MXPA99001784A - Agents for controlling harmful fungi - Google Patents

Abstract

Agents for controlling harmful fungi contain in a solid or liquid carrier (a) at least one compound of formula (I), in which M1 and M2 have different meanings, and (b) at least one valine amide of formula (II), in which R1 stands for C3-C4-alkyl and R2 stands for naphthyl or phenyl, the phenyl radical being substituted at position 4 by a halogen atom, a C1-C4-alkyl or C1-C4-alkoxy group. Also disclosed is a process for controlling harmful fungi by using these agents.

Description

COMPOSITIONS FOR CONTROLLING DONOS FUNGI AND METHOD FOR CONTROLLING HARMFUL FUNGI SAID COMPOSITIONS The present invention relates to compositions for controlling harmful fungi, in particular to mixtures with fungicidal action of certain carbamates or ethers of oximes and valine amides. Furthermore, the invention relates to a method for controlling harmful fungi using these compositions. Compounds of formula Illa wherein R ", R12, R13, R14, R15, myn have various meanings and X is an oxygen or amine group, their preparation and their use to control harmful fungi or pests of animal origin, have been disclosed in WO-A -96 / 01256. Corresponding triazole derivatives are described in WO-A-96 / 01258. The oldest German patent application DE-A-195 28 651 describes oxime ethers of formula Illb. where X is O or NH, Y is CH, CHO or NO, Z is O, S, NH or, for example, N-alkyl, and Ra, Rb and Rc can have a number of different meanings. These compounds are used to control harmful fungi or pests of animal origin. Compounds of the same type are also described in WO-A-95/21 153 and WO-A-95/21 15. Furthermore, in the prior art a series of amide amino acid compounds and their use for controlling harmful fungi are described. In this context, reference can be made, for example, to EP-A-0 398 072, WO-A-96/07638, DE-A-43 21 897 and the oldest German patent application DE-A-195 31 814. For example, DE-A-195 31 814 discloses valine amide derivatives of formula IIIc in which Rx and Ry have different meanings and the two optically active centers are in the configurations (S) and (R) respectively.

In addition EP-A-0 610 764 discloses combinations of fungicidal action components comprising a valine amide derivative of formula Illd H3C ^ ^ CH3 CH Rx or CO NH CH- CO NH CH (y) IV (Hld) * CH3 in which Rx and Ry have various meanings, together with at least one other active component selected from dichlofluanid, tololylfluanid, chlorothalonil, propineb, thiram, mancozeb, dyrene, copper oxychloride, captan, dimetomofh, dithianon, phaltan, cymoxanil, propamocarb , fosetyl, metalaxyl, oxadixyl, fluazinam, methoxy acrylates, methoximinoacetates, furalaxyl, azoles, such as, for example, triadimenol, bitertanol, triadimefon and tebuconazole, etridiazol and pencycuron. It is the object of the present invention to provide new combinations of active components for the best control of harmful fungi. In particular, the objective is to provide those mixtures that are distinguished by a synergistic effect that in this way allow to reduce the amounts to be applied of the active components. We have found that this objective has been achieved by providing mixtures of fungicidal action comprising, in a solid or liquid support or carrier, a) at least one compound of formula I where (al) M1 is a group of formula where X is CH or N and the radicals Ra and Rb, independently of each other, are a hydrogen atom, a halogen atom, a CrC4-alkyl group or a CrC4-halogenoalkyl group; and M2 is a group of formula CH3o N > OCH3 (a2) M1 is a group of formula Z-R 'where Z is O, S, NH or N-CrC4-alkyl; R 'is C, -C6-alkyl, C, -C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, C3-C6-cycloalkylmethyl, or benzyl it may be partially or wholly halogenated and / or may be bonded thereto from one to three of the following radicals: cyano, C, -C 4 -alkyl, -halogenoalkyl, -C ^ alkoxy, CrC 4 -haloalkoxy and CrC 4 -alkylthio; and M2 is a group of formula where X is O or NH; and Y is CH or N; and b) at least one valine amide of formula II where R1 is C3-C4-alkyl and R 2 is naphthyl or phenyl, the phenyl radical being substituted in the 4-position by a halogen atom, a C-C 4 -alkyl group or a -alkoxy group. The compositions of the present invention comprise as compounds of formula I in particular carbamates of formula where X, Ra and Rb are as defined above oximes of formula OR where X, Y, Z and R 'are as defined above. It was found, in particular, that better control of harmful fungi is possible by applying the compounds of formulas I and II together, than by using the compounds individually. A combined use for the purpose of the present invention comprises the simultaneous or sequential use of the compounds according to the invention in any desired sequence. For simultaneous use, the compounds can be applied together or separated from each other. The aforementioned objective is also achieved by providing a method to control harmful fungi, which includes the treatment of harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free of fungi, with an amount effective of a composition like the one defined above. In the compounds according to the invention used, halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Examples of CrC4-alkyl radicals are straight or branched chain saturated hydrocarbon radicals having from 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2- methylpropyl, 1, 1 -dimethylethyl. Examples of C, -C 4 -haloalkyl radicals are straight or branched chain saturated hydrocarbon chains having from 1 to 4 carbon atoms as defined above, it being possible that some or all of the hydrogen atoms in these groups are replaced by halogen atoms, such as, for example, chloromethyl, dichloromethyl, trichloromethyl, fluomethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichloro fluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoromethyl, 2,2,2-trifluoroethyl , 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, 1 -, 2- or 3-fluoro-phenyl, 1 -, 2- or 3-chloropropyl; 1 -fluor- or 1-chlorobutyl. Examples of C, -C 6 -alkyl radicals are straight or branched chain saturated hydrocarbon radicals having from 1 to 6 carbon atoms, such as the examples given above for CrC 4 -alkyl, as well as pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbyl, 2-ethylbutyl, 1,1,2-trimethylpropyl , 1, 2,2-trimethylpropyl, 1-ethyl-1-methylpropyl and 1-ethyl-2-methylpropyl. Examples of C, -C20-alkyl radicals are straight or branched chain saturated hydrocarbon radicals having from 1 to 20 carbon atoms, for example, CrC6-alkyl radicals as mentioned above, as well as straight chain alkyl radicals longer, such as heptyl, octyl, nonyl, decyl, undecyl, lauryl, tridecyl, myristyl, pentadecyl, palmityl, heptadecyl, stearyl, nonadecyl and arachinyl, as well as analogs thereof with simple branching or multiple branches. Examples of CrC6-halogenoalkyl radicals are straight or branched chain saturated hydrocarbon chains having from 1 to 6 carbon atoms, as defined above, where the hydrogen atoms of these groups may be partially or completely replaced by halogen atoms, such as the examples given above for CrC4-haloalkyl as well as 1-fluoro- or 1-chloropentyl; 1 -fluor- or 1-chlorohexyl. Examples of C2-C5-alkenyl radicals are straight or branched chain unsaturated hydrocarbon radicals having from 2 to 6 carbon atoms and a double bond at any position, for example, ethenyl, 1-propenyl, 2-propenyl, -methylethyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, -methyl-l-butenyl, 3-methyl-l-butenyl, 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-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl , l-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1 -pentenyl, 2-methyl-1-pentenyl, 3-methyl-1 -pentenyl, 4-methyl-1 -pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentynyl , 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, -methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1, 2 -dimethyl-3-butenyl, 1,3-dimethyl-l-butenyl, l, 3-dimethyl-2-bute nyl, l, 3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-l-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3- butenyl, 3,3-dimethyl-l-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-l-butenyl, 1-ethyl-2-butenyl, l-ethyl-3-butenyl, 2-ethyl- 1 -butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, l-ethyl-l-methyl-2-propenyl, l-ethyl-2- methyl-1-propenyl and l-ethyl-2-methyl-2-propenyl. Examples of C2-C6-haloalkenyl radicals are straight or branched chain hydrocarbon radicals having from 2 to 6 carbon atoms and a double bond at any position, as defined above, some or all of the hydrogen atoms being replaced by atoms of halogens, for example, 1 -fluor- or 1-chloroethenyl; 1-fluoro- or 1-chloro-1-propenyl, 1-fluoro- or 1-chloro-2-propenyl; 3 -fluor- or 3-chloro-2-propenyl, or 2,3,3-trichloro-2-propenyl. Examples of C3-C6-alkynyl radicals are straight or branched chain hydrocarbon groups having from 3 to 6 carbon atoms and a triple ligation at any posn, such as 1-propynyl, 2-propynyl, 1-butynyl, 2- Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-ynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl -3-butynyl, 3-methyl-l-butynyl, l, l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , l-methyl-2-pentynyl, l-methyl-3-pentynyl, l-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, -methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1, 1-dimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1, 2-dimethyl-3 -butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-butynyl, l-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and l-ethyl -l-methyl-2-propynyl. Examples of C3-C6-haloalkynyl radicals are straight or branched chain hydrocarbon groups having from 3 to 6 carbon atoms and a triple ligation at any posn as defined above, some or all of the hydrogen atoms being replaced by carbon atoms. halogens, for example, 3-fluorine- or 3-chloro-1-propynyl, 1-fluorine- or 1 - . 1-chloro-2-propynyl. Examples of C3-C6-cycloalkyl groups include monocyclic alkyl groups having from 3 to 6 carbon ring members, such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl. Examples of C, -C 4 -alkoxy groups are straight or branched chain alkyl radicals having from 1 to 4 carbon atoms, as defined above, which are attached to the molecule by means of an oxygen atom, for example, methoxy , ethoxy, 1- or 2-propoxy and 1 -butoxy. Examples of C, -C4-halogenoalkoxy groups are straight or branched chain alkoxy groups, as defined above, having from 1 to 4 carbon atoms, where some or all of the hydrogen atoms may be replaced by halogen atoms, by example, chloromethoxy, fluormetoxy, 2-fluoro- or 2-chloroethoxy, 3-fluoro- or 3-chloropropoxy or 4-fluoro- or 4-chlorobutoxy. Examples of CrC 4 -alkylthio radicals are straight or branched chain alkyl radicals having from 1 to 4 carbon atoms, as defined above, which are attached to the molecule by means of a sulfur atom, for example, methylthio, ethylthio , 1- or 2-propylthio and 1-butylthio. Fungicidal compositions preferably comprise oximes of formulas IA or IB where in each case is O and R 'is C, -C6-alkyl, C, -C6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-cycloalkylmethyl, benzyl or benzyl which is halogenated in the ring. Compounds of formulas IA and IB of special preference are those whose radicals Z-R 'have the meanings given below in table I: TABLE 1 Examples of compounds of special preference are IA.2 and IA.4. In the oxime ethers of formula I the double bond C = Y- can be present in the E or Z configuration (in relation to the carboxylic acid function). In any case, the mixtures according to the invention can comprise pure E or Z isomers or mixtures of E / Z isomers. The mixture of E / Z isomers or the E-isomer are preferably used in each case, the E-isomer of the oxime ether being particularly preferred. The double bonds C = N of the side chain of bisoxime ether of the oxime ethers can also exist in the pure forms E or Z or as mixtures of E / Z isomers. Either way, both the mixtures of isomers and also the pure isomers in relation to the double-crosslinking C = N can be used in the mixtures according to the invention. In particular, in any case, oxime ethers having the following E / Z configuration in the side chain are preferably: The oxime ethers of formula I which are part of the compositions according to the invention, and their preparation, are in themselves known from the oldest German patent application DE-A-195 28 651, thus making reference here to the content complete of it. According to this publication the oxime ethers of formula I can be prepared, for example, by reacting a benzyl derivative of formula IV where L1 is a nucleophilically replaceable starting group, for example, halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate, with a hydroxyzine of formula V CH3 HO NOCH3 (y) N Z-R ' The reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (for example, sodium hydride, potassium hydroxide, potassium carbonate and triethylamine) according to the methods described in Houben-Weyl, 4th Edition, Vol. E 14b, p. 370 yrs. and Houben-Weyl, Vol. 10/1, p. 1189 et seq. The required hydroxyzine V is obtained, for example, by reacting an appropriate dihydroximine VI with the nucleophilically substituted reagent H3CL2 where L2 is a nucleophilically replaceable starting group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, mesylate, tosylate and triflate.

Z-R ' The reaction is carried out in a manner known per se in a solvent inert organic in the presence of, a base (eg, potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine), according to the methods described in Houben-Weyl, Vol. E 14b, p. 307 ff., P. 370 yrs. and p. 385 ff .; Houben-Weyl, 4th Ed., Vol. 10/4, p. 55 ff., P. 180 and next. and pgs 217 ff .; Houben-Weyl, VoL E 5, p. 780 yrs. Those compounds of formula VI which are not yet known (DE-A-26 21 102) can be obtained by known methods. Other compositions preferably comprise carbamates of formula IC where X has the above-mentioned meaning and at least one of the radicals R a and R b is not a hydrogen atom and is, for example, chosen from halogen and C, -C 4 -alkyl.

The carbamates used according to the invention are known per se. Their preparation is described, for example, in WO-A-96/01256 and WO-A-96/01258, to which we expressly refer in this way. Examples of carbamates of formula I that can preferably be mentioned are compounds IC.l to IC.52 which are listed below in table II.

TABLE? Í Compounds IC.12, IC.23, IC.32 and IC.38 are particularly preferred, in particular IC.32 and IC.38. The compounds of formula II used according to the invention are also known per se. A first preferred group of valine amide derivatives are the compounds of formula II ' where R1 is as defined above and X is halogen, C, -C4-alkyl or CrC4-alkoxy. Compounds of this type and their preparation are described, for example, in EP-A-0 610 764 and EP-A-0 398 072, to which we expressly refer in this way. Another preferred group of valine amide derivatives are the compounds of formula II " where R1 is as defined above. Compounds of this type and their preparation are described, for example, in DE-A-43 21 897 and WO-A-96/07638, to which we expressly refer in this way.

Preferred compounds of formula II are those in which R1 is isopropyl, sec-butyl and tert-butyl. Of equal preference are the compounds of formula II wherein R 2 is α-naphthyl, β-naphthyl and phenyl, the phenyl being substituted in the 4 position by chlorine, bromine, Cj-alkyl or CrC 4 -alkoxy. Particularly preferred compounds of formula II are those in which R2 is β-naphthyl, 4-chlorophenyl, 4-methylphenyl and 4-methoxyphenyl. Preferred examples of valine amides which can be used according to the invention are compiled below in Table III. TABLE III Compounds II.1, II.2 and II.9 are particularly preferred, in particular II.1 and II.2.

The structural formula of the compounds of formula II shows that these compounds have two asymmetrically substituted carbons. The compounds can therefore be used in the mixture according to the invention both as mixtures of various isomers and also in the form of pure isomers. According to another preferred embodiment, compounds of formula II are used in which the amino acid residue is formed by alkoxycarbonyl-L-valine (S configuration) and the phenethylamine residue or the naphthylethylamine moiety has the R configuration. they can be described by the formula lia ( MR) wherein R1 and R2 have the meanings mentioned for the compounds of formula II. The preferred isomers of formula Ia are prepared by methods similar to those described in the oldest German patent application DE-A-195 31 814. In this way, the express reference to the disclosure of this application is made. The isomerically pure compounds of formula Ha can be prepared in a manner known per se, starting from the corresponding carbamoylcarboxylic acids Vil, which are derived from L-valine. For example, the Ha compounds are obtained by means of the processes described in the following, wherein a carbamoylcarboxylic acid VII is employed together with an amine VIII (the "Houben-Weyl" references refer to: Houben-Weyl, "Methoden der Organischen Chemie "[Methods of Organic Chemistry], 4th Edition, Editorial Thieme, Stuttgart): (VII) (VIII) The carbamoylcarboxylic acids VII are known or can be prepared by known methods, in particular starting from the amino acid L-vaiine (cf. "Houben-Weyl", Volume 15/1, pp. 46-305, mainly pages 1 17-125). Amines VIII are also known or can be easily obtained (compare with Organikum [Organic Chemistry], VEB (Company Own of the People) Deutscher Verlag der Wissenschaften (German Publishing House of the Sciences), 15th Edition, Berlin, 1977, p. 610 ff .; "Houben-Wey 1", Volume 15/1, pgs. 648-665; Indian J. Chem. 10,? Ag. 366 (1972); J. Am. Chem. Soc. 58, (1936), p. 1808-181 1). The R-isomers can be separated from the racemates of the amines VIII in a manner known per se, for example, by fractional crystallization with optically active tartaric acid or, preferably, by means of esterification catalyzed by means of enzymes and subsequent hydrolysis (compare, for example, WO-A-95/08636). This process is preferably carried out in such a manner that the carbamoylcarboxylic acids VII are first converted into the carboxyl-activated derivatives, in particular in acylcyanides or anhydrides (cf. Tetrahedron Letters, Volume 18, (1973), pp. 1595-1598, or "Houben Weyl", Volume 15/1, pp. 28-32). These derivatives are then reacted with the amines VI in the presence of bases. An example of a reaction which is suitable for the preparation of the carboxyl-activated acylcyanides is the reaction of the carbamoyl carboxylic acids VII with diethyl cyanophosphonate, mainly in an inert solvent such as tetrahydrofuran or toluene. For the preparation of carboxyl-activated anhydrides, the reaction of carbamoylcarboxylic acid VII with carbonic acid chlorides such as isobutyl chloroformate is preferably carried out in the presence of bases and, if appropriate, in an inert solvent, such as toluene or tetrahydrofuran. The reaction of the amines VIII with the carboxyl-activated carbamoylcarboxylic acids VII is preferably carried out in a solvent such as dichloromethane, tetrahydrofuran or toluene. Amines VIII can also act as bases; Normally they are then recovered from the raw product. In a preferred embodiment of this process step, the carbamoylcarboxylic acid VII, the amine VIII, the reagent which is suitable for producing the carboxyl-activated derivative of the carbamoylcarboxylic acid VII, and the base are all reacted together in a vessel, if appropriate, in an inert solvent and then the crude product is reconditioned in a manner known per se, to isolate the carbamoylcarboxamide Ha. Due to its basic nature the compounds of formulas I and II are capable of forming salts or adducts with inorganic acids or organic or with metal ions, which can also be used according to the invention.

Examples of inorganic acids are hydrohalogenated acids such as hydrofluoric, hydrochloric, hydrobromic 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, trichloroacetic and propionic acid, and also glycolic, thiocyanic, lactic, succinic, citric, benzoic, cinnamic, oxalic acids, alkylsulfonic acids ( sulfonic acids having straight or branched chain alkyl radicals of 1 to 20 carbon atoms), arylsulfonic or aryldisulfonic acids (aromatic radicals such as phenyl or naphthyl which have one or two sulfo groups attached thereto), alkylphosphonic acids (phosphonic acids which they have straight or branched chain alkyl radicals of 1 to 20 carbon atoms), arylphosphonic or aryl diphosphonic acids (aromatic radicals such as phenyl or naphthyl having one or two phosphoric acid radicals attached thereto), it being possible for the alkyl or aryl have more substituents attached to them, for example, p-toluenosul acid phonic, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid, 2-acetoxybenzoic acid, etc.

Suitable metal ions are, in particular, the ions of the elements of the second main group, in particular calcium and magnesium, and of the third and fourth major groups, in particular aluminum, tin and lead, and of the first to the eighth subgroups, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc and others. Of special preference are the metal ions of the elements of the subgroups of the fourth period. In this case the metals can be in the different valences that they can adopt. In preparing the mixtures it is preferred to use the pure active components I and II, to which other active components can then be added against harmful fungi or other pests, such as insects, arachnids or nematodes, or other components, herbicides or regulatory active components. of growth or fertilizers, if so required. The mixtures of the compounds I and II, or the simultaneous use, that is to say, together or separately, of the compounds I and II are distinguished by an outstanding activity against a broad spectrum of phytopathogenic fungi, in particular of the classes of the Ascomycetes, Deuteromycetes, Ficomycetes and Basidiomycetes. Some of them act in a systemic way and therefore can be used as foliar and soil fungicides. They are especially important for controlling a large number of fungi in a variety of cultivated plants, such as cotton, vegetable species (eg, cucumbers, beans and cucurbits), barley, turf, oats, coffee, corn, fruit species, rice , rye, soybeans, vine, wheat, ornamental plants, sugarcane, bananas and a variety of seeds.

They are particularly suitable for controlling the following phytopathogenic fungi: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits, Podosphaera leucotricha in apples, Puccinia species in cereals, Rhizoctonia species in cotton, rice and grass, species of Ustilago in cereals and sugar cane, Venturia inaequalis (scab) in apples, Helminthosporium species in cereals, Septoria nodorum in wheat, Botrytis cinerea (gray mold) in strawberries, vegetables, ornamental plants and vine, Cercospora arachidicola in peanuts, Pseudocercosporella herpotrichoides in wheat and barley, Pyricularia oryzae in rice, Phytophthora infestans in potatoes and tomatoes, species of Pseudoperonospora in cucurbits and hops, Plasmopara viíicola in vine, Alternate species in vegetables and fruit trees, Mycosphaerella species in bananas, and Fusarium species and Verticillium They can also be used to protect materials (for example, in wood protection), for example, against Paecilomyces variotii. Compounds I and II are normally used in a weight ratio of 10: 1 to 0.1: 1, preferably 5: 1 to 0.2: 1, in particular 5: 1 to 1: 1. As non-limiting examples of useful combinations active against fungi may be mentioned: At least one compound of formula IA or IB and at least one compound of formula II, such as, for example, compounds of table I, such as IA.2 or IA.4, each combined with compounds from Table III, as II.1.

At least one compound of formula IC and at least one compound of formula II, such as, for example, compounds of table II, such as IC.32 or IC.38, each combined with compounds of table III, such as II .1 or II.2. The amounts to be applied of the mixtures according to the invention are from 0.01 to 3 Kg / ha, preferably from 0.1 to 1.5 Kg / ha, in particular from 0.1 to 1.0 Kg / ha, depending on the type of effect desired. In the case of the compounds I, the amounts to be applied are from 0.01 to 0.5 Kg / ha, preferably from 0.05 to 0.5 Kg / ha, in particular, from 0.05 to 0.4 Ke / ha. Correspondingly, in the case of the compounds II, the amounts to be applied are from 0.01 to 0.5 Kg / ha, preferably from 0.05 to 0.5 Kg / ha, in particular from 0.05 to 0.4 Kg / ha. For the treatment of seeds the amounts to be applied of the mixture are generally from 0.001 to 50 g / Kg of seeds, preferably from 0.01 to 10 g / Kg, in particular from 0.01 to 8 g / Kg. If phytopathogenic harmful fungi are to be controlled, the application, separately or together, of compounds I and II or mixtures of compounds I and II is carried out by spraying or spraying the seeds, plants or soils before or after the treatment. sowing of the plants or before or after the emergence of the plants. The synergistic fungicidal mixtures of the compounds I and II, according to the invention, can be formulated, for example, in the form of ready-to-spray solutions, powders and suspensions, or in the form of suspensions, dispersions, aqueous, oily or other emulsions, highly concentrated, oily dispersions, pastes, powders, spreading agents or granules and are applied by spraying, atomizing, spraying, spreading or irrigating. The way of use depends on the purpose of the application; in any case the finest and uniform distribution of the mixture according to the invention must be guaranteed. The formulations are prepared in a manner known per se, for example, by adding solvents and / or carriers or vehicles. It is usual to add inert additives, such as emulsifiers or dispersants to the formulations. Suitable surfactants are the alkali metal, alkaline earth metal salts and ammonium salts of aromatic sulphonic acids, for example, ligno-, phenol-, naphthalene- and dibutylnaphthalene sulfonic acid and of fatty acids, of alkyl and alkylarylsulfonates, of alkyl sulfates, lauryl ethers and fatty alcohols, and salts of sulfated hexa, hepta and octadecanols or glycol ethers of fatty alcohols, condensates of sulfonated naphthalene and their derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acids with phenol and formaldehyde, ether polyoxyethylene of octylphenol, isooctyl-, octyl- or nonylphenol ethoxylate, alkylphenyl-polyglycol or tributylphenyl-polyglycol ethers, alkylaryl-polyester alcohols, isotridecyl alcohol, fatty alcohol / ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl or polyoxypropylene alkyl ethers, acetate of polyglycol ether of lauryl alcohol, esters of s orbitol, lignin-sulphite residual liquors or methylcellulose. Powders, spreading and spraying agents can be prepared by mixing or milling compounds I or II or the mixture of compounds I and II together with a solid support. Granules (for example, coated granules, impregnated granules or homogeneous granules) are usually prepared by joining the active component, or the active components, to a solid support. Filling materials or solid supports are, for example, mineral soils such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium sulfate, sulphate magnesium, magnesium oxide, ground synthetic materials, and fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of plant origin such as cereal flour, tree bark, sawdust and walnut sheaf meal , cellulose powders or other solid supports. The formulations generally contain from 0.1 to 95% by weight, preferably from 0.5 to 90%) by weight of one of the compounds I or II, or of the mixture of the compounds I and II. The active components are used in a purity of 90% to 100%, preferably 95% to 100% (according to NMR or HPLC spectrum). The compounds I or II, or the mixtures, or the corresponding formulations, are applied by treating the harmful fungi or the plants, seeds, soils, areas, materials or spaces to be kept free of the fungi, with an effective amount as a fungicide, of the mixture, or compounds I and II, in the case of separate application. The application can be made before or after the infection by the harmful fungi. Examples of the synergistic action of the mixture according to the invention against harmful fungi. The fungicidal activity of the compounds and mixtures was demonstrated by means of the following experiments: The active components, separately or together, were formulated in the form of a 10% emulsion "in a mixture of cyclohexanone and an emulsifier ( such as, for example, Nekanil® LN (Lutenesol® AP6, emulsifying and dispersing action moisturizer, based on ethoxylated alkylphenols) and 10% by weight of Emulphor® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) and diluted in water to give them the concentration The evaluation was carried out by determining the infected surface of leaves in percentage, these percentages were converted into efficiencies, The expected efficiencies of the mixtures of the active components were determined using Colby's formula [RS Colby, Weeds 15, 20-22 (1967)] and were compared with the observed efficiencies. Colby's formula: E = x + y - x.y / 100 E expected efficacy expressed in% of the untreated control, using the mixture of active components A and B at concentrations a and b x efficiency, expressed in% of the untreated control, using the active component A at a concentration a and efficacy, expressed in% of the untreated control, using the active component B at a concentration b The efficiency (W) was calculated as follows using the Abbot formula: W = (l-) .100 / ß a is the fungal infection of the treated plants in% and ß is the fungal infection of the untreated plants (control) in% An efficacy of 0 means that the level of infection of the treated plants corresponds to that of the control plants not treated; an efficacy of 100 means that the treated plants were not infected. Example 1: Action against Phytophthora infestans in tomatoes The leaves of potted tomatoes of the variety "GroBe Fleischtomate" (Large fleshy tomato) were sprinkled to the drip with an aqueous suspension that was prepared from a stock solution consisting of 10% of active component, 63% cyclohexanone and 27% emulsifier. The next day these leaves were infected with an aqueous suspension of zoosporos of Phytophthora infestans. Then the plants were placed in a chamber saturated with water vapor at temperatures of 16 to 18 ° C. Six days later the pest had developed in the untreated but infected control plants, to an extent that allowed the visual determination of the infection in%. The visually determined values for the percentage of infected leaf surface were converted to efficiency values in% of the untreated control. The expected efficacy values were calculated according to Colby's formula as described above.

Example 2: Action against Plasmopara viticola The vine leaves of the "Müller Thurgau" variety were sprinkled to the drop with an aqueous suspension that was prepared from a stock solution consisting of 10% active component, 63% > of cyclohexanone and 27% of emulsifier. To allow an evaluation of the permanent effect of these substances, the plants were placed in a greenhouse for 7 days, the sprayed layer being dried before inoculating their leaves with an aqueous suspension of zoosporous Plasmopara viticola. Then the vines were first placed in a chamber saturated with water vapor for 48 hours and then left in a greenhouse at temperatures of 20 to 30 ° C for 5 days. After this time the plants were again placed in a humid chamber for 16 hours to accelerate the germination of the sporangia carrier. Then the degree of infection was determined visually on the lower surfaces of the leaves. The visually determined values for the percentage of infected leaf surface were converted to efficiency values in% of the untreated control. The expected efficacy values were calculated according to Colby's formula as described above.

The results reported in the above tables show that the efficiencies obtained with the new mixtures are considerably higher than the efficiencies calculated according to the Colby formula.

Claims (9)

1.- A composition for controlling harmful fungi, characterized in that it comprises, in a solid or liquid carrier or carrier, a) at least one compound of formula I where (al) M1 is a group of formula l RX Rb where X is CH 0 N and the radicals R a and R b, independently of each other, are a hydrogen atom, a halogen atom, a C, -C 4 -alkyl group or a C, -C 4 -haloalkyl group; and M2 is a group of formula CH30-, N- OCH3 O (a2) Ml is a group of formula CH3 Z-R 'where Z is O, S, NH or N-CrC4-alkyl; R 'is C, -C6-alkyl, CrC6-haloalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C-C6-alkynyl, Cj-haloalkynyl, C3-C6-cycloalkylmethyl, or benzyl which may be partial or fully halogenated and / or may be bonded thereto from one to three of the following radicals: cyano, CI-C4-alkyl, CrC4-haloalkyl, - -alkoxy, CrC4-haloalkoxy and C, -C4-alkylthio; and M2 is a group of formula OR where X * is O or NH; e is CH or N; b) at least one valine amide of formula II where R1 is C3-C4-alkyl and R 2 is naphthyl or phenyl, the phenyl radical being substituted in the 4-position by a halogen atom, a C-C 4 -alkyl group or a C-C 4 -alkoxy group.

2. A composition according to claim 1, characterized in that it comprises at least one oxime ether of formula IA or IB wherein in each case Z is O and R 'is CrC6-alkyl, CrC6-halogenoalkyl, C2-C6-alkenyl, C2-C6-haloalkenyl, C3-C6-cycloalkylmethyl, benzyl or benzyl which is halogenated in the ring.

3. A composition according to claim 1, characterized in that it comprises at least one carbamate of formula IC where X has the meaning mentioned above and at least one of the radicals Ra and Rb is not a hydrogen atom.

4. - A composition according to any of the preceding claims, characterized in that it comprises at least one valine amide of formula II, wherein R 1 is i-propyl, sec-butyl or tert-butyl and R 2 is 4-Cl-, 4-methyl - or 4-methoxyphenyl, or 2-naphthyl.

5. A composition according to any of the preceding claims, characterized in that it comprises at least one valine amide of formula where R1 and R2 have the meanings mentioned above.

6. A composition according to any of the preceding claims, characterized in that the weight ratio of the compound of formula I to the compound of formula II is 10: 1 to 1: 10.

7. A composition according to any of the preceding claims, characterized in that it is conditioned in two parts, one part comprising the compound of formula I in a solid or liquid support or carrier and the other part comprising the compound of formula II in a solid or liquid support or carrier.

8. A method for controlling harmful fungi, characterized in that it comprises the treatment of harmful fungi, their environment, or the plants, seeds, soils, areas, materials or spaces to be kept free of fungi, with an effective amount of less a composition as claimed in any of claims 1 to 7.

9. A method according to claim 8, characterized in that at least one compound of formula I and at least one compound of formula II are applied simultaneously together or separated, or in succession in any order.