Title of Invention	FUNGICIDAL COMPOSITION CONTAINING BENZOPHENONES AND N-BIPHENYL NICOTINAMIDES
Abstract	Fungicidal composition containing benzoplienones and n-biphenyl nicotinamides in which the substituents are as described in the description. in which the substituents are as described in the description in a synergistically effective amount. Moreover, the invention relates to compositions conditioned in two parts.

Full Text

The present invention relates to fungicidal compositions, comprising in which R1 is chlorine, methyl, methoxy, acetoxy, pivaloyloxy or hydroxyl; R2 is chlorine or methyl; R3 is hydrogen, halogen or methyl; and R4 is C1-C6-alkyl or benzyl, where the phenyl moiety of the benzyl radical may carry a halogen or methyl substituent, and in which R6 and R7 are identical or different and are halogen, nitro, cyano, C1-C6-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C6-haloalkyl, C2-C8-haloalkenyl, C2-C8-haloalkynyl, C1-C6-alkoxy, C1-C8-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C8-alkylsulfinyl or C1-C8-alkylsulfonyl; X is 1, 2, 3 or 4; and y is 1, 2, 3, 4 or 5; in a synergistically effective amount. Moreover, the invention relates to compositions conditioned in two parts. The compounds of the formula 1, their preparation and their action against harmful fungi are known from the literature (EP-A 727 141; EP-A 897 904; EP-A 899 255; EP-A 967 196). Mixtures of benzophenones of the formula I with other fungicidally active compounds are known from EP-A 1 023 834. Also known are the amide compounds of the formula II, their preparation and their action against harmful fungi (EP-A 545 099). It is an object of the present invention to provide mixtures which have an improved activity against harmful fungi combined with a reduced total cimount of active compounds applied (synergistic mixtures), with a view to reducing the application rates and improving the activity spectrum of the known compounds I and II. We have found that this object is achieved by the mixtures defined at the outset. Moreover, we have found that applying the compounds I and the compounds II simultaneously, i.e. together or separately, or applying the compounds I and the compounds II in succession provides better control of harmful fungi than is possible with the individual compounds alone. The mixtures according to the invention act synergistically and are therefore particularly suitable for controlling harmful fungi and in particular powdery mildew fungi in cereals, vegetables, fruit, ornamental plants and grapevines. The following compounds of the formula I are preferred mixing components, where the individual preferences apply on their own and in combination. Preference is given to compounds I in which R1 is chloR1ne, methoxy, acetoxy or hydroxyl, and particular preference is given to compounds in which R1 is methoxy, acetoxy or hydroxyl. Very particular preference is given to compounds in which R1 is methoxy. Mixtures compR1sing compounds I in which R2 is chloR1ne or methyl are mixtures according to the invention. Preference is given to compounds I in which R2 is methyl. Moreover, preference is given to compounds I in whiCh R3 is hydrogen, methyl/ chloR1ne or bromine, particularly preferably hydrogen, chloR1ne or bromine. In addition, preference is given to compounds I in which R^ is C1-C4-alkyl or benzyl, where the phenyl moiety of the benzyl radical may carry a halogen or methyl substituent. Particular preference is given to compounds of the formula I in which R^ is C1-C4-alkyl, preferably methyl. Furthermore, preference is given to compounds of the formula I in which the substituents R^, R2, R3 and R^ are as defined below: R1 is methoxy, acetoxy or hydroxy1; R2 is methyl; R3 is hydrogen, chloR1ne or bromine; and R4 is C1-C4-alkyl. Particularly suitable are compounds II in which R6 is located in the 2-position of the pyR1dine R1ng and R7 is located in the 4-position of the terminal benzene R1ng (formula II.1): Particular preference is given to the compounds II.1 in which R^ is CF3 or halogen and R7 is halogen. Preference is given to fungicidal mixtures which compR1se, as component a), one of the compounds: 1-33, 1-35, 1-42, 1-44, 1-46, 1-60, or preferably 1-18, 1-28, 1-37, and, as component b), one of the compounds: II-7, II-8 or, preferably, II-4 or II-5. Owing to the basic character of their nitrogen atoms, the compounds II are capable of forming salts or adducts with inorganic or organic acids or with metal ions. Examples of inorganic acids are hydrohalic acids, such as hydrogen fluoR1de, hydrogen chloR1de, hydrogen bromide and hydrogen iodide, carbonic acid, sulfuR1c acid, phosphoR1c acid and nitR1c acid. Suitable organic acids are, for example, formic acid, and alkanoic acids, such as acetic acid, tR1fluoroacetic acid, tR1chloroacetic acid and propionic acid, and also glycolic acid, lactic acid, succinic acid, citR1c acid, benzoic acid, cinnamic acid, oxalic acid, p-toluenesulfonic acid, salicylic acid, p-aminosalicylic acid, 2-phenoxybenzoic acid or 2-acetoxyben2oic acid. Suitable metal ions are, in particular, the ions of the elements of the first to eighth transition group, in particular chromium, manganese, iron, cobalt, nickel, copper, zinc, and additionally those of the second main group, in particular calcium and magnesium, and of the third and fourth main group, in particular aluminum, tin and lead. If appropR1ate, the metals can exist in the vaR1ous valencies which they can assume. When prepaR1ng the mixtures, it is preferred to employ the pure active compounds I and II, to which further active compounds against harmful fungi or other pests, such as insects, arachnids or nematodes, or else herbicidal or growth-regulating active compounds or fertilizers can be admixed. The mixtures of the compounds I and II, or the compounds I and II used simultaneously, jointly or separately, exhibit outstanding activity against a wide range of phytopathogenic fungi, in particular from the classes of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them act systemically and can therefore be employed also as foliar- and soil-acting fungicides. They are especially important for controlling a large number of fungi in a vaR1ety of crop plants, such as cotton, vegetable species (e.g. cucumbers, beans, tomatoes, potatoes and cucurbits), barley, grass, oats, bananas, coffee, maize, fruit species, R1ce, rye, soya, grapevine, wheat, ornamentals, sugar cane, and a vaR1ety 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 leucotR1cha in apples, Uncinula necator in grapevines, Puccinia species in cereals, Rhizoctonia species in cotton, R1ce and lawns, Ustilago species in cereals and sugar cane, VentuR1a inaequalis (scab) in apples, HelminthospoR1um species in cereals, SeptoR1a nodorum in wheat, Botrytis cinera (gray mold) in strawberR1es, vegetables, ornamentals and grapevines, Cercospora arachidicola in groundnuts, Pseudocercosporella herpotR1choides in wheat and barley, PyR1culaR1a oryzae in R1ce, Phytophthora infestans in potatoes and tomatoes, Plasmopara viticola in grapevines, Pseudocercosporella species in hops and cucumbers, AlternaR1a species in vegetables and fruit, Mycosphaerella species in bananas and FusaR1um and verticillium species. They can furthermore be employed in the protection of mateR1als (for example the protection of wood), for example against Paecilomyces vaR1otii. The compounds I and II can be applied simultaneously, that is either together or separately, or successively, the sequence, in the case of separate application, generally not having any effect on the result of the control measures. The compounds I and II are usually applied in a weight ratio of from 20:1 to 1:20, in particular from 10:1 to 1:10, preferably from 5:1 to 1:5. Depending on the kind of effect desired, the application rates of the mixtures according to the invention are, in particular in agR1cultural crop areas, from 0.01 to 8 kg/ha, preferably 0.1 to 5 kg/ha, in particular 0.5 to 3.0 kg/ha. The application rates of the compounds I are from 0.005 to 3.0 kg/ha, preferably 0.02 to 2.0 kg/ha, in particular 0.04 to 1.0 kg/ha. Correspondingly, in the case of the compounds ii, tne application rates are from 0.005 to 5 kg/ha, preferably 0.08 to 3.0 kg/ha, in particular 0.06 to 2.0 kg/ha. For seed treatment, the application rates of the mixture are generally from 0.001 to 250 g/kg of seed, preferably 0.01 to 100 g/kg, in particular 0.01 to 50 g/kg. If phytopathogenic harmful fungi are to be controlled, the separate or joint application of the compounds I and II or of the mixtures of the compounds I and II is effected by spraying or dusting the seeds, the plants or the soils before or after sowing of the plants, or before or after plant emergence. The fungicidal synergistic mixtures according to the invention or the compounds I and II can be formulated for example in the form of ready-to-spray solutions, powders and suspensions or in the form of highly concentrated aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, mateR1als for broadcasting or granules, and applied by spraying, atomizing, dusting, broadcasting or wateR1ng. The use form depends on the intended purpose; in any case, it should ensure as fine and uniform as possible a distR1bution of the mixture according to the invention. The formulations are prepared in a known manner, e.g. by adding solvents and/or carR1ers. The formulations are usually admixed with inert additives, such as emulsifiers or dispersants. Suitable surfactants are the alkali metal salts, alkaline earth metal salts and euranonium salts of aromatic sulfonic acids, e.g. ligno-, phenol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl- and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts of sulfated hexa-, hepta- and octadecanols, or of fatty alcohol glycol ethers, condensates of sulfonated naphthalene and its deR1vatives with formaldehyde, condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenyl or tR1butylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotR1decyl alcohol, fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignosulfite waste liquors or methylcellulose. Powders, mateR1als for broadcasting and dusts can be prepared by mixing or jointly gR1nding the compounds I or II or the mixture of the compounds I and II with a solid carR1er. Granules (e.g. coated granules, impregnated granules or homogeneous granules) are usually prepared by binding the active compound, or active compounds, to a solid carR1er. Fillers or solid carR1ers are, for example, mineral earths, such as silicas, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic mateR1als and fertilizers, such as ammonium sulfate, cumnonium phosphate, cimmonium nitrate, ureas, and products of vegetable oR1gin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carR1ers. The formulations generally compR1se from 0.1 to 95% by weight, . preferably 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 compounds are employed in a puR1ty of from 90% to 100%, preferably 95% to 100% (according to NMR spectrum or HPLC). The compounds I or II, the mixtures, or the corresponding formulations, are applied by treating the harmful fungi, their habitat, or the plants, seeds, soils, areas, mateR1als or spaces to be kept free from them with a fungicidally effective amount of the mixture, or of the compounds I and II in the case of separate application. Application can be effected before or after infection by the harmful fungi. Use Example The synergistic activity of the mixtures according to the invention was demonstrated by the following expeR1ments: The active compounds, separately or together, were formulated as a 10% emulsion in a mixture of 70% by weight of cyclohexanone, 20% by weight of Nekanil® LN (lutensol® AP6, wetting agent having emulsifying and dispersing action based on ethoxylated alkylphenols), and 10% by weight of Emulphor® EL Emulan® EL, emulsifier based on ethoxylated fatty alcohols), and diluted with water to the desired concentration. Evaluation was carR1ed out by determining the infected lekf areas in percent- These percentages were converted into efficacies. The efficacy (W) was calculated as follows using Abbot's formula: a corresponds to the fungal infection of the treated plants in % and P corresponds to the fungal infection of the untreated (control) plants in % An efficacy of 0 means that the infection level of the treated plants corresponds to that of the untreated control plants; an efficacy of 100 means that the treated plants were not infected. The expected efficacies of the mixtures of the active compounds were determined using Colby's formula [R.S. Colby, Weeds 15.f 20-22 (1967)] and compared with the observed efficacies. E expected efficacy, expressed in % of the untreated control, when using the mixture of the active compounds A and B at the concentrations a and b X efficacy, expressed in % of the untreated control, when using active compound A at a concentration a y efficacy, expressed in % of the untreated control, when using active compound B at a concentration b- Use Example 1: Protective activity against mildew of cucumbers caused by Sphaerotheca fuliginea Leaves of cucumber seedlings of the cultivar "Chinesische Schlange" which had been grown in pots were, at the cotyledon stage, sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution compR1sing 10% of active compound, 85% of cyclohexanone and 5% of emulsifier. 20 hours after the spray coating had dR1ed on, the plants were inoculated with an aqueous spore suspension of mildew of cucumbers (Sphaerotheca fuliginea).The plants were then cultivated in a greenhouse at temperatures between 20 and 24'C and at 60 to 80% relative atmospheR1c humidity for 7 days. The extent of the development of the mildew was then determined visually in % infection of the cotyledon area. The visually determined values for the percentage of infected leaf areas were converted into efficacies as % of the untreated control. An efficacy of 0 means the same degree of infection as in the untreated controlr an efficacy of 100 means 0% infection. The expected efficacies for combinations of active compounds were determined using Colby's formula (Colby, S.R. (Calculating synergistic and antagonistic responses of herbicide Combinations" [sic], Weeds, 15, p. 20-22, 1967) and compared to the observed efficacies. *) calculated using Colby's formula The test results show that in all mixing ratios the observed efficacy is higher than the efficacy which had been calculated beforehand using Colby's formula (from Synerg 166A. XLS)- We claim: 1. A fungicidal composition, comprising in which R1 is chlorine., methyl, methoxy, acetoxy, pivaloyloxy or hydroxy1; R2 is chlorine or methyl; R3 is hydrogen, halogen or methyl; and R4 is C1-C6-alkyl or benzyl, where the phenyl moiety of the benzyl radical may carry a halogen or methyl substituent, and in which R6 and R7 are identical or different and are halogen, nitro, cyano, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C1-C8-haloalkyl, C2-C8-haloalkenyl, C2-C8-haloalkynyl, C1-C6-alkoxy, C1-C8-haloalkoxy, C1-C6-alkylthio, C1-C6-haloalkylthio, C1-C8-alkylsulfinyl or C1-C6-alkylsulfonyl; X is 1, 2, 3 or 4; and y is 1, 2, 3, 4 or 5; in a synergistically effective amount. 2. The fungicidal composition, as claimed in claim 1, where in formula I R1 is methoxy, acetoxy or hydroxyl; R2 is methyl; R3 is hydrogen, chlorine or bromine; and R4 is C1-C4-alkyl. -3, The fungicidal composition, as claimed in claim 1, where the mixing components b) used are compounds of the formula II. 1 in which R^ is halogen, halomethyl, methyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl and R^ is halogen or cyano. 4. The fungicidal composition, as claimed in claim 1, wherein the weight ratio of the benzophenones I to the amide compounds of the formula II is from 20:1 to 1:20. 5. The fungicidal composition, as claimed in claim 1, which is conditioned in two parts, one part comprising benzophenones of the formula I as set forth in claim 1 in a solid or liquid carrier and the other part comprising amide compounds of the formula II as set forth in claim 1 in a solid or liquid carrier in a synergistically effective amount.

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