Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

• the present invention relates to new derivatives of the 3-arylpyrazole family, their methods of preparation, the compositions containing them and their use for the protection of plants against fungal diseases.
• a more specific subject of the invention is 3-arylpyrazole derivatives, characterized in that they are of formula I:
• X 1 , X 2 , X 3 , X 4 and X 5 identical or different, are:
• - a hydrogen or halogen atom, a hydroxy, cyano, thiocyanato, nitro, nitroso or amino group optionally substituted by one or two alkyls or phenyls,
• alkyl hydroxyalkyl, alkoxyalkyl, alkylthioalkyl alkylsulfinylalkyl, alkylsulfonylalkyl, benzyl, alkenyl, alkynyl, cyanoalkyl, alkoxy, alkenoxy, alkylthio, formyl, acetyl, alkyl- or alkoxy (thio) -carbonyl, mono or di alkylamino (thio) carbonyl radical , iminocarbonyl, mono- or
• a phosphoryl group substituted by two groups chosen from the group comprising alkyl, alkoxy, alkylthio and dialkylamino, benzyloxy, phenyloxy or phenyl,
• Two of the adjacent X 1 , X 2 , X 3 X 4 and X 5 may also be linked together by a carbon bridge comprising from 2 to 4 links, at least one of which may be replaced by an oxygen or sulfur atom. or nitrogen, the carbons of this bridge may or may not be substituted by at least one halogen atom and / or at least one hydroxy, amino, alkyl, alkoxy .alkylthio, mono or di alkylamino, alkylsulfinyl or -sulfonyl group. alkyl part being as defined above,
• Y is a hydrogen or halogen atom, a nitro, nitrile, thiocyanato or alkyl, alkoxy or alkylthio, alkylsulfinyl or -sulfonyl group, the alkyl part of these radicals being optionally mono- or polyhalogenated, an amino optionally substituted by a or two alkyls or phenyls;
• Y and X1 or X5 can also be linked together by a carbon bridge comprising from 5 to 7 links, at least one of which can be replaced by an oxygen, sulfur or nitrogen atom, the carbons of this bridge possibly be or not substituted by at least one halogen atom and / or at least one hydroxy, alkoxy, alkylthio, mono or di alkylamino, alkylsulfinyl or - sulfonyl group, the alkyl part being as defined above,
• GR4 a hydrogen, halogen atom, a cyano, nitro, hydroxy group or - alkyl, haloalkyl, cycloalkyl or cycloalkyl -alkyl the cycloalkyl part which may be substituted by the group GR4, defined below, or
• Z 1 is an oxygen or sulfur atom or an alkylamino or imino or arylamino group
• a phosphoryl group substituted by two radicals chosen from the group comprising alkyl, alkoxy, alkylthio, dialkylamino, cycloalkyl or cycloalkyl -alkyl, alkenyl or alkynyl, phenyl phenylalkyl, Het or Het-alkyl, phenyl or Het,
• the hydrocarbon part of these groups may comprise from 1 to 7 carbon atoms and may be optionally halogenated (from 1 to 8 halogen atoms), the cycloalkyl part of these groups can comprise from 3 to 7 carbon atoms and be optionally substituted by at least one substituent chosen from the group GR4,
• 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
• Het is a heterocyclic radical, mono or bicyclic, containing from 5 to 10 atoms, of which 4 are heteroatoms (oxygen, sulfur, nitrogen, phosphorus).
• Y is a chlorine or bromine atom.
• Other preferred derivatives are such that, in formula I, Z is a hydrogen atom or a group C (Z 1) Z 2 , in which Z 1 is an oxygen or sulfur atom.
• X 1 , X 2 and X 4 are a hydrogen or halogen atom or a nitro or optionally halogenated alkyl group of 1 to 4 carbon atoms.
• X 3 is a hydrogen or fluorine atom.
• acylating agent is meant a compound of formula Z 4 C (Z 1 ) Z 2 or Z 5 S (Z 1 ) (Z 3 ) Z 2 , in which Z 1 , Z 2 and Z 3 are defined as above and Z4 and Z5 are chosen from the group comprising a halogen atom, a hydroxyl, alkoxy, alkylthio, amino, mono- or dialkylamino group, the alkyl part of these groups containing from 1 to 4 carbon atoms.
• the derivatives of formula II according to the invention can be prepared using various methods per se known in particular in the compilations "Comprehensive Heterocyclic Chemistry", ARKatritzky and CW.Rees 1984, Nol.5, pages 239 to 241 and 263, Pergamon Press; "Advances in Heterocyclic Chemistry", A. ⁇ .Kost etI.I.Grandberg, 1966, Vol.6, ⁇ ages 391 to 396, Académie Press and "The chemistry of heterocyclic compounds", L.CBehr, R.Fusco and CH.Jardoe, 1967 J.Wiley & sons.
• a first process for manufacturing the compounds of formula JJ, in which Z is a hydrogen atom and Y is a halogen atom, consists in reacting a 3-arylpyrazole of formula III:
• X 1 , X 2 , X 3 , X 4 and X 5 and Z have the same meaning as in formula I and Y is a hydrogen atom, with a halogenating agent.
• halogenating agent as chlorination agent, of chlorine, preferably in an aqueous medium such as in water, or organic such as acetic acid or carbon tetrachloride, or alternatively acid
• hypochlorous hydrochloric acid in the presence of hydrogen peroxide in acetic acid, or sulfuryl chloride or an N-chloroimide such as N-chlorosuccinimide in a chlorinated solvent such as dichloromethane, or phosphorus pentachloride .
• the chlorination can be carried out with chlorine in an organic solvent medium, preferably a lower carboxylic acid, at a temperature of
• the reactants being in a substantially stoichiometric molar ratio.
• N-chlorosuccinimide in an organic solvent medium, preferably a chlorinated solvent such as dichloromethane, 1,2 dichloroethane at a temperature of 0 ° C to 80 ° C, and preferably from 20 ° C to 50 ° C , the reactants being in a substantially stoichiometric molar ratio.
• brominating agent preferably in an aqueous solvent such as water, in an acid medium, for example nitric or acetic, in the presence or absence of a base such as sodium acetate, or in an organic solvent such as, for example, chloroform, or alternatively pyridinium perbromide.
• the bromination can be carried out, for example, with bromine in an organic solvent medium such as a lower carboxylic acid, at a temperature of 16 ° C. to preferably at room temperature.
• an organic solvent medium such as a lower carboxylic acid
• iodine can be used in the presence of hypoiodous acid or in the presence of a base such as an alkali hydroxide or a basic salt such as sodium acetate, or in the presence of a nickel salt ( D); iodine can also be used on the silver salt (J) of the pyrazole of formula III.
• a base such as an alkali hydroxide or a basic salt such as sodium acetate
• D nickel salt
• iodine can also be used on the silver salt (J) of the pyrazole of formula III.
• the fluorination can be carried out using derivatives of formula II in which Y is an amino group, by preparation of the diazonium tetrafluoroborate derivative derived from an amino group and then irradiation of this compound.
• a second method per se known for preparing the derivatives of formula JJ according to the invention, in which Y is a bromine atom, consists in reacting a compound of formula II, in which Y is a formyl group, with bromine in l acetic acid to give 4-bromo-3-phenylpyrazole.
• the enaminone compounds of formula lu can be prepared, in a manner known per se, by reaction of a derivative of formula IV:
• W is a hydroxyl radical or a chlorine atom or a mono or dialkylamino or phenylamino group and X 1 to X 5 have the same meanings as in formula I, with hydrazine hydrate, at a temperature of 10 ° C to 150 ° C, preferably from 20 ° C to 120 ° C, advantageously in an organic solvent medium, preferably a lower carboxylic acid or in an alcohol, in the presence of an organic or inorganic acid catalyst, the molar ratio of 2 reagents being substantially stoichiometric.
• dialkoylamino X 1 to X 5 being defined as above, can be obtained, in a manner known per se, by reaction of acetophenones of formula V:
• X 1 to X 5 are defined as above, with amide acetals, ester aminals or orthoaminals, preferably in the absence of organic solvent with dialkoyl (preferably dimethyl or diethyl) acetals of the N, N-dimethylformamide, at a temperature of 20 ° C to 130 ° C and preferably from 70 ° C to 130 ° C
• acetophenones of formula V are mostly commercial. Those which are not can be prepared in a manner known per se
• one of the Xi, Xj is a group capable of directing in metallo the metallation, by a strong lithiated base (alkyllithiens or dialkylamides of lithium) and reaction with an electrophile, the metallation agent and the electrophile being described in the reference V.Snieckus above.
• X3 is an amino, with an alkali or alkyl nitrite, preferably at 0 ° C., then reacting the diazonium salt with a reducing agent such as hypophosphorous acid, an alcohol or an ether, preferably at a temperature of 0 ° C at room temperature.
• a reducing agent such as hypophosphorous acid, an alcohol or an ether
• a second method per se known for the preparation of derivatives of formula II according to the invention, in which Y is a bromine atom, consists in reacting a compound of formula II, in which Y is a formyl group, with bromine in the acetic acid to give 4-bromo-3-phenylpyrazole.
• a third process for the preparation of derivatives of formula II according to the invention consists in reacting an enaminone of formula IV, in which W is a hydroxyl, alkoxyl, alkylthio, alkylsulfinyl or -sulfonyl or halogen radical, an amino, mono or dialkylamino group or phenylamino or a halogen and in which X1, X2, X3, X4, X5 have the same meanings as above and Y is halogen or cyano, with hydrazine hydrate at a temperature of 10 ° C to 150 ° C, preferably from 20 ° C to 120 ° C, advantageously in an organic solvent medium, preferably a lower carboxylic acid or in an alcohol in the presence of an organic or inorganic acid catalyst, the molar ratio of the 2 reactants being substantially stoichiometric.
• acetophenones of formula V in which X 1 . at X 5 are defined as above and Y a halogen atom or a cyano, with amide acetals, ester aminals or orthoaminals, in the absence of organic solvent with dialkyls (preferably dimethyl or diethyl ) acetals of N, N-dimethylformamide, or in an inert organic solvent medium such as toluene cyclohexane, hexane, heptane or tetrahydrofuran, at a temperature of 10 ° C to 50 ° C and preferably from 15 ° C to 40 ° C.
• the derivatives of formula V can be prepared, in a manner known per se, by the action of a halogenoacetyl chloride in the presence of anhydrous aluminum chloride on a substituted benzene of formula VI.
• the compounds of formula IV for which Y is halogen can also be obtained, in a manner known per se, by reaction of a ⁇ -halosuccinimide in a chlorinated solvent with the compounds of formula IV for which Y is hydrogen.
• a fourth process for the preparation of compounds II consists in reacting a compound of formula II in which at least one of the groups X is halogenated with a nitrogenous or oxygenated or sulfur-containing nucleophile, preferably a thiolate in a solvent medium, preferably apolar protic.
• a fifth process for the preparation of compounds II consists in reacting a compound of formula II in which at least one of the groups X is alkylthio with an oxidizing agent, such as hydrogen peroxide, organic or mineral peracids, preferably a persulfate in medium solvent, preferably polar protic.
• an oxidizing agent such as hydrogen peroxide, organic or mineral peracids, preferably a persulfate in medium solvent, preferably polar protic.
• Diazonium chloride of 2-amino-3-bromo-5-methyl benzoic acid is obtained by pouring dropwise at -5 ° C an aqueous solution of sodium nitrite (0.013 mole) onto a solution containing 0.0109 mole of 2-amino-3-bromo-5-methyl benzoic acid, 10 ml of hydrochloric acid, 10 ml of water and 30 ml of acetic acid. The reaction medium is thus stirred at 0 ° C for 30 minutes then poured into a large volume flask containing 0.013 mole of copper chloride in 10 ml of acetic acid. The mixture obtained is brought to 60 ° C, stirred for 2 hours, then hydrolyzed after cooling by adding ice. The precipitate obtained is filtered and washed with water. 3-bromo-2-chloro-5-methyl benzoic acid is obtained: (Yield 58%, mp 160 ° C)
• acetophenones are obtained from the benzoic acids previously obtained according to the following procedure:
• decarboxylation is carried out by heating in a DMSO-water mixture.
• This solution is poured dropwise onto a solution of 28.5 g (0.48 mole) of acetaldoxime, 25.0 g (0.10 mole) of copper sulphate pentahydrate, of 20.5 g (0.018 mole) of anhydrous sodium sulfite and 121 g (1.50 mole) of sodium acetate in 250 ml of water maintained at 15 ° C. After 1 h of stirring, the medium is acidified by addition of concentrated hydrochloric acid .
• the mixture is allowed to return to ambient temperature then 10 l of water are added and the aqueous phase is extracted with dichloromethane. After the decanted organic phase has dried, concentration and distillation of the crude, 591 g is obtained (78% yield, boiling point: 91-95 ° C under 1mm Hg) of (3,5-dichloro) phenyl ethanone in the form of a light yellow liquid.
• reaction medium is then extracted with dichloromethane and washed with water. After drying the organic phase over MgSO4 and evaporation, the residue obtained is purified by passage over a column of silica (dichloromethane) to lead to the production of a liquid:
• Example 5 The procedure is as in Example 5, starting with the suitably substituted acetophenone and the second suitable reagent.
• the pyrazole 4-chloro-3- (3-amino-2,5-dimethylphenyl) pyrazole (compound 295) is obtained in an identical manner (melting point 70 ° C; yield 85%).
• reaction medium is poured into 800 ml of water, filtered through sintered glass, rinsed with water and dried to give a white solid (yield: 90%, mp: decomposition at 300 ° C) 3- (2-amino-3,5-dichlorophenyl) 4-chloro pyrazole.
• the pyrazole 4-chloro-3- (3-amino-5-chlorophenyl) pyrazole is obtained identically with a melting point of 150 ° C. (yield 41%) (compound 297).
• This compound is obtained by diazotization of 3- (2-amino-3,5-dichlorophenyl) -4- chloro pyrazole, according to the methods described in the literature: Yield 30%, honey.
• EXAMPLE 16 Obtaining a compound of formula II from another compound of formula II by aromatic nucleophilic substitution.
• 4-chloro-3- (3,5-dichlorophenyl) pyrazole hydrochloride (compound 307): 2 g (0.008 mol) of 4-chloro-3- (3,5-dichlorophenyl) are dissolved at room temperature and with stirring pyrazole in 200ml of diethyl ether. Hydrochloric acid is then bubbled until the precipitation stops, the white solid is filtered, rinsed with ether to give 1.1 g (52% yield, melting point: 175 ° C) of hemichlorohydrate. 4-chloro-3- (3,5-dichlorophenyl) pyyazole. By operating as in the example above, the following salts were obtained:
• This compound is prepared from 1.66 g (0.0059 mole) 6-bromo-2-dimethylaminomethylene tetralone and 0.58 g (0.008 mole) of hydrazine hydrate in ethanol as described in Example 7 : yield: 31%, melting point: 155 ° C
• An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:
• This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
• the inoculum is then supplied using a syringe by depositing drops (3 per leaflet) of a suspension of Botrvtis cinerea spores. sensitive to benzimidazoles or resistant to benzimidazoles, obtained from 15 day cultures, then suspended at a rate of 150,000 units per cm 3 .
• the control is made 6 days after the contamination in comparison with an untreated control.
• An aqueous suspension of the active material to be tested having the following composition is prepared by fine grinding:
• This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
• Rice, sown in pots in a 50/50 mixture of enriched peat and pozzolan, is treated at the 10 cm height stage by spraying the above aqueous suspension.
• the rice plants are placed for 24 hours in incubation (25 ° C, 100% relative humidity), then placed in an observation cell, under the same conditions, for 5 days. Reading is done 6 days after contamination.
• An aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding:
• This aqueous suspension is then diluted with water to obtain the desired concentration of active material.
• Vine cuttings (Vitis vinifera). Chardonnay variety, are grown in pots. When these plants are 2 months old (8 to 10 leaf stage, 10 to 15 cm high), they are treated by spraying with the above aqueous suspension.
• Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
• each plant is contaminated by spraying with an aqueous suspension of Plasmopara viticola spores obtained from a 7-day culture, then suspended at the rate of 100,000 units per cm 3 .
• the contaminated plants are then incubated for two days at approximately 18 ° C, in an atmosphere saturated with humidity and then for 5 days at approximately 20-22 ° C under 90-100% relative humidity.
• the reading is done 7 days after contamination, in comparison with the control plants. Under these conditions, at the dose of 1 g / l, good (at least 75%) or total protection is observed with the following compounds: 20, 21, 25, 31, 33, 34, 36, 37, 41, 43, 200 to 204, 206, 207, 212, 213, 219 to 221, 223 to 228, 230, 231, 234, 236 to 239, 243 to 245, 248, 254 to 256, 291, 294, 305, 307 and 313.
• An aqueous suspension of the active ingredient to be tested having the following composition is prepared by fine grinding:
• Plants, used as controls are treated with an aqueous solution not containing the active ingredient.
• an aqueous suspension of spores (100,000 sp / cm 3 ) is sprayed onto the wheat; this suspension was obtained from contaminated plants.
• the wheat is then placed for 24 hours in an incubation cell at approximately 20 ° C. and at 100% relative humidity, then for 7 to 14 days at 60% relative humidity.
• the condition of the plants is checked between the 8th and 15th day after contamination, by comparison with an untreated control.
• compositions which can be used as fungicidal agents, contain as active material a compound according to the invention as described above in admixture with solid or liquid carriers, acceptable in agriculture and surfactants also acceptable in agriculture.
• surfactants also acceptable in agriculture.
• these compositions also form part of the invention.
• compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilizers, sequestrants, etc. More generally the compounds used in the invention can be combined with all the solid or liquid additives corresponding to the usual techniques of formulation.
• compositions according to the invention usually contain from 0.05 to 95% approximately (by weight) of a compound according to the invention (hereinafter called active material), one or more solid or liquid carriers and, optionally, one or more surfactants.
• support in the present description, is meant an organic or mineral, natural or synthetic material, with which the compound is combined to facilitate its application on the plant, on seeds or on the ground. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant.
• the support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water; alcohols, in particular butanol, etc.).
• the surfactant can be an emulsifying, dispersing or wetting agent of ionic or nonionic type or a mixture of such surfactants. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic acids or
• naphthalenesulfonic polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of esters of sulfosuccinic acids, derivatives of taurine (in particular alkyltaurates), phosphoric esters of polyoxyethyl alcohols or phenols, esters of fatty acids and of polyols, the derivatives containing sulfates, sulfonates and phosphates of the preceding compounds.
• the presence of at least one surfactant is generally essential when the compound and / or the inert support are not soluble in water and the vector agent for the application is water.
• compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 0.05% to 95% (by weight).
• Their surfactant content is
• compositions according to the invention are themselves in fairly diverse forms, solid or liquid.
• powders for dusting with a compound content of up to 100%
• granules in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation with from a powder (the compound content in these granules being between 0.5 and 80% for the latter cases), the effervescent tablets or tablets.
• the compounds of formula (I) can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.
• liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, powders wettable (or spray powder), pasta, gels.
• solutions in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, powders wettable (or spray powder), pasta, gels.
• the emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.001 to 20% of active material.
• emulsifiable concentrates can contain, when necessary, 2 to 20% of suitable additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives previously mentioned- From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to crops.
• suitable additives such as stabilizers, surfactants, penetration agents, corrosion inhibitors, dyes or adhesives previously mentioned- From these concentrates, emulsions of any desired concentration can be obtained by dilution with water, which are particularly suitable for application to crops.
• composition of some emulsifiable concentrates is the composition of some emulsifiable concentrates:
• the concentrated suspensions are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0 , 1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.
• Wettable powders are usually prepared so that they contain 20 to 95% of active ingredient, and they usually contain, in addition to the solid support, 0 to 30% of a wetting agent, 3 to 20% of a dispersing agent, and, when necessary, from 0.1 to
• the active ingredients are intimately mixed in the appropriate mixers with the additional substances and ground with mills or other suitable grinders.
• pasta can be made.
• the conditions and methods of making and using these pastes are similar to those of wettable powders or spraying powders.
• compositions of wettable powders As an example, here are various compositions of wettable powders (or spraying powders):
• This wettable powder contains the same ingredients as in the previous example, in the proportions below:
• non-ionic (wetting agent) 2.5%
• 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 can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".
• the compounds according to the invention can be formulated in the form of water-dispersible granules also included within the scope of the invention.
• the active material content of these granules is generally between approximately 1% and 90%, and preferably between 25% and 90%.
• the rest of the granule is essentially composed of a solid filler and optionally surfactant additives giving the granule properties of dispersibility in water.
• These granules can be essentially of two distinct types depending on whether the selected filler is soluble or not in water.
• the filler When the filler is water-soluble, it can be mineral or, preferably, organic. Excellent results have been obtained with urea.
• an insoluble filler it is preferably mineral, such as for example kaolin or bentonite. It is then advantageously accompanied by surfactants
• the granule (at a rate 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 an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline lignosulfonate -te ⁇ eux, the rest being constituted by nonionic or anionic wetting agents such as an alkali or alkaline-earth alkyl naphthalene sulfonate.
• essentially anionic such as an alkaline or alkaline earth polynaphthalene sulfonate or an alkaline or alkaline lignosulfonate -te ⁇ eux, the rest being constituted by nonionic or anionic wetting agents such as an alkali or alkaline-earth alkyl naphthalene sulfonate.
• the granule according to the invention can be prepared by mixing the necessary ingredients and then granulation according to several techniques known per se (bezel, fluid bed, atomizer, extrusion, etc.). It generally ends with a crushing followed by sieving to the particle size chosen within the limits mentioned above.
• Example GD1 Dispersible granules
• Example GD2 Dispersible granules
• This mixture is granulated in a fluid bed, in the presence of water, then dried, crushed and sieved so as to obtain granules of size between 0.15 and 0.80 mm.
• These granules can be used alone, in solution or dispersion in water so as to obtain the desired dose. They can also be used to prepare combinations with other active materials, in particular fungicides, the latter being in the form of wettable powders, or aqueous granules or suspensions.
• compositions suitable for storage and transport they more advantageously contain from 0.5 to 95% (by weight) of active substance.
• a subject of the invention is also the use of the compounds according to the invention for combating fungal diseases of plants by treatment preventive or curative, on the foliage or the propagation material, of the latter or their place of growth.

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• Life Sciences & Earth Sciences (AREA)
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• Pest Control & Pesticides (AREA)
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  • 1993-04-27 ZA ZA932945A patent/ZA932945B/xx unknown
• 1994
  • 1994-10-26 FI FI945034A patent/FI945034A/fi not_active IP Right Cessation

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