MXPA99005069A - 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 one or more compounds selected from the organophosphoric acid ester-type compounds represented by general formulae (I) or (II), wherein X represents oxygen or sulfur atom, Y represents oxygen or sulfur atom, group or single bond represented by -S(CH2)nS- (n is 1 or 2), R1 represents C1-C6 alkyl group, R2 represents C1-C8 alkoxy group, C1-C8 alkylthio group, C1-C4 alkylcarbonylamino group, C1-C6 alkylamino group or phenyl group, and R3 represents C1-C8 alkyl group, C2-C6 alkenyl group, amino group, phenyl group, or heteroaryl group, which are substituted by 1 to 4 same or different substituents selected from the substituent group A mentioned below or formula (III) (wherein R1, R2 and X mean the same as the above-mentioned) or unsubstituted. Substituent group A:C1-C8 alkyl group, C1-C8 alkoxy group, C1-C6 aliphatic acyl group, C1-C6 alkoxy-carbonyl group, C1-C6 alkylthio group, C1-C6 alkylamino group, di-C1-C6 alkylamino group, C1-C4 alkylsulfinyl group, C1-C4 haloalkyl group, N-C1-C4 alkylcarbamoyl group, N,N-di-C1-C4 alkylcarbamoyl group, N-C1-C4 alkyl-N-formylcarbamoyl group, heteroaryl group which may be substituted, phenyl group which may be substituted, halogen atom, nitro group, cyano group, hydroxy group and acetylamino group. 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- (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile (hereinafter referred to as chlorfenapyr) which is an active ingredient of the insecticidal and acaricidal composition of the present invention, it is known that is effective against insects such as insect pests such as leafhoppers (Doltocephalidae), lepidopteran pests such as the diamond back moth (Plutella xylostella), the common pruning caterpillar (Spodoptera li tura) and the leaf-eating insect of the apple tree (Phyllonoycter ringoniella) and thysanoptera pests such as Thrips palmi and the insect of yellow leaf tea (Spirtothrips dorsalis) and horticultural pests such as mites, such as the tick spider of REF: 30007 two spots (Tetranychus urticae koch), the tick spider of Kanzawa (Tetranychus kanzawai kishida) and Aculops pelekassi [Publication of Japanese Patent Laid-open (Kokai) No. 104042/89]. The second active ingredient of the insecticidal and acaricidal composition of the present invention includes one or more organophosphoric acid ester compounds which are known to be effective insecticidal and acaricidal agents against horticultural pests such as hemipterans, lepidoptera and coleoptera insects and mites, besides being fungicidal agents against diseases coming from the air and the soil in rice fields. 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 spider ticks (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, they require only a few days for development, they 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. Nevertheless, this approach does not necessarily produce satisfactory control of pests. Therefore, after 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 organophosphoric acid ester type compounds demonstrates a joint action or synergistic effect, which could not be anticipated from of each individual ingredient alone. 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 (Del tociphalidae), Coccinea, insects of the family Thripidae, diamondback moth (Plutella xylostella), Mamestra brassicae, leaf beetles (Chrysomelidae) , white flies (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. The compounds of the organophosphoric acid ester type, which are suitable for use as a second active ingredient in the composition according to the present invention, are compounds represented by the General Formulas (I) or (II), wherein X represents an oxygen atom or a sulfur atom, Y represents an oxygen atom or a sulfur atom, a radical represented by -S (CH2) nS- (where n is 1 or 2) or a single bond , R1 represents an alkyl radical of 1 to 6 carbon atoms, R represents an alkoxy radical of 1 to 8 carbon atoms, thioalkyl of 1 to 8 carbon atoms, alkylcarbonylamino of 1 to 4 carbon atoms, alkylamino of 1 to 6 carbon or phenyl atoms and R represents an alkyl radical of 1 to 8 carbon atoms, alkenyl of 2 to 6 carbon atoms, amino, phenyl or heteroaryl, which are substituted or unsubstituted with 1 to 4 same or different substituents, which are selected from the group of substituents Group A mentioned above, or the following Formula (III). (wherein R 1, R 2 and X are as previously mentioned) Group A of Substituents: alkyl radical of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, aliphatic acyl of 1 to 6 carbon atoms, alkoxycarbonyl from 1 to 6 carbon atoms, thioalkyl of 1 to 6 carbon atoms, alkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 atoms carbon, N-alkylcarbamoyl of 1 to 4 carbon atoms, N, N-dialkylcarbamoyl of 1 to 4 carbon atoms, N-alkyl-N-formylcarbamoyl of 1 to 4 carbon atoms, heteroaryl which may be substituted, phenyl which may be substituted, a halogen atom, a nitro, cyano, hydroxy and acetylamino radical In General Formulas (I) and (III), the term "alkyl radical of 1 to 6 carbon atoms" in the definition of R1 is a straight or branched chain alkyl radical having from 1 to 6 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, 2-methylbutyl, neopentyl, 1-ethylpropyl , n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3, 3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl , 2,3-dimethylbutyl and 2-ethylbutyl. In General Formulas (I) and (III), the term "alkoxy radical of 1 to 8 carbon atoms" in the definition of R, is a straight or branched chain alkoxy radical having from 1 to 8 carbon atoms, such as, for example, methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, i-pentoxy, 2-ethylbutoxy, neopentoxy, n-hexyloxy , 4-methylpentoxy, 3-ethylpentoxy, 2-methylpentoxy, 3, 3-dimethylbutoxy, 2,2-dimethylbutoxy, 1, 1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, n heptyloxy and n-octyloxy. The term "thioalkyl radical of 1 to 8 carbon atoms" in the definition of R is a straight or branched chain thioalkyl radical having from 1 to 8 carbon atoms, such as, for example, thiomethyl, thioethyl, n-propylthio , i-propylthio, n-butylthio, n-pentylthio, n-hexylthio, n-heptylthio and n-octylthio. The term "alkylcarbonylamino radical of 1 to 4 2 carbon atoms" in the definition of R, is a carbonylamino group to which is attached a straight or branched chain alkyl radical having from 1 to 4 carbon atoms, such as for example , methylcarbonylamino, ethylcarbonylamino, n-propylcarbonylamino, i-propylcarbonylamino, n-butylcarbonylamino, s-butylcarbonylamino and t-butylcarbonylamino. The term "alkylamino radical of 1 to 6 carbon atoms" in the definition of R, is an amino group to which is attached a straight or branched chain alkyl radical having from 1 to 6 carbon atoms, such as for example , methylamino, ethylamino, n-propylamino, i-propylamino, n-butylamino, i-butylamino, s-butylamino, t-butylamino, n-pentylamino and n-hexylamino.

In General Formulas (I) and (II), the term "alkyl radical of 1 to 8 carbon atoms" in the definition of R3 and Group A of substituents, is a straight or branched chain alkyl radical having 1 to 8 carbon atoms. to 8 carbon atoms, such as, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, 2-methylbutyl, neopentyl, 1- ethylpropyl, n-hexyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 3, 3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3- dimethylbutyl, 2,3-dimethylbutyl, 2-ethylbutyl, n-heptyl and n-octyl. The term "2- to 6-carbon-3-carbon alkenyl" in the definition of R is a straight or branched chain alkenyl radical having from 2 to 6 carbon atoms, such as, for example, vinyl, 1-propenyl, 2-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, 2-methyl-2-propenyl, 2-ethyl-2-propenyl, 1-butenyl, 2-butenyl, 1-methyl-2 butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-ethyl-2-butenyl, 3-butenyl, l-methyl-3-butenyl, 2-methyl-3-butenyl, l-ethyl- 3-butenyl, 1-pentenyl, 2-pentenyl, l-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-pentenyl, l-methyl-3-pentenyl, 2-methyl-3-pentenyl, 4- pentenyl, l-methyl-4-pentenyl, 2-methyl-4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl and 5-hexenyl. The term "heteroaryl radical" in the definition of R3 and Group A of substituents, is a 5- to 8-membered heterocyclic radical which can be condensed and which contains from 1 to 5 identical or different atoms which are selected from the group consisting of oxygen atoms, sulfur atoms and nitrogen atoms, such as, for example, furanyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, thienyl, pyridyl, pyridazinyl, pyrazolyl, imidazolyl, triazinyl, thiadiazolyl, imidazothiazolyl, benzoisoxazolyl, chromenyl, quinolinyl , benzothianyl, quinixalinyl and benzotriazinyl. The term "alkoxy radical of 1 to 8 carbon atoms" in the definition of Group A of substituents is a straight or branched chain alkoxy radical having from 1 to 8 carbon atoms, such as for example methoxy, ethoxy, n- propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, n-pentoxy, i-pentoxy, 2-methylbutoxy, neopentoxy, n-hexyloxy, 4-methylpentoxy, 3-methylpentoxy, 2- methylpentoxy, 3,3-dimethylbutoxy, 2,2-dimethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,3-dimethylbutoxy, n-heptyloxy and n-octyloxy. The term "aliphatic acyl radical of 1 to 6 carbon atoms" in the definition of Group A substituents is a straight or branched chain aliphatic acyl radical with 1 to 6 total carbon atoms, for example, formyl, acetyl, propionyl, butyryl and valeryl. The term "alkoxycarbonyl radical of 1 to 6 carbon atoms" in the definition of Group A substituents is a carbonyl radical to which is attached a straight or branched chain alkoxy radical having from 1 to 6 carbon atoms, such as for example, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, t-butoxycarbonyl, n-pentoxycarbonyl and n-hexyloxycarbonyl. The term "thioalkyl radical of 1 to 6 carbon atoms" in the definition of Group A substituents is a straight or branched chain thioalkyl radical having 1 to 6 carbon atoms, such as, for example, thiomethyl, thioethyl, n-propylthio, i-propylthio, n-butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio and n-hexylthio. The term "C 1 -C 6 alkylamino radical" in the definition of Group A substituents, is an amino radical to which is attached a straight or branched chain alkyl radical having from 1 to 6 carbon atoms, such as for example, methylamino, ethylamino, n-propylamino, i-propylamino, n-butylamino, i-butylamino, s-butylamino, t-butylamino, n-pentylamino and n-hexylamino.

The term "dialkylamino radical of 1 to 6 carbon atoms" in the definition of Group A substituents is an amino radical to which are attached two identical or different straight or branched chain alkyl radicals having from 1 to 6 carbon atoms , for example dimethylamino, diethylamino, methylethylamino, dipropylamino and dibutylamino. The term "alkylsulphinyl radical of 1 to 4 carbon atoms" in the definition of Group A substituents is a sulfinyl radical to which a straight or branched chain alkyl radical having 1 to 4 carbon atoms is attached, such as for example, methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, i-butylsulfinyl, s-butylsulfinyl and t-butylsulfinyl. The term "haloalkyl radial of 1 to 4 carbon atoms" in the definition of Group A substituents is a straight or branched chain haloalkyl radical having from 1 to 4 carbon atoms, for example fluoromethyl, chloromethyl, bromomethyl, difluoromethyl , dichloromethyl, dibromomethyl, trifluoromethyl, trichloromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 3-chloropropyl, 3-bromopropyl, 2, 2, 3, 3, 3 - pentafluoropropyl, 2,2,2-trifluoro-1-methylethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and 2,2,3,3,4,4,4-heptafluorobutyl. The term "N-alkylcarbamoyl radical of 1 to 4 carbon atoms" in the definition of Group A substituents is a carbamoyl radical to which is attached a straight or branched chain alkyl radical having from 1 to 4 carbon atoms, such as, for example, N-methylcarbamoyl, N-ethylcarbamoyl, Nn-propylcarbamoyl, Ni-propylcarbamoyl, Nn-butylcarbamoyl, Ni-butylcarbamoyl, Ns-butylcarbamoyl and Nt-butylcarbamoyl. The term "N, N-dialkylcarbamoyl radical from 1 to 4 carbon atoms "in the definition of the Group A of substituents, is a carbamoyl radical to which two identical or different straight or branched chain alkenyl radicals are linked, having 1 to 6 carbon atoms, such as for example N , N-dimethylcarbamoyl, N, N-diethylcarbamoyl, N-ethyl-N-methylcarbamoyl, N-methyl-N-propylcarbamoyl and Ni-propyl-N-methylcarbamoyl The term "N-alkyl-N-formylcarbamoyl radical from 1 to 4 carbon atoms "in the definition of Group A substituents, is a formylcarbamoyl radical to which is attached a straight or branched chain alkyl radical having from 1 to 4 carbon atoms, such as for example, N-formyl-N- methylcarbamoyl, N-ethyl-N-formylcarbamoyl, N-formyl-Nn-propylcarbamoyl, N-formyl-Ni-propylcarbamoyl, N-formyl-Nn-butylcarbamoyl, N-formyl-Ni-butylcarbamoyl, N-formyl-Ns-butylcarbamoyl and N-formyl-Nt-butylcarbamoyl The term "halogen atom" in the definition of Group A substitute For example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Among the exemplary generic and chemical names of the organophosphoric acid esters represented by the general formulas (I) and (II) are those names that are shown below. However, these examples are not intended to limit the scope of the present invention. Name Chemical Name Generic: BRP: Dimethyl-1, 2-dibromo-2, 2-dichloroethylphosphate CVMP: 2-chloro-l- (2,4,5-trichlorophenyl) -vinyldimethylphosphate CVP: 2-chloro-l- (2, 4-dichlorophenyl) -vinyldiethylphosphate CYAP: 0, G-dimethyl-0-p-cyanophenylthiophosphate DDVP: Dimethyl-2,2-dichlorovinylphosphate DEP: Dimethyl-2,2,2-trichloro-l-hydroxyethyl phosphate DMTP: 0,0-dimethyl -S- [5-methoxy-l, 3,4-thiadiazol-2 (3H) nil- (3) -methyl] -dithiophosphate EPN: ethyl p-nitrophenylbenzenephosphonate ESP: Dimethylethylsulfinyl isopropylthiophosphate (IBP): 0-diisopropyl-S- MEP benzylthiophosphate: 0,0-dimethyl-0- (3-methyl-4-nitrophenyl) -thiophosphate MPP: 0,0-dimethyl-O- [3-methyl-4- (thiomethyl) -phenyl] -thiophosphate PAP: Dimethyldithiophosphorylphenylacetate of ethyl PMP: 0, 0-dimethyl-S-phthalimidomethylthiophosphate Acetate: 0, S-dimethyl-N-acetylphosphoramidothioate Isoxatión: 0, 0-dietil-0- (5-phenyl-3-isoxazolyl) -phosphorothioate Isofenfos: 0-etil-0-2- isopropoxycarbonylphenylisopropylphosphoramidothioate Etión: 0, 0 ', 0' -tetraetil-S, S '-metilenbisfosforoditioato Ethylthiometon: 0, 0-diethyl-S-2- (ethylthio) -ethyl phosphorodithioate Etrimphos: 0-6-ethoxy-2-ethylpyrimidin-4-yl-0,0- dimethylphosphorothioate Quinalfos: 0,0-diethyl-0-quinoxalin- 2-yl-phosphorothioate Chlorpyrifos: 0, 0-diethyl-0-3, 5,6-trichloro-2-pyridylphosphorothioate Chlorpyrifosmethyl: 0, O-dimethyl-O-3, 5,6-trichloro-2-pyridylphosphorothioate Salithion: 2 -methoxy-4H-l, 3, 2-benzodioxafosforin-2-sulfur Dimethylvinfos: 2-chloro-l- (2,4-dichlorophenyl) -vinyl dimethylphosphate dimethoate: 0,0-dimethyl-S- (N-methylcarbamoylmethyl) -dithiophosphate Sulphophos: 0-ethyl-0-4-methylthiophenyl-S-propyl-phosphorodithioate Diazinon: (2-isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate Tiometon: Dimethyl-S-ethylthioethyldithiophosphate Vomidothion: Dimethyl-methylcarbamoylethylthioethylphosphorothioate Piraclofos: (RS) - (0-1- (4-chlorophenyl) -pyrazol-4-yl) -O-ethyl-S-propyl-phosphorothioate Pyridaffention: 0,0-diethyl-0- (3-oxo-2-phenyl-2H-pyridazin- 6-yl) -phosphoirothioate Pyrimiphosmethyl: 2-diethylamino-6-methylpyrimidin-4-yl-dimethylphosphorothioate Protiofos: 0-2,4-dichlorophenyl-O-ethyl-S-propylphosphorodithioate Propaphos: 0,0-dipropyl-0-4- methylthiophenilphosphate Profenofos: 0-4-bromo-2-chlorophenyl-0-ethyl-S-propyl-phosphorothioate Fosalone: 3-diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone Formothion: 0,0-dimethyl-S- (N-methyl-N-formylcarbamoyl) - Dithiophosphate Malathon: Dimethyldicarbethoxyethyldithiophosphate Monocrotophos: 3- (dimethoxyphosphinyloxy) -N-methyl-cis-crotonamide The names of the abovementioned insecticidal and fungicidal agents are generic names written in "Agrochemicals Handbook 1992 Edition" published on July 30, 1992 by the Japanese Plant Protection Association and "SHIBUYA INDEX-1996- (7th Edition)" published on April 1, 1996 by ZENNOH. In the present invention, among the aforementioned agents, especially preferred are 0.0-dimethyl-Op-cyanophenylthiophosphate (CYAP), ethyl para-nitrophenylbenzenephosphonate (EPN), 0.0-diisopropyl-S-benzylthiophosphate (IBP), 0,0-dimethyl-O- (3-methyl-4-nitrophenyl) -thiophosphate (MEP), 0,0-dimethyl-O- [3-methyl-4- (thiomethyl) -phenyl] -thiophosphate (MPP), Ethyl dimethyl dithiophosphenylphenylacetate (PAP), 0.01 ', 0'-tetraethyl-S, S'-methylenebiphosphorodithionate (Ethion), 0-diethyl-0-3,5,6-trichloro-2-pyrilphosphothioate (Chlorpyrifos), 0, 0-dimethyl-0-3, 5,6-trichloro-2-pyridylphosphorothioate (Chlorpyrifosmethyl), 0-ethyl-0-4-methylthiophenyl-S-propyl-phosphorodithioate (Sulprofos), (2-isopropyl) -4-methylpyrimidyl-6) -diethylthiophosphate (Diazinon), 0.0-diethyl-O- (3-oxo-2-phenyl-2H-pyridazin-6-yl) -phosphorothioate (Pyridaffention), 0-2, 4- dichlorophenyl-O-ethyl-S-propylphosphorodithioate (Protiofos), 3-diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone (Fosalone) and dimethyl dicarbetoxyethyldithiophosphate (Malathon), due to its 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 the organophosphoric acid ester compound or compounds, with a suitable vehicle and auxiliaries, such as emulsifiers, 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. Various surfactants, stabilizers and other auxiliary ingredients can be used, 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 the organophosphoric acid ester compound or compounds 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 0.5-0.20. parts by weight of a compound or compounds of the organophosphoric acid ester type. 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 the compound or compounds of the organophosphoric acid ester type, is from about 0.1 to 1000 g, preferably from about 20 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 CYAP 40 parts Xylene 25 parts Dimethylformate 20 parts Sorpol 3005X 0 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 PAP 50 parts Carplex # 80 15 parts (White carbon manufactured by Shionogi &Co., Ltd., trade name) Zeeklite SP 22 parts (Mixture of kaolinite and cericite manufactured by Zeeklite Ind., Trade name) Calcium lysisulfonate 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 Chlorpyrifosmethyl 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, Chlorpyrifosmethyl 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 MEP 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 (adult) imagos of the Kansawa tick spider (Tetranychus kanzawai kishida) was evaluated, with resistance to chlorfenapyr. 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 an organophosphoric acid ester compound or compounds 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 • = X 100 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 coefficient of co-toxicity 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. are determined.

The actual toxicity index of the mixture M = Mtl.

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 M theoretical toxicity index of the mixture M = Th.Mt :? = toxicity index of A x% A in M + toxicity index of B x% B in M. toxicity index of B = Bt: " LC50 of A Btx = x 100 LC50 of B toxicity index of A = Atx A l = 100 TABLE I Evaluation of the Effect of Test Compounds Against Imagos Female of the Kanzawa Spider Tick with Acquired Resistance Against Clorfenapir TEST COMPOUND LC50 (ppm) Chlorfenapyr 1500 CYP 3200 EPN 3100 IBP 1300 MEP 3200 MPP 1100 PAP 2000 Etium 3100 Chlorpyrifos 3200 Chlorpyrifosmethyl 790 Sulphophobes 320 Diazinon 3200 Pyridathione 1900 Phosphonates 260 Phosalone 350 Malathion 3400 The tested mite was a female imago 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 Kanzawa tick spiders that had been collected in the countryside. 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. As this Kansawa tick spider came from a colony that had acquired resistance to the organophosphoric acid esters already at the time of being collected in the field, all tested organophosphoric acid esters 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 LC50 (Clorfena (ppm) pir: another ingredient) Chlorfenapyr + CYAP 1: 8 310 920 Chlorfenapyr + EPN 1: 9 300 930 Chlorfenapyr + IBP 1:12 460 290 Chlorfenapyr + MEP 1:11 130 2300 Clorfenapyr + MPP 1:10 290 390 Chlorfenapyr + PAP 1:10 180 1100 Clorfenapyr + Erosion 1:10 120 2400 Clorfenapyr + Chlorpyrifos 1: 8 220 1300 Clorfenapyr + Chlorpyrifosmethyl 1: 5 97 880 Chlorfenapyr + Sulphophos 3:20 170 210 Chlorfenapyr + Diazinon 5: 34 430 650 Chlorfenapyr + Pyridathione 1:10 340 550 Chlorfenapyr + Protiofos 1: 9 100 280 Chlorfenapyr + Fosalone 1: 7 180 220 Chlorfenapyr + Malathion 1:10 370 820 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 the compound or compounds of the ester type of organophosphoric acid. . 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 an organophosphoric acid ester compound or compounds to demonstrate such action. Therefore, a second ingredient of the insecticidal and acaricidal composition is thought to be not limited to the organophosphoric acid ester compounds tested in the aforementioned Examples and the organophosphoric acid ester type compounds 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 (15)

2. The invention having been described as an antecedent, it is recounted as a counting property in the following claims: 1. An insecticidal and acaricidal composition, characterized in that it contains as active ingredients 4-bromo-2- (4-chlorophenyl) -1- ( ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3-carbonitrile (chlorfenapyr) in combination with one or more compounds selected from the group consisting of organophosphoric acid ester compounds, represented by the General Formulas (I) or ( II) wherein X represents an oxygen or sulfur atom, Y represents an oxygen or sulfur atom, a radical represented by -S (CH2) nS- (where n is 1 or 2) or a single bond, R1 represents a alkyl radical of 1 to 6 carbon atoms, R represents an alkoxy radical of 1 to 8 carbon atoms, thioalkyl of 1 to 8 carbon atoms, alkylcarbonylamino of 1 to 4 carbon atoms, alkylamino of 1 to 6 carbon atoms or phenyl, 3 R represents an alkyl radical of 1 to 8 carbon atoms, alkenyl of 2 to 6 carbon atoms, amino, phenyl or heteroaryl, which may be unsubstituted or may be substituted with 1 to 4 same or different substituents, which are selected from the group A of substituents mentioned above, or represented by the following Formula (III)
3. R'- O X '\ P - (111) R * X (where R, R and X are like previously mentioned) . Group A of substituents: alkyl radical of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, acylalytic of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 6 carbon atoms, thioalkyl of 1 to 6 carbon atoms , alkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, N-alkylcarbamoyl of 1 to 4 carbon atoms, N, N-dialkylcarbamoyl of 1 to 4 carbon atoms, N-alkyl-N-formylcarbamoyl of 1 to 4 carbon atoms, heteroaryl which may be substituted, phenyl which may be substituted, a halogen atom, a nitro radical, cyano, hydroxy and acetylamino. The composition according to claim 1, characterized in that the chlorfenapyr is present in a ratio of about 1 part by weight to about 0.01-100 parts by total weight of one or more compounds of the organophosphoric acid ester type. 3. The composition according to any of claims 1 or 2, characterized in that the compounds of the organophosphoric acid ester type are at least one of the following described in items 1 to 15: 1) O, O-dimethyl- Op-cyanophenylthiophosphate 2) ethyl p-nitrophenylbenzenephosphonate 3) 0,0-diisopropyl-S-benzylthiophosphate
4. 4) O, O-dimethyl-O- (3-methyl-4-nitrophenyl) -thiophosphate
5. 5) O, O-dimethyl- O- [3-methyl-4- (thiomethyl) -phenyl] -thiophosphate
6. 6) Ethyl dimethyldithiophosphorylphenylacetate
7. 7) 0,0,0 ', 0'-tetraethyl-S, S' -methylenebisphosphorodithioate
8. 8) 0, 0-diethyl-0-3,5,6-trichloro-2-pyridylphosphorothioate
9. 9) 0, O-dimethyl-O-3, 5,6-trichloro-2-pyridylphosphorothioate
10. 10) 0-ethyl-0-4-methylthiophenyl-S-propyl-phosphorodithioate
11. 11) (2-isopropyl-4-methylpyrimidyl-6) -diethylthiophosphate
12. 12) 0,0-Diethyl-O- (3-oxo-2-phenyl-2H-pyridazin-6-yl) -phosphorothioate
13. 13) 0-2, 4-dichlorophenyl-0-ethyl-S-propylphosphorodithioate
14. 14) 3-diethoxyphosphorylthiomethyl-6-chlorobenzoxazolone
15. 15) Dimethyldicarbethoxyethyldithiophosphate 4. The composition according to claim 1, characterized in that the chlorfenapyr is present in a ratio of about 1 part by weight to about 0.01-100 parts by total weight of one or more organophosphoric acid ester compounds which are selected from among the compounds described in claim 3. The composition according to claim 1, characterized in that the ratio is about 1 part by weight of chlorfenapyr to about 0.5-20 parts by total weight of one or more compounds of the organophosphoric acid ester type selected from the compounds described in claim 3. 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. 7. The process according to claim 6, characterized in that the active ingredients comprise chlorfenapyr in combination with one or more compounds of the organophosphoric acid ester type selected from the compounds described in claim 3. 8. The compliance process with 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 one or more compounds of the organophosphoric acid ester type which are selected from the compounds described in the claim 3. SUMMARY OF THE INVENTION The present invention relates to an insecticidal and acaricidal composition which contains as active ingredients chlorfenapyr (4-bromo-2- (4-chlorophenyl) -1- (ethoxymethyl) -5- (trifluoromethyl) -pyrrole-3- carbonitrile in combination with one or more compounds selected from the group consisting of organophosphoric acid ester compounds, represented by the General Formulas (I) or (II), wherein X represents an oxygen or sulfur atom, Y represents an oxygen or sulfur atom, a radical represented by -S (CH2) nS- (where n is 1 or 2) or a single bond, R represents an alkyl radical of 1 to 6 carbon atoms, R represents an alkoxy radical of 1 to 8 carbon atoms, thioalkyl of 1 to 8 carbon atoms, alkylcarbonylamino of 1 to 4 carbon atoms, alkylamino of 1 to 6 carbon atoms or phenyl, R represents an alkyl radical of 1 to 8 carbon atoms, alkenyl of 2 to 6 carbon atoms, amino, phenyl or heteroaryl, which may be substituted with 1 to 4 identical or different substituents, which are selected from the group A of substituents mentioned above, or Formula (III), (wherein R 1, R 2 and X are as previously mentioned) or unsubstituted. Group A of substituents: alkyl radical of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms, aliphatic acyl of 1 to 6 carbon atoms, alkoxycarbonyl of 1 to 6 carbon atoms, thioalkyl of 1 to 6 carbon atoms carbon, alkylamino of 1 to 6 carbon atoms, dialkylamino of 1 to 6 carbon atoms, alkylsulfinyl of 1 to 4 carbon atoms, haloalkyl of 1 to 4 carbon atoms, N-alkylcarbamoyl of 1 to 4 carbon atoms, N , N-dialkylcarbamoyl of 1 to 4 carbon atoms, N-alkyl-N-formylcarbamoyl of 1 to 4 carbon atoms, heteroaryl which may be substituted, phenyl which may be substituted, a halogen atom, a nitro radical, cyano, hydroxy and acetylamino. The insecticidal and acaricidal composition according to the present invention is effective against pests and mites that are resistant to commercial insecticidal and acaricidal agents.