MXPA00005336A - Fungicide mixtures based on amide compounds and azoles - Google Patents

Abstract

The invention relates to fungicide mixtures containing, as active components, a) an amide compound of formula (I) A-CO-NR1R2, wherein A represents an aryl group or an aromatic or non-aromatic, 5- or 6-structured heterocyclic compound having 1 to 3 heteroatoms selected from O, N, S;whereby the aryl group or the heterocyclic compound can optionally comprise 1, 2 or 3 substituents selected independently of one another from alkyl, halogen, CHF2, CF3, alkoxyl, haloalkoxyl, alkylthio, alkyl sulfinyl and alkyl sulfonyl;R1 represents a hydrogen atom;R2 represents a phenyl group or cycloalkyl group optionally containing 1, 2 or 3 substituents selected independently of one another from alkyl, alkenyl, alkynyl, alkoxyl, alkenyloxyl, alkynyloxyl, cycloalkyl, cycloalkenyl, cycolalkyloxyl, cycloalkenyloxyl, phenyl and halogen, whereby the aliphatic and cycloaliphatic radicals can be partially or completely halogenated and/or the cycloaliphatic radicals can be substituted by 1 to 3 alkyl groups, whereby the phenyl group can contain 1 to 5 halogen atoms and/or 1 to 3 substituents selected independently of one another from alkyl, haloalkyl, alkoxyl, haloxyl, alkylthio and haloalkylthio, and whereby the amidic phenyl group is optionally condensed with a saturated 5-structured ring which is optionally substituted by one or more alkyl groups and/or can comprise a heteroatom selected from O and S, and b) an azole derivative (II). The active components are provided in a synergistically effective quantity.

Description

FUNGICIDE MIXTURES BASED ON AMIDA AND AZOLES COMPOUNDS Description The present invention relates to fungicidal mixtures for controlling harmful fungi, as well as methods for controlling harmful fungi using these mixtures.

WO 97/08952 describes mixtures of amide compounds of the formula I A-CO-NRiR2 (I) wherein A is an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from O, N and S; The aryl group or the heterocycle may optionally have 1, 2 or 3 substituents, each of which may be independently selected from the group consisting of alkyl, halogen, CHF 2, CF 3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R1 means a hydrogen atom; R2 means a phenyl or cycloalkyl group, optionally having 1, 2 or 3 substituents, which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen , whose aliphatic and cycloaliphatic radicals can be partially or completely halogenated and / or the cylcoaliphatic radicals can be substituted by 1 to 3 alkyl groups, and whose phenyl group can have from 1 to 5 halogen atoms and / or 1 to 3 substituents, are independently selected from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and the amide phenyl group of which may be fused with a saturated 5-membered ring, which is optionally substituted by one or more alkyl groups and / or one heteroatom selected from O, and S, and as acaricide the active substance known as Fenazaquin These mixtures are described as being especially effective against botrytis. fungicide mixtures, containing as an active component one of the aszoles II.1. until 11.17. 1- [(2R £ 4gS; 2RS, 4 = R) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofuryl] -lH-1, 2,4-triazole (II.1) 2- (-chlorophenyl) -3-cyclopropyl-1- (1H-1,2,4-tri- azol-1-yl) -butan-2-ol (II.2) (±) -4-chloro-4- [4-methyl-2- (1H-1, 2,4-triazpl-l-ylmethyl) • l, 3-dioxolan-2-yl] -phenyl-4-chlorophenyl ether (II.3) (E) - (R, S) -l- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H-1, 2,4-triazol-1-yl) pent-1-en -3-ol (II.4) (Z) -2- (1 H-1,2,4-triazol-1-ylmethyl) -2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane (II.5) 4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4-triazolylmethyl) -butyronitrile (II.6) CN 3- (2,4-dichlorophenyl) -6-f-luoro-2- (1H-1,2,4-triazol-1-yl) quinazolin-4 (3H) -one (II.7) bis (4-fluorophenyl) (methyl) (1 H-1,2,4-triazol-1-ylmethyl) silane (II.8) CH 3 (R, S) -2- (2,4-dichlorofenyl) -1- (1 H-1,2,4-tria-zol-1-yl) -hexan-2-ol (II.9) (1RS, 5R £, 5 = R) -5- (4-chlorobenzyl) -2, 2-dimethyl-1- (1H-1,2,4-triazol-1-ylmethyl) cyclopentanol (11.10) N-propyl-N- [2- (2,4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide (11.11) (±) -1- [2- (2,4-dichlorophenyl) -4-propyl-l, 3-dioxolan-2-ylmethyl] -lH-l, 2,4-triazole (11.12) (R, S) -1- (4-chlorophenyl) -4,4-dimethyl-3- (1H-1,2,4-triazol-1-yl-methyl) -pentan-3-ol (11.13) (±) -2- (2,4-dichlorophenyl) -3- (1 H-1,2,4-triazol-yl) -propyl-1, 1,2, 2-tetrafluoroethyl ether (11.14) and CH2OCF2CHF2 (E) -l- [l - [[4-chloro-2- (trifluoromethyl) -phenyl] imino] -2-propoxyethyl] -lH-imidazole (11.15) alcohol (RS) -2,4 '-difluoro-a- (1H-1,2,4- triazol-1-ylmethyl) -benzhydroyl alcohol (11.16) 2-p-chlorophenyl-2- (1H-1,2,4-triazol-1-ylmethyl) -hexanenitrile (11.17) CH2- (CH2) 2-CH3 The azole II derivatives, their obtaining and action against harmful fungi themselves are known: II.1: common name: bromouconazole, Proc. Br. Crop Prot. Conf.- Pests Dis., 5-6, 439 (1990); II .2 common name: cyproconazole, US-A 4,664,696; II .3 common name: diphenoconazole, GB-A 2,098,607; II .4 common name: diniconazole, CAS RN [83657-24-3]; II .5 common name (proposed): epoxiconazole, EP-A 196 038; II 6 common name: fenbuconazole (proposed), EP-A 251 775; II 7 common name: fluquinconazole, Proc. Br. Crop Prot. Conf. Pests Dis. , 5-3, 411 (1992); II 8 common name: flusilazole, Proc. Br. Crop Prot. Conf.- Pests Dis. , 1, 413 (1984); II 9. common name: hexaconazole, CAS RN [79983-71-4]; II 1C): common name: metconazole, Proc. Br. Crop Prot. Conf.- Pests Dis. , 5-4, 419 (1992); 11. 12 common name: propiconazole, GB-A 1,522,657; 11. 13 common name: tebuconazole, US-A 4,723,984; 11. 14 common name: tetraconazole, Proc. Br. Crop Prot. Conf. - Pests Dis., 1, 49 (1988); 11. 15 common name: triflumizole, JP-A 79 / 119,462 11. 16 common name: flutriafol, CAS RN [76674-21-0] 11. 17 common name: myclobutanil, CAS RN [88671-89-0].

The present invention has for its object to provide other additional products for controlling harmful fungi and especially for certain indications.

Surprisingly it has been found that this object is achieved with a mixture containing as active substances compounds amide of formula I defined above and as another component of fungicidal active substance fungicide class of azoles II.1 to 11.17.

The mixtures according to the invention have synergetic action, so they are suitable for controlling harmful fungi and especially for controlling the powdery mildew in legumes and grapes.

In the sense of the present invention, halogen means fluorine, chlorine, bromine and iodine, and especially fluorine, chlorine and bromine. The term "alkyl" embraces linear or branched alkyl groups. Preferably, they are linear or branched alkyl groups of 1 to 12 and especially 1 to 6 carbon atoms. Examples of alkyl groups are alkyl, such as, especially 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 dimethylbuyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, 1,2-trimethylpropyl, 1,2,2- trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 1-ethylpentyl, 2-ethylpentyl, 1-propylbutyl, octyl, decyl, dodecyl.

Halogenoalkyl represents an alkyl group defined above, which is partially or completely halogenated with one or more halogen atoms, especially fluorine and chlorine. Preferably it will contain from 1 to 3 halogen atoms, with preference being given to the difluoromethane group or the trifluoromethyl group. and haloalkyl alkyl are analogously valid for the alkyl and haloalkyl groups in alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl and alkylsulfonyl.

The alkenyl group comprises linear and branched alkenyl groups. Preferably, they are linear or branched alkenyl groups with 3 to 12 and especially 3 to 6 carbon atoms. Examples of alkenyl groups are 2-propenyl, 2-butenyl, 3-bute-nyl, l-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- hexe-nile, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, l-methyl-3-pentenyl, 2-methyl- 3-pente-nyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, l-methyl-4-pente-nyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4- methyl-4-pente-nile, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-2-butenyl, 1, 2-dimethyl-3-butenyl, 1,3-dime yl-2-butenyl, 1, 3-dimethyl-3-butenyl, 2, 2-dimethyl-3-butenyl, 2, 3-dimethyl-2-butenyl , 2, 3-dimethyl-3-butenyl, 1-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1, 1.2 -trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl and l-ethyl-2-methyl-2-propenyl, especially 2-propenyl, 2-bute-nyl, 3-methyl-2-butenyl and 3-me til-2-pentenyl.

The alkenyl group can be partially or completely halofenode with one or more halogen atoms, especially fluoro and chloro. Preferably, it will have from 1 to 3 halogen atoms.

The alkynyl group comprises linear or branched alkynyl groups. Preferably, these are linear or branched alkynyl groups having 3 to 12 carbon atoms and especially 3 to 6 carbon atoms. Examples of 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-penti-nyl, 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. nyl and its halogen substituents, as well as the alkynyl group, are analogously used for f-alkenyloxy and alkynyloxy.

In the cycloalkyl group, it is preferably a C3-C6-cycloalkyl group, such as, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. When the cycloalkyl group is substituted, then it will preferably have 1 to 3 C? -C4-alkyl radicals as substituents.

Cycloalkenyl represents, preferably a C-C6-cycloalkenyl group, such as, for example, cyclobutenyl, cyclopentenyl or cyclohexenyl. When the cycloalkenyl group is substituted, then, it will preferably have 1 to 3 C? -C4-alkyl radicals as substituents.

A cycloalkoxy group is preferably a Cs-Cg-cycloalkoxy group, such as, for example, cyclopentyloxy or cyclohexyloxy. When the cycloalkoxy group is substituted, then it will preferably have 1 to 3 C? -C4-alkyl radicals as substituents.

The cycloalkenyloxy group is preferably a C5-C6-cycloalkenyloxy group, such as, for example, cyclopentyloxy or cyclohexyloxy. When the cycloalkenyloxy group is substituted, then it preferably has 1 to 3 alkyl radicals having 1 to 4 carbon atoms. carbon as substituents.

Aryl preferably represents phenyl.

When A means a phenyl group, it may contain one, two or three of the abovementioned substituents in an arbitrary position. Preferably, these substituents will be selected, independently, from alkyl, difluoromethyl, trifluoromethyl and halogen, especially chlorine, bromine and iodine. The fe-nyl group very preferably has a substituent at position 2.

When A is a 5-membered heterocycle, it is in particular a furyl, thiazolyl, pyrazolyl, imidazolyl, oxazolyl, thienyl, triazolyl or thiadiazolyl radical or a corresponding dihydro or tetrahydro derivative. A thiazolyl or pyrazolyl radical is preferred.

When A represents a 6-membered heterocycle, then it is a pyridyl radical or a radical of the formula: where one of the radicals X and Y means O, S or NR23, meaning R23 H or alkyl and the other radical representing X and Y CH2, S, SO, S0 or NR23. The dotted line means that a double bond is eventually present.

Most preferably, the 6-membered aromatic heterocycle is a pyridyl radical, especially a 3-pyridyl radical, or a radical of the formula (A3) where X is CH2, S, SO or S02.

The aforementioned heterocyclic radicals can optionally have 1, 2 or 3 of the abovementioned substituents, the substituents being selected, preferably, each independently of the other, from alkyl, halogen, difluoromethyl or trifluoromethyl.

Most preferably, A means a radical of the formulas: (A5) (A7) CH3 where R3, R4, R6, R7, R8 and R9 signify, each independently of the other, hydrogen, alkyl, especially methyl, halogen, especially chloro, CHF2 or CF3. hydrogen atom.

The radical R 2 in the formula I preferably means a phenyl radi-lime. Preferably, R2 has a substituent, which is very particularly at position 2. The (or substituents) are preferably selected from alkyl, cycloalkyl, cycloalkenyl, halogen or phenyl.

The substituents of the radical R.sup.2 may in turn be replaced again. The aliphatic or aromatic substituents may be partially or completely halogenated, especially fluorinated or chlorinated. Preferably, they will have 1, 2 or 3 fluorine or chlorine atoms. When the substituent of the radical R2 is a phenyl group, then it can be substituted, preferably, by 1 to 3 halogen atoms, especially chlorine atoms, and / or by a radical, which is selected, preferably, from alkyl and alkoxy Especially preferred is the phenyl group with a halogen atom in the p-position, that is to say the especially preferred substituent of the radical R 2 is a phenyl radical substituted by halogen in p. The radical R2 can also be condensed with a five-membered ring, the ring itself being able to have from 1 to 3 alkyl substituents.

R2 represents, then, for example, indanyl, thiaindanyl and oxaindanyl. Preferred are indanyl and 2-oxaindanyl, which are linked, especially via the 4-position with the nitrogen atom.

In a preferred variant, the product according to the invention contains, as the amide compound, a compound of the formula I, wherein A has the following meanings: phenyl, pyridyl, dihydropyranyl, dihydrooxathiinyl, dihydroxyatinyl oxide, dihydrooxathiinyl dioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, the groups may have 1, 2 or 3 substituents, independently selected from alkyl, halogen, difluoromethyl and trifluoromethyl.

According to another preferred variant A means: pyridin-3-yl, which optionally is stabilized in the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; phenyl, which is optionally substituted in the 2-position by methyl, trifluoromethyl, chloro, bromo or iodo; 2-methyl-5,6-dihydro-l, 4-oxatiin-3-yl or the 4-oxide or 4,4-dioxide; 2-methyl-furan-3-yl, which is optionally substituted in the 4-position and / or 5 by methyl; thiazol-5-yl, which is optionally substituted in the 2-position and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; thiazol-4-yl, which is optionally substituted in the 2-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; l-methylpyrazol-4-yl, which is optionally substituted in the 3-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; or oxazol-5-yl, which, optionally, is substituted in the 2-position and / or 4 by methyl or chloro.

According to another preferred variant, the products according to the invention contain as the amide compound a compound of the formula I, wherein R 2 represents a phenyl group, which is optionally substituted by 1, 2 or 3 of the aforementioned substituents.

According to another preferred variant, the products according to the invention contain, as the amide compound, a compound of the formula I, wherein R2 denotes a phenyl group, which in the 2-position has one of the following substituents: C3-Cs-alkyl, C5-C6- cycloalkenyl, Cs-Cd-cycloalkyloxy, cycloalkenyloxy, which groups may be substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, phenyl, which is substituted by 1 to 5 halogen atoms and / or 1 to 3 groups, independently selected from C! -C -alkyl, C? -C4-haloalkyl, C? -C -alkoxy, C? -C4-halogen-alkoxy, C? -C -alkylthio and C? -C4-haloalkylthio, indanyl or oxaindanyl, which, optionally, is substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms.

According to another preferred variant, the products according to the invention contain, as the amide compound, a compound of the formula la, where A means (Al) (A2) (A3) (A7) (A8) X means methylene, sulfur, sulfinyl or sulfonyl (S02), R3 signifies methyl, difluoromethyl, trifluoromethyl, chloro, bromo or iodo, R4 signifies trifluoromethyl or chloro, R5 signifies hydrogen or methyl, R6 signifies methyl, difluoromethyl, trifluoromethyl or chloro, R7 means hydrogen or, methyl or chloro, R8 signifies methyl, difluoromethyl or trifluoromethyl, R9 signifies hydrogen or, methyl, difluorosmethyl, trifluoromethyl or chloro, R10 signifies C? -C4-alkyl, C? -4-alkoxy, C? -4- alkylthio or halogen. nen as the amide compound a compound of the formula Ib where R4 means halogen and Rll means phenyl, which is substituted by halogen.

Suitable amide compounds of formula I are those, of EP-A-545 099 and 589 301, which are incorporated herein by reference in their entirety.

The preparation of the amide compounds of the formula I is known, for example, from EP-A-545 099 or 589 301 or can be carried out according to analogous processes.

The mixtures according to the invention contain as component II an azole derivative II selected from the group of compounds II.1 bis 11.17 in order to develop the synergistic effect, since a small proportion of the amide compound of the formula I is sufficient. Preferably, the compound is used of amide and azole in a quantitative ratio of 20: 1 to 1:20, especially 10: 1 to 1:10.

Thanks to the basic character of the nitrogen atoms contained in them, azoles II are capable of forming salts or adducts with inorganic or organic acids or with salts of metal ions.

Examples of inorganic acids are the halogenated hydroxides, such as, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid and hydroiodic acid, sulfuric acid, phosphoric acid and nitric acid.

Suitable organic acids are, for example, formic acid, carbonic acid and alkanoic acids, such as acetic acid, trifluoroacetic acid, trichloroacetic acid and propionic acid, as well as glycolic acid, thiocyanic acid, lactic acid, succinic acid, citric acid, benzoic acid, cinnamic acid, oxalic acid, alkylsulfonic acids (sulfonic acids with linear or branched alkyl radicals with 1 sulfonic acids (aromatic radicals, such as phenyl and naphthyl, carrying one or two sulfonic acid groups), alkyl acids -phosphonic (phosphonic acids with linear or branched alkyl radicals with 1 to 20 carbon atoms), aryl-phosphonic or aryl-diphosphonic acids (aromatic radicals, such as phenyl and naphthyl, bearing one or two phosphoric acid radicals), the radicals of which alkyl or aryl can carry additional substituents, such as, for example, p-toluenesulfonic acid, licicollic, p-aminosalicyclic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

As metal ions, especially the ions of the first to eighth secondary group elements, especially chromium, manganese, iron, cobalt, nickel, copper, zinc and, in addition, of the second main group, especially calcium, are especially suitable. and magnesium, from the third and fourth main group, especially, aluminum, tin and lead. Metals may even be present in their corresponding valences.

Preferably, pure substances I and II are used in the preparation of the mixtures, to which other active substances can be added against harmful fungi or against other parasites, such as insects, arachnids, nematodes or also active herbicidal or regulating substances. of growth or fertilizers.

The mixtures of compounds I and II or the combined or separate use of compounds I and II provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of ascomycetes, basidiomycetes, ficomycetes and deuteromycetes. . In part they have systemic action, so they can also be used as foliar and soil fungicides.

They are especially important for combating countless fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soybeans, vine, barley, ornamental plants, sugar cane and countless seeds.

They are especially suitable for combating the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbitáces, Podosphaera leucotricha in apples, Uncinula necator in the vine, Puccinia species in cereals, Rhizoctonia species in al-godón , rice and grass, Ustilago species in cereals and sugarcane, Venturia inaequalis in apples, Helminthos-porium species in cereals, Septoria nodorum in wheat, Botrytis ciñera Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, species of Pseudspe-ronospora in cucurbitáces and hops, Plasmopara viticola in the vine, species of Alternaria in legumes and fruits, as well as species of Fusarium and Verticillium.

The mixtures according to the invention are most preferably used to control powdery mildew in vine and vegetable crops, as well as ornamental plants.

The compounds I and II can be applied simultaneously together or separately or successively; in the separate application, generally, the order in which the compounds are applied has no effect on the success of the treatment.

The application rates of the mixtures according to the invention vary, especially in agricultural growing areas, according to the desired effect of 0.01 to 8 kg / ha, preferably 0.1 to 5 kg / ha, especially 0.2 to 3.0 kg / ha.

The application rates of the compounds I vary from 0.01 to 2.5 kg / ha, preferably 0.05 to 2.5 kg / ha, especially 0.1 to 1.0 kg / ha. The application rates of compounds II vary, correspondingly, from 0.01 to 10 kg / ha, preferably 0.05 to 5 kg / ha, especially 0.05 to 2.0 kg / ha.

In the treatment of the seeds, the mixtures are applied in amounts of 0.001 to 250 g / kg of seeds, preferably 0.01 to 100 g / kg, especially 0.01 to 50 g / kg.

Whenever the plants are to combat phytopathogenic fungi, the separate or combined application of compounds I and II or mixtures from compounds I and II is carried out by spraying or spraying the seeds, plants or the soils before or after the planting of the plants, or before or after the emergence of the plants.

The synergistic fungicidal mixtures of the invention or compounds I and II can be used in the form of directly pulverisable solutions, powders and suspensions or in the form of aqueous, oleic or other highly concentrated suspensions, dispersions, emulsions, dispersions. of oil, spraying agents, spraying agents, directly sprayable granules, The forms of application depend entirely on the respective application purposes; in all cases, the finest possible distribution of the mixtures of the invention should be ensured.

The formulations are prepared in known manner, eg by mixing the active substance with solvents and / or support substances, if desired, using emulsifiers and dispersants, being precise, that in the case of using water as a diluent, they can be used also other organic solvents as auxiliary solvents. Suitable acyl substances are essentially: solvents, such as aromatics (eg xylenes), chlorinated aromatics (eg chlorobenzenes), paraffins (eg petroleum fractions), alcohols (eg methanol, butanol), ketones (eg cyclohexanone), amines (eg ethanolamine, dimethylformamide) and water; carrier substances, such as natural stone pilings (eg kaolins, clays, talcum) and synthetic stone powders (eg highly disperse silicic acid, silicates); emulsifiers, such as non-ionogenic and anionic emulsifiers (eg polyoxyethylene-fatty alcohol, alkylaryl and aryl sulfonates) and dispersants, such as sulphite residual liquors and methylcellulose.

Suitable surface-active substances are the alkaline earth metal and ammonium salts of lignin sulphonic acid, naphthalamine acid, phenolsulfonic acid, dibutyl naphthalene sulphonic acid, fatty acids, alkyl and alkylaryl sulphonates, alkyl sulfates, lauryl ether sulphates and alcohol sulfates. fatty acids, as well as salts of sulphonated hexa-, hepta- and octadecanoles, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene-noctilphenol ethers, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol condensates, ethylene oxide, ethoxylated castor oil, polyoxyethylene alkyl ether, polyoxypropylene ethoxylated, polyglycol ether-ketal of lauryl alcohol, sorbitol ester, lignin sulfite residual liquors icas and methylcellulose.

The powders, spraying and spreading agents can be obtained by mixing or co-grinding the compounds I or II or the mixture from the compounds I and II with a solid support. homogeneous pellets can be prepared by joining active substances with solid supports.

Suitable solid fillers or carriers are, for example, mineral earths, such as silica gel, siliceous acids, silicates, aleo, kaolin, attaclay, limestone, chalk, bolus, loess, dolomite, diatomaceous earth, magnesium sulfate and sulphate. calcium, magnesium oxide, ground plastics, fertilizers, such as eg ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and vegetable products, such as cereal flours, bark powders of trees, wood and nut shell, cellulose powder and other solid supports.

The formulations generally contain between 0.1 and 95% by weight, preferably between 0.5 to 90% by weight, of one of the compounds I or II or of the mixture of the compounds I or II. The active substances are used here in a purity of 90% up to 100%, preferably 95% up to 100% (according to HPLC spectrum).

The compounds I or II or of the mixtures or the corresponding formulations are applied, treating the harmful fungi, their living space or the plants, seeds, floors, areas, materials or enclosures to be kept free of them, with an ac -Fungicidal compound of compounds I and II in the separate application.

The application can be made before or after infection by harmful fungi.

Examples of formulations of this type, which contain the active substances, are: I. a solution from 90 parts by weight of the active substances and 10 parts by weight of N-methylpyrrolidone, suitable for use in the form of tiny drops; II, a mixture of 20 parts by weight of the active substances, 80 parts by weight of xylene, 10 parts by weight of the addition product of 8 to 10 moles of ethylene oxide to 1 mole of N-monoethanolamide of acid oleic, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight of the addition product of 40 moles of ethylene oxide to 1 moles of castor oil; by distributing the solution finely in water a dispersion is obtained; . active substances, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 moles of ethylene oxide to 1 mole of castor oil; IV. an aqueous dispersion from 20 parts by weight of the active substances, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral acid fraction from the boiling point of 210 to 280 ° C and 10 parts by weight of the product of addition of 40 moles of ethylene oxide to 1 mole of castor oil; V. a milled mixture in a hammer mill from 80 parts by weight of the active substances, 3 parts by weight of the sodium salt of diisobutylnaphthalene-1-sulphonic acid, 10 parts by weight of the sodium salt of a lignin sulphonic acid of a sulphite residual liquor and 7 parts by weight of powdery silica gel; by distributing the mixture finely in water, a spray mixture is obtained; SAW. an intimate mixture from 3 parts by weight of the active substances and 97 parts by weight of finely particulate kaolin; this spraying agent contains 3% by weight of active substance; VII. an intimate mixture is 30 parts by weight of the active substances, 92 parts by weight of pulverulent silica gel and 8 parts by weight of paraffin oil applied on the surface of this silica gel; this preparation gives an active substance with good adhesion; VIII. a stable aqueous dispersion from 40 parts by weight of the active substances, 10 parts by weight of the sodium salt of a condensate of phenolsulfonic acid, urea-formaldehyde, 2 parts by weight of silica gel and 48 parts by weight of water, which can be be further diluted; IX. a stable olefin dispersion from 20 parts by weight of the active substances, 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of the fatty alcohol polyglycol ether, 20 parts by weight of the sodium salt of an acid condensate phenylsulphonic-urea-formadehyde and 88 parts by weight of a paraffinic mineral oil.

Application example The synergistic effect of the mixtures according to the invention can be demonstrated by the following tests: dyed as a 10% emulsion in a mixture from 63% by weight of cyclohexanone and 27% by weight of an emulsifier, and are diluted in water to the desired concentration.

The evaluation is done, determining the area of the leaves infested in percent. These percentage values are converted into degrees of action. The degree of action (W) is determined by means of the formula of Abbot in the following way: W = (1 - a) -100 / ß a is equivalent to the fungal infection of the plants treated in% and ß is equivalent to the fungal infection of the untreated (control) plants in%.

Given a degree of action equal to O, the infestation of the treated plants is equivalent to that of the untreated control plants; in the case of a 100% action grade, the treated plants do not show any infestation.

The expected degrees of action of the mixtures of active substances are determined by the formula of Colby [R.S. Colby, Weeds 23., 20-22 (1967)] and compared with the observed degrees of action.

Colby's formula: E - x + y - -y / 100 E 'signifies the expected degree of action, translated in% of the untreated control, when using the mixture from the active substances A and B in the concentrations a and b; x is the degree of action, translated in% of the untreated control, by using the active substance A in the concentration a; and it is the degree of action, translated in% of the untreated control, by using the active substance B in the concentration b.

Efficiency against Botrytis cinerea in peppers Slices of green peppers are pulverized until they drip with an aqueous preparation of active substance prepared from a wood solution composed of 10% active substance, 63% cyclohexanone and 27% emulsifier. 2 hours after drying the spore board of Botrytis cinerea, which contains 1.7 x 106 spores per ml of an aqueous solution of 2% malt. It is incubated for four days. The botrytis infection is then visually evaluated in the slices of the infected fruits.

The values determined for the percentage of the infected leaf surface are converted into action degrees based on the untreated control. A degree of action equal to O means the same infection as in the untreated control, a degree of action equal to 100 means 0% infection. The expected action levels for active substance combinations are determined according to Colby's formula (Colby, SR (Calculating synergistic and antagonistic responses of herbicide Combinations, Weeds, 15, pp. 20-22, 1967) and compared with the observed degrees of action.

The following components are used as compounds of formula I: The results can be derived from the following tables 1 and 2.

Table 2 *) calculated according to Colby's formula From the results of the test it can be deduced that the degree of action observed is with all the mixing ratios higher than the degree of action calculated according to the Colby formula.

Claims (6)

Claims Fungicidal mixtures containing as active components a) an amide compound of the formula I A-CO-NR! R2 where A denotes an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from O, N and S; The aryl group or the heterocycle may optionally have 1, 2 or 3 substituents, each of which may be independently selected from the group consisting of alkyl, halogen, CHF, CF3, alkoxy, haloalkoxy, alkylthio, alkylsulfinyl and alkylsulfonyl; R means a hydrogen atom; R2 means a phenyl or cycloalkyl group, optionally having 1, 2 or 3 substituents, which are selected from alkyl, alkenyl, alkynyl, alkoxy, alkenyloxy, alkynyloxy, cycloalkyl, cycloalkenyl, cycloalkyloxy, cycloalkenyloxy, phenyl and halogen, aliphatic and cycloaliphatic radicals can be partially or completely halogenated and / or the cylcoaliphatic radicals can be substituted by 1 to 3 alkyl groups, and whose phenyl group can have from 1 to 5 halogen atoms and / or 1 to 3 substituents, which are selected independently, from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and whose amide phenyl group can be fused with a saturated 5-membered ring, which is optionally substituted by one or more alkyl groups and / or a heteroatom selected from between O, and S, and b) an azole derivative II selected from compounds II.1 to 11.17

1- [(2RS, 4RS; 2R £, 4SR) -4-bromo-2- (2,4-dichlorophenyl) tetrahydrofuryl] -1H-1, 2,4-triazole (II .1) Lf azol-l-il) -butan-2-ol (II.2) (+) - 4-chloro-4- [4-methyl-2- (lH-l, 2,4-triazol-l-ylmethyl) -1,3-dioxolan-2-yl] -phenyl-4-chlorophenyl ether (II.3) (E) - (R, S) -l- (2,4-dichlorophenyl) -4,4-dimethyl-2- (1H-1, 2,4-triazol-1-yl) pent-1-en-3 -ol (II .4) 10 (Z) -2- (1 H-1,2,4-triazol-1-ylmethyl) -2- (4-fluorophenyl) -3- (2-chlorophenyl) -oxirane (II.5) 4- (4-chlorophenyl) -2-phenyl-2- (1H-1,2,4-triazolylmethyl) -butryronitrile (II.6) 15 3- (2,4-dichlorophenyl) -6-fluoro-2 - (1H-1,2,4-tri- azol-l-yl) quinazolin-4 (3H) -one (II.7) bis (4-fluorophenyl) (methyl) (1H-1,2,4-triazol-1-ylmethyl) silan (II.8) (R, S) -2- (2,4-dichlorophenyl) -l- (lH-1, 2,4-triazol-1-yl) hexan-2-ol (II.9) 25 (1R £, 5RS: 1RS, 5SB) -5- (4-chlorobenzyl) -2, 2-dimenthyl-1- (1H-1, 2,4-triazol-1-ylmethyl) cyclopentanol (II.10) N-propyl-N- [2- (2, 4,6-trichlorophenoxy) ethyl] imidazole-1-carboxamide (II.11) 30 (+) -1- [2- (2,4-dichlorophenyl) -4- propyl-1, 3-dioxolan-2-ylmethyl] -lH-1, 2,4-triazole (11.12) (R, S) -1- (4-chlorophenyl) -4,4-dimethyl-3- (1H-1, 2,4-tri- 35-azole-1-ylmethyl) -pentan-3-ol (II.13 ) (±) -2- (2,4-dichlorophenyl) -3- (1 H-1,2,4-triazol-yl) -propyl-1, 1,2, 2-tetrafluoroethyl ether (11.14) and 40 (E) -l- [1 - [[4-chloro-2- (trifluoromethyl) -phenyl] imino] -2-propyl-ethyl] -lH-imidazole (11.15) alcohol (RS) -2,4 '-difluoro-a- (1H-1, 2,4-triazol-1-ylmethyl) -benzhydryl (II.16) Lf trilo (11.17) in an active synergetic quantity. Fungicidal mixture according to claim 1, wherein in the formula I the radical A means one of the following groups: phenyl, pyridyl, dihydropyranyl, dihydrooxathiinyl, dihydrooxathiinyl oxide, dihydrooxathiinyl dioxide, furyl, thiazolyl, pyrazolyl or oxazolyl, which groups may have 1, 2 or 3 substituents independently selected from alkyl, halogen, difluoromethyl and trifluoromethyl. Fungicidal mixture according to claim 1, wherein in the formula I the radical A means one of the following groups: pyridin-3-yl, which is optionally substituted at the 2-position by halogen, methyl, difluoromethyl, trifluoromethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl; phenyl, which is optionally substituted in the 2-position by methyl, trifluoromethyl, chloro, bromo or iodo; 2-methyl-5,6-dihydropyran-3-yl; 2-methyl-5,6-dihydro-l, 4-oxatiin-3-yl or 4-oxide or 4,4-dioxide thereof;

2-methyl-furan-

3-yl, which is optionally substituted in the

4-position and / or 5 by methyl; thiazol-

5-yl, which is optionally substituted in the 2-position and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; thiazol-4-yl, which is optionally substituted in the 2-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; l-methylpyrazol-4-yl, which is optionally substituted in the 3-position and / or 5 by methyl, chloro, difluoromethyl or trifluoromethyl; tion 2 and / or 4 by methyl or chlorine. Fungicidal mixture according to one of the preceding claims, which contains a compound of the formula I, wherein R 2 represents a phenyl group, which is optionally substituted by 1, 2 or 3 of the substituents indicated in claim 1. Fungicidal mixture according to claim 4, wherein R2 means a phenyl group, which has in position 2 one of the following substituents: C3-C

6-alkyl, C5-C6-cycloalkenyl, Cs-Cg-cycloalkyloxy, cycloalkenyloxy, whose groups may be substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms, phenyl, which may be substituted by 1 to 5 halogen atoms and / or 1 to 3 groups, independently selected from C! -C -alkyl, Ci -Cj-haloalkyl, C? -C -alkoxy, C? -C4-halogenoalkoxy, C? -C-alkylthio and C? -C -haloalkylthio, or where R2 means indanyl or oxaindanyl, which is optionally substituted by 1, 2 or 3 alkyl groups with 1 to 4 carbon atoms. Fungicidal mixture according to one of claims 1 to 5, which contains an amide compound of the formula as follows: where it means (Al) (A2) (A3) (A7) (A8) X means methylene, sulfur, sulfinyl or sulfonyl (S02), R3 means methyl, difluoromethyl, trifluoromethyl, chloro, bromo or iodo, R4 means trifluoromethyl or chloro, R5 means hydrogen or methyl, R6 means methyl, difluoromethyl , trifluoromethyl or chloro, R7 means hydrogen, methyl or chloro, R8 means methyl, difluoromethyl or trifluoromethyl, R9 means hydrogen, methyl, difluoromethyl, trifluoromethyl or chloro, Ri ° means C? -C4-alkyl, C? -C-alkoxy, C? -C-alkylthio or halogen. Fungicidal mixture according to one of claims 1 to 5, which contain as compounds of amide a compound of the following formula Ib: where R 4 is halogen and R 11 is phenyl, which is substituted by halogen. as the amide compound a compound of the following formulas: Fungicidal mixture according to one of the preceding claims, which is conditioned in two parts, the first containing the amide compound I in a solid or liquid support and the second part an azole of the formulas II.1 to 11.17 in a solid or liquid support . Process for controlling harmful fungi, characterized in that the fungi, their living space or the materials, plants, seeds, soils, areas or enclosures to be kept free from infestation by the fungi are treated with a fungicidal mixture according to one of the claims 1 to 9, it being possible to apply the active substances, amide compounds, I and an azole of the formulas II.1 to 11.17 simultaneously, that is, jointly or separately, or successively.