owing to the basic character of its nitrogen atoms , the compound i is 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 fluoride , hydrogen chloride , hydrogen bromide and hydrogen iodide , 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 , and also glycolic acid , thiocyanic acid , lactic acid , succinic acid , citric acid , benzoic acid , cinnamic acid , oxalic acid , alkylsulfonic acids ( sulfonic acids having straight - chain or branched alkyl radicals of 1 to 20 carbon atoms ), arylsulfonic acids or - disulfonic acids ( aromatic radicals , such as phenyl and naphthyl , which carry one or two sulfonic acid groups ), alkylphosphonic acids ( phosphonic acids having straight - chain or branched alkyl radicals of 1 to 20 carbon atoms ), arylphosphonic acids or - diphosphonic acids ( aromatic radicals , such as phenyl and naphthyl , which carry one or two phosphonic acid radicals ), where the alkyl or aryl radicals may carry further substituents , for example p - toluenesulfonic acid , 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 , of the third and fourth main group , in particular aluminum , tin and lead , and also of the first to eighth transition group , in particular chromium , manganese , iron , cobalt , nickel , copper , zinc and others . particular preference is given to the metal ions of the elements of the transition groups of the fourth period . the metals can be present in the various valencies that they can assume . when preparing the mixtures , it is preferred to employ the pure active compounds i to xxi , to which may be added further active compounds against harmful fungi or against other pests , such as insects , arachnids or nematodes , or else herbicidal or growth - regulating active compounds or fertilizers . the mixtures of the compound i with at least one of the compounds ii to xxi , or the compound i and at least one of the compounds ii to xxi applied simultaneously , together or separately , exhibit outstanding activity against a wide range of phytopathogenic fungi , in particular from the classes ascomycetes , basidiomycetes , phycomycetes and deuteromycetes . some of them act systemically and can therefore also be employed as foliar - and soil - acting fungicides . they are especially important for controlling a large number of fungi in a variety of crop plants , such as cotton , vegetable species ( for example cucumbers , beans , tomatoes , potatoes and cucurbits ), barley , grass , oats , bananas , coffee , corn , fruit species , rice , rye , soya , grapevine , wheat , ornamentals , sugar cane , and a large number of seeds . they are particularly suitable for controlling the following phytopathogenic fungi : blumeria graminis ( powdery mildew ) in cereals , erysiphe cichoracearum and sphaerotheca fuliginea in cucurbits , podosphaera leucotricha in apples , uncinula necator in grapevines , puccinia species in cereals , rhizoctonia species in cotton , rice and lawns , ustilago species in cereals and sugar cane , venturia inaequalis ( scab ) in apples , helminthosporium species in cereals , septoria nodorum in wheat , botrytis cinera ( gray mold ) in strawberries , vegetables , ornamentals and grapevines , cercospora arachidicola in groundnuts , pseudocercosporella herpotrichoides in wheat and barley , pyricularia oryzae in rice , phytophthora infestans in potatoes and tomatoes , plasmopara viticola in grapevines , pseudoperonospora species in hops and cucumbers , alternaria species in vegetables and fruit , mycosphaerella species in bananas and also fusarium and verticillium species . the compound i and at least one of the compounds ii to xiii can be applied simultaneously , that is together or separately , or in succession , 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 employed 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 . the compounds i and iii are usually employed 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 . the compounds i and iv are usually employed 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 . the compounds i and v are usually employed 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 . the compounds i and vi are usually employed 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 . the compounds i and vii are usually employed 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 . the compounds i and viii are usually employed 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 . the compounds i and ix are usually employed 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 . the compounds i and x are usually employed 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 . the compounds i and xi are usually employed 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 . the compounds i and xii are usually employed 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 . the compounds i and xiii are usually employed 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 . the compounds i and xiv are usually employed 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 . the compounds i and xv are usually employed 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 . the compounds i and xvi are usually employed 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 . the compounds i and xvii are usually employed 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 . the compounds i and xviii are usually employed 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 . the compounds i and xix are usually employed 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 . the compounds i and xx are usually employed 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 . the compounds i and xxi are usually employed 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 agricultural crop areas , from 0 . 01 to 8 kg / ha , preferably from 0 . 1 to 5 kg / ha , in particular from 0 . 1 to 3 . 0 kg / ha . the application rates of the compounds i are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 05 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds ii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds iii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds iv are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds v are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds vi are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds vii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds viii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds ix are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds x are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xi are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xiii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xiv are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xv are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xvi are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xvii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xviii are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xix are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xx are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . the application rates of the compounds xxi are accordingly from 0 . 01 to 1 kg / ha , preferably from 0 . 02 to 0 . 5 kg / ha , in particular from 0 . 05 to 0 . 3 kg / ha . for seed treatment , the application rates used of the mixture are generally from 0 . 001 to 250 g / kg of seed , preferably from 0 . 01 to 100 g / kg , in particular from 0 . 01 to 50 g / kg . if phytopathogenic harmful fungi are to be controlled , the separate or joint application of the compound i and at least one of the compounds ii to xxi or of the mixtures of the compound i with at least one of the compounds ii to xxi 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 compound i and at least one of the compounds ii to xxi 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 , materials for broadcasting or granules , and applied by spraying , atomizing , dusting , broadcasting or watering . the use form depends on the intended purpose ; in any case , it should ensure as fine and uniform as possible a distribution of the mixture according to the invention . the formulations are prepared in a known manner , for example by adding solvents and / or carriers . the formulations are usually admixed with inert additives , such as emulsifiers or dispersants . fungicidal compositions comprise the fungicidal mixture and a solid or liquid carrier . suitable surfactants are the alkali metal salts , alkaline earth metal salts and ammonium salts of aromatic sulfonic acids , for example ligno -, phenol -, naphthalene - and dibutylnaphthalenesulfonic acid , and of fatty acids , alkyl - and alkylarylsulfonates , alkyl , lauryl ether and fatty alcohol sulfates , and also salts of sulfated hexa -, hepta - and octadecanols , or of fatty alcohol glycol ethers , condensates of sulfonated naphthalene and its derivatives with formaldehyde , condensates of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde , polyoxyethylene octylphenol ether , ethoxylated isooctyl -, octyl - or nonylphenol , alkylphenyl or tributylphenyl polyglycol ethers , alkylaryl polyether alcohols , isotridecyl 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 , materials for broadcasting and dusts can be prepared by mixing or jointly grinding the compound i and at least one of the compounds ii to xxi or the mixture of the compound i with at least one of the compounds ii to xxi with a solid carrier . granules ( for example coated granules , impregnated granules or homogeneous granules ) are usually prepared by binding the active compound or active compounds to a solid carrier . fillers or solid carriers 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 minerals , and also fertilizers , such as ammonium sulfate , ammonium phosphate , ammonium nitrate , ureas , and products of vegetable origin , such as cereal meal , tree bark meal , wood meal and nutshell meal , cellulose powders or other solid carriers . the formulations generally comprise from 0 . 1 to 95 % by weight , preferably from 0 . 5 to 90 % by weight , of the compound i and at least one of the compounds ii to xxi or of the mixture of the compound i with at least one of the compounds ii to xxi . the active compounds are employed in a purity of from 90 % to 100 %, preferably from 95 % to 100 % ( according to nmr spectrum or hplc ). the compound i and at least one of the compounds ii to xxi , the mixtures , or the corresponding formulations , are applied by treating the harmful fungi , their habitat , or the plants , seeds , soils , areas , materials or spaces to be kept free from them with a fungicidally effective amount of the mixture , or of the compound i and at least one of the compounds ii to xxi in the case of separate application . application can be effected before or after infection by the harmful fungi . the synergistic activity of the mixtures according to the invention was demonstrated by the following experiments : the active compounds , separately or together , were formulated as a 10 % emulsion in a mixture of 85 % by weight of cyclohexanone and 5 % by weight of emulsifier , and diluted with water to the desired concentration . evaluation was carried out by determining the infected leaf areas in percent . these percentages were converted into efficacies . the efficacy ( w ) was calculated as follows using abbot &# 39 ; s formula : α corresponds to the fungal infection of the treated plants in % and β 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 &# 39 ; s formula [ r . s . colby , weeds 15 , 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 of a y efficacy , expressed in % of the untreated control , when using active compound b at a concentration of b . use example 1 : activity against mildew of wheat caused by erysiphe [ syn . blumeria ] graminis form a specialis . tritici leaves of wheat seedlings of the cultivar “ kanzler ”, grown in pots , were sprayed to runoff point with an aqueous preparation of active compound which had been prepared from a stock solution comprising 10 % of active compound , 85 % of cyclohexanone and 5 % of emulsifier , and 24 hours after the spray coating had dried on , the leaves were dusted with spores of mildew of wheat ( erysiphe [ syn . blumeria ] graminis form a specialis . tritici ). the test plants were then placed in a greenhouse at 20 - 24 ° c . and 60 - 90 % relative atmospheric humidity . after 7 days , the extent of the mildew development was determined visually in % infection of the entire leaf area . the visually determined values for the percentage of diseased leaf areas were converted into efficacies in % of the untreated control . an efficacy of 0 means the same disease level as in the untreated control , an efficacy of 100 means a disease level of 0 %. the expected efficacies for the combinations of active compounds were determined using colby &# 39 ; s formula , mentioned above , and compared with the observed efficacies . the test results show that in all mixing ratios the observed efficacy is higher than the efficacy calculated beforehand using colby &# 39 ; s formula ( from synerg 176 . slx ) use example 2 : protective activity against mildew of cucumber caused by sphaerotheca fuliginea leaves of cucumber seedlings of the cultivar “ chinese snake ”, 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 comprising 10 % of active compound , 85 % of cyclohexanone and 5 % of emulsifier . 20 hours after the spray coating had dried on , the plants were inoculated with an aqueous spore suspension of mildew of cucumber ( sphaerotheca fuliginea ). the plants were then cultivated in a greenhouse at 20 - 24 ° c . and 60 - 80 % relative atmospheric humidity for 7 days . the extent of the mildew development was then determined visually in % infection of the cotyledon area . the visually determined values for the percentage of diseased leaf areas were converted into efficacies in % of the untreated control . an efficacy of 0 means the same disease level as in the untreated control , an efficacy of 100 means a disease level of 0 %. the expected efficacies for the combinations of active compounds were determined using colby &# 39 ; s formula , mentioned above , and compared with the observed efficacies . the test results show that in all mixing ratios the observed efficacy is higher than the efficacy calculated beforehand using colby &# 39 ; s formula ( from synerg 176 . slx )
the invention relates to a fungicidal mixture comprising prothioconazole or a salt or adduct thereof with an inorganic acid an organic acid or a metal ion ; and at least one further fungicidal compound , selected from the group consisting of thiram , fenoxanil , benthivalicarb , metalaxyl , fludioxonil and prochloraz , in a synergistically effective amount and to methods for controlling harmful fungi , comprising applying the fungicidal mixture .