JP3159859B2 - Insecticidal nitro compounds - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to novel nitro or cyano compounds, processes for their preparation, their use as insecticides, and novel intermediates useful for synthesizing said nitro or cyano compounds.

[0002]

2. Description of the Related Art A nitro or cyano compound is described in Japanese Patent Application Laid-Open No. 2-258881, which was known before the filing of the present application. The compound of the present invention is disclosed in
881, but not specifically disclosed.

[0003]

The present inventors have found that a nitro or cyano compound represented by the following formula (I) exhibits excellent insecticidal activity. formula:

Embedded image In the formula, A represents 6-chloro-3-pyridyl or 2-chloro-5-thiazolyl, R ¹ represents a hydrogen atom or methyl, X represents an oxygen atom or a sulfur atom, and R ² represents
Y represents a hydrogen atom or C _1-4 alkyl, and Y represents nitro or cyano, provided that when X represents a sulfur atom, R ² represents C _1-4 alkyl. The nitro or cyano compound can be synthesized, for example, by the following production method. A) When R ² represents C _1-4 alkyl:

Embedded image Wherein A, R ¹ , X and Y are the same as defined above, and a compound represented by the formula (III) R ⁴ —R ³ (III) wherein R ³ represents C _1-4 alkyl; ⁴ is
A production method characterized by reacting with a compound represented by the formula: or b) the following formula (IV)

Embedded image Wherein R ² , X and Y are the same as defined above, and a compound represented by the formula (V)

Embedded image Wherein A, R ¹ and R ⁴ are reacted with the same compound as described above, or c) when R ² represents a hydrogen atom and X represents an oxygen atom: Equation (VI)

Embedded image In the formula, A, R ¹ and Y are the same as described above, and a compound represented by the following formula is reacted with formaldehyde.

[0004] Surprisingly, the compounds of the present invention show a strong insecticidal activity. According to the present invention, the nitro or cyano compound of the formula (I) can be prepared, for example, by the method described in JP-A-2-23588.
It exhibits substantially superior insecticidal activity as compared to similar compounds described in No. 1. Further, the compound of the present invention can also be used as an intermediate for producing an insecticidal compound described in JP-A-2-288860. In the compound of the present invention, A preferably represents 6-chloro-3-pyridyl or 2-chloro-5-thiazolyl, R ¹ represents a hydrogen atom, X represents an oxygen atom or a sulfur atom. , R ²
Y represents a hydrogen atom or C _1-4 alkyl, and Y represents nitro, provided that when X represents a sulfur atom, R ² represents C _1-4 alkyl. More preferably, A is 6-chloro-3 shows a pyridyl or 2-chloro-5-thiazolyl, R ¹ represents a hydrogen atom, X is an oxygen atom or a sulfur atom, R ² is C Y represents _1-4 alkyl and Y represents nitro.

[0005] Specific examples of the nitro or cyano compound of the present invention include the following compounds. 3- (6-chloro-3-pyridylmethyl) -4-cyanoiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3, 5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine, 3-
(6-chloro-3-pyridylmethyl) -5-methyl-4
-Nitroiminotetrahydro-1,3,5-thiadiazine, 3- (6-chloro-3-pyridylmethyl) -5-methyl-4-cyanoiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro -3-pyridylmethyl) -5-ethyl-4-nitroiminotetrahydro-
1,3,5-oxadiazine, 3- (6-chloro-3-
Pyridylmethyl) -5-ethyl-4-cyanoiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -5-n-propyl-4-
Nitroiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -5-t
-Butyl-4-nitroiminotetrahydro-1,3,5
-Oxadiazine, 3- (6-chloro-3-pyridylmethyl) -5-t-butyl-4-nitroiminotetrahydro-1,3,5-thiadiazine, 3- (1- (6-chloro-3-pyridyl) Ethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (1- (6
-Chloro-3-pyridyl) ethyl) -5-methyl-4-
Nitroiminotetrahydro-1,3,5-oxadiazine, 3- (1- (6-chloro-3-pyridyl) ethyl)
-5-methyl-4-nitroiminotetrahydro-1,
3,5-thiadiazine,

3- (2-chloro-5-thiazolylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (2-chloro-5-thiazolylmethyl) -4-cyanoiminotetrahydro-1,3 , 5-oxadiazine, 3- (2-chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydro-
1,3,5-oxadiazine, 3- (2-chloro-5-
Thiazolylmethyl) -5-methyl-4-cyanoiminotetrahydro-1,3,5-oxadiazine, 3- (2-
(Chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-thiadiazine,
3- (2-chloro-5-thiazolylmethyl) -5-ethyl-4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (1- (2-chloro-5-thiazolyl) ethyl) -4-nitro Iminotetrahydro-1,
3,5-oxadiazine, 3- (1- (2-chloro-5
-Thiazolyl) ethyl) -4-nitroiminotetrahydro-1,3,5-thiadiazine, 3- (1- (2-chloro-5-thiazolyl) ethyl) -5-methyl-4-nitroiminotetrahydro-1,3 , 5-oxadiazine.

In the above process a), for example, when 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine and methyl iodide are used as raw materials, It is represented by the reaction formula.

Embedded image In the above-mentioned production method b), as raw materials, for example, 4-nitroiminotetrahydro-1,3,5-oxadiazine and 2
Using -chloro-5-chloromethylthiazole is represented by the following reaction formula.

Embedded image In the above production method c), for example, N- (6-
The use of (chloro-3-pyridylmethyl) -N'-nitroguanidine and formalin is represented by the following reaction formula.

Embedded image

In the above-mentioned production method a), the compound of the formula (II) as the starting material is ^one based on the definition of A, R ¹ , X and Y, and preferably the compounds of A, R ¹ , X and Y is shown based on each preferred definition. Examples of the compound of the formula (II) include the compound of the present invention and can be synthesized by the above-mentioned production method (c).
The following compounds can be mentioned. 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-
3-pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (2
-Chloro-5-thiazolylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (6
-Chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-thiadiazine. When X represents a sulfur atom in the compound of the formula (II), it can be synthesized by the following production method (d). Production method (d) The compound represented by the above formula (VI) is combined with formaldehyde and hydrogen sulfide. A production method characterized by reacting.

In the above production method (a), the compound represented by the formula (III) has the definition based on the definition of R ³ and R ⁴ , preferably, R ³ represents methyl, and R ⁴ represents methyl.
Indicates iodine. The compound represented by the formula (III) is
It is a well-known compound in the field of organic chemistry. Formula (III)
Examples of the compound represented by the following include chloromethyl, iodomethane, iodoethane and 1-bromopropane. In the above process (b), a compound represented by the material of formula (IV), a definition based on the above definitions of X and R ^2, preferably said X and R ²
The meaning is as defined for each preferred definition.

The compound of formula (IV) is a novel compound,
For example, it can be synthesized by the following production methods (e), (f) and (g). Production method (e) When X represents an oxygen atom: the following formula (VII)

Embedded image In the formula, R ² and Y are the same as described above, and a production method characterized by reacting the compound represented by
Or (f) when X represents a sulfur atom: a method comprising reacting a compound represented by the above formula (VII) with formaldehyde and hydrogen sulfide, or (g) R ² When C _1-4 alkyl is represented by the following formula (VIII)

Embedded image Wherein X and Y are the same as defined above, and a compound represented by the formula (III) is reacted.

In the above processes (e) and (f), the compound of the formula (VII) as a raw material is a compound well-known in the field of organic chemistry, and specific examples thereof include the following compounds. it can. N-cyanoguanidine, N-nitroguanidine, N-methyl-N'-nitroguanidine, N-
Ethyl-N'-nitroguanidine, Nn-propyl-
N'-nitroguanidine. In the above production method (g), the starting compound of formula (VIII) is a novel compound included in the above formula (IV). The compound of the formula (VIII) can be prepared by the above process (e)
Alternatively, it can be synthesized by the production method (f). Specific examples thereof include the following compounds. 3-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine, 3-methyl-4-nitroiminotetrahydro-1,3,5-thiadiazine.

[0012] In the above process (c), compounds represented by formula (VI), wherein A, shows the definition based on the definition of R ¹ and Y, preferably preferred the A, R ¹ and Y, respectively Shows the same meaning as the definition. The compound of the formula (VI) is, for example, a known compound described in JP-A-2-288885 or 2-288860, and can be synthesized by the method described in JP-A-Hei. Examples of the compound represented by the formula (VI) include the following compounds, N- (6-chloro-3-pyridylmethyl)-
N'-nitroguanidine, N- (2-chloro-5-thiazolylmethyl) -N'-nitroguanidine, N- (6-
Chloro-3-pyridylmethyl) -N'-cyanoguanidine, N- (2-chloro-5-thiazolylmethyl) -N '
-Cyanoguanidine.

In carrying out process (a) above, suitable inert diluents include all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene , Xylene, dichloromethane, chlorobenzene, dichlorobenzene; and other ethers such as ethyl ether, methyl ethyl ether, isopropyl ether,
Butyl ether, dioxane, dimethoxyethane (DM
E), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); and other ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (M
IBK); other, nitriles such as acetonitrile, propionitrile, acrylonitrile; other, alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol;
Esters, for example, ethyl acetate, amyl acetate;
Acid amides such as dimethylformamide (DMF),
Dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA); other sulfones, sulfoxides such as dimethyl sulfoxide (DMSO), sulfolane; In addition, bases such as pyridine can be exemplified.

The production method (a) can be carried out in the presence of an acid binder, such as an alkali metal hydroxide, carbonate and bicarbonate as an inorganic base.
Examples thereof include sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, and calcium hydroxide. Inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide and the like can be mentioned. Alcoholates, tertiary amines, dialkylaminoanilines and pyridines as organic bases,
For example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N, N-dimethylaniline, N, N-diethylaniline, pyridine,
-Dimethylaminopyridine (DMAP), 1,4-diazabicyclo [2,2,2] octane (DABCO) and 1,8-diazabicyclo [5,4,0] undec-7-
And en (DBU). Organic lithium compounds, for example, methyl lithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, phenyl lithium, dimethyl copper lithium, lithium diisopropylamide, lithium cyclohexylisopropylamide, lithium dicyclohexylamide, n-butyllithium DABCO , N-butyllithium.DBU and n-butyllithium.TMEDA.

The above production method (a) can also be carried out by a method using a phase transfer catalyst. Suitable diluents include all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene ,
Xylene, dichloromethane, chlorobenzene, dichlorobenzene; other ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DM
E), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); and others. Examples of the phase transfer catalyst include quaternary ions such as tetramethylammonium bromide,
Crown ethers such as tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium bisulfate, tetrabutylammonium iodide, trioctylmethylammonium chloride, benzyltriethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, and benzyltriethylammonium chloride For example, dibenzo-18
-Crown-6, dicyclohexyl-18-crown-
6, 18-crown-6 and the like, cryptands, for example,
[2.2.2] -cryptate, [2.1.1] -cryptate, [2.2.1] -cryptate, [2.2.
B] - cryptate [2 _O 2 _O 2 _S] - cryptate [3.2.2] - can be exemplified cryptate and the like.

Process (a) can be carried out within a substantially wide temperature range. Generally, when utilizing an acid binder, from about -80 to about 150 ° C, preferably
It can be carried out between about 0 and about 120 ° C. When a phase transfer catalyst is used, it can be carried out at about -70 to about 150 ° C, preferably at about 0 to about 100 ° C. The reaction is desirably performed under normal pressure, but can be operated under increased or reduced pressure. In carrying out the production method (a), for example, when an acid binder is used, 1 mol to 10 mol of the compound of the formula (III) in a diluent such as DMF is added to 1 mol of the compound of the formula (II). The target compound can be obtained by reacting the compound in the presence of sodium hydride. Also, for example, when using a phase transfer catalyst,
1 mol of the compound of the formula (II) is reacted with 1 mol to 10 mol of the compound of the formula (III) in a diluent such as toluene in the presence of tetrabutylammonium chloride to obtain the desired compound. Can be.

In carrying out process (b) above, suitable diluents include all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene , Xylene, dichloromethane, chlorobenzene, dichlorobenzene; and other ethers such as ethyl ether, methyl ethyl ether, isopropyl ether,
Butyl ether, dioxane, dimethoxyethane (DM
E), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); other ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MI
BK); other nitriles such as acetonitrile,
Propionitrile, acrylonitrile; other alcohols such as methanol, ethanol, isopropanol, butanol, ethylene glycol; other esters such as ethyl acetate, amyl acetate; other acid amides such as dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone,
1,3-dimethyl-2-imidazolidinone, hexamethylphosphoric triamide (HMPA);
Sulfones, sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane; and other bases such as pyridine.

The production method (b) can be carried out in the presence of an acid binder, and examples of the acid binder include all the acid binders exemplified in the above production method (a). The production method (b) can be carried out in the presence of a phase transfer catalyst. As an example of the diluent and the phase transfer catalyst for performing such a reaction, the production method (b) is carried out in the presence of the phase transfer catalyst of the production method (a). Examples of the reaction can be given. Production method (b)
Can be performed within a substantially wide temperature range. Generally, from about -80 to about 150C, preferably
It can be carried out between about 0 and about 120 ° C. When a phase transfer catalyst is used, it can be carried out at about -70 to about 150 ° C, preferably at about 0 to about 100 ° C. The reaction is desirably performed under normal pressure, but can be operated under increased or reduced pressure. In carrying out the production method (b), for example, 1 mol to 2 mol of the compound of the formula (V) in a diluent such as DMF is added to 1 mol of the compound of the formula (IV) in the presence of sodium hydride. The target compound can be obtained by reacting under the following conditions. For example, when a phase transfer catalyst is used, 1 to 10 mol of a compound of the formula (III) in a diluent such as toluene is added to 1 mol of the compound of the formula (II) in the presence of tetrabutylammonium chloride. The target compound can be obtained by reacting under the following conditions.

In carrying out process (c) above, suitable diluents include all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated or nitrated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, Benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, nitromethane, nitroethane, nitropropane, nitrobutane; other ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (T
HF), diethylene glycol dimethyl ether (DG
M); other ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK); other nitriles such as acetonitrile, propionitrile, acrylonitrile; other alcohols such as methanol;
Ethanol, isopropanol, butanol, ethylene glycol; other esters such as ethyl acetate;
Amyl acetate; other acid amides such as dimethylformamide (DMF), dimethylacetamide (DM
A), N-methylpyrrolidone, 1,3-dimethyl-2-
Other examples include imidazolidinone, hexamethylphosphoric triamide (HMPA); other sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane; and other bases such as pyridine.

The production method (c) can be carried out in the presence of an acid. Examples of such an acid include mineral acids such as hydrochloric acid, nitric acid and sulfuric acid. Process (c) can be performed within a substantially wide temperature range. Generally, from about 0 to about 150 ° C, preferably from about 50 to about 120 ° C.
C. can be carried out. The reaction is desirably carried out under normal pressure, but can be carried out under increased or reduced pressure. In carrying out the production method (c), for example, 1 mol to 50 mol of formalin in a diluent, for example, nitroethane is added to 1 mol of the compound of the formula (VI) in 0.0 mol.
The target compound can be obtained by reacting in the presence of 01 mol to 10 mol of hydrochloric acid.

In carrying out process (d), suitable inert diluents include all inert organic solvents. Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (optionally chlorinated or nitrated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, Benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene, nitromethane, nitroethane, nitropropane, nitrobutane; other ethers such as ethyl ether, methyl ethyl ether,
Isopropyl ether, butyl ether, dioxane,
Dimethoxyethane (DME), tetrahydrofuran (T
HF), diethylene glycol dimethyl ether (DG
M); other ketones such as acetone, methyl ethyl ketone (MEK), methyl-isopropyl ketone, methyl isobutyl ketone (MIBK); other nitriles such as acetonitrile, propionitrile, acrylonitrile; other alcohols such as methanol;
Ethanol, isopropanol, butanol, ethylene glycol; other esters such as ethyl acetate;
Amyl acetate; other acid amides such as dimethylformamide (DMF), dimethylacetamide (DM
A), N-methylpyrrolidone, 1,3-dimethyl-2-
Other examples include imidazolidinone, hexamethylphosphoric triamide (HMPA); other sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolane; and other bases such as pyridine.

The production method (d) can be carried out in the presence of an acid. Examples of the acid include mineral acids, hydrochloric acid, nitric acid and sulfuric acid. Process (d) can be performed within a substantially wide temperature range. Generally, about 0
It can be carried out at about 150C, preferably between about 50C and about 120C. The reaction is desirably carried out under normal pressure, but can be carried out under increased or reduced pressure. In carrying out the production method (d), for example, 1 mol to 50 mol of formalin and 1 mol to 50 mol of hydrogen sulfide in a diluent, for example, concentrated hydrochloric acid, are added to 1 mol of the compound of the formula (VI). To give the desired compound.

In carrying out process (e), suitable inert diluents include all inert organic solvents. Examples of such a diluent include the same organic solvents as in the above-mentioned production method (c). The production method (e) can be carried out in the presence of an acid, and examples of the acid include mineral acids,
For example, hydrochloric acid, nitric acid, and sulfuric acid can be exemplified. Process (e) can be performed within a substantially wide temperature range. Generally, it can be carried out between about 0 and about 150 ° C, preferably between about 50 and about 120 ° C. The reaction is desirably carried out under normal pressure, but can be carried out under increased or reduced pressure. In carrying out the production method (e), for example, 1 mol to 50 mol of formalin is added to 0.001 mol to 10 mol of hydrochloric acid in a diluent such as nitroethane per 1 mol of the compound of the formula (VII). The target compound can be obtained by reacting under the following conditions.

In carrying out the above process (f), suitable inert diluents include all inert organic solvents. Examples of such a diluent include the same organic solvents as in the above-mentioned production method (d). The production method (f) can be performed in the presence of an acid, and examples of the acid include mineral acids,
For example, hydrochloric acid, nitric acid, and sulfuric acid can be exemplified. Process (f) can be performed within a substantially wide temperature range. Generally, it can be carried out between about 0 and about 150 ° C, preferably between about 50 and about 120 ° C. The reaction is desirably carried out under normal pressure, but can be carried out under increased or reduced pressure. In carrying out the production method (f), for example, 1 mol to 50 mol of formalin and 1 mol to 50 mol of hydrogen sulfide in a diluent such as concentrated hydrochloric acid are added to 1 mol of the compound of the formula (VII). To give the desired compound.

In carrying out process (g) above, suitable inert diluents include all inert organic solvents. Examples of such a diluent include the same organic solvents as in the above-mentioned production method (a). The production method (g) can be performed in the presence of an acid binder, and examples of the acid binder include the same acid binders as in the above production method (a). The above production method (g) can also be carried out by a method using a phase transfer catalyst. Examples of suitable diluents and phase transfer catalysts include the diluents and phase transfer catalysts described in process (a) above. Production method (g)
Can be performed within a substantially wide temperature range. Generally, when an acid binder is utilized, about -8
It can be carried out between 0 and about 150 ° C, preferably between about 0 and about 120 ° C. When using a phase transfer catalyst,
About -70 to about 150C, preferably about 0 to about 100C
Can be implemented between The reaction is desirably performed under normal pressure, but can be operated under increased or reduced pressure. In carrying out the production method (g), for example, when an acid binder is used, 1 mol to 10 mol of the compound of the formula (III) in a diluent, for example, DMF is used per 1 mol of the compound of the formula (VIII). Is reacted in the presence of sodium hydride to give the desired compound. When a phase transfer catalyst is used, for example, 1 mole of the compound of the formula (VIII) is added in a diluent such as toluene in an amount of 1 mole to 10 moles.
The target compound can be obtained by reacting a molar amount of the compound of the formula (III) in the presence of triethylbenzylammonium chloride.

The compounds of the formula (I) according to the invention exhibit a strong insecticidal action. Therefore, they can be used as insecticides. And the active compound of the formula (I) of the present invention exerts an accurate control effect on harmful insects without causing phytotoxicity to cultivated plants. In addition, the compounds of the present invention can be used for controlling a wide variety of pests, harmful sucking insects, biting insects and other plant parasitic pests, storage pests, sanitary pests, and the like, and can be applied for their eradication. Examples of such pests include the following pests. As insects, Coleoptera pests,
For example, the beetle weevil (Callosobruchu)
chinensis) and weevil (Sitop)
hilus zemais)
rivolium castaneum) and Epiachna vicint
ioctomaculata), brown beetle (Agriotes fusicollis),
Japanese turtle (Anomala rufocupre)
a), Colorado potato beetle (Leptinotar)
sa decemlineata), diabloteica (Diabrotica spp.), pine beetle (Monochamus alternata)
s), rice weevil (Lissorhoptrus)
oryzophilus, Flycatcher beetle (Ly)
ctus bruneus);

Lepidoptera, for example, the gypsy moth (Lyma)
ntria dispar)
osoma neustria)
israpae), Lotus armyworm (Spodopte)
ra litura), armyworm (Mamestra b)
rassicae), Nikamechu (Chilosu)
ppressalis, Awanomeiga (Pyraus)
ta nubilalis), and the locust moth (Ep.)
estia cautella, Kamamon citrus (Adoxophyes orana), codling moth (Carpocapsa pomonella), Kaburayaga (Agrotis fucosa), honey moth (Galleria mellonella, Hellinga geronella, Helium nipponella)
s), Citrus conch (Phyllocnistis)
citrulla); Hemiptera, for example, Nephotettix cincticep
s), brown planthopper (Nilaparvata lu)
gens), Pseudoco (Pseudoco)
cucus comstocki, Unaspis yanonensis, peach aphid (Myzus persicae), apple aphid (Aphis pomi), cotton aphid (Aphis gossypisphi)
rassicae), Nashigumbai (Stephani)
tis nashi), Green stink bug (Nezaras)
pp. ), Bed Bug (Cimex electrical)
ius), Whiteflies (Trialeurod)
es vapororiorum, psyllium (Psy
lla spp. );

Orthoptera, for example, German cockroaches (B
ratella germanica), American cockroach (Periplaneta americana),
Kera (Grylotalpa africana),
Grasshopper (Locusta migratoria mi)
grateriodes); Isoptera, for example, the termite (Deucotermes sparatu)
s), House termites (Copttermes for)
mosanus); Diptera, for example, housefly (Mu)
sca domestica), Aedes aegypti (Ae
des aegypti) and the fly (Hylemia)
platura), Culex pipiens (Culex pipe)
iens), Anopheles s
inensis), Culex pipiens (Culex t)
ritaeniorhynchus). Examples of mites include mites spider mite (Tetranychus terarius), spider mites (Tetranychus urticae),
Citrus red mite (Panonychus citri),
Citrus rust mite (Aculops pelekass)
i) Dust mites (Taronemus spp.)
And the like. Nematodes include, for example, sweet potato nematodes (Meloidog).
yne incognita), pine wood nematode (Bursaphelenchus lignicol)
us Mamiya et Kiyohara, Rice phalaenopsis (Aphelenchoides)
besseyi), soybean cyst nematode (Hete)
rodera glycines), and a nematode (Pratylenchus spp.).

Furthermore, in the pharmaceutical field of veterinary medicine, the novel compounds of the present invention are effective against various harmful animal parasites (endo and ectoparasites), such as insects and helminths. Examples of such animal parasites include:
The following pests can be exemplified. Insects include, for example, horse flies (Gastrophilus sp.)
p. ), Sand flies (Stomoxys spp.), Whiteflies (Trichodicts spp.), Sand turtles (Rhodnius spp.), Dog flea (Ct.
enocephalides canis) and the like. Examples of mites include, for example, Kazuki mites (Ornithodoros spp.) And ticks (I
xodes spp. ), Ox tick (Boophi)
russpp. ) And the like.

In the present invention, a substance having an insecticidal action on insects including all of them is sometimes referred to as an insecticide. The active compounds according to the invention can be in the usual formulation. And such forms include solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets,
Granules, aerosols, active compound infiltration-natural and synthetic,
Formulations with microcapsules, seed coating, combustion equipment (eg fumigation and fume cartridges, cans and coils as combustion equipment), and ULV [cold mist, warm mist (warm mist)
mist)]. These preparations can be manufactured by a known method. Such a method is
For example, the active compound may be formulated with a developing agent, ie, a liquid diluent; a liquefied gas diluent; a solid diluent or carrier, optionally with a surfactant, ie, an emulsifier and / or dispersant and / or foam former. And by mixing.
If water is used as the developing agent, for example, organic solvents can also be used as auxiliary solvents.

The liquid diluent or carrier generally includes aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, chlorides). Ethylenes, methylene chloride, etc.), aliphatic hydrocarbons [eg, cyclohexane, etc., paraffins (eg, mineral oil fractions, etc.)], alcohols (eg, butanol, glycol and their ethers, esters, etc.), ketones (eg, For example, acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, etc., strong polar solvents (eg, dimethyl formamide, dimethyl sulfoxide, etc.)
And water. The liquefied gas diluent or carrier is a gas at normal temperature and pressure, examples of which include butane, propane, nitrogen gas, carbon dioxide, and aerosol propellants such as halogenated hydrocarbons. it can. Examples of the solid diluent include soil natural minerals (eg, kaolin, clay, talc, chalk, quartz, attapull guide, montmorillonite or diatomaceous earth), and soil synthetic minerals (eg, highly dispersed silicic acid, alumina, silicate, etc.). be able to. Solid carriers for granules include ground and fractionated rocks (eg,
Fine particles of calcite, marble, pumice, sepiolite, dolomite, synthetic particles of inorganic and organic powders, and organic substances (for example, sawdust, coconut, corn cob and tobacco stem). The body can be mentioned.

Examples of the emulsifier and / or foaming agent include nonionic and anionic emulsifiers (eg, polyoxyethylene fatty acid ester, polyoxyethylene fatty acid alcohol ether (eg, alkylaryl polyglycol ether, alkyl sulfonate, alkyl sulfate) , Arylsulfonates, etc.]] and albumin hydrolysis products. Dispersants include, for example, lignin sulfite waste liquors and methylcellulose. Fixatives can also be used in the formulation (powder, granules, emulsions) and include carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate. Can be. Coloring agents can also be used, and as such coloring agents, inorganic pigments (for example, iron oxide,
Titanium oxide and Prussian blue), and organic dyes such as alizarin dyes, azo dyes or metal phthalocyanine dyes, and also trace elements such as iron, manganese, boron, copper, cobalt, molybdenum and zinc salts thereof. Can be. The formulations may generally contain between 0.1 and 95% by weight of the active ingredient, preferably between 0.5 and 90% by weight.

The active compounds of the formula (I) according to the invention can, in their commercially useful formulations and in the use forms prepared by these formulations, contain other active compounds such as insecticides, baits, fungicides, They can also be present as admixtures with acaricides, nematicides, fungicides, growth regulators or herbicides. Here, examples of the insecticide include organophosphorus agents, carbamates, carboxylates, chlorinated hydrocarbons, and insecticides produced by microorganisms. Furthermore, the active compounds of the formula (I) according to the invention can also be present as admixtures with synergists, and such preparations and use forms can be those which are commercially useful. The synergist is itself a compound which need not be active, but which amplifies the action of the active compound. The content of the active compounds of the formula (I) according to the invention in commercially useful forms of use can be varied within wide limits. The working concentrations of the active compounds of the formula (I) according to the invention are, for example, from 0.0000001 to 100% by weight, preferably from 0.00001 to 1% by weight. The compound of the formula (I) of the present invention can be used in a usual manner suitable for the use form. When used in sanitary pests, pests on stored products, the active compounds are distinguished by a good stability against alkali on lime substances, as well as excellent residual action in wood and soil .

Next, the contents of the present invention will be specifically described with reference to examples, but the present invention should not be limited to these.

【Example】

 Synthesis Example 1

Embedded image 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine (1.2 g), triethylbenzylammonium chloride (0.3 g), dimethyl sulfate (0.7 g) A 50% aqueous sodium hydroxide solution (4 ml) was added dropwise to the methylene chloride solution (50 ml) at room temperature. After vigorous stirring for 5 hours, the methylene chloride layer was separated and purified by silica gel column chromatography (elution solvent: chloroform: ethanol = 10: 1) to give 3- (6-chloro-3).
-Pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine (0.5 g)
Get. mp. 121-122 ° C

Synthesis Example 2

Embedded image 5-methyl-4-nitroiminotetrahydro-1,3,
5-oxadiazine (1.6 g), triethylbenzylammonium chloride (0.5 g), 2-chloro-5
A 50% aqueous sodium hydroxide solution (8 ml) was added dropwise to a methylene chloride solution (50 ml) of -chloromethylthiazole (1.7 g) at room temperature. After stirring for 8 hours, the methylene chloride layer was separated and subjected to silica gel column chromatography (elution solvent: chloroform: ethanol = 10:
Purification in 1) gives 3- (2-chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydro-
1,3,5-oxadiazine (0.3 g) is obtained. mp. 147-150 ° C

Synthesis Example 3

Embedded image N- (6-chloro-3-pyridylmethyl) -N'-nitroguanidine (2.3 g), formalin (28% 10
ml) and concentrated hydrochloric acid (1 ml) were mixed in 30 ml of nitroethane and heated under reflux for 10 hours. After evaporating nitroethane with an evaporator, the residue was subjected to silica gel column chromatography (elution solvent: chloroform: ethanol = 10:
Purification in 1) gives 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine (1.0 g). mp. 164-166 ° C

The compounds synthesized in the same manner as in Synthesis Examples 1, 2 and 3 are shown below together with the compounds of the above Synthesis Examples. Compound No. 1: 3- (6-chloro-3-pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-
1,3,5-oxadiazine mp. 121-122 ° C Compound No. 2: 3- (2-chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydro-
1,3,5-oxadiazine mp. 147-150 ° C Compound No. 3: 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine mp. Compound No. 4: 3- (2-chloro-5-thiazolylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine mp. 173-175 ° C Compound No. 5: 3- (6-chloro-3-pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-
1,3,5-thiadiazine mp. 119-123 ° C

Synthesis Example 4 (Preparation of Intermediate)

Embedded image N- (6-chloro-3-pyridylmethyl) -N'-nitroguanidine (2.3 g), formalin (28% 2m
l), concentrated hydrochloric acid (10 ml) and sodium sulfide / 9-hydrate (2.4 g) were mixed in 30 ml of nitroethane, and the mixture was heated under reflux for 5 hours. After distilling off nitroethane with an evaporator, the residue is purified by silica gel column chromatography (elution solvent: chloroform: ethanol = 100: 6) to give 3- (6-chloro-3-pyridylmethyl) -4-.
Obtain nitroiminotetrahydro-1,3,5-thiadiazine (0.8 g). mp. 169-171 ° C

Synthesis Example 5 (Preparation of Intermediate)

Embedded image Nitroguanidine (10.4 g), formalin (28%
20 ml) and concentrated hydrochloric acid (4 ml) in nitromethane (3 ml).
0 ml) under reflux for 5 hours. After cooling to room temperature, the precipitated crystals are recrystallized from an aqueous ethanol solution (50%) to give 4-nitroiminotetrahydro-1,3,5-oxadiazine (4 g). mp. 300 ℃ or more

Embedded image The raw materials were changed to dicyandiamide (8.4 g), formalin (28% 20 ml), and concentrated hydrochloric acid (1 ml).
-Cyanoiminotetrahydro-1,3,5-oxadiazine (1.5 g) was synthesized.

Embedded image The raw materials were nitroguanidine (10.4 g), formalin (20 g), concentrated hydrochloric acid (22 ml) and sodium sulfide.
Changing to 9-hydrate (24 g) gives 4-nitroiminotetrahydro-1,3,5-thiadiazine (4 g) in the same manner. mp. 186-189 ° C

Synthesis Example 6 (Preparation of Intermediate)

Embedded image 4-nitroiminotetrahydro-1,3,5-oxadiazine (2.9 g), sodium hydride (60% 0.1%).
8 g) was dissolved in DMF (20 ml), and methyl iodide (2.8 g) was added thereto at room temperature, followed by stirring at 60 ° C. for 8 hours. After concentration by an evaporator, the residue was purified by silica gel column chromatography (elution solvent: chloroform: ethanol = 7: 1) to obtain 3-methyl-4-nitroiminotetrahydro-1,3,5-oxazine (1 g). mp. 134-137 ° C

Reference Example 3- (6-chloro-3-pyridylmethyl) -5-methyl-4-nitroiminotetrahydrooxadiazine (2.
9 g) was dissolved in ethanol (100 ml), concentrated hydrochloric acid (2 ml) was added thereto, and the mixture was stirred at 50 to 60 ° C for 1 hour.
After cooling, ethanol was distilled off under reduced pressure, aqueous sodium bicarbonate was added to the residue, and the precipitated crystals were collected by filtration to give N- (6-chloro-3-).
Pyridylmethyl) -N'-methylnitroguanidine (1
g) was obtained. mp. 157-159 ° C Raw material 3- (6-chloro-3-pyridylmethyl) -5-
When methyl-4-nitroiminotetrahydrooxadiazine is replaced with 3- (2-chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydrooxadiazine, N- (2-chloro-5-thiazolylmethyl)-
N'-methylnitroguanidine can be synthesized.

Biological Test Example Comparative Compound

Embedded image Test for organic phosphorus and carbamate resistant peach aphids. Preparation of Drug Solvent: Xylol 3 parts by weight Emulsifier: polyoxyethylene alkyl phenyl ether 1 part by weight 1 part by weight of the active compound is mixed with the above amount of the solvent containing the emulsifier in order to make a suitable active compound formulation. The mixture was diluted with water to a predetermined concentration. Test Method About 200 heads per plant of organic phosporus and carbamate-resistant peach aphids bred in eggplant seedlings (meguro long eggplants) about 20 cm in height planted in a clay pot with a diameter of 15 cm, and one day after inoculation A sufficient amount of the prepared active compound diluted with water was sprayed using a spray gun. After spraying 2
It was left at a temperature of 8 ° C. and two days after spraying, the insecticidal rate was calculated. The test was repeated twice. As a result, the compounds of compound numbers 1, 2, 3, 4 and 5 have an effective amount of 40
ppm showed an insecticidal rate of 100%, while the comparative compound (C
C) was 60%.

[0043]

The compound of the formula (I) of the present invention has excellent activity as an insecticide, as shown in the above Examples.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Akemi Ito 934-7 Kamitani, Koyama City, Tochigi Prefecture (56) References JP-A-2-235881 (JP, A) JP-A-6-183918 (JP, A) Chemical Abstracts, vol. 113, Abstract No. 216882 Chemical Abstracts, vol. 111, abstract number 157006 (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 413/06 A01N 43/88 101 C07D 417/06 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) 3- (6-chloro-3-pyridylmethyl)
-4-cyanoiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (6-chloro-3 -Pyridylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-thiadiazine, 3- (6-chloro-3-pyridylmethyl) -5-t-butyl-4-nitroiminotetrahydro-1, 3,5-oxadiazine, 3- (6-chloro-3-pyridylmethyl) -5-t-butyl-4-nitroiminotetrahydro-1,3,5-thiadiazine, 3- (1- (6-chloro-3 -Pyridyl) ethyl) -4
-Nitroiminotetrahydro-1,3,5-oxadiazine, 3- (1- (6-chloro-3-pyridyl) ethyl) -5
-Methyl-4-nitroiminotetrahydro-1,3,5
-Oxadiazine, 3- (1- (6-chloro-3-pyridyl) ethyl) -5
-Methyl-4-nitroiminotetrahydro-1,3,5
-Thiadiazine, 3- (2-chloro-5-thiazolylmethyl) -4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (2-chloro-5-thiazolylmethyl) -4-cyanoiminotetrahydro-1,3 , 5-oxadiazine, 3- (2-chloro-5-thiazolylmethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-thiadiazine, 3- (1- (2-chloro-5-thiazolyl) ethyl )-
4-nitroiminotetrahydro-1,3,5-oxadiazine, 3- (1- (2-chloro-5-thiazolyl) ethyl)-
4-nitroiminotetrahydro-1,3,5-thiadiazine and 3- (1- (2-chloro-5-thiazolyl)
A compound selected from the group consisting of ethyl) -5-methyl-4-nitroiminotetrahydro-1,3,5-oxadiazine. 2. An insecticide comprising, as an active ingredient, one compound selected from the group of compounds according to claim 1.