JPH0460114B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel nitromethylene derivative, a method for producing the same, and an insecticide. More specifically, the present invention relates to a novel nitromethylene derivative represented by the following formula (). General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3. Further, the nitromethylene derivative of the above formula () of the present invention can be produced by the following method, and the present invention also relates to this production method. ) Manufacturing method: General formula: In the formula, R, m and n are the same as above, and a compound represented by the general formula: In the formula, R' represents a lower alkyl or benzyl group, or two R's taken together represent a lower alkylene group of C2 _or more, which may form a ring with the adjacent sulfur atom, A method for producing a nitromelene derivative of the general formula (), which comprises reacting the compound represented by the formula (2). The present invention also relates to an insecticide containing the nitromethylene derivative of the general formula () as an active ingredient. The compound of the general formula (), which is an intermediate for the production of the nitromelene derivative of the general formula () of the present invention, is a new compound that has not been described in any known publication before the filing date of the present invention, and the compound of the general formula () is , the following method). ) Manufacturing method: - General formula: In the formula, R and n are the same as above, and X represents a halogen atom or a group _-OSO2R '', where R'' represents a lower alkyl group or an aryl group, and a compound represented by the general formula: H ₂ N-(CH ₂ )m-NH ₂ () In the formula, m is the same as above. A method for producing a compound of the general formula (), which is characterized by reacting with a compound represented by the following. West German patent publication number known before the filing date of the present application
No. 2514402 has the following general formula It is described that 2-nitromethylene-imidazolidine derivatives and 2-nitromethylene-hexahydropyrimidine derivatives represented by the following have insecticidal activity. The case where n = 2, R ₁ = phenyl-(C ₁ -C ₂ ) alkyl group, and R ₂ = R ₃ = hydrogen atom is included, and in the specification, a compound represented by the following formula is described. has been done. Similarly, in West German patent publication number 2732660,
General formula below It is described that a 1-substituted benzyl-2-nitromethylene-imidazolidine derivative represented by the following formula has insecticidal activity. The specification describes a compound represented by the following formula. The present inventors have carried out the synthesis and biological screening of nitromelene-tetrahydropyrimidine-based compounds and nitromelene-imidazolidine-based compounds in order to create novel useful compounds with biological activity. We succeeded in synthesizing a nitromelene derivative of the general formula (), which has not been described in any literature, and discovered that this compound has excellent control activity against harmful insects. According to the knowledge obtained by the present inventors, the nitromelene derivative specified by the general formula () of the present invention is a novel compound that has never been described in any prior art literature. The compound of the present invention is characterized by its chemical structure consisting of 2
-nitromethylene-tetrahydropyrimidine, or 2-nitromethylene-imidazolidine, and also 2-nitromethylene-hexahydro-1,
The basic skeleton is 3-diazepine, and one of the heterocycles is
As is clear from the above general formula (), the nitrogen atom at the - position is substituted with a 2-chloro-5-pyridyl alkyl group, and surprisingly, the chemical structure and high activity (control) It was found that there is an excellent correlation between Furthermore, as will be specifically shown later, the compound of the present invention has a lower It was discovered that it has extremely excellent control activity at a low dosage. Furthermore, the compounds of the present invention can be used against insects that are resistant to organophosphorus and carbamate insecticides that have been used for many years, particularly those of the order Hemiptera (Hemiptera). puncture-absorbing pests represented by (tera),
For example, it was discovered that it has a remarkable control effect on aphids, planthoppers, leafhoppers, etc. In addition, in the method for producing the compound of general formula () of the present invention, the compound of general formula (), which is an intermediate thereof, is also a new compound that has never been described in any prior art document, and as described above. As such, it is a compound that is useful as an industrially useful intermediate for the compound of general formula (). Therefore, an object of the present invention is to provide a novel nitromethylene derivative of the general formula (), a method for producing the same, and its use as an insecticide. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The active compound of the present invention exhibits an accurate control effect against harmful insects without causing any phytotoxicity to cultivated plants. Furthermore, the compounds of the present invention can be used to control a wide variety of pests, such as harmful sap-sucking insects, biting insects, and other plant-parasitic pests, storage pests, sanitary pests, etc., and can be applied to exterminate them. Examples of such pests include the following. Insects include Coleoptera pests, such as the bean weevil (Callosobruchus chinensis),
Sitophilus zeamais, Tribolium castaneum, Epilachna
vigihtioctomaculata), Agriotes fuscicollis, Anomala rufocuprea, Colorado potato beetle (Leptinotarsa decemkineata), Diabrotica spp., Monochamus alternatus, rice weevil (Lissorhoptrus oryzophilus) ), Hirataki beetle (Lyctus bruneus); Lepidopteran insects, such as the gypsy moth (Lymantria dispar), the porcupine beetle (Malacosoma neustria), and the green caterpillar (Pieris).
rapae), Spodoptera litura,
Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria
mellonella), diamondback moth (Plutella maculipennis),
Orange leafhopper (Phyllocnistis citrella); Hemiptera insects, such as Nephotettix cincticeps,
Brown planthopper (Nilaparvata lygens), Pseudococcus comstocki,
Unaspis yanonesis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp. , Bedbug (Cimex
lectularius), whitefly (Trialeurodes vaporariorum), woodlice (Psylla spp.); orthoptera, such as Blatella germanica, Periplaneta americana, Gryllotalpa africana, Locusta
migratoria migratoriodes); Isoptera, such as deucotermes speratus, Coptotermes formosanus; Diptera, such as Musca domestica, Aedes aegypti, Hylemia
platura), Culex pipiens, Anopheles slnensis, Culex tritaeniorhynchus, and the like. Furthermore, in the field of veterinary medicine, the novel compounds of the invention can be used effectively against various harmful animal parasites (endo- and ectoparasites), such as insects and helminths. Examples of such animal parasites include the following pests. Examples of insects include Gastrophilus spp., Stomoxys spp., and Trichodectes spp.
spp.), assassin bugs (Rhodnius spp.), and dog fleas (Ctenocephalides canis). In the present invention, a substance having an insecticidal action against all of these insects may be referred to as an insecticide. The nitromethylene derivative of the general formula () of the present invention can be easily produced, for example, by the following method. Manufacturing method):- (In the formula, R, m, n and R' are the same as above.) In the above reaction formula, R represents a lower alkyl group, specifically, methyl, ethyl, propyl, isopropyl, n-(iso-, sec-, or tert-)
Butyl etc. can be exemplified. m represents 2, 3 or 4, and n represents 0, 1, 2 or 3.
R' represents a lower alkyl group or a benzyl group, or two R's together represent a lower alkyl group of C ₂ or more, where specific examples of the lower alkyl group include those exemplified above for R. An example similar to this can be given. Furthermore, two R's together represent a lower alkylene group having C2 _or more, and they may form a ring together with the adjacent sulfur atom; examples of such alkylene groups include, for example, ethylene group, etc. can do. In the method for producing a compound of the general formula () of the present invention shown in the above reaction formula, the general formula () which is a raw material is
Specific examples of compounds include, for example, N-(2-chloro-5-pyridylmethyl)ethylenediamine, N-[2-(2-chloro-5-pyridyl)ethyl]ethylenediamine, N-(2-chloro-5-pyridylmethyl)ethylenediamine, -pyridylmethyl)trimethylenediamine, N-[2-(2-chloro-5-pyridyl)ethyl]trimethylenediamine, N-[1-(2-chloro-5-pyridyl)ethyl]trimethylenediamine, N- [3-(2-chloro-5-pyridyl)propyl]trimethylenediamine, N-[1-(2-chloro-5-pyridyl)ethyl]ethylenediamine, N-(2-chloro-5-pyridylmethyl)tetramethylene Diamine, N-[4-(2-chloro-5-pyridyl)butyl]trimethylenediamine, N-[1-(2-chloro-5-pyridyl)propyl]trimethylenediamine, N-[2-methyl-1 -(2-chloro-5-pyridyl)propyl]ethylenediamine and the like can be exemplified. Similarly, specific examples of compounds of general formula () which are raw materials include: 1-nitro-2,2-bis(methylthio)ethylene, 1-nitro-2,2-bis(ethylthio)ethylene 1-nitro- Examples include 2,2-bis(benzylthio)ethylene, 2-nitromethylene-1,3-dithiolane, and the like. Next, the above manufacturing method will be specifically explained using representative examples. The method for producing the above compounds of the present invention can be carried out desirably using a solvent or a diluent. All inert solvents and diluents can be used for this purpose. Examples of such solvents or diluents include water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as hexane, cyclohexane, petroleum ether, ligroin, benzene, Toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, ethylene chloride and trichloroethylene, chlorobenzene; other ethers such as diethyl ether, methyl ethyl ether, di-iso-propyl ether, dibutyl ether, propylene oxide, dioxane, tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl-iso-propyl ketone, methyl-iso-butyl ketone; nitrites such as acetonitrile,
Propionitrile, acrylonitrile; alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol;
Esters such as ethyl acetate, amyl acetate; acid amides such as dimethylformamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine. The above method can be carried out within a wide temperature range. Generally can be carried out between about -20°C and the boiling point of the mixture, preferably from about 0 to about 100°C.
It can be carried out between Further, although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. The compound of the general formula () of the present invention is produced by the above manufacturing method)
In addition, it can also be produced by another method shown in the reaction formula below. Alternative method 1:- (In the formula, X, R, m and n are the same as above.) Moreover, the compound of the general formula () of the present invention can be produced, for example, by the following method. Manufacturing method):- (In the formula, R, m, n and
Further, X represents a halogen atom of fluoro, chloro, bromo, or iodo, or a group -SO ₂ R'', where,
R'' represents the same lower alkyl group as exemplified in the above production method) or an aryl group such as phenyl, p-tolyl, etc. In the process for producing the compound of the general formula () of the present invention shown in the above reaction formula, General formula () that is the raw material
Specific examples of compounds include 2-chloro-5-pyridylmethyl chloride,
2-(2-chloro-5-pyridyl)ethyl chloride, 1-(2-chloro-5-pyridyl)ethyl chloride 3-(2-chloro-5-pyridyl)propyl chloride, 2-chloro-pyridylmethyl p-toluene Examples include sulfonates and the like. Similarly, specific examples of the compound of general formula () which is a raw material include ethylenediamine, trimethylenediamine, tetramethylenediamine, and the like. Next, the above manufacturing method will be specifically explained using representative examples. When implementing the above method, the same inert solvents and diluents as exemplified in the production method) can be used. Moreover, the above reaction can be carried out in the presence of an acid binder. Such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholates, etc., and tertiary amines such as triethylamine, diethylaniline, pyridine, etc. . Further, the above production method can be carried out within a wide temperature range similar to the above production method, and although it is preferable to carry out the reaction under normal pressure, it is also possible to operate under increased pressure or reduced pressure. In the compound of the general formula (), when R=H and n=0, in addition to the above-mentioned production method, it can also be synthesized by a method represented by the following general formula. Alternative method 2:- In the formula, m is the same as above. As shown in the above reaction formula, Schiff's base is synthesized by the reaction of 6-chloronicotinaldehyde and the compound of general formula (), and a reducing agent such as sodium borohydride (NaBH ₄ ) is added to this. By reacting, a compound of general formula (') can be synthesized. Furthermore, the compound of the above general formula (') can also be synthesized by a method represented by the following general formula. Alternative method 3:- In the formula, m is the same as above. As shown in the above reaction formula, nicotinamide is synthesized by reacting 6-chloronicotinoyl chloride with the compound of general formula (), and by reacting this with a reducing agent such as lithium aluminum hydride (LiAlH ₄ ). , general expression (″)
can be synthesized. Furthermore, in the compound of the general formula (), R
In the case of =H, n=o, and m=3, it can be further synthesized by a method represented by the following general formula. Alternative method 4:- As shown in the above reaction formula, acrylonitrile is added to 5-chloropicolylamine, and this adduct is reduced in the same manner as in Alternative Method 2 above to obtain the target compound N- shown in Compound No.-2 below.
(2-chloro-5-pyridylmethyl)trimethylenediamine can also be synthesized. Furthermore, in the compound of general formula (), m=2
Alternatively, in the case of , it can be synthesized by a method represented by the following general formula. Alternative method 5:- In the formula, R and n are the same as above. As shown in the above reaction formula, 2 of the general formula ()
A compound of the general formula ('') can also be synthesized by reacting -chloro-5-pyridylalkylamine with ethyleneimine. The compound of the present invention can also exist in the form of a salt, and as the salt, Examples of the salts include inorganic acid salts, sulfonate salts, organic acid salts, metal salts, etc. Examples of the salts of the compounds of the present invention include the following: 1-( 2-chloro-5-pyridylmethyl)-2-
(Nitromethylene)tetrahydropyrimidine-hydrochloride, 1-(2-chloro-5-pyridylmethyl)-2-
(nitromethylene)tetrahydropyrimidine-p
-Toluenesulfonate, 1-(2-chloro-5-pyridylmethyl)-2-
(Nitromethylene)imidazolidine-hydrochloride, 1-(2-chloro-5-pyridylmethyl)-2-
(Nitromethylene)imidazolidine-cupric acetate salt. When the compound of the general formula () of the present invention is used as an insecticide, it can be used directly as it is after being diluted with water, or by a method commonly used in the agricultural chemical manufacturing field using an agricultural chemical auxiliary. It can be used in various formulation forms. In actual use, these various formulations can be used directly or diluted with water to a desired concentration. Examples of agrochemical auxiliaries mentioned here include diluents (solvents, extenders, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, fixing agents,
Examples include propellants for aerosols, synergists, and the like. Solvents include water: organic solvent; hydrocarbons [e.g., n-hexane, petroleum ether, petroleum fractions (paraffin wax, kerosene, light oil, middle oil, heavy oil), benzene, toluene, xylenes], halogenated hydrocarbons. [e.g., methylene chloride, carbon tetrachloride, ethylene chloride, ethylene dibromide, chlorobenzene, chloroform], alcohols [e.g., methyl alcohol, ethyl alcohol, propyl alcohol, ethylene glycol], ethers [e.g., ethyl ether, ethylene oxide, dioxane], alcohol ethers [e.g. ethylene glycol monomethyl ether],
Examples include ketones (eg, acetone, isophorone), esters (eg, ethyl acetate, amyl acetate), amides (eg, dimethylformamide, dimethylacetamide), and sulfoxides (eg, dimethyl sulfoxide). Examples of fillers or carriers include inorganic powders such as slaked lime, magnesium lime, gypsum, calcium carbonate, silica, perlite, pumice, calcite,
Diatomaceous earth, amorphous silicon oxide, alumina, zeolite, clay minerals (e.g. pyrophyllite, talc, montmorillonite, beidellite, vermiculite, kaolinite, mica), etc.; vegetable powders such as grain flour, starch, modified starch ,sugar,
Glucose, crushed plant stems, etc.; Synthetic resin powder such as phenol resin, urea resin, vinyl chloride resin, etc. Examples of surfactants include anionic surfactants such as alkyl sulfates (e.g., sodium lauryl sulfate), arylsulfonic acids (e.g., alkylaryl sulfonates,
sodium alkylnaphthalene sulfonate], succinates, polyethylene glycol alkylaryl ether sulfate salts; cationic surfactants, such as alkylamines [e.g., laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride] , polyoxyethylene alkyl amines; nonionic surfactants such as polyoxyethylene glycol ethers [e.g., polyoxyethylene alkylaryl ethers and condensates thereof], polyoxyethylene glycol esters [e.g., polyoxyethylene fatty acid esters] ], polyhydric alcohol esters [for example, polyoxyethylene sorbitan monolaurate]; amphoteric surfactants; and the like. In addition, stabilizers, fixing agents [e.g., agricultural soap, caseinate lime, sodium alginate, polyvinyl alcohol (PVA), vinyl acetate adhesives, acrylic adhesives], propellants for aerosols [e.g.
Trichlorofluoromethane, dichlorofluoromethane, 1,2,2-trichloro-1,1,2-trifluoroethane, chlorobenzene, LNG, lower ether]: Combustion regulator (for smoking agents) [e.g.
Nitrite, zinc powder, dicyandiamide]: Oxygen supply agent [e.g. chlorate]: Efficacy extender: Dispersion stabilizer [e.g. casein, tragacanth, carboxymethyl cellulose (CMC), polyvinyl alcohol (PVA)]: Synergist can be mentioned. The compounds of the present invention can be manufactured into various formulations by methods commonly practiced in the agricultural manufacturing field. Forms of preparations include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, smoking agents, tablets, aerosols, pastes, capsules, etc. can. The insecticide of the present invention contains the active ingredient, for example about
0.1 to about 95% by weight, preferably about 0.5 to about 90% by weight
It can contain. In actual use, the various formulations and spray preparations described above (ready-to-use)
The active compound content in the preparation) is e.g.
0.0001 to about 20% by weight, preferably about 0.005 to about 10
A range of weight percent is suitable. The content of these active ingredients can be appropriately changed depending on the form of the preparation, the method of application, purpose, timing, location, and pest outbreak status. If necessary, the compound of general formula () of the present invention may be used as an agent for other agricultural purposes, such as insecticides, fungicides, acaricides, nematicides, antiviral agents, herbicides, plant growth regulators, and attractants. , [For example, organic phosphoric acid ester compounds, carbamate compounds, dithio (or thiol) carbamate compounds, organic chlorine compounds, dinitro compounds, organic sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea triazine-based compounds] or/and fertilizers, etc. may also be present. Various formulations or ready-to-use prepara- tions containing the active ingredients of the invention are available.
tion) are the application methods and spraying methods commonly used in the agricultural manufacturing field [e.g., liquid spraying (spraying),
misting, atomizing, dusting, dusting, surface application, pouring]: fuming: soil application, [e.g., mixing, sprinkling, vaporing, irrigation]: surface application, [e.g.
Banding, dressing, coating]: Immersion: Poison baiting, etc. can be used. Also, the so-called ultra-low-concentration, small-volume spraying method
volume) can also be used. In this way it is possible to have 100% active ingredient content. Application rates per unit area are, for example, from about 0.03 to about 10 active compounds per hectare.
Kg, preferably about 0.3 to about 6 Kg. However, in special cases it is possible, and sometimes even necessary, to exceed or fall below these ranges. According to the present invention, the compound of the general formula () is included as an active ingredient, and a diluent (solvent and/or filler and/or carrier) and/or
Alternatively, an insecticidal composition containing a surfactant and, if necessary, a stabilizer, a fixing agent, a synergist, etc. can be provided. Furthermore, according to the present invention, the compound of the general formula () is applied to pests and/or their habitat or occurrence sites either alone or with a diluent (solvent and/or filler and/or carrier) and/or surfactant. Furthermore, if necessary, a method for controlling pests can be provided in which a stabilizer, a fixing agent, and a synergist are mixed and applied. EXAMPLES Next, the content of the present invention will be specifically explained with reference to Examples, but the present invention should not be limited thereto. Example 1 N-(2-chloro-5-pyridylmethyl)ethylenedialene (18.6g) 1-nitro2,2-bis(methylthio)ethylene (16.5g) and methanol (100ml) were mixed at room temperature and the contents were poured into a mixture. Gradually warm up while stirring, then stir at 50°C until the evolution of methyl mercaptan has stopped. After the reaction was completed, the crystals were cooled to room temperature and formed to obtain the desired pale yellow 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-imidazolidine (19 g) represented by the following formula. It will be done. mp.165~166℃ According to the same method as in Example 1 above, 1-(2-chloro-5-pyridylmethyl)-2-(nitromethylene)-tetrahydropyrimidine represented by the following formula was synthesized. Furthermore, by substantially the same method as in Example 1 above,
The synthesized compounds of the general formula () of the present invention are shown in Table 1 below.

[Table] Example 2 (Intermediate Synthesis) 2-chloro-5-chloromethyl-pyridine (16.2 g) was dissolved in acetonitrile (16.2 g) in a solution of ethylenediamine (18 g) in acetonitrile (100 ml) at room temperature.
Add 30ml solution dropwise over 1 hour. After the dropwise addition, the mixture was stirred at room temperature for 1 hour and at 40°C for 2 hours, and then acetonitrile was distilled off under reduced pressure, ether was added to the residue, and insoluble inorganic salts were separated. When the ether and the excess ethylenediamine are distilled off under reduced pressure, the target N-(2-chloro-5
-pyridylmethyl)ethylenediamine (16 g) is obtained. n ²⁰ _D 1.5627 According to the same method as in Example 2 above, N-(2-chloro-5-pyridylmethyl)trimethylenediamine represented by the following formula was synthesized. Furthermore, by a method almost the same as in Example 2 above,
Table 2 shows compounds of general formula () that can be synthesized.

[Table] Example 3 (hydrate) Compound No. 1 of the present invention, 15 parts, mixture of powdered diatomaceous earth and powdered clay (1:5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, alkylnaphthalene Three parts of sodium sulfonate formalin condensate were ground and mixed to prepare a wettable powder. This is diluted with water and sprayed onto pests and/or their habitat or occurrence locations. Example 4 (Emulsion) Compound No. 2 of the present invention, 30 parts, xylene, 55 parts, polyoxyethylene alkyl phenyl ether, 8
part, calcium alkylbenzenesulfonate, 7
Mix and stir to form an emulsion. This is diluted with water and sprayed onto pests and/or their habitat or occurrence locations. Example 5 (Powder) Compounds No. 1 and 2 of the present invention and 98 parts of powdered clay were pulverized and mixed to prepare a powder. This powder is sprinkled on pests and/or areas where they live or occur. Example 6 (Granules) To a mixture of 10 parts of the present compound No. 2, 30 parts of bentonite (montmorillonite), 58 parts of talc, and 2 parts of lignin sulfonate, 25 parts of water was added. , knead well and use extrusion type granulator.
Form into granules of 10 to 40 mesh and dry at 40 to 50°C to make granules. This is sprinkled on pest insects and/or their habitat or occurrence locations. Example 7 (Granules) Clay mineral particles with a particle size distribution of 0.2 to 2 mm, 95
1 part was placed in a rotary mixer, and while rotating, 5 parts of Compound No. 1 of the present invention dissolved in an organic solvent was sprayed on the mixer to evenly coat the mixer, and then dried at 40 to 50 DEG C. to form granules. This is sprinkled on pest insects and/or their habitat or occurrence locations. Example 8 (Oil agent) 0.5 parts of the compound No. 1 of the present invention and 99.5 parts of kerosene are mixed and stirred to prepare an oil agent. This is sprayed on pests and/or their habitat or occurrence locations. Example 9 (Biological test) Preparation of test solution against organophosphorus-resistant leafhopper One part by weight of the compound was mixed with the amount of solvent containing the amount of emulsifier, and the mixture was diluted with water to the desired concentration. Test method: Rice plants with a plant height of about 10 cm were planted in pots with a diameter of 12 cm.
10 ml of the active compound diluted in water at a predetermined concentration prepared as above was sprayed per pot. After the sprayed chemical solution had dried, a wire mesh with a diameter of 7 cm and a height of 14 cm was covered, and 30 female adult leafhoppers of a strain that is resistant to organic phosphorus agents were released into the mesh, and the number of dead insects was counted after 2 days by placing them in a constant temperature room. The insect killing rate was calculated. The results are shown in Table 3.

[Table] A-1: B-1: Example 10 (Biological test) Test method for planthoppers: Rice plants with a plant height of about 10 cm were planted in pots with a diameter of 12 cm.
10 ml of an active compound diluted with water at a predetermined concentration prepared in the same manner as in Example 9 was sprinkled per pot. After the sprayed chemical solution had dried, a wire mesh with a diameter of 7 cm and a height of 14 cm was placed over the mesh, and 30 female adult brown planthoppers of a strain that is resistant to organic phosphorus agents were released into the mesh, and the number of dead insects was counted after 2 days by placing them in a constant temperature room. The insect killing rate was calculated. In the same manner as above, the insecticidal rate against the brown-bottomed planthopper and the organophosphate-resistant brown planthopper was calculated. The results are shown in Table 4.

[Table] Ji.
Example 11 (Biological test) Test against organic phosphorus agent and carbamate agent resistant peach aphid Test method: Organic phosphorus agent reared in eggplant seedlings (deep black long eggplant) with a height of about 20 cm planted in clay pots with a diameter of 15 cm , and carbamate-resistant green peach aphids (approximately 200 aphids per seedling). One day after inoculation, a sufficient amount of the active compound diluted with water at a predetermined concentration prepared as in Example 9 was inoculated using a spray gun. Spread. 28℃ after spraying
The insecticide rate was calculated 24 hours after spraying. The test was repeated twice. The results are shown in Table 5.

[Table] The present invention described above in the detailed description section can be summarized as follows. (1) General formula: A nitromelene derivative represented by the following formula: where R represents a hydrogen atom or a lower alkyl group, m represents 2, 3, or 4, and n represents 0, 1, 2, or 3. (2) General formula: In the formula, R, m, and n are the same as above, and a compound represented by the general formula: In the formula, R' represents a lower alkyl group or a benzyl group, or two R's taken together
A method for producing a nitromellene derivative of the general formula (), which is characterized by reacting a compound represented by: which represents a lower alkylene group of C ₂ or more and which may form a ring together with an adjacent sulfur atom. . (3) An insecticide containing a nitromethylene derivative of general formula () as an active ingredient. (4) The nitromethylene derivative of the general formula () can be used alone or with a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, a stabilizer, a fixing agent, or a synergistic agent. A method of controlling pests that involves mixing and applying a mixture of pesticides and insecticides.

Claims (1)

[Claims] 1. General formula In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0,
A nitromethylene derivative or a salt thereof representing 1, 2 or 3. 2. The nitromethylene derivative or salt thereof according to claim 1, wherein m is 2 or 3. 3 formula: 1-(2-chloro-5-pyridylmethyl)- according to claim 1 or 2, represented by
2-(nitromethylene)tetrahydropyrimidine. 4 formula: 1-(2-chloro-5-pyridylmethyl)- according to claim 1 or 2, represented by
2-(nitromethylene)imidazolidine. 5 General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3, and a compound represented by the general formula: In the formula, R' represents a lower alkyl group or a benzyl group, or two R's taken together represent a lower alkylene group of C2 _or more, which may form a ring with the adjacent sulfur atom. The general formula is characterized by reacting with a compound represented by: A method for producing a nitromethylene derivative or a salt thereof, wherein R, m and n are the same as above. 6 General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3. Insecticides contained.