MXPA99005070A - Insecticidal and miticidal compositions - Google Patents

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

INSECTICIDES AND ACCARICIDES COMPOSITIONS FIELD OF THE INVENTION The present invention relates to insecticidal and acaricidal compositions that can be applied effectively in the horticultural field. In more detail, it relates to insecticidal and acaricidal compositions containing two or more active ingredients and which are especially effective against pests and mites that have acquired resistance to commercial insecticidal and acaricidal agents. BACKGROUND OF THE INVENTION 4-bromo-2- ( 4-chlorophenyl) -1- (ethoxyethyl) -5- (trifluoroethyl) -pyrrole-3-carbonitrile (hereinafter referred to as chlorfenapyr) which is an active ingredient of the insecticidal and acaricidal composition of the present invention, is knows that it is effective against insects such as hemipteran pests such as leafhoppers (Dol tocephalidae), lepidopteran pests such as the diamond back moth (Plutella xylostella), the common pruning caterpillar (Spodoptera li t? ra) and the devourer insect of leaves of the apple tree (Phyllonoycter ringoniella) and pests of Thysanoptera such as Thrips palmi and the insect of the yellow leaf tea (Spirtothrips dorsalis) and horticultural pests such c omo mites, like the tick spider of REF .: 29998 two spots. { Tetranychus urticae koch), the tick spider of Kanzawa (Tetranychus kanzawai kishida) and Aculops pelekassi [Japanese Patent Laid-open Publication (Kokai) No. 104042/89]. The second active ingredient of the insecticidal and acaricidal composition of the present invention includes at least one carbamate-type compound which are known to be effective insecticidal and acaricidal agents against agricultural pests such as hemiptera, lepidoptera and coleoptera insects and mites. Although insecticidal and acaricidal agents have been developed in order to control various pests such as horticultural pests or hygienic pests and have been used in practice as a single agent or as a mixture of agents, pests have appeared that have acquired resistance against several pests. agents as a result of the repeated use of said agents. In particular, pests of economic importance in horticulture such as tick spiders. { Tetranychidae), which are prone to easily develop resistance against pesticide agents due to their ability to deposit large numbers of eggs and produce large numbers of generations which, in turn, require only a few days for development, are of great concern . The development of resistance in this family of pests is also favored by a high rate of mutations and frequent inbreeding, due to minimal migration. For these reasons, the two-spotted tick spider (Tetranychus urticae koch), the Kansawa tick spider (Tetranychus kanzawai kishida), Aculops pelekassi and the like have acquired resistance, to some degree, against almost all existing pesticide agents. Therefore, in order to prevent and control the damage caused by tick spiders, the development of a new insecticidal and acaricidal agent that demonstrates a high effect against tick spiders that have acquired resistance against conventional acaricidal agents is highly desirable. . However, to obtain an insecticidal and acaricidal composition that does not demonstrate cross-resistance with existing insecticidal and acaricidal agents, which has no toxicity problems and has little negative impact on the environment, is extremely difficult. Therefore, we are always looking for a means to delay or prevent the development of resistant strains of pest species. In order to apply an effective agent as long as possible, a rotational application of agents with different mechanisms of action is adopted, as a good practice in the management of pests.

However, this approach does not necessarily produce satisfactory control of pests. ThusAfter a resistance problem has occurred, countermeasures are studied through the combination of insecticidal and acaricidal agents. However, a high synergistic action is not always found. Therefore, an object of the present invention is to provide an insecticidal and acaricidal composition demonstrating a high control effect even against tick spiders that have acquired resistance against chlorfenapyr. BRIEF DESCRIPTION OF THE INVENTION In order to establish a countermeasure for the resistance problem of tick spiders against chlorfenapyr before such a problem occurs, the synergistic action was studied with the existing insecticidal, acaricidal and fungicidal agents, using resistant species that They were artificially established in the laboratory by selecting tick spiders that have been treated with chlorfenapyr. Thus, it has been found that an insecticidal and acaricidal composition containing chlorfenapyr as active ingredients in combination with at least one of the carbamate-type insecticidal ingredients shows a joint action or synergistic effect, which could not be anticipated from each ingredient individual by itself. DETAILED DESCRIPTION OF THE INVENTION The insecticidal and miticidal composition of the present invention is particularly effective for controlling spiders and ticks such as the two-spotted tick spider (Tetranychus urticae koch), Tetranychus cinnabarinus (Boisduval), the Kansawa tick spider (Tetranychus). kanzawai kishida), the spider tick of horns (Tetranychus viennensis zacher) and the like. Advantageously, the insecticidal and acaricidal composition of the present invention not only shows a synergistic acaricidal effect against the aforementioned tick spiders, but also demonstrates simultaneous control of problematic pests such as leaf-spinning moths (Tortricidae), Carposinidae, moth-eating moths. leaves (Lyonetiidae), plant insects (Pentatomidae), aphids (Aphididae), leafhoppers (From tociphalidae), insects of the family Thripidae, diamondback moth (Plutella xylostella), Mamestra brassicae, leaf beetles (Chryso elidae), whiteflies (Aleyrodidae) and the like in important agronomic crops such as fruit trees, for example citrus, apple and pear trees; tea plants; vegetables and the like. Chlorfenapyr, which is an active ingredient of the insecticidal and acaricidal composition of the present invention, is a known compound described in Japanese Patent Publication No. 104042/89 (Kokai) and its manner of using it as an insecticidal agent and horticultural acaricide is shows in the Publication. It can also be easily synthesized in accordance with the method described in the Publication. Since the carbamate-type insecticidal ingredients are suitable for use as a second active ingredient in the composition according to the present invention, many compounds are known. For example, generic and chemical illustrative names are listed below. However, these examples are not intended to limit the scope of the present invention.

Name Chemical Name Generic: BPMC 2-sec-butylphenyl-N-methylcarbamate MIPC 2-isopropylphenyl-N-methylcarbamate MTMC m-tolyl-N-methylcarbamate MPMC 3,4-xylil-N-methylcarbamate NAC: 1-naphthyl-N-methylcarbamate PHC: 2-isopropoxyphenyl-N-methylcarbamate XMC: 3, 5-xylyl-N-methylcarbamate Alanicarb: (Z) -N-benzyl-N-. { [methyl- (1-methylthioethylideneaminoxycarbonyl) -a] -thio} -β-ethyl alaninate Etiofencarb: 2- (ethylthiomethyl) -phenyl methyl-carbamate Oxamyl: N, N'-dimethyl-N- [(methylcarbamoyl) -oxy] -1-methyl thioxamidate Carbosulfan: 2,3-dihydro carbamate -2, 2-dimethyl-7-benzo [b] -furanyl-N-dibutyl-aminothio-N-methyl Thiodicarb: 3,7,9, 13-tetramethyl-5, l-dioxa-2, 8, 14-trityl - 4,7,9, 12-tetraazapentadeca-3, 12-dien-6, 10-dione Piri icarb: 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate Bendiocarb: 2,2-dimethyl-methylcarbamate l, 3-benzodioxol-4-yl Benfuracarb: N- [2,3-dihydro-2, 2-dimethylbenzofuran-7-yl-oxycarbonyl- (ethyl) -a inothio] -N-isopropyl-β-alaninate ethyl Metomil : (S) -N- [(Methylcarbamoyl) -oxy] -thioacetimidate methyl The names of the aforementioned insecticidal and fungicidal agents are generic names described in "Agroche icals Handbook 1992 Edition" published on July 30, 1992 by the Association Japanese Plant Protection and "SHIBUYA INDEX-1996- (7th Edition)" publi on April 1, 1996 by ZENNOH. In the present invention, among the aforementioned agents, 2-sec-butylphenyl-N-methyl carbamate and 1-naphthyl-N-methyl carbamate are especially preferred because of their high synergistic action with chlorfenapyr. For the preparation of the insecticidal and miticidal composition of the present invention, it is suitable to formulate it in the form of a wettable powder, aqueous concentrate, emulsion, liquid concentrate, sol (flowable agent), powder, aerosol or the like, by conventional methods such such as mixing chlorfenapyr and a publicly known carbamate-type insecticidal ingredient (s) with a suitable vehicle and auxiliaries, such as ulsifiers, dispersants, stabilizing agents, suspension improvers, penetrants and the like. The total content of active ingredients of the composition of the present invention, expressed by weight /% by weight, is preferably in the range of about 1-90% for formulations in wettable powder, aqueous concentrate, emulsion, liquid concentrate and sol . The total preferred content of active ingredients is from about 0.5 to 10% for powder formulations and from about 0.01 to 2% for aerosol formulations. Suitable vehicles for use in the insecticidal and acaricidal compositions of the present invention can be any solid or liquid vehicle that is commonly used for a horticultural composition. Several surfactants can be used, stabilizers and other auxiliary ingredients, according to the needs. In commercially useful formulations, the composition of the present invention may also be present in a mixture with other active agents, for example various insecticidal, acaricidal, fungicidal and herbicidal agents, plant growth regulators, repellents, attractants, synergists and fertilizers. and fragrances, in order to expand its applicability. The ratio of chlorfenapyr to a carbamate-type insecticidal ingredient or ingredients publicly known in the insecticidal and acaricidal composition of the present invention is about 1 part by weight of chlorfenapyr to about 0.01-100 parts by weight, preferably about 0.5-20 parts by weight of a publicly known carbamate-type insecticidal ingredient (s). Although the applied amount of the composition of the present invention may differ in accordance with the prevailing conditions such as the population density, the type of crop, the shape of the target crop, the climatic conditions, the manner of application and the like, in general , the total amount of chlorfenapyr in combination with a publicly known carbamate-type insecticidal ingredient or ingredients is from about 0.1 to 1000 g, preferably from about 40 to 500 g per 10 areas. In actual practice, the composition of the present invention when it is in the form of a wettable powder, aqueous concentrate, emulsion, liquid concentrate, sol or the like, can be diluted with water and applied to the crop at an application rate of about 100. to 700 liters per 10 areas. When formulating the composition of the present invention in powder or aerosol form, the crop can be treated with the undiluted formulation. The insecticidal and acaricidal composition of the present invention is further illustrated by the following Examples. These Examples are not intended to limit the scope of the present invention. All parts are given in parts by weight. EXAMPLE 1 FORMULATION OF EXAMPLE 1. EMULSION. Chlorfenapyr 5 parts BPMC 40 parts Xylene 25 parts Dimethylformamide 20 parts Sorpol 3005X 10 parts (Polyoxyethylene surfactant manufactured by Toho Chemical Industry Co., Ltd., trade name). An emulsion is obtained by homogeneously mixing and dissolving the aforementioned ingredients. EXAMPLE 2 FORMULATION OF EXAMPLE 2. HUMECTABLE DUST. Chlorfenapyr 5 parts NAC 50 parts Carplex # 80 15 parts (White carbon manufactured by Shionogi &Co., Ltd., trade name) Zeeklite SP 22 parts (Mix of kaolinite and cericite manufactured by Zeeklite Ind., Trade name) Calcium lingisulfonate 8 parts A wettable powder is obtained by homogeneously mixing the aforementioned ingredients in an air injection mixer. EXAMPLE 3 FORMULATION OF EXAMPLE 3. SOL (AGENT WITH FLUIDITY). Chlorfenapyr 5 parts NAC 25 parts Ethylene glycol 8 parts Sorpol AC3020 5 parts (Toho Chemical Ind. Co., Ltd., trade 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, mix well in water and disperse. This grout is pulverized in a Dynomill equipment (Shinmaru Enterprises), to obtain a sun (agent with fluidity).

EXAMPLE 4 FORMULATION OF EXAMPLE 4. DUST. Chlorfenapyr 0.5 parts BPMC 3.5 parts White carbon 5 parts Clay 91 parts (Nippon Tale Co., Ltd., trade name) The aforementioned ingredients are mixed homogeneously and pulverized to obtain a powder. Each of the formulations prepared above is suitable for use as an agrochemical formulation. EXAMPLE 5 EXAMPLE OF TEST 1. In this experiment, the acaricidal effect against female agoutis (adults) of the Kansawa tick spider (Tetranychus kanzawai kishida), with resistance to chlorfenapyr, was evaluated. Discs of round leaves (2 cm diameter) were cut from a first bean leaf with an undercut for leaves and 4 leaf discs were placed on wet sanitary cotton in a plastic cup (8 cm in diameter). In each leaf disc, 4 female imagos were inoculated from the Kansawa tick spider (Tetranychus kanzawai kishida) that had acquired a strong resistance to chlorfenapyr. After the inoculation, chlorfenapyr and a carbamate-type insecticidal agent (s) were dispersed in water containing 200 ppm of an extender.

(Sorpol 3005X, manufactured by Toho Chemical Industry, Ltd.) and diluted in such a way as to obtain a predetermined concentration of the active ingredient. Each plastic cup was sprayed with 3.5 ml of a test solution with a rotary tower sprayer (Mizuho Scientific Co., Ltd.) and stored in a chamber at a constant temperature maintained at 25 ± 1 ° C (32 individuals were tested by concentration, 4-5 concentrations per formulation were evaluated and the experiments were done in duplicate). Two days after the treatment, the number of live and dead female imagoes of the Kanzawa tick spider (Tetranychus kanzawai kishida) that had acquired a strong resistance to chlorfenapyr was counted, and mortality (%) was calculated in accordance with the Formula that is shown below: Mortality (%) = Number of dead mites x 100 Number of live mites + Number of dead mites Using these data, LC50 values were obtained by conventional analysis techniques.

A coefficient of cotoxicity was calculated by applying the Sun and Johnson Formula (J. Econ.Inst., Vol.53, p.887, 1980), which is generally used to determine the degree of synergistic activity. The LC50 value of each individual effective ingredient constituting the insecticidal and acaricidal composition of the present invention is shown in Table I. The LC50 values and the cotoxicity coefficients of the composition of the present invention are shown in Table 1. Table II. Cotoxicity coefficient = Tc actual toxicity index of the mixture tc = theoretical toxicity index of the mixture For Tc values greater than 100, a larger value indicates a strong synergistic action. For a value of Tc equal to 100, an additive action is indicated. For Tc values less than 100, lower values indicate a mostly antagonistic action. A more detailed description of the cotoxicity coefficient calculations using the aforementioned Sun and Johnson Formula is as follows: The LC50 values of Test Compound A alone and of Test Compound B alone and the LC50 value of the mixture (A + B), M.

The actual toxicity index of the mixture M = M 1.

Each LC50 value of ingredient A effective and of the effective ingredient B and the LC50 value of the mixture A + B, are used to determine the actual toxicity index as shown in the following equation: LC50 of A Mtx = x 100 LC50 of B theoretical toxicity index of the mixture M = Th.M = toxicity index of A x% A in M + * toxicity index of B x% B in M. toxicity index of B = Btl LC50 of A BtX = x 100 LC50 of B toxicity index of A = A 1 Afcl = 100 TABLE I Evaluation of the Effect of Test Compounds Against Imagos Female of the Kanzawa Spider Tick with Acquired Resistance Against Clorfenapir COMPOSITE OF TEST LC50 (ppm) Chlorfenapyr 1500 BPMC 3200 NAC 2700 Etiofencar 2100 The tested mite was a female aggro of the Kansawa tick spider resistant to chlorfenapyr, which was obtained by a long procedure of artificial selection against chlorfenapyr, in a laboratory, in a colony of tick spiders of Kanzawa that had been collected in field. As the LC50 value of chlorfenapyr against a susceptible strain of the tick spider is about 5 ppm, this strain developed a resistance with a factor of approximately 300 to chlorfenapyr. It is generally known that the effect of the carbamate-type insecticidal agents against tick spiders is weak and that all the carbamate-type insecticidal agents tested showed only low acaricidal effects. TABLE II Evaluation of the Effect of Test Mixtures Against Imagos Female of the Kanzawa Tick Spider with Acquired Resistance Against Clorfenapyr TEST MIX Ratio tc LC50 (Clorfena (ppm) pir: carbamate Clorfenapir + BPMC 1: 10 310 940 Clorfenapir + NAC 1: 10 480 520 Clorfenapyr + Etiofencarb 1: 10 440 460 As can be seen from the data in Table II, the coefficient of cotoxicity of the mixtures of is a value greater than 100, which indicates a strong synergistic action between chlorfenapyr and BPMC, NAC or Etiofencarb. Although the detailed mechanism of the synergistic action of the composition according to the present invention is not clear, it is estimated that the metabolic system (group of enzymes), with which tick spiders that have developed resistance to chlorfenapyr are detoxified and decompose the compound, is inhibited by a carbamate-type insecticidal ingredient or ingredients to demonstrate such action. Therefore, a second ingredient of the insecticidal and acaricidal composition is thought to be not limited to the carbamate-type insecticidal agents tested in the aforementioned Examples and the carbamate-type insecticidal agents specifically named above. It is noted that in relation to this date, the best method known to the applicant to carry out the aforementioned invention, is that which is clear from the present description of the invention.

Claims (8)

1. CLAIMS Having described the invention as an antecedent, the content of the following claims is claimed as property: 1. An insecticidal and acaricidal composition, characterized in that it contains chlorfenapyr [4-bromo-2- (4-chlorophenyl) -1 as active ingredients. - (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile] in combination with at least one carbamate-type insecticidal compound
2. 2. The composition according to claim 1, characterized in that the carbamate-type insecticidal compound is selected from group consisting of 2-sec-butylphenyl-N-methylcarbamate, 2-isopropylphenyl-N-methylcarbamate, m-tolyl-N-methylcarbamate, 3,4-xylyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate, 2- isopropoxyphenyl-N-methylcarbamate, 3, 5-xylyl-N-methylcarbate, (Z) -N-benzyl-N-. { [methyl- (1-methylthioethylideneaminoxycarbonyl) -amino] -thio} ethyl β-alaninate, 2- (ethylthiomethyl) -phenyl methylcarbamate, methyl N, N'-dimethyl-N- [(methylcarbamoyl) -oxy] -1-thioxamidate, 2,3-dihydro-2 carbamate, 2-dimethyl-7-benzo [b] -furanyl-N-dibutylaminothio-N-methyl, 3,7,9, 13-tetramethyl-5,11-dioxa-2, 8, 14-trityl-4, 7, 9 , 12-tetraazapentadeca-3, 12-dien-6, 10-dione, 2-dimethylamino-5,6-dimethylpyrimidin-4-yl dimethylcarbamate, 2,2-dimethyl-l, 3-benzodioxol-4-yl methylcarbamate , N- [2,3-dihydro-2,2-dimethylbenzofuran-7-yloxycarbonyl- (methyl) -aminothio] -N-isopropyl-β-alaninate ethyl and (S) -N- [(methylcarbamoyl) -oxi] -Methyl thioacetimidate.
3. 3. The composition according to claim 2, characterized in that the carbamate-type insecticidal compound is selected from the group consisting of 2-sec-butylphenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate and 2- (ethylthio ethyl) -phenylmethylcarbamate . The composition according to any of claims 1 to 3, characterized in that the chlorfenapyr is present in a ratio of about 1 part by weight to about 0.01-100 parts by weight of the carbamate-type insecticidal ingredient (s). The composition according to claim 4, characterized in that the ratio is from about 1 part by weight of chlorfenapyr to about 0.5-20 parts by weight of the carbamate-type insecticidal ingredient (s). 6. A process for the preparation of a composition according to claim 1, characterized in that it comprises mixing the active ingredients with a horticulturally acceptable solid or liquid carrier. The process according to claim 6, characterized in that the active ingredients comprise chlorfenapyr in combination with at least one compound selected from the group consisting of 2-sec-butylphenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate and 2- (ethylthiomethyl) -phenylmethylcarbamate. The process according to claim 7, characterized in that the chlorfenapyr is present in a ratio of about 1 part by weight to about 0.5-20 parts by weight of at least one compound selected from the group consisting of 2-sec. -butylphenyl-N-methylcarbamate, 1-naphthyl-N-methylcarbamate and 2- (ethylthiomethyl) -phenylmethylcarbamate.