MXPA98001683A - Compositions and methods to control mushrooms harmful - Google Patents

Abstract

The present invention relates to compositions for controlling harmful fungi comprising, as active ingredients, phenazequine and at least one amide compound of formula I, wherein A, r1 and R2 have the meanings given in the description. The compositions according to the invention are particularly useful for controlling botrit

Description

"COMPOSITIONS AND METHODS TO CONTROL HARMFUL FUNGI" The present invention relates to compositions for controlling deleterious fungi and to methods for controlling harmful fungi using these compositions. Patent Number EP-A-545 099 describes anuida compounds of the formula wherein A is phenyl which is substituted at the 2-position by methyl, trifluoromethyl, chloro, bromo or iodo, or is a certain aromatic or non-aromatic heterocyclic radical which may be unsubstituted or substituted by methyl, chloro or trifluoromethyl and R is a a certain aliphatic or cycloaliphatic radical which may be unsubstituted or substituted by halogen, or is phenyl which is unsubstituted or substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms or halogen. These compounds are useful for controlling botrytis.

Patent Number EP-A-589 301 describes the anilide compounds of the same formula wherein A is a cyclic radical of the formulas: CH3 wherein R 1 is hydrogen or alkyl of 1 to 4 carbon atoms; R ^ is halogen or alkyl of 1 to 4 carbon atoms; R ^ is alkyl of 1 to 4 carbon atoms or haloalkyl of 1 to 4 carbon atoms; n is 1 or 2; and R has essentially the meanings given above. These compounds are also useful for the treatment of botrytis. Patent Number WO 93/11117 describes the compounds of the formula wherein Q alkyl of 1 to 3 carbon atoms, alkenyl of 2 to 3 carbon atoms, alkynyl of 2 to 3 carbon atoms, - (CH2) mCH = o - (CH2) m -X-CH2) m-; n is 0 or 1; each m independently of the others is 0, 1, 2 or 3; each x independently is 0 or S; Rl is a certain alicyclic radical; R ^ is hydrogen, fluorinated methyl, methyl, ethyl, alkenyl of 2 to 6 carbon atoms, chloroalkyl of 3 to 6 carbon atoms, phenyl, alkylthioalkyl, alkoxyalkyl, haloalkylthioalkyl, haloalkoxyalkyl or hydroxyalkyl; R3 is halomethyl, halomethoxy, methyl, ethyl, halogen, cyano, methylthio, nitro, aminocarbonyl or aminocarbonylmethyl; R ^ is hydrogen, halogen or methyl; R5, R and R7 in each case independently of the other are selected from hydrogen, halogen, cyano, - - alkyl of 1 to 6 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkynyl of 2 to 6 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, cycloalkyl of 3 to 4 carbon atoms and halomethoxy. These compounds are fungicidally active. An object of the present invention is to provide a better possibility for controlling harmful fungi, in particular botrytis. Surprisingly, we have found that this object is achieved by a composition comprising, as the active ingredients, fenazaquine, which is known as an acaricide (The Pesticide Manual, Tenth Edition, 1994, CAS Registry Number 120928-09-8) and the amide compounds of the formula I which will be described below. The present invention therefore relates to compositions for controlling deleterious fungi comprising, in a solid or liquid carrier, phenazaquin, of the formula and at least one amide compound of the formula I which is presented below A-CO-NR1R2 (I) wherein A is an aryl group or an aromatic or non-aromatic heterocycle, having 5 or 6 members having from 1 to 3 heteroatoms selected from 0, N and S; it is possible that the aryl group or the heterocyclic is unsubstituted or has 1, 2 or 3 substituents which, independently of one another, are selected from alkyl, halogen, CHF2, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 is a hydrogen atom; R2 is a phenyl or cycloalkyl group which is unsubstituted or having 1, 2 or 3 substituents selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, it being possible for the aliphatic and cycloaliphatic radicals to be partially or completely halogenated and / or the cycloaliphatic radicals to be substituted by 1 to 3 alkyl groups, and it being possible for the phenyl group to have from 1 to 5 halogen atoms, and / or from 1 to 3 substituents which, independently of one another, are selected from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and of the amide phenyl group is fused to a saturated 5-membered ring which is unsubstituted or substituted by 1 or more alkyl groups and / or which may have a heteroatom selected from 0 to S. The compositions according to with the invention they act synergistically and therefore are particularly suitable for controlling harmful fungi, in particular botrytis. Within the scope of the present invention the halogen is fluorine, chlorine, bromine and iodine, in particular fluorine, chlorine and bromine. The term "alkyl" embraces the straight and branched chain alkyl groups. Preferably they are straight or branched chain alkyl groups of 1 to 12 carbon atoms, in particular, alkyl groups of 1 to 6 carbon atoms. Examples of the alkyl groups are alkyl, such as in particular methyl, ethyl propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl , 3-methylbutyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,2 -di ethylbutyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,1-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-ethyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl. The haloalkyl is an alkyl group as defined above is partially or completely halogenated by one or more halogen atoms, in particular fluorine and chlorine. Preferably from 1 to 3 halogen atoms, with the difluoromethyl group or the trifluoromethyl group being especially preferred. What has been said above about the alkyl group and the haloalkyl group is applied analogously to the group of alkyl and haloalkyl in alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl and alkylsulfonyl. The alkenyl group encompasses the straight and branched chain alkenyl groups. Preferably, they are straight or branched chain alkenyl groups of 3 to 12 carbon atoms, in particular, alkenyl groups of 3 to 6 carbon atoms. Examples of the alkenyl groups are 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l- methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1, l- dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, l-ethyl-2-propenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-2-pentenyl, 2- methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl- 3-pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1, l-dimethyl-2-butenyl, 1, l- dimethyl-3-butenyl, 1, l-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-2-butenyl, 1, 3- dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, l-ethyl-2-butenyl, l-ethyl-3- butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-pro penyl, l-ethyl-l-methyl-2-propenyl and 1-ethyl-2-methyl-2-propenyl, in particular 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2- pentenyl. The alkenyl group may be partially or completely halogenated by one or more halogen atoms, in particular fluoro and chlorine. It preferably has from 1 to 3 halogen atoms.

The alkynyl group embraces the straight and branched chain alkynyl groups. Preferably, straight and branched chain alkynyl groups of 3 to 12 carbon atoms, in particular alkynyl groups of 3 to 6 carbon atoms. Examples of the alkynyl groups are 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-3-butynyl, 2- methyl-3-butynyl, l-methyl-2-butynyl, 1, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-alkynyl, 5-hexynyl, l- methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-4-pentynyl, 4-methyl- 2-pentynyl, 1,2-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, l-ethyl-2- butynyl, l-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl-l-methyl-2-propynyl. What has been said above about the alkynyl group and its halogen substituents and about the alkynyl groups is applied analogously to alkenyloxy and alkynyloxy. The cycloalkyl group is preferably a cycloalkyl group of 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. If the cycloalkyl group is substituted, it preferably has from 1 to 3 alkyl radicals of 1 to 4 carbon atoms or substituents. The cycloalkenyl is preferably a cycloalkenyl group of 4 to 6 carbon atoms such as cyclobutenyl, cyclopentenyl, cyclohexenyl. If the cycloalkenyl group is substituted, it preferably has from 1 to 3 alkyl radicals of 1 to 4 carbon atoms as the substituents. A cycloalkoxy group is preferably a cycloalkoxy group of 5 to 6 carbon atoms such as cyclopentyloxy or cyclohexyloxy. If the cycloalkoxy group is substituted, it preferably has from 1 to 3 alkyl radicals of 1 to 4 carbon atoms as substituents. The cycloalkenyloxy group is preferably a cycloalkenyloxy group of 5 to 6 carbon atoms such as cyclopentyloxy or cyclohexyloxy. If the cycloalkenyloxy group is substituted, it preferably has from 1 to 3 alkyl radicals of 1 to 4 carbon atoms as the substituents. The aryl is preferably phenyl. If A is a phenyl group, this group can have 1, 2 or 3 of the aforementioned substituents at any position. These substituents are preferably selected independently from each other from alkyl, difluoromethyl, trifluoromethyl and halogen, in particular, chlorine, bromine and iodine. The especially preferred phenyl group has a substituent at the 2-position. If A is a 5-membered heterocycle, the particular heterocycle is a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, thiazolyl or thiadiazolyl radical, or the derivatives thereof. corresponding to dihydro or tetrahydro thereof. A thiazolyl or pyrazolyl radical is preferred. If A is a 6-membered heterocycle, this particular heterocycle is a pyridyl radical or a radical of the formula: wherein one of the radicals X and Y is 0, S or NR9, where R9 is H or alkyl, and the other of the radicals X and Y is CH2, S, SO, S02 or NR9. The broken line indicates that a double bond may be present. The especially preferred 6-membered aromatic heterocycle is a pyridyl radical, in particular a 3-pyridyl radical or a radical of the formula (A3) where X is CH2, S, SO or S02. The aforementioned heterocyclic radicals may be unsubstituted or have 1, 2 or 3 of the aforementioned substituents, these substituents being preferably selected, independently of each other, from alkyl, halogen, difluoromethyl or trifluoromethyl. A is especially preferably a radical of the formulas: (To the) wherein R3, R4, R6, R7, R8 and R9, independently of one another are hydrogen, alkyl in particular methyl, halogen in particular chlorine, CHF or CF3. The radical R 1 in the formula I is preferably a hydrogen atom. The radical R2 in the formula I is preferably a phenyl radical. R2 preferably has at least one substituent, particularly preferably at position 2. The substituent is selected (or substituents are selected) preferably from alkyl, cycloalkyl, cycloalkenyl, halogen or phenyl. The substituents of the radical R2, in turn, can also be substituted. The aliphatic and cycloaliphatic substituents can be partially or completely halogenated, in particular fluorinated or chlorinated. They preferably have 1, 2 or 3 fluorine or chlorine atoms. If the substituent of the radical R2 is a phenyl group, this phenyl group can be preferably substituted by 1 to 3 halogen atoms, in particular chlorine atoms and / or by a radical which is preferably selected from alkyl and alkoxy . The phenyl group is particularly preferably substituted by a halogen atom in the p-position, that is to say the especially preferred substituent of the radical R2 is a phenyl radical substituted with p-halogen. The radical R2 can also be fused to a saturated 5-membered ring, it being possible for this ring, in turn, to have from 1 to 3 alkyl substituents. In this case, R2 is, for example, indanyl, thiadandanyl and oxaindanyl. Preferred are indanyl and 2-oxaindanyl which are linked to the nitrogen atom, in particular through the 4-position. In a preferred embodiment, the composition according to the invention comprises, as an amide compound, a compound of the formula I wherein A has the following meanings: phenyl oxide, pyridyl, dihydropyranyl, dihydrooxathiinyl, dihydrooxathiinyl dihydrooxathiinyl dioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, it being possible for these groups to have 1, 2 or 3 substituents which, independently of one another, they are selected from alkyl, halogen, difluoromethyl and trifluoromethyl. In a further preferred embodiment, A is: pyridin-3-yl which is unsubstituted or substituted in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; phenyl which is unsubstituted or substituted in position 2 by methyl, trifluoromethyl, chlorine, bromine or iodine; 2-methyl-5,6-dihydropyran-3-yl; 2-methyl-5,6-dihydro-l, -oxatiin-3-yl or the oxide 4 or dioxide 4.4 thereof; 2-methyl-furan-3-yl which is unsubstituted or which is substituted in the 4-position and / or 5 by methyl; thiazol-5-yl which is unsubstituted or substituted in position 2 and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; thiazol-4-yl which is unsubstituted or substituted at position 2 and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; l-methylpyrazol-4-yl which is unsubstituted or substituted in the 3-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; or oxazol-5-yl which is unsubstituted or substituted in position 2 and / or 4 by methyl or chloro. In a preferred embodiment, the compositions according to the invention comprise, as the amide compound, a compound of the formula I wherein R2 is a phenyl group which is unsubstituted or which is substituted by 1, 2 or 3 of the aforementioned substituents. In a further preferred embodiment, the compositions according to the invention comprise, as the amide compound, a compound of the formula I wherein R2 is a phenyl group having one of the following substituents at the 2-position: alkyl of 3 to 6 carbon atoms, cycloalkenyl of 5 to 6 carbon atoms, cycloalkyloxy of 5 to 6 carbon atoms, cycloalkenyloxy, it being possible for these groups to be substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms, the phenyl which are substituted by 1 to 5 halogen atoms and / or from 1 to 3 groups which are independently selected from each other of alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms and haloalkyl of 1 to 4 carbon atoms, indanyl or oxaindanyl each of which is not substi tuted or is substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms. In a further preferred embodiment, the compositions according to the invention comprise, as the amide compound, a compound of the formula where A is (Al) (A2) (A3) X methylene, sulfur, sulfinyl or sulfonyl (S0), R3 is methyl, difluoromethyl, trifluoromethyl, chloro, bromo or iodo, R4 is trifluoromethyl or chloro, R5 is hydrogen or methyl, R6 is methyl, difluoromethyl, trifluoromethyl or chloro, R7 is hydrogen, methyl or chloro, R8 is methyl, difluoromethyl or trifluoromethyl, R9 is hydrogen, methyl, difluoromethyl, trifluoromethyl or chloro, R! is alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms or halogen. In an especially preferred embodiment, the compositions comprise, as the amide compound, a compound of the formula Ib wherein R 4 is halogen, and R 2 is phenyl which is substituted by halogen. Useful amide compounds are mentioned in Patents Number EP-A-545 099 and No. 589 301, to which reference is made herein in its entirety. The preparation of the amide compounds of the formula 1 is disclosed, for example, in the Patents Number EP-A-545 099 and Number 589 301 or it can be carried out by similar processes. Even a small amount of the amide compound of the formula I is sufficient to act synergistically.

Preferably, the phenazaquin and the amide compound are used in a weight ratio in the range of 20: 1 to 1:20, in particular 10: 1 to 1:10. The invention also relates to a method for controlling harmful fungi comprising treating the fungi, their environment or the materials, plants, seeds, soils, areas of spaces to be protected against fungal infection, with a composition of conformity. as claimed in any of claims 1 to 9, it being possible to apply the active ingredients, the phenazaquin and the amide compound simultaneously, i.e., concomitantly or separately, or in succession. For example, the compositions according to the invention can be applied in the form of directly sprayable solutions, powders, suspensions, also other highly concentrated suspensions, aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, fine powders. , materials to disperse or granules, by means of atomization, spraying, sprinkling, dispersing or emptying. The forms of use depend on the proposed purposes; in any case, they must guarantee the finest possible distribution of the active ingredients according to the invention.

Normally, the plants are sprinkled or sprinkled with the active ingredients, or the seeds of the plants are treated with the active ingredients. The formulations are prepared in a known manner, e.g., by diluting the active ingredient with solvents and / or carriers, if desired using emulsifiers and dispersants, it being also possible to use other organic solvents as auxialiary solvents if water is used as the diluent. . The auxialiaries are essentially: solvents such as aromatic substances (eg, xylene), chlorinated aromatic substances (e.g., chlorobenzenes), paraffins (e.g., mineral oil fractions), alcohols (e.g., methanol, butanol), ketones (e.g., cyclohexanone), amines (e.g., ethanolamine, dimethylformamide) and water; carriers such as ground natural minerals (e.g., kaolins, clays, talc, chalk) and ground synthetic minerals (e.g., silica, highly dispersed silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates) and dispersants, such as the residual liquids of lignosulfite and methylcellulose. Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of the aromatic sulfonic acids, eg, ligno-, phenol-, naphthalene-, and dibutylnaphthalenesulfonic acid, and of the fatty acids, alkyl and alkylarylsulfonates, sulfonates. of alkyl alcohol, lauryl ether and fatty acid and also the salts of the sulphonated hexa-, hepta- and octa-decanoles, the fatty alcohol glycol esters, sulfonated naphthalene condensates and their derivatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids, with phenol and formaldehyde, ethoxylated polyoxyethylene, isoctyl-, octyl- and nonylphenyl octylphenol ether, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates , ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, polyuric alcohol ether of luryl alcohol, sorbitol esters, residual liquids of lignin-sulphite or methylcellulose. Powders, dispersion materials and fine powders can be prepared by mixing or concomitantly grinding the active ingredients together with a solid carrier. The granules, eg, the coated granules, the impregnated granules and the homogeneous granules can be prepared by binding the active ingredients to the solid carriers. Solid carriers are mineral earths such as silica gel, silicas, silica gels, silicates, talc, kaolin, limestone, lime, clay, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, oxide of magnesium, ground synthetic materials, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and products of vegetable origin, such as cereal flour, bark meal, wood flour and nutmeat meal , cellulose powders and other solid carriers. Examples of these preparations comprising the active ingredients, the phenazaquin and the amide compound in a weight ratio of 8: 1 are: I. a solution of 90 parts by weight of the active ingredients and 10 parts by weight of N- methylpyrrolidone, this solution being suitable for use in the form of microdroplets; II. a mixture of 20 parts by weight of the active ingredients, 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide per one mole of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate, 5 parts by weight of the adduct of 40 moles of ethylene oxide to one mole of castor oil; a dispersion is obtained by distributing the solution finely in water; III. an aqueous dispersion of 20 parts by weight of the active ingredients, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 40 moles of ethylene oxide per one mole of castor oil; IV. an aqueous dispersion of 20 parts by weight of the active ingredients, 25 parts by weight of cyclohexanol, 65 parts by weight of a fraction of the mineral oil boiling temperature of 210 ° C to 280 ° C and 10 parts by weight of the adduct of 40 moles of ethylene oxide for one mole of castor oil. V. a mixture, milled in a hammer mill of 80 parts by weight of the active ingredients, 3 parts by weight of sodium diisobutyl naphthalene-1-sulfonate; 10 parts by weight of the sodium salt of a lignosulfonic acid of sulphite residual liquid and 7 parts by weight of pulverulent silica gel; a spray mixture is obtained by finally distributing the mixture in water; SAW. an intimate mixture of 3 parts by weight of the active ingredients and 97 parts by weight of kaolin finally divided; this fine powder consists of 3 weight percent of the active ingredient; VII. an intimate mixture of 30 parts by weight of the active ingredients, 92 parts by weight of the pulverulent silica gel and 8 parts by weight of paraffin oil which have been sprayed to the surface of this silica gel; this formulation imparts good adhesion properties to the active ingredient; VIII. a stable aqueous dispersion of 40 parts by weight of the active ingredients, 10 parts by weight of the sodium salt of a phenolsulfonic acid / urea / formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water; this dispersion can be further diluted; IX. a stable oily dispersion of 20 parts by weight of the active ingredients, 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of the fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt, a phenolsulfonic acid condensate. urea / formaldehyde and 88 parts by weight of a paraffin mineral oil. The compositions according to the invention have a remarkable activity against a broad spectrum of phytopathogenic fungi, in particular against botrytis. In some cases, they act systematically (that is, they can be absorbed by the treated plant without loss of efficiency and, if appropriate, translocated within the plant) and can be used as fungicides for foliage and for soil activation. They are especially important for controlling a large number of fungi in a variety of crop plants such as wheat, barley, rye, oats, rice, corn, grass, cotton, soybeans, coffee, sugarcane, grapes, fruit species, species Ornamentals and vegetables such as cucumbers, beans and curcubitáceas and the seeds of these plants. The compositions are applied by treating the fungi or seeds the plants, materials or soil to be protected against fungal infection, with a fungicidally active amount of the active ingredients. The application is made before or after the infection of the materials, plants or seeds by fungi. Specifically, the compositions are suitable for controlling the following plant diseases: Erysiphe? Framinis (powdery mildew) in cerals, Erysiphe cichoracearum and Sphaerotheca fuliginea in curcubitáceas, Podosphaera leucotrica in apples, Uncinula necator in vines, Venturia inaequalis (scab) in apples, The species of Helminthosporium in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries and vines, Cercospora. arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, The species Fusarium and Verticillium in a variety of plants, The species Alternating it in legumes and fruits, The species Monilinia in fruit, and The species Sclerotinia in seed rape oil and vegetables. Use against botrytis is preferred. The compositions can also be used in the protection of materials (wood protection), e.g., against Paecilorayces variotii. Generally, the fungicidal compositions comprise from 0.1 percent to 95 percent, preferably from 0.5 percent to 90 percent by weight of the active ingredient. Depending on the nature of the desired effect, the application regimes are 0.02 to 3 kilograms of the active ingredient per hectare. In the treatment of seeds, the amounts of the active ingredient from 0.001 to 50 grams, preferably from 0.01 to 10 grams are usually required per kilogram of seeds. In the form of use as fungicides, the compositions according to the invention may also comprise other active ingredients, e.g., herbicides, insecticides, growth regulators, fungicides or also fertilizers. A mixture with fungicides in many cases can result in an extended fungicidal spectrum of action. The following list of fungicides together with which the compounds can be used in accordance with the invention is intended to illustrate the possible combinations, but not imposing any limitation: sulfur, dithiocarbamates and their derivatives, such as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithiocarbamate, manganese ethylene dicadithiocarbamate, manganese-zinc ethylene diamine bisdithiocarbamate, tetramethyl thioramyl disulfide, ammonia complex ( N, N-ethylenebisdithiocarbamate) of zinc, ammonia complex of zinc (N, N'-propylenebisdithiocarbamate), zinc (N, N'-propylenebistiocarbamate), N, N'-polypropylenebis (thiocarbamoyl) disulfide; nitro derivatives, such as dinitro (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethyl acrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate, Di-isopropyl 5-nitroisophthalate; heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino-s-triazine, 0-diethyl phthalimidophosphothioate, 5-amino-1- [bis- (dimethylamino ) -phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyan-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4,5-n] quinoxaline, 1- ( methyl butylcarbamoyl) -2-benzimidazolcarbamate, 2-methoxycarbonylaminobenzimidazole, 2- (furyl- (2)) benzimidazole, 2- (thiazolyl-4 (4)) benzimidazole, N (1,1,2,2-tetrachloroethio) tetrahydrophthalimide, N-trichloromethiotetrahydroftalimide, N-trichloromethiophthalimide, diamide N-dichlorofluoromethio-N ', N' -dimeti-1-N-phenylsulfuric acid, 5-ethoxy-3-trichlormethyl-l, 2,3-thiadiazole, 2-thiocyanate, thiocyanate thiobenzothiazole, 1,4-dichloro-2,5-dimethoxybenzene, 4 - (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, 2-thio-l-pyridine oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiane, 4, 4, 2,3-dihydro-5-carboxanilido-6-methyl-l, -oxatiin dioxide, 2-methyl-1-5,6-dihydro-4H-pyran-3-carboxanilide dioxide, 2- methyl-furan-3-carboxanilide, 2,5-dimethyl-furan-3-carboxanilide, 2,4-trimethyl-furan-3-carboxanilide, N-cyclohexyl-2,5-dimethyl-furan-3-carboxamide, N-cyclohexyl-N-methoxy- 2, 5-dimethyl-furan-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholin-2, 2, 2-trichloroethyl acetate, piperazine -1,4-diylbis (1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -l-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N- tridecyl morpholine or its salts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine, N- [3 - (p-tert-butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H-1,2 , 4-triazole, 1- [2- (2, 4-dichlorophenyl) -4-n-propyl-l, 3-dioxolan-2-yl-ethyl] -1H-1,2,4-triazole, N- ( n-propyl) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole il) -2-butanone, 1- (4-chlorophenyl) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, alpha- (2-chlorophenyl) -alpha- (4-chlorophenyl-5-pyrimidinemethanol, 5-buty1-2-dimethylamino-4-hydroxy-6-methy1pyridine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl-2) -thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene, and a variety of fungicides, such as or dodecylguanidine acetate, 3- [3- (3, 5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] -glutarimide, hexachlorobenzene, N- (2,6-dimethylphenyl) -N- (2-furoyl) -DL Methyl alaninate, methyl ester of DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L- 2-aminobutyrolactone, methyl ester of DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo -l, 3-oxazolidine, 3- [3,5-dichlorophenyl- (5-methyl-5-methoxymethyl] -1,3-oxazolidin-2,4-dione, 3- (3,5-dichlorophenyl) -1- isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropan-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- (2, 4 -dichlorophenyl) pentyl] -1H-1, 2,4-triazole, 2,4-difluoro-alpha- (1H-1, 2,4-triazolyl-1-methyl) benzhydryl alcohol, N- (3-chloro- 2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- ((bis (4-fluorophenyl) methylsilyl) me til-1H-1, 2,4-triazole. The synergistic action of the compositions according to the invention is illustrated with the help of the following examples of use: EXAMPLE OF USE 1 The activity against Botrytis cinerea The shoots of the pepper cv. "Neusiedler Ideal Elite "were sprayed to the point of dripping with aqueous suspensions comprising 80 percent of the active ingredient and 20 percent of the emulsifier in the dry matter after 4 to 5 sheets had been properly developed. , the plants were sprayed with a conidia suspension of the fungus Botrytis cinerea and placed in a chamber at a temperature of 22 ° C to 24 ° C at high atmospheric humidity, after 5 days, the disease in the untreated control plants It had developed to such an extent that the gangrene of the foliage formed covered most of the area of the leaves (disease level 83 percent). The useful amide compounds were compounds 1.1 and 1.2 of the formulas The visually determined data for the percentage of diseased leaf area was converted to efficacy levels as a percentage of the untreated control. An efficacy of 0 indicates the same level of disease in the untreated control, an efficacy of 100 indicates a disease level of 0 percent. The expected efficacies in the combinations of the active ingredients were determined using Colby's formula (SR Coiby (Calculating synergistic and antagonistic responses of herbicide Combinations ", Weeds, 15, pages 20 to 22, 1967) and compared with the observed efficacies. The results are shown in Table 1, which is presented below.

Table 1 Ingredient Ingredient Concentration Active Active Efficacy Level [parts per million] in% Control Fenazaquina Ingrediente Observed Calculated *) Active 1.1 or 1.2 Control (treated bo) (Fenazaquina) 250 1. 1 31 70 16 64 1. 2 31 40 16 Fenazaquina 250 31 71 + 1.1 250 16 76 65 Fenazaquina 250 31 63 42 + 1.2 250 16 52 ) calculated using the Coiby formula It can be seen from the experimental results that the efficiency observed in all the mixing ratios exceeds the efficacy of the additive previously calculated using the Coiby formula, that is, a synergistic effect is present.

EXAMPLE OF USE 2 Activity against Botrytis cinerea in the fruits of the pepper The discs of the fruits of the green pepper were sprayed to the point of dripping with an aqueous preparation of the active ingredient comprising 80 percent of the active ingredient and 20 percent of the emulsifier in the dried material. Two hours after the spraying emulsifier had dried, the fruit discs were inoculated with a suspension of Botrytis cinerea spores containing 1.7 X 106 spores per milliliter of a Biomatz solution of 2 percent concentration. The fruit discs inoculated subsequently were incubated for four days in humid chambers at 18 ° C. The development of Botrytis on the discs of the infected fruit was then visually evaluated (disease level of 94 percent). The amide compounds used were the aforementioned compounds II and III.

The visually determined data for the percentages of the diseased leaves area were converted to efficacy levels as a percentage of the untreated control. An efficacy of 0 indicates the same level of disease as in the untreated control, an efficacy of 100 indicates a disease level of 0 percent. The expected efficacies of the active ingredient combinations were determined using the Coiby formula (SR Coiby (Calculating synergistic and antagonistic responses of herbicide Combinations ", Weeds, 15, pages 20 to 22, 1967) and compared with the observed efficacies. Results are shown in Table 2 presented below.

Table 2 Ingredient Ingredient Concentration Active Active Efficacy Level [parts per million] in% Control Fenazaquina Ingrediente Observed Calculated *) Active 1.1 or 1.2 Control (not treated) Fenazaquina 250 15 1. 1 - 31 68 1. 2 31 95 16 36 Fenazaquina 250 31 89 73 + 1.1 Fenazaquina 250 31 100 95 + 1.2 250 16 95 45 *) calculated using the Coiby formula It can be seen from the experimental results that the efficiency observed in all the mixing ratios exceeds the efficacy of the additive previously calculated using the Coiby formula, that is, a synergistic effect is present. Similar results are obtained when the amide compound used is one of the compounds mentioned in Table 3 below, of the formula la: where A (Al) (A2) (A3) (A7) < A5) or another individual compound mentioned in Patents Number EP-A-545 099 and Number 589 301. in or O?

Claims (10)

R E I V I N D I C A C I O N S

1. A composition for controlling harmful fungi comprising, in a liquid solid carrier, phenazaquine of the formula: and at least one amide compound of the formula given below: A-CO-NRIR2 wherein A is a 5- or 6-membered aromatic or non-aromatic heterocycle selected from thiazolyl, pyrazolyl, imidazolyl, oxazolyl, triazolyl, thiadiazolyl or pyridyl; it being possible that the heterocycle is not substituted or has 1, 2 or 3 substituents which, independently of one another, are selected from alkyl, halogen, CHF2, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 is a hydrogen atom;

R 2 is a phenyl or cycloalkyl group which is unsubstituted or has 1, 2 or 3 substituents which, independently of one another, are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy , phenyl and halogen, it being possible for the aliphatic and cycloaliphatic radicals to be partially or completely halogenated and / or for the cycloaliphatic radicals to be substituted by g to 3 alkyl groups, it being possible for the phenyl group to have from 1 to 5. halogen atoms, and / or from 1 to 3 substituents which, independently of one another, are selected from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, it being possible for the phenyl-to-idic group to be founded in a saturated ring of 5 members which is not substituted or substituted by 1 or more alkyl groups, and / or may have a heteroatom selected from O and S. 2. A com position according to claim 1, wherein in the formula I, the radical A is one of the following groups: pyridyl, thiazolyl, pyrazolyl or oxazolyl, it being possible for these groups to have 1, 2 or 3 substituents, independently of one of the another, they are selected from alkyl, halogen, dichloromethyl and trifluoromethyl.

3. A composition according to claim 1, wherein in the formula I, the radical A is one of the following groups: pyridin-3-yl, which is not substituted or which is substituted at the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl. thiazol-5-yl, which is unsubstituted or substituted in position 2 and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; thiazolyl-4-yl, which is unsubstituted or substituted in position 2 and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; l-methylpyrazol-4-yl, which is unsubstituted or substituted in position 3 and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; or oxazol-5-yl, which is unsubstituted or substituted in position 2 and / or 4 by methyl or chloro.

4. A composition according to any of the preceding claims, comprising a compound of the formula I, wherein R ^ is a phenyl group, is substituted or is substituted by 1, 2 or 3 of the substituents mentioned in the reivvindiciation 1.

5. A composition according to claim 4, wherein R2 is a phenyl group having one of the following substituents in the 2-position: alkyl of 3 to 6 carbon atoms, cycloalkenyl of 5 to 6 atoms of carbon, cycloalkyloxy of 5 to 6 carbon atoms, cycloalkenyloxy, it being possible for these groups to be substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms, phenyl which is substituted by 1 to 5 halogen atoms and / or from 1 to 3 groups which are selected, independently from each other, from alkyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, haloalkoxy of 1 to 4 atoms of carbon, alkylthio of 1 to 4 carbon atoms and haloalkylthio of 1 to 4 carbon atoms, or wherein R 2 is indanyl or oxaindanyl, which is unsubstituted or is substituted by 1, 2 or 3 alkyl groups of 1 to 4 carbon atoms.

6. A composition according to any of claims 1 to 5, comprising an amide compound of the formula la, which is presented below: where (A6) (A5) (A8) ' X methylene, sulfur, sulfinyl or sulfonyl (SO 2), R is methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, R 4 is trifluoromethyl or chlorine, R 5 is hydrogen or methyl, Rβ is methyl, di fluoromethyl, trifluoromethyl or chlorine, R is hydrogen, methyl or chloro, R8 is methyl, difluoromethyl or trifluoromethyl, R9 is hydrogen, methyl, difluoromethyl, trifluoromethyl or chloro, R10 is alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms or halogen.

7. A composition. according to any of claims 1 to 5, comprising, as the amide compound, a compound of formula Ib which is presented below: wherein R ^ is halogen, and RH is phenyl which is substituted by halogen.

8. A composition according to claim 1, comprising, as the amide compound, a compound of one of the formulas presented below:

9. A composition according to any of the preceding claims which is formulated in two parts, one part comprises phenazaquin in a solid or liquid carrier and the other part comprises the amide compound in a solid or liquid carrier.

10. A method for controlling harmful fungi, which comprises treating the fungi, their environment of the materials, plants, seeds, lands, areas or spaces to be protected against fungal infection with a composition of similarity with any of the claims. 1 to 9, it being possible to apply the active ingredients of phenazaquin and the amide compound simultaneously, i.e., concomitantly or separately, or in succession.