WO2009095242A2 - Fungicidal mixtures and compositions for the control of phytopathogenic fungi - Google Patents

Abstract

Fungicidal mixtures and compositions are described, comprising 3-allyloxy-l, 2-benzoisothiazole 1,1-dioxide in a mixture with at least one triazole or antipenorosporic fungicide, and their use for the control of phytopathogenic fungi.

Description

FUNGICIDAL MIXTURES AND COMPOSITIONS FOR THE CONTROL OF PHYTOPATHOGENIC FUNGI

The present invention relates to new fungicidal mixtures and compositions, in particular for the control of phytopathogenic fungi which cause considerable economical damage to agricultural crops .

More specifically, the present invention relates to the use of synergistic mixtures and compositions based on a derivative of benzisothiazole mixed with known fungicides.

The use of 3-allyloxy-l, 2-benz [d] isothiazole 1,1- dioxide (common name: probenazole) for the control of diseases in rice, in particular those caused by the phytopathogenic fungus Pyricularia oryzae has been known for some time. The product does not have a direct fungicidal action but acts as activator of the defense system of rice plants attacked by the fungus, ensuring an effective and long-lasting control of the disease (Pesticide Outlook - February 2001, pages 28-31) . It is also known that probenazole exhibits synergistic effects in the control of Pyricularia oryzae on rice when associated with some particular triazole fungicides such as 2, 2-bisfluoro-methyl-5- (4-chloro- phenyl) -3- (1, 2, 4-triazol-l-yl-methyl) -pentan-3-ol (American patent US 4,623,653, Example A) and 2,2- bisfluoro-methyl-5-cyclohexyl-4- (1, 2, 4-triazol-l-yl) - pentan-3-ol (German patent DE 3333449, Example A) . The mixtures described in the above two patents were tested by the Applicant for the control of pathogenic fungi in crops different from rice, but no synergistic effect was observed.

After all, probenazole is a commercial product currently used exclusively for the control of diseases of rice . The Applicant has now surprisingly found that, in spite of its specific mechanism of action, probenazole can also contribute to effectively controlling fungal pathogens different from Pyricularia oryzae, on crops of economical interest different from rice,- in particular, compositions consisting of probenazole mixed with some known fungicides specified hereunder, have a considerable synergistic effect in the control of pathogenic fungi of crops different from rice, such as Erysiphe spp., Puccinia spp., Septoria spp. on cereals and vegetable crops, Venturia inaequalis on apples, Phakopsora pachyrhizi on soybeans, Cercospora beticola on sugar beet, in addition to Oomycetes on potatoes, vines, tomatoes, tobacco.

An object of the present invention therefore relates to fungicidal mixtures comprising: A) probenazole: 3-allyloxy-l, 2-benz [d] isothiazole 1,1- dioxide of structural formula (I) ;

(D

B) at least a second component selected from: the following triazole fungicides:

(II) tetraconazole: (RS) -2- (2 , 4-dichlorophenyl) -3- (IH-I, 2, 4-triazol-l-yl) propyl 1, 1, 2 , 2-tetrafluoroethyl ether;

(III) azaconazole: 1- [ [2- (2, 4-dichlorophenyl) -1, 3- dioxolan-2-yl] -methyl] -IH-I, 2, 4-triazole;

(IV) bitertanol: 1- (biphenyl-4-oxy) -3, 3 -dimethyl-1- (lH-l,2,4-triazol-l-yl)butan-2-ol;

(V) bromuconazole : 1- [ (2RS, 4RS: 2RS, 4Si?) -4-bromo-2- (2, 4-dichlorophenyl) tetrahydrofurfuryl] -IH-I, 2, 4 -triazole ;

(VI) cyproconazole : (2RS, 3RS: 2RS, 3SR) -2- (4-chloro- phenyl) -S-cyclopropyl-l- (IH-I, 2, 4-triazol-l-yl) butan-2- ol ;

(VII) difenoconazole: 3-chloro-4- [4-methyl-2- (IH- 1,2, 4-triazol-l-ylmethyl) -1, 3-dioxolan-2-ylmethyl] phenyl 4-chlorophenyl ether;

(VIII) diniconazole: (E) - [RS) -1- (2, 4-dichlorophenyl) - 4, 4 -dimethyl-2- (IH-I, 2 , 4-triazol-l-yl) pent-l-en-3-ol;

(IX) epoxiconazole : (2RS, 3SR) -1- [3-(2-chlorophenyl) - 2,3-epoxy-2 - (4 -fluoropheny1) propyl] -IH-1 , 2 , 4 -1riazole ;

(X) fenbuconazole : 4- (4-chlorophenyl) -2 -phenyl-2- ( IH-1,2,4-triazol- 1-ylmethyl) butyronitrile ;

(XI) fluquinconazole : 3- (2, 4-dichlorophenyl) -6- fluoro-2- (IH-I, 2 , 4-triazol-l-yl) quinazolin-4 (3H) -one; (XII) flusilazole: bis (4 -fluorophenyl) (methyl) (IH- 1,2, 4-triazol-1-ylmethyl) silane;

(XIII) flutriafol: (RS) -2 , 4 ' -difluoro-α- (IH-I, 2 , 4- triazol-1-ylmethyl) benzhydryl alcohol;

(XIV) metconazole: (IRS, 5RS: IRS, 5SR) -5- (4-chloro- benzyl) -2 , 2-dimethyl-l- (IH-I, 2 , 4-triazol-l-ylmethyl) - cyclopentanol ;

(XV) myclobutanil: 2-p-chlorophenyl-2- (IH-I, 2 , 4- triazol- 1-ylmethyl) hexanenitrile ;

(XVI) penconazole: 1- [2- (2 , 4-dichlorophenyl)pentyl] - IH-I, 2, 4-triazole;

(XVII) propiconazole: 1- [2- (2 , 4-dichlorophenyl) -4- propyl-1, 3-dioxolan-2-ylmethyl] -IH-I, 2, 4-triazole;

(XVIII) prothioconazole: (RS) -2- [2- (1-chlorocyclo- propyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2 , 4-dihydro- 1, 2, 4-triazol-3-thione,- (XIX) triadimenol: (IRS, 2RS: IRS, 2SR) -1- (4-chloro- phenoxy) -3, 3 -dimethyl-1- (IH-I, 2 , 4-triazol-l-yl) butan-2- ol ;

(XX) triticonazole: (±) - (E) -5- (4-chlorobenzylidene) -2, 2- dimethyl- 1- (IH-I, 2, 4-triazol-l-ylmethyl) cyclo-pentanol ; the following antiperonosporic fungicides:

(XXI) zoxamide: (RS) -3 , 5-dichloro-N- (3-chloro-l- ethyl-1-methyl-2 -oxopropyl) -p-toluamide ;

(XXII) methyl 3- (4-chlorophenyl) 3- [ [ (N-isopropoxy- carbonyl) -L-valyl] amino] propanoate (ISO name proposed: valifenalate) , as diastereoisomeric mixtures in any ratio or as single S-R or S-S isomers;

(XXIII) benthiavalicarb-isopropyl: isopropyl [(S)-I- { [ (IJ?) -1- (6-fluoro-1, 3-benzothiazol-2-yl) ethyl] -carba- moyl}-2-methylpropyl] carbamate;

(XXIV) cyazofamid: 4-chloro-2-cyano-JV,.N-dimethyl-5-p- tolylimidazole-1-sulfonamide ;

(XXV) cymoxanil: 1- (2-cyano-2-methoxyiminoacetyl) -3- ethylurea; (XXVI) famoxadone: (J?S) -3-aniline-5-methyl-5- (4- phenoxyphenyl) -1, 3-oxazolidin-2 , 4-dione;

(XXVII) fenamidone: (5) -l-anilino-4-methyl-2-methyl- thio-4-phenylimidazolin-5-one;

(XXVIII) fluopicolide: 2 , 6-dichloro-iV- [3-chloro-5- (trifluoromethyl) -2-pyridylmethyl] benzamide; (XXIX) iprovalicarb: isopropyl 2-methyl-l-{ [ (RS) -1-p- tolylethyl] carbamoyl}- (S) -propylcarbamate,-

(XXX) mandipropamid: (RS) -2- (4 -chlorophenyl) -N- [3- methoxy-4- (prop-2-ynyloxy)phenethyl] -2- (prop-2-ynyloxy) - acetamide.

Preferred compositions are those in which component B is selected from: tetraconazole, bromuconazole, cyproconazole, diniconazole, fenbuconazole, flusilazole, metconazole, penconazole, propiconazole, prothioconazole, triticonazole, valifenalate, iprovalicarb, benthia- valicarb-isopropyl .

Compounds (I)-(XXX) are known products, indicated herein with their common ISO names and chemical names according to IUPAC. The structure formulae and their uses as fungicides are described, for example, in "The Pesticide Manual", 14^th edition (2006), edited by Clive Tomlin and published by the British Crop Protection Council, Farnham (UK) . Compound (XXII) is described in European patent EP1028125. The fungicidal compositions comprising probenazole mixed with at least one of the compounds (II) - (XXX) , object of the present invention, have a high fungicidal activity with respect to important fungal species. Their use is advantageous with respect to the use of components A and B applied alone, as it is possible to obtain the same fungicidal effect using lower doses of the two components of the mixture, or a greater fungicidal effect with the same applicative doses.

A further object of the present invention therefore relates to the use of the compositions comprising probenazole and at least one of the compounds (II) -(XXX), as fungicides for the control of phytopathogenic fungi.

Examples of pathogens which can be controlled by the above compositions and the relative application crops are indicated hereunder:

Erys±phe graminis (cereals) ;

Puccinia recondita, Puccinia graminis (cereals) ;

Helminthosporium spp (cereals) ;

Rhynchosporium (cereals) ; Septoria nodorum (cereals) _/

Plasmopara viticola (vines) ;

Uncinula necator (vines) ;

Pythium spp (vegetables) ;

Phytophthora infestans (potatoes) ; Phytophtora nicotianae (tobacco, ornamental plants) ;

Sphaerotheca fuliginea (cucumbers) ;

Podosphaera leucotricha (apples) ;

Phakopsora pachyrhizi (soybeans) ;

Venturia spp. (fruit trees) ; Fusarium spp. (cereals) ; Alternaria spp. (fruit trees and vegetables) ; Cercospora beticola (sugar beet) .

The compositions, object of the invention, are capable of exerting a high fungicidal action allowing preventive, protective, prophylactic, systemic, curative and eradicating treatments to be effected.

In the fungicidal compositions, object of the present invention, components A and B can be mixed within a very wide ratio, in relation to different factors such as the component B selected, the crop, pathogen, environmental conditions, type of formulation adopted.

The fungicidal compositions according to the present invention generally envisage the following application dosages per hectare : - 20-200O g of probenazole,-

- 5-300 g for each fungicide from (II) to (XXX) present in the composition.

The application of the compositions, object of this invention, can be effected on all parts of the plant, for example, on the leaves, stems, branches and roots, or on the seeds themselves before being planted, or also on the ground in which the plant grows .

A further object of the present invention therefore relates to a method for controlling phytopathogenic fungi by the application of the compositions mentioned above. For practical uses in agriculture, it is preferable to use the fungicidal compositions, object of the present invention, in the form of suitable formulations. This can be effected by formulating component A and component (s) B together, in the desired ratios, to give the final composition, and also by producing the composition at the moment of use by mixing the relative quantities of component A and component (s) B formulated separately.

Formulations can be used in the form of dry powders, wettable powders, emulsifying concentrates, micro- emulsions, pastes, granules, granules dispersible in water, solutions, suspensions, etc. The choice of the type of composition will depend on the specific use.

The compositions are prepared according to known methods, for example by diluting or dissolving the active substances with a solvent medium or a solid diluent, optionally adding surface-active agents, dispersing agents, suspending agents, stabilizers, etc. to the mixtures . Solid inert diluents, or supports, which can be used are: kaolin, alumina, silica, talc, bentonite, chalk, quartz, dolomite, attapulgite, montmorillonites, diatomaceous earth, calcium carbonate, magnesia, clays, synthetic silicates, sepiolite, cellulose, starch, etc. Inert liquid diluents which can be used are water, or organic solvents such as aromatic hydrocarbons

(xylols, alkylbenzol mixtures, etc.), halogenated aromatic hydrocarbons (chlorobenzol, etc.), aliphatic hydrocarbons (hexane, cyclohexane, heptane, petroleum fractions, etc.), alcohols (methanol, propanol, butanol, octanol, glycerin etc.), amines, amides (N, N- dimethylformamide, N-methylpyrrolidone) , ketones

(cyclohexanone, acetone, acetophenone, isophorone, ethylamylketone) , derivatives of fatty acids (for example vegetable oils such as rape oil or sunflower oil, mineral oils) , esters (isobutyl acetate, methyl esters of fatty acids obtained for example by the transesterification of vegetable oils) .

Surface-active agents which can be used are wetting and emulsifying agents of the non- ionic type (polyethoxylated alkylphenols, polyethoxylated fatty alcohols, polyethoxylated esters of sorbitol, etc.), of the anionic type (alkylbenzenesulfonates, alkyl- sulfonates, etc.), of the cationic type (quaternary salts of alkylammonium, etc.) .

Dispersing agents which can be used are for example lignin and its salts, cellulose derivatives, alginates, etc..

The compositions can also contain special additives for particular purposes such as for example adhesion agents, such as Arabic rubber, polyvinyl alcohol, polyvinyl pyrrolidones .

In the fungicidal compositions, object of the present invention, the concentration of active substances varies from 0.1% to 98%, preferably from 0.5% to 90%.

If desired, it is possible to add other active ingredients to the compositions, object of the present invention, such as, for example, other fungicides, phytoregulators, antibiotics, herbicides, insecticides, fertilizers.

Examples of other fungicides which can be added to widen the range and/or improve the efficacy of the compositions are: acibenzolar, amisulbrom, ampropylfos, anilazine, azoxystrobin, benalaxyl, benalaxyl-M, benomyl, bixafen, blasticidin-S, boscalid, bupirimate, buthiobate, captafol, captan, carbendazim, carboxin, carpropamid, chinomethionat , chloroneb, chlorothalonil, chlozolinate, cyflufenamid, cyprodinil, debacarb, dichlofluanid, dichlone, diclobutrazol, dichlomezine, dicloran, diclocymet, diethofencarb, diflumetorim, dimethirimol, dimethomorph, dimoxystrσbin, dinocap, dipyrithione, ditalimfos, dithianon, dodemorph, dodine, edifenphos, etaconazole, ethaboxam, ethirimol, ethoxyguin, etridiazole, fenaminosulf , fenapanil, fenarimol, fenfuram, fenhexamid, fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flumetover, flumorph, fluorpyram, fluoroimide, fluotrimazole, fluoxastrobin, flusulfamide, flutolanil, folpet, fosetyl, fosetyl-aluminium, fuberidazole, furalaxyl, furametpyr, furconazole, furconazole-cis, guazatine, hexaconazole, hymexazol, hydroxyquinoline sulfate, ICIA0858, imazalil, imibenconazole, iminoctadine, ipconazole, iprobenfos, iprodione, isoprothiolane, isotianil, kasugamycin, kresoxim-methyl, mancopper, mancozeb, maneb, mebenil, mepanipyrim, mepronil, metalaxyl, metalaxyl-M, methfuroxam, metiram, metominostrobin, metrafenone, metsulfovax, natamycin, nitrothal-isopropyl, nuarimol, ofurace, orysastrobin, oxadixyl, oxpoconazole, oxycarboxin, pefurazoate, pencycuron, pentachlorophenol and its salts, phthalide, penthiopyrad, picoxystrobin, piperalin, Bordeaux mixture, polyoxins, prochloraz, procymidone, propamocarb, propineb, proquinazid, prothiocarb, pyracarbolid, pyraclostrobin, pyrazophos, pyribencarb, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur, quinacetol, quinazamid, quinconazole, quinoxyfen, quintozene, rabenzazole, copper hydroxide, copper oxychloride, copper (I) oxide, copper sulfate, silthiofam, simeconazole, spiroxamine, streptomycin, tebuconazole, thiabendazole, thiadifluor, thicyofen, thifluzamide, thiophanate, thiophanate-methyl, thiram, tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triaritnol, triazbutil, triazoxide, tricyclazole, tridemorf, trifloxystrobin, triflumizole, triflorine, uniconazole, uniconazole-P, validamycin, vinclozolin, zineb, ziram, sulfur.

The following examples are now provided for a better understanding of the present invention, which should be considered as non- limiting thereof, and in which the synergistic effect of a composition is evaluated by comparing the activity observed experimentally (E_ObS) with the expected activity, calculated according to the Limpel formula ("Pesticide Science" (1987), vol. 19, pages 309- 315) :

Eexp = E_A + EB - (E_AXEB/100) wherein:

- E_exp is the fungicidal activity expected from a mixture obtained by mixing component A at the dose D_A and component B at the dose D_B;

- E_A is the activity observed for component A when used alone at the dose D_A;

- E_B is the activity observed for component B when used alone at the dose D_B; There is a synergistic effect when the E_obs/E_eχp ratio is > 1 .

EXAMPLE 1

Determination of the fungicidal activity against Puccinia recondita on wheat. Leaves of wheat plants (cultivar Gemini) , grown in vases, in a conditioned environment (20±l°C, 70% relative humidity) , are treated by spraying both sides of the leaves with hydroacetonic dispersions (at 20% v/v of acetone and with the addition of 0.3% of Tween 20) of the products and mixtures under examination.

After remaining 5 days in a conditioned environment, the plants are sprayed on both sides with an aqueous suspension of conidia of Puccinia recondita (200,000 conidia per cm³) . The plants are kept in a humidity saturated environment, at a temperature ranging from 18 to 24⁰C, for the incubation period of the fungus .

At the end of this period (14 days) , the fungicidal activity is evaluated according to an evaluation percentage scale from 0 (completely infected plant) to

100 (healthy plant) .

Table 1 indicates the results obtained with probenazole (I) and tetraconazole (II) , from which it appears evident that the compositions illustrated have a considerable synergistic effect. Synergistic effects were also found for mixtures of probenazole (I) with azaconazole (III) , bitertanol (IV) bromuconazole (V) , cyproconazole (VI) , difenoconazole (VII) , diniconazole (VIII) , epoxiconazole (IX) , fenbuconazole (X) , fluquinconazole (XI) , flusilazole (XII) , flutriafol (XIII) , metconazole (XIV) , myclobutanil (XV) , penconazole (XVI) , propiconazole (XVII) , prothioconazole (XVIII) , triadimenol (XIX) , triticonazole (XX) .

Table 1. Fungicidal activity against Puccinia recondita. on wheat .

EXAMPLE 2

Determination of the fungicidal activity against

Phytophthora infestanβ on potatoes.

Leaves of potato plants, Primura variety, grown in vases, in a conditioned environment (20±l°C, 70% relative humidity) , are treated by spraying both sides of the leaves with hydroacetonic dispersions (at 20% v/v of acetone and with the addition of 0.3% of Tween 20) of the products and mixtures under examination. After remaining 7 days in a conditioned environment, the plants are infected on the lower side with an aqueous suspension of spores of Phytophthora infestans (100,000 spores per cm³) .

The plants are kept in a humidity saturated environment, at a temperature ranging from 18 to 24⁰C, for the incubation period of the fungus and, at the end of this period (7 days) , the fungicidal activity is evaluated according to an evaluation percentage scale from 100 (healthy plant) to 0 (completely infected plant) .

Table 2 indicates the results obtained with probenazole (I) and methyl 3- (4-chlorophenyl) 3- [ [ (N- isopropoxycarbonyl) -L-valyl] amino] propanoate (XXII, ISO proposed name: valifenalate) , from which it appears evident that the compositions illustrated have a considerable synergistic effect.

Synergistic effects were also found for mixtures of probenazole (I) , with zoxamide (XXI) , benthiavalicarb- isopropyl (XXIII) , cyazofamid (XXIV) , cymoxanil (XXV) , famoxadone (XXVI) , fenamidone (XXVII) , fluopicolide (XXVIII) , iprovalicarb (XXIX) , mandipropamid (XXX) .

Table 2. Fungicidal activity against Phytophthora infestans on potatoes.

* Diastereoisomeric mixture SR/SS - 1:1

Claims

1. A fungicidal mixture comprising:

A) probenazole: 3-allyloxy-l, 2-benz [d] isothiazole 1,1- dioxide, the compound having structural formula (I) ;

CH₂ 1

(I) and B) at least one compound belonging to one of the following groups: - triazole fungicides:

(II) tetraconazole: (.RS) -2- (2, 4-dichlorophenyl) -3- ( IH- 1,2,4-triazol- 1-yl) propyl 1,1,2,2-tetrafluoroethyl ether;

(III) azaconazole: 1- [ [2- (2, 4-dichlorophenyl) -1, 3- dioxolan-2-yl] -methyl] -IH-I₇2, 4 -triazole;

(IV) bitertanol: 1- (biphenyl-4-oxy) -3 , 3-dimethyl-l- (IH-I, 2,4-triazol-l-yl)butan-2-ol; (V) bromuconazole : 1- [ (2RS₁ ARS: 2RS₁ ASR) -4-bromo-2- (2, 4-dichlorophenyl) tetrahydrofurfuryl] -IH-I, 2, 4 -triazole ;

(VI) cyproconazole : {2RS, 3RS: 2RS₁3SR) -2- (4-chloro- phenyl) -S-cyclopropyl-l- (IH-I, 2, 4-triazol-l-yl) butan-2- ol ;

(VII) difenoconazole: 3-chloro-4- [4-τnethyl-2- (IH- 1,2, 4-triazol-l-ylmethyl) -1, 3-dioxolan-2-ylmethyl] phenyl 4-chlorophenyl ether;

(VIII) diniconazole: (E) - (RS) -1- (2, 4 -dichlorophenyl) - 4,4-dimethyl-2- (IH-I, 2, 4-triazol-l-yl) pent- l-en-3-ol;

(IX) epoxiconazole: (2RS, 3SR) -1- [3-(2-chlorophenyl) - 2 , 3-epoxy-2- (4 -fluorophenyl) propyl] -IH-I, 2 , 4-triazole; (X) fenbuconazole : 4- (4-chlorophenyl) -2 -phenyl-2- (IH-I, 2, 4-triazol-l-ylmethyl) butyronitrile;

(XI) fluquinconazole : 3- (2, 4 -dichlorophenyl) -6- fluoro-2- (IH-I, 2, 4-triazol-l-yl) quinazolin-4 (3H) -one;

(XII) flusilazole: bis (4 -fluorophenyl) (methyl) (IH- 1,2, 4-triazol-l-ylmethyl) silane;

(XIII) flutriafol: (RS) -2 , 4 ' -difluoro-α- (IH-I, 2 , 4- triazol- 1-ylmethyl) benzhydryl alcohol ;

(XIV) metconazole: (IRS, 5RS: IRS, 5SR) -5- (4-chloro- benzyl) -2 , 2-dimethyl-l- (IH-I, 2 , 4-triazol-l-ylmethyl) - eyelopentanol ;

(XV) myclobutanil: 2-p-chlorophenyl-2- (IH-I, 2 , 4- triazol-1-ylmethyl) hexanenitrile,-

(XVI) penconazole: 1- [2- (2 , 4-dichlorophenyl) pentyl] - IH-I, 2, 4-triazole; (XVII) propiconazole: 1- [2- (2, 4 -dichlorophenyl) -4- propyl-1, 3-dioxolan-2-ylmethyl] -IH-I, 2, 4-triazole,- (XVIII) prothioconazole : (RS) -2- [2- (1-chlorocyclo- propyl) -3- (2-chlorophenyl) -2-hydroxypropyl] -2, 4-dihydro- 1,2,4-triazol-3 -thione; (XIX) triadimenol : (IRS, 2RS: IRS, 2SR) -1- (4-chloro- phenoxy) -3, 3 -dimethyl-1- (IH-I, 2, 4- triazol-1-yl) butan-2- ol ;

(XX) triticonazole: (±) - (E) -5- (4-chlorobenzylidene) -2, 2- dimethyl-1- (IH-I, 2, 4-triazol-l-ylmethyl) cyclo-pentanol; - antiperonosporic fungicides:

(XXI) zoxatnide: (RS) -3 , 5-dichloro-N- (3-chloro-l- ethyl- 1-methyl-2 -oxopropyl) -p-toluamide ;

(XXII) methyl 3- (4-chlorophenyl) 3- [ [ (IV-isopropoxy- carbonyl) -L-valyl] amino] propanoate (ISO name proposed: valifenalate) , as diastereoisomeric mixtures in any ratio or as single S-R or S-S isomers;

(XXIII) benthiavalicarb-isopropyl: isopropyl [(S)-I- { [ (IJ?) -1- (6-fluoro-1, 3-benzothiazol-2-yl) ethyl] -carbamoyl}-2-methylproyl] carbamate; (XXIV) cyazofamid: 4-chloro-2-cyano-_V, W-dimethyl-5-p- tolylimidazole-1-sulfonamide ;

(XXV) cymoxanil: 1- (2-cyano-2-methoxyiminoacetyl) -3- ethylurea;

(XXVI) famoxadone: (J?S) -3-aniline-5-methyl-5- (4- phenoxypheny1) -1, 3-oxazolidin-2 , 4-dione; (XXVII) fenamidone: (S) -l-anilino-4-methyl-2-methyl- thio-4 -phenylimidazolin-5 -one;

(XXVIII) fluopicolide: 2, 6-dichloro-W- [3-chloro-5- (trifluoromethyl) -2-pyridylmethyl] benzamide; (XXIX) iprovalicarb: isopropyl 2-methyl-l-{ [ (RS) -1-p- tolylethyl] -carbamoyl}- (S) -propylcarbamate,- (XXX) mandipropamid: (RS) -2- (4-chlorophenyl) -N- [3- methoxy-4- (prop-2-ynyloxy) phenethyl] -2- (prop-2-ynyloxy) - acetamide .

2. The mixture according to claim 1, wherein compound (XXII) is used as a diastereoisomeric mixture or as a single S-R or S-S isomer.

3. A fungicidal composition, characterized in that it comprises a mixture according to any of claims 1-2 as active principle together with other phyto- pharmacologically acceptable adjuvants and/or excipients.

4. The fungicidal composition according to claim 3, characterized in that it comprises at least one further active principle having a fungicidal activity.

5. Use of the mixture according to any one of claims 1- 2, or of the compositions according to any one of the claims 3-4 as a fungicide for the control of phytopathogen fungi in agricultural crops.

6. Use according to claim 5, wherein said phytopathogen fungi are fungi which infect crops of vines, tobacco, sugar beet, vegetables, Cucurbitaceae, fruit trees or cereals .

7. Use according to claim 6, wherein said phytopathogen fungi are selected from the group consisting in Erysiphe graminis (cereals) ; Puccinia recondite, Puccinia graminis (cereals) ; Helminthosporium spp (cereals) ; Rhynchosporium (cereals) ; Septoria nodorum (cereals) ; Plasmopara viticola (vines) ; Uncinula necator (vines) ; Pythium spp (vegetables) ; Phytophthora infestans (potatoes) ; Phytophtora nicotianae (tobacco, ornamental plants) ; Sphaerotheca fuliginea (cucumbers) ; Podosphaera leucotricha (apples) ; Phakopsora pachyrhizi (soybeans) ; Venturia spp. (fruit trees) ; Fusarium spp. (cereals) ; Alternaria spp. (fruit trees and vegetables) ; Cercospora beticola (sugar beet) .

8. Use according to any one of claims 5-7, wherein the dose of each compound is:

- for the compound having formula (I) ranging from 20- 2,000 g per hectare; - for at least one of the fungicidal compounds having formula (II) - (XXX) within the range of 5-300 g per hectare .

9. Use according to any one of claims 5-8, characterized in that the mixture or composition is formulated in the form of dry powder, wettable powder, emulsifiable concentrate, microemulsion, paste, granules, solution or suspension.

10. Use according to any one of claims 5-9, wherein the treatment is of a preventive, protective, prophylactic, systemic, curative or eradicating nature.

11. A method for the control of phytopathogen fungi in agricultural crops by the application of a fungicidal mixture as defined according to any one of claims 1-2 or by the application of a fungicidal composition as defined according to claim 3.

12. The method according to claim 11, characterized in that the fungicidal mixture or composition has the following application dose of each compound:

- 20-2,000 g per hectare for the compound having formula (I);

- 5-300 g per hectare for at least one of the fungicidal compounds having formula (II) - (XXX) .

13. The method according to any one of claims 11-12, characterized in that the mixture or composition also comprises other compatible active principles such as for example other fungicides, phytoregulators, antibiotics, herbicides insecticides and fertilizers.

14. The method according to any one of claims 11-13, characterized in that the application takes place on all parts of the plant, or on the seeds themselves before planting, or on the ground in which the plant grows.

15. The method according to any one of claims 11-14, characterized in that the application for preventive, protective, prophylactic, systemic, curative and eradicating treatment .