Patent Publication Number: US-6335355-B1

Title: Crop protection products

Description:
The instant application is the national phase application filed under 35 USC §371 of PCT/EP96/02672 filed on Jun. 20, 1996. 
     The present invention relates to novel plant-protecting active ingredient mixtures having synergistically enhanced action, comprising at least two active ingredient components together with a suitable carrier, wherein component I is a compound having plant-immunising action of formula I                    
     wherein 
     Z is CN, COOH or a salt thereof, CO—OC 1 -C 4 alkyl or CO—SC 1 -C 4 alkyl; 
     and wherein component II is a compound having microbicidal action selected from the group 
     A) α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-trazole-1-ethanol, (“tebuconazol”), (reference: EP-A40 345); 
     B) 1-[[3-(2-chlorophenyl)-2-(4-fluorophenyl)oxiran-2-yl]methyl]-1H-1,2,4-triazole, (“epoxyconazol”), (reference: EP-A-196 038); 
     C) α-(4-chlorophenyl)-α-(1 -cyclopropylethyl)-1H-1,2,4-triazole-1-ethanol, (“cyproconazol”), (reference: U.S. Pat. No. 4,664,696); 
     D) 5-(4-chlorobenzyl)-2,2-dimethyl-1-(1H-1,2,4-triazol-1-ylmethyl)-cyclopentanol, (“metconazol”), (reference: EP-A-267 778); 
     E) 2-(2,4-dichlorophenyl)-3-(1H-1,2,4-triazol-1-yl)propyl-1,1,2,2-tetrafluoroethyl ether, (“tetraconazol”), (reference: EP-A-234 242); 
     F) methyl-(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin4-yloxy]phenyl}-3-methoxyacrylate, (“ICI A 5504”, “azoxystrobin”), (reference: EP-A-382 375); 
     G) methyl-(E)-2-methoximino-2-[α-(o-tolyloxy)-o-tolyl]acetate, (“BAS 490 F”, “cresoxime methyl”), (reference: EP-A-400 417); 
     H) 2-(2-phenoxyphenyl)-(E)-2-methoximino-N-methylacetamide, (reference: EP-A-398 692); 
     J) [2-(2,5-dimethylphenoxymethyl)-phenyl]-(E)-2-methoximino-N-methylacetamide, (reference: EP-A-398 692); 
     K) (1R,3S/1S,3R)-2,2-dichloro-N-[(R)-1-(4-chlorophenyl)ethyl]-1-ethyl-3-methylcyclo-propanecarboxamide, (“KTU 3616”), (reference: EP-A-341 475); and 
     L) manganese ethylenebis (dithiocarbamate) polymer-zinc complex, (“mancozeb”); (reference: U.S. Pat. No. 2,974,156). 
     The invention relates also to salts and metal complexes of compounds I and II. 
     Of the compounds of formula I, preference is given to those wherein Z is COOH (compound IA) or a salt thereof, CN (compound IB), COOCH 3  (compound IC) or COSCH 3  (compound ID). 
     Preferred salts are alkali metal and alkaline earth metal salts, especially lithium, sodium, potassium, magnesium or calcium salts, and also organic salts, especially salts of salt-forming amines, for example trimethylamine, triethylamine, N,N-dimethylaniline, pyridine, triethanolamine, morpholine. 
     Very special preference is given to the compound of formula I wherein Z is COSCH 3  (compound ID). 
     It is known that compounds of formula I activate the plant&#39;s own latent defence system against pathogenic microbial influences and accordingly are able to protect the plant against pathogens (EP-A-313 512). 
     At low rates of application those compounds have no direct action on the noxious organisms, but they immunise the healthy plant against diseases. 
     The disadvantage in using compounds of formula I to control plant diseases is that the action is often inadequate at low rates of application. 
     Surprisingly, it has now been found that compounds of formula I in admixture with one of the conventional microbicides IIA to IIL have synergistically enhanced action. Using such mixtures it is possible to control plant diseases on the one hand by strengthening the plant by activating its own defence system and on the other hand by additionally controlling the pathogens directly. Compared with the customary methods of controlling plant diseases, unexpectedly small amounts of active ingredients are required. 
     A particular advantage of the mixtures according to the invention is further that, because the modes of action of components I and II are completely different, the threat of resistance being developed in the control of plant diseases is effectively prevented. 
     The synergistically enhanced action of mixtures of components I and II manifests itself, for example, in lower rates of application, a longer duration of action and altogether higher crop yields. Such enhancements were not to be expected from the sum of the actions of the individual components. 
     The present invention relates also to a method of protecting plants against plant diseases, especially against fungus infestation, by treating the plants, parts of the plants or their surroundings with a component I and a component II in any desired sequence or simultaneously. 
     Advantageous mixing ratios of the two active ingredients are I:II=from 1:30 to 10:1, preferably I:II=from 1:20 to 2:1 and from 1:10 to 1:1. 
     Especially advantageous mixing ratios are further for I:IIK, from 1:1 to 100:1, preferably from 1:1 to 10:1; and for I:IIL, from 1:10 to 1:100, preferably from 1:10 to 1:50. 
     The active ingredient mixtures I+II according to the invention have very advantageous properties for protecting plants against disease infestation. 
     The active ingredient mixtures of the invention can be used to inhibit or destroy the microorganisms which occur on plants or on parts of plants (the fruit, blossom, leaves, stems, tubers or roots) of different crops of useful plants, while at the same time parts of plants that grow later are also protected against such microorganisms. They can also be used as dressings in the treatment of plant propagation material, especially seed (fruit, tubers, grains) and plant cuttings (e.g. rice), to provide protection against fungus infections as well as against phytopathogenic fungi which occur in the soil The active ingredient mixtures according to the invention are distinguished by the fact that they are especially well tolerated by plants and are environmentally friendly. 
     The active ingredient mixtures are effective against phytopathogenic fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia, Rhizoctonia, Puccinia); Fungi imperfecti (e.g. Botrytis, Helminthosporium, Rhynchosporum, Fusarium, Septoria, Cercospora, Altemaria, Pyricularia and, especially, Pseudocercosporella herpotrchoides); Oomycetes (e.g. Phytophthora, Peronospora, Bremia, Pythium, Plasmopara). 
     Target crops for the areas of indication disclosed herein comprise within the scope of the present invention e.g. the following species of plants: cereals (wheat, barley, rye, oats, rice, sorghum and related crops); beet (sugar beet and fodder beet); pomes, stone fruit and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and black-berries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (marrows, cucumber, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocados, cinnamon, camphor); or plants such as maize, tobacco, nuts, coffee, sugar cane, tea, vines, hops, bananas and natural rubber plants, as well as omamentals (flowers, shrubs, broad-leaved trees and evergreens, such as conifers). This list does not represent any limitation. 
     The active ingredient mixtures according to the invention are especially advantageous for use in cereals, more especially in wheat; also in potatoes, vines, lawn areas, hops, tobacco, bananas and vegetables. The mixtures I+IIK are especially suitable for the treatment of rice, and the mixtures I+IIL are especially suitable for fruits, fruit and vegetables. 
     The mixtures of active ingredients of formulae I and II are generally used in the form of compositions. The active ingredients of formulae I and II can be applied to the area or plant to be treated either simultaneously or in succession on the same day, if desired together with further carriers, surfactants or other application-promoting adjuvants customarily employed in formulation technology. 
     Suitable carriers and adjuvants can be solid or liquid and are the substances ordinarily employed in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilisers. 
     A preferred method of applying an active ingredient mixture comprising at least one of each of the active ingredients I and II is application to the parts of the plants that are above the soil, especially to the leaves (foliar application). The frequency and rate of application depend upon the biological and climatic living conditions of the pathogen. The active ingredients can, however, also penetrate the plant through the roots via the soil or via the water (systemic action) if the locus of the plant is impregnated with a liquid formulation (e.g. in rice culture) or if the substances are introduced in solid form into the soil, e.g. in the form of granules (soil application). In order to treat seed, the compounds of formulae I and II can also be applied to the seeds (coating), either by impregnating the tubers or grains with a liquid formulation of each of the active ingredients in succession, or by coating them with an already combined wet or dry formulation. In addition, in special cases, other methods of application to plants are possible, for example treatment directed at the buds or the fruit trusses. 
     The compounds of the combination are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology, and are therefore formulated in known manner e.g. into emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, or by encapsulation in e.g. polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. Advantageous rates of application of the active ingredient mixture are normally from 50 g to 2 kg a.i./ha, preferably from 100 g to 1000 g a.i./ha, especially from 150 g to 700 g a.i./ha. In the case of the treatment of seed, the rates of application are from 0.5 g to 1000 g, preferably from 5 g to 100 g, a.i. per 100 kg of seed. 
     The formulations are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, e.g. solvents, solid carriers and, where appropriate, surface-active compounds (surfactants). 
     Suitable solvents are: aromatic hydrocarbons, preferably the fractions containing 8 to 12 carbon atoms, e.g. xylene mixtures or substituted naphthalenes, phthalates, such as dibutyl phthalate or dioctyl phthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols and their ethers and esters, such as ethanol, ethylene glycol, ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethyl sulfoxide or dimethylformamide, as well as vegetable oils or epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water. 
     The solid carriers used, e.g. for dusts and dispersible powders, are normally natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers. Suitable granulated adsorptive carriers are porous types, for example pumice, broken brick, sepiolite or bentonite, and suitable nonsorbent carriers are, for example, calcite or sand. In addition, a great number of pregranulated materials of inorganic or organic nature can be used, e.g. especially dolomite or pulvensed plant residues. 
     Depending upon the nature of the active ingredients of formulae I and II to be formulated, suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants having good emulsifying, dispersing and wetting properties. The term “surfactants” will also be understood as comprising mixtures of surfactants. 
     Particularly advantageous application-promoting adjuvants are also natural or synthetic phospholipids of the cephalin and lecithin series, e.g. phosphatidylethanolamine, phosphatidylserine, phosphatidylglycerol and lysolecithin. 
     The agrochemical compositions generally comprise 0.1 to 99%, preferably 0.1 to 95%, of active ingredients of formulae I and II, 99.9 to 1%, preferably 99.9 to 5%, of a solid or liquid adjuvant and 0 to 25%, preferably 0.1 to 25%, of a surfactant. 
     Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. 
    
    
     The Examples which follow serve to illustrate the invention, “active ingredient” denoting a mixture of compound I and compound II in a specific mixing ratio. 
     FORMULATION EXAMPLES 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Wettable powders 
                 a) 
                 b) 
                 c) 
               
               
                   
               
             
            
               
                 active ingredient [I:II = 1:3(a), 1:2(b), 1:1(c)] 
                 25%  
                 50%  
                 75%  
               
               
                 sodium lignosulfonate 
                 5% 
                 5% 
                 — 
               
               
                 sodium laurylsulfate 
                 3% 
                 — 
                 5% 
               
               
                 sodium diisobutylnaphthalenesulfonate 
                 — 
                 6% 
                 10%  
               
               
                 octylphenol polyethylene glycol ether 
                 — 
                 2% 
                 — 
               
               
                 (7-8 mol of ethylene oxide) 
               
               
                 highly dispersed silicic acid 
                 5% 
                 10%  
                 10%  
               
               
                 kaolin 
                 62%  
                 27%  
                 — 
               
               
                   
               
            
           
         
       
     
     The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration. 
     
       
         
           
               
               
             
               
                   
                   
               
               
                   
                 Emulsifiable concentrate 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 active ingredient (I:II = 1:6) 
                 10%  
               
               
                   
                 octylphenol polyethylene glycol ether 
                 3% 
               
               
                   
                 (4-5 mol of ethylene oxide) 
               
               
                   
                 calcium dodecylbenzenesulfonate 
                 3% 
               
               
                   
                 castor oil polyglycol ether (35 mol of ethylene oxide) 
                 4% 
               
               
                   
                 cyclohexanone 
                 30%  
               
               
                   
                 xylene mixture 
                 50%  
               
               
                   
                   
               
            
           
         
       
     
     Emulsions of any required dilution, which can be used in plant protection, can be obtained from this concentrate by dilution with water. 
     
       
         
           
               
               
               
               
             
               
                   
               
               
                 Dusts 
                 a) 
                 b) 
                 c) 
               
               
                   
               
             
            
               
                 active ingredient [I:II = 1:6(a), 1:2(b), 1:10(c)] 
                  5% 
                  6% 
                  4% 
               
               
                 talcum 
                 95% 
                 — 
                 — 
               
               
                 kaolin 
                 — 
                 94% 
                 — 
               
               
                 mineral filler 
                 — 
                 — 
                 96% 
               
               
                   
               
            
           
         
       
     
     Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mixture in a suitable mill. Such powders can also be used for dry dressings for seed. 
     
       
         
           
               
               
             
               
                   
                   
               
               
                   
                 Extruder granules 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 active ingredient (I:II = 2:1) 
                 15% 
               
               
                   
                 sodium lignosulfonate 
                  2% 
               
               
                   
                 carboxymethylcellulose 
                  1% 
               
               
                   
                 kaolin 
                 82% 
               
               
                   
                   
               
            
           
         
       
     
     The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air. 
     
       
         
           
               
               
             
               
                   
                   
               
               
                   
                 Coated granules 
               
               
                   
                   
               
             
            
               
                   
               
            
           
           
               
               
               
            
               
                   
                 active ingredient (I:II = 1:10) 
                 8% 
               
               
                   
                 polyethylene glycol (mol. wt. 200) 
                 3% 
               
               
                   
                 kaolin 
                 89%  
               
               
                   
                   
               
            
           
         
       
     
     The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner. 
     
       
         
           
               
             
               
                   
               
               
                 Suspension concentrate 
               
               
                   
               
             
            
               
                   
               
            
           
           
               
               
            
               
                 active ingredient (I:II = 1:8) 
                 40% 
               
               
                 propylene glycol 
                 10% 
               
               
                 nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 
                  6% 
               
               
                 sodium lignosulfonate 
                 10% 
               
               
                 carboxymethylcellulose 
                  1% 
               
               
                 silicone oil (in the form of a 75% emulsion in water) 
                  1% 
               
               
                 water 
                 32% 
               
               
                   
               
            
           
         
       
     
     The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion. 
     BIOLOGICAL EXAMPLES 
     A synergistic effect exists whenever the action of an active ingredient combination is greater than the sum of the actions of the individual components. 
     The action to be expected E for a given active ingredient combination obeys the so-called COLBY formula and can be calculated as follows (COLBY, S. R. “Calculating synergistic and antagonistic responses of herbicide combinations”. Weeds, Vol.15, pages 20-22; 1967): 
     ppm=milligrams of active ingredient (=a.i.) per liter of spray mixture 
     X=% action by active ingredient I using p ppm of active ingredient 
     Y=% action by active ingredient II using q ppm of active ingredient. 
     According to Colby, the expected (additive) action of active ingredients I+II using p+q ppm of active ingredient is        E   =     X   +   Y   -       X   ·   Y     100                       
     If the action actually observed (O) is greater than the expected action (E), then the action of the combination is superadditive, i.e. there is a synergistic effect. O/E=synergy factor (SF). In the Examples which follow, the infestation of the untreated plants is assumed to be 100%, which corresponds to an action of 0%. 
     Description of the Biological Tests 
     A1: Action gainst  Erysiphe graminis  on Barley 
     a) Residual-protective Action Barley plants about 8 cm in height are sprayed to drip point with an aqueous spray mixture (max. 0.02% active ingredient) and are dusted 3 to 4 days later with conidia of the fungus. The infected plants are stood in a greenhouse at 22°. Fungus infestation is generally evaluated 10 days after infection. 
     b) Systemic Action Barley plants about 8 cm in height are watered with an aqueous spray mixture (max. 0.002% active ingredient, based on the volume of the soil). Care is taken that the spray mixture does not come into contact with parts of the plants above the soil. The plants are dusted with conidia of the fungus 3 to 4 days later. The infected plants are stood in a greenhouse at 22°. Fungus infestation is generally evaluated 10 days after infection. 
     A2: Action Against  Colletotrichum lagenarium  on  Cucumis sativus  L. 
     a) After a cultivation period of 10 to 14 days, cucumber plants are sprayed with a spray mixture prepared from a wettable powder formulation of the test compound. After 3 to 4 days, the plants are infected with a spore suspension (1.0×10 5  spores/ml) of the fungus and incubated for 30 hours at high humidity and a temperature of 23° C. Incubation is then continued at normal humidity and 22° C. to 23° C. Evaluation of protective action is made 7 to 10 days after infection and is based on fungus infestation. 
     b) After a cultivation period of 10 to 14 days, cucumber plants are treated by soil application with a spray mixture prepared from a wettable powder formulation of the test compound. After 3 to 4 days, the plants are infected with a spore suspension (1.5×10 5  spores/ml) of the fungus and incubated for 30 hours at high humidity and a temperature of 23° C. Incubation is then continued at normal humidity and 22° C. Evaluation of protective action is made 7 to 10 days after infection and is based on fungus infestation. 
     A3: Action Against  Cercospora nicotianae  on Tobacco Plants 
     Tobacco plants (6 weeks old) are sprayed with a formulated solution of the test compound (concentration: max. 0.02% active ingredient). Four days after treatment, the plants are inoculated with a sporangia suspension of  Cercospora nicotianae  (150 000 spores/ml) and kept at high humidity for 4 to 5 days and then incubated further under a normal day/night sequence. Evaluation of the symptoms in the tests is based on the leaf surface infested with fungus. 
     A4: Action Against  Pyricularia oryzae  on Rice Plants 
     Rice plants about 2 weeks old are placed together with the soil around the roots in a container filled with spray mixture (max. 0.006% active ingredient). 96 hours later, the rice plants are infected with a conidia suspension of the fungus. Fungus infestation is evaluated after incubating the infected plants for 5 days at 95-100% relative humidity and about 24° C. 
     Results of the biological tests 
     Example B1 
     component I: compound IA (benzothiadiazole-7-carboxylic acid) 
     component II: compound IID (metconazol) 
     Action against  Erysiphe graminis  on barley 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. IA 
                 a.i. IID 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.6 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 2 
                   
                   
                 40 
               
               
                 3 
                 6 
                   
                   
                 89 
               
               
                 4 
                   
                 0.6 
                   
                 10 
               
               
                 5 
                   
                 2 
                   
                 40 
               
               
                 6 
                   
                 6 
                   
                 51 
               
               
                 7 
                   
                 20 
                   
                 65 
               
               
                 8 
                 0.6 
                 0.6 
                 1:1  
                 37 
                 10 
                 3.7 
               
               
                 9 
                   
                 2 
                 1:3  
                 59 
                 40 
                 1.5 
               
               
                 10  
                   
                 6 
                 1:10 
                 81 
                 51 
                 1.6 
               
               
                 11  
                   
                 20 
                 1:30 
                 78 
                 65 
                 1.2 
               
               
                 12  
                 2 
                 6 
                 1:3  
                 78 
                 71 
                 1.1 
               
               
                 13  
                   
                 20 
                 1:10 
                 98 
                 79 
                 1.2 
               
               
                   
               
            
           
         
       
     
     Example B2 
     component I: compound IA (benzothiadiazole-7-carboxylic acid) 
     component II: compound IIE (tetraconazol) 
     Action against  Erysiphe graminis  on barley 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. IA 
                 a.i. IIE 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.6 
                   
                   
                 14 
                   
                   
               
               
                 2 
                 2 
                   
                   
                 27 
               
               
                 3 
                   
                 0.6 
                   
                 45 
               
               
                 4 
                   
                 2 
                   
                 63 
               
               
                 5 
                 0.6 
                 0.6 
                 1:1 
                 70 
                 53 
                 1.3 
               
               
                 6 
                   
                 2 
                 1:3 
                 82 
                 68 
                 1.2 
               
               
                 7 
                 2 
                 0.6 
                 3:1 
                 79 
                 60 
                 1.3 
               
               
                   
               
            
           
         
       
     
     Example B3(a) 
     component I: compound IA (benzothiadiazole-7-carboxylic acid) 
     component II: compound IIF (azoxystrobin) 
     Action against  Colletotrichum lagenaeum  on  Cucumis sativus  L./foliar application 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. IA 
                 a.i. IIF 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.06 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 0.2 
                   
                   
                  5 
               
               
                 3 
                 2 
                   
                   
                 22 
               
               
                 4 
                   
                 0.06 
                   
                  5 
               
               
                 5 
                   
                 0.2 
                   
                  9 
               
               
                 6 
                   
                 0.6 
                   
                 12 
               
               
                 7 
                   
                 6 
                   
                 17 
               
               
                 8 
                 0.06 
                 0.06 
                 1:1 
                 16 
                  5 
                 3.2 
               
               
                 9 
                 2 
                 0.2 
                 10:1  
                 65 
                 29 
                 2.2 
               
               
                 10  
                   
                 0.6 
                 3:1 
                 49 
                 31 
                 1.6 
               
               
                 11  
                   
                 6 
                 1:3 
                 44 
                 35 
                 1.3 
               
               
                   
               
            
           
         
       
     
     Example B3(b) 
     component I: compound IA (benzothiadiazole-7-carboxylic acid) 
     component II: compound IIF (azoxystrobin) 
     Action against  Colletotrichum lagenarium  on  Cucumis sativus  L./soil application 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. IA 
                 a.i. IIF 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.006 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 0.02 
                   
                   
                 40 
               
               
                 3 
                 0.06 
                   
                   
                 49 
               
               
                 4 
                 0.2 
                   
                   
                 91 
               
               
                 5 
                   
                 0.2 
                   
                  0 
               
               
                 6 
                   
                 0.6 
                   
                  9 
               
               
                 7 
                   
                 2 
                   
                 28 
               
               
                 8 
                   
                 6 
                   
                 66 
               
               
                 9 
                 0.006 
                 0.2 
                 1:30  
                 11 
                  0 
                 * 
               
               
                 10  
                   
                 0.6 
                 1:100 
                 30 
                  9 
                 3.3 
               
               
                 11  
                   
                 2 
                 1:300 
                 83 
                 28 
                 3.0 
               
               
                 12  
                 0.02 
                 6 
                 1:300 
                 97 
                 80 
                 1.2 
               
               
                 13  
                 0.06 
                   
                 1:100 
                 100  
                 82 
                 1.2 
               
               
                   
               
               
                 *synergy factor SF cannot be calculated  
               
            
           
         
       
     
     Example B4 
     component I: compound IA (benzothiadiazole-7-carboxylic acid) 
     component II: compound IIG (cresoxime methyl) 
     Action aginst  Colletotrichum lagenarium  on  Cucumis sativus  L./foliar application 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. IA 
                 a.i. IIG 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.2 
                   
                   
                  3 
                   
                   
               
               
                 2 
                 0.6 
                   
                   
                 51 
               
               
                 3 
                   
                 2 
                   
                  0 
               
               
                 4 
                   
                 20 
                   
                 41 
               
               
                 5 
                 0.2 
                 2 
                 1:10  
                 15 
                  3 
                 5   
               
               
                 6 
                   
                 20 
                 1:100 
                 61 
                 43 
                 1.4 
               
               
                   
               
            
           
         
       
     
     Example B5 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIA (tebuconazol) 
     Action against  Cercospora nicotianae  on tobacco plants 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIA 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.2 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 2 
                   
                   
                 17 
               
               
                 3 
                 6 
                   
                   
                 55 
               
               
                 4 
                 20 
                   
                   
                 78 
               
               
                 5 
                   
                 2 
                   
                  0 
               
               
                 6 
                   
                 6 
                   
                  0 
               
               
                 7 
                 0.2 
                 2 
                  1:10 
                 87 
                  0 
                 * 
               
               
                 8 
                   
                 6 
                  1:30 
                 97 
                  0 
                 * 
               
               
                 9 
                 2 
                 2 
                 1:1 
                 87 
                 17 
                 5.1 
               
               
                 10  
                   
                 6 
                 1:3 
                 94 
                 17 
                 5.5 
               
               
                 11  
                 6 
                 2 
                 3:1 
                 87 
                 55 
                 1.6 
               
               
                 12  
                   
                 6 
                 1:1 
                 90 
                 55 
                 1.6 
               
               
                 13  
                 20 
                 2 
                 10:1  
                 97 
                 78 
                 1.2 
               
               
                 14  
                   
                 6 
                 3:1 
                 97 
                 78 
                 1.2 
               
               
                   
               
            
           
         
       
     
     Example B6 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIB (epoxyconazol) 
     This mixture has a synergistic action against  Cercospora nicotianae  on tobacco plants. 
     Example B7 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIC (cyproconazol) 
     Action against  Cercospora nicotianae  on tobacco plants 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIC 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.2 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 2 
                   
                   
                 17 
               
               
                 3 
                 6 
                   
                   
                 55 
               
               
                 4 
                 20 
                   
                   
                 78 
               
               
                 5 
                   
                 2 
                   
                  0 
               
               
                 6 
                   
                 6 
                   
                  0 
               
               
                 7 
                 0.2 
                 2 
                  1:10 
                 78 
                  0 
                 * 
               
               
                 8 
                   
                 6 
                  1:30 
                 84 
                  0 
                 * 
               
               
                 9 
                 2 
                 2 
                 1:1 
                 90 
                 17 
                 5.3 
               
               
                 10  
                   
                 6 
                 1:3 
                 94 
                 17 
                 5.5 
               
               
                 11  
                 6 
                 2 
                 3:1 
                 87 
                 55 
                 1.6 
               
               
                 12  
                   
                 6 
                 1:1 
                 93 
                 55 
                 1.7 
               
               
                 13  
                 20 
                 2 
                 10:1  
                 100  
                 78 
                 1.3 
               
               
                 14  
                   
                 6 
                 3:1 
                 100  
                 78 
                 1.3 
               
               
                   
               
            
           
         
       
     
     Example B8 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IID (metconazol) 
     Action against  Erysiphe graminis  on barley 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIC 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.6 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 2 
                   
                   
                 33 
               
               
                 3 
                   
                 6 
                   
                 17 
               
               
                 4 
                   
                 20 
                   
                 33 
               
               
                 5 
                   
                 60 
                   
                 50 
               
               
                 6 
                 0.6 
                 6 
                 1:10  
                 33 
                 17 
                 1.9 
               
               
                 7 
                   
                 20 
                 1:30  
                 50 
                 33 
                 1.5 
               
               
                 8 
                   
                 60 
                 1:100 
                 83 
                 50 
                 1.7 
               
               
                   
               
            
           
         
       
     
     Example B9(a) 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIF (azoxystrobin) 
     Action against  Colletotrichum lagenanum  on  Cucumis sativus  L./foliar application 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIF 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.06 
                   
                   
                 16 
                   
                   
               
               
                 2 
                 0.2 
                   
                   
                 22 
               
               
                 3 
                 6 
                   
                   
                 60 
               
               
                 4 
                   
                 2 
                   
                 18 
               
               
                 5 
                   
                 6 
                   
                 75 
               
               
                 6 
                 0.06 
                 2 
                 1:30 
                 43 
                 31 
                 1.4 
               
               
                 7 
                 0.2 
                   
                 1:10 
                 57 
                 36 
                 1.6 
               
               
                   
               
            
           
         
       
     
     Example B9(b) 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIF (azoxystrobin) 
     Action against  Colletotrichum lagenarium  on  Cucumis sativus  L./soil application 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIF 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 0.006 
                   
                   
                  0 
                   
                   
               
               
                 2 
                 0.02 
                   
                   
                  6 
               
               
                 3 
                 0.06 
                   
                   
                 23 
               
               
                 4 
                 0.2 
                   
                   
                 36 
               
               
                 5 
                   
                 0.02 
                   
                  1 
               
               
                 6 
                   
                 0.06 
                   
                  5 
               
               
                 7 
                   
                 0.6 
                   
                 27 
               
               
                 8 
                   
                 2 
                   
                 61 
               
               
                 9 
                   
                 6 
                   
                 93 
               
               
                 10  
                 0.006 
                 0.02 
                 1:3  
                 26 
                  1 
                 26   
               
               
                 11  
                   
                 0.6 
                 1:100 
                 44 
                 27 
                 1.6 
               
               
                 12  
                   
                 2 
                 1:300 
                 84 
                 61 
                 1.4 
               
               
                 13  
                 0.02 
                 0.02 
                 1:1  
                 23 
                  7 
                 3.3 
               
               
                 14  
                   
                 2 
                 1:100 
                 77 
                 64 
                 1.2 
               
               
                 15  
                 0.06 
                 0.02 
                 3:1  
                 42 
                 24 
                 1.8 
               
               
                 16  
                   
                 2 
                 1:30  
                 92 
                 70 
                 1.3 
               
               
                 17  
                 0.2 
                 2 
                 1:10  
                 93 
                 75 
                 1.2 
               
               
                   
               
            
           
         
       
     
     Example B10 (field test on chilli) 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIL (mancozeb) 
     Action against Colletotrichum sp. (anthracnose) and Cercospora sp. (leaf spot) on chilli; effects on crop yield. 
     In a plot of land about 10 m 2  (test location: Cikampek, Java, Indonesia), chilli plants are sprayed a total of 7 times at intervals of about 7 days with 500-700 litres of spray mixture per hectare. Three days after the first spraying, the plants are infected artificially with the fungus. 
     1) Action against Colletotrichum. Evaluation is made by assessing infestation on the chilli fruits after the fifth spraying. 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIL 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
               
                 1 
                 5 
                   
                   
                 55 
                   
                   
               
               
                 2 
                   
                 100 
                   
                 12 
               
               
                 3 
                 5 
                 100 
                 1:20 
                 77 
                 59 
                 1.3 
               
               
                   
               
            
           
         
       
     
     2) Action against Cercospora. Evaluation is made by assessing infestation on the leaves after the sixth spraying. 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIL 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 5 
                   
                   
                 76 
                   
                   
               
               
                 2 
                   
                 100 
                   
                  8 
               
               
                 3 
                 5 
                 100 
                 1:20 
                 87 
                 78 
                 1.1 
               
               
                   
               
            
           
         
       
     
     3) Action on crop yield. The chillis are harvested after the sixth spraying. 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIL 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 5 
                   
                   
                 459 
                   
                   
               
               
                 2 
                   
                 100 
                   
                  8 
               
               
                 3 
                 5 
                 100 
                 1:20 
                 1400  
                 ca 460 
                 ca 3 
               
               
                   
               
            
           
         
       
     
     Example B11 
     component I: compound ID (benzothiadiazole-7-carboxylic acid thiomethyl ester) 
     component II: compound IIK (KTU 3616) 
     Action against  Pyricularia oryzae  on rice plants 
     
       
         
           
               
               
               
               
               
            
               
                   
                   
               
               
                   
                 mg a.i. per liter (ppm) 
                   
                 % action 
                 SF 
               
            
           
           
               
               
               
               
               
               
               
            
               
                 Test no. 
                 a.i. ID 
                 a.i. IIK 
                 I:II 
                 O (found) 
                 E (expected) 
                 O/E 
               
               
                   
               
            
           
           
               
               
               
               
               
               
               
            
               
                 1 
                 6 
                   
                   
                 15 
                   
                   
               
               
                 2 
                   
                 0.02 
                   
                  0 
               
               
                 3 
                   
                 0.06 
                   
                 28 
               
               
                 4 
                   
                 0.2 
                   
                 47 
               
               
                 5 
                   
                 0.6 
                   
                 79 
               
               
                 6 
                   
                 2 
                   
                 83 
               
               
                 7 
                   
                 6 
                   
                 91 
               
               
                 8 
                 6 
                 0.02 
                 300:1 
                 42 
                 15 
                 2.8 
               
               
                 9 
                   
                 0.06 
                 100:1 
                 76 
                 39 
                 1.9 
               
               
                 10  
                   
                 0.2 
                  30:1 
                 98 
                 55 
                 1.8 
               
               
                 11  
                   
                 0.6 
                  10:1 
                 98 
                 82 
                 1.2 
               
               
                 12  
                   
                 2 
                  3:1 
                 100  
                 86 
                 1.2 
               
               
                 13  
                   
                 6 
                  1:1 
                 98 
                 92 
                 1.1