Patent Publication Number: US-4585763-A

Title: Fungicides containing Phosetyl-Al and an oxazolidenylacetamide

Description:
This is a division of application Ser. No. 459,761, filed Jan. 21, 1983, now U.S. Pat. No. 4,507,310. 
    
    
     The present invention relates to fungicides, more particularly to oomycetes controlling fungicides. 
     Although a wide variety of fungicides including various oomycetes controlling fungicides are known, the need exists for still more effective fungicides. 
     It has been found that the use of 
     (a) an oomycetes controlling fungicide having the structure element of formula I ##STR2## in which X is CH or N, in association with 
     (b) a compound of formula II ##STR3## hereinafter referred to by the common name CYMOXANIL or of formula III ##STR4## hereinafter referred to by the common name Phosetyl-Al is particularly effective in combatting or preventing fungal diseases. 
     Aryl, as used in formula I, is intended to embrace any aromatic radical, unsubstituted or substituted, e.g. phenyl unsubstituted or substituted. 
     Acyl, as used in formula I, is intended to embrace any organic radical tied by a CO-group to the N-atom. 
     An example of a group of oomycetes controlling fungicides having the structure element of formula I (hereinafter designated compounds of formula I) suitable for use in the invention are those of formula Ia ##STR5## wherein R 1 , R 2  and R 3 , independently, are H, C 1-4  alkyl, C 1-4  alkoxy, C 1-4  alkylthio or halogen selected from F, Cl and Br, 
     A is selected from a group --CH(R 4 )--R 5  or a group --N(R 6 )--COOR 7 , 
      in which 
     R 4  is H or C 1-4  alkyl, 
     R 5  is COZR 8 , CO-N(R 9 )OR 10 , CN, CHO, ##STR6##  C.tbd.C-R 14 , allene; or is 2,2-dihalo-1-cyclopropyl unsubstituted or substituted by C 1-4  alkyl; or is phenyl unsubstituted or substituted, 
     R 6  is C 1-3  alkyl, 
     R 7  is C 1-6  alkyl, C 3-6  alkenyl or C 3-6  alkinyl, whereby R 6  and R 7  may be linked together to form CH 2  --CH 2  ; 
     and wherein 
     Z and Z&#39; are O or S 
     R 8  is C 1-6  alkyl, C 3-6  alkenyl, or C 3-6  alkinyl, and whereby ZR 8  may be linked with R 4  to form the bridge ZCH(R 15 )--CH 2  in which Z is as defined above and R 15  is H or CH 3  ; 
     R 9 , R 9  &#39; and R 9  &#34; are H or C 1-4  alkyl, 
     R 10 , R 10  &#39; and R 10  &#34; are C 1-4  alkyl, whereby R 9  may be linked with R 10 , resp. R 9  &#39; with R 10  &#39;, resp. R 9  &#34; with R 10  &#34; and signify alkylene, to form a 5- or 6-membered heterocyclic ring, 
     R 11 , R 12 , R 13 , independently, are H, C 1-4  alkyl, or halogen selected from F, Cl or Br, 
     R 14  is H, C 1-4  alkyl or halogen selected from Cl, Br or I, and 
     Y is H; 
     a hydrocarbon selected from C 1-6  alkyl, C 2-6  alkenyl and C 2-6  alkinyl unsubstituted or substituted by halogen, selected from F, Cl or Br, or by CN; 
     C 2-6  epoxyalkylene; C 3-6  cycloalkyl; a 5-membered heterocyclic ring comprising 1 to 3 heteroatoms selected from O, S and N, which is unsubstituted or substituted by C 1-4  alkyl or halogen selected from F, Cl or Br; 
     (A 1 ) n  --Az; (A 1 ) n  --Y 1  --NR 9a  R 10a  ; 
     (A 1 ) n  Z 1  H and esters or ethers thereof; 
     benzyl unsubstituted or substituted, 
      in which 
     A 1  is CH 2  or CH(CH 3 ) 
     n is 0 or 1, 
     AZ is a 1-azolyl comprising 1 to 3 nitrogen atoms, 
     Y 1  is a covalent bond or NH, 
     R 9a  is H or C 1-4  alkyl, 
     R 10a  is C 1-4  alkyl, 
     Z 1  is O or S. 
     Where any of R 1 , R 2 , R 3  and R 4  is or comprises C 1-4  alkyl, this is preferably CH 3 . 
     Where R 5  is 2,2-dihalo-1-cyclopropyl both halogens comprised therein signify F, Cl or Br, particularly Cl or Br, especially Cl; both halogens are preferably identical. Any C 1-4  alkyl substituent of 2,2-dihalo-1-cyclopropyl signifies preferably CH 3 . 
     Where R 5  is substituted phenyl, it is conveniently mono- or disubstituted. Suitable substituents of phenyl are e.g. C 1-4  alkyl (CH 3 ), C 1-4  alkoxy (OCH 3 ) and halogen (F, Cl, Br). 
     R 6  is preferably CH 3 . 
     Where any of R 7  and R 8  is C 1-6  alkyl, it is conveniently C 1-3  alkyl, preferably CH 3 . 
     Where any of R 9 , R 9  &#39;, R 9  &#34;, R 10 , R 10  &#39; and R 10  &#34; is C 1-4  alkyl, it is e.g. CH 3 . 
     Where R 9  and R 10 , resp. R 9  &#39; and R 10  &#39; resp. R 9  &#34; and R 10  &#34; are linked together and represent alkylene, such alkylene is conveniently unbranched. 
     Where any of R 11 , R 12  and R 13  is C 1-4  alkyl, this is preferably CH 3 . 
     Where any of R 11 , R 12  and R 13  is halogen, this is preferably Cl or Br, particularly Cl. 
     Where R 14  is C 1-4  alkyl, this may be straight or branched and signifies for example CH 3 . 
     Where Y is hydrocarbon substituted by halogen, such halogen is conveniently Cl or Br. 
     Where Y is substituted hydrocarbon, the hydrocarbon signifies preferably C 1-6  alkyl, particularly C 1-3  alkyl. 
     Where Y is C 1-6  alkyl, unsubstituted, it is preferably C 3-5  alkyl, particularly unbranched C 3-5  alkyl or 2-methyl-1-butyl. 
     Where Y is C 3-6  alkenyl, it is preferably CH═CH--CH 3 . 
     Where Y is C 3-6  cycloalkyl, it is preferably cyclopropyl or cyclobutyl. 
     Where Y is a 5-membered heterocycle, this may be aromatic oder hydrogenated; examples of suitable heterocyclic radicals are furyl (e.g. 2-furyl), tetrahydrofuryl, thienyl, isoxazyl and thiadiazolyl. Suitable substituents of such heterocyclic groups are particularly Cl, Br, CH 3 . Any substituted heterocycle is particularly mono-substituted. 
     Suitable significances of Az are e.g. pyrazol-1-yl, imidazol-1-yl and 1H-1,2,4-triazol-1-yl. 
     Where R 9a  is C 1-4  alkyl, this is especially CH 3  or C 2  H 5 . 
     R 10a  signifies preferably CH 3 . 
     Suitable examples of compounds of formula Ia, wherein Y is esterified (A) n  Z 1  H are esters with an alkane carboxylic acids (such as CH 3  COOH), an alkane sulfonic acid (e.g. CH 3  SO 2  OH), a dialkylsulfamic acid (e.g. (CH 3 ) 2  NSO 2  OH), a functional derivative of a carbonic acid etc. 
     Suitable examples of compounds of formula Ia, wherein Y is etherified (A 1 ) n  Z 1  H are e.g. compounds of formula Ia, wherein Y is (A 1 ) n  Z 1  W, in which A 1 , n and Z 1  are as defined above and W is a group selected from C 1-8  alkyl (particularly CH 3 , C 2  H 5 ), C 3-6  alkenyl (particularly CH 2  --CH═CH 2 ), C 3-6  alkinyl (particularly CH 2  C.tbd.CH), C 1-4  alkoxy-C 1-3  alkyl (particularly CH 2  OCH 3 ), C 1-4  alkylthio-C 1-3  alkyl (particularly CH 2  SCH 3 ) unsubstituted or substituted by halogen (F, Cl, Br) or a pyranyl group. 
     Preferred compounds of formula Ia have one or more of the following features: 
     at least one of R 1 , R 2 , R 3  is different from H, 
     R 3  is hydrogen, 3-Cl or 3-Br, 
     R 1  is in the 2-position, 
     R 1  and R 2  are in the 2,6-position, 
     R 1  and R 2  are selected from H, CH 3 , Cl and OCH 3 , 
     R 1  and R 2  are identical, 
     R 1  and R 2  are CH 3  in the 2,6-position and R 3  is H, 3-Cl or 3-Br, 
     X is CH(R 4 )COZR 8 , N(CH 3 )--COOC 1-6  alkyl, or 2-oxo-3-oxazolidinyl, 
     Z and Z&#39; are 0, 
     R 8  is C 1-6  alkyl, 
     R 8  is linked with R 4  to form CH 2  CH 2 , 
     Y is CH 2  OH, CH 2  OCH 3 , CH 2  OC 2  H 5 , CH 2  O--CH 2  --CH═CH 2 , CH 2  O--CH 2  --C.tbd.CH, CH 2  --OCH 2  OCH 3 , CH 2  OSO 2  N(CH 3 ) 2 , CH 2  Cl, n--C 4  H 9 , cyclopropyl, CH═CH--CH 3 , 2-furyl, benzyl, 2-tetrahydrofuryl. 
     A preferred sub-group of compounds of formula Ia, are compounds of formula Ib ##STR7## wherein X is as defined above, 
     either R a  and R b  are both H or together form a covalent bond Y a  is C 3-5  alkenyl; CH 2  OC 1-5  alkyl; CH 2  --OC 3-6  alkenyl; CH 2  --OC 3-6  alkinyl; furyl; benzyl; CH 2  Cl or C 3-6  cycloalkyl, 
     either R 1  &#39; and R 2  &#39; are both CH 3  in the 2- and 6-positions or R 1  &#39; is 3-Cl and R 2  &#39; is H, 
     and R 3  &#39; is H, CH 3 , Cl or Br. 
     Where Y a  is CH 2  OC 1-5  alkyl, this is preferably CH 2  OCH 3 . 
     Where Y a  is C 3-6  cycloalkyl, this is preferably cyclopropyl. 
     Where Y a  is furyl, this is preferably 2-furyl. 
     Where Y a  is CH 2  OC 3-6  alkenyl, this is preferably CH 2  Oallyl or --CH 2  O--(2-butenyl). 
     Where Y a  is CH 2  OC 3-6  alkinyl, this is preferably CH 2  O(2-propinyl). 
     Where in the compounds of formula I R 3  &#39; is Cl, Br or CH 3  this is preferably in the 3-position, particularly when R 1  &#39; and R 2  40 are 2-- and 6--CH 3  resp. 
     Examples of valuable oomycetes controlling fungicidal compounds of formula Ib are those wherein X, R a , R b , Y a , R 1  &#39;, R 2  &#39; and R 3  &#39; are 
     (i) CH, H, H, 2--furyl, 2--CH 3 , 6--CH 3  and H resp. (common name furalaxyl) 
     (ii) CH, H, H, CH 2  --OCH 3 , 2--CH 3 , 6--CH 3  and H resp. (common name metalaxyl) 
     (iii) CH, H, H, benzyl, 2--CH 3 , 6--CH 3  and H resp. (common name galben) 
     (iv) CH, covalent bound (R a  +R b ), CH 2  Cl, 2--CH 3 , 6--CH 3  and H (common name milfuram) 
     (v) N, covalent bound (R a  +R b ), CH 2  --OCH 3 , 2--CH 3 , 6--CH 3  and H (hereinafter designated compound I) 
     (vi) N, covalent bound (R a  +R b ), CH 2  --OCH 3 , 2--CH 3 , 6--CH 3 , 3--Cl 
     (vii) N, covalent bound (R a  +R b ), CH 2  --OCH 3 , 2--CH 3 , 6--CH 3 , 3--Br 
     (viii) CH, covalent bound (R a  +R b ), cyclopropyl, 3--Cl, H and H. 
     (ix) CH, covalent bound (R a  +R b ), CH 2  OCH 3 , 2--CH 3 , 6--CH 3  and H. 
     Compounds of formula I are known or may be obtained according to known processes. 
     Cymoxanil and Phosetyl-Al are also known systemic fungicides having a fungicidal effect against Plasmopara spp and Phytophthora spp. 
     It has been found, that the use of Cymoxanil or Phosetyl-Al in combination with a compound of formula I particularly one of formula Ia, more particularly one of formula Ib, e.g. one of the compounds (i) to (ix) indicated above, surprisingly and substantially enhances the effectiveness of the latter against such fungi, and vice versa. The risk of fungi developing resistance against oomycetes controlling having the structure element of formula I is also significantly decreased when using them in association with Cymoxanil or Phosetyl-Al. Moreover, the method of the invention is also surprisingly active against acylalanine resistant field strains of Phytophthora spp and Plasmopara spp as indicated i.a. by a significant decrease of the factor of resistance (the ratio of the funigicidal activity at the 90% level against resistant and sensitive strains). The term &#34;acylalanine resistant field strains&#34; as used herein means oomycetes that developed resistance against acylalanine type fungicides (see e.g. Resistance to acylalanine-type fungicides in Peronosporales, Phytopathology 71(5) 558 (1981). Finally, the method of the invention is effective against a wider spectrum of fungi than that that can be combatted with the active ingredients of this method when used solely. 
     Accordingly, the invention provides an improved method of combatting fungi, particularly fungi of the class Oomycetes such as Phytophthora spp., Plasmopara spp., Peronospora spp., Pseudoperonospora spp., Sclerophthora spp., Bremia spp. and Pythium spp., in crop locus, especially in grapevines, tomato, hops, cacao, tobacco, potato and lettuce cultures, and an eucalyptus locus which comprises applying to the locus, in admixture or separately, a fungicidally effective aggregate amount of a compound of formula I and Cymoxanil or Phosetyl-Al. 
     The term crop as used herein is intended to embrace any desired plant growth. 
     Preferably the compounds of formula I are applied at a rate of 100-400 g/ha, particularly 150-300 g/ha, e.g. 200 g/ha in association with 40-160 g/ha, particularly 60-120 g/ha, e.g. 80 g/ha Cymoxanil or 750-2500 g/ha, particularly 1000-2000 g/ha, e.g. 1500 g/ha Phosetyl-Al. 
     Other pesticides e.g. fungicides, bactericides, insecticides, acaricides, herbicides or plant growth regulating agents may be used in addition to the above associated active ingredients, to enhance the activity of the association of the invention or to widen its spectrum of activity; it is particularly advantageous to use an additional contact fungicide in the method of the invention. 
     Contact fungicides particularly indicated for use together with the association of the invention are one or more fungicides selected from a copper fungicide, e.g. cuprous oxide, copper (II) oxychloride, cupric hydroxide, copper (II) calcium sulphate, copper (II) calcium oxychloride, Bordeaux mixture or Burgundy mixture; captan; dichlofluanid; folpet; mancozeb; maneb; zineb; chlorothalonil; propineb and dithianon or mixture thereof. Such additional contact fungicide(s) may in general be applied at a rate of 200-2000 g/ha. Mancozeb is particularly appropriate for use in the method of this invention. It has an additional synergistic effect on the compound of formula I combinations with Cymoxanil or Phosetyl-Al. 
     The invention also provides fungicidal compositions comprising a compound of formula I and Cymoxanil or Phosetyl-Al. 
     In the composition of the invention the weight ratio compound of formula I: Cymoxanil lies preferably in the range of 10:1 to 1:3, more preferably 5:1 to 1:1, particularly 4:1 to 2:1 e.g. 2.5:1. The synergistic effect is evident from the various experimental data in the tables hereinafter, where synergism is i.a. illustrated for the weight ratio compound of formula I: Cymoxanil in the range 1:0.3 to 1:3. 
     In the compositions of the invention the weight ratio compound of formula I: Phosetyl-Al lies preferably in the range of 1:25 to 1:2, more preferably in the range of 1:15 to 1:3, particularly 1:10 to 1:5 e.g. 1:7. 
     Where the compositions of the invention comprise additionally a contact fungicide, the weight ratio compound of formula I: contact fungicide lies preferably in the range of 1:2 to 1:10, and where Mancozeb, Folpet, Captan or Maneb are used, more preferably 1:4 to 1:9, particularly 1:5 to 1:8 e.g. 1:7. It is particularly advantageous to incorporate Mancozeb in the compositions of the invention. 
     The composition of the invention may be employed in any conventional form, for example in the form of a twin pack, an instant granulate, a flowable or a wettable powder in association with fungicidally acceptable diluents. Such compositions may be produced in conventional manner, e.g. by mixing the active ingredients with a diluent (carrier) and other formulating ingredients such as surfactants. 
     The term of diluents as used herein means any liquid or solid agriculturally acceptable material which may be added to the active constituents to bring it in an easier or improved applicable form, respectively to a usable or desirable strength of activity. It can for example be talc, kaolin, diatomaceous earth, xylene, or water. 
     Particularly formulations to be applied in spraying forms such as water dispersible concentrates or wettable powders may contain surfactants such as wetting and dispersing agents, e.g. the condensation product of formaldehyde with naphthalene sulphonate, an alkylarylsulphonate, a lignin sulphonate, a fatty alkyl sulphate, an ethoxylated alkylphenol and an ethoxylated fatty alcohol. 
     In general, the formulations include from 0.01 to 90% by weight of active agent from 0 to 20% fungicidally acceptable surfactant and 10 to 99.99% solid or liquid diluent(s), the active agent consisting of at least one compound of formula I together with Cymoxanil or Phosetyl-Al, and optionally other active agents, particularly contact fungicides. Concentrate forms of compositions generally contain between about 2 to 80%, preferably between about 5 and 70% by weight of active agent. Application forms of formulation may for example contain from 0.01 to 20% by weight, preferably from 0.01 to 5% by weight of active agent. 
    
    
     The invention is illustrated by the following Examples wherein parts and percentages are by weight and temperatures are in °C. 
     TEST A: Fungicidal effect against Phytophtora infestans strains resistant against acylalanine type fungicides 
     Young potted tomato or potato plants (3-5 leaf stage) are sprayed with an aqueous spray liquid of 
     mixture A, containing 0.05 to 0.0002% compound of formula I and 0.05 to 0.0002% CYMOXANIL, 
     or mixture B, containing 0.05 to 0.0002% compound of formula I and 2 to 0.2% Phosetyl-Al 
     or mixture C, containing 0.05 to 0.0002% compound of formula I and 0.2 to 0.003% of a contact fungicide such as Mancozeb, Folpet, Captan, dichlofluanid, Maneb or copper fungicides. 
     Two hours (or 4, 8, 16, 32 or 64 hours later) the treated plants or leaves thereof are washed vigorously, e.g. by simulated rain washing at a rain rate of 10-50 mm/hour. Two hours after the washing procedure, the treated plants or leaves are inoculated with a spore suspension (10 5  sporangia/ml) of Phytophthora infestans strains that developed resistance against compounds of formula I. The plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperature of 16° and a day length of 16 hours. Disease control is evaluated 4-5 days thereafter, by comparing the treated plants (leaves) with untreated, similarly inoculated plants (leaves). Where, with the mixtures A and B complete control of the fungal infestation is observed, the degree of fungicidal activity provided by mixture C is significantly less pronounced. Similar results are obtained in grape vines against Plasmopara viticola strains which are resistant against acylalanine type fungicides. 
     TEST B: Synergistic activity 
     In this test, the fungicidal activity provided by the compounds of formula I, CYMOXANIL or Phosetyl-Al alone, is compared with the activity provided by a compound of formula I when used in association with CYMOXANIL or Phosetyl-Al. The presence of an eventual synergistic effect between two active ingredients is then established with the aid of the Colby equation ##EQU1## wherein A and B are the fungicidal activites of the active ingredients when used alone and p is the fungicidal activity that theoretically would have been obtained with the mixture if there was no interaction between the active ingredients. If p is lower than the experimentally established fungicidal effect, there is synergism. 
     Young potted potato plants are sprayed with an aqueous spray liquid containing either a compound of formula I, CYMOXANIL or Phosetyl-Al alone or in the association according to the invention. The compounds of formula I and CYMOXANIL are applied in concentrations of 0.0125 to 0.00002%, Phosetyl-Al in concentrations of 0.8 to 0.0125%, until the run-off. 
     Two hours later, the treated plants are inoculated with a spore suspension of Phytophthora infestans and the plants are then transferred to a tent providing 100% relative atmospheric humidity at an ambient temperatue of 16° C. and a day length of 16 hours. Disease control is evaluated 4-5 days later by comparing the treated plants with untreated, similarly inoculated plants. Analogous tests are run using grape plants infested with Plasmopara viticola. 
     A more than additive effect is obtained as illustrated in the following tables, in which Comp. is Compound I, Cym is Cymoxanil, Phos. is Phosetyl-Al, M is Mancozeb, the underlined figures are p(Colby) and the non-underlined figures are the experimentally established fungicidal effect. 
     
                       TABLE I                                                     
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Phytophthora/Tomato                                                       
______________________________________                                    
          Comp.                                                           
         ppm                                                              
Cym.        0        2         8       32                                 
0           0        60        80     100                                 
2          10        80.sub.64                                            
                               90.sub.82                                  
                                      100                                 
8          40       100.sub.76                                            
                              100.sub.88                                  
                                      100                                 
32         60       100.sub.84                                            
                              100.sub.92                                  
                                      100                                 
ppm                                                                       
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                       TABLE II                                                    
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Phytophthora/Tomato                                                       
______________________________________                                    
 Comp.                                                                    
ppm                                                                       
Cym.    0        0.2    0.6      1.8  5.4                                 
0       0         0.sup.                                                  
                        20.sup.  40.sup.                                  
                                       70.sup.                            
0.2     0        10.sub.0                                                 
                        30.sub.20                                         
                                 50.sub.40                                
                                       90.sub.70                          
0.6     0        20.sub.0                                                 
                        30.sub.20                                         
                                 60.sub.40                                
                                       90.sub.70                          
1.8     20       .sup. 20.sub.20                                          
                        40.sub.36                                         
                                 65.sub.52                                
                                      100.sub.76                          
5.4     40       .sup. 40.sub.40                                          
                        60.sub.52                                         
                                 80.sub.64                                
                                      100.sub.82                          
ppm                                                                       
______________________________________                                    
 
    
     
                       TABLE III                                                   
______________________________________                                    
Phytophthora/Tomato                                                       
______________________________________                                    
          Comp.                                                           
         ppm                                                              
Phos.       0        2         8       32                                 
 0          0        60.sup.   80     100                                 
125        20        70.sub.68                                            
                               90.sub.84                                  
                                      100                                 
500        50        90.sub.80                                            
                              100.sub.90                                  
                                      100                                 
2000       70       100.sub.88                                            
                              100.sub.94                                  
                                      100                                 
ppm                                                                       
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                       TABLE IV                                                    
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Phytophthora/Potato                                                       
______________________________________                                    
          Comp.                                                           
         ppm                                                              
Phos.       0        2         8       32                                 
 0          0        50        80     100                                 
125        10        60.sub.54                                            
                               80.sub.82                                  
                                      100                                 
500        30        80.sub.65                                            
                              100.sub.86                                  
                                      100                                 
2000       80       100.sub.90                                            
                              100.sub.96                                  
                                      100                                 
ppm                                                                       
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                       TABLE V                                                     
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Plasmopara/grape vine                                                     
______________________________________                                    
 Comp.                                                                    
ppm                                                                       
Cym.    0        0.2    0.6      1.8  5.4                                 
0        0        0.sup.                                                  
                        30        50.sup.                                 
                                       60.sup.                            
0.2      0       30.sub.0.sup.                                            
                        40.sub.30                                         
                                  55.sub.50                               
                                       70.sub.60                          
0.6     20       40.sub.20                                                
                        50.sub.44                                         
                                  60.sub.60                               
                                       80.sub.68                          
1.8     50       50.sub.50                                                
                        80.sub.65                                         
                                  90.sub.75                               
                                      100.sub.80                          
5.4     60       60.sub.60                                                
                        90.sub.72                                         
                                 100.sub.80                               
                                      100.sub.84                          
ppm                                                                       
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                       TABLE VI                                                    
______________________________________                                    
Plasmopara/grape vine                                                     
______________________________________                                    
 Comp.                                                                    
ppm                                                                       
Phos.   0         0.2    0.6     1.8  5.4                                 
 0       0         0.sup.                                                 
                          0.sup. 40.sub.                                  
                                      50.sub.                             
10      10        10.sub.10                                               
                         30.sub.28                                        
                                 50.sub.46                                
                                      60.sub.55                           
30      20        20.sub.20                                               
                         40.sub.36                                        
                                 60.sub.52                                
                                      70.sub.60                           
90      40        40.sub.40                                               
                         60.sub.52                                        
                                 70.sub.64                                
                                      80.sub.70                           
270     50        50.sub.50                                               
                         70.sub.60                                        
                                 80.sub.70                                
                                      90.sub.75                           
ppm                                                                       
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                       TABLE VII                                                   
______________________________________                                    
Phytophthora/Tomato                                                       
______________________________________                                    
Comp.                                                                     
0             0.125   0.375   1.13   3.38 ppm                             
Cym.    0         0.9     2.7   8.1    24.3 ppm                           
0       0         10      20     40     60                                
0.1     0         2.5.sub.10                                              
                          30.sub.20                                       
                                 50.sub.40                                
                                        80.sub.60                         
0.3     0         35.sub.10                                               
                          40.sub.20                                       
                                 60.sub.40                                
                                        90.sub.60                         
0.9     20        45.sub.28                                               
                          50.sub.36                                       
                                 70.sub.52                                
                                       100.sub.68                         
2.7     35        50.sub.41                                               
                          55.sub.48                                       
                                100.sub.61                                
                                       100.sub.74                         
ppm                                                                       
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                       TABLE VIII                                                  
______________________________________                                    
Plasmopara/grape vine                                                     
______________________________________                                    
Comp.                                                                     
0             0.125   0.375   1.13   3.38 ppm                             
Cym.     0        0.9     2.7   8.1    24.3 ppm                           
0        0        30       50    60     70                                
0.1      0        30.sub.30                                               
                           60.sub.50                                      
                                 70.sub.60                                
                                       100.sub.70                         
0.3     20        50.sub.44                                               
                           70.sub.60                                      
                                 80.sub.68                                
                                       100.sub.76                         
0.9     40        60.sub.58                                               
                           80.sub.70                                      
                                100.sub.76                                
                                       100.sub.82                         
2.7     60        80.sub.72                                               
                          100.sub.80                                      
                                100.sub.84                                
                                       100.sub.88                         
ppm                                                                       
______________________________________                                    
 
    
     Based on the results in Table I-VIII--which indicate a synergism--the factor of synergism can be calculated with the aid of the Wadley equations: ##EQU2## wherein a, b, etc. are the weight ratios at which the active ingredients are used in the mixture; EC 90, EC 90 (exp.) and EC&#39;(theor.) the concentrations allowing a 90% fungicidal control resp. of the active ingredient when used alone as determined by experiment, of the tested composition as determined by experiment and of the tested composition as calculated. SF is the factor of synergism (in case of synergism it is≧1). 
     The factor of synergism (SF) found with mixtures of Compound I/Cymoxanil and of Compound I/Cymoxanil/Mancozeb resp. tested on tomato (Phytophthora infestans) and grape vine (Plasmopara Viticola) under greenhouse conditions, calculated according to Wadley, are given: 
     
                                           TABLE IX                                
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          Tomato (Phyt.)                                                  
                        Grape vine (Plasm.)                               
          EC 90.sup.(2) EC 90.sup.(2)                                     
Comp./Cym*                                                                
          theor.                                                          
              exp.   SF.sup.(2)                                           
                        theor.  exp.                                      
                                   SF.sup.(2)                             
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1:0       --  17        --      19                                        
1:0.3     21   7     3.0                                                  
                        23      11 2.1                                    
1:1       31  10     3.1                                                  
                        26       5 5.2                                    
1:3       49  16     3.1                                                  
                        30       4 7.5                                    
0:1       --  125               36                                        
Comp./Cym/M                                                               
1:0.3:7   69  29     2.4                                                  
                        49      16 3.1                                    
1:2.4:7   76  32     2.4                                                  
                        46       6 7.7                                    
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                  Formulation Examples (Wettable powders)                 
                  A  B  C  D  E  F  G  H                                  
                  % by weight                                             
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Compound of formula I                                                     
                  8  10 7  10 40 7  10 25                                 
(e.g. Compound I)                                                         
CYMOXANIL         3.2                                                     
                     5  -- 10 24 -- 5  10                                 
Phosetyl-Al       -- -- 50 -- -- 50 -- --                                 
Contact fungicide e.g.        -- --    --                                 
Mancozeb          56 25 -- --       25                                    
Copper (II) oxychloride                                                   
                  -- 10 -- --       17.5                                  
Copper (II) calcium sulphate                                              
                  -- 5  -- --       18.5                                  
Folpet            -- -- 23 30       --                                    
Surfactant:                                                               
       Wetting agent (e.g.                                                
                  1  1  1  1  1  1  1  1                                  
       Na alkyl naphthalene                                               
       sulphonate)                                                        
       Dispersing agent (e.g.                                             
                  5  5  5  5  5  5  5  5                                  
       Na lignin sulphonate)                                              
Diluent:                                                                  
       Silica     5  5  5  5  5  5  5  5                                  
       Kaolin     21.8                                                    
                     34 9  39 25 28 13 54                                 
Prussian blue     -- -- -- -- -- 4  -- --                                 
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 *weight ratio                                                            
 .sup.(2) see Wadley                                                      
 
    
     The formulations are obtained by mixing the components, subsequently milling the mixture and a second mixing in conventional manner. 
     In general, the active ingredients are used in technical form. An example of a formulation comprising technical active ingredients is as follows: 
     EXAMPLE J 
     Compound I technical (95%): 10.5% 
     Cymoxanil--technical (95%): 5.3% 
     Mancozeb--technical (80%): 31.3% 
     Copperoxy (II) chloride (57% Cu): 17.5% 
     Copper (II) calcium sulphate (27% Cu): 18.7% 
     Surfactant and Silica: 11.0% 
     Kaolin: 5.7% 
     EXAMPLE K 
     Flowable 440 g/l 
     
         ______________________________________                                    
4.2% w/w    Compound I techn. 95%                                         
1.7% w/w    Cymoxanil techn. 95%                                          
35.0% w/w   Mancozeb techn. 80%                                           
4.0% w/w    Surfactant                                                    
6.0% w/w    1,2-Propylene glycol (Anti-freezing)                          
0.3% w/w    Sticker                                                       
0.5% w/w    Stabilisator (e.g. citric acid)                               
48.3% w/w   Water                                                         
100.0% w/w                                                                
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     The formulation is produced by mixing the components, wet grinding and mixing. 
     EXAMPLE L 
     Granules 67% w/w WG 
     8.4% w/w Compound I techn. 95% 
     3.4% w/w Cymoxanil techn. 95% 
     70.0% w/w Mancozeb techn. 80% 
     10.0% w/w Dispersing/binding agent (e.g. Na-lignin-sulfonate) 
     7.7% w/w Diluent (e.g. kaolin) 
     0.5% w/w Stabilisator (e.g. citric acid). 
     The formulation is produced by mixing and grinding the components followed by pan-granulation or fluid bed-granulation. The granules disperse well in water, forming a sprayable suspension.