Abstract:
The invention relates to an insecticidal and miticidal composition which contains as active ingredients 4-bromo-2-(4-chlorophenyl)-1-(ethoxymethy)-5-(trifluoromethyl)pyrrole-3-carbonitrile in combination with one or more compounds selected from the group consisting of formamidine-type insecticidal and miticidal agents, organosulfur-type insecticidal and miticidal agents, thiocarbamate-type insecticidal and miticidal agents, phenisobromolate, pyrimidifen, milbemectin and dinitromethylheptylphenyl crotonate. The insecticidal and miticidal composition of the invention is effective against pests and mites having resistance to commercial insecticidal and miticidal agents.

Description:
The present Application is a national phase entry of PCT/JP97/04274, filed Nov. 25, 1997, which claims priority of Japanese Application 8/313571, filed Nov. 25, 1996. 
    
    
     FIELD OF THE INVENTION 
     This invention relates to insecticidal and miticidal compositions which contain as active ingredients 4-bromo-2-(4-chloropheny)-1-(ethoxymethyl)-5-(trifuloromethyl)pyrrole-3-carbonitrile (hereinafter referred to as chlorfenapyr) in combination with a second insecticidal and miticidal ingredient(s) which can be effectively applied especially in the agrohorticultural field. 
     BACKGROUND OF THE INVENTION 
     Chlorfenapyr, which is an active ingredient of the insecticidal and miticidal composition of the invention, is known to be effective against insects such as Hemiptera pests such as leafhoppers (Doltocephalidae), Lepidoptera pests such as diamond back moth ( Plutella xylostella ), common cutworm ( Spodoptera litura ) and apple Ieafminer ( Phyllonorycter ringoniella ) and Thysanoptera pests such as Thrips palmi and yellow tea thrips ( Spirtothrips dorsalis ) and agrohorticultural pests such as mites such as two-spotted spider mite ( Tetranychus urticae koch ), Kanzawa spider mite ( Tetranychus kanzawai kishida ) and  Aculops pelekassi.    
     The second active ingredient of the insecticidal and miticidal composition of the invention includes one or more of the following compounds: 
     1) formamidine-type compounds such as 3-methyl-1,5-bis(2,4-xylyl)-1,3,5-triazapenta-1,4-diene (amitraz), N′-(2-methyl-4-chlorophenyl)-N, N-dimethyl-formamidine hydrochloride (Chlorfenamidine) and the like which are known as effective compounds against agrohorticultural pests such as Hemiptera insects and mites: 
     2) organosulfur-type compounds such as 2,4,5,4′-tetrachlorodiphenyisulfone (tetradifon), p-chlorophenyl p-chlorobenzenesulfonate (CPCBS) and the like which are known to be effective insecticidal and miticidal agents; 
     3) thiocarbamate-type compounds such as S-4-phenoxybutyl-dimethylthiocarbamate (fenothiocarb) and the like which are known to be effective against a wide spectrum of agrohorticultural pests; 
     4) isopropyl 4,4′-dibromobenzilate (fenisobromolate) which is known to be effective against insect and mite pests; 
     5) 5-chloro-N-{2-[2,3-dimethyl-4-(2-ethoxyethyl)phenoxy]ethyl}-6-ethyl-4-pyrimidinamine (pyrimidifen) which is known to be effective against Hemiptera and Lepidoptera insects and mites; 
     6) 3:7 mixture of (10E, 14E, 16E, 22Z)-(1R, 4S, 5′S, 6R, 6′R, 8R, 13R, 20R, 21R, 24S)-21, 24-dihydroxy-5′, 6′,11,13,22-pentamethyl-3,7, 19-trioxatetra-cyclo[15.6.1.1 4.8 . 0 20 , 24]pentacosa-10,14,16,22-tetraene-6-spiro-2′-tetrahydropyran-2-one and (10E, 14E, 16E, 22Z)-(1R, 4S, 5′S, 6R, 6′R, 8R, 13R, 20R, 21R, 24S)-6′-ethyl-21,24-dihydroxy-5′, 11,13,22-tetramethyl-3,7,19-trioxatetra-cyclo[15.6.1.1 4.8 .0 20 ,24]pentacosa-10,14,16,22-tetraene-6-spiro-2′-tetrahydropyran-2-one (milbemectin) which is known to be effective against agrohorticultural mites such as Tetranychidae; and 
     7) dinitrophenol-type compounds such as dinitromethylheptylphenyl crotonate [hereinafter referred to as DPC (Dinocap)] which is known to be effective against agrohorticultural mites such as Tetranychidae and agrohorticultural pathogenic fungi such as powdery mildew. 
     Although insecticidal and miticidal agents have been developed in order to control various pests such as agrohorticultural pests or hygienic pests and in practice have been used as a single or a mixed agent, pests which have acquired resistance against various agents have been appearing as a result of the repeated use of these agents. 
     In particular, important economic pests in agrohorticulture such as Tetranychidae, which have a propensity to easily develop resistance against pesticidal agents due to their ability to deposit large numbers of eggs and produce large numbers of generations which, themselves, require only a few days for development are of great concern. Resistance development in this pest family is also favored by a high mutation rate and frequent inbreeding, due to minimal migration. For these reasons, two-spotted spider mite ( Tetranychus urticae koch ), Kanzawa spider mite ( Tetranychus kanzawai kishida ),  Aculops pelekassi , and the like have acquired resistance, to some degree, against almost all existing pesticidal agents. Therefore, in order to prevent and control the damage caused by Tetranychidae, development of a new insecticidal and miticidal agent which shows a high effect against Tetranychidae which have acquired resistance against the conventional miticidal agents is highly desirable. 
     However, to obtain an insecticidal and miticidal composition which shows no cross-resistance with existing insecticidal and miticidal agents, has no toxicity problems and has little negative impact on the environment, is extremely difficult. Therefore, a means to delay or prevent the development of resistant strains of pest species is always being sought. In order to apply an effective agent as long as possible, a rotational application of agents with different mechanisms of action is adopted for good pest management practice. However, this approach does not necessarily give satisfactory pest control. Therefore, after a resistance problem has occurred, a countermeasure to resistance by combining insecticidal and miticidal agents has been studied. However, a high synergistic action has not always been found. 
     Eventhough, chlorfenapyr, is a highly effective miticidal agent at present, it has been recently introduced to the agrochemical market and, in time, may ultimately develop a resistance problem, as has happened with new pesticidal compounds so often in the past. 
     Therefore, it is an object of this invention to provide an insecticidal and miticidal composition which demonstrates a high controlling effect even against Tetranychidae which have acquired resistance against chlorfenapyr. 
     SUMMARY OF THE INVENTION 
     In order to establish a countermeasure to a resistance problem in Tetrachychidae against chlorfenapyr before such a problem occurs, the synergistic action with the existing insecticidal, miticidal and fungicidal agents was studied using resistant species which have been artificially established in the laboratory by selecting Tetrachychidae which have been treated with chlorfenapyr. Thus, it has now been found that an insecticidal and miticidal composition which contains as active ingredients chlorfenapyr in combination with one or more compounds specified in a select group of insecticidal and miticidal ingredients shows a joint action or synergistic effect which could not be foreseen from each individual ingredient alone. Namely, the invention exists in the insecticidal and miticidal composition which contains as active ingredients chlorfenapyr in combination with one or more compounds selected from the group consisting of formamidine-type insecticidal and miticidal agents, organosulfur-type insecticidal and miticidal agents, thiocarbamate-type insecticidal and miticidal agents, phenisobromolate, pyrimidifen, milbemectin and dinitromethylheptylphenyl crotonate (hereinafter referred to as Group A). 
     DETAILED DESCRIPTION OF THE INVENTION 
     Chlorfenapyr, which is an active ingredient of the insecticidal and miticidal composition of the invention, is a known compound (Japanese Laid-open (Kokai) Patent Publication No. 104042/89). Compounds which are suitable for use as the second active ingredient in the composition of the invention such as one or more of the following compounds: 
     1) formamidine-type compounds, preferably amitraz end chlorphenamidine: 
     2) organosulfur-type compounds, preferably tetradifon and p-chlorophenyl p-chlorobenzenesulfonate; 
     3) thiocarbamate-type compounds, preferably fenothiocarb; 
     4) fenisobromolate; 
     5) pyrimidifen; 
     6) milbemectin and 
     7) dinitromethylheptylphenyl crotonate are all known compounds and are commercial products which are readily available. 
     For the preparation of the insecticidal and miticidal composition of the invention, it is suitable to formulate as a wettable powder, aqueous concentrate, emulsion, liquid concentrate, sol (flowable agent), powder, aerosol, or the like, by conventional methods such as admixing chlorfenapyr and one or more compounds of Group A with a suitable carrier and auxiliaries, such as emulsifiers, dispersants, stabilizers, suspending agents, penetrants, and the like. 
     The content of the total active ingredients of the composition of the invention, expressed as weight/weight %, is preferably in the range of about 1-90% for wettable powder, aqueous concentrate, emulsion, liquid concentrate and sol formulations. The preferable content of total active ingredients is about 0.5-10% for powder formulations and about 0.01-2% for aerosol formulations. 
     Carriers suitable for use in the insecticidal and miticidal compositions of the invention may be any solid or liquid carrier which is commonly used for an agrohorticultural composition. Various surfactants, stabilizers and other auxiliary ingredients may be used according to the necessity. In commercially useful formulations, the composition of the invention may also be present in a mixture with other active agents, for example various insecticidal, miticidal, fungicidal and herbicidal agents, plant growth regulators, repellants, attractants, synergists and fertilizers and fragrances, in order to expand its applicability. 
     The ratio of chlorfenapyr to the compound(s) of Group A in the insecticidal and miticidal composition of the invention is about 1 weight part of chlorfenapyr to about 0.01-100 weight parts, preferably about 0.1-20 weight parts, of a compound(s) of Group A. 
     The insecticidal and miticidal composition of the invention is particularly effective for the control of Tetranychidae such as two-spotted spider mite ( Tetranychus urticae koch ),  Tetranychus cinnabarinus  (boisduyal), Kanzawa spider mite ( Tetranychus Kanzawai kishida ),  Tetranichus viennensis zacher , and the like. 
     Advantageously, the insecticidal and miticidal composition of the invention shows not only a synergistic miticidal effect against the above-mentioned Tetranychidae, but also demonstrates simultaneous control of troublesome pests such as leafroller moths (Tortricidae), Carposinidae, leafminer moths (Lyonetiidae), plant bugs (Pentatomidae), aphids (Aphididae), leaf-hoppers (Deltociphalidae), thrips (Thripidae), diamond back moths ( Plutella xylostella ),  Mamestra brassicae , leaf beetles (Chrysomelidae), whiteflies (Aleyrodidae) and the like on important agronomic crops such as fruit trees, for example citrus, apple and pear; tea plants; vegetables and the like. 
     Although the application amount of the composition of the invention may differ according to prevailing conditions such as the population density, the kinds and cultivation form of the target crop the weather conditions, the manner of application, and the like, in general, the total amount of chlorfenapyr in combination with the compound(s) of Group A is about 0.1-1,000 g, preferably about 40-500 g, per 10 ares. In actual practice, the composition of the invention when in the form of a wettable powder, aqueous concentrate, emulsion, liquid concentrate, sol, or the like may be diluted with water and applied to the crop at an application rate of about 100-700 liters per 10 ares. When the inventive composition is formulated as a powder or aerosol, the crop may be treated with the undiluted formulation. 
     The insecticidal and miticidal composition of the invention is further illustrated in the examples set forth hereinbelow These examples are not intended to limit the scope of the invention. All parts are parts by weight. 
    
    
     EXAMPLE 1 
     FORMULATION EXAMPLE 1 EMULSION 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Clorfenapyr 
                 10 
                 parts 
               
               
                   
                 Amitraz 
                 30 
                 parts 
               
               
                   
                 Xylene 
                 25 
                 parts 
               
               
                   
                 Dimethyl formamide 
                 20 
                 parts 
               
               
                   
                 Sorpol 3005X 
                 15 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     (Polyoxyethylene type surfactant manufactured by Toho Chemical Industry Co., Ltd., commercial name) 
     An emulsion is obtained by mixing homogneously and dissolving the above-mentioned ingredients. 
     EXAMPLE 2 
     FORMULATION EXAMPLE 2 WETTABLE POWDER 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Chlorfenapyr 
                 10 
                 parts 
               
               
                   
                 Tetradifon 
                 10 
                 parts 
               
               
                   
                 Carplex #80 
                 20 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     (White carbon manufactured by Shionogi &amp; Co., Ltd, commercial name) 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Zeeklite SP 
                 52 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     (Mixture of kaolinite and cericite manufactured-by Zeeklite Ind., commercial name) 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Calcium ligninsulfonate 
                 8 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     A wettable powder is obtained by homogeneously mixing the above-mentioned ingredients by jet air mill. 
     EXAMPLE 3 
     FORMULATION EXAMPLE 3 SOL (FLOWABLE AGENT) 
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Chlorfenapyr 
                 5 
                 parts 
               
               
                   
                 Fenothiocarb 
                 25 
                 parts 
               
               
                   
                 Ethylene glycol 
                 8 
                 parts 
               
               
                   
                 Sorpol AC3020 
                 5 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     
       
         
               
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 Xanthan gum 
                 0.1 
                 parts 
               
               
                   
                 Water 
                 56.9 
                 parts 
               
               
                   
                   
               
             
          
         
       
     
     Chiorfenapyr, fenothiocarb and a previously prepared mixture of ethylene glycol, Sorpol AC3020 and xanthan gum are well mixed in water and dispersed. This slurry is then wet pulverized by Dynomill (Shinmaru Enterprises) to obtain a sol (flowable agent). 
     Each of the above-prepared formulations is suitable to be used as an agrochemical. 
     EXAMPLE 4 
     TEST EXAMPLE I 
     In this experiment, the miticidal effect against female imagines (adults) of Kanzawa spider mite ( Tetranychus kanzawai kishida ) which are registrant to chlorfenapyr is evaluated. 
     Round leaf disks (2 cm diameter) are cut out of a first leaf of kidney bean by a leaf punch and 4 sheets of the disks are placed on wet sanitary cotton in a plastic cup (8 cm diameter). On each leaf disk, 4 female imagines of Kanzawa spider mite ( Tetranychus kanzawai kishida ) which had acquired a strong resistance to chlorfenapyr are inoculated. 
     After the inoculation, chlorfenapyr and a compound(s) selected from group A are dispersed in water containing 200 ppm of an extender (Sorpol 3005X) and diluted such that a predetermined concentration of active ingredient is obtained. Each plastic cup is sprayed with 3.5 ml of a test solution with a rotary spray tower (Mizuho Scientific Co., Ltd.) and stored in a constant temperature chamber held at 25±1° C. (32 individuals are tested per concentration, 4−5 concentrations are evaluated per formulation, and 2 performances were repeated). Two days after treatment, the number of living and dead female imagines of Kanzawa spider mite ( Tetranychus kanzawai kishida ) which had acquired a strong resistance to chlorfenapyr is counted and the mortality (%) is calculated according the formula shown hereinbelow. 
     Mortality (%)=         Mortality                   (   %   )       =         Number                 of                 dead                 mite         Number                 of                 alived                 mite     +     Number                 of                 dead                 mite         ×   100                            
     Using these data, the LC 50  values are obtained by conventional probit analysis techniques. A co-toxicity coefficient is calculated by applying Sun and Johnson&#39;s formula (J. Econ. Ent., Vol 53, p. 887, 1980) which is generally used to determine the degree of synergistic activity. 
     The LC 50  value of each individual effective ingredient which constitutes the insecticidal and miticidal composition of the invention is shown in Table I. The LC 50  values and the co-toxicity coefficients of the composition of the invention are shown in Table II. 
     Co-toxicity coefficient=T c            T   c     =         Actual                 toxicity                 index                 of                 mixture       Theoretical                 toxicity                 index                 of                 mixture       ×   100                            
     For T c  values greater than 100, the greater value indicates a stronger synergistic action. For a T c  value equal to 100, an additive action is indicated. For T c  values less than 100, the lesser value indicates a greater antagonistic action. A more detailed description of the calculation of the co-toxicity coefficient using the above-referenced Sun and Johnson formula follows. 
     The LC 50  values of Test Compound A alone and Test Compound B alone and the LC 50  value of the (A+B) mixture M is determined. 
     Actual toxicity index of mixture M=M ti    
     Each LC 50  value of effective ingredient A and effective ingredient B and the LC 50  value of the mixture of A+B are used to determine the actual toxicity index as shown in the equation below.          M   ti     =           LC   50                   of                 A         LC   50                   of                 M       ×   100                            
     Theoretical toxicity index of mixture M=Th.M ti   
     
       
         Th.M ti =(Toxicity index of A×%A in M+Toxicity index of B×%B in M) 
       
     
     Toxicity index of B=B ti           B   ti     =           LC   50                   of                 A         LC   50                   of                 B       ×   100                            
     Toxicity index of A=A ti    
     A ti =100 
     
       
         
               
             
               
               
               
             
               
               
               
             
           
               
                 TABLE I 
               
             
             
               
                   
               
               
                 Evaluation Of The Effect Of Test Compounds Against 
               
               
                 Female Imago Of Kanzawa Spider Mite Which Have 
               
               
                 Acquired Resistance Against Chlorfenapyr 
               
             
          
           
               
                   
                 TEST COMPOUND 
                 LC 50  (ppm) 
               
               
                   
                   
               
             
          
           
               
                   
                 Chlorfenapyr 
                 1500 
               
               
                   
                 Amitraz 
                 200 
               
               
                   
                 Tetradifon 
                 4900 
               
               
                   
                 Kelthane (Dicofol) 
                 32 
               
               
                   
                 Phenisobromalate* 
                 280 
               
               
                   
                 Fenothiocarb 
                 1000 
               
               
                   
                 Pyrimidifen 
                 10 
               
               
                   
                 Avermectins 
                 0.13 
               
               
                   
                 Milbemectin 
                 0.28 
               
               
                   
                 Binapacryl a−   
                 180 
               
               
                   
                 DPC 
                 630 
               
               
                   
                   
               
               
                   
                 *2,4-dinitro-6-sec-butylphenyldimethyl-acrylate  
               
             
          
         
       
     
     By comparison, the LC 50  value for chlorfenapyr against a susceptible strain of Kanzawa spider mite is about 5 ppm. 
     As can be seen from the data on Table I, the resistant strain of Kanzawa spider mite which was obtained by a long artificial selection procedure against chlorfenapyr in a laboratory on a colony of Kanzawa spider mite which had been collected in the field, has developed about a 300-fold resistance to chlorfenapyr. 
     In the case of amitraz, phenisobromolate, Binapacryl and DPC, this Kanzawa spider mite is thought to originate from a colony which had acquired resistance to these insecticidal and miticidal agents prior to the time of collection in the field. These compounds all showed low effects. 
     The test compounds: Kelthane (dicofol), pyrimidifen, avermectins and milbemectin all demonstrate a high miticidal effect in this experiment. 
     The test compounds tetradifon and fenothiocarb demonstrate a low miticidal effect in this experiment. 
     
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE II 
               
             
             
               
                   
               
               
                 Evaluation Of The Effect Of Test Mixtures Against 
               
               
                 Female Imago Of Kanzawa Spider Mite Which Have 
               
               
                 Acquired Resistance Against Chlorfenapyr 
               
             
          
           
               
                 TEST MIXTURE 
                 RATIO 1   
                 LC 50  ppm) 
                 T C   
               
               
                   
               
             
          
           
               
                 Chlorfenapyr + Amitraz 
                 1:5 
                 64 
                 370 
               
               
                 Chlorfenapyr + Tetradifon 
                   1:3.2 
                 72 
                 4400  
               
               
                 Chlorfenapyr + Kelthane 
                   1:5.3 
                 34 
                 110 
               
               
                 Chlorfenapyr + Phenisobromolate 
                 1:6 
                 97 
                 330 
               
               
                 Chlorfenapyr + Fenothiocarb 
                  1:10 
                 270 
                 380 
               
               
                 Chlorfenapyr + Pyrimidifen 
                 4:5 
                 4.0 
                 450 
               
               
                 Chlorfenapyr + Avermectins 
                 5:1 
                 0.56 
                 140 
               
               
                 Chlorfenapyr + Milbemectin 
                 5:1 
                 0.75 
                 220 
               
               
                 Chlorfenapyr + Binapacryl 
                  1:10 
                 150 
                 130 
               
               
                 Chlorfenapyr + DPC 
                  5:12 
                 140 
                 540 
               
               
                   
               
               
                   1 Chlorfenapyr:Second active Ingredient  
               
               
                 T C  = Co-toxicity Coefficient  
               
             
          
         
       
     
     As can be seen from the data on Table II, the co-toxicity coefficient of each of the test mixtures containing chlorfenapyr in combination with either amitraz or tetradifon or phenisobromolate or fenothiocarb or pyrimidifen or milbemectin or DPC is a value significantly greater than 100, which is indicative of strong synergistic action.