Abstract:
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.

Description:
CROSS REFERENCE TO RELATED APPLICATION(S) 
       [0001]    This application is a continuation of U.S. application Ser. No. 10/508,208, filed Sep. 20, 2004, which is a 35 U.S.C. §371 National Phase Entry Application from PCT/EP2003/002845, filed Mar. 19, 2003, and designating the United States. This application also claims the benefit of German Application No. 10212704.2, filed Mar. 21, 2002, the disclosure of which is incorporated herein in its entirety by reference. 
     
    
     BACKGROUND OF THE INVENTION 
       [0002]    1. Technical Field 
         [0003]    The present invention relates to fungicidal mixtures, comprising 
         [0000]    (1) 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione (prothioconazole) of the formula I or a salt or adduct thereof 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and at least one further fungicidal compound, selected from the group consisting of
 
(2) boscalid of formula II
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(3) carboxin of formula III
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(4) metrafenone of formula IV
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(5) a compound of formula V
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(6) a compound of formula VI
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(7) quinoxyfen of formula VII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(8) dithianon of formula VIII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(9) thiram of formula IX
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(10) mepiquat chloride of formula X
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(11) cyazofamid of formula XI
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(12) fenoxanil of formula XII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(13) a compound of formula XIII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(14) thiophanate-methyl of formula XIV
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(15) carbendazim of formula XV
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(16) metalaxyl of formula XVI
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(17) fludioxonil of formula XVII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(18) thiabendazole of formula XVIII
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(19) quintozen of formula XIX
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(20) prochloraz of formula XX
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    and
 
(21) anthraquinone of formula XXI
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    in a synergistically effective amount. 
         [0004]    Moreover, the invention relates to a method for controlling harmful fungi using mixtures of the compounds I and at least one of the compounds II to XXI, and to the use of the compounds I and at least one of the compounds II to XXI for preparing such mixtures, and to compositions comprising these mixtures. 
         [0005]    2. Description of the Background Art 
         [0006]    Prothioconazole of formula I, i.e. 2-[2-(1-chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]triazole-3-thione, is already known from WO 96/16048. 
         [0007]    WO 98/47367 discloses a number of active compound combinations of prothioconazole with a large number of other fungicidal compounds. 
         [0008]    Boscalid of formula II and its use as crop protection agent are described in EP-B 0 545 099. 
         [0009]    Carboxin of formula III is already known and described in U.S. Pat. No. 3,249,499. 
         [0010]    Metrafenone of formula IV is likewise known and described in EP-A-727 141, EP-A 897 904, EP-A 899 255 and EP-A-967 196. 
         [0011]    The compound of formula V is described in WO 96/19442. 
         [0012]    The compound of formula VI is described in EP-A-1017670, EP-A-1017671 and DE 19753519.4. 
         [0013]    Quinoxyfen of formula VII is known from EP-A-0 326 330. 
         [0014]    Dithianon of formula VIII is described in GB 857 383. 
         [0015]    Thiram of formula IX is described in DE-A-06 42 532. 
         [0016]    Mepiquat chloride of formula X is known from DE-A-22 07 575. 
         [0017]    Cyazofamid of formula XI is described in PCT/EP/02/00237 
         [0018]    Fenoxanil of formula XII is described in PCT/EP/01/14785. 
         [0019]    The compound of formula XIII is described in WO 99/56551. 
         [0020]    Thiophanate-methyl of formula XIV is known from DE-A-1930540. 
         [0021]    Carbendazim of formula XV is described in U.S. Pat. No. 3,657,443. 
         [0022]    Metalaxyl of formula XVI is described in U.S. Pat. No. 4,151,299. 
         [0023]    Fludioxonil of formula XVII is known from EP-A-206 999. 
         [0024]    Thiabendazole of formula XVIII is known from U.S. Pat. No. 3,017,415. 
         [0025]    Quintozene of formula XIX is described in DE-A-682048. 
         [0026]    Prochloraz of formula XX is described in U.S. Pat. No. 3,991,071. 
         [0027]    Anthraquinone of formula XXI is described in The Pesticide Manual, 12th Ed. (2000), page 39. 
         [0028]    It is an object of the present invention to provide mixtures which have improved activity against harmful fungi combined with a reduced total amount of active compound applied (synergistic mixtures), with a view to reducing the application rates and improving the activity specetrum of the known compounds I to XXI. 
         [0029]    We have found that this object is achieved by the mixture, defined at the outset, of prothioconazole with at least one further fungicide. Moreover, we have found that applying the compound I simultaneously, that is jointly or separately, with at least one of the compounds II to XXI or applying the compound I with at least one of the compounds II to XXI in succession provides better control of harmful fungi than is possible with the individual compounds alone. 
         [0030]    2-[2-(1-Chlorocyclopropyl)-3-(2-chlorophenyl)-2-hydroxypropyl]-2,4-dihydro-[1,2,4]-triazole-3-thione of the formula I is known from WO 96-16 048. The compound can be present in the “thiono” form of formula I 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    or in the tautomeric “mercapto” form of formula Ia. 
         [0000]    
       
                 
         
             
             
         
       
     
         [0031]    For the sake of simplicity, only the “thiono” form is shown in each case. 
         [0032]    Boscalid of formula II 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from EP-B-0 545 099. 
         [0033]    Carboxin of formula III 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from U.S. Pat. No. 3,249,499. 
         [0034]    Metrafenone of formula IV 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from EP-A-727 141, EP-A-897 904, EP-A-899 255 and EP-A-96 196. 
         [0035]    The compound of formula V 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from WO 96/19442. 
         [0036]    The compound of formula VI 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in EP-A-1017 670, EP-A-1017 671 and DE 197 535 19.4. 
         [0037]    Quinoxyfen of formula VII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from EP-A-0 326 330. 
         [0038]    Dithianon of formula VIII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in GB 857 383. 
         [0039]    Thiram of formula IX 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is known from DE-A-06 42 532. 
         [0040]    Mepiquat chloride of formula X 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in DE-A-22 07 575. 
         [0041]    Cyazofamid of formula XI 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in PCT/EP/02/00237. 
         [0042]    Fenoxanil of formula XII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in PCT/EP/01/14785. 
         [0043]    A compound of formula XIII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in WO 99/56 551. 
         [0044]    Thiophanate-methyl of formula XIV 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in DE-A-1 930 540. 
         [0045]    Carbendazim of formula XV 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in U.S. Pat. No. 3,657,443. 
         [0046]    Metalaxyl of formula XVI 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in U.S. Pat. No. 4,151,299. 
         [0047]    Fludioxonil of formula XVII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in EP-A-206 999. 
         [0048]    Thiabendazole of formula XVIII 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in U.S. Pat. No. 3,017,415. 
         [0049]    Quintozene of formula XIX 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in DE-A-682 048. 
         [0050]    Prochloraz of formula XX 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in U.S. Pat. No. 3,991,071. 
         [0051]    Anthraquinone of formula XXI 
         [0000]    
       
                 
         
             
             
         
       
     
         [0000]    is described in The Pesticide Manual, 12th Ed. (2000), page 39. 
       SUMMARY OF THE INVENTION 
       [0052]    Preference is given to mixtures of prothioconazole with boscalid of the formula II. 
         [0053]    Preference is furthermore also given to mixtures of prothioconazole with carboxin of the formula III. 
         [0054]    Preference is also given to mixtures of prothioconazole with metrafenone of the formula IV. 
         [0055]    Preference is furthermore given to mixtures of prothioconazole with the compound of the formula V. 
         [0056]    Preference is furthermore given to mixtures of prothioconazole with the compound of the formula VI. 
         [0057]    Preference is furthermore given to mixtures of prothioconazole with quinoxyfen of the formula VII. 
         [0058]    Preference is furthermore given to mixtures of prothioconazole with dithianon of the formula VIII. 
         [0059]    Preference is furthermore given to mixtures of prothioconazole with thiram of the formula IX. 
         [0060]    Preference is furthermore given to mixtures of prothioconazole with mepiquat chloride of the formula X. 
         [0061]    Preference is furthermore given to mixtures of prothioconazole with cyazofamid of the formula XI. 
         [0062]    Preference is furthermore given to mixtures of prothioconazole with fenoxanil of the formula XII. 
         [0063]    Preference is furthermore given to mixtures of prothioconazole with the compound of the formula XIII. 
         [0064]    Preference is furthermore given to mixtures of prothioconazole with thiophanate-methyl of the formula XIV. 
         [0065]    Preference is furthermore given to mixtures of prothioconazole with carbendazim of the formula XV. 
         [0066]    Preference is furthermore given to mixtures of prothioconazole with metalaxyl of the formula XVI. 
         [0067]    Preference is furthermore given to mixtures of prothioconazole with fludioxonil of the formula XVII. 
         [0068]    Preference is furthermore given to mixtures of prothioconazole with thiabendazole of the formula XVIII. 
         [0069]    Preference is furthermore given to mixtures of prothioconazole with quintozene of the formula XIX. 
         [0070]    Preference is furthermore given to mixtures of prothioconazole with prochloraz of the formula XX. 
         [0071]    Preference is furthermore given to mixtures of prothioconazole with anthraquinone of the formula XXI. 
         [0072]    Preference is furthermore given to mixtures of prothioconazole with two further fungicidal compounds of the formulae II to XXI. 
     
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
       [0073]    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. 
         [0074]    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. 
         [0075]    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. 
         [0076]    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. 
         [0077]    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. 
         [0078]    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. 
         [0079]    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. 
         [0080]    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. 
         [0081]    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. 
         [0082]    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. 
         [0083]    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. 
         [0084]    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. 
         [0085]    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. 
         [0086]    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. 
         [0087]    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. 
         [0088]    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. 
         [0089]    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. 
         [0090]    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. 
         [0091]    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. 
         [0092]    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. 
         [0093]    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. 
         [0094]    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. 
         [0095]    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. 
         [0096]    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. 
         [0097]    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. 
         [0098]    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. 
         [0099]    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. 
         [0100]    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. 
         [0101]    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. 
         [0102]    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. 
         [0103]    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. 
         [0104]    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. 
         [0105]    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. 
         [0106]    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. 
         [0107]    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. 
         [0108]    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. 
         [0109]    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. 
         [0110]    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. 
         [0111]    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. 
         [0112]    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. 
         [0113]    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. 
         [0114]    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. 
         [0115]    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. 
         [0116]    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. 
         [0117]    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. 
         [0118]    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. 
         [0119]    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. 
         [0120]    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. 
         [0121]    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. 
         [0122]    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. 
         [0123]    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. 
         [0124]    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. 
         [0125]    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. 
         [0126]    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. 
         [0127]    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. 
         [0128]    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. 
         [0129]    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. 
         [0130]    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. 
         [0131]    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. 
         [0132]    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). 
         [0133]    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. 
         [0134]    Application can be effected before or after infection by the harmful fungi. 
       EXAMPLES 
     Use Example 
       [0135]    The synergistic activity of the mixtures according to the invention was demonstrated by the following experiments: 
         [0136]    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. 
         [0137]    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: 
         [0000]    
       
         
           
             W 
             = 
             
               
                 ( 
                 
                   1 
                   - 
                   
                     α 
                     β 
                   
                 
                 ) 
               
               · 
               100 
             
           
         
       
       
         α corresponds to the fungal infection of the treated plants in % and 
         β corresponds to the fungal infection of the untreated (control) plants in %. 
       
     
         [0140]    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. 
         [0141]    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. 
         [0000]      Colby formula:  E=x+y−xy/ 100   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.     
         [0145]    Use example 1: Activity against mildew of wheat caused by  Erysiphe  [syn.  Blumeria] graminis  form a specialis.  tritici    
         [0146]    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. 
         [0147]    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. 
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 1 
               
               
                   
                   
               
               
                   
                   
                   
                 Efficacy 
               
               
                   
                   
                 Concentration of active 
                 in % of the 
               
               
                   
                   
                 compound in the spray 
                 untreated 
               
               
                   
                 Active compound 
                 liquor in ppm 
                 control 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Control 
                 (90% infection) 
                 0 
               
               
                   
                 (untreated) 
               
               
                   
                 Compound I = 
                 4 
                 42 
               
               
                   
                 prothioconazole 
                 1 
                 0 
               
               
                   
                   
                 0.25 
                 0 
               
               
                   
                 Compound II = 
                 4 
                 0 
               
               
                   
                 boscalid 
                 1 
                 0 
               
               
                   
                   
                 0.25 
                 0 
               
               
                   
                   
                 0.06 
                 0 
               
               
                   
                 Compound IV = 
                 0.06 
                 53 
               
               
                   
                 metrafenone 
                 0.015 
                 30 
               
               
                   
                 Compound VI 
                 0.25 
                 53 
               
               
                   
                   
                 0.06 
                 0 
               
               
                   
                 Compound VIII = 
                 4 
                 0 
               
               
                   
                 dithianon 
                 1 
                 0 
               
               
                   
                   
                 0.25 
               
               
                   
                 Compound XI = 
                 1 
                 22 
               
               
                   
                 cyazofamid 
                 0.25 
                 22 
               
               
                   
                   
                 0.06 
                 0 
               
               
                   
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 2 
               
               
                   
                   
               
               
                   
                 Combinations according to the 
                 Observed 
                 Calculated 
               
               
                   
                 invention 
                 efficacy 
                 efficacy*) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Compound I = prothioconazole + 
                 19 
                 0 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 0.25 + 4 ppm 
               
               
                   
                 mixture 1:16 
               
               
                   
                 Compound I = prothioconazole + 
                 92 
                 0 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 1 + 4 ppm 
               
               
                   
                 mixture 1:4 
               
               
                   
                 Compound I = prothioconazole + 
                 53 
                 0 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 0.25 + 1 ppm 
               
               
                   
                 mixture 1:4 
               
               
                   
                 Compound I = prothioconazole + 
                 30 
                 0 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 1 + 0.25 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = protioconazole + 
                 19 
                 0 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 1 + −.06 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 65 
                 53 
               
               
                   
                 Compound IV metrafenone 
               
               
                   
                 0.25 + 0.06 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 65 
                 53 
               
               
                   
                 Compound IV metrafenone 
               
               
                   
                 1 + 0.06 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 42 
                 30 
               
               
                   
                 Compound IV metrafenone 
               
               
                   
                 0.25 + 0.015 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 65 
                 53 
               
               
                   
                 Compound VI 
               
               
                   
                 1 + 0.25 ppm 
               
               
                   
                 mixture 1:16 
               
               
                   
                 Compound I = prothioconazole + 
                 18 
                 0 
               
               
                   
                 Compound VI 
               
               
                   
                 0.25 + 0.06 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 88 
                 77 
               
               
                   
                 Compound VI 
               
               
                   
                 4 + 0.25 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 33 
                 0 
               
               
                   
                 Compound VII = 
               
               
                   
                 dithianon 0.25 + 4 ppm 
               
               
                   
                 mixture 1:16 
               
               
                   
                 Compound I = prothioconazole + 
                 33 
                 0 
               
               
                   
                 Compound VII = 
               
               
                   
                 dithianon 1 + 4 ppm 
               
               
                   
                 mixture 1:4 
               
               
                   
                 Compound I = prothioconazole + 
                 97 
                 0 
               
               
                   
                 Compound VII = 
               
               
                   
                 dithianon 0.25 + 0.25 ppm 
               
               
                   
                 mixture 1:1 
               
               
                   
                 Compound I = prothioconazole + 
                 22 
                 0 
               
               
                   
                 Compound VII = 
               
               
                   
                 dithianon 1 + 0.25 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 56 
                 22 
               
               
                   
                 Compound XI = 
               
               
                   
                 cyazofamid 0.06 + 1 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 56 
                 22 
               
               
                   
                 Compound XI = 
               
               
                   
                 cyazofamid 1 + 0.25 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 33 
                 22 
               
               
                   
                 Compound XI = 
               
               
                   
                 cyazofamid 1 + 0.25 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 22 
                 0 
               
               
                   
                 Compound XI = 
               
               
                   
                 cyazofamid 1 + 0.06 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                   
               
               
                   
                 *)Efficacy calculated using Colby&#39;s formula 
               
             
          
         
       
     
         [0148]    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) 
         [0149]    Use example 2: Protective activity against mildew of cucumber caused by  Sphaerotheca fuliginea    
         [0150]    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. 
         [0000]    
       
         
               
               
               
             
               
               
               
             
           
               
                 TABLE 3 
               
               
                   
               
               
                   
                 Concentration of active 
                 Efficacy in % of 
               
               
                   
                 compound in the spray 
                 the untreated 
               
               
                 Active compound 
                 liquor in ppm 
                 control 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                 Control (untreated) 
                 (90% infection) 
                 0 
               
               
                 Compound I = 
                 1 
                 78 
               
               
                 prothioconazole 
                 0.25 
                 56 
               
               
                 Compound II = 
                 4 
                 78 
               
               
                 boscalid 
                 0.25 
                 0 
               
               
                   
                 0.06 
                 0 
               
               
                 Compound IV = 
                 0.06 
                 0 
               
               
                 metrafenone 
                 0.015 
                 0 
               
               
                 Compound VI 
                 0.06 
                 33 
               
               
                   
                 0.015 
                 0 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
               
               
               
             
               
               
               
               
             
           
               
                   
                 TABLE 4 
               
               
                   
                   
               
               
                   
                 Combinations according to the 
                 Observed 
                 Calculated 
               
               
                   
                 invention 
                 efficacy 
                 efficacy*) 
               
               
                   
                   
               
             
             
               
                   
               
             
          
           
               
                   
                 Compound I = prothioconazole + 
                 99 
                 90 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 0.25 + 4 ppm 
               
               
                   
                 mixture 1:16 
               
               
                   
                 Compound I = prothioconazole + 
                 89 
                 78 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 1 + 0.25 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 78 
                 56 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 0.25 + 0.06 ppm mixture 
               
               
                   
                 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 94 
                 78 
               
               
                   
                 Compound II = 
               
               
                   
                 boscalid 1 + 0.06 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 78 
                 56 
               
               
                   
                 Compound IV = metrafenone 
               
               
                   
                 0.25 + 0.06 ppm mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 94 
                 78 
               
               
                   
                 Compound IV = metrafenone 
               
               
                   
                 1 + 0.06 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 78 
                 56 
               
               
                   
                 Compound IV = metrafenone 
               
               
                   
                 0.25 + 0.015 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                 Compound I = prothioconazole + 
                 89 
                 70 
               
               
                   
                 Compound VI 
               
               
                   
                 0.25 + 0.06 ppm 
               
               
                   
                 mixture 4:1 
               
               
                   
                 Compound I = prothioconazole + 
                 72 
                 56 
               
               
                   
                 Compound VI 
               
               
                   
                 0.25 + 0.015 ppm 
               
               
                   
                 mixture 16:1 
               
               
                   
                   
               
               
                   
                 *)Efficacy calculated using Colby&#39;s formula 
               
             
          
         
       
     
         [0151]    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)