) ethanone 30 ml of ether are refluxed for 3 hours a mixture of 0.87 g (0.0076 mole) magnesium ethylate and 1.17 ml (0.0076 mole) ethyl malonate. We then add to this heterogeneous solution 2g (0.0064 mole) of acid chloride obtained previously diluted in 5 ml of ether. The reaction medium is then stirred at reflux during 3 hours.
After cooling, 10 ml of a dilute sulfuric acid solution are added to reaction medium which is then extracted with ether and washed with water. After drying on MgSO4 and evaporation of the solvent, an oil is obtained which is directly engaged in the stage of decarboxylation: dilution in a mixture of 5 ml of acetic acid, 5 ml of water and 1 ml concentrated sulfuric acid then heating to 70 ° C for approximately 2 hours.
The middle ~ WO 96/02138 9 PCT / FR95 / 00921 reaction is then extracted with ethyl acetate and neutralized with a aqueous solution of welded. After drying over MgSO4 and evaporation of the solvent, an oil is obtained:
(2,3-dibromo-5-methylphenyl) ethanone.
In the same way as above, the following acetophenones are obtained (cf.
table below), from benzoic acids substituted in a appropriate:

0 * Me O
X, X2, X3, X4, X. Yield (%). FC) or Analysis.
H, Br, F, Cl, H. 50 Analysis.
F, Cl, F, Cl, F. 58 Analysis.
F, Cl, F, Cl, H. 63 48, 5 Me, Cl, F, Cl, H. 13 62 Cl, Cl, H, N02, H. 87 Analysis.
Me, N02, H, F, H. 89 50 F3C, Cl, H, H, H. 42 NMR
Cl, OCF3, H, Br, H. 61 NMR
Cl, OCF3, H, NO, H. 82 NMR
Br, OCF3, H, NO, H. 89 NMR
F, Br, F, Cl, H. 50 NMR
F, Me, F, Cl, H. 10 NMR
F, Cl, H, F, H. 46 NMR
H, F, H, Br, H. 54 73 NO, Cl, H, Me, H. 70 130 H, F, H, OMe, H. 68 66 H, Cl, H, Me, H. 52 NMR
B) Preparation of (3 5-dichlorophenyl) ethanone from 3.5-dichloroaniline (cf Example 4F of application WO 93/22281:

300 ml of water and 70 ml of concentrated hydrochloric acid are added to 48.6 g (0.30 mole) 3,5-dichloroaniline. 30 minutes later, pour in drop by drop 27.5 g (0.40 mole) of sodium nitrite in 32 ml of water keeping the temperature between 0 and 5 C. To 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) acetaldoxime, 25, 0 g (0.10 mole) of copper sulphate pentahydrate, 20.5 g (0.018 mole) of sulfite anhydrous sodium and 121 g (1.50 mole) of sodium acetate in 250 ml of water maintained at C. After 1 hour of stirring, the medium is acidified by adding acid hydrochloric concentrated. After steam entrainment and chromatography of the raw product on column 10 of silica (heptane 90, ethyl acetate 10), 16.6 g (30%) of (3.5-dichlorophenyl) ethanone, as a colorless liquid.
By operating as above, starting from 3-bromo-5-trifluoromethylaniline, we obtains (3-bromo-5-trifluoromethylphenyl) ethanone (yield: 35%; NMR).
b) from 4-acetyl-2,6-dichloroaniline:
15 We recrystallize 814 g (4 moles) of 4-acetyl-2,6-dichloroaniline, prepared according to patent DD 273,435 dated 15-11-1989, in a mixture of 1200 ml of acid hydrochloric concentrated and 5200 ml of concentrated acetic acid. After cooling to 0 C, we sink in a solution a solution of 290 g (4.2 moles) of sodium nitrite in 770 ml of water. After 2:30 at this temperature, the solution is poured onto a solution at 5 C of 2200 ml of acid hypophosphorous at 50% in water. At the end of the casting, we let go back to temperature ambient then 10 l of water are added and the aqueous phase is extracted with dichloromethane.
After the decanted organic phase has dried, concentration and distillation of the gross, we obtains 591 g (yield 78%, boiling point: 91-95 C under lmm Hg) of (3,5-dichloro) phenyl ethanone as a light yellow liquid.
By operating as above from 4-acetyl-6-bromo-2-chloroaniline, we gets 89%
of (3-bromo-5-chloro) phenyl ethanoneRMN).
By operating as above from 3,4,5-trichloroaniline, we have got (3,4,5-trichlorophenyl) -ethanone (yield: 20%; F: 75 C).

Example 3: 2-chloroacetophenones (preparation of chloracetophenone by chloracetylation (Friedel-Crafts) of the 2-chloro-1-(2-chloro-4-fluoro-5-methylphenyl) ethanone (Example 4 I of application WO

WO 93/22287) 14.1 g (0.125 mol) of monochloroacetyl chloride are poured in dropwise in a suspension of 16.66 g (0.125 mol) of anhydrous aluminum chloride in 100 ml of 1,2-dichloroethane dry maintained at a temperature of -5 C by an ice bath-acetone.
14.46 g (0.1 mole) of 4-chloro-2-fluorotoluene are then poured in dropwise To the same temperature in the solution obtained. The reaction mixture is stirred for 1 hour to -C then left to stand overnight, finally brought to 60 C until the end of release gaseous. After cooling by an ice bath, it is poured drop by drop a solution 5 n-il hydrochloric acid concentrated in 100 ml of water. After decantation the sentence organic is washed successively with 50 ml of water, 50 ml of saturated solution of NaHCO3 5 and 50 ml of water and then dried over anhydrous magnesium sulfate. After evaporation of solvent, 22.3 g of pale yellow oil of 2-chloro-1- (2-chloro-4-fluoro-methylphenyl) ethanone, which crystallizes on cooling (melting point:
32 C;
yield: 100%).
Likewise, 2-chloro-1- (3-methyl-4-fluoro-5-methylphenyl) ethanone was obtained.
(point 86 C, 87% yield) (FG 993) and 2-chloro-1- (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 g) are added mole) of 4-fluoroacetophenone dissolved in 10 ml of 1,2-dichloroethane. The middle reactionary is heated to + 55 C and poured, drop by drop, 51 ml of bromine in 1 hour about.
Agitation is continued for 5 hours at + 55 C. The reaction medium is brought to at room temperature, poured into iced acidulated water and extracted with dichloromethane.
The organic phases are dried over magnesium sulfate and then concentrated under vacuum.
6.7 g of 3-bromo-4-fluoro-5-bromo acetophenone are obtained (yield: 23%;
point of fusion: 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.
After half an hour at + 10 ° C., 15.0 g (0.104 mole) of 2-fluoro-3chloro toluene in solution in 10 ml of 1,2-dichloroethane. The reaction medium is brought to room temperature and then heated for 3 hours at + 50 C. After cooling, the mixture is poured into 1N HCl and extracted with dichloromethane. The phases organic are dried over magnesium sulfate and then concentrated in vacuo. 11.6 g are obtained from 3-methyl-4-fluoro-5-chloro acetophenone.

Example 6: Enaminones (cf. Examples 5 and 6 of application WO 93/22287) 1- (3,5-dichlorophenyl) -3-dimethylaminopropen-2-one-1:
10 g (0.053 mole) of

3 ', 5'-dicholoroacetophenone in 50 ml of N, N-dimethylformamide dimethylacetal.
The agitation is maintained and the reaction mixture is heated for 2 h at 90 C. The middle east concentrated to dryness under reduced pressure. The residue is taken up with 150 ml heptane. The residue orange is filtered to give 10.0 g (77% yield, melting point: 100 C) from 1- (3,5-dichlorophenyl) -3-dimethylaminopropen-2-one-1.
By operating in an analogous manner, starting from acetophenone suitably substituted and the second appropriate reagent, the enaminone derivatives were obtained of formula below, gathered in the following table.

W
OH

with W = N (CH3) 2 Xl, X2, X3, X4, X5. YId (%). F (C) or Analyzes H, Br, F, Cl, H. 80 Analysis.
H, Br, F, Br, H. 82 143 H, Me, F, Cl, H. 28 89 F, Cl, F, Cl, F. 81 128 H, Cl, Cl, Cl, H. 85 143 Me, Cl, F, Cl, H. 69 127 Cl, Cl, H, N02, H. 60 Analysis.
H, Cl, H, Me, H 91 Analysis F, Br, F, C1, H. 87 121 F, Me, F, Cl, H. 40 NMR
H, F, H, OMe, H. 76 70 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 dimethylacetal from dimethylformamide 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 them crystals obtained washed with heptane and then dried (3.2 g). By evaporation partial filtrate on obtains a new batch of crystals which are treated in the same way (0.8 g). Both combined batches are then chromatographed on silica gel with elution by a mix of 70% heptane and 30% ethyl acetate, then 50% heptane and 50% acetate ethyl. We obtains 1.84 g of starting 2-chloro-3 ', 5'-dimethyl-4'-fluoroacetophenone and 1.55 g of 1-(3,5-dimethyl-4-fluorophenyl) -2-chloro-3-dimethylamino-2-propene-1-one, white crystals decomposing at 177.5 C (yield: 20%).
By operating in an analogous manner, starting from acetophenone suitably substituted and the second suitable reagent, (3,5-dichloro-2,4-difluorophenyl) -2-chloro-3-dimethylamino-2-propene-1-one (see NMR analysis, yield = 100%).

Example 8: 1H-Pvrazoles (see Example 7 of application WO 93/22287) 3- (3,5-dichlorophenyl) 1H-pyrazole.
2.4 g (0.05 mole) of hydrate are added slowly and at room temperature hydrazine 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 crushed 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 enaminone suitably substituted and of the second suitable reagent, the pyrazole derivatives of formula ci- were obtained below, gathered in the following table.

NOT
NOT
H
X, X2, X3, X4, X. Yield (%). F (C) or Analysis.
H, Br, F, Cl, H. 77 261 H, Br, F, Br, H. 86 201 H, Me, F, Cl, H. 93 156 F, Cl, F, Cl, F. 47 155 H, Cl, Cl, Cl, H. 69 208 Me, Cl, F, Cl, H. 97 130 Cl, Cl, H, N02, H. 60 Analysis.
Me, N02, H, F, H. 81 98 H, Cl, H, Me, H 80 Analysis.
F, Br, F, Cl, H. 88 161 F, Cl, H, Cl, F. 70 150 F, CF, H, Cl, H. 12 NMR
CF, Cl, H, H, H. 97 NMR
Cl, OCF3, H, Br, H. 82 NMR
CI, OCF3, H, NO, H. 50 NMR
Br, OCF3, H, NO, H. 66 NMR
F, H, H, C1, H. 75 NMR
Cl, H, H, CF3, H. 90 NMR
H, F, H, Br, H. 69 NMR
NO, Cl, H, Me, H. 82 175 H, F, H, OMe, H. 38 83 3-Napht-2-yl 87 162 3-Benzo (b) thien-4-yl 60 147 EXAMPLE 9: 4-Chloropyrazoles.
A) 3- (3,5-dimethyl-4-fluorophenyl) -4-chloropyrazole (compound n 1).
With stirring and at room temperature, a cold solution of 1.5 g hydrate of hydrazine in 30 ml of glacial acetic acid is added quickly to one 3.10 g (0.0122 mole) suspension of 1- (3,5-dimethyl-4-fluorophenyl) -2-chloro-dimethylamino-2-propene-1-one in 20 ml of glacial acetic acid.
After 7 a.m.
stirring at room temperature the reaction medium is poured into 200 ml of water. The lo solid formed is filtered, washed with water and dried under vacuum in the presence of P205 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- are obtained chloropyrazole, white solid melting at 144 C (yield: 76%).
By operating in a similar manner, starting from 1H-pyrazole suitably substituted and the second suitable reagent, 3- (3,5-difluoro-4-fluorophenyl) -4-chloropyrazole (compound # 2).

B) 4-chloro-3- (3,5-dichorophenyl) 1H-pyrazole (compound 3) :( Example 9a of WO 93/22287): Halogenation of pyrazoles 2.3 g (0.0152 mole) of 3- are dissolved at room temperature and with stirring.
(3,5-dichlorophenyl) 1H-pyrazole in 300 ml of dichloromethane. We add then 2, 07 g (0.016 mole) of N-chlorosuccinimide, then stirring is continued for 4 days at temperature ambient. The reaction mixture is then concentrated and then chromatographed on column of silica (eluent heptane / ethyl acetate 70/30). 1.4 g are obtained (yield: 57%, Point of fusion: 192 C) of 4-chloro-3- (3,5-dichlorophenyl) 1H-pyrazole.
By operating in a similar manner, starting from 1H-pyrazole suitably lo substituted and the second suitable reagent, 4-chloro derivatives were obtained pyrazoles of formula below, gathered in the following table.

N ~
NOT

H
Compound Xl, X2, X3, X4, X5. Y Yield (%) F (C) or n Analysis.

4 H, Br, F, Cl, H. Cl 84 169

5 H, Br, F, Br, H. Cl 88 169

6 H, Me, F, Cl, H. Cl 69 174

7 F, Cl, F, Cl, F. Ci 79 143

8 H, Cl, Cl, CI, H. Cl 61 208

9 F, Cl, F, Cl, H. Cl 30 158 Me, Cl, F, Cl, H. Cl 81 53 11 Cl, Cl, H, N02, H. Cl 70 172 12 Me, N02, H, F, H. Cl 55 126 1 p.m., Cl, H, Me, H. Cl 85 175 40 F, Br, F, Cl, H. Cl 92 167 41 CF, Cl, H, H, H. Cl 68 78 WO 96/02138 16 ~ PCT / FR95 / 00921 42 Cl, F, H, OMe, H. Cl 75 156 43 H, F, H, OMe, H. Ci 45 127 44 F, Me, F, Cl, H. Cl 20 119 45 Cl, OCF3, H, Br, H. Cl 56 109 46 l, OCF, H, NO, H. Cl 44 132 47 3r, OCF3, H, NO, H. Cl 86 150 48 H, F, H, Br, H. Cl 39 155 49 F, H, H, Cl, H. Cl 19 116 50 Cl, H, H, CF, H. Cl 71 110 51 F, Cl, H, Cl, F. Cl 75 152 52 NO, Cl, H, Me, H. Cl 55 172 53 3-Napht-2-yl Cl 37 140 C) 4-Chloro-pyrazoles (cf. Example 12 (Example 12 of the WO application 93/22287).
a - Acetylation:
A 11.0 g (0.046 mole) of 4-chloro, 3- (2,2-difluorobenzo-l, 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 (0.0442 mole) of triethylamine. This solution is poured, drop by drop drop and at 0 C, a solution of 3.6 g (0.046 mole) of acetyl chloride in 50 ml of THF.
The agitation is continued for 3 h at room temperature. The reaction mixture is poured in 300 ml of water and extracted with ethyl acetate. After drying of the organic phase and concentration under vacuum, the residue is triturated with 50 ml of heptane, filtered and dried. We let's get 12.8 g 1-acetyl-4-chloro-3- (2,2-difluorobenzo-1,3-dioxol-4-yl) pyrazole (compound 14) fondant 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 CH2C12 are added, in small batches portions and at 0 C, 6.3 g (0.063 mole) of KNO3. The reaction medium is stirred for 3 hours at 0 C then poured poured over 300 cm3 of ice. The precipitate is recovered by filtration, washed at water then to heptane and dried. We obtain 8.05 g of 4-chloro-3- (2,2-difluoro-5-nitrobenzo-1,3-dioxol-4-yl) pyrazole melting at 180 C (yield 63%) (compound 15).
By operating in a similar manner, starting from 1H-pyrazole suitably substituted and the second suitable reagent, 4-chloro derivatives were obtained pyrazoles of formula above, gathered in the following table.

_ WO 96/02138 17 PCT / FR95 / 00921 Compound Xl, X2, X3, X4, X5. Y Yield (%). F (C) or n Analysis.
16 F, Cl, H, N02, H. Cl 74 147 17 F, Br, H, N02, H. Cl 34 154 18 N02, Cl, H, Cl, H, Cl 55 173 54 F, NO, H, Cl, H. Cl 46 177 55 Cl, NO, H, CF, H. Cl 22 128 56 NO, OMe, H, F, H. Cl 50 158 Example 10: 3- (2-amino) phenyl-4-chloro pyrazoles (see Example 14 of the 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-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 mole) of powdered iron are introduced in portions. The reaction medium is then kept under agitation at 70 C for 5 hours. After cooling, the reaction medium is poured in 800 ml of water, filtered through a sintered glass, rinsed with water and dried to yield obtaining a solid White (Yield: 90%, PF: decomposition at 300 C) of 3- (2-amino-3,5-dichlorophenyl) chloro pyrazole.
By operating in an analogous manner, starting from 4-chloro-pyrazole suitably substituted, the 4-chloro pyrazole derivatives of formula below were obtained, gathered in the following table.

NOT
NOT

H

~ 19491 ~

compound Xl, X2, X3, X4, X5. Y Yield (%). F (C) o n Analysis.
20 NH, Cl, F, Cl, H. Cl 68 160 21 NH, Br, H, Br, H. Cl 47 169 22 Cl, Cl, H, NH, H CI 69 150 23 F, Cl, H, NH, H. Cl 90 145 24 F, Br, H, NH, H. Cl 75 155 57 NH Cl, H, Cl, F. Cl 85 150 58 NO, Cl, H, NH2, H Cl 26 198 Example 11: 4-chloro p, vrazoles (Example 15 of application WO 93/222871.
3- (2-methvlthio-3.5-dichloro) phenvl-4-chloro pvrazole (compound 25) 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 reagent of suitable, the 3-phenyl-4-choro or bromo pyrazole compounds of formula ci above, shown in the following table, in which the group introduced is marked by a asterisk:

N ~
NOT

H
Compound Xl, X2, X3, X4, X. Y Yield (%). F (C) or n Analysis.
26 F *, Cl, H, Cl, H CI 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: 3-12-Nitrolphenyl-4-chloro-pvrazoles 3- (2-nitro-3,5-dichloro-4-fluoro phenyl) -4-chloro pyrazole (compound 30).
0.43 ml (0.0104 mole) of fuming nitric acid is added dropwise (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 the WO 9322287, compound 266) in 25 ml of 100% sulfuric acid. The middle reaction is stirred cold for 20 minutes then at room temperature during a lo hour and finally poured over 150 g of ice. The precipitate formed is extracted by 150 ml acetate ethyl. The solution obtained is washed with 100 ml of water, 100 ml of a saturated solution sodium hydrogen carbonate, 100 ml water, dried over magnesium sulfate and evaporated in vacuo. 2.78 g of 3- (2-nitro-3,5-dichloro-4- are obtained.
fluorophenyl) -4-chloro pyrazole, white solid melting at 196.4 C (yield: 95%).
By operating in an analogous manner, starting from 4-chloro-pyrazole suitably substituted, the 3- (2-nitro) phenyl-4-chloro pyrazoles derivatives of formula below above, gathered in the following table.

Compos Xl, X2, X3, X4, X5 Y Yield (%) F (C) o n Analysis 31 N02, Br, H, Br, H. Cl 25 196 32 NO, Br, F, Br, H. Cl 73 221 33 NO, Me, F, Cl, H. Cl 19 214 34 N02, Cl, F, Me, H. Cl 20 205 61 NO, Me, H, Br, H. Cl 13 184 Example 13: 3-15-fluorophenyll-4-chloropvrazoles 3- (2,3-dichloro5-fluoro phenyl) 4-chloro pyrazole (compound 35).
3- (5-amino-2,3-dichlorophenyl) -4-chloro- diazonium tetrafluoroborate pyrazole is obtained by pouring dropwise at 0 C an aqueous solution of nitrite sodium (0.0021 mol) on a solution containing 0.002 mol of 3- (5-amino-2,3-dichloro-phenyl) -4-chloro-pyrazole and 5 ml of tetrafluoroboric acid in solution 50% aqueous.
The reaction medium is thus stirred at 0 C for 1 hour and then poured into 50 ml of water and of ice. The precipitate obtained is dried quickly under vacuum and then decomposed thermally dry at 145 C. After cooling, the reaction medium is resumed at dichloromethane and purified by chromatography on silica gel with as mixed eluent Ethyl acetate / Heptane (25/75) (yield: 19%; melting point:
122 C).
By operating in an analogous manner, starting from 4-chloro-pyrazole suitably substituted, 3- (3-chloro-2,5-difluoro phenyl) -4-chloro pyrazole was obtained (compound 36) (yield: 17%; melting point: 150 C).

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

Example 15: 3- (3-chloro 5-fluoro Qhenvl) 4-chloro pyrazole (compound 37).
In a 500 ml three-necked flask at 0 ° C., 17.4 g (0.075 mole) of 4-chloro-3- (3-amino-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 dissolved in 10 ml of water are poured in drop in now the temperature between 0 and 5 C. Stirring is continued for one hour at ambient temperature. The solid obtained is filtered through sintered glass, washed at water then at pentane. Once dry, the solid is decomposed at 150 C to give an oil brown cover in hot isopropanol. After chromatography on a silica column (eluent: heptane /
ethyl acetate 70/30), 7.9 g (0.0342 mole are obtained; yield: 45.6%;
Fusion point:
150 C) of 4-chloro-3- (3-chloro-5-fluoro phenyl) pyrazole.

Example 16: N-SUBSTITUTED PYRAZOLES (Example 19D of the request WO 93/22287).
1-acetoxymethvl-4-chloro-3- (3 5-dichlorophenyl) pvrazole (compound 38) 0.15 ml of 1,8-diazabicyclo (5.4.0) undecen-7-ene is added at temperature ambient, 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 restless 4 h at room temperature. A solution of 1.20 g (0.015 mole) of chloride acetyl in ml of THF, is poured dropwise at 0 C and stirring continued for 6 h at temperature ambient. The reaction medium is concentrated to dryness. The residue is taken up with 15 ml heptane and then dried. We obtain 3.05 g of 1-acetoxymethyl-4-chloro-3- (3,5-dichlorophenyl) pyrazole melting at 95 C.
5 By operating in an analogous manner, starting from 1-H-4-chloro-pyrazole substituted, we got the co-derivatives of formula I below Y

NOT

Z
Compound Xl, X2, X3, X4, YZ Rdt F (C) n X5. (%). or Analysis.
39 NO2, Cl, F, Cl, H. Cl CH2OA 97 100 vs 40 F, Cl, H, Cl, H. Cl CH2OA 95 90 vs Example 17: 4-chloro-3- (5-chloro-3-cvano-2-fluorophén ~ ÉI) pyrazole (compound 62).
3- (3-bromo-5-chloro-2-fluorophenyl) -4-chloropyrazole (0.45 g;
0.0014 mole) and copper cyanide (0.14 g; 0.0015 mole) in dimethylformamide (DMF) (10 ml) and the whole is heated at 180 ° C. for 8 hours. After cooling to at room temperature, the mixture is poured into a 14% NH4OH solution (50 ml), then extracted with ethyl acetate (2x50 ml), dried over MgSO4, evaporated under empty. The purification of the oily residue on a dry silica column (elution with 30% acetate ethyl in heptane) produces 0.1 g of a yellow solid (yield: 28%;
Fusion point:
128 C).

219491 ~
-Example 18: 4-chloro-1- (4-methylphenylsulfon y1) pyrazole (compound 63).
Pyrazole (34 g; 0.5 mole) is dissolved in CH2Cl2 (350 ml) at 10 C and add, dropwise, a solution of sulfuryl chloride (77.6 g; 0.575 mole) in CH2C1 (150 ml). When the addition is complete, the mixture is heated to reflux during 18 hours. The dichloromethane is then removed under vacuum, the residue put in suspension in pyridine (200 ml) and p- chloride is added in portions toluenesulfonyl (95.33 g;
0.5 mole). This mixture is then heated to reflux and allowed to cool to temperature ambient. The mixture is cooled in an ice bath and water is added (800 ml) under vigorous agitation. After one hour a solid forms. He is collected by filtration, washed with water and recrystallized from ethanol to give 102 g of 4-chloro-l- (4-methylphenylsulfonyl) pyrazole in the form of a white powder (yield:
80%; Point of fusion: 96-97 C).

Example 19: 4-chloro-5- (3-fluorophenyl) -1- (4-methylphenvlsulfonyl) pvrazole (compound 64).
2.4 g (0.0093 mole) of 4-chloro-1- (methylphenylsulfonyl) pyrazole are dissolved in tetrahydrofuran (THF) (20 ml) and cools to -78 C under argon. We add, drop to drop, 2.5 M n-Butyl lithium (3.92 ml; 0.0098 mole) for 10 minutes and The mixture is kept stirring at -78 C for 1.25 hours. We add, drop by drop one zinc chloride solution in THF (10 ml; 0.01 mole) for 10 minutes. The mixture is kept stirring at -78 ° C. for 0.5 hour and then at temperature room for 2 hours. So we add tetrakis (triphenylphosphine) palladium (Pd (PPh3) 4 (0.35 g; 0.0003 mole) 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 left cool to room temperature, diluted with EDTA solution (50 ml) then subject to an extraction with (3 x 50 ml) of ether. The organic extract is washed with water, dried out MgSO4, filtered and evaporated to give a yellow oil (4.1 g). Purification on column dry silica (elution with 10% ethyl acetate in heptane) gives 1.05 g of 4-chloro-5- (3-fluorophenyl) -1- (4-methylphenylsulfonyl) pyrazole (yield: 48%; Point of fusion: 110-111 C).

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

R Cl N: N

s02 . ~ I

Compound R. Yield F (C).
n M.
65 Benzo b thien-4- l 56 133 66 (2-Carbomethoxy) 69 170 benzo thien-4- 1 67 Benzo furan-4- 1 67 102 Appropriate intermediate reagents are obtained according to the procedures following:
a) 2-carbomethoxy-4-iodobenzo (b) thiophene:
30.0 g (0.012 mole) of 2-fluoro-6-iodobezaldehyde are dissolved at temperature ambient and under an argon atmosphere, in dry dimethyl sulfoxide (150 ml).
We add, drop by drop, in one minute, 14.05 g (0.0119 mole of thioglycolate methyl then lo 25.85 g (0.255 mole) of triethylamine. The whole is heated to 60 C
during 2 hours, cooled to room temperature and poured, with stirring, into a mixture water and ice (1000m1). The yellow precipitate is recovered by filtration, air-dried, put in suspension in 300m1 of methanol and heated to reflux for 10 minutes. The solution is cooled to 0 C, the precipitate recovered 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 suspension) is suspended.
oil dispersion) in 100 ml of tetrahydrofuran under atmosphere argon. The medium is cooled between + 5 C and + 10 C using an ice water bath. We add, drop to drop, in 30 minutes, a solution of 10.3 g (0.115 mole) of thioglycolate methyl in 50 ml of THF. The whole is stirred for 5 minutes at this temperature. We add, drop drop, in 30 minutes, a solution of 21 g (0.084 mole) of 2-fluoro - 6-iodobenzadehyde in 50 ml of THF. The temperature of the medium spontaneously rises to + 40 C.
The 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 at 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:
10M aqueous sodium hydroxide solution (5.8m1) is added to a mixture 17.0 g (0.053 mole) of 2-carbomethoxy-4-iodobenzo (b) thiophene in 150 ml ethanol. The whole is heated at reflux for one hour and then concentrated to dry under reduced pressure. The residue is dissolved in water (300 ml) and washed with acetate ethyl (100 ml).
The aqueous phase is acidified to pH = 1 with 36% HCl. The precipitate is recovered by lo filtration, washed with water and diisopropyl ether, dried under pressure reduce to 70 C for 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 everything is heated to 200 C. 13.0 g are added in portions (0.043 mole) of 2-carboxy-4-iodobenzo (b) thiophene. After cessation of gas evolution (approximately minutes), the medium is brought to room temperature, poured into a mixture HCl 36%
(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 (2x 150 ml), washed with water (400 ml) dried (MgSO4), concentrated under reduced pressure to give 11.65 g of an oil Brown. The purification on a silica column (elution with pure heptane) gives 9.6 g of a solid yellow (yield: 86%; melting point: 37-39 C).

Example 20: 4-chloro-3- (benzo (b) thien-4-yl) pyrazole (compound 68).
5- (Benzo (b) thien-4-yl) -4-chloro-l- (4-methylphenylsulfonyl) is dissolved pyrazole (3.3 g; 0.00844 mole) in DMF (25 ml) then heated to 110 C
during 18 hours. After cooling to room temperature, the mixture is poured in some ice with stirring with production of an oily product. It is extract with ethyl acetate (2x50 ml), washed with water (3x100 ml), dried. Elution on a dry column silica (with 20% ethyl acetate in heptane produces 1.4 g of a solid yellow after crushing (yield: 70%; Melting point: 123 C).
By operating as above from an appropriate reagent, the 4-chloro-3-(benzo (b) furan-4-yl) pyrazole (yield: 64%; Melting point: 122 C) (compound 69).
Example 21 (Metallation) = 4-chloro-3- (5-chloro-2-fluoro-3-12hénvlthionhénvl) pyrazole (compound 70).
3- (3-Bromo-5-chloro-2-fluorophenyl) pyrazole (1.10 g; 0.0035) mole) in tetrahydrofuran (THF) (20 ml) and cools to -78 C under argon. We add, drop WO 96/02138 25,219 4,913 PCT / FR95 / 00921 drop, 1.6 M n-Butyl lithium (5.5 ml; 0.0088 mole) for 10 minutes and the mixture is kept under stirring at -78 C for 0.5 hour. We dissolve, drop at drop, diphenyldisulfide (1.53 g; 0.007 mole) in THF (10 ml) and mixture is maintained under stirring for 1 hour at -78 ° C. and then overnight at temperature ambient. Then add 100 ml of water. The mixture is extracted with 2x50 ml acetate ethyl, dried over MgSO4, evaporated in vacuo to give an oily residue. Purification on column dry of silica (elution with 30% ethyl acetate in heptane) gives 0.45 g of 4-chloro-3- (5-chloro-2-fluoro-3-phenylthiophenyl) pyrazole 38%; 1H NMR & 13C).
By operating as above from 4-chloro-3- (3-bromo-5-chloro-2-fluorophenyl) pyrazole and a suitable reagent, the compounds of formula below below and indicated in the following table, in which the group introduces is marked by an asterisk:

X3 ~ X5 1 ~ Y

X1 r73r NH
Compound Xl, X2, X3, X4, X5. Y Yield F (C).

no%).

71 F, CO H *, H, Cl, H. Cl 37 184 72 F, CHO *, H, Cl, H. Cl 26 NMR
73 F, CO Et *, H, Cl, H. Cl 51 100 Example 22: Metal Complex of 4-chloro-3- (3.5-dichlorophenvl) 12vrazole and of copper chloride (compound 74) l.
Copper chloride dihydrate (1.70 g; 0.01 mole) is dissolved in ethanol absolute (10 ml) and triethylorthoformate (1 ml) is added. This mixture is kept under agitation 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 I ~

next day. The precipitate is recovered by filtration, washed with ether ethyl, dry under reduced pressure to give 11.8 g of a light green solid (Yield:
quantitative; Point of fusion: 288 C (decomposition).

By operating as above from the pyrazole and the metal salt appropriate, we obtains, with a quantitative yield, the compounds of formula I - L- M + -I and indicated in the following table:

Compound Xl, X2, X3, Xq, X5. M + L- Color. F (C).
no 75 H, Cl, H, Cl, H. Cu Br greenish 264 (dec.) 76 H, Cl, H, Cl, H. Cu NO blue 190 (dec.) 77 H, Cl, H, Cl, H. Zn Cl white 195 dec.
78 H, Cl, H, Cl, H. Zn AcO white> 300 79 H, Cl, H, Cl, H. Ni Cl cream> 300 80 NO, 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 0 538,156 are also tested:
compound 82: 4-chloro-3- (2'-2 'difluoro-1', 3'-benzodioxol) pyrazole (compound n 25) European demand 0 538 156) compound 83: 4-chloro-3- (2,3-dichlorophenyl) pyrazole (compound no 12 of the request European 0 538 156) compound 84: 4-chloro-3- (2 nitro, 3-chlorophenyl) pyrazole (compound no 120 Requirement European 0 538 156) The present invention also relates to a method for treating plants.
cultivated affected or likely to be affected by diseases fungal characterized in what is applied to the propagation material of these plants a dose effective of a compound according to formula (I). By effective dose is meant an amount sufficient for 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 mushroom to be controlled, the type of crop, the climatic conditions, and according to the compound used.
In practice, the compounds are advantageously applied in doses of 0.1 to g of active ingredient per quintal of seed, and preferably 1 to 400 g / quintal .
By fungal diseases is meant diseases caused by fungi phytopathogens, especially those of the oomycete family, ascomycetes and basidiomycetes.

Among the crops that can be treated with fungicide using of a compound according to the invention, mention may be made of rice, cereals, especially wheat and barley as well than vegetable plants. Rice is a favorite crop for fungicide treatments using a compound according to the invention.
EXAMPLE 23 In Vivo Seed Disinfection Test Two types of protocols are used depending on whether seeds are used naturally infected (Drechslera gramineal Drechslera teres barley) or artificially infected (Cochliobolus sativus / Fusarium culmorum / Fusarium snow /
Septoria nodorum):
30 g of seeds are treated in a HEGE bowl with active ingredients according to the invention under form of concentrated aqueous suspensions, at a concentration of 1.5 liters per hundredweight.
We sow 30 seeds in pots (7x7x8 cm) on pozzolan peat substrate and 3 pots are made by treatment. One contaminated untreated witness and one untreated witness contaminated (in the artificial contamination) are sown under the same conditions.
In the case of artificial contamination, the healthy seeds treated are sown and a spore suspension is brought in at a 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 400,000 Fusarium nivale Septoria nodorum wheat 250,000 The pots are placed in a climatic chamber at 5 ° C. with hygrometry saturating, during a period which depends on the test carried out, namely 3 weeks for Drechslera gramineaJDrechslera 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. diurnal; 4 p.m. 80% relative humidity, until expression of symptoms.
The scoring is done visually in comparison with the untreated witness contaminated.
Under these conditions, good protection is observed at a dose of 100 g / q (at minus 75% or total):
- 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;

219491.-to - 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 for treating plants.
cultivated affected or likely to be affected by diseases fungal characterized in what we apply to the aerial parts of these plants a dose effective of a compound new of formula (I) as defined above. By effective dose is meant an amount sufficient to allow control or destruction of fungi present on these cultivated plants. The doses of use can however vary within wide limits depending on the fungus to be controlled, the type of crop, the conditions climatic, and according to compound used.
In practice, the compounds are advantageously applied in doses of 0.002 to kg / ha, and preferably from 0.005 to 1 kg / ha.
By fungal diseases is meant diseases caused by fungi phytopathogens, especially those of the oomycete family, ascomycetes and basidiomycetes.
Among the crops that can be treated with fungicide using of a compound according to the invention, mention may be made of rice, cereals, especially wheat and barley as well than vegetable plants. Rice is a favorite crop for fungicide treatments using a compound according to the invention.

Example 24: In vivo test on Botrytis cinerea on excised tomato leaf:
(sensitive strains and strains resistant to benzimidazoles):
An aqueous suspension of the active ingredient is prepared by fine grinding.
test having the following composition:
- 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 ingredient.
Tomatoes grown in a greenhouse (Marmande variety) aged 30 days are processed by spraying with aqueous suspensions as defined above and various concentrations of the test compound.

After 24 hours the leaves are cut and put in a box of Petri dish (diameter 14 cm), the bottom of which has been previously lined with a paper disc filtered wet (10 leaflets per box).
The inoculum is then brought using a syringe by depositing drops (3 through leaflet) of a suspension of Botrytis cinerea spores, sensitive to benzimidazoles or resistant to benzimidazoles, obtained from 15-day cultures, put then in suspension at the rate of 150,000 units per cm3.
The control is done 6 days after contamination in comparison with a witness untreated.
Under these conditions, good protection is observed at a dose of 1 g / l (at minus 75%) or total 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 Pyricularia ory3ae Responsible for rice piriculariosis:
An aqueous suspension of the active ingredient is prepared by fine grinding.
test having the following composition:
- 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 ingredient.
Rice, sown in pots in a 50/50 mixture of enriched peat and pozzolan, is treated at the 10 cm high stage by spraying the aqueous suspension above.
After 24 hours, an aqueous suspension of spores of Pyricularia oryzae, obtained from a 15 day culture, then put in suspension at the rate of 100,000 units per cm3.
Rice plants are incubated for 24 hours (25 C, 100%
relative humidity), then put in observation cell, in the same conditions, during 5 days.
Reading is done 6 days after contamination.
Under these conditions, good protection is observed at a dose of 1 g / l (at minus 75%) or total 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.

219491 ~
WO 96/02138 30 PCT / FTt95 / 00921 Example 26: In vivo test on Plasmopara viticola:
An aqueous suspension of the active ingredient is prepared by fine grinding.
test having the following composition:
- 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 ingredient.
Vine cuttings (Vitis vinifera), Chardonnay variety, are cultivated in buckets. When these plants are 2 months old (8-10 leaf stage, height from 10 to 15 cm), they are treated by spraying using the aqueous suspension above.
above.
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 of an aqueous suspension of Plasmopara viticola spores obtained from a culture 7 days, then suspended at the rate of 100,000 units per cm3.
Contaminated plants are then incubated for two days at 18 C
approximately, in an atmosphere saturated with humidity then for 5 days at 20-22 C
about under 90-100% relative humidity.
Reading is done 7 days after contamination, in comparison with plants witnesses.
Under these conditions, good protection is observed at a dose of 1 g / l (at minus 75%) or total 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 (wheat rust):
An aqueous suspension of the active ingredient is prepared by fine grinding.
test having the following composition:
- active ingredient: 60 mg - Tween 80 surfactant, (polyoxyethylenated derivative of sorbitan oleate) diluted at 10% in water: 0.3 ml - make up to 60 ml of water to obtain a suspension / solution at 1 g / l.
This aqueous suspension is then optionally diluted with water to obtain the desired concentration of active ingredient.
Wheat, in pots, sown on a peat soil 50/50 pozzolan, is treated at 10 cm high 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 / cm3) is sprayed on wheat; this suspension was obtained from plants contaminated. We place then the wheat for 24 hours in an incubation cell at about 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 the 15th day after the contamination, compared to an untreated control.
Under these conditions, good protection is observed at a dose of 1 g / l (at minus 75%) or total 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 which can be used as fungicidal agents, containing as active ingredient (s) one (or more) composed according to formula (I) as described above, mixed with the supports solid or liquids, acceptable in agriculture and also surfactants acceptable in Agriculture. In particular, the inert and usual supports can be used and surfactants usual assets.
These compositions can also contain all kinds of other ingredients such as than, for example, protective colloids, adhesives, thickeners, agents thixotropes, penetration agents, stabilizers, sequestrants, etc ... More generally the compounds used in the invention can be combined with all solid or liquid additives corresponding to the usual techniques of setting formulation.
In general, the compositions according to the invention contain usually from about 0.05 to 95% (by weight) of a compound according to the invention (called thereafter active material), one or more solid or liquid supports and, eventually, one or more surfactants.
By the term "support", in the present description, is meant a material organic or mineral, natural or synthetic, with which the compound is combined to facilitate its application on the plant, on seeds or on the soil. This support is therefore generally inert and must be acceptable in agriculture, especially 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. We can quote by example of polyacrylic acid salts, salts of lignosulfonic acids, salts phenolsulfonic or naphthalenesulfonic acids, polycondensates oxide ethylene on fatty alcohols or on fatty acids or on amines oily, 21949 ~~

substituted phenols (especially alkylphenols or arylphenols), salts esters sulfosuccinic acids, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, esters fatty acids and polyols, sulfate, sulfonate and phosphate derivatives of previous compounds.
The presence of at least one surfactant is generally essential when the compound and / or inert carrier are not soluble in water and the agent vector of the application is water.
Thus, the compositions for agricultural use according to the invention can contain the active ingredients according to the invention within very wide limits, ranging from 0.05% to 95%
(in weight). Their content of surfactant is advantageously understood between 5% and 40 % in weight.
These compositions according to the invention are themselves in fairly various, solid or liquid.
As forms of solid compositions, mention may be made of powders for dusting (with compound content of up to 100%) and granules, in particular those obtained by extrusion, by compaction, by impregnation of a granulated support, through granulation from a powder (the content of compound in these granules being between 0.5 and 80% for the latter cases), effervescent tablets or tablets.
The compounds of formula (I) can also be used in the form of powders for dusting; it is also possible to use a composition comprising 50 g of active ingredient and 950 g of talc; it is also possible to use a composition comprising 20 g of active ingredient, 10 g of finely divided silica and 970 g of talc; we mix and grind these constituents and we apply the mixture by dusting.

As forms of liquid compositions or intended to constitute liquid compositions during application, there may be mentioned the solutions, in especially the water-soluble concentrates, emulsifiable concentrates, emulsions, the concentrated suspensions, aerosols, wettable powders (or spray), pasta, gels.
Emulsifiable or soluble concentrates most often include 10 to 80 % of active ingredient, emulsions or solutions ready for application containing, as for them, 0.001 to 20% of active ingredient.
In addition to the solvent, emulsifiable concentrates may contain when it is necessary, 2 to 20% of suitable additives such as stabilizers, agents surfactants, penetrating agents, corrosion inhibitors, dyes or adhesives previously cited.

From these concentrates, dilution with water can be obtained emulsions of any desired concentration, which are particularly suitable for the application on cultures.
As an example, here is the composition of some emulsifiable concentrates :
Example CE 1:
- active ingredient 400 g / l - alkaline dodecylbenzene sulfonate 24 g / l - oxyethylated nonylphenol with 10 molecules ethylene oxide 16 g / l - cyclohexanone 200 g / l - aromatic solvent qs 1 liter According to another formula of emulsifiable concentrate, the following are used:
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 Concentrated suspensions, also applicable for spraying, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain 10 to 75% active ingredient, 0.5 to 15%
agents surfactants, 0.1 to 10% thixotropic agents, 0 to 10% additives appropriate, such as defoamers, corrosion inhibitors, stabilizers, agents of penetration and adhesives and, as a carrier, water or an organic liquid in which matter active is little or not soluble: certain organic solids or mineral salts can be dissolved in the holder to help prevent sedimentation or as antifreeze for water.

As an example, here is a concentrated suspension composition:
Example SC 1:
- active ingredient 500 g - polyethoxylated tristyrylphenol phosphate 50 g - polyethoxylated alkylphenol 50 g - sodium polycarboxylate 20 g - ethylene glycol 50 g - organopolysiloxane oil (antifoam) 1 g - polysaccharide 1.5 g - water 316.5 g Wettable powders (or spray powder) are usually prepared of so that they contain 20 to 95% of active ingredient, and they contain usually, in addition to the solid support, from 0 to 30% of a wetting agent, from 3 to 20%
a dispersing agent, and, when necessary, 0.1 to 10% of one or several stabilizers and / or other additives, such as penetrating agents, adhesives, or agents anti-caking agents, dyes, etc.
To obtain the spraying powders or wettable powders, mix intimately the active ingredients in the appropriate mixers with the substances additional and it is ground with mills or other suitable grinders. We get over there spray 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 the application on plant leaves.
Instead of wettable powders, pasta can be made. Conditions and methods of making and using this pasta are similar to those of powders wettable or sprayable powders.
As an example, here are various compositions of wettable powders (or powders to spray):

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, C 13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75%
- neutral calcium lignosulfonate (agent dispersant) 12%
- calcium carbonate (inert filler) qs 100%

Example PM 3:
This wettable powder contains the same ingredients as in the example above, in the following proportions:
- active ingredient 75%
- wetting agent 1.50%
- dispersing agent 8%
- calcium carbonate (inert filler) qs 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 surfactants and non-ionic (wetting agent) 2.5%
- sodium lignosulfonate (dispersing agent) 5%
- kaolin clay (inert support) 42.5%

Aqueous dispersions and emulsions, for example the compositions obtained in diluting with water a wettable powder or an emulsifiable concentrate according to the invention are included within the general scope of the present invention.
Emulsions can be water-in-oil or oil-in-water 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 granules dispersible in water also included within the scope of the invention.
These dispersible granules, of apparent density generally between about 0.3 and 0.6 have a particle size generally between about 150 and 2000 and preferably between 300 and 1500 microns.
The active material content of these granules is generally between about 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 two separate types 219491` ~

depending on whether the charge selected is soluble or not in water. When the charge East water-soluble, it can be mineral or, preferably, organic. We have got excellent results with urea. In the case of an insoluble filler, this is mineral preference, like kaolin or bentonite, for example. It is then advantageously accompanied surfactants (2 to 20% by weight of the granule) of which more than half is, for example, consisting of at least one dispersing agent, essentially anionic, such than an alkaline or alkaline earth polynaphthalene sulfonate or a alkali lignosulfonate or alkaline earth, the remainder being non-ionic wetting agents or anionic such than an alkaline or alkaline earth alkyl naphthalene sulfonate.
Furthermore, although it is not essential, we can add others adjuvants such as defoamers.
The granule according to the invention can be prepared by mixing the ingredients necessary then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). We usually end with a crushing followed of a sieving to the particle size chosen within the limits mentioned above above. We can still use granules obtained as above and then impregnated with a composition containing the active ingredient.
Preferably, it is obtained by extrusion, operating as indicated in the examples below.
Example GD 1: Dispersible granules In a mixer, 90% by weight of active material and 10% are mixed.
urea beads. The mixture is then ground in a pin mill. We get a powder which is moistened with about 8% by weight of water. Wet powder is extruded in a perforated roller extruder. We obtain a granule which is dried, then crushed and sieved, so as to keep respectively only the granules of a dimension included 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 from in order to obtain the dose sought. They can also be used for prepare combinations with other active ingredients, especially fungicides, these last being under the form of wettable powders, or aqueous granules or suspensions.
With regard to the compositions suitable for storage and transport, they more advantageously contain from 0.5 to 95% (by weight) of active substance.

Claims (16)

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

(I) in which:
X1, X2, X3, X4 and X5, identical or different, are:
- a hydrogen or halogen atom, a hydroxy, mercapto, cyano group, thiocyanato, nitro, nitroso, amino optionally substituted by one or two alkyls or phenyls, - an alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl, alkylsulfonyl radical alkylthioalkyl alkylsulfinylalkyl, alkylsulfonylalkyl, benzyl, alkenyl, alkynyl, cyanoalkyl, alkoxy, alkenoxy, alkylthio, alkylsulfinyl, alkylsulfonyl, formyl, acetyl, alkyl- or alkoxy(thio)carbonyl, 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 - an alkyl- or alkoxy- or mono or di alkylamino- phenyl-sulfenyl radical or sulfinyl or sulfonyl, - a sulphonic group, its salts, esters and derived amides, - a phosphoryl group, substituted by two groups chosen from the group including alkyl, alkoxy, alkylthio and dialkylamino, benzyloxy, phenyloxy or phenyl, - a trialkyl- or alkylphenyl-silyl group, two of adjacent X1, X2, X3, X4 and X5 can also form a bridge comprising from 2 to 4 links, at least one of which may be replaced by a un atom of oxygen, sulfur or nitrogen, and which may 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 possibly be where unsubstituted by at least one halogen atom and/or at least one group hydroxy, amino, alkyl, alkoxy alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl or alkoxycarbonyl, the alkyl part being as defined below, provided that X1 to X5 cannot each be an atom hydrogen;
Y is hydrogen, halogen, nitro, cyano, hydroxy, alkylcarbonyloxy, alkoxycarbonyloxy, aminocarbonyloxy, mercapto, carboxyl, carboxylate, formyl, alkyl(thio)carbonyl, arylcarbonyl, alkoxy(thio)carbonyl, carbamoyl, 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 X1 or X5 which can also form a bridge comprising 1 to 3 links, which may contain one or more of the following atoms or groups C, O, S, N, C=O, C=S, SO, SO2, CH=CH, the carbons of this bridge possibly being substituted or not by at minus one halogen atom and/or at least one hydroxy, alkoxy, alkylthio, mono or said alkylamino, alkylsulfinyl or -sulfonyl, the alkyl part being such that defined below, Z is:
- a hydrogen, halogen, cyano or nitro group, hydroxy or - alkyl, haloalkyl, hydroxyalkyl, formyloxylalkyl, alkyl- or aryl(thio)carbonyloxyalkyl, alkoxy(thio)carbonyloxyalkyl, amino(thio)carbonyloxyalkyl, mono or dialkylamino(thio)-carbonyloxyalkyl, cycloalkyl or cycloalkyl -alkyl, the cycloalkyl part which may be substituted by the group GR4, defined below, - alkoxy optionally substituted by a hydroxy, an alkoxy, an 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 from 3 to 7 atoms of carbon, optionally substituted - phenyl or Het, optionally substituted - a group of formula C(=Z1)Z2 in which:
- Z1 is an oxygen or sulfur atom or a group alkylamino or alkylimino or arylamino or arylimino and - Z2 is:
- a hydrogen or halogen atom, a group hydroxy, mercapto, cyano, amino, - alkyl, alkoxy, haloalkoxy, alkylthio, - alkenyl or alkynyl or alkenyloxy, each containing 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, or alkyl- or arylsulphonylamino, - a phosphoryl group substituted by two chosen radicals 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(=Z1)(=Z3)Z2, in which Z1 and Z2 have the same meanings as above and Z3 has the same meanings as without must be equal to Z1, as well as the tautomeric forms of formula I bis, when Z is an atom hydrogen or isomers when Z is a group of formula C(=Z1)Z2. or S(=Z1)(=Z3)Z2, as well as the salts of hydracid or of perchloric or nitric acid or sulfuric or alkyl- or phenyl (optionally substituted) sulfonic acids of the derivatives deformulas I
or I bis and their metal complexes, and their N-oxides, it being understood that in all the above meanings, - the linear hydrocarbon part of these groups can comprise from 1 to 7 carbon atoms and possibly be halogenated (from 1 to 8 atoms halogen), - the cycloalkyl part of these groups can comprise from 3 to 7 atoms of carbon and optionally be substituted by at least one substituent chosen from the group GR4 defined below, - the phenyl part denotes the optionally substituted phenyl ring by 1 to 5 substituents selected from the group comprising an atom halogen, an alkyl or alkoxy with 1 to 3 carbon atoms and nitro, - Het is a heterocyclic radical, mono or bicyclic, containing 5 to 10 atoms, of which 4 are heteroatoms (oxygen, sulphur, nitrogen, phosphorus);.
-the GR4 group includes:
- a halogen atom, or a cyano, nitro, mono or dialkylamino, - an alkyl, alkoxy, alkylsulfenyl, alkylsulfonyl, alkycarbonyl, alkylthiocarbonyl, alkoxycarbonyl, alkoxythiocarbonyl, mono- or dialkylaminocarbonyl or mono- or dialkylaminothiocarbonyl, mono or dialkylaminosulfonyl, (the alkyl part of all these substituents containing therefrom 4 carbon atoms and which may be 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 one of claims 1 and 2, characterized in that that, in the formula I, Z is a hydrogen atom or a group C(=Z1)Z2, in which Z1 is a oxygen or sulfur atom. 4. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, X1, X2 and X4 are a hydrogen or halogen atom or a group nitro, amino or alkyl, optionally halogenated, of 1 to 4 carbon atoms. 5. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, X3 is hydrogen or fluorine. 6. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, X1 and/or X5 are a hydrogen atom. 7. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, two adjacent substituents selected from X1, X2, X3, X4 and X5 form a bridge comprising 3 or 4 members, in particular a methylenedioxi bridge eventually halogenated and preferably fluorinated. 8. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, X1, X3 and X5 are a hydrogen atom and X2, X4 are each a atom of chlorine. 9. Compositions according to one of claims 1 to 3, characterized in that, in the formula I, X1 is nitro, X2, X4 are each chlorine atom X3 is chlorine atom fluorine and X5 is a hydrogen atom. 10. Compositions according to claim 7, characterized in that, in the formula I, X1 is a fluorine atom, X2, X4 are each a chlorine atom X3 is a atom of fluorine, X3 and X5 are hydrogen. 11. Process for processing plant propagating material against the fungal diseases, characterized in that a composition according to one of claims 1 to 8. 12. New compounds of the family of 3-phenyl-pyrazoles, characterized in what they are chosen from the group of formula I:

in which:
Y is a chlorine atom and Z is a hydrogen atom, X1 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 the formula I:
X2 is chlorine or bromine;
X3 and X5, identical or different, are each a hydrogen or fluorine. 14. Derivatives according to claim 12, chosen from the group comprising derivatives of formula I, in which:
X1= H; X2 = CH3; X3=F; X4= CH3; and X5= H
X1= NO2; X2= Cl; X3=F; X4 = Cl; and X5= H
X1= NH2; X2= Cl; X3= F; X4 = Cl; and X5= H
X1= F; X2= Cl; X3= F; X4 = Cl; and X5= F
X1= H; X2= Cl; X3= H; X4=F; and X5= H;
X1= F; X2= Cl; X3= H; X4 = Cl; and X5= H
X1= F; X2= Br; X3= H; X4= Br; and X5= H

X1= CH3; X2= NO2; X3= H; X4=F; and X5=H;
X1= F; X2= Cl; X3=F; X4 = Cl; and X5=H;
X1= F; X2= Cl; X3= H; X1= F; X2= Cl; X3= H;
X1= H; X2= Cl; X3=F; X4 = Cl; and X5= H 15. Compositions for foliar treatment of plants against diseases fungal, characterized in that they contain, as active ingredient, at least one derivative 3-phenylpyrazole according to one of claims 11 to 13. 16. Process for the foliar treatment of plants against diseases fungal, characterized in that at least one 3- derivative is used as active ingredient phenylpyrazole according to one of claims 11 to 13.