FR2707295A1 - Pyrazole fungicides substituted at position 3 by a heterocycle. - Google Patents

Abstract

1) Pyrazoles substituted in position 3 by a heterocycle. 2) They are of formula: (CF DRAWING IN BOPI) with Het: heterocycle which can be substituted Y1, Y2: H, hal, nitro, CN, alkyl, alkoxy, acyl, Z: H, nitro, CN, (halo) alkyl , alkylS (O) n with n = 1 or 2, aminoalkyl evt substituted, acyl, aminocarbonyl alkoxycarbonyl. 3) Fungicides for agriculture.

Description

Pyrazole fungicides substituted at position 3 by a heterocycle

  The present invention relates to novel derivatives of the pyrazole family substituted in the 3-position by a heterocycle, their methods of preparation, the compositions containing them and their use for the protection of plants against

fungal diseases.

  More specifically, the invention relates to pyrazole derivatives of formula I and their tautomeric forms Ia, Het k Hety1 NN Y2 Z fN-N Y2 N2I their salts and their metal or metalloid complexes as well as the N- corresponding oxides, in which: Y1 and Y2, which may be different or identical, are: - a hydrogen or halogen atom, a hydroxy, mercapto, nitro, cyano, thiocyanato group, - an alkyl, alkenyl or alkynyl group alkoxy or alkylthio, each of these groups optionally being halogenated, - an acyl or thio acyl radical which may be: a formyl radical, an alkyl or alkenyl carbonyl or thiocarbonyl group, the alkyl or alkenyl radical may be linear or branched - an alkoxy- or alkylthiocarbonyl group - an optionally substituted phenoxy, - an amino substituted or not by one or two alkyls or phenyls, - an alkylsulfinyl or alkylsulfonyl group, it being understood that the alkyl part of all the groups above comprises from 1 to 4 carbon atoms; Z is: -a) - a hydrogen atom, a nitro, amino, hydroxy, cyano, alkyl or haloalkyl group, I

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  b) - an alkyl- or haloalkyl- or cycloalkyl-thio, -sulfinyl group or -

  sulfonyl, alkoxy- or haloalkoxy-sulphonyl, alkenyl- or alkynylsulphonyl, phenyl- or benzyl-sulphenyl or sulphonyl, -c) - an aminomethylene group in which the amino radical may be substituted by one or two identical or different groups which are: an alkyl group optionally substituted with a substituent cyano, nitro,

  alkoxy, cycloalkyl, alkyl- or alkoxy- or monoalkylamino-

  or dialkylamino-carbonyl, alkylthio, alkylsulfonyl, an optionally substituted phenyl ring or an optionally substituted heterocyclic group, an alkenyl or alkynyl group, an optionally substituted phenyl group

  an optionally substituted heterocyclic radical.

  When the amino group is disubstituted, the two substituents can

  constitute a nitrogen heterocycle comprising 5 or 6 atoms.

  -d) - a linear or branched alkyl radical substituted with: one or more halogen atoms,

  a cyano, nitro, alkyl- or alkoxy- or monoalkylamino group;

  or dialkylamino-carbonyl, dialkoxy- or dibenzyloxy- or diphenoxyphosphono, trialkylsilyl, phenyl- one or two alkoxy, alkenoxy, alkynoxy, phenoxy or benzyloxy radicals, which can, when they are two, form a 5- or 6-membered heterocycle of which 2 oxygen,

  an alkyl- or alkenyl- or alkynyl- or phenyl- or benzyl-

  thio which can, when they are two, form a heterocycle with 5 or 6 atoms, of which 2 is sulfur,

  an alkyl- or alkenyl- or alkynyl- or phenyl- or benzyl-

  sulfonyl or -sulfinyl, - hydroxy, acyloxy, alkoxycarbonyloxy, - e) - an acyl or thio acyl radical which may be: - a formyl radical - an alkyl- or alkenyl-carbonyl or -thiocarbonyl group, the alkyl or alkenyl radical which may be linear or branched and substituted by one or more halogen atoms, a cyano, nitro, alkoxy, cycloalkyl, alkyl- or alkoxy- or monoalkylamino- or dialkylamino-carbonyl, alkylthio group,

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  alkylsulfonyl, dialkyl-, alkylphenyl- or alkylbenzylamino, optionally substituted phenyl or an optionally substituted heterocyclic radical, - an alkynylcarbonyl group, - an optionally substituted benzoyl or thio benzoyl radical, - a picolinyl, nicotinyl, isonicotinyl, furoyl or thenoyl radical. substituted, -f) - an aminocarbonyl or aminothiocarbonyl group substituted with two identical or different radicals which may be: a hydrogen atom, an optionally substituted alkyl, cycloalkyl, alkenyl, alkynyl group, an optionally substituted phenyl or benzyl group, - g) - an alkoxy- or alkylthio-, cycloalkoxy- or cycloalkylthio- group,

  alkenoxy-, alkynoxy-, phenoxy- or phenylthio-, benzyloxy- or benzylthio-

  heterocyclyloxycarbonyl, the hydrocarbon radicals may be substituted, it being understood that in all of the foregoing: - an alkyl group has 1 to 4 carbon atoms and that, unless otherwise indicated, it may be substituted by one or more atoms

  halogen, cyano, nitro, alkoxy, cycloalkyl, alkyl- or alkoxy-

  or monoalkylamino- or dialkylamino-carbonyl, benzoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, phenylsulfinyl, phenylsulfonyl, trialkylsilyl, - the phenyl ring of the aromatic substituents may be substituted with 1 to 5 substituents selected from the group consisting of halogens, nitro groups, cyano, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, alkoxycarbonyl, alkylsulfinyl, alkylsulfonyl radicals, the alkyl part of these substituents having from 1 to 4 carbon atoms and that the aromatic heterocyclic rings may comprise from 1 to 4

  substituents, depending on the heterocycles, chosen from the same group.

  Het is an unsaturated or unsaturated heterocyclic radical, mono- or bi-cyclic comprising 5 to 10 atoms comprising from 1 to 4 heteroatoms which may be an oxygen or sulfur atom and / or one to three nitrogen atoms, such as furan nucleus, thiophene nucleus, pyrrole ring, oxazole, thiazole, isoxazole and isothiazole rings, imidazole, pyrazole, 1,2,3-triazole or 1,2,4-triazole, pyridine ring, pyridazine rings, pyrimidine, pyrazine, 1,3,5-triazine and 1,2,4-triazine, as well as heterocyclic rings fused with a benzene ring such as

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  benzofuran, benzothiophene, indole, quinoline and isoquinoline as well as N-oxide derivatives of heterocycles having at least one nitrogen atom; this heterocycle being connected to the pyrazole ring by any of its atoms and which may be substituted by one or more radicals, which may be identical or different, which are: a halogen atom, a hydroxyl, mercapto, cyano, thiocyanato or nitro group; , nitroso, amino optionally substituted by one or two alkyls or phenyls or acyls, imines, enamines and amidines derived from this amino group, an alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, arylalkyl radical such as benzyl, alkenyl, haloalkenyl, alkynyl, cyanoalkyl alkoxy, haloalkoxy, alkenoxy, halo, alkenoxy, alkynoxy, formyl, acetyl, alkyl- or alkoxy- or alkylthio-carbonyl, mono or dialkylamino (thio) carbonyl, mono or diarylamino or alkylarylanmino (thio) carbonyl, carboxyl, carbamoyl or benzoyl optionally substituted, - a phenyl, phenoxy or phenylthio, benzyloxy or benzylthio radical which may also be substituted,

  an alkyl-, alkoxy-, mono- or dialkylamino-, phenyl-

  sulfenyl or sulfinyl or sulphonyl; acyloxy, carbamoyloxy, alkyl- or phenyl-sulphonyloxy or sulphamoyloxy; it being understood that, in all the radicals mentioned above, the alkyl part may be linear or branched and preferably has 1 to 4 carbon atoms, the halogenated alkyl groups may comprise one or more identical or different halogen atoms and the phenyl radicals may be substituted by a halogen atom, a methyl, methoxy, methylthio or trifluoromethyl radical,

  trifluoromethoxy, a nitro group, cyano or methylsulfonyl.

  Preferred compounds are those in formulas I and Ia of which Het is a furan, thiophene, pyridine or pyrimidine ring which may be substituted by one or more radicals, which may be identical or different, which may be: a methyl, allyl or propargyl radical methoxy, methylthio, trifluoromethyl, trifluoromethoxy, nitro, cyano, amino, mono or dimethylamino, acetoxy, carbomethoxy, methylsulfmyl, methylsulfonyl, mono or dimethylaminosulfonyl, phenoxy, phenylthio or benzyloxy optionally substituted on the phenyl ring by an atom

  halogen, a methyl, methoxy, trifluoromethyl or a nitro group.

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  The compounds in Formulas I and IB are particularly preferred.

  of which Het is a thiophene ring.

  Other preferred compounds are those in formulas I and Ia of which Y1 and Y2, which may be identical or different, are a hydrogen or halogen atom or a cyano group. Other preferred compounds are those in formulas I and Ia of which Z is hydrogen, acyl or substituted methyleneamino or alkylcarbonyloxyalkylene. The derivatives of formulas I and Ia, in which Z is different from hydrogen, may be prepared according to a process characterized in that it is reacted on compounds of formulas II and II bis HetY He. 1 Het Y

N Y2

I 2H N Y2

  In which Het, Y1 and Y2 have the same meanings as in formula I, with an acylating agent as described in the compilations "Comprehensive Heterocyclic Chemistry", A.R. Katritzky and C.W.Rees 1984, Vol.5, pp. 222-236, Pergamon Press and in "The chemistry of heterocyclic compounds", L.C. Behr,

  R.Fusco and C.H.Jardoe, 1967, pp. 137-140, J.Wiley & sons.

  By acylating agent is meant a compound of formula Z T in which Z is defined as above and T is selected from the group consisting of a halogen atom, a hydroxyl group, alkoxy, alkylthio, amino, mono- or dialkylamino, the

  alkyl part of these groups containing from 1 to 4 carbon atoms.

  According to another first process for the preparation of compounds of formula I, in which Z is Z (d) or Z (f), an aldedyhe or a ketone is reacted in the presence of a primary or secondary substance with a pyrazole of formula II. at a temperature between ambient and reflux point, in a solvent medium, optionally in

  presence of a catalytic amount of strong acid.

  As an example of a solvent medium, it is generally possible to use a solvent, or a mixture of solvents, an aromatic chosen from the group comprising toluene and xylene, or a solvent or a mixture of solvents, aprotic chosen from the group comprising diethyl ether. , tetrahydrofuran, acetone, acetonitrile or a

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  solvent, or a mixture of solvents, polar protic selected from the group consisting of

  water, methanol, ethanol, isopropanol and acetic acid.

  As an example of a strong acid, it is possible to use acetic acid and para-

  toluene. The compounds of formulas II or IIa in which Y1 is a halogen atom can be prepared, in a manner known per se, in the compilations "Comprehensive Heterocyclic Chemistry" AR Katritzky and CWRees 1984, Vol.5, pages 239 to 241. and 263 Pergammon Press; Advancies in Heterocyclic Chemistry, AN Kost and LI .. Grandberg, 1966, Vol 6, 391-396, Aceademic Press and "The Chemistry of Heterocyclic Compounds", LC Behr, R. Fusco and CHJardoe, 1967, pp. 91 and Table 41, J.Wiley & sons by halogenation of compounds of formula IIm in which Het has the same meaning as in formulas I and Ia: Het

N [III

  NH The chlorination of these compounds can be carried out using different reagents: chlorine in aqueous medium or organic preference, in a chlorinated solvent such as dichloromethane or preferably in a lower carboxylic acid, such as the acid at room temperature, the reactants being in a molar ratio close to the stichiometry. an N-chloroimide such as N-chlorosuccinimide in an inert solvent such as dichloromethane, 1,2-dichloroethane or tetrahydrofuran at a temperature ranging from 0 ° C. to 80 ° C. and preferably between 20 ° C. and 50 ° C., the reactants being

  in a molar ratio close to stoichiometry.

  sulphuryl chloride in a solvent such as dichloromethane or

  chloroform at a temperature between 0 C and 30 C.

  The bromination may be carried out by: - bromine in a solvent which may be water or nitric acid but more preferably an organic solvent such as chloroform, dichloromethane or a lower carboxylic acid such as acetic acid in the presence or no of a base

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  as sodium acetate, at a temperature between 0 C and 1000C and

  preferably at room temperature.

  When the molar ratio is close to stoichiometry, the bromination takes place mainly in position 4 of the pyrazole ring (Y1 = Br). When the molar ratio is greater than the stoichiometry and preferably equal to or greater than 2 times the

  stichiometry, there is also bromination at the 5-position of the pyrazole ring (Y1 = Y2 = Br).

  The compounds of formula III may be prepared, in a manner known per se, by reaction of hydrazine, preferably in the form of its hydrate, with a compound of formula IV, Het W O. in which Het has the same meaning as in formulas I and Ia and W is a halogen atom or a hydroxyl, alkoxy, alkylthio or dialkylamino radical, at a temperature ranging from 20 ° C. to 110 ° C. and preferably between 50 ° C. and C °, in an organic solvent which is advantageously an alcohol such as ethanol or a water-alcohol mixture or a lower carboxylic acid such as acetic acid, in the presence or absence of an organic or inorganic acid catalyst. The molar ratio of hydrazine to the compound of formula IV can be between 1 and 2.5

  and preferably of the order of 1.2.

  The compounds of formula IV may be advantageously prepared, in a manner known per se, by reaction of heterocyclic methylketones of formula V: Het-C (= O) -CH3 in which Het has the same meaning as in formulas I and I bis, with an amide acetal, an ester amine or a orthoamide formiques, preferably the dialkylacétal of a dialkylformamide such as dimethyl- or diethyl-acetal dimethylformamide, in very clear excess, that is to say say 2 to 5 times the stichiometry, in an inert solvent such as toluene or xylene or without solvent, at a temperature ranging from 20 C to 150 C and preferably between 70 C and 140 C, for periods of

between 1 hour and 48 hours.

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  The following examples are given to illustrate the preparation and properties

  fungicides of the compounds according to the invention.

  EXAMPLE 1 Preparation of 3- (2,5-dichloro-3-thienyl) -4-chloropyramidole (Compound No. 1) (Formula) 3.20 g (0.024 mol) of toluene are added at room temperature with vigorous stirring.

  N-chlorosuccinimide to a suspension of 5.00 g (0.0228 moles) of 3- (2,5-dichloro-3-

  thienyl) pyrazole in 110 ml of dry dichloromethane. After 4 hours of stirring, there is complete dissolution, giving a clear yellow liquid. After stirring for 2 hours, the reaction medium is washed with water (50 ml), decanted, dried over anhydrous magnesium sulphate and the solvent evaporated. 6.63 g of beige crystalline solid which is recrystallized in 150 ml of cyclohexane yielding 4.62 g of

  white crystals melting at 121 ° C. (yield = 80%).

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  Similarly, from the correctly substituted pyrazoles, with N-chloro- or N-bromo-succinimide, the compounds of formula II are obtained, as shown in the following table. Compound Het Y1 Y2 Yield FC no (%) 2 2 -thienyl C1 H 34 128 3 5-chloro-2-thienyl C1 H 61 114 4 3-thienyl C1 H 52 123 5-methyl-2-thienyl C1 H 55 85 6 5-chloro-2-thienyl C1 H 63 145 7 2-pyridyl C1 H 75 163 8 3-pyridyl C1 H 72 142 9 4-pyridyl C1 H11135 5-methyl-3-pyridyl C1 H115 119 il 3,4,5-trichloro-2- C1 H55 175 thienyl 12 5-methyl-3-pyridyl Br H 76 116 13 3,5-dimethyl-3-br H 84 131 pyridyl 4-methyl-2-pyridyl Br H 57 147 21 4-methyl-2-pyridyl C1 H 56 156 22 2-methyl-3-pyridyl Br H 63 116 23 2-methyl-3-pyridyl C1 H 58 116 24 2-pyridyl-1-oxide C1 H 60 172 4,6-dimethyl-2-C1 H 29 112 pyridyl 26 2 -Thiazolyl CI H 57 187 27 2-Thiazolyl Br H 58 182 28 3,4-dichlorothienyl C H 64 132 Example 2 Bromination of 3- (3-pyridyl) pyrazole

  4.38 g (0.0246 mole) of N was added at room temperature with stirring.

  bromosuccinimide to a suspension of 3.0 g (0.0205 moles) of 3- (3-pyridyl) pyrazole.

  There is immediate dissolution. After stirring overnight at ambient temperature, the reaction medium is washed three times with 100 ml of water each time, dried over sodium sulfate

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  anhydrous magnesium and evaporated. 3.85 g of brown solid are obtained. Thin-layer chromatography reveals that this solid is a mixture of 2 constituents which are then separated by chromatography on silica gel with elution

  using a mixture of ethyl acetate and dichloromethane 65% of the second.

  S 2.85 g of 3- (3-pyridyl) -4-bromopyrazole (compound 14) (formula II) are obtained,

  melting cream powder at 145 ° C. (yield = 56%) and 0.79 g of 3- (3-pyridyl) -4,5-

  dibromopyrazole (compound 15) (Formula 11), beige powder melting at 145 ° C.

(yield = 13%).

  In the same way, with N-bromo-succinimide or excess chlorine gas, the compounds of formula II are obtained. Compound Het Y1 Y2 Yield FC n (%) 16 2-pyridyl Br Br 3,215 17 2-pyridyl Br H 55 205 18 4-pyridyl Br Br 11 223 19 4-pyridyl Br H 50 147 29 6-Methyl-2-pyridyl Br H 58 116 6-Methyl-2-pyridyl Br Br 54 160 31 6-Methyl-2-pyridyl C1 EXAMPLE 3 Preparation of 3- (3-Chloro-2-thienyl) pvrazole (Formula III) (Compound 100n) The mixture is stirred for 3 hours at a temperature of 30.degree. between 55 C and 60 C, a

  solution of 7.55 g (0.035 mole) of 1- (3-chloro-2-thienyl) -3-dimethylamino-2-propene

  1-one and 2.00 g (0.040 mole) of hydrazine hydrate in 75 ml of 95% ethanol.

  The reaction medium is then evaporated to dryness, giving a whitish solid which is recrystallized from 100 ml of cyclohexane. We obtain: 6,03 g of melting beige crystals

at 110 C (yield = 93%).

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  In the same way, from the corresponding dimethylaminopropenones, the compounds of formula II are obtained. Compound n Het Yield FC (%) 101 2-thienyl 94 98 102 3-thienyl 83 112 103 3-Methyl-2-thienyl 87 80 104 5 2-methyl-2-thienyl 96 126 5-chloro-2-thienyl 86 167 106 2,5-dichloro-3-thienyl 71 147 107 2-pyridyl 90 119 108 3 -pyridyl 93 NMR 109 4-pyridyl 88 152 5-methyl 3-pyridyl 69 123 111 3,5-Dimethyl-2-pyridyl 82 80 123 2-methyl-3-pyridyl 88 86 124 3-pyrazolyl 652 Example 4: Preparation of 1- (4,6-dimethyl-2-pyridyl) 3-dimethylamino-2-propen-1-one (compound 112) (formula IV) A mixture of 5.10 g (0.035 mole) of 2-acetyl-4 is heated in an oil bath at 120 ° C. for 9 hours. 6 dimethylpyridine and 8.31 g (0.070 mole) of dimethylformamide dimethylacetal. Then 4.16 g (0.035 mol) of the last reactant is added and the mixture is heated again for 5 hours. The reaction medium is then evaporated to dryness, giving 7.19 g of an orange honey which crystallizes on cooling. It is recrystallized from 15 ml of isopropyl ether and there are obtained: 5.90 g of bright yellow crystals melting at 84 ° C. (yield = 83%). In the same way, from the appropriate acetylated heterocycles, the following compounds are prepared: formula IV with W = N (CH3) 2 Compound H and Yield FC n (%) 113 2-thienyl 77 114 114 3-thienyl 56 94 3-Chloro-2-thienyl 79 93

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  3-Methyl-2-thienyl 35 56 117-Methyl-2-thienyl 45 122 118 5-chloro-2-thienyl 83 119 119 2,5-Dichloro-3-thienyl 74 98 2 -pyridyl 84 121 121 3- EXAMPLE 5 In Vivo Test Alternaria Brassicae on Radish An aqueous suspension, of concentration 1 g / l, of the active substance tested is obtained by milling 60 mg of this in the following mixture. : -acetone: 5 ml - surfactant (TWEEN 80, polyoxyethylene sorbitan derivative oleate) diluted to%: 0.3 ml

  then the volume is adjusted to 60 ml with water.

  This aqueous suspension is then diluted with water to obtain the concentration

desired in active matter.

  Radish plants (Pernot variety), sown on a peat / pozzolan / 50 soil peat substrate and grown in the greenhouse, are treated at the cotyledon stage by spraying the plant.

  active ingredient suspension described above.

  Plants, used as controls, are treated by spraying a solution

  aqueous solution that does not contain the active ingredient.

  24 hours after treatment, the plants are contaminated by spraying a solution

  aqueous spore (40000 sp / ml) harvested from a crop aged 13 days.

  After contamination, the plants are placed at 18-20 C in an atmosphere saturated with moisture. The notation, in comparison with the control plants, is carried out 6 days

after contamination.

  Under these conditions, at the dose of 1 g / l, a good protection (at least ...)

  or total with the compounds 3, 5, 6, 10, 11, 17, 18.

  EXAMPLE 6 In Vivo Test on Pyricularia Orvzae Responsible for Rice Piriculariasis: Fine grinding is used to prepare an aqueous suspension of the active ingredient to be tested, having the following composition: active ingredient: 60 mg

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

- complete with 60 ml of water.

  This aqueous suspension is then diluted with water to obtain the desired concentration of active material. Rice, sowed in buckets in a 50/50 mixture of enriched peat and pozzolan, is treated at the stage 10 cm high by spraying the suspension

aqueous above.

  After 24 hours, an aqueous suspension of Pyricularia oryzae spores, obtained from a culture of 15 days, is applied to the leaves.

  in suspension at a rate of 100,000 units per cm3.

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

during 5 days.

  The reading is done 6 days after the contamination.

  Under these conditions, at a dose of 1 g / l, a good (at least 75%) or total protection is observed with the following compounds: 1, 3, 6, 8, 11, 13, 20, 21, 25, EXAMPLE 7 In Vivo Test on Plasmopara Viticola: 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, polyoxyethylene sorbitan derivative oleate ) diluted to 10% in water: 0.3 ml

- complete with 60 ml of water.

  This aqueous suspension is then diluted with water to obtain the

  desired concentration of active ingredient.

  Vine cuttings (Vitis vinifera), variety Chardonnay, are grown in buckets. When these plants are 2 months old (stage 8 to 10 leaves, height

  10 to 15 cm), they are sprayed with the aqueous suspension described 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 with an aqueous suspension of Plasmopara viticola spores obtained from a 7-day culture, then suspended at a rate of 100,000 units.

by cm3.

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  The infected plants are then incubated for two days at about 18 ° C, in a saturated atmosphere of moisture and then for 5 days at 20 ° C to 22 ° C.

  about 90-100% relative humidity.

  The reading is done 7 days after the contamination, in comparison with the control plants. Under these conditions, at a dose of 1 g / l, a good (at least 75%) or total protection is observed with the following compounds: 3 to 6, 10 to 13, 18, 20, 25, 27, 30, 31. These results clearly show the good fungicidal properties of the derivatives according to the invention against fungal diseases of plants due to fungi belonging to the most diverse families such as Phycomycetes, Basidiomycetes, Ascomycetes, Adelomycetes or fungi imperfecti, in

  especially the Alternaria sp., Pyricularia oryzae, the downy mildew of the vine.

  For their practical use, the compounds according to the invention are rarely used alone. Most often these compounds are part of compositions. These compositions, which can be used as fungicidal agents, contain as active ingredient at least one compound according to the invention as described above in admixture with solid or liquid carriers, which are acceptable in agriculture and surfactants which are also acceptable in agriculture. In particular, the usual inert carriers and surfactants are usable. These compositions also make

part of the invention.

  These compositions may also contain any other kind of ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestering agents, etc. More generally the compounds used in the invention can be combined with all solid or liquid additives corresponding to the usual techniques of formulation. In general, the compositions according to the invention usually contain from about 0.05 to about 95% (by weight) of a compound according to the invention (hereinafter referred to as active ingredient), one or more solid or liquid carriers. and,

  optionally, one or more surfactants.

  By the term "carrier" in the present specification is meant an organic or inorganic material, natural or synthetic, with which the compound is combined to facilitate its application on the plant, on seeds or on the ground. 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,

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  silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, especially

butanol etc ...).

  The surfactant may be an emulsifier, dispersant or wetting agent of ionic or nonionic type or a mixture of such surfactants. There may be mentioned, for example, salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulphonic or naphthalenesulphonic acids, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines. substituted phenols (especially alkylphenols or arylphenols), salts of sulfosuccinic acid esters, taurine derivatives (especially alkyltaurates), phosphoric esters of polyoxyethylated alcohols or phenols, acid esters and polyols, sulfates, sulfonates and phosphates-based derivatives of the foregoing compounds. The presence of at least one surfactant is generally indispensable when the compound and / or the inert carrier are not soluble in water

  and that the application vector agent is water.

  Thus, the compositions for agricultural use according to the invention may contain the active ingredients according to the invention in very wide limits, ranging from 0.05% to 95% (by weight). Their content of surfactant is advantageously included

between 5% and 40% by 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 dusting powders (with a compound content of up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation with from a powder (the content of compound in these granules being between 0.5 and 80% for the latter cases), tablets or effervescent tablets. The compounds of formula (I) can still be used in the form of dusting powders; a composition comprising 50 g of active material and 950 g of talc can also be used; a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc can also be used; we mix and

  grind these constituents and apply the mixture by dusting.

  As forms of compositions which are liquid 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 and powders. wettable

spray), pasta, gels.

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  The emulsifiable or soluble concentrates most often comprise 10% of active material, the emulsions or solutions ready for application containing,

  as for them, 0.001 to 20% of active ingredient.

  In addition to the solvent, the emulsifiable concentrates may contain, when necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes or

adhesives previously mentioned.

  To perfume these concentrates, it is possible to obtain, by dilution with water, emulsions of any desired concentration, which are particularly suitable for

application on crops.

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

Example CE 1:

  active ingredient 400 g / l - alkaline dodecylbenzene sulfonate 24 g / ll nonylphenol oxyethylated with 10 molecules of ethylene oxide 16 g / l cyclohexanone 200 g / l - aromatic solvent qsp1 liter According to another formula of emulsifiable concentrate, uses:

Example CE 2

  active ingredient 250 g - epoxidized vegetable oil 25 g - mixture of alkylaryl sulphonate and polyglycol ether and fatty alcohols 100 g dimethylformamide 50 g - xylene 575 g The concentrated suspensions, also applicable in spraying, are prepared from in order to obtain a stable fluid product which does not deposit and usually contains from 10 to 75% of active substance, from 0.5 to 15% of surfactants, from 0.1 to 10% of thixotropic agents, from 0 to to 10% of suitable additives, such as antifoams, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as a carrier, water or an organic liquid in which the active ingredient is little or no not soluble: some organic solids

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  or mineral salts can be dissolved in the carrier to help prevent the

  sedimentation or as antifreezes for water.

  By way of 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 in such a way that they contain 20 to 95% active ingredient, and usually contain, in addition to the solid carrier, from 0 to 30% of a wetting agent, from 3 to 20% of a dispersing agent, and, when necessary, from 0.1 to 10% of one or more stabilizers and / or other additives, such as penetration agents,

  adhesives, or anti-caking agents, dyes, etc.

  In order to obtain the spraying powders or wettable powders, the active ingredients in the appropriate mixers are intimately mixed with the additional substances and milled with suitable mills or other mills. Spray powders are thus obtained, the wettability and suspension of which are advantageous; they can be suspended with water at any desired concentration and these suspensions can be used very advantageously, particularly for

  the application on the leaves of the plants.

  In place of the wettable powders, pasta can be made. The terms and conditions for the production and use of these pastas are similar to those of

  wettable powders or powders for spraying.

  By way of example, here are various compositions of wettable powders (or powders for spraying):

Example PM 1

  - active ingredient 50% - ethoxylated fatty alcohol (wetting agent) 2.5% ethoxylated phenylethylphenol (dispersing agent) 5% - chalk (inert carrier) 42, 5%

18 2707295

Example PM 2:

  active ingredient 10% - oxo synthetic alcohol of branched type, C13 ethoxylated with 8 to 10 ethylene oxide (wetting agent) 0.75% neutral calcium lignosulfonate (dispersing agent) 12% - calcium carbonate (inert filler) qs 100%

Example PM 3:

  This wettable powder contains the same ingredients as in the preceding example, in the following proportions: active ingredient 75% wetting agent 1.50% dispersing agent 8% calcium carbonate (inert filler) q.s. 100%

Example PM 4:

  active substance 90% - ethoxylated fatty alcohol (wetting agent) 4% ethoxylated phenylethylphenol (dispersing agent) 6%

Example PM 5:

  active substance 50% - mixture of anionic and nonionic surfactants (wetting agent) 2.5% - sodium lignosulfonate (dispersing agent) 5% - kaolinic clay (inert carrier) 42.5% 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 may be of the water-in-oil or oil-in-water type and

  they can have a thick consistency like that of a "mayonnaise".

19 2707295

  The compounds according to the invention can be formulated in the form of

  dispersible granules in water also included in the scope of the invention.

  These dispersible granules, having an apparent density generally of between approximately 0.3 and 0.6, have a particle size generally of between approximately 150 and 2000 and preferably between 300 and 1500 microns. The active ingredient 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 adjuvants conferring on the granule properties of dispersibility in water. These granules can be essentially of two distinct types depending on whether the charge retained is soluble or not in water. When the filler is water soluble, it may be inorganic or, preferably, organic. Excellent results have been obtained with urea. In the case of an insoluble filler, it is preferably mineral, such as kaolin or bentonite. It is then advantageously accompanied by surfactants (in a proportion of 2 to 20% by weight of the granule) of which more than half is, for example, constituted by at least one dispersing agent, essentially anionic, such as polynaphthalene. alkali or alkaline earth sulfonate or an alkaline or alkaline earth lignosulfonate, the remainder being nonionic or anionic wetting agents such as alkyl naphthalene

  alkaline or alkaline earth sulfonate.

  Moreover, although this is not essential, we can add other

  adjuvants such as antifoam agents.

  The granulate according to the invention can be prepared by mixing the necessary ingredients and then granulating according to several techniques known per se (dredger, fluid bed, atomizer, extrusion, etc ...). We usually finish with a follow-up crushing

  particle size sieving selected within the limits mentioned above.

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

examples below.

  Example GD1: Dispersible granules In a mixer, 90% by weight of active material and 10% of urea beads are mixed. The mixture is then milled in a pin mill. A powder is obtained which is moistened with about 8% by weight of water. The wet powder is extruded in a perforated roll extruder. A granule is obtained which is dried, then crushed and sieved so as to keep only the granules of a

  dimension between 150 and 2000 microns.

2707295

  EXAMPLE GD2 Dispersible Granules In a mixer, the following constituents are mixed: active ingredient 75% wetting agent sodium alkylnaphthalene sulphonate 2% dispersing agent sodium polynaphthalene sulphonate 8% water-insoluble inert filler (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 with a size of 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 ingredients, especially fungicides, the latter being in the form of wettable powders, or granules or suspensions.

aqueous.

  With regard to compositions suitable for storage and transport,

  they more preferably contain from 0.5 to 95% (by weight) of active substance.

  The subject of the invention is also the use of the compounds according to the invention for the fight against plant fungal diseases by preventive or curative treatment, on foliage or propagation material, of the latter or

of their place of growth.

21 2707295

Claims (8)

  1. Derivatives of pyrazole, of formula I, and their tautomeric forms: ## STR1 ## corresponding N-oxides, as well as the metal or metalloid salts and complexes of these derivatives, in which Y1 and Y2, which may be different or identical, are: a hydrogen or halogen atom, a hydroxy, mercapto, nitro, cyano, thiocyanato group, an alkyl, alkenyl, alkynyl, alkoxy or alkylthio group, each of these groups being optionally halogenated, - an acyl or thio acyl radical which may be: a formyl radical, an alkyl- or alkenyl-carbonyl or -thiocarbonyl radical, the alkyl or alkenyl radical may be linear or branched, or alkylthio-carbonyl - an optionally substituted phenoxy, - an amino substituted or unsubstituted by one or two alkyls or phenyls, - an alkylsulphinyl or alkylsulfonyl group, it being understood that the alkyl part of all the above groups comprises from 1 to 4 atoms of carbon; Z is: 22 2707295   a) - a hydrogen atom, a nitro, amino, hydroxy, cyano, alkyl or haloalkyl group,   -b) - an alkyl- or haloalkyl- or cycloalkyl-thio, -sulfinyl group or -   sulfonyl, alkoxy- or haloalkoxy-sulphonyl, alkenyl- or alkynylsulphonyl, phenyl- or benzyl-sulphenyl or sulphonyl, -c) - an aminomethylene group in which the amino radical may be substituted by one or two identical or different groups which are: an alkyl group optionally substituted with a substituent cyano, nitro,   alkoxy, cycloalkyl, alkyl- or alkoxy- or monoalkylamino-   or dialkylarnino-carbonyl, alkylthio, alkylsulfonyl, an optionally substituted phenyl ring or an optionally substituted heterocyclic group, an alkenyl or alkynyl group, an optionally substituted phenyl group   an optionally substituted heterocyclic radical.   When the amino radical is disubstituted, the two substituents may constitute a nitrogen heterocycle comprising 5 or 6 atoms; -d) - a linear or branched alkyl radical substituted with: one or more halogen atoms,   a cyano, nitro, alkyl- or alkoxy- or monoalkylamino-group;   or dialkylamino-carbonyl, dialkoxy- or dibenzyloxy- or diphenoxyphosphono, trialkylsilyl, phenyl- one or two alkoxy, alkenoxy, alkynoxy, phenoxy or benzyloxy radicals, which can, when they are two, form a 5- or 6-membered heterocycle of which 2 oxygen,   an alkyl- or alkenyl- or alkynyl- or phenyl- or benzyl-   thio which can, when they are two, form a heterocycle with 5 or 6 atoms, of which 2 is sulfur,   an alkyl- or alkenyl- or alkynyl- or phenyl- or benzyl-   sulfonyl or -sulphinyl, - hydroxy, acyloxy, alkoxycarbonyloxy, -e) - an acyl or thio acyl radical which may be: - a formyl radical an alkyl- or alkenyl-carbonyl or -thiocarbonyl group, the alkyl or alkenyl radical being be linear or branched and substituted by one or more halogen atoms, a group 23 2707295   cyano, nitro, alkoxy, cycloalkyl, alkyl- or alkoxy- or monoalkylamino- or dialkylamino-carbonyl, alkylthio, alkylsulfonyl, dialkyl-, alkylphenyl or alkylbenzylamino, optionally substituted phenyl or an optionally substituted heterocyclic radical, an alkynylcarbonyl group, a radical optionally substituted benzoyl or thio benzoyl; - optionally substituted picolinyl, nicotinyl, isonicotinyl, furoyl, thenoyl; - f) - an aminocarbonyl or aminothiocarbonyl group substituted with two identical or different radicals which may be: a hydrogen atom, a group alkyl, cycloalkyl, alkenyl, alkynyl, optionally substituted, an optionally substituted phenyl or benzyl radical, - g) - an alkoxy- or alkylthio-, cycloalkoxy- or cycloalkylthio- group,   alkenoxy-, alkynoxy-, phenoxy- or phenylthio-, benzyloxy- or benzylthio-   heterocyclyloxycarbonyl, the hydrocarbon radicals may be substituted, it being understood that in all of the foregoing: - an alkyl group has 1 to 4 carbon atoms and that, unless otherwise indicated, it may be substituted by one or more atoms   halogen, cyano, nitro, alkoxy, cycloalkyl, alkyl- or alkoxy-   or monoalkylamino- or dialkylamino-carbonyl, benzoyl, alkylthio, alkylsulfinyl, alkylsulfonyl, phenylsulfinyl, phenylsulfonyl, trialkylsilyl, - the phenyl ring of the aromatic substituents may be substituted with 1 to 5 substituents selected from the group consisting of halogens, nitro groups, cyano, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, alkoxycarbonyl, alkylsulfinyl, alkylsulfonyl radicals, the alkyl portion of these substituents having from 1 to 4 carbon atoms and that the aromatic heterocyclic rings may comprise from 1 to 4   substituents, depending on the heterocycles, chosen from the same group.   Het is an unsaturated or unsaturated heterocyclic radical, mono- or bi-cyclic comprising 5 to 10 atoms comprising from 1 to 4 heteroatoms which may be an oxygen or sulfur atom and / or one to three nitrogen atoms, such as the furan nucleus, the thiophene nucleus, the pyrrole nucleus, the oxazole, thiazole, isoxazole and isothiazole nuclei, imidazole, pyrazole, 1,2,3-triazole or 1,2,4-triazole, the pyridine nucleus, 24 2707295   the pyridazine, pyrimidine, pyrazine, 1,3,5-triazine and 1,2,4triazine rings, as well as the heterocyclic rings fused with a benzene ring such as benzofuran, benzothiophene, indole, quinoline and isoquinoline as well as the N-oxide derivatives of heterocycles comprising at least one nitrogen atom; this heterocycle being connected to the pyrazole ring by any of its atoms and which may be substituted by one or more radicals, which may be identical or different, which are: a halogen atom, a hydroxyl, mercapto, cyano, thiocyanato or nitro group; , nitroso, amino optionally substituted by one or two alkyls or phenyls or acyls, imines, enamines and amidines derived from this amino group, - an alkyl, haloalkyl, hydroxyalkyl, alkoxyalkyl, arylalkyl radical such as benzyl, alkenyl, haloalkenyl, alkynyl, cyanoalkyl, alkoxy, haloalkoxy, alkenoxy, halo, alkenoxy, alkynoxy, formyl, acetyl, alkyl- or alkoxy- or alkylthio-carbonyl, mono or dialkylamino (thio) carbonyl, mono or diarylamino or alkylarylamino (thio) carbonyl, carboxyl, carbamoyl or benzoyl optionally substituted, - phenyl, phenoxy or phenylthio, benzyloxy or benzylthio which may also be substituted,   an alkyl-, alkoxy-, mono- or dialkylamino-, phenyl-   sulfenyl or sulfinyl or sulphonyl; acyloxy, carbamoyloxy, alkyl- or phenyl-sulphonyloxy or sulphamoyloxy; it being understood that, in all the radicals mentioned above, the alkyl part may be linear or branched and preferably has 1 to 4 carbon atoms, the halogenated alkyl groups may comprise one or more identical or different halogen atoms and the phenyl radicals may be substituted by a halogen atom, a methyl, methoxy, methylthio or trifluoromethyl radical,   trifluoromethoxy, a nitro group, cyano or methylsulfonyl.   2. Derivatives according to the claim, characterized in that in formulas I and Ibis, Het is a furan, thiophene, pyridine or pyrimidine ring which may be substituted with one or more radicals, which may be identical or different, which may be: a methyl radical allyl, propargyl, methoxy, methylthio, trifluoromethyl, trifluoromethoxy, nitro, cyano, amino, mono or dimethylamino, acetoxy, carbomethoxy, methylsulfmyl, methylsulfonyl, mono or dimethylaminosulfonyl, phenoxy, phenylthio or I 2707295   benzyloxy optionally substituted on the phenyl ring by a halogen atom, a   methyl, methoxy, trifluoromethyl or a nitro group.   3. Derivatives according to claim 2, characterized in that in formulas I and Ia, Het is a thiophene radical. 4. Derivatives according to claim 1, characterized in that in the formulas I and Ia, Y1 and Y2, which are identical or different, are a hydrogen or halogen atom or a cyano group.   5. Derivatives according to claim 1, characterized in that in formulas I and Ibis, Z is a hydrogen atom, an acyl group, substituted methyleneanmino or carbonyloxyalkylene, 6. Process for preparing the derivatives of formulas I and Ibis, in Z is different from hydrogen and, characterized in that it is reacted, on compounds of formulas II and IIa Het He Het _ _ Y1 N Y2Ye 1 2 H N Y2   In which Het, Y1 and Y2 have the same meanings as in formula I, an acylating agent. 7. Process for the Preparation of the Derivatives of Formulas I and Ia, in which Z is Z is Z d) or Z f), characterized in that it is reacted on compounds of formulas II and II bis 26 2707295 Het Y1 Het _Y1 N Y2 1H / N Y2   II IIbis in which Het, Y1 and Y2 have the same meanings as in formula I, an aldedyhe or a ketone, in the presence of a primary or secondary, on a pyrazole of formula II, at a temperature between room temperature and the reflux point, in the middle   solvent, optionally in the presence of a catalytic amount of strong acid.   11. Process for the preparation of the derivatives of formulas II and IIa, in which Y1 is a halogen atom and Y2 is a hydrogen atom, characterized in that a halogenation of compounds of formula HII: Het N is carried out 12. Process for the Preparation of the Derivatives of Formula III, by the Reaction of Hydrazine to an Enone Compound of Formula I and W IV in which Het has the Same Significance as in Formulas I and Ia and W is an Atomic Acid halogen, hydroxy, alkoxy, alkylthio or dialkylanyl, to a   temperature ranging from 20 C to 110 C.   13. Compounds of formulas IHI and IV, 27 2707295 Het ".1 NsNH III Het \ I. IV H O. usable as intermediaries.   14. Compositions for the protection of plants against fungal diseases characterized in that they contain as active ingredient at least one compound of formula I according to claim 1.   15. A method of treating cultures against fungal diseases characterized in that at least one compound of formula I is applied according to one of the Claims 1 to 5.