INSECTICIDAL AND MITICIDAL COMPOSITIONS

Abstract: The invention relates to an insecticidal and miticidal composition which contains as active ingredients chlorfenapyr (4-bromo-2-(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)pyrrole-3-carbonitrile) in combination with a carbamate-type insecticidal ingredient(s). The insecticidal and miticidal composition of the invention is effective against pests and mites having resistance to commercial insecticidal and miticidal agents.

Description: DESCRIPTION INSECT I Cl DAL AND MITICIDAL COMPOSITIONS FIELD OF THE INVENTION This invention relates to insecticidal and miticidal compositions which can be effectively applied in the agrohort i cu I tura I field. In more detail, it relates to insecticidal and miticidal compositions which contain two or more active ingredients and are especially effective against pests and mites which have acquired resistance to commercial insecticidal and miticidal agents. BACKGROUND OF THE INVENTION 4-Bromo-2- (4~ch I oropheny I ) -1- (ethoxymethy I ) -5- (tr if luoromethy I) pyrro I e-3-carboni tr i le (hereinafter referred to as 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 (Do lto- cepha I idae) , Lepidoptera pests such as diamond back moth (PI ute l la xy loste I la) , common cutworm (Spodoptera l itura) and apple leaf iner (Phy I lonorycter r ingonie l la) and Thysanoptera pests such as Thrips palmi and yellow tea thrips (Spi rtothr ips dorsa l is) and agrohort i cu I tura I pests such as mites such as two-spotted spider mite ( Tetranychus urticae koch) , Kanzawa spider mite ( Tetra- nychus kanzawa i kishida) and Aculops pe lekass i [Japanese La id-open (Kokai) Patent Publication No. 104042/89]. The second active ingredient of the insecti ¬ cidal and miticidal composition of the invention in ¬ cludes at least one of the oarbamate-type compounds which are known to be effective insecticidal agents against agricultural pests such as Hemiptera, Lepidoptera and Coleoptera insects and mites. Although insecticidal and miticidal agents have been developed in order to control various pests such as agrohort i cu I tura I 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 or the repeated use of these agents. In particular, important economic pests in agrohort i culture such as spider mites ( Tetranych idae) , which have a propensity to easi ly 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 devel- opment 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 kanzawa i kishida) , Aculops pe lekassi, 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 spider mites, development of a new insecticidal and miticidal agent which shows a high effect against spider mites which have acquired resistance against the conven ¬ tional miticidal agents is highly desirable. However, to obtain an insecticidal and miti ¬ cidal 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 rota- tional application of agents with different mechanisms of action is adopted for good pest management practice. However, this approach does not necessarily give satis ¬ factory 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. Therefore, it is an object of this invention to provide an insecticidal and miticidal composition which demonstrates a high controlling effect even against spider mites which have acquired resistance against chlorfenapyr. SUMMARY OF THE INVENTION In order to establish a countermeasure to a resistance problem in spider mites 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 spider mites which have been treated with chlorfenapyr. Thus, it has now been found that an insecticidal and miticidal composition which contains as active ingredient chlorfenapyr in combination with at least one of the carbamate-type insecticidal ingredients shows a joint action or synergistic effect which could not be foreseen from each individual ingredient alone. DETAILED DESCRIPTION OF THE INVENTION The insecticidal and miticidal composition of the invention is particularly effective for the control of spider mites such as two-spotted spider mite ( Tetra ¬ nychus urticae koch) , Tetranychus cinnabar inus (Bo i sduva I) , Kanzawa spider mite ( Tetranychus Kanzawa i kishida) , hawthorn spider mite ( Tetranychus vi ennens i ε zacher) , and the like. Advantageously, the insecticidal and miticidal composition of the invention shows not only a synergistic miticidal effect against the above-mentioned spider mites, but also demonstrates simultaneous control of troublesome pests such as leafroller moths ( Tortri- cidae) , Carpos i ni dae, leafminer moths (Lyoneti idae) , plant bugs (Pentatomi dae) , aphids (Aphidi dae) , leaf- hoppers (De ltocipha I idae) , thrips ( Thr i p i dae) , diamond back moths (Plute l la xyloste l la) , Mamestra brass icae, leaf beetles (Chryso e I idae) , whiteflies (A leyrodidae) and the like on important agronomic crops such as fruit trees, for example citrus, apple and pear; tea plants; vegetables and the like. Chlorfenapyr, which is an active ingredient of the insecticidal and miticidal composition of the i nven- tion, is a known compound described in Japanese La i d- open (Kokai) Patent Publication No. 104042/89 and its way of using as agrohort i cu I tura I insecticidal and miticidal agent is shown in the Publication. It can also be easily synthesized according to the method described in the Publication. As carbamate-type insecticidal ingredients which are suitable for use as the second active ingredi ¬ ent in the composition of the invention, many compounds are known. For example, illustrative generic names and chemical names are listed hereinbelow. These examples, however, are not intended to limit the scope of the i nvent i on. Generic name: Chemical name BPMC : 2-sec-Buty I pheny I -N-methy I carbamate Ml PC: 2- 1 sopropy I pheny I -N-methy I carbamate MTMC: m-Toly l-N-methy lcarbamate MPMC: 3, 4-Xy I y l-N-methy I carbamate NAC: 1-Naphthy l-N-methy I carbamate PHC: 2-I sopropoxypheny l-N-methy I carbamate XMC: 3, 5-Xy I y l-N-methy Icarbamate A I anycarb : Ethy I (Z) -N-benzy I -N- { [methy I (1 -methy I th i oethy I i - denea i noxycarbony I) a i no] thi o} -β-a lani nate Eth i ofencarb : 2- (Ethy I th i omethy I) pheny I methy Icarbamate Oxamy I : Methy l-N, N' -di ethy l-N-[ (methy Icarbamoy I) oxy]- 1-thi oxami i date Carbosu I fan : 2, 3-Dihydro-2, 2-dimethy l-7-benzo[b] furany I N- d i buty I -am i noth i o-N-methy I carbamate Thi odi carb; 3, 7, 9, 13-Tetramethyl-5, 11-dioxa-2, 8, 14-trithia- 4, 7, 9, 12~tetraazapentadeca-3, 12-diene-6, 10-dione Pi r imi carb : 2-D i methy I am i no-5, 6-d i methy I pyr i m i d i n-4-y I dimethy Icarbamate Bend i ocarb: 2, 2-D i ethy 1-1 , 3 ~ benzodi oxo I —4—y I methy Icarbamate Benfuracarb: Ethyl N-[2, 3-dihydro-2, 2-dimethy I benzofuran-7- yloxycarbonyl (methy I) ami nothi o]-N-i sopropy l-β- a I an i nate Methomy I : S-methy I -N- [ (methy I carbamoy I ) oxy] th i oacet i m i date The above-mentioned names of insecticidal agents are generic names described in "Agrochemi ca I s Handbook 1992 Edition" published on July 30, 1992 by Japan Plant Protection Association and "SHIBUYA IN- DEX-1996-(7th Edition)" published on April 1, 1996 by ZENNOH. In this invention, among the above-mentioned agents, especially 2-sec-buty I pheny l-N-methy I -carbamate and 1-naphthy l-N-methy Icarbamate are preferable due to a high synergistic action with chlorfenapyr. 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 publicly known carbamate-type insecticidal i ngredi ent (s) with a suitable carrier and aux i I I i ar i es, such as e ulsifiers, dispers- ants, 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 formu- I at i ons. 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 agrohort i cu I tura I composition. Various surfactants, stabi lizers 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, repellents, attrac- tants, synergists and fertilizers and fragrances, in order to expand its applicability. The ratio of chlorfenapyr to the publicly known carbamate-type insecticidal i ngredi ent (s) 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 0.5-20 weight parts, of a publicly known carbamate-type insecticidal ingredi ¬ ent (s) . Although the application amount may differ according to prevai ling conditions such as the popula- tion 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 publicly known carbamate-type insecticidal i ngred i ent (s) 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 appJi- cation 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 formul at i on. 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. The parts all mean weight parts. EXAMPLE 1 FORMULATION EXAMPLE 1 EMULSION Clorfenapyr 5 parts BPMC 40 parts Xylene 25 parts Dimethyl formamide 20 parts Sorpol 3005X 10 parts (Polyoxyethy I ene type surfactant manufactured by Toho Chemical Industry Ltd. , commercial name) An emulsion is obtained by mixing homoge ¬ neously and dissolving the above-mentioned ingredients. EXAMPLE 2 FORMULATION EXAMPLE 2 WETTABLE POWDER Chlorfenapyr 5 parts NAC 50 parts Carplex #80 15 parts (White carbon manufactured by Shionogi & Co., Ltd., commercial name) Zeekl ite SP 22 parts (Mixture of kaolinite and cericite manufactured by Zeekl ite Ind. , commercial name) Calcium I igni nsu I fonate 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 NAC 25 parts Ethylene glycol 8 parts Sorpol AC3020 5 parts (Toho Chemical Ind. Co., Ltd., commercial name) Xanthan gum 0.1 parts Water 56.9 parts Chlorfenapyr, NAC 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 Dyno i I I (Shin aru Enter- prises) to obtain a sol (flowable agent). EXAMPLE 4 FORMULATION EXAMPLE 4 POWDER Chlorfenapyr 0.5 parts BPMC 3.5 parts White carbon 5 parts Clay 91 parts (Nippon Talc Co., Ltd., commercial name) The above-mentioned ingredients are homoge ¬ neously mixed and pulverized to obtain a powder Each of the above-prepared formulations is suitable to be used as an agrochemi ca I . EXAMPLE 5 TEST EXAMPLE 1 In this experiment, the miticidal effect against female imagines (adults) of Kanzawa spider mite ( Tetranychus kanzawa i kishida) which are resistant 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 carbamate-type insecticidal agent (s) are dispersed in water containing 200 ppm of an extender (Sorpol 3005X manufactured by Toho Chemical Industry Ltd.) and di luted such that a predetermined concentration of active ingre- dient 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 a re tested per concentration, 4-5 concentrations are evaluated per formulation and 2 performances are repeated). Two days after treatment, the number of living and dead female imagines of Kanzawa spider mite ( Tetranychus kanzawai k ishida) which had acquired a strong resistance to chlorfenapyr is counted and the mortality (%) is calcu- lated according to the formula shown here inbe low. Mortality (%) = Number of dead mite x 100 Number of living mite + Number of dead mite Using these data, the LC 50 values are obtained by conventional probit analysis techniques. A co-toxi- city coefficient is calculated by applying Sun and Johnson's formula (J. Econ. Ent., Vol 53, p. 887, 1960) 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 miti- cidal composition of the invention is shown in Table I. The LC 50 values and the qo-toxicity coefficients of the composition of the invention are shown in Table II. Co-toxicity coefficient = T r c = Actual toxicity index of mixture T c = : 1 . x 100 Theoretical toxicity index of mixture For T° values greater than 100, the greater value indicates a stronger synergistic action. For a T° value equal to 100, an additive action is indicated. For T values less than 100, the lesser value indicates a greater antagonistic action. A more detailed description of the calculation or the co-toxicity coefficient using the above-referenced Sun and Johnson formula fo I lows. 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 are determined. Actual toxicity index of mixture M = M*' 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. t i Theoretical toxicity index of mixture M = Th. M Th. M* ' = Toxicity index of A x %A in M + Toxicity index of B x SB in M Toxicity index of B = B B t t ,, _ LCs. n o of A χ 100 LC 50 of B Toxicity index of A = A A t j = 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 Rn (ppm) Chlorfenapyr 1500 BPMC 3200 NAC 2700 Ethiofencarb 2100 The tested mite was a female imago of the ch I orfenapyr-res i stant strain of Kanzawa spider mite which was obtai ed by a long artificial selection proce ¬ dure against chlorfenapyr in a laboratory on a colony of Kanzawa spider mite which had been collected in the field. As the LC 50 value for chlorfenapyr against a susceptible strain of spider mite is about 5 ppm, this strain has developed about a 300-fold resistance to chl orfonapyr. It is generally known that the effect of carbamate-type insecticidal agents against spider mites is weak, and all the tested carbamate-type insecticidal agents showed only low miticidal effects. TABLE I I Evaluation Of The Effect Of Test Mixtures Against Female Imago Of Kanzawa Spider Mite Which Have Acquired Resistance Against Chlorfenapyr LC 50 TEST MIXTURE RATIO (ppm) τ c (Ch I orfenapyr carbamate) Chlorfenapyr + BPMC 1 : 10 310 940 Chlorfenapyr + NAC 1 : 10 480 520 Chlorfenapyr + Ethiofencarb 1 10 440 460 As can be seen from the data on Table II, the co-toxicity coefficient of the test mixtures is a value greater than 100, which is indicative of strong synergistic action between ch lorphenapyr and BPMC, NAC or Ethiofencarb. Though the detailed mechanism of the synergistic action of the composition of the invention is not clear, it is estimated that the metabolic system (group of enzymes), with which the spider mites, which has developed resistance to chlorfenapyr, detoxifies and decomposes the compound, be inhibited by a carbamate- type insecticidal i ngredi ent (s) to demonstrate such an action. Therefore, a second ingredient of the insecti ¬ cidal and miticidal composition is thought not to be limited to the carbamate-type insecticidal agents tested in the above-mentioned examples and the carbamate-type insecticidal agents concretely mentioned above.

Claims: CLA I MS 1. An insecticidal and miticidal composition which contains as active ingredients chlorfenapyr [4-bromo-2-(4~ch loropheny I) -1- (ethoxymethy I) -5-(tr i- f I uoromethy I) pyr ro le-3-carbonit i le] in combination with at least one of a carbamate-type insecticidal compound. 2. The composition according to claim 1 wherein the carbamate-type insecticidal compound is selected from the group consisting of 2-sec-buty I pheny l-N- methy I carbamate, 2-i sopropy I pheny I -N-methy Icarbamate, m-to I y l-N-methy I carbamate, 3, 4-χy ly l-N-methy Icarbamate, 1-naphthy l-N-methy I carbamate, 2-i sopropoxypheny l-N- methy Icarbamate, 3, 5-χy ly l-N-methy Icarbamate, ethyl (Z) -N-benzy I -N- { [methy I (1 -methy I th i oethy I i denea i nooxy- carbony I) ami no] thi o} -β-a lani nate, 2- (ethy I thiomethy I) - pheny I methy I carbamate, methy l-N, N' -d imethy l-N-[ (methy I- carbamoy I) oxy] -1 -thi oxamimi date, 2, 3-di hydro-2, 2- d i methy I -7-benzo [b] furany I N ~ d i buty I am i noth i o-N-methy I - carbamate, 3, 7, 9, 13-Tetramethy I -5, 11-di oxa-2, 8, 14- tr i thi a-4, 7, 9, 12-tetraazapentadeca-3, 12~diene-6, 10- di one, 2-dimethy I a i no~5, 6~d imethy I pyr imid i n-4-y I dimethy I carbamate, 2, 2-dimethy 1-1 , 3-benzodi oxo I —4—y I methy I carbamate, ethyl N-[2, 3-di hydro-2, 2-dimethy Ibenzo- furan-7-y I oxycarbony I (methy I) ami noth i o]-N~i sopropy l-β- alaninate and S-methy l-N-[ (methy Icarbamoy I) oxy] thi o- acet i idate. 3. The composition according to claim 2 wherein the carbamate-type insecticidal compound is selected from 2-sec-buty I pheny l-N-methy Icarbamate, 1-naphthy l-N- methy I carbamate and 2- (ethy I th i omethy I) pheny I methylcar- bamate. 4. The composition according to any of claims 1-3 wherein the chlorfenapyr is present in a ratio of about 1 weight part to about 0.01-100 weight parts of the carbamate-type insecticidal i ngredi ent (s) . 5. The composition according to claim 4 wherein the ratio is about 1 weight part of chlorfenapyr to about 0.5-20 weight parts of the carbamate-type insecticidal i ngredient (s) . 6. A process for the preparation of a composition of claim 1 which comprises admixing the active ingredients with an agrohort i cu I tura I I y acceptable solid or I i qui d carr i er. 7. The process according to claim 6 wherein the active ingredients comprise chlorfenapyr in combination with at least one selected from 2-sec-buty I pheny l-N- methy Icarbamate, 1-naphthy l-N-methy Icarbamate and 2- (ethy I thi omethy I) pheny I methy I carbamate. 8. The process according to claim 7 wherein the chlorfenapyr is present in a ratio of about 1 weight part to about 0.5 -20 weight parts of at least one selected from 2-sec-buty I pheny l-N-methy Icarbamate, 1-naphthy l-N-methy Icarbamate and 2-(ethy I thi omethy I) - pheny I methy I carbamate.

Inventors: FUKUCHI TOSHIKI, FUKUCHI, TOSHIKI
Applicants: AMERICAN CYANAMID CO, FUKUCHI TOSHIKI, AMERICAN CYANAMID COMPANY, FUKUCHI, TOSHIKI
Application year: 1997
Main classification: A01N43
IPC codes: A01N43, A01N47