MXPA00005388A - Fungicide mixtures based on amide compounds and pyridine derivatives - Google Patents

Abstract

The invention relates to fungicide mixtures containing, as active components, a) an amide compound of formula (I) A-CO-NR1R2 and b) a dithiocarbamate (II) selected from the group:manganese-ethylene bis(dithiocarbamate) (zinc complex) (IIa);manganese-ethylene bis(dithiocarbamate) (IIb);zinc ammoniate-ethylene bis(dithiocarbamate) (IIc) and zinc-ethylene bis(dithiocarbamate) (IId), and/or c) a carbamate of formula (III) (CH3)2N-CH2CH2CH2-NH-CO2-CH2CH2CH3 and/or b) a N-acetonyl-benzamide of formula (IV) or one of the salts thereof or adducts, and/or b) an active substance of formula (V), and/or an active substance of formula (VI), and/or e) an active substance of formula (VII), whereby the substituents have the meanings given in the description. The active components are provided in a synergistically effective quantity.

Description

FUNGICIDE MIXTURES BASED ON AMID COMPOUNDS AND PIRIDINE DERIVATIVES Description The present invention relates to fungicidal mixtures for controlling harmful fungi, which contain A-CO-NRiR2 (I) wherein A means an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from 0, 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, halogenoalkoxy, 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 , which are independently selected 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 O, and S, b) a dithiocarbamate (II) selected from the group manganese-ethylenebis (dithiocarbamate) (zinc complex) (Ha), manganese-ethylenebis (dithiocarbamate) (Ilb), zinc ammonium-ethylenebis (dithiocarbamate) (la) and - zinc- ethylenebis (dithiocarbamate) (lid) c) a carbamate of the formula III (CH3) 2N-CH2CH2CH2-NH-C02-CH2CH2CH3 (III) I d) an N-acetonyl-benzamide of formula IV wherein the substituents have the following meanings: R12, R14 each independently of the other, halogen or C? -C-alkyl; R13 cyano, C? -C-alkyl, C2-C4-alkenyl, C-alkynyl or C? -C-alkoxy; R15 hydrogen or C? -C-alkyl; R16 C2-C-alkyl; R17 thiocyano, isothiocyano or halogen, or one of its salts or adducts, I e) an active substance of the formula V, H Rl8 _ or - P 0 Y (V) § in which the substituents have the following meanings: main of the periodic system or a group NR19R20R21R22 R18 hydrogen, a CL-Cis-alkyl group, which may be substituted by halogen or a nitro group, a C2-Cs-alkenyl, or C2-C8-alkynyl group, which may be substituted by halogen or a nitro group, a C group C8-alkoxy-Ci-C-alkyl or a C2-C8-alkenyl-C-C8-alkyl group, an aryl group optionally substituted with 6 to 14 carbon atoms, a C3-C-cycloalkyl group, a C group C4-alkylaryl or a heterocyclic group with 5 or 6 ring atoms and a heteroatom of the group N, 0 or S, whose heterocyclic group can be linked directly or via an aliphatic chain with the oxygen atom, and R19-R22 mean, each independently of the other, a C? -C4-alkyl group or a C? -C4-hydroxyalkyl group, I f) an active substance of formula VI, I g) an active substance of the formula VII, wherein the substituents R23 to R26 have the following meanings: quinilo, C? -C4-alkoxycarbonyl, C? -C4-alkylcarbonyl, C3-C7-cycloalkyl, C6-C? or -aryl, optionally substituted by C? -C4-alkyl, C? -C4-alkoxy, nitro or halogen, C? -C6-alkoxy, C2-C6-alkoxyalkyl, C2-C5-alkylthioalkyl, di- C? -C4-alkylaminoalkyl, pyridyl, thiazolyl, furilo or tendinole means 0, S or S = 0 in an active synergetic quantity.

The amide compounds of the formula I are known per se and are described in the literature (EP-A 545 099).

In WO 97/08952 fungicidal mixtures are described, which contain, together with the compounds of the formula I, still phenazaquin as another additional component. These are described as very effective against botrytis.

Also known are dithiocarbamates II (lia: common name: mancozeb, US-A 3,379,610; Iib: common name: maneb, US-A 2,504,404; lie: previous common name: metiram, US-A 3,248,400; lid: common name: zineb, US-A 2,457,674), its preparation and its action against harmful fungi.

Compound III, its preparation and use is also known (DE-OS 15 67 169, common name: propamocarb).

Synergistic mixtures of the compounds IV with dithiocarbamates, their preparation and their action against harmful fungi are conicides of EP-A 753 258 and US-A 5,304,572.

Compounds V are described in the literature as fungicides and insecticides (for example DE 24 63 046 and the literature cited therein) A known representative of this class of active substances is marketed under the common name fosethyl or fosethyl-Al.

Compound VI is known under the proposed common name fa o-xadone (Proc. Brighton Crop Protection Conference 1996, Peste and Diseases, pages 21-26).

The compounds of formula VII are known, among others, from EP-A 551,048 and EP-A 629,616.

The object of the present invention is to provide mixtures, which enable a better effect against harmful fungi to be obtained by applying lower total amounts of the active substances (synergistic mixtures).

Therefore, the mixtures defined above were found. In addition, it was found that by simultaneously applying, separately or jointly, the compounds I and compounds II to V or by applying the compounds I and compounds II to V successively, the harmful fungi are better controlled than with the compounds I or II to V by themselves.

The mixtures according to the invention have a synergetic effect, so they are suitable for combating harmful fungi and especially powdery mildew on grapes and cereals.

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-methylpennyl, 1,2-dimethyl-butyl, 1,3-dimethylbutyl, 2,3-dimethylbutyl, 1,1-dimethylbutyl, , 2-dimethylbutyl, 3,3-dimethylbutyl, 1, 1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethylbutyl, 2-ethylbutyl, l-ethyl-2-methylpropyl, n-heptyl, -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.

The explanations given above with respect to the alkyl and haloalkyl group are analogously valid for the alkyl and haloalkyl groups in alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl and alkylsulfonyl. fallen. 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-nyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pente-nyl, 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-nyl, 1, l-dimethyl-2-butenyl, 1, l-dimethyl-3-butenyl, 1,1-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 -bu-tenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, l-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl-2-butenyl, -ethyl-3-butenyl, 1, 1, 2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl and l-ethyl-2-methyl-2-propenyl, especially 2-propenyl, 2-butenyl, 3-methyl-2-butenyl and 3-methyl-2-pente-nyl.

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.

The explanations given above with respect to the alkenyl group and its halogen substituents, as well as for the alkynyl group, are analogously valid for f-alkenyloxy and alkynyloxy.

Cβ-Cg-cycloalkyl, 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 C4-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? -Calkyl radicals as substituents.

A cycloalkoxy group is preferably a C5-C6-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 phenyl group very preferably has a substituent at the 2-position.

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: when R23 H or alkyl is represented and the other radical represents X and Y CH, 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) 15 where X is CH2, S, SO or S02.

The heterocyclic radicals mentioned can present, even¬ • 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: 40 where R3, R4, R6, R7, R8 and R9 signify, each independently of the other, hydrogen, alkyl, especially methyl, halogen, especially chloro, CHF2 or CF3. 45 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 2 can themselves 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 R 2 represents a phenyl group, which in the 2-position has one of the following substituents: C 3 -C 6 -alkyl, Cs-Cg- 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? -C4-alkyl, C? -C4-haloalkyl, C? -C-alkoxy, C? -C4-halo-alkoxy, C? -C4-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 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, R 7 is hydrogen or, methyl or chloro, R 8 is methyl, difluoromethyl or trifluoromethyl, R 9 is hydrogen q, methyl, difluoromethyl, trifluoromethyl or chloro, halogen.

According to a particularly preferred variant, the products contain, as an amide compound, a compound of the formula where R 4 represents halogen and Rii 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. 25 Formula IV represents, in particular, N-acetonyl-benzamides, in which the combination of the substituyents corresponds to a line in the following table: Especially preferred are the general and preferred N-acetonyl-benzamide, indicated in EP-A 753 258. those which R18 means hydrogen or a C-C4-alkyl group, and especially an ethyl group (-CH2CH3) and Y is a metal of the Iller group of the periodic system of elements. Also suitable are the first and second secondary group metals, such as Li, K, Na, Cs, Mg or Ca, to mention a few as examples.

But basically also compounds V are suitable, in which Ri8 and R19_R22 have the meanings indicated above.

As the compound V, the active substance known under the name fosethyl or its aluminum salt, fosethyl-Al is especially preferred.

The compound of formula VI (proposed common name: famoxa-dona), its preparation and its fungicidal properties are found in Proc. Brighton Crop Prot. Conference 1996, pages 21 to 26.

The compounds of formula VII and their preparation are described, for example in EP-A 551,048, EP-A 629,616 and EP-A 668,270. Preferred compounds of the formula VII are those which are described in the tables on pages 10, 11, 13, 14, 15 (for B = NH), 18 and 19 of EP-A 551,048.

Especially preferred are compounds VII, wherein R23 is Ci-Cg-alkyl (especially methyl, ethyl or propyl), C6-C6-haloalkyl or phenyl, R24 means c6-C6-alkyl (preferably methyl), C6-C6. -alkylthio (preferably methylthio), R25 means phenyl, optionally substituted by C? -C4-alkyl, halogen, nitro, C? -C4-alkoxy, C? -C4-alkylcarbonyl, pyridyl, furyl, thienyl, thiazolyl, thienyl or naphthyl , optionally substituted by C? -C4-alkyl and R26 means hydrogen or C? -C6-al-chyl.

In order to develop the synergistic effect, a small proportion of the amide compound in formula I is sufficient. Preferably, the amide compound is reacted with the active substance of formula II and / or III to V in a weight ratio of 50: 1 to 1:50, especially 10: 1 to 1:10. Here it is also possible to use ternary mixtures, which together with the amide compound I also contain compounds II as well as the compounds III, IV and / or V. In such mixtures the mixing ratio between compounds II, III, IV and V between them, at 50: 1 to 1:50, preferentially 10: 1 to 1:10. they, compounds IV 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: up to 20 carbon atoms), arylsulfonic and aryldi-sulphonic acids (aromatic radicals, such as phenyl and naphthyl, bearing one or two sulfonic acid groups), alkyl phosphonic acids (phosphonic acids with radicals) linear or branched alkyl 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), whose alkyl or aryl radicals can carry additional substituents , such as, for example, p-toluenesulfonic acid, salicylic acid, p-aminosalicyclic acid, 2-f acid enoxiben-zoic 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 to V 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 herbicidally active substances. or growth regulators or fertilizers.

The mixtures of the compounds I and II and / or III and / or IV and / or V or the joint or separate use of the compounds I and II and / or III and / or IV and / or V provide an excellent effect against a broad spectrum of phytopathogenic fungi, especially of the class of the part have systemic action, so they can also be used as foliar and fungal fungi.

They are especially important for combating a myriad of fungi in different crop plants, such as cotton, legumes (eg cucumbers, beans, tomatoes, potatoes and cucurbits), barley, turf, oats, coffee, corn, rice, rye, soy, 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 cotton, rice and grass, Ustilago species in cereals and sugar cane, Venturia inaequalis in apples, Helminthos-porium species in cereals, Septoria nodorum in wheat, Botrytis ciñera (gray rot) in strawberries, legumes, ornamental plants and vine, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, Pseudope-ronospora species in cucurbitas and hops, Plasmopara viticulture in the vine, Alternate species 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 and mildew on vine and pulse crops, as well as ornamental plants and cereals.

Compounds i and II and / or III to VII 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. and / or V and / or VI and / or VII vary, correspondingly, from 0.001 to 5 kg / ha, preferably 0.005 to 2 kg / ha, especially 0.01 to 1.0 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 and / or III and / or IV and / or V and / or VI and / or VII or mixtures of the compounds I and II and / or III and / or IV and / or V and / or VI and / or VII by spraying or spraying the seeds, plants or soils before or after sowing of the plants, or before or after the emergence of the plants.

The synergistic fungicidal mixtures of the invention or compounds I and II and / or III and / or IV and / or V and / or VI and / or VII can be used in the form of solutions, powders and suspensions directly sprayable or in the form of aqueous, oleic or other highly concentrated suspensions, dispersions, emulsions, oil dispersions, spraying, spraying agents, directly sprayable granules, by spraying, spraying, spraying, spraying or spraying . 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. alkaline earth metal and ammonium carbonate, co-naphthalisulfonic acid, phenolsulfonic acid, dibutylnaphthalene sulphonic acid, as well as fatty acids, alkyl and alkylaryl sulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, as well as salts of sulfated hexa, hepta and octadecanols, sulfonated naphthalene condensates and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalene sulfonic 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 sulphite residual liquors and methyl cellulose.

The powders, spraying and spreading agents can be obtained by mixing or co-grinding the compounds I or II and / or III and / or IV and / or V and / or VI and / or VII or the mixture from the compounds I and II and / or III and / or IV and / or V and / or VI and / or VII with a solid support.

Granules, eg coated granules, impregnated granules and homogeneous granules can be prepared by bonding 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 and / or III and / or IV and / or V and / or VI and / or VII or of the mixture of compounds I or II and / or III and / or IV and / or V and / or VI and / or VII. The active substances are used here in a purity of 90% up to 100%, preferably 95% up to 100% (according to the spectrum of HPLC). of the mixtures or the corresponding formulations are applied, treating the noxious fungi, their living space or the plants, seeds, soils, areas, materials or enclosures to be kept free of them, with an active fungicidal amount of the compounds I or II and / or II and / or IV and / or V and / or VI and / or VII 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 from 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 oleic acid N-monoethanolamide, 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; III. an aqueous dispersion from 20 parts by weight of the 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 oil of castor 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 silicagel; 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; active, 92 parts by weight of powdery silicagel 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 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: The active substances, used separately or together, are formulated 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 carried out, determining the area of the leaves in-festedas 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 0, the infestation of the treated plants is equivalent to that of the untreated control plants; in the case of 100% action, the treated plants do not present any infestation. vas are determined by means of Colby's formula [R.S. Colby, Weeds .15, 20-22 (1967)] and compared with the observed degrees of action.

Colby's formula: E = x + y - x-y / 100 E means 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.

Application example 1 Efficiency against Phytophthora infestans in tomatoes The leaves of tomato plants of the variety "Große Fleichto-mate" grown in pots are sprayed until they drip with an aqueous suspension, prepared from a stock solution composed of 10% active substance, 63% cyclohexanone and 27% emulsifier The next day the leaves are infected with an aqueous suspension of zoospores of Phytophthora infestans. Next, the plants are placed in a chamber saturated with water vapor at temperatures between 16 and 18 ° C. After 6 days the infection has developed so strongly in the sintered but infected control plants, that the infection can be evaluated visually in%.

The following components are used as compounds of formula I: 1. 2 Table 1 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 (5)

Claims

1. Fungicidal mixtures containing as active components a) an amide compound of the formula I A-CO-NR! R2 I where A means an aryl group or an aromatic or non-aromatic heterocycle with 5 or 6 members, having 1 to 3 heteroatoms selected from 0, 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; Ri 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, which are selected independently from alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio and haloalkylthio, and whose amidic phenyl group can be fused with a saturated 5-membered ring, which is optionally substituted by one or more alkyl groups and / or a selected heteroatom between 0, and S, and b) a dithiocarbamate (II) selected from the group manganese-ethylene bis (dithiocarbamate) (zinc complex) (lía), manganese-ethylenebis (dithiocarbamate) (Ilb), zinc ammoniac-ethylenebis (dithiocarbamate) (He) and zinc-ethylenebis (dithiocarbamate) (lid) c) a carbamate of formula III (CH3) 2 -CH2CH2CH2-NH-C? 2-CH2CH2CH3 (lll) I d) an N-acetonyl-benzamide of formula IV wherein the substituents have the following meanings: Ri2, Rl4 each independently of the other, halogen or C? -C4-alkyl; Ri3 cyano, C? -C4-alkyl, C2-C4-alkenyl, C2-C4-al-quinyl or C? -C4-alkoxy; l5 hydrogen or C? -C-alkyl; R16 C2-C4-alkyl; RI7 thiocyano, isothiocyano or halogen, or one of its salts or adducts, I e) an active substance of the formula V, H Rl8 0 - P - O Y (V) wherein the substituents have the following meanings: main group of the periodic system or a group NRi9R20R2iR22; Ri8 hydrogen, a C? -C? 8-alkyl group, which may be substituted by halogen or a nitro group, a C2-C8-alkenyl group, or C-C8-alkynyl group, which may be substituted by halogen or a nitro group, a C? -C8 alkoxy-Ci-Cs-alkyl group or a C2-C8-alkenyl-C? -C8-alkyl group, an aryl group optionally substituted with 6 to 14 carbon atoms, a C3-C-cycloalkyl group, a C? -C4-alkylaryl group or a heterocyclic group with 5 or 6 ring atoms and a heteroatom of the group N, O or S, the heterocyclic group of which can be linked directly or via an aliphatic chain with the oxygen atom, and R19_R22 mean, each independently of the other, a C? -C4-alkyl group or a C? -C4-hydroxyalkyl group, I f) an active substance of formula VI, I g) an active substance of formula VII, (VII) following: H, C? -C6-alkyl, C? -C6-haloalkyl, C2-C6-alkenyl, C2-C6-alkynyl, C? -C4-alkoxycarbonyl, C? -C4-alkylcarbonyl, formyl-C3-C- cycloalkyl, C6-C? o-aryl, optionally substituted by C? -C4-alkyl, C? -C-alkoxy, nitro or halogen, C? -C6-alkoxy, C2-C6-alkoxyalkyl, C2-C6- alkylthioalkyl, di-C? -C -alkylaminoalkyl, pyridyl, thiazolyl, furyl or thienyl and W means O, S or S = 0.

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 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-dihydropyran-3-yl; 2-methyl-5,6-dihydro-l, 4-oxatiin-3-yl or the 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 position 2 and / or 4 by methyl, chloro, difluoromethyl or trifluoromethyl; 2 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 is optionally substituted in position 2 and / or 4 by methyl or chloro.

4. Fungicidal mixture according to one of the preceding claims, which contains a compound of the formula I, wherein R2 means a phenyl group, which is optionally substituted by 1, 2 or 3 of the substituents indicated in claim 1.

5. Fungicidal mixture according to claim 4, wherein R2 means a phenyl group, which has in position 2 one of the following substituents: C3-C6-alkyl, Cs-Cg-cycloalkenyl, C5-C6-cycloalkyloxy, cycloalkenyloxy, whose groups can 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 , C?-C4-haloalkyl, C?-C4-alkoxy, C?-C4-haloalkoxy, C?-C4-alkylthio and C?-C4-haloalkylthio, or where R 2 represents indanyl or oxaindanyl, which optionally It is 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: • 35 45 where it means (A7) (A8) X means methylene, sulfur, sulfinyl or sulfonyl (S02), R3 means methyl, difluoromethyl, trifluoromethyl, chlorine, bromine or iodine, R4 means trifluoromethyl or chlorine, 5 means hydrogen or methyl, R6 means methyl, difluoromethyl , trifluoromethyl or chloro, R7 signifies hydrogen, methyl or chloro, R8 signifies methyl, difluoromethyl or trifluoromethyl, R9 signifies hydrogen, methyl, difluoromethyl, trifluoromethyl or chloro, Ri ° signifies C? -C4-alkyl, C? -C-alkoxy, C? -C4-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 signifies halogen and Ri means 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 containing compounds II and / or III to VII in a solid or liquid support. , Procedure 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 compounds II and / or III to VII simultaneously, namely, together or separately, or successively. SUMMARY OF THE INVENTION Fungicide mixtures to control harmful fungi, which contain A-CO-NRlR2 (I) b) a dithiocarbamate (II) selected from the group manganese-ethylenebis (dithiocarbamate) (zinc complex) (Ha), - manganese-ethylenebis (dithiocarbamate) (Ilb), zinc ammonate-ethylenebis (dithiocarbamate) (la) and - zinc -ethylenebis (dithiocarbamate) (lid) I c) a carbamate of the formula III (CH3) 2 -CH2CH2CH2-NH-C? 2-CH2CH2CH3 (lll) I d) an N-acetonyl-benzamide of formula IV or one of its salts or adducts, I e) an active substance of the formula V, H Rl8 _ or - P - O Y (V) f) an active substance of the formula VI, I g) an active substance of formula VII, wherein the substituents have the meanings indicated in the description.