JPS60218386A - Nitromethylene derivative, its intermediate, preparation thereof and insecticide - Google Patents

Abstract

NEW MATERIAL:A compound of formula I (R is H or lower alkyl; m is 2, 3 or 4; n is 0, 1, 2 or 3). EXAMPLE:1-(2-Chloro-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrim idine. USE:An insecticide capable of exhibiting improved activity particularly against aphids, planthoppers and leafhoppers, etc. PREPARATION:A compound of formula II is reacted with a compound of formula III (R' is lower alkyl, benzyl or two R's together may represent >=2C lower alkylene or may form a ring with the adjacent S atoms) in an inert solvent at 0-100 deg.C to give the aimed compound of formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel nitromethylene derivatives, processes for their preparation, and insecticides.

More specifically, the present invention relates to a novel nitromethylene derivative represented by the following formula (1).

General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, m indicates 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 1), and the present invention also relates to this production method.

i) Production method A compound represented by the general formula: In the formula, R' represents a lower alkyl or benzyl group, or two R's taken together are C! It is characterized by reacting with a compound represented by the above lower alkylev group, which may form a ring with an adjacent sulfur atom,
A method for producing the nitromethylene derivative j) of the general formula (summer).

The present invention also relates to an insecticide containing the nitromethylene derivative of general formula (1) as an active ingredient.

The compound of the general formula (II), which is an intermediate for the production of the nitromethylene derivative of the general formula (1) of the present invention, is a new compound that has not been described in publicly known publications before the filing date of the present invention, and the present invention is directed to the compound. It also relates to The compound of the general formula (, U) can be produced by the following method 11),
The invention also relates to the process.

11) Production method General formula: In the formula, R and n are the same as above, and X represents a halogen atom or a group -050,R", where R" represents a lower alkyl group or an aryl group. A method for producing a compound of the general formula (1), which is characterized by reacting a compound represented by the general formula: % formula %(), where m is the same as above.

West German patent publication number 4514402 known before the filing date of the present application
Q4-1. is represented by the following general formula. ;IhI'' methylene-imidazolidine derivatives and 2-nitromethylene-hexahydropyrimidine derivatives are described to have insecticidal activity.
) alkyl group, R2=R, -hydrogen atom, and the specification describes a compound represented by the following formula.

Similarly, West German Patent Publication No. 473-660 describes that 1-substituted penzyl-2-nitromethylene-imidazolidine derivatives represented by the following general formula have insecticidal activity. The specification describes a compound represented by the following formula.

The present inventors have performed synthesis and biological screening of nitromethylene-tetrahydropyrimidine-based compounds and nitromethylene-imidazolidine-based compounds in order to create new useful compounds with biological activity. The present inventors succeeded in synthesizing a nitromethylene derivative of the general formula (1), which has not been described in any known literature, and discovered that this compound has excellent control activity against harmful insects.

According to the knowledge obtained by the present inventors, the nitromethylene derivative specified by the general formula (1) of the present invention is a novel compound that has never been described in any prior art document. be. The compound of the present invention is characterized by its chemical structure of 2-nitromethylene-tetrahydropyrimidine, 2-nitromethylene-imidazolidine, and ii% or 2-nitromethylene-hexahydro-1
゜The basic skeleton is 3-diazepine, and at the 1-position nitrogen atom of the heterocycle, as is clear from the general formula (summer), 2
Surprisingly, it was found that there is an excellent correlation between the chemical structure and the expression of high activity (control).

Furthermore, the compound of the present invention, as specifically shown later,
The most similar formula (,4
-1) and insect pests resistant to these insecticides that have been produced as a result of the use of insecticides that have extremely superior control activity at lower doses than the compounds of (B-1>); In particular, it has been discovered that it exhibits a remarkable control effect on puncturing insect pests represented by the order of Hemiptera (Hamiptera), such as aphids, planthoppers, and leafhoppers.

Furthermore, in the method for producing the compound of general formula (1) of the present invention,
The compound of general formula (1), which is an intermediate thereof, is also a new compound that has never been described in any prior art literature.As mentioned above, the compound of general formula (1) is industrially useful.
) is a compound that is useful as an intermediate for the compound.

Therefore, an object of the present invention is to provide novel nitromethylene derivatives of the general formula (R), intermediates thereof, processes for their production, and use thereof as insecticides.

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 Callosobrwchwschi.
nensis), brown weevil (5itophilus
zeamais), S Nustomodoki (TriboLiw)
naastanewm), Japanese ladybug (E
pilachnavigitiocto-macwla
ta), Tobiiromu Naponoko Plating (Agri-otg
sfsacicollts), Anoma
Colorado Boted Beetle (Lep-1tnotaraadecemkineat)
a), Diabrotica spp.
), Monochamusal
ternatua), rice weevil (Lissor)
hoptrwsoryzophilus), Lyctwsbruneua; lepidopterous insects, such as Lymantriαdispαde, Malacosorruxnewstria
, Pierisrapae, /S Spodoptera 1itura), Spodoptera Brassicae, Chiloswppressalis, 777
Pyrasstan5biLaLis, Epheattacautella,
Adoycophyttsoran
a), Carpocap-sapomone
lla), Caprayaga (Agrotisfbco-8α)
), honey hemlock (Ga1leria mellonell)
a), diamondback moth (plutellamat, rblipa)
nnis), mandarin orange 7% mogriga (Phyllocni
hemiptera, such as the leafhopper (Nephotattizcinct);
iceps), brown planthopper (Ntlaparvat)
alugens), pse'u
tiococcwscomstochi>, Unaspiayanonenais, -
1-Mo7 Aphid (Myzuspgraicas)
, apple aphid (Aphsapo=i), cotton aphid (Aphisgoes νpii), radish aphid (RhopaLoaiphumpseud)
obraasicas), Nasigunpai (5tapha)
nitisnaahi), green stink bug (Nazara
spp, ), Bedbug (Cjmgzleetwlar)
iws), whitefly (Tria-1exro)
desvaporariorum), Phyllus CPay
tL-lαapp・); Orthoptera insects, such as the German cockroach (BLat@LLagermanic
a), American cockroach (periplangtaamg)
ricana), Keller (GdayLLotαtpααf
rtca%a), ノ (Locustamigra
toriatnigratoriodes); isopteran insects, e.g.
s), Coptotarmgaform
, osanus): Diptera insects, such as the house fly (Muscadomesticα), Aedes aegypti (Agdgaaegypti), and the grain fly (Hy
lemiαplatrbra), Culex pipiens (CrbL)
gzpipiens), Chinese Anopheles (Anophe)
lgs5lnenais), Lesser thane 7 Culex ((sb
leztritaeniorhynchus), etc.

Furthermore, in the pharmaceutical field of veterinary medicine, the novel compounds of the invention can be used to treat various harmful animal parasites (internal and external parasites).
, for example, are effective for use against insects and helminths. Examples of such animal parasites include the following pests.

Insects include, for example, Gatrophilus spp., Stomogcysspp.
ichodect-easpp, ), assassin bug (Rho
dniwaapp, ), dog flea (Ctenoceph)
alideacanis) and the like.

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 (1) of the present invention can be easily produced, for example, by the following method 1).

Production method i) Ni (1) (II) , (+) (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, inglovir, n-(1s
Examples include o-, 5et-, or tert-)butyl. Kabuto indicates 2, 3 or 4, n is 0, 1
．． Indicates 2 or 3. R' represents a lower alkyl group or a benzyl group, or two R's together represent a lower alkylene group of 02 or more, where specific examples of the lower alkyl group include those exemplified above for R. Similar examples can be given. Further, two R's together represent a lower alkylene group of 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. be able to.

In the method for producing the compound of general formula (1) of the present invention shown in the above reaction formula, specific examples of the compound of general formula (II) as a raw material include, for example, N-(2-chloro-5-pyridylmethyl) Ethylenediamine, #-(2-(2-chloro-5-pyridyl)ethyl)ethylenediamine, N-(2-chloro-5-pyridylmethyl)trimethylenediamine, #-(2-(2-chloro-5-pyridyl) Ethyl]trimethylenediamine, #-(1-(2-chloro-5-pyridyl)ethyl)trino, ethylenediamine, A'-(3-(2-chloro-5-pyridyl)propyl)
Trimethylenediamine, A'-(1-(2-chloro-5-pyridyl)ethyl)ethylenediamine, N-(2-chloro-5-pyridylmethyl)tetramethylenediamine, #-(4-(2-chloro-5 -pyridyl)butyl]trimethylenediamine, #-(1-(2-chloro-5-pyridyl)propyl]trimethylenediamine, N-[2-methyl-1-(2-chloro-5-pyridyl)
Furovir] ethylenediamine, etc. can be exemplified.

Specific examples of the compound of general formula (1) which is also a raw material include 1-nitro-2,2-bis(methylthio)ethylene, 1-nitro-2,2-bis(ethelthio)ethylene, 1- Examples include nitro-2,2-bis(benzylthio)ethylene and 2-nitromethylene-1,3-dithiene.

Next, the above manufacturing method will be specifically explained using representative examples.

The method for producing the above-mentioned 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 dichloroethylene, chlorobenzene; Other ethers such as diethyl ether, methyl ethyl ether, di-180-propyl ether, diptyl ether, propylene oxide, dioxane, tetrahydrofuran; Ketones such as acetone, methyl ethyl ketone, methyl- is.

-Oh. ,,2,71. ,. -1ao-7' Ayaga,
:/; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol, ethanol, 1ao-7' lobanol, phthanol, ethylene glycol; Esters such as ethyl acetate, amyl acetate; Acid amides such as dimethyl Formamide, dimethylacetamide; sulfones, sulfoxides such as dimethylsulfoxide, sulfolane; and bases such as pyridine.

The above method can be carried out within a wide temperature range. It can generally be carried out between about -20°C and the boiling point of the mixture, preferably between about θ and about 100°C. 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.

In addition to the above-mentioned manufacturing method i), the chemical food of the general formula (1) of the present invention can be prepared by:
It can also be produced by another method shown in the reaction formula below.

Alternative method (M) (In the formula, X, R, m and n are the same as above.) Furthermore, the compound of general formula (1) of the present invention can be produced, for example, by the following method 11). I can do it.

Production method ii): - (1/) (V) (Rei) (In the formula, R, m, n and The same can be exemplified by 1fcXd fluor, chlor, bromo, iotonohalogen atom, or group -0502
R'' represents a lower alkyl group as exemplified in the above production method 1), or an aryl group such as phenyl, p-tolyl, etc.

In the method for producing a compound of the uninvented general formula (1) shown in the above reaction formula, specific examples of the compound of the general formula (1) as a raw material include 2-chloro-5-pyridylmethyl chloride, 2-( 2
-Chloro-5-pyridyl)ethyl chloride, 1-(2-chloro-5-pyridyl)ethyl chloride, 3-(2-chloro-s-biydyl)globyl chloride, 2-di-4-5-pyridylmethyl Examples include p-toluenesulfonate.

Similarly, specific examples of the compound of general formula (V) 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 carrying out 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. Examples of such acid binders include commonly used alkali metal hydroxides, carbonates, bicarbonates, alcoholades, etc., and tertiary amines such as triethylamine, diethylanilino, pyridine, etc. I can do it.

Further, the above production method can be carried out within a wide temperature range similar to the above production method i), 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 general formula (II), R=H and n=0
In this case, in addition to the above production method 11), it can also be synthesized by a method represented by the following general formula.

Alternative method 2 knee (V) ←C) In the ceremony, the emotion is the same as above.

As shown in the above reaction formula, a thick base is synthesized by the reaction of 6-chloronicotinaldehyde with a compound of general formula (V), and this is combined with, for example, sodicum porohydride 2ide (NaBE4), etc. By reacting the reducing agent of
A compound of the general formula (厘′) can be synthesized.

Furthermore, the compound of the above general formula (II') can also be synthesized by a method represented by the following general formula.

Alternative method 3 knee (V) (1 person In the formula, m is the same as above.

As shown in the above reaction formula, nicotinamide is synthesized by the reaction of 6-chloronicotinoyl chloride with the compound of general formula (V), and then a reducing agent such as lithium aluminum hydride (LiAIH) is added to this. By reacting, one compound can be synthesized using the general formula.

Furthermore, in the compound of the general formula (door), R: H1n
In the case where ==Q and m=3, it can be further synthesized by a method represented by the following general formula.

Alternative method 4 (1-2) In accordance with the reaction formula shown above, acrylonitrile is added to 5-chloropicolylamine, and this adduct is reduced in the same manner as in Alternative method 2 above. Compound AI72
The target compound N-(2-chloro-5-pyridylmethyl)trimethylenediamine shown in can also be synthesized.

Furthermore, in the compound of general formula (II), to 1°-
In the case of 2, it can be synthesized alternatively by a method represented by the following general formula.

Alternative method 5 knee (■) (I') In the formula, R9 and n are the same as above.

As shown in the above reaction formula, a compound of general formula (n'') can also be synthesized by reacting 2-chloro-5-pyridylalkylamine of general formula (■) with ethyleneimine. .

The compound of the present invention can also exist in the form of a salt, and examples of the salt include inorganic acid salts, sulfonate salts, organic acid salts, metal salts, and the like.

Examples of the salts of the compounds of the present invention include the following.

1-(2-chloro-5-pyridylmethyl)-2-totromethylene)nato-2hydropyrimidine-hydrochloride, 1-(2-chloro-5-pyridylmethyl)-2-totromethylene)nato-2hydropyridine-p-toluene Sulfonate, 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)imidazolidine-hydrochloride, 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)imidazolidine-acetic acid Cupric salt.

When the compound of general formula (1) of the present invention is used as an insecticide, it can be used directly as it is by diluting it with water, or it can be used by a method commonly used in the agricultural chemical manufacturing field using an agricultural chemical auxiliary. However, 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 pesticide adjuvants mentioned here include diluents (solvents, fillers, carriers), surfactants (solubilizers, emulsifiers, dispersants, wetting agents), stabilizers, fixing agents, and propellants for aerosols. , synergists, etc.

Solvents include water: organic solvents; hydrocarbons [e.g.
-Hexane, petroleum ether, petroleum distillates (paraffin wax,
kerosene, light oil, medium oil, heavy oil), benzene, toluene, xylenes], halogenated hydrocarbons [e.g., methylene chloride, carbon tetrachloride, ethylene chloride, ethylene dibromide, chloropene, zene, chloroform], alcohols [ Examples: Eva, methyl alcohol, ethyl alcohol,
propyl alcohol, ethylene glycol], ethers C examples, ethyl ether, ethylene oxide; dioxane], alcohol ethers [e.g. ethylene glycol monomethyl ether], ketones [e.g. acetone, inophorone], esters [e.g. ethyl acetate] , amyl acetate], amides [for example, dimethylformamide, dimethylacetamide], and sulfoxides [for example, 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). light, talcum, montmorillonite, beidellite, vermiculite, kaolinite, mica), etc.; vegetable powders such as grain flour, starch, modified starch, sugar, glucose, crushed plant stems, etc.; synthetic resin powders, such as phenol Examples include resin, urea resin, and vinyl chloride resin.

Examples of surfactants include anionic surfactants such as alkyl sulfate esters [e.g. sodium lauryl sulfate], aryl sulfo/acids [e.g. alkylaryl sulfonate, sodium alkylnaphthalene sulfonate], succinates, Polyethylene glycol alkylaryl ether sulfate salts; cationic surfactants, such as alkylamines [e.g., laurylamine, stearyltrimethylammonium chloride, alkyldimethylbenzylammonium chloride], polyoxyethylene alkylamines; nonionic interfaces Activators such as polyoxyethylene glycol ether A [e.g., polyoxyethylene alkylaryl ether and condensates thereof], polyoxyethylene glycol esters [e.g., polyoxyethylene fatty acid ester], polyhydric alcohol esters [e.g. Examples include polyoxyethylene rubitan monolaurate; amphoteric surfactants; and the like.

Other stabilizers, fixing agents [e.g., agricultural soap, casein lime, sodium alginate, polyvinyl alcohol]
PVA), vinyl acetate MN agent, acrylic adhesive],
Aerosol propellants [e.g., trichlorofluoromethane, dichlorofluoromethane, 1,2,2-) dichloro-1,1,2-trifluoroethane, chlorobenzene,
LNG.

Lower ether]: Combustion regulator (for smoking agents) (e.g. nitrite, zinc dust, dicyandiamide): Oxygen supply agent [
For example, chlorate]: Efficacy extender Bidispersion stabilizer [e.g., casein, tosigant, carboxymethyl cellulose (CMC), polyvinyl 7/lz col (PVA)):
Mention may be made of synergists.

The compound of the present invention can be manufactured into various formulations by methods generally practiced in the agricultural chemical manufacturing field.

Forms of preparations include emulsions, oils, wettable powders, aqueous solutions, suspensions, powders, granules, powders, smoking agents, tablets, aerosols, pastes, capsules, etc. I'll cross.

The insecticide of the present invention may contain, for example, about 0.1 to about 95% by weight, preferably about 0.5 to about 90% by weight of the active ingredient.

In actual use, the various formulations and spray preparations described above are used.
The active compound content in tion) is, for example, about 0.000
1 to about 20% by weight, preferably about 0.005 to about 10%
A range of - is appropriate.

The amount of these active ingredients can be changed as appropriate depending on the form of the preparation, the method of application, purpose, timing, location, pest infestation status, etc.

The compound of the general formula <1) of the present invention may further be used, if necessary, with other agricultural chemicals, such as insecticides, fungicides, acaricides, nematicides,
Antiviral agents, herbicides, plant growth regulators, attractants, [e.g., organic phosphate compounds, carbamate compounds, dithio (or thiol) carbamate compounds,
Organochlorinated metal compounds, dinitro compounds, organic sulfur or metal compounds, antibiotics, substituted diphenyl ether compounds, urea compounds, triazine compounds] or/and fertilizers can also be present.

Various formulations or ready-to-use preparations containing the active ingredients of the invention.
-tion) are application methods, spraying, spraying, spraying, misting, atomizing (α
tomizing), dusting, granulation, water surface application, pouring: l: Smoking: soil application, [e.g., mixing, sprinkleling,
fumigation (vaporing), irrigation] two-surface application, [e.g., coating, banding, dressing, coating]
: Soaking: Poison baiting etc. can be used. In addition, the so-called ultra-high concentration small amount spraying method (uttrα
-1ow-volume).

“In this way it is possible to contain 100 units of active ingredient.

The application amount per unit area is, for example, about 0.03 to about 10 kg, preferably about 0.3 to about 6 kg, based on 1 hectare of active compound.

However, in special cases it may be possible, and sometimes even necessary, to exceed these ranges.

According to the present invention, the compound of the general formula (1) is included as an active ingredient, and further includes a diluent (solvent and/or filler and/or carrier) and/or surfactant, and if necessary, a stabilizer, for example. An insecticidal composition containing a sticking agent and a synergist can be provided.

Furthermore, according to the present invention, the compound of the general formula (1) 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! A pest control method can be provided in which a mixture of a surfactant, a stabilizer, a fixing agent, and a synergist is applied if necessary.

Next, the content of the present invention will be specifically explained using examples.
The present invention should not be limited to this only.

Example I N-(2-chloro-5-pyridylmethyl)ethylenediarene (18,61I) 1-nitro2,2-bis(methylthio)ethylene (1e,sI)menol (100m
J) is mixed at room temperature, the contents are gradually warmed while stirring, and then stirred at 50° C. until the generation of methyl mercaptan stops. After the reaction is completed, the resulting crystals are cooled to room temperature and are expressed by the following formula with a pale yellow color. 1-(2-
chloro-5-pyridylmethyl)-2-tromethylene)
-Imidazolidine (19#) is obtained. tnp, 16
5-166°C According to the same method as in Example 1 above, 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)-tetrahydropyrimidine represented by the following formula was synthesized.

Further, compounds of the general formula (1) of the present invention synthesized by substantially the same method as in Example 1 are shown in Table 1 below.

Table 1 Example 2 (Intermediate Synthesis) Ethylenediamine (tsg) in acetonitrile (100
m) 2-chloro-5-chloromethyl- in solution at room temperature
A 30 d solution of pyridine (16,2,9) in acetonitrile is added dropwise over 1 hour. After dropping at room temperature for 1 hour at 40°C
After stirring for 2 hours, acetonitrile was distilled off under reduced pressure, ether was added to the residue, and insoluble inorganic salts were separated by F. Ether and excess ethylenediamine are distilled off under reduced pressure to obtain the desired colorless oily N-(2-chloro-5-pyridylmethyl)ethylenediamine (16,
9) is obtained. n"1.5627 (Compound Shop ■-1) According to the same method as in Example 2 above, N-(2-chloro-5-pyridylmethyl)trimethylenediamine represented by the following formula was synthesized.

(Compound n-2) Furthermore, Table 2 shows compounds of the general formula (It) of the present invention, which were synthesized by substantially the same method as in Example 2 above.

Table 2 Example 3 (Irrigation agent) Compound AI of the present invention, 15 parts, mixture of powdered diatomaceous earth and powdered clay (1:5), 80 parts, sodium alkylbenzenesulfonate, 2 parts, sodium alkylnaphthalenesulfonate Three parts of the formalin condensate were pulverized and mixed to make an irrigation agent. This is diluted with water and sprayed onto pests and/or their habitat or occurrence locations.

Example 4 (Emulsion) 2.30 parts of the compound A of the present invention, 55 parts of xylene, 8 parts of polyoxyethylene alkylphenyl ether, and 7 parts of calcium alkylbenzenesulfonate were mixed and stirred to prepare an emulsion. This is diluted with water and sprayed onto pests and/or their habitat or occurrence locations.

Example 5 (Powder) 41 parts and 2 parts of the compound 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 2.10 parts of the compound of the present invention, 30 parts of bentonite (montmorillonite), 58 parts of talc, and 2 parts of lignin sulfonate, 25#e71° was added. ,. . bLs*, 1flL-A, 10~4
It is made into 0 mesh granules and dried at 40 to 50°C to form granules. This is sprinkled on pest insects and/or their habitat or occurrence locations.

Example 7 (granules) 95 parts of clay mineral particles having a particle size distribution of 0.2 to 2 m were placed in a rotary mixer, and while rotating, 1.5 parts of the compound A of the present invention dissolved in an organic solvent was sprayed. After soaking evenly, 40
Dry at ~50°C to form granules.

This is sprinkled on pest insects and/or their habitat or occurrence locations.

Example 8 (Oil agent) 0.5 part of the compound AI of the present invention and 99.5 parts of kerosene were 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 sample solution against organophosphorus resistant leafhopper Solvent: 3 parts by weight of xylene Emulsifier: 1 part by weight of polyoxyethylene alkylphenyl ether Active compound to prepare a suitable active compound formulation One part by weight 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 planted in pots with a diameter of 12 cFrL were sprayed with a plod per pot of a diluted solution of the active compound in water at a predetermined concentration prepared as described above. After drying the sprayed chemical solution,
A wire mesh with a diameter of 7 cm and a height of 14 cm was placed over the mesh, and 30 female adult leafhoppers of a strain that is resistant to organic phosphorus agents were released into the mesh, placed in a thermostatic chamber, and two days later, the number of deaths was measured to calculate the insect kill rate.

The results are shown in Table 3.

Table 3 (Note) 1) The compound layer is the same as above.

2) Comparison, 4-1, and B-1 are the same as those described above, and represent the following compounds.

, 4-1: B-1: Example 10 (biological test) Test on planthoppers Test method: A predetermined amount of the active compound prepared in the same manner as in Example 9 was applied to rice plants with a plant height of about 10 cIIL planted in a pot with a diameter of 12 cIIL. 16io7 per pot of diluted solution with water! Spread.

After the sprayed chemical solution has dried, cover it with a wire mesh with a diameter of 7α and a height of 14 cm, and release 30 female adult brown planthoppers of a strain that is resistant to organic phosphorus agents into the mesh, place them in a constant temperature room, and count the number of deaths after 2 days. 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 4 (Note) 1) The compound layer is the same as above.

2) Comparison, 4-1, and Z? -1 is the same as Table 3.

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) about 20 degrees in height planted in clay pots with a diameter of 15 cWL Approximately 200 peach aphids resistant to carbamate agents and carbamate agent resistant peach aphids were inoculated per seedling, and one day after inoculation, a water dilution solution of a predetermined concentration of the active compound prepared as in Example 9 was inoculated using a spray gun. , was sprayed in sufficient quantity. After spraying, leave in a greenhouse at 28℃ and spray for 24 hours.
After a period of time, the insecticidal rate was calculated. The test was repeated twice.

The results are shown in Table 5.

Table 5 (Note) 1) Comparison of Compound A, 4-1, and B-x are the same as above.

2) Estoz:, S-2-ethylsulfinyl-1-
Methyl ethyl dimethyl phosphorothiolate 45% emulsion The present invention described above in the detailed description section can be summarized as follows.

In the formula, R represents a hydrogen atom or a lower alkyl group, The bait shows 2.3 or 4, and n represents 0.1, 2, or 3; A nitromethylene derivative coated with

(2) A compound represented by the general formula: where R, m, and n are the same as above, and the general formula: where R' represents a lower alkyl group or a pendyl group, or two R' is a lower alkylene group of C1 or more, which together may form a ring with an adjacent sulfur atom. A method for producing a nitromethylene derivative.

(3) An insecticide containing the nitromethylene derivative of general formula (1) as an active ingredient.

(4) The nitromethylene derivative of the general formula (+) alone,
or diluents (solvents and/or fillers and/or carriers) and/or surfactants, and if necessary,
A pest control method that involves applying a mixture of stabilizers, fixing agents, and synergists.

(5) General formula: In the formula, R, m and the others are the same as above, A compound represented by

(6) General formula: In the formula, R and n are the same as above, and X represents a halogen atom or a group -OSO,R//, where R'' represents a lower alkyl group or an aryl group. A method for producing a compound of the general formula (1), which is characterized by reacting a compound represented by the general formula: % formula %(), where m is the same as above.

Continuing from page 1 ■Int, CI, 'Identification code Office serial number 239:00
) 7166-4C Procedural Amendment July 2, 1980 Director General of the Japan Patent Office Manabu Shiga 1, Indication of the case Patent Application No. 1987-72966 2, Title of the invention 3, Person making the amendment Patent applicant related to the case Address: 2-4-4 Nihonbashi Honmachi, Chuo-ku, Tokyo; Agent:
107 (1 other person) 6. Subject of amendment (attached sheet) (1) In the BA affidavit, page 26, down line 82, [l "R 1 1, page 27, line 1, [R t -"] t do it.

On page 28, bottom line 2, [ (4) On the last line of page 28,

Claims (1)

[Claims] 1) General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, and m is 2
．． 3 or 4, and n represents 0, 1.2 or 3, or a salt thereof. 2) The nitromethylene derivative or derivatives thereof according to claim 1, wherein 〇 is 2 or 3. 3) Formula: Claim 1 or 2 expressed by +
7) 1-(2-chloro-5-pyridylmethyl)-2-totromethylene)tetrahydropyrimidine 0 4) Claim 1 or Claim 2, represented by the formula: 1
7) 1-(2-chloro-5-pyridylmethyl)-2-tromethylene)imidazolidine. 5) General formula: R where R represents a hydrogen atom or a lower alkyl group, R represents 2.3 or 4, and n represents 0, 1.2 or 3; 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 C8 or more, and they may form a ring with the adjacent sulfur atom. A method for producing a nitromethylene derivative or a salt thereof represented by the following general formula: 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, or a nitromethylene derivative or its An insecticide containing salts as an active ingredient. 7) A compound represented by the general 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. 8) General formula: In the formula, R represents a hydrogen atom or a lower alkyl group, n represents 0, 1.2 or 3, and X represents a halogen atom or a group -050,R'', where: R" represents a lower alkyl group or an aryl group, and a compound represented by the general formula: A method for producing a compound represented by the general formula: where R, m and n are the same as above.