Abstract:
Novel synergistic fungicidal compositions used for protecting seeds, plants and other vegetative material against fungi contain a mixture of one or more compounds selected from group A and one or more compounds selected from group B. Compounds from group A are selected from β-Amino butyric acid and its N-benzoyl-octyl ester derivatives. Compounds from group B are selected from the group of fosetyl aluminum, dimethomorph, a mixture of folpet and ofurace (45:5), folpet, fencaramid (Bayer SZX), mancozeb, cymoxanil, methalaxyl, the single optical isomer of metalaxyl, a mixture of cymoxanil and mancozeb (4:1), copper sulfate, copper hydroxide, copper sulfate hydrate, azoxystrobin, and acibenzolar-s-methyl.

Description:
INTRODUCTION  
         [0001]    The present invention concerns synergistic fungicidal mixtures. The present invention more particularly concerns synergistic mixture of β-aminobutyric acid (hereinafter referred to as BABA) and its N-benzoyl-octyl ester derivatives for the control of plant diseases.  
         BACKGROUND OF THE INVENTION  
         [0002]    Fungicides are often combined in mixtures for 3 main reasons: 1. to widen the spectrum of antifungal activity to control several diseases occurring simultaneously in a crop 2. to exploit synergistic interaction between fungicides, by which the overall activity is increased and the concentration of the compounds reduced, and 3. to delay the selection process of resistant fungal individuals to one component of the mixture (Gisi, Phytopathology 86 1273-1279,1996).  
           [0003]    Avoidence of plant disease in agricultural production may be accomplished not only by using fungicides or fungicidal mixtures but also by using “plant activators”, molecules which enhance the natural resistance (defense) of the plant. Such activators which have no direct fungicidal effect on the pathogen (Ryals et al The Plant Cell 8: 1809-1819,1996), induce systemic acquired resistance (SAR) in the plant several days after application (Ibid).  
           [0004]    To date only few molecules were reported to induce SAR in crop plants viz. salicylic acid (SA), 2,6-dichloroisonicotinic acid (INA) benzol (1,2,3) thiadiazole-7-carbothiouic acid S-methyl ester (BTH) (Ibid), and DL-3-amino butyric acid (BABA, Cohen et al Plant Physiology 104: 56-59,1994).  
           [0005]    However whereas SA, INA or BTH have to be applied to the crop ahead of infestation (Ryals, et al Ibid) BABA can be applied post—infectionaly (Cohen et al Ibid).  
           [0006]    The idea behind the present invention is to combine two methods of disease control—the direct—kill method operating on the target pathogen and the indirect method of activating the natural defense approach of the crop plant. Such two methods are combined by using mixtures of a fungicide or fungicides (direct—kill) with BABA or its N-benzoyl-octyl ester derivative(SAR).  
           [0007]    We show here that such mixtures are synergistic in controlling plant diseases.  
         OBJECTIVES OF THE INVENTION  
         [0008]    It is the objective of the present invention to provide novel mixtures of fungicides of β-aminobutyric acids. It is an objective of the present invention to provide a synergistic mixture of BABA and/or its N-benzoyl-octyl ester derivative with various other fungicides.  
         SUMMARY OF THE INVENTION  
         [0009]    In accordance with the present invention there is provided synergistic fungicidal compositions comprising one or more compounds selected from Group A and one or more compounds selected from Group B, wherein the compounds of Group A are selected from the group consisting of DL-3 aminobutyric-acid and its N-Benzoyl octyl ester, and the compounds of Group B are selected from the group consisting of fosetyl aluminum, dimethomorph, a mixture of folpet and ofturace (45:5), folpet, fencaramid (Bayer SZX), mancozeb, cymoxanil, methalaxyl, the single optical isomer of metalaxyl, a mixture of cymoxamil and mancozeb (4:1), copper sulfate, copper hydroxide, copper sulfate hydrate, azoxystrobin, and acibenzolar-s-methyl.  
           [0010]    The present invention also provides an improved method of controlling fungi, especially late blight and downy mildews, applying to the plant a composition containing an effective amount of one of these mixtures. The present invention further provides an improved method of controlling  phytophthora infertan  in potato or tomatoe,  Pseudoperonospora cubensis  in cucumber or melon,  Plasmopera viticola  in grapes, and  Peronospora tabacina  in tabacco. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION  
       [0011]    Methodology  
         [0012]    Plants 1. Potato (cultivar Alpha) were grown from tubers in 1 liter pots in sandy soil in the greenhouse. At 5 weeks after planting when they had several shoots in a pot, with 10-12 leaves per shoot, plants were taken for assays.  
         [0013]    2. Cucumber (cultivate Dlila) plants were grown from seed in 0.251 liter pots containing sandy soil in the greenhouse. At 3 weeks after sowing, when they developed 2 leaves they were used.  
         [0014]    3. Grapes (cultivate Superior) plants were grown from cuttings (first in perlite and then in sandy soil) in pots in the greenhouse. At 8 weeks after planting leaves were detached for experiments.  
         [0015]    Fungal Pathogens. Potatoes were inoculated with sporangic of  Phytophthora infestans  (resistant to metalaxyl). Cucumbers were inoculated with sporangia of  Pseudoperonospora cubensis  (resistance to metalaxyl). Grapes were inoculated with  Plasmopara viticola  Chemicals.  
         [0016]    1. DLβ-amino-butanoic acid (BABA)  
         [0017]    2. DL-4-benzoyl-3-amino butanoic acid octylester (039-81)  
         [0018]    3. Cymoxanil (Curzate)  
         [0019]    4. phosetyl-aluminium (Alliette)  
         [0020]    5. Mancozeb  
         [0021]    6. Folpet  
         [0022]    7. Metalaxyl, metalaxyl-Gold  
         [0023]    8. Copper sulphate, copper hydroxide  
         [0024]    9. (Mancozeb+dimethomorph, prepacked 600 g+90 g a.i. per 1 kg)  
         [0025]    10. (Mancozeb+metalaxyl, prepacked 560 g+75 g a.i. per 1 kg)  
         [0026]    11. Folpet+ofurace, 450 g+60 g a.i. per 1 kg)  
         [0027]    12. Bayer-SZX (Fencaramid)  
         [0028]    13. Mancozeb+Cymoxanil (4:1)  
         [0029]    14. Azoxystrobin  
         [0030]    15. Acibenzolar-s-methyl  
         [0031]    16. Dimethomorph  
         [0032]    Except BABA which was dissolved in water, all other chemicals or prepacked mixtures produced a suspension or emulsion in water.  
         [0033]    Spraying The chemicals were sprayed onto the upper leaf surfaces of either potatoes or cucumbers with the aid of a fine glass atomizer. Control plants were sprayed with water. Experiments with grapes were carried out using 12 mm leaf discs floating on 1 ml of the test compound(s) in 24-well titer plates, upperside down.  
         [0034]    Inoculation  
         [0035]    Potatoes and cucumbers were inoculated one day after spraying. Grape leaf discs were inoculated soon after floating. Inoculation of potato was done by spraying the upper leaf surfaces of the plants with a sporangial suspension containing 2000 sporangia/ml. Sporangia were harvested 0.5 h before inoculation from infected potato tuber slices. Cucumbers were sprayed with a sporangial suspension containing 1500 sporangia/ml. Sporangia were harvested from infected cucumber plants kept in humid growth chambers (at 15° C.). Leaf discs of grapes were inoculated with 2 sporangial droplets containing each 300 sporangia. Sporangia were harvested from infected leaves kept in petri dishes on wet filter paper at 15° C. Inoculated plants or titer plates were placed in a dew chamber at 18° C. overnight and then transferred to a growth chamber at 20° C. (12 h light/day 100 pE.m −2 .S −1 ) for symptom production (late blight in potato and downy mildew in cucumber), or for sporulation of  P. viticola  in grape leaf discs.  
         [0036]    General Procedure for Tabacco  
         [0037]    One month old tobacco plants (cv.xanthi nc.). were sprayed onto their foliage with the test compounds. Two days later they were inoculated with 10 4  spores/ml of  Perouospora latacin  of either the S or the R strain. Inoculated plants were placed in 100% relative humidity over night and then incubated at 20° C. with 12 h light/day. A week after innoculation plants were again placed at 100%-RH at 18° C. in the dark to induce fungal sporulation. Sporulation was quantitated by removing 2 cm 2  leaf discs from each leaf and counting with the aid of a haemocytometer. The extent of sporulation inhibition was calculated relative to that in control (untreated) inoculated plants. Ed go  was computed after linear regression and of was calculated according to Wadely.  
         [0038]    General Procedure for Grapes  
         [0039]    Leaf discs (2-cm 2 ) were removed from the top leaves of grape plants (cv. Superior) grown in the greenhouse. Discs were floated (lower surface uppermost on the test solutions over filter paper of 9 cm diameter). Petri dishes. Leaf discs were immediately innoculated with 2 (10 ml) droplets of sporangial suspension (10 4 /ml) of  Plasmopara viticola  per disc. Dishes were inculcated at 20° C. with 12 h light/day for 10 days until fungal sporulation was quantified.  
         [0040]    Disease Assessment  
         [0041]    At the time intervals post inoculation specified in the Examples, infected leaf area in potato and cucumber was assessed visually. In control inoculated plants most or all of the foliage (80-100%) was devastated by the disease. Percentage control of the disease by a chemical treatment was calculated as 
         % control=(1 −x/y )×100 
         [0042]    whereas  
         [0043]    x=proportion leaf area diseased in treated plants  
         [0044]    and  
         [0045]    y=proportion leaf area diseased in control plants.  
         [0046]    In grapes, proportion of leaf discs showing sporulation were similarly used.  
         [0047]    Calculation of Control Efficacy and Synergism  
         [0048]    Each chemical and each mixture was applied to plants at various doses of the active ingredient. Dose—response curves were produced and transferred to log—dose probit response curves as described by Kosman and Cohen (Phytopatholagy 86: 1263-1272, 1996). ED 90  values (dose required for achieving 90% control of the disease) taken from the log-probit 7 curves were used to calculate the Cotoxicity Factor (CF) according to the Wadely procedure (Kosman and Cohen, Ibid; Gisi phytopatcology 86: 1273-1279,1966). “CF” is defined as the ratio between the expected dose and the observed dose that provide the same level of disease control (Kosman and Cohen, Ibid). The observed dose of each component of a mixture is taken from the experiment and the expected dose of all mixture made of that components is calculated by the Wadely formula:  
           ED   90                   expected     =       a   +   b         a       ED   90                     obs   .   A         +     b       ED   90                     obs   .   B                                   
 
         [0049]    where a and b are the absolute amounts of the components A and B in a mixture and ED 90 . obs.A and Ed 90  obs.B are the ED 90  values of A and B obtained by the experiment. CF values of&gt;2.0 are considered to represent a strongly synergistic mixture (Gisi, Ibid).  
         [0050]    According to a further feature of the invention, there is provided a fungicidal composition which comprises a compound of the invention together with carrier. The active compound can be employed as a wide variety of formulations, for example as an aqueous dispersion, a dispersible powder, as seed dressing, granules or dust. As a dispersion the composition comprises an active compound together with a dispersing agent dispersed in a liquid medium, preferably water. It can be in a form of a concentrated primary composition which requires dilution with a suitable quantity of water or other diluent before application. Such primary compositions are a convenient way of supplying the consumer and preferred example is a dispersible powder. A dispersible powder comprises an active compound, a dispersing agent and solid carrier. The latter can be, for example, kaolin, talc, or diatomaceous earth and in addition, the dispersible powder can contain a wetting agent.  
         [0051]    Other formulations include seed dressing, granules or dusts, in all of which the active compound is associated with a solid carrier and which are intended for direct application. They can be made by methods well known in the art. Preferably all compositions comprising a solid carrier are made by mixing the active compound in particulate form with a particulate carrier.  
         [0052]    The concentration of the active compound in the composition of the inventioncan vary widely. In the case of a primary composition it is preferably from 15% to 95% by weight, more especially from 50% to 80% by weight. A composition intended for direct application to a crop preferably comprises from 0.001% to 10% more, especially from 0,005% to 5% by weight of the active compound, although the aerial spraying of a crop is contemplated compositions having higher concentrations, for example up to 30% by weight may be chosen in preference.  
         [0053]    The fungicidal composition of the present invention may be applied as a ready-mixed composition, as a tank mix, or applying the compounds of each group separately.  
         [0054]    Following the methods outlined above numerous mixtures were prepared and their activity against a variety of diseases were studied. The results of 35 studies are listed in Tables 1-35.  
         [0055]    While the invention will now be described in connection with certain preferred embodiments in the following examples it will be understood that it is not intended to limit the invention to these particular embodiments. On the contrary, it is intended to cover all alternatives, modifications and equivalents as be included within the scope of the invention, as defined by the appended claims. Thus, the following examples which iclude preferred embodiments, will serve to illustrate the practice of this invention, it being understood that the particulars shown are by way of example and for purposes of illustrative discussion of preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of procedures as well as of the principles and conceptual aspects of the invention.  
                                                                                                                         TABLE 1                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       COPPER SULFATE HYDRATE MIXTURE a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   2   8   32   125   250   1000   mg/L   CF                    BABA   —   —   —   0   0   0   13   2678   —       Cu +2      —   0   0   63   83   —   —   143       BABA + Cu +2      80 + 20   0   0   13   88   —   —   126   4.7           70 + 30   0   0   50   93   —   —   101   4.2           60 + 40   0   0   85   93   —   —   85   3.9                                  
 
         [0056]    [0056]                                                                                                                 TABLE 2                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       CYMOXANIL MIXTURE (CURZATE R ) a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA   —       3   24   18   64   1498   —       Cymoxanil   —   36   73   64   98       128   —       BABA +   80 + 20   9   9   3   79   —   294   1.6       Cymoxanil   50 + 50   73   76   82   98   —   114   2.1                                    
         [0057]    [0057]                                                                                                                                                       TABLE 3                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       FOSETYL ALUMINUM MIXTURE a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90              Comounds   Ratio   16   62   250   1000   mg/L   CF                    Cultivar Cara b              BABA       9   9   9   24   3233   —       Fosetyl − Al       9   24   24   70   1390   —       BABA +   75 + 25   9   9   39   70   1311   1.9       Fosetyl − Al   25 + 75   9   9   39   79   1142   1.4            Cultivar Draga c              BABA       0   0   0   53   1533   —       Fosetyl − Al       33   33   50   93   856   —       BABA +   75 + 25   67   67   93   93   639   1.7       Fosetyl − Al   25 + 75   0   0   93   100   245   3.9                                            
         [0058]    [0058]                                                                                                                 TABLE 4                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       MIXTURES OF MANCOZEB + DIMETHOMORPH MIXTURES a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90               Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA   —   —   3   24   18   64   1498   —       MANCOZEB +   —   70   73   82   98   —   115   —       DIMETHOMORPH       BABA +   80 + 20   64   73   70   82   —   287   1.5       (MANCOZEB C  +   50 + 50   85   70   70   91   —   189   1.1       DIMETHOMORPH)                    
         [0059]    [0059]                                                                                                                 TABLE 5                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       FOLPET/OFURACE (45 + 5) MIXTURE a                      Percent Disease Control b                         @ mg/L Active Ingredient -   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   14   14   14   36   2617           FOLPET/       77   89   99   100   —   19       OFURACE       BABA +       (FOLPET/   50 + 50   74   81   99   100   —   22   1.8       OFURCE)                                    
         [0060]    [0060]                                                                                                         TABLE 6                           CONTROL OF LATE BLIGHT IN POTATO BY BABA       FOLPET - CYMOXANIL MIXTURE a                      Percent Disease Control b                          mg/L Active Ingredient   ED 90               Compounds   Ratio   16   62   250   1000   mg/L   CF                    BABA       22   22   22   69   1481           FOLPET       81   95   98   100   84       CYMOXANIL       83   86   91   100   183       BABA + FOLPET   60 + 25 + 15   72   89   98   100   95   2.5       + CYMOXANIL           25 + 60 + 15   92   86   95   100   104   1.3                                    
         [0061]    [0061]                                                                                                                                 TABLE 7                           CONTROL OF LATE BLIGHT IN POTATO BY THE       N - BENZOYL OCTYL ESTER OF BABA AND FENCARAMID a                      Percent Disease Control               Com-       mg/L Active Ingredient b     ED 90              pounds   Ratio   2   8   32   125   250   1000   2000   mg/L   CF                    BABA       —   —   —   15   25   50   53   2395           Deriv-       ative       Fenc-       0   50   98   100   —   —   —   19       aramid       BABA       DERI-   80 + 20   44   63   85   100   —   —   —   31   3.0       VAT-       IVE +       FENC-   90 + 10   13   50   56   94   —   —   —   97   1.8       ARA-       MID                    
         [0062]    [0062]                                                                                                                 TABLE 8                           CONTROL OF LATE BLIGHT IN POTATO BY N-BENZOYL       OCTYL ESTER OF BABA, Cu (OH) 2 , (as 50% a.i), MANCOZEB a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90               Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    N-benzoyl octyl       —   3   25   25   75   1261           ester derivative of       BABA       Cu(OH) 2         0   0   13   75   —   298       Cu(OH) 2  +   70 + 30   0   3   44   50   —   416       Mancozeb                    
         [0063]    [0063]                                                                                                                 TABLE 9                           CONTROL OF LATE BLIGHT IN POTATO BY       N-BENZOYL OCTYL ESTER DERIVATIVE OF       FOLPET/OFURACE (45 + 5) AND THEIR MIXTURES a                      Percent Disease Control                       @ mg/L Active Ingredient b     ED 90               Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    N-benzoyl octyl       —   0   0   0   25   2011           ester derivative       of BABA       Folpet +       0   0   3   73   —   301       Ofurace (9 + 1)       N-benzoyl octyl                    
         [0064]    [0064]                                                                                                                 TABLE 10                           CONTROL OF LATE BLIGHT IN POTATO BY       N-BENZOYL OCTYL ESTER DERIVATIVE OF BABA,       AND MANCOZEB + CYMOXANIL; 4:1 AND THEIR MIXTURES a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90               Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    N-benzoyl octyl       —   0   0   0   25   2011           ester derivative       of BABA       Mancozeb +       0   25   25   75   —   313       Cymoxanil       N-benzoyl octyl   67:33   25   68   70   95   —   169   4.3       ester derivative   50:50   5   63   88   98   —   95   5.7                    
         [0065]    [0065]                                                                                                                                 TABLE 11                           CONTROL OF LATE BLIGHT IN POTATO BY       N-BENZOYL OCTYL ESTER DERIVATIVE OF BABA,       FOLPET AND THEIR MIXTURES a                      Percent Disease Control b                 Com-       mg/L Active Ingredient   ED 90              pounds   Ratio   4   16   62   250   500   1000   2000   mg/L   CF                    N-                                   1514           benzoyl       octyl       ester       —   —   —   63   69   85   89       deriv-       ative       of       BABA       Folpet       70   75   90   95   —   —   —   141       N-   80 + 20   50   80   85   93   —   —   —   167   3.1       benzoyl   67 + 33   13   76   86   96   —   —   —   130   2.8       octyl   33 + 67   63   76   78   88   —   —   —   224   0.9       ester   33 + 67   63   76   78   88   —   —   —   224   0.9       deriv-       ative       of       BA-       BA +       Folpet                                    
         [0066]    [0066]                                                                                                                                 TABLE 12                           CONTROL OF LATE BLIGHT IN POTATO BY       N-BENZOYL OCTYL ESTER DERIVATIVE OF BABA,       FENCARAMID (BAYER SZX) AND THEIR MIXTURES a                      Percent Disease Control b                 Com-       mg/L Active Ingredient   ED 90              pounds   Ratio   2   8   31   25   500   1000   2000   mg/L   CF                    N-                                       —       benzoyl       octyl       ester       —   —   —   15   25   50   53   3204       deriv-       ative       of       BABA       Fenc-       0   50   98   100   —   —   —   19   —       aramid                                               —       N-   90:10   13   50   56   94   —   —   —   83   2.2       benzoyl   80:20   44   63   85   100   —   —   —   31   3.0       octyl       ester       deriv-       ative       of       BABA       +       Fenc-       armid                                    
         [0067]    [0067]                                                                                                                       TABLE 13                       CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA,       COPPER SULPHATE HYDRATE (EXPRESSED AS mg/L Cu ++ )       AND THEIR MIXTURES a                                      Percent Disease Control b                     mg/L Active Ingredient   ED 90              Compounds   Ratio   16   62   250   1000   mg/L   CF               BABA       43   43   57   72   1468                        Percent Disease Control b                     mg/L Active Ingredient   ED 90              Compounds   Ratio   2   8   32   125   mg/L   CF               Cu ++         57   72   80   89   105       BABA + Cu ++     80 + 20   72   72   86   89   102   4.0                    
         [0068]    [0068]                                                                                                                 TABLE 14                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA,       (EXPRESSED AS Cu(OH) 2 )       (Cu(OH) 2  + MANCOZEB) AND THEIR MIXTURES                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   33   33   50   67   1576           Cu(OH) 2         67   67   77   80   —   304       Cu(OH) 2  + mancozeb   70 + 30   67   67   83   93   —   174                    
         [0069]    [0069]                                                                                                                 TABLE 15                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA       (FOLPET/OFURACE 45 + 5)                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   0   29   57   71   1273   —       Vamin       43   57   71   91   —   206   —       BABA + Vamin   67 + 33   14   21   57   97   —   166   2.8           50 + 50   14   43   71   89       217   2.1           33 + 67   29   57   74   89       214   1.3                    
         [0070]    [0070]                                                                                                                 TABLE 16                           CONTROL OF DOWNY MILDEW CUCUMBER BY BABA       AND (MANCOZEB + CYMOXANIL; 4:1)                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   0   29   57   71   1273   —       (Mancozeb +           14   80   97   100   33   —       Cymoxanil)       BABA +   67 + 33   21   57   77   97   —   135   0.7       (Mancozeb +   50+:50   57   74   100   100   —   20   3.2       Cymoxanil)   33+:67   29   94   100   100   —   14   3.5                                    
         [0071]    [0071]                                                                                                                 TABLE 17                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY       BABA + (MANCOZEB + METALAXYL)                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   0   15   3   59   1443   —       Mancozeb + Metalaxyl       34   53   71   82   —   268   —       BABA + Mancozeb +   88 + 12   0   0   9   96   —   221   4.3       Metalaxyl   75 + 25   18   44   53   81   —   281   2.4           50 + 50   38   76   76   96   —   150   3.0                                    
         [0072]    [0072]                                                                                                                 TABLE 18                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY       BABA, FOLPET &amp; METALAXYL a  87:13)                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/LF   CF                    BABA       —   0   15   3   59   1443   —       Folpet &amp; Metalaxy       0   0   56   76   —   280   —       (87 + 13)       BABA + [Folpet +   88 + 12   12   0   59   81   —   260   3.7       metalaxyl]   75 + 25   68   53   56   71   —   393   1.8           50 + 50   0   38   62   68   —   339   1.4                    
         [0073]    [0073]                                                                                                                 TABLE 19                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA;       FOLPET &amp; METALAXYL a , (7 + 1) (MANCOZEB +       METALAXYL), (FOLPET + OFURACE) AND THEIR MIXTURES                    Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   12   19   25   31   3218           Folpet + metalaxyl       62   82   90   97   —   112                    
         [0074]    [0074]                                                                                                                 TABLE 20                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY       BABA, METALAXYL SINGLE ISOMER MANCOZEB       AND THEIR MIXTURES a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   8   8   8   38   2155           mancozeb       0   8   23   72   —   315       Metalaxyl Single       0   0   0   8   —   844       Isomer       BABA +   55 + 40 + 5    23   23   54   75   —   313   2.0       mancozeb +   50 + 40 + 10   38   25   31   80       314   2.0       Metalaxyl   40 + 40 + 20   8   15   8   31       689   0.9       Single Isomer   45 + 50 + 5    8   8   54   72       309   1.7           40 + 50 + 10   8   31   54   89       228   2.3           30 + 50 + 10   8   15   31   83       273   1.9           35 + 60 + 5    54   54   78   86       239   2.0           30 + 60 + 10   46   38   54   85       268   1.7           20 + 60 + 20   61   69   69   83       281   1.6           25 + 70 + 5    38   46   78   97       139   3.0           20 + 70 + 10   38   23   63   94       194   2.1           10 + 70 + 20   38   69   23   78       362   1.1                                    
         [0075]    [0075]                                                                                                         TABLE 21                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA,       ALIETTE, CYMOXANIL AND THEIR MIXTURES                    Percent Disease Control a                         mg/L Active Ingredient   ED 90               Compounds   Ratio   16   62   250   1000   mg/L   CF                    BABA       37   67   76   85   975   —       Aliette       45   85   98   99   245   —       Cymoxanil       0   20   58   72   1229   —       BABA + Aliette +   60 + 25 + 15   63   70   88   95   584   1.0       Cymoxanil   25 + 60 + 15   70   85   98   100   100   3.4                    
         [0076]    [0076]                                                                                                                 TABLE 22                           CONTROL OF DOWNEY MILDEW IN CUCUMBER BY       BABA, MANCOZEB, CYMOXANIL AND THEIR MIXTURES                    Percent Disease Control a                         mg/L Active Ingredient   ED 90              Compounds   Ratio   4   16   62   250   1000   mg/L   CF                    BABA       —   0   13   50   63   1413   —       Mancozeb       75   87   90   92   —   167   —       Cymoxanil       13   25   38   50   —   506   —       BABA + Manco-   60 + 25 + 15   63   75   83   95       152   3.0       zeb + Cymoxanil   25 + 60 + 15   75   87   90   95       136   1.8                    
         [0077]    [0077]                                                                                                                                 TABLE 23                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY       BABA, BAYER SZX (FENCARAMID) AND THEIR MIXTURES                    Percent Disease Control b                 Com-       @ mg/L Active Ingredient   ED 90              pounds   Ratio   2   8   31   125   500   1000   2000   mg/L   CF                    BABA                       61   72   74   2354           FENC-       78   83   95   100               19       ARA-       MID       BABA   80 + 20   38   58   83   100               33   2.8       +   50 + 50   60   80   98   100               14   2.7       FENC-   20 + 80   78   85   98   100               13   1.8       ARA-       MID                                    
         [0078]    [0078]                                       TABLE 24                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA,       BAYER DIMETHOMORPH (DMN)AND       THEIR MIXTURES                        Percent Disease Control b             Compounds   Ratio   @ mg/L Active Ingredient                       BABA 1000   gave   17% Control           DMN 5 ppm   gave   32% Control           BABA + DMN   gave   74% Control           1000 + 5 ppm                                                  Synergy                 ratio     =       74   =   74       17   =     32   -         (     17                 32     )                   33     100                       =   2.24                                                  
         [0079]    [0079]                                                                                                         TABLE 25                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA,       FOLPET, CYMOXANIL AND THEIR MIXTURES a                      Percent Disease                       Control b  mg/L               @ Active Ingredient   ED 90               Compounds   Ratio   16   62   250   1000   mg/L   CF                    BABA       6   22   48   82   1072           FOLPET       43   84   95   97   403               48   63   82   97   524       BABA + FOLPET +   25 + 60 + 15   76   87   95   99   247   2.0       CYMOXANIL                                    
         [0080]    [0080]                                                                                                         TABLE 26                           CONTROL OF DOWNY MILDEW IN CUCUMBER BY BABA       PHOSETYL-ALUMINIUM       AND THEIR MIXTURES a                      Percent Disease Control b                         mg/L Active Ingredient   ED 90              Compounds   Ratio   16   62   250   1000   mg/L   CF                    BABA       10   43   43   71   1386   —       Phosetyl-Aluminium       71   71   94   86   638   —       BABA +   12 + 88   43   43   86   100   261   4.7       Phosetyl-Aluminium   25 + 75   0   14   71   97   551   1.9           50 + 50   0   14   57   83   1009   0.9           75 + 25   —   57   57   86   918   0.8           88 + 12   14   29   71   86   931   0.7                                    
         [0081]    [0081]                                                                                                 TABLE 27                           CONTROL OF LATE BLIGHT IN POTATO BY BABA, BION       AND THEIR MIXTURES a                      Percent Disease                       Control mg/L               Active Ingredient   ED 90              Compounds   Ratio (w/w)   250   500   1000   mg/L   CF                    BABA   38   75   93   776   —           BION   13   25   78   1173   —       BABA +       38   78   98   639   1.3       ACIBENZOLAR-       S-METHYL (10 + 1)                    
         [0082]    [0082]                                                                                                                         TABLE 28                           CONTROL OF LATE BLIGHT IN TOBACCO BY BABA       AZOXYSTROBINE MIXTURE       AND THEIR MIXTURES, FUNGAL ISOLATE = R                    Percent Disease Control                   Ratio   mg/L Active Ingredient   ED 90              Compounds   (w/w)   5   10   25   50   100   200   mg/L   CF                    BABA       —   —   —   0   13   100   171           AZOXY-   13   81   81   81   93   —   —   27       STROBINE       BABA +       AZOXY-       STROBINE        5 + 1               25   100   100   100   41   2.2       10 + 1               38   81   100   100   54   2.1       15 + 1               50   81   100   100   53   2.4                    
         [0083]    [0083]                                                                                                 TABLE 29                           CONTROL OF DOWNY MILDEW IN TOBACCO BY BABA,       ACIBENZOLAR-S-METHYL, RIDOMIL-GOLD       AND THEIR MIXTURES: Fungal isolate = R                    Percent Disease                       Control mg/L               Active Ingredient   ED 90              Compounds   Ratio (w/w)   16   62   250   mg/L   CF                    BABA   —   3   27   51   406           BION   —   76   76   99   88       RIDOMILGOLD   —   49   37   58   416       BABA +   75 + 1   48   78   99   90   3.1       ACIBENZOLAR-S-   10 + 1   45   93   100   52   5.9       METHYL   15 + 1   22   84   91   186   1.8           20 + 1   14   74   98   116   3.5       BABA + RIDOMIL GOLD   7.5 + 1    27   63   97   150   2.7           10 + 1   34   44   99   145   2.8           15 + 1   23   52   78   282   1.4           20 + 1   0   20   91   239   1.4       BABA +   7.5 + 1 + 1    37   63   95   174   1.7       ACIBENZOLAR-S-   10 + 1 + 1   45   71   92   190   1.7       METHYL +   15 + 1 + 1   37   84   82   230   1.5       RIDOMIL-GOLD   20 + 1 + 1   57   98   98   84   4.2                    
         [0084]    [0084]                                                                                                 TABLE 30                           CONTROL OF DOWNY MILDEW IN TOBACCO BY BABA,       ACIBENZOLAR-S-METHYL, CURZATE RIDOMIL-GOLD       AND THEIR MIXTURES: Fungal isolate = R                    Percent Disease                       Control mg/L               Active Ingredient   ED 90              Compounds   Ratio (w/w)   100   200   400   mg/L   CF                    BABA   —   37   62   100   270   —       ACIBENZOLAR-   —   37   50   80   443   —       S-METHYL       CURZATE   —   25   25   62   596   —       RIDOMILGOLD       20   35   42   &gt;1000   —       BABA +   10 + 1   62   100   100   113   2.5       ACIBENZOLAR-   15 + 1   50   100   100   118   2.3       S-METHYL       BABA + CURZATE   10 + 1   62   100   100   113   2.5            5 + 1   37   62   100   270   1.1                    
         [0085]    [0085]                                                                                                 TABLE 31                           CONTROL OF DOWNY MILDEW IN TOBACCO BY BABA,       ACIBENZOLAR-S-METHYL, RIDOMIL-GOLD       AND THEIR MIXTURES: Fungal isolate = S                    Percent Disease                       Control mg/L               Active Ingredient   ED 90              Compounds   Ratio (w/w)   0.5   5   50   mg/L   CF                    BABA   —   0   27   59   78   —       ACIBENZOLAR-   —   54   76   85   52   —       S-METHYL       RIDOMILGOLD       100   100   100   0.2   —       BABA +   7.5 + 1    85   85   99   15   4.9       ACIBENZOLAR-S-   10 + 1   86   94   100   4   18.7       METHYL   15 + 1   75   84   100   5   15.1       BABA +   7.5 + 1    94   100   100   0.5   3.3       RIDOMIL-GOLD   10 + 1   99   100   100   0.4   5.4           15 + 1   88   90   100   4.3   2.1       BABA +   7.5 + 1 + 1    99   100   100   0.4   4.4       ACIBENZOLAR-S-   10 + 1 + 1   100   100   100   0.2   12.2       METHYL +   15 + 1 + 1   73   100   100   0.6   5.3       RIDOMIL-GOLD                    
         [0086]    [0086]                                                                           TABLE 32                           CONTROL OF DOWNY MILDEW IN GRAPES BY BABA       ACIBENZOLAR-S-METHYL AND THEIR MIXTURES IN LEAF DISCS                Percent Disease Control                   mg/L Active Ingredient   ED 90              Compounds   Ratio (w/w)   0.31   1.25   5   20   50   100   mg/L   CF               BABA       —   —    15    93   95   99   38     —       ACIBENZOLA   0   27   75   100   —   —    6   —       R-S-METHYL       BABA +   10 + 1    0   37    68   100   —   —    6.6    3.9       ACIBENZOLA       R-S-METHYL           15 + 1   60   82   100   100   —   —    1.4   19.8                    
         [0087]    [0087]                                                                           TABLE 33                           CONTROL OF DOWNY MILDEW IN GRAPES BY BABA, ALLIETTE       AND THEIR MIXTURES IN LEAF DISCS                Percent Disease Control                   mg/L Active Ingredient   ED 90              Compounds   Ratio (w/w)   1.25   2.5   5   10   20   50   mg/L   CF               BABA       —   38   44   81   86   92   33   —       ALLIETTE   13   36   38   40   48   81   —   24       BABA + ALLIETTE   1 + 1   44   81   87   89   92   —   12   2.3           3 + 1   44   69   88   92   95   —   10   3.0           5 + 1   25   31   43   47   83   —   22   1.4           7 + 1   24   31   34   56   62   —   30   1.0           9 + 1   22   34   39   55   61   —   31   1.0                    
         [0088]    [0088]                                                                           TABLE 34                           CONTROL OF DOWNY MILDEW IN GRAPES BY BABA, CURZATE       AND THEIR MIXTURES, IN LEAF DISCS                Percent Disease Control                   mg/L Active Ingredient   ED 90              Compounds   Ratio (w/w)   1.25   2.5   5   10   20   50   mg/L   CF               BABA   —   —   25   36   78   83   91   36   —       CURZATE       11   39   58   66   55   —   27   —       BABA + CURZATE   1 + 1   51   61   68   81   89   —   16   1.9           3 + 1   62   70   77   86   93   —   13   2.6           5 + 1   69   74   81   89   95   —   11   3.1           7 + 1   49   68   74   78   89   —   16   2.2           9 + 1   21   39   58   73   82   —   17   2.1