JPH0582391B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel nitromethylene derivative, its preparation method, and an insecticide. More specifically, the present invention relates to a novel nitromethylene derivative represented by the following formula (). General formula:

[Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom or a lower alkyl group, l represents 1, 2, 3 or 4, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3, provided that in the formula,

[Formula] part is

It is never [expression]. 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:

[ka] In the formula, R, X, l, m and n are the same as above, However, during the ceremony,

[Formula] part is

It is never [formula], A compound represented by General formula:

[Chemical formula] In the formula, R' represents a lower alkyl group or a benzyl group, or two R's taken together represent a lower alkyl group of C ₂ or more, and together with the adjacent sulfur atom, they form a ring. A method for producing a nitromethylene derivative of the general formula (), characterized by reacting the nitromethylene derivative with a 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 nitromethylene derivative of the general formula () 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 is produced by the method below. The present invention also relates to the manufacturing method. Manufacturing method:-

[Chemical formula] In the formula, R, X, l and n are the same as above, and Y represents a halogen atom or a group -OSO ₂ R'', where R'' represents a lower alkyl group or an aryl group, provided that the formula During,

[Formula] part is

[Formula] is not the case, and a compound represented by the general formula: H ₂ N-(CH ₂ ) _n -NH ₂ (), where m is the same as above, is reacted. A method for producing a compound of the general formula (), characterized in that: 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 formula 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.

[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. We have now succeeded in synthesizing a nitromethylene derivative of the general formula (), which has not been previously described in any known literature, and have 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 () of the present invention is a novel compound that has never been described in any prior art literature. and,
The characteristics of the compound of the present invention are its chemical structure:
2-nitromethylene-tetrahydropyrimidine,
or 2-nitromethylene-imidazolidine, furthermore 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 pyridyl alkyl group, and surprisingly there is a correlation between the chemical structure and the expression of high activity (control). It turns out that appears. 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 certain dosage. Moreover, the compounds of the present invention are
As a result of the long-standing use of organophosphorus and carbamate insecticides, pests that are resistant to these insecticides, particularly puncturing insects represented by Hemiptera, For example, it has been 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 sucking insects, cam 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 Callosobruchus Chinensis,
Sitophilus zeamais, Tribolium castaneum, Epilachna
vigintioctomaculata), 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, Ephestiacautella, Adoxophyesorana, Carpocapsa
hemiptera, such as Nephotettix cincticeps,
Niiaparvata lugens, Pseudococcus comstocki,
Unaspis yanonensis, Myzus persicas, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas, Stephanitis nashi, Nazara spp. , Bedbug (Cimex
lectularius), Trialurodes vaporariorum, Psylla spp.; orthoptera, such as Blatella germanica, Periplaneta americana, Gryllotalpa africana, Locustamigratoria migratoriodes, etc. Pteran insects, e.g. deucotermes speratus, Coptotermes formosanus; Diptera e.g. Musca domestica, Aedes aegypti, Hylemia
platura), Culex pipiens, Anopheles slnensis, Culex tritaeniorhychus, and the like. Furthermore, in the field of veterinary medicine, the novel compounds of the invention can be used effectively against various harmful animal parasitoids (endo- and ectoparasites), such as insects and helminths. Examples of such animal parasitism 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, X, l, m, n and R' are the same as above.] In the above reaction formula, R represents a hydrogen atom or a lower alkyl group, and the lower alkyl group is specifically can be exemplified by methyl, ethyl, propyl, isopropyl, n-(iso-, sec-, or tert-)butyl, and the like. X represents a halogen atom or a lower alkyl group, and specific examples of the halogen atom include fluor, chromium, bromine,
An example is iodine. Further, as the lower alkyl group, specifically, the groups illustrated in Table 3 and Table 4 below can be mentioned. l represents 1, 2, 3 or 4, 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 taken together represent a lower alkylene group of ₂ or more carbon atoms, where specific examples of the lower alkyl group include those exemplified above for R. I can give an example of something similar to that. 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,

[Table] Rimethylenediamine,

[Table] Ethylenediamine,

【table】

[Table] etc. 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-2,2-bis(methylthio)ethylene, 1-nitro-2,2-bis(ethylthio)ethylene, Examples include -2,2-bis(benzylthio)ethylene and 2-nitromethylene-1,3-dithiolane. Next, the above manufacturing method will be specifically explained using representative examples.

embedded image The method for producing the above compound 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; Nitriles such as acetonitrile,
Propiotrile, 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 dimethyl sulfoxide , 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:-

embedded image (In the formula, R, X, l, m, n and Y are the same as above.) Furthermore, the compound of the general formula () of the present invention can be produced, for example, by the following method. Manufacturing method:-

[Chemical formula] (In the formula, R, X, l, m, n, and Y are the same as above.) In the above reaction formula, R, X, l, m, and n are the same as those shown in the above production method. or Y is fluor, chloro, bromine,
It represents a halogen atom of iodine or a group _-OSO2R '', where R'' is a lower alkyl group as exemplified in the above production method), or for example phenyl, p-
Indicates an aryl group such as tolyl. 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,

[Table] Ido,

[Table] Rolide,

[Table] Examples include chloride, and instead of the chloride, bromide and p-toluenesulfonate can also be used. 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.

[Image Omitted] 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, alcoholates, etc., and tertiary amines such as triethylamine, diethylalniline, pyridine, etc. can. 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 case of the compound of the general formula (), when n=0, in addition to the above production method), as an alternative method, it can also be produced by the method represented by the general formula below:
Can be synthesized.

embedded image In the formula, X, R, l and m are the same as above. As shown in the above reaction formula, an imine is synthesized by the reaction of the pyridine aldehyde or pyridyl alkyl ketone of the general formula () with the compound of the general formula (), and to this, for example, sodium borohydride (NaBH ₄ ) is added. The compound of general formula (') can be synthesized by reacting with a reducing agent such as Furthermore, in the compound of the general formula (), R
When =H and n=0, the synthesis can be alternatively performed by the method represented by the general formula below.

embedded image In the formula, X, l and m are the same as above. As shown in the above reaction formula, nicotinamide or picolinamide is synthesized by the reaction of pyridyl carbonyl chloride of general formula () with a compound of general formula (), and a reducing agent such as lithium aluminum hydride (LiAlH ₄ ) is added to this. A compound of general formula ('') can be synthesized by reacting R.
In the case of =H, n=0, and m=3, it can be further synthesized by a method represented by the following general formula.

embedded image In the formula, X and l are the same as above. As shown in the above reaction formula, acrylonitrile is added to the compound of the general formula (), and this adduct is reduced in the same manner as in Alternative Method 2 above, whereby the general formula (

Claims (1)

[Claims] 1 General formula: [Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom or a lower alkyl group, l represents 1, 2, 3 or 4, m represents 2, 3 or 4, and n represents 0, 1, 2 or 3, provided that in the formula, the [formula] part is not [formula], a nitromethylene derivative or a salt thereof represented by . 2. The nitromethylene derivative or salt thereof according to claim 1, wherein m is 2 or 3. 3 Formula: 1-(2-fluoro-5-pyridylmethyl) according to claim 1 or 2, represented by the formula
-2-(nitromethylene)tetrahydropyrimidine. 4 Formula: 1-(2-fluoro-5-pyridylmethyl) according to claim 1 or 2, represented by the formula
-2-(nitromethylene)imidazolidine. 5 Formula: 1-(2-bromo-5-pyridylmethyl)- according to claim 1 or 2, represented by the formula
2-(nitromethylene)tetrahydropyrimidine. 6 Formula: 1-(2-bromo-5-pyridylmethyl)- according to claim 1 or 2, represented by the formula
2-(nitromethylene)imidazolidine. 7 1-(2-Methyl-5-pyridylmethyl)-2-(nitromethylene)tetrahydropyrimidine according to claim 1 or claim 2, represented by the formula: 8 General formula: [Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom or a lower alkyl group, l represents 1, 2, 3 or 4, and m represents 2, 3 or 4, and n represents 0, 1, 2, or 3, provided that the [formula] part in the formula is not [formula], and the compound represented by the general formula: [formula] in the formula, R' represents a lower alkyl group or a benzyl group, or two R's taken together represent a lower alkyl group of ₂ or more carbon atoms, which may form a ring with the adjacent sulfur atom, represented by A method for producing a nitromethylene derivative or a salt thereof represented by the general formula: wherein R, X, l, m and n are the same as above. 9 General formula: [Chemical formula] In the formula, R represents a hydrogen atom or a lower alkyl group, X represents a halogen atom or a lower alkyl group, l represents 1, 2, 3 or 4, and m represents 2, 3 or 4, and n represents 0, 1, 2, or 3, provided that the [formula] part in the formula is not [formula], and contains as an active ingredient a nitromethylene derivative or its salts represented by Insecticide.