JPH0730070B2 - New heterocyclic compound - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel heterocyclic compounds, and to processes for making the compounds and their utility. Known publications prior to the filing date of the present application include, for example, West German Patent Publication No. 2,514,
No. 402 has the following general formula It is described that the 2-nitromethylene-imidazolidine derivative represented by and the 2-nitromethylene-hexahydropyrimidine derivative have insecticidal activity. In the specification, the compound represented by the following formula is described.

The present inventors have now found a novel heterocyclic compound represented by the following formula (I).

General formula: In the formula, n represents 0 or 1, R ¹ , R ² , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ represent a hydrogen atom, Hydroxy or carbon number 1
4 is an alkyl group, X is S, O, N—R ⁷ or CH—R ⁸ , where R ⁷ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms (the alkyl group is An alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, cyano, chloro, diethylamino or trimethylsilyl may be substituted), chloro-substituted allyl, benzyl (the benzyl being methyl, methoxy). , Optionally substituted with at least one selected from chloro and nitro), an alkylcarbonyl group having an alkyl having 1 to 5 carbon atoms (the alkylcarbonyl group is methoxy, 2,4-dichlorophenoxy, chloro or Optionally substituted by bromine), benzoyl (wherein benzoyl is chloro, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy) , Optionally substituted with at least one selected from isopropyl and nitro), an alkoxycarbonyl group having an optionally substituted fluoroalkyl having 1 to 4 carbon atoms, phenoxycarbonyl (the phenoxycarbonyl is Optionally substituted with methyl or chloro),
Dimethylaminocarbonyl, phenylaminocarbonyl (the phenylaminocarbonyl may be substituted with methyl or chloro), an optionally substituted chloro-substituted alkylsulfonyl group having 1 to 4 carbon atoms, phenylsulfonyl (the phenylaminocarbonyl). Enylsulfonyl may be substituted with at least one selected from methyl, chloro and nitro), O, O-dimethylphosphono group, O-ethyl-Sn
- propyl phosphono group, group -CH ₂ -W or group -CO-W
(In the above group, W represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole or pyridine,
These rings may be substituted with a halogen atom or a lower alkyl group), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, phenyl or benzyl, and Y represents N or C—R ⁹ Wherein R ⁹ is a hydrogen atom, bromine, or an alkyl group having 1 to 2 carbon atoms (the alkyl group is fluoro, chloro, hydroxy, alkoxy having 1 to 2 carbon atoms,
It may be substituted with alkylthio having 1 to 2 carbons, cyano, dimethylamino, alkylcarbonyl having alkyl having 1 to 2 carbons, or alkoxycarbonyl having alkyl having 1 to 2 carbons), 1-hydroxy-
2,2,2-trichloroethyl group, an alkylcarbonyl group having an alkyl group having 1 to 4 carbon atoms (the alkylcarbonyl group may be substituted with methoxy or chloro),
A benzoyl group (the benzoyl group may be substituted with at least one selected from chloro, bromo, methoxy and methyl), an alkoxycarbonyl group having an optionally substituted fluoroalkyl group having 1 to 4 carbon atoms,
A phenoxycarbonyl group (the phenoxycarbonyl group may be substituted with chloro, methyl, methoxy or nitro), benzoylaminocarbonyl (the benzoylaminocarbonyl may be substituted with methyl, fluoro or chloro) Phenyl), phenylsulfonylaminocarbonyl (wherein the phenylsulfonylaminocarbonyl group may be substituted with methyl or chloro), phenylthio (wherein the phenylthio may be substituted with methyl or chloro), or chloro-substituted. And optionally represents phenylsulfonyl, Often, R represents a hydrogen atom or methyl, and Z is a heterocycle consisting of thiophene, pyrazole, isoxazole, thiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, pyridine, pyrimidine, pyridazine or pyrazine. A group, these rings may be a halogen-substituted lower alkyl group, a chloro-substituted C2-3 alkenyl group, a halogen atom, propargyl, a fluoro-substituted methoxy, It may be substituted with one or two selected from optionally substituted methylthio, methylsulfinyl, methylsulfonyl, thiocyanato, trichloroacetamide, nitro, cyano and methoxycarbonyl.

However, in the above, when n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents NH, and Y represents CH, n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents S, Y represents CH, and Z is substituted. Optionally pyridyl group (wherein the substituent is a halogen atom, an optionally halogenated lower alkyl group, nitro, cyano, optionally fluorosubstituted methoxy, optionally fluorosubstituted methylthio, methylsulfinyl) , Methylsulfonyl and at least one selected from an optionally substituted alkenyl group having 2 to 3 carbon atoms), and n is 0 or 1, and R ¹ , R ² , R ³ , R ^4, R ⁵ and R ⁶ is a hydrogen atom, X represents NH, Y represents N, and Z Optionally substituted pyridyl group (the substituent is a halogen atom, a halogen-substituted lower alkyl group, nitro, cyano, optionally fluoro-substituted methoxy, optionally fluoro-substituted methylthio, Methylsulfinyl, methylsulfonyl, optionally substituted alkenyl group having 2 to 3 carbon atoms, and at least one selected from trichloroacetamide and methoxycarbonyl). Formula compound.

The compound of the above formula (1) can be synthesized by the following general method.

Production method a): [In the formula (I), X is S, O or N—R ¹⁰ , and
When Y is C-R ⁹ ] General formula: In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R and Z are the same as above, X ¹ is S, O or N—R ¹⁰ , and R ¹⁰ is the above R. ^In the definition of ⁷ , a compound other than a group corresponding to an acyl group (including a sulfonyl group and a phosphono group) is represented by the general formula: In the formula, R ′ represents a lower alkyl group or a benzyl group, or two R ′ together represent a C ₂ or higher lower alkylene group, which may form a ring with an adjacent sulfur atom. R ⁹ is the same as the above, and is reacted with a compound represented by
The above general formula (I) [where X is S, O or NR]
^{10. A} method for producing a compound according to ¹⁰ , wherein Y is (when —R ⁹ ).

Production method b): [In the formula (I), X and Y are the same as in the production method a)] The compound of the general formula (II): In the formula, Hal represents a halogen atom, and R ″ represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group or a phenyl group, and a compound represented by the formula: I) [where X is S, O or N-R
^And the case where Y is C—R ⁹ ].

Production method c): [In the formula (I), X and Y are the same as in the production method a)] The compound of the general formula (II): In the formula, Hal and R ″ are the same as the above, and a compound represented by the formula:
R ¹⁰ and Y is C—R ⁹ ].

Production method d): [In the formula (I), X is S, O or N—R ¹⁰ , and
When Y is N] The compound of the general formula (II): Of nitroguanidine of the formula (I) [wherein X is S, O or NR]
^In the case where ¹⁰ is Y and N is N], the production method of the compound.

Manufacturing method e): [In the formula (I), when Y is N] General formula: In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, R and Z are the same as defined above, and a fuming nitric acid is reacted. A method for producing a compound of the above general formula (I) [where Y is N].

Manufacturing method f): General formula: In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X and Y are the same as the above, and a compound represented by the general formula: In the formula, R and Z are the same as above, M is a halogen atom or -OSO ₂ T, and T is a lower alkyl group, a phenyl group or a tolyl group, and the compound represented by ,
A method for producing the compound of the general formula (I).

According to the invention, the compounds of the general formula (I) have a high insecticidal activity and, surprisingly, in low doses compared to similar compounds of the invention, for example the previously known compounds (A-1), It has a very remarkable insecticidal action.

The compound of the present invention is, in addition to the above-mentioned strong insecticidal activity, further pests resistant to these insecticides resulting from the use of organophosphorus and carbamate insecticides, especially in the past for many years. Shows a remarkable control effect on puncture-absorptive insects represented by Hemiptera, such as aphids, planthoppers, leafhoppers and the like.

Therefore, an object of the present invention is to provide a novel heterocyclic compound of the above formula (I), a process for producing the same and a use thereof as an insecticide.

These and many other objects and advantages of the present invention will become more apparent from the description below.

In the general formula (I) of the compound of the present invention, preferably n is 0 or 1, R ¹ , R ² , R ⁵ and R ⁶ are each a hydrogen atom or methyl, and R ³ and R ⁴ are respectively , Hydrogen atom or methyl, X is S,
O, N—R ⁷ or CH—R ⁸ , wherein R ⁷ is a hydrogen atom, an alkyl group having 1 to 2 carbon atoms (wherein the alkyl group is substituted with methoxy, ethoxy, methylthio, ethylthio, cyano, chloro or trimethylsilyl). Optionally, allyl optionally substituted with chloro, benzyl optionally substituted with methyl and / or chloro, an alkylcarbonyl group having an alkyl of 1 to 3 carbon atoms (the alkylcarbonyl group is methoxy, 2,4-dichlorophenoxy or chloro may be substituted), benzoyl (the benzoyl may be substituted with at least one selected from chloro, methyl, trifluoromethyl, methoxy and nitro), Substituted with an alkoxycarbonyl group having an optionally substituted C 1-2 alkyl, methyl or chloro Which may be phenoxyethanol carbonyl,
Dimethylaminocarbonyl group, phenylaminocarbonyl which may be substituted with methyl or chloro, methylsulfonyl which may be substituted with chloro, phenylsulfonyl which may be substituted with methyl, O, O-dimethylphosphono group, O -Ethyl S-n-propylphosphono group, group -CH
_2- W or (In the above group, W represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole or pyridine,
These rings may be substituted with chloro, bromine or methyl), R ⁸ represents a hydrogen atom, methyl, phenyl or benzyl, Y is N or C—R ⁹ , wherein R ⁹ Is a hydrogen atom, bromine, alkyl having 1 to 2 carbon atoms (the alkyl group may be substituted with fluoro, chloro, hydroxy, methoxy, cyano, dimethylamino, acetyl or methoxycarbonyl), or chloro substituted. Good acetyl,
Benzoyl, fluor optionally substituted carbon number 1
Alkoxycarbonyl group having 2 alkyl, phenoxycarbonyl optionally substituted with methyl or chloro, benzoylaminocarbonyl optionally substituted with methyl or chloro, phenylsulfonylaminocarbonyl optionally substituted with methyl, chloro Optionally substituted phenylthio or phenylsulfonyl, and R ⁹ is R is a hydrogen atom or methyl, and Z is from thiophene, pyrazole, isoxazole, thiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, pyridine, pyrimidine, pyridazine or pyrazine. A heterocycle group consisting of
It may be substituted with chloro, bromo, methyl, fluoro substituted methyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro, cyano, trifluoromethoxy, trifluoromethylthio, allyl, tri.

However, in the above, when n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents NH, and Y represents CH, n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents S, Y represents CH, and Z is substituted. Pyridyl group (wherein the substituent is selected from fluoro, chloro, bromo, methyl, fluoro-substituted methyl, nitro, cyano, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl and allyl). At least one), and n is 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen atoms, X is NH, and Y is Y. Represents N, and Z is an optionally substituted pyridyl group (wherein the substituent is fluoro, Group, bromine, methyl, fluoro-substituted methyl, nitro, cyano, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl, allyl, trichloroacetamide and methoxycarbonyl.) Except when

Then, as specific examples of the compound of the general formula (I) of the present invention, the following can be mentioned in particular. That is, 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) pyrrolidine, 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyrimidine, 1- (2-chloro- 5-pyrimidinylmethyl) -2-
(Nitroimino) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -4-methyl-2- (nitromethylene) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -3- (3-
Pyridylmethyl) -2- (nitromethylene) imidazolidine, 1- (2-chloro-5-pyridylmethyl) -2- (bromonitroimethylene) imidazolidine, 1- (2-chloro-5-pyridylmethyl)- 2- (1-
Nitro-2-oxopentylidene) imidazolidine, ethyl, nitro [3- (2-chloro-5-pyridylmethyl) thiazolidine-2-ylidene] acetate, 1-acetyl-3- (2-chloro-5-pyridylmethyl) ) -2- (Nitroimino) imidazolidine, N-phenylsulfonyl, nitro [1- (2-chloro-
5-Pyridylmethyl) imidazolidine-2-ylidene]
Acetamide, 3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) thiazolidine.

The compound of the general formula (I) of the present invention can be synthesized by the following general method.

Production method a): In the formula (I), X is S, O or N—R ¹⁰ , and Y
Is C-R ^9- In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z, X ¹ , R ′
And R ⁹ are the same as above. ) In the above reaction formula, for example, if 2-amino-1- (2-chloro-5-pyridylmethylamino) propane and 1-nitro-2,2-bis (methylthio) ethylene are used as raw materials, It is represented by the reaction formula.

Production method b): In the formula (I), X is S, O or N—R ¹⁰ , and Y
Is C-R ^9- (In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z, X ¹ ,
R ″ and Hal are the same as above.) In the above reaction formula, for example, 2- (2-
The use of methyl-5-pyrazinylmethylamino) ethanethiol and 2,2-dichloronitroethylene is represented by the following reaction formula.

Process c): In formula (I), X is S, O or N—R ¹⁰ , and Y
Is C-R ^9- (In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z, X ¹ ,
R ″ and R ⁹ are the same as the above.) In the above reaction formula, for example, 2- (2-
The use of chloro-5-thiazolylmethylamino) ethanethiol and 1,2,2,2-tetrachloro-1-nitroethane is represented by the following reaction formula.

Process d): In formula (I), X is S, O or N—R ¹⁰ , and Y
Is N- (In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z, and X ¹ are the same as the above.) In the above reaction formula, for example, N- (1, 2,5
When -thiadiazol-3-ylmethyl) ethylenediamine and nitroanidine are used, they are represented by the following reaction formula.

Manufacturing method e): In the formula (I), when Y is N- (In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, X and Z are the same as above.) In the above reaction formula, for example, 2-imino-3 as a raw material is used. Using-(4-pyridylmethyl) thiazolidine and fuming nitric acid is represented by the following reaction formula.

Manufacturing method f): (In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, Y, R, Z
And M are the same as above.

In the above reaction formula, for example, when 2-nitroiminothiazolidine and 2-chloro-pyridylmethyl chloride are used as raw materials, they are represented by the following reaction formula.

In the above-mentioned production method a), the compound of the general formula (II) which is a raw material is n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z and X ^{1 described above.}
Based on the above definition, preferably, they have the same meaning as the above-mentioned preferred definitions.

The compound of the general formula (II) includes both known compounds and novel compounds. A specific example thereof is Japanese Patent Application Laid-Open No. 60-172976 (Japanese Patent Application No. 59-26020) filed by the same applicant as the present application.
No.), No. 60-218386 (No. 59-72966), No. 61-12682.
No. 59-132943, No. 61-178981 (No. 60-18627)
No. 61-178982 (No. 60-18628), No. 61-18327
No. 1 (No. 60-23683) and No. 61-267561 (No. 60-1068)
Each of the compounds disclosed in No. 53) can be mentioned, and in addition, the following compounds can be exemplified.

2-amino-1- (4-pyridylmethylamino) propane, 2-amino-2-methyl- (3-pyridylmethylamino) propane, N- (4-pyridylmethyl) -2,2-dimethyltrimethylene diamine, 2-amino-1- (2-chloro-5-pyridylmethylamino) propane, N- (2-chloro-5-pyridylmethyl) -2-methyltrimethylenediamine, N- (3-pyridylmethyl) -N ' -Methylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N'-methylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N'-methyltrimethylenediamine, N- (2-fluoro -5-pyridylmethyl) -N'-isopropylethylenediamine, N- (2-chloro-5-pyridylmethyl) -N'-benzylethylenedi Min, N-(2-chloro-5-pyridylmethyl) -N '- (3
-Pyridylmethyl) ethylenediamine, N- (2-chloro-5-pyridylmethyl) -N '-(1
-Methyl-4-pyrazolylmethyl) ethylenediamine, 2-methyl-2- (2-methyl-5-pyridylmethylamino) ethanethiol, 1-methyl-2- (2-chloro-5-pyridylmethylamino) ethanethiol, 2- (4-pyridylmethylamino) ethanol, 2- (3-pyridylmethylamino) ethanol, 3- (α-methyl-3-pyridylmethyl) propanol, 2- (2-methyl-5-pyridylmethyl) ethanol, 2- (2-chloro-5-pyridylmethyl) ethanol, 3- (2-trifluoromethyl-5-pyridylmethyl)
Propanol, N- (1-methyl-4-pyrazolylmethyl) -2,2-dimethyltrimethylenediamine, N, N'-bis- (5-methyl-2-furfuryl) ethylenediamine, N- (3-methyl-5) -Isoxazolylmethyl)-
N '-(1-methyl-4-pyrazolylmethyl) ethylene (or trimethylene) diamine, 2- (3-methyl-5-isoxazolylmethylamino) ethanethiol, 3- (1-isopropyl-4-pyrazolylmethyl) Amino) propanethiol, 2- (1,2,5-thiadiazol-3-ylmethylamino) ethanethiol, 2- (2-trifluoromethyl-5-thiazolylmethylamino) ethanethiol, 2- (3- Methyl-5-isoxazolylmethylamino) ethanol, 2- (4-isothiazolylmethylamino) ethanol, 2- (5-oxazolylmethylamino) ethanol, 2- (3-trifluoromethyl-5- Isoxazolylmethylamino) ethanol, 2- (5-pyrimidinylmethylamino) ethanethiol, 2- (3-to Fluoromethyl-6-pyridazinylmethylamino) ethanethiol, 2- (2-methyl-5-pyrazinylmethylamino) ethanethiol, 2- (3-pyrazinylmethylamino) ethanol, 2- (3 -Chloro-6-pyridazinylmethylamino) ethanol, 2-amino-1- (2-pyrazinylmethyl) aminopropane, N- (5-pyrimidinylmethyl) -N '-(1-methyl-4-pyrazolylmethyl) Ethylenediamine, N- (3-chloro-6-pyridazinylmethyl) -N'-
Methyl ethylenediamine.

The compound of the general formula (II) can be prepared, for example, by the following method.
Can be synthesized.

Production method g): [When X ¹ is O or N—R ^{10 in} the formula (II)] General formula: In the formula, Z, R and M are the same as defined above, and a compound represented by the general formula: In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as above, X ²
Represents O or N—R ¹⁰ , and R ¹⁰ is the same as the above, and is reacted with a compound represented by
A method for producing a compound of the above general formula (II) [where X ¹ is O or N—R ¹⁰ ].

Manufacturing method h): General formula: In the formula, Z and R are the same as defined above, and a compound represented by the general formula: Wherein n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are the same as defined above, and then the product is reduced. Process for producing compound of general formula (II). The general formula (VI) as a raw material in the above production method g)
The compound of II) is the same as the raw material in the production method f) described later. The compound represented by formula (IX) is a known compound, and the compound can be easily produced by a known method. As a specific example, West German Patent Publication No. 27
Examples thereof include ethylenediamine and trimethylenediamine described in 32660 and French Patent 1,499,785, and 2-aminoethanol and 3-aminopropanol which are well known in the field of organic chemistry. Further, it is described in JP-A-60-78971, West German Published Patent No. 2514402, West German Published Patent No. 2,732,660, and JP-A-61-227571 (Japanese Patent Application No. 60-68551) by the same applicant as the present application. N-benzyl-ethylene (or trimethylene) diamines, and JP-A-60-172976 (Japanese Patent Application No. 59-26020) filed by the same applicant as this application.
No.), No. 60-218386 (No. 59-72966), No. 61-12682.
No. (No. 59-132943), No. 61-183271 (No. 60-23683)
No. 6) and No. 61-267561 (No. 60-106853), ethylene (or trimethylene) diamines are also mentioned as corresponding compounds of the formula (IX).

In carrying out the above-mentioned production method g), the compound of the formula (VIII) is used in an inert solvent as exemplified in the production method a) described in detail later.
The desired compound of general formula (II) can be easily obtained by reacting the compound with the compound of formula (IX).

In carrying out the above-mentioned production method g), for example, general formula (VI
By reacting the compound of the general formula (IX) in excess with, for example, about 5 times the molar amount of the compound of II), and by carrying out the reaction at a temperature in the range of 0 to 50 ° C., for example. It can be done easily.

In the above production method h), most of the compounds of the general formula (X) which are the starting materials are known compounds, and specific examples thereof include, for example, JP-A-60-
No. 218386 (Japanese Patent Application No. 59-72966), No. 61-178981 (No. 6)
0-18627), 61-178982 (60-18628), 6
No. 1-183271 (No. 60-23683), No. 61-267561 (No. 60)
-106853), and 61-267575 (60-106854)
The compounds described in can be exemplified.

In addition, the compound of the general formula (XI) includes the compound of the general formula (IX), and further includes 2-aminoethanethiol and the 2-aminoethanethiol described in Japanese Patent Application No. Examples thereof include 3-aminopropanethiol, and examples thereof include aminoalkanethiol having them as a basic chain.

In carrying out the above-mentioned production method h), for example, when X ³ is S, the method is described in J. Org. Chem., 27, 2452-2457 and 47.
It can be carried out by the same method as described on pages 12-4713.

Then, as a first step of such reaction, thiazolidine is prepared by reacting the compound of general formula (X) with the compound of general formula (XI) in the presence of an inert solvent such as benzene. Alternatively, an intermediate product of a tetrahydrothiazine derivative is synthesized, and then an exemplary reducing agent such as sodium borohydride, lithium aluminum hydride, aluminum borohydride, potassium borohydride, etc.,
It can be done by reducing.

In carrying out the above reaction, the intermediate product thiazolidine or tetrahydrothiazine derivative is reacted under reduced pressure, e.g.
It can be obtained by distilling off the volatiles associated with the first stage reaction at mHg, about 50-80 ° C, but can also be directly reduced without isolation.

Further, when X ³ is N—R ¹⁰ , the method is carried out in an inert solvent (benzene or the like), as shown in Examples below.
The desired compound of general (IIb) can be obtained by heating under reflux and then directly reducing by a conventional method without separating the intermediate product Schiff's base or imines.

In carrying out the above-mentioned production method h), for example, general formula (X)
It is preferable to react the compound of the general formula (XI) in excess with respect to 1 mol of the compound of the formula (1), for example, to react it in a molar amount of about 5 times, and the reaction temperature is usually in the range of 0 to 100 ° C. under normal pressure. Is preferred.

In the general formula (II), when X ¹ is S, as an alternative, a compound of the formula (II) in which X ¹ corresponds to O is halogenated with a halogenating agent such as thionyl chloride, and then A compound in which X ¹ in the general formula (II) corresponds to S can be obtained by reacting with potassium hydrosulfide or the like.

The compound of the general formula (III) which is a raw material in the production method a) includes both a known compound and a novel compound, and known compound examples are described, for example, in Chem. Ber., Vol. 100, pages 591-604. . And as specific examples thereof, for example, 1-nitro-2,2-bis (methylthio) ethylene, 1-nitro-2,2-bis (ethylthio) ethylene, 1-nitro-2,2-bis (benzylthio) Examples thereof include ethylene and 2-nitromethylene-1,3-dithiolane.

These compounds are easily obtained by a conventional reaction with nitromethane, carbon disulfide and an alkylating agent, but by reacting with another nitroalkane in place of nitromethane, the compound represented by the above formula (III) A compound corresponding to (1) can be easily synthesized, and nitromethane having an acyl group also reacts in the same manner to obtain the corresponding compound of the formula (III). For example, benzoyl methane [Beilstei
n (byylshutain), Vol. 7, p. 289], 1-benzoyl-1-nitro-2,2-bismethylthioethylene was obtained, and 1-acetyl-1-nitro-2,2-bismethylthioethylene was obtained from acetylnitromethane. Ethylene is obtained and these compounds are undocumented compounds.

In the above-mentioned production method b), the compound of the general formula (IV) as a raw material is a known compound, for example, Chem. Abst., (Chemical Abstracts), Volume 44, 1011f, JP-A-59-137.
No. 473 and the like. As a concrete example,
For example, 2,2-dichloronitroethylene, 1,2,2-toxylchloronitroethylene, 1-fluoro-2,2-dichloronitroethylene, 1-methyl-2,2-dichloronitroethylene, etc. may be exemplified. it can.

In the above-mentioned production method c), the compound of the general formula (V) as a raw material is a known compound, for example, J.Org.Chem., (Journal Organic Chemistry) Vol. 25, page 1312,
J. Org. Chem., Vol. 28, pages 1281-1283, Chem. Ber. (Chemifeverichte) 75B, pages 1323-1330, JP-A-60-48978 and the like. Specific examples thereof include 2,2,2-trichloro-1-nitroethane, 1,2,2,2-tetrachloro-1-nitroethane, and 2,2,2-trifluoro-1-nitroethane. can do.

In the above production method e), the compound of (VI) which is a raw material is
The above-mentioned definition of n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X, R and Z means, and preferably, they have the same meanings as those defined above. Show.

The compound of the general formula (VI) is a known compound in part.
And, for example, 2-imino-3- (4-pyridylmethyl) thiazolidine is described in J. Med. Chem., (Jeanal Medeisanal Chemistry) Vol. Other compounds corresponding to the formula (VI) can also be synthesized according to the method described in the literature.

The compound of the general formula (VII), which is the raw material in the above-mentioned production method f), means a compound based on the definition of n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , X and Y described above. , Preferably they have the same meaning as the preferred definitions given above.

Most of the compounds of the general formula (VII) are known compounds. And specific examples thereof include, for example, 2-nitromethyleneimidazolidine, 2-nitromethylenetetrahydropyrimidine, 4,4-dimethyl-2-nitromethyleneimidazolidine, 3-methyl-2-nitromethyleneimidazolidine, 3-allyl- 2-nitromethylene imidazolidine, 3-propargyl-2-nitromethylene imidazolidine, 3- (3-chloroallyl) -2-nitromethylene imidazolidine, 3-acetyl-2-nitromethylene imidazolidine, 3-chloroacetyl-2 -Nitromethyleneimidazolidine, 3-benzoyl-2-nitromethyleneimidazolidine, 3- (p-tosyl) -2-nitromethyleneimidazolidine, 2-nitromethylenethiazolidine, 2-nitromethylenetetrahydro-2H-1,3- Thiazine, 2-nitro Methylene-5-methylthiazolidine, 2-nitromethyleneoxazolidine, 2-nitromethylene-4-methyloxazolidine, 2-nitromethylenetetrahydro-2H-1,3-oxazine, 2-nitromethylenepyrrolidine, 2-nitromethylenepiperidine, 2 -(1-Nitroethylidene) imidazolidine, 2- (1-nitro-2-fluoroethylidene) imidazolidine, 2- (phenylnitromethylene) imidazolidine, 2- (1-nitro-2,2,2-tri Fluoroethylidene)
Imidazolidine, ethyl, nitro (imidazolidin-2-ylidene) acetate, n-butyl, nitro (tetrahydropyrimidine-2-ylidene) acetate, o-tolyl, nitro (imidazolidin-2-ylidene)
Acetate, p-chlorophenyl, nitro (imidazolidine-2-ylidene) acetate, p-nitrophenyl, nitro (imidazolidine-2-ylidene) acetate, 2- (methylthionitromethylene) imidazolidine, 2- (propylthionitromethylene) Imidazolidine, 2-[(4-chlorophenylthio) nitromethylene] imidazolidine, 2- (acetylnitromethylene) imidazolidine, 2- (dinitromethylene) imidazolidine, 2- (benzoylnitromethylene) imidazoline, ethyl, Nitro (1-ethoxycarbonylimidazolidine-2-ylidene) acetate, phenyl, nitro (1-phenylthiocarbonylimidazolidine-2-ylidene) thiol acetate, 2- (phenylthionitromethylene)- - phenylene thioether imidazolidine, 2- (1-nitro-ethylidene) - tetrahydro-1H-1,
3-thiazine, 2- (1-nitro-3-butynylidene) thiazolidine, 2- (1-nitro-3-butynylidene) -tetrahydro-2H-1,3-thiazine, 2- (1-nitro-2-phenyl) Ethylidene) thiazolidine, 2- (3-acetyl-1-nitropropylidene) -tetrahydro-2H-1,3-thiazine, 2- (3-cyano-1-nitropropylidene) -tetrahydro-2H-1,3- Thiazine, methyl, 4-nitro-4- (thiazolidine-2-ylidene) butyrate, 2- (2-ethylthio-1-nitroethylidene-tetrahydro-2H-1,3-thiazine, 2- (2-dimethylamino-1) -Nitroethylidene) thiazolidine, ethyl, nitro (tetrahydro-2H-1,3-thiazine-
2-ylidene) acetate, phenyl, nitro (tetrahydro-2H-1,3-thiazine-2-ylidene) acetate, 2-formylnitromethylenethiazolidine, 2-acetylnitromethylene-tetrahydro-2H-1,3
-Thiazine, 2-benzoylnitromethylene-tetrahydro-2H-1,
3-thiazine, 2-phenylthionitromethylene-tetrahydro-2H-
1,3-thiazine, ethyl, nitro (oxazolidine-2-ylidene) acetate, ethyl, nitro (tetrahydro-2H-1,3-oxazine-2-ylidene) acetate, 3-methyl-2-nitromethylenepyrrolidine, 3- Fluoro-2-nitromethylenepiperidine, methyl, nitro (pyrrolidine-2-ylidene) acetate, 3-methylthio-2-nitromethylenepiperidine, ethyl, nitro (thiazolidine-2-ylidene) acetate, 2-nitroiminoimidazolidine, 4 , 4-Dimethyl-2-nitroiminoimidazolidine, 2-nitroiminotetrahydropyrimidine, 3-methyl-2-nitroiminoimidazolidine, 3-isopropyl-2-nitroiminoimidazolidine, 3- (2-ethoxyethyl)- 2-nitroimino imidazolidi 3-ethoxycarbonyl-2-nitroiminoimidazolidine, 3-phenylthio-2-nitroiminoimidazolidine, 3-formyl-2-nitroiminoimidazolidine, 3-acetyl-2-nitroiminotetrahydropyrimidine, 3- (2 -Bromo-3,3-dimethylbutyryl) -2-nitroiminoimidazolidine, 3- (2,4-dichloro-3-methylbenzoyl) -2-
Nitroiminoimidazolidine, 3- (3-chloropropylsulfonyl) -2-nitroiminoimidazolidine, 3-phenoxycarbonyl-2-nitroiminoimidazolidine, 3- (2-methylthiazol-5-ylcarbonyl)-
2-nitroiminoimidazolidine, 3- (diethoxyphosphono) -2-nitroiminoimidazolidine, 3- (5-nitro-2-methylbenzenesulfonyl)-
2-nitroiminoimidazolidine, 2-nitroiminothiazolidine, 2-nitroiminotetrahydro-2H-1,3-thiazine, 2-nitroiminooxazolidine, 4-methyl-2-nitroiminooxazolidine, 2-nitroiminopyrrolidine, 2 -Nitroiminopiperidine, 3-methyl-2-nitroiminopyrrolidine, 2-nitroiminotetrahydro-2H-1,3-oxazine, 3- (2-trifluoromethylbenzoyl) -2-nitroiminoimidazolidine, 3- ( 4-methoxybenzoyl) -2-nitroiminoimidazolidine, 3- (2-difluoromethoxybenzoyl) -2-nitroiminotetrahydropyrimidine, 3- (2-furoyl) -2-nitroiminotetrahydropyrimidine and the like can be illustrated.

In the compound of the general formula (VII), 2-nitromethylene imidazolidines and 2-nitrotetrahydropyrimidines are Chem.Ber., (Chemihue Berichte) 100
Vol. 591-604, Belgian Patent No. 821,281 and U.S. Patent No. 3,971,774.
The acyl compound can be synthesized according to the reactions described in JP-A-60-67473 and JP-A-60-61575.

Further, in the 2-position methylene group of 2-nitromethyleneimidazolidines and 2-nitromethylenetetrahydropyrimidines, another group (or atom) other than the nitro group
Compounds to which are attached are disclosed in U.S. Pat.
4,002,765, 4,042,696, 4,052,411, 4,053,619, 4,053,622, 4,053,623,
It can be synthesized according to the methods described in JP-A-52-151,727 and Belgian Patent No. 821,282.

Almost all of 2-nitromethylene thiazolidines and 2-nitromethylene tetrahydro-2H-1,3-thiazines are known compounds, and these are the compounds of the formula (III) or (IV) or the aminoalkanethiols. It is easily obtained by reacting with a compound of formula (V), and the product can be obtained by various known methods (US Pat. No. 3,962,234).
No. 4,022,775, 4,024,254, 4,044,12
No. 8, No. 4,045,434, No. 4,076,813 and JP-A-50
-151,882), the 2-position can be substituted, and a desired starting material can be synthesized.

2-Nitromethylene oxazolidine and 2-nitromethylene tetrahydro-2H-1,3-oxazines are also known compounds, and include aminoalkanols and the compounds of the above formula (III) or formula (IV) or formula (V). It can be synthesized by reacting. (Adv.Pestic.Sci., Plenary Lect.S
ymp.Pap.Int.Congr.Pestic.Chem.4th, 1978,206〜217
(See Chemical Abstracts, Vol. 91, 103654), U.S. Pat.
2-Nitromethylenepyrrolidine, 2-nitromethylenepiperidines are also known compounds, for example, obtained by reaction of 2-methoxypyrroline-1 with desired nitroalkanes (Dutch Patent No. 7306020, the same number). No. 7306145).

2-Nitroimino compounds are also known compounds, for example,
2-Nitroiminooxazolidine is commercially available from J. Am. Chem. Soc.
(Journal American Chemical Society)
73, 2213-2216, 2-nitroiminoimidazolidines, 2-nitroiminotetrahydropyrimidines and their N-acetyl, N-alkyl derivatives are described in JA
CS, (Journal American Chemical Society) Volume 73, 2201-2205, British Patent No. 2055796. N-acyl, -sulphenyl, -sulfonyl, -phosphono compounds other than N-acetyl are novel compounds, but they can be synthesized by the same method as the above-mentioned British patent.

2-Nitroiminothiazolidines, 2-Nitroiminotetrahydro-2H-1,3-thiazines, 2-Nitroiminopyrrolidines, and 2-Nitroiminopiperidines are also described in the above-mentioned British patent, and are equivalent to nitroguanidine. By a reaction with a diamine, aminoalkanol, or aminoalkanethiol, or by nitrating a 2-imino compound with sulfuric acid and nitric acid.

In the above-mentioned production method f), the compound of the general formula (VIII), which is a raw material, means one based on the definitions of Z and R described above, and preferably they have the same meanings as the above-mentioned preferred definitions.

The compound of the general formula (VIII) is disclosed in JP-A-60-172976 (Japanese Patent Application No. 59-26020) and
-218386 (59-72966), 61-12682 (59-)
132943), 61-178981 (60-18627), 61
-178982 (60-18628), 61-183271 (60)
-23683), 61-267561 (60-106853) and 61-267575 (60-106854), and specific examples thereof are disclosed in these publications. The same chlorides and bromides as those mentioned above can be exemplified, and further p-toluenesulfonates can be mentioned.

In the compounds of formula (I) obtained by the above-mentioned production methods a), b), c), d), e) and f), when X is NH or Y is CH, the compounds of NH or CH Each hydrogen atom can be replaced or added to another group. Specifically, for a compound in which Y is CH, a compound having an active olefin-type double bond, such as methyl vinyl ketone, ethyl acrylate, or acrylonitrile, can be added in a reaction including a Michael type addition. It is also possible (see JP-A-50-151882), and the Mannich reaction and similar reactions are also possible. For example, a dialkylaminomethyl group can be introduced at the α-position of a methylene group, which is active. Aldehydes such as formaldehyde and chloral can also be used for addition reaction (see JP-A-50-151882).

Furthermore, halogen itself, N-chlorosuccinide, N
One or both of the protons in NH of X and CH of Y in the formula (I) can be halogenated by a halogenating agent such as -bromosuccinimide or perchloryl fluoride. -54,532, U.S. Pat.No. 3,933,89
No. 0, U.S. Pat. No. 3,962,233), and in this case, the compound of formula (I) may also have a structure corresponding to the following formula.

(In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R, Z and Hal
Is the same as above, and L represents a halogen atom, a phenylthio group or an alkoxycarbonyl group.) Glyoxylic acid, dimethylformaldehyde dimethyl acetal and the like can also react with the α carbon of the nitromethylene group to take the structural formula shown by the following formula.

(In the formula, n, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R and Z are the same as the above.) Also, the nitrogen atom on the ring in the formula (I) and the nitromethylene group The α-carbon can also be variously acylated, sulfenylated and sulfonylated, respectively (Dutch patent 73).
06145, U.S. Patents 3,985,736, 3996372, 4020061, 4022775, 4,052,411, and
See 4,053,662 and 4,076,813). Therefore, the compounds synthesized by the above-mentioned production methods a), b), c), d), e) and f) can be similarly acylated, sulfenylated and sulfonylated.

Furthermore, acyl isocyanate and sulfonyl isocyanates can also react with α carbon of nitromethylene (US Patent Nos. 4013766, 4025634 and 402979).
See No. 1, 4034091).

Regarding the nitrogen atom on the ring in the formula (I), an alkylation reaction (see Belgian Patent No. 821,282) is also possible, and this reaction was used to alkylate the 3-position of imidazolidine or tetrahydropyrimidine. Inventive Formula (I)
Compounds corresponding to can also be synthesized.

In carrying out the process a) mentioned above, use may be made, as suitable diluent, of any inert organic solvent.

Examples of such diluents are water; aliphatic, cycloaliphatic and aromatic hydrocarbons (which may optionally be 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, diptyl ether, propylene oxide, dioxane,
Tetrahydrofuran; Nitriles such as acetonitrile, propionitrile, acrylonitrile; Alcohols such as methanol, ethanol, iso-propanol, butanol, ethylene glycol; Acid amides such as dimethylformamide, dimethylacetamide; Sulfone, sulfoxides such as dimethyl sulfoxide , Sulfolane; and bases such as pyridine.

The above method can be carried out within a wide temperature range. Generally it can be carried out between about -20 ° C and the boiling point of the mixture, preferably between about 50 and about 120 ° C. Further, the reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

In carrying out the above method a), for example, the compound represented by the general formula (I
With respect to 1 mol of the compound of I), an equimolar amount to about 1.2 times the molar amount of the compound of the general formula (III), preferably an equimolar amount to about 1.1 times the molar amount, an inert solvent such as an alcohol (eg, methanol, The desired novel compound can be obtained by reacting in an (ethanol) solvent until generation of mercaptan is stopped.

In carrying out the above-mentioned production methods b) and c), suitable diluents include the same inert organic solvents as those exemplified in the production method a), and further, as a base, for example, an alkali metal hydroxide. Compounds, carbonates, bicarbonates, alcoholates, etc., and tertiary amines such as triethylamine,
Examples thereof include diethylaniline and pyridine.

The above methods b) and c) can be carried out within a wide temperature range. Generally it can be carried out between about -20 ° C and the boiling point of the mixture, preferably between about 0 and about 50 ° C. Further, the reaction is preferably carried out under normal pressure, but it is also possible to operate under increased pressure or reduced pressure.

In carrying out the above production methods b) and c), for example,
The compound of the general formula (IV) or (V) can be used in an amount of about 0.9 to about 4 times, and preferably about 1 to about 3 times the molar amount of the compound of the general formula (II). In addition, a base is further added in a molar amount of about 1 to about 5 times, preferably about 2
~ About 4 times the molar amount can be used.

In carrying out the above-mentioned production method d), as a suitable diluent,
Mention may be made of all inert organic solvents similar to those exemplified under preparation process a).

In carrying out the above production method, for example, the compound represented by the general formula (II)
Nitroguanidine to 1 mol of the compound of
The desired compound can be easily obtained by reacting about 1.2-fold molar amount, preferably equimolar amount to about 1.1-fold molar amount, for example, in an aqueous solvent with heating.

The above-mentioned production method d) can be carried out, for example, at a temperature of about 0 ° C to about 100 ° C, preferably about 30 ° C to about 80 ° C.

Further, the reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

In carrying out the above-mentioned production method e), it is usual to dissolve the compound of the general formula (VI) in an acid such as concentrated sulfuric acid to react.

In carrying out the above-mentioned production method, for example, general formula (VI)
The desired compound can be obtained by reacting the compound of (1) with fuming nitric acid (purity of 98% or more) under low temperature conditions, preferably at about 0 ° C or lower (British Patent Application No. 2,055,796). Application of the issue).

In carrying out the above-mentioned production method f), as a suitable diluent,
The same inert organic solvents as exemplified in the production method a) can be mentioned, and further, as the base, hydroxides and carbonates of hydride alkali metal such as sodium hydride and potassium hydride can be mentioned.

The above-mentioned preparation method f) can be carried out within a wide temperature range, and is generally about 0 ° C to about 100 ° C, preferably about 10 ° C.
It can be carried out between 0 ° C and about 80 ° C.

Further, the reaction is preferably carried out under normal pressure, but it may be carried out under pressure or reduced pressure.

In carrying out the above-mentioned production method f), for example, sodium hydride is used as a base in an amount of about 1.1 to 1.2 times the molar amount of the compound of the general formula (VI) with respect to 1 mol of the compound of the general formula (VII).
The target compound can be obtained by reacting the compound of II) in an equimolar amount to about 1.2-fold molar amount, preferably an equimolar amount to about 1.1-fold molar amount in an inert solvent such as dimethylformamide. . In the above production method, the compound of the general formula (VII) is treated with sodium hydride,
It is preferable in advance to form the sodium salt in terms of the reaction, and it is desirable to carry out the reaction under a nitrogen gas atmosphere in view of the characteristics of sodium hydride.

Some of the compounds of formula (I) of the present invention are tautomers (tautomers), as represented below.

When X = NH and Y = CH: When X = NH and Y = N Further, when Y is C—R ⁹ , it includes both E and Z isomers.

The compound of the general formula (I) of the present invention may exist in the form of a salt, and examples of the salt include inorganic acid salts, sulfonic acid salts, organic acid salts, metal salts and the like. Therefore, in the present invention, the novel heterocyclic compound of formula (I) is
Includes its salt forms.

The compound of formula (I) of the present invention exhibits a strong insecticidal action.
Therefore, they can be used as insecticides. Then, the active compound of formula (I) of the present invention exerts a proper controlling effect against harmful insects without giving phytotoxicity to cultivated plants. Further, the compound 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 exterminating and eradicating them.

Examples of such pests include the following pests. Examples of insects include Coleoptera pests such as azuki bean weevil (Callosobruchus chinensis), a weevil (Sitophilus zeamais), and a peanut beetle (Tr
ibolium castaneum), Yellow-tailed ladybird (Epila)
chna vigintioctomaculata), Red-breasted beetle (Agriotes fuscicollis), Red beetle (Anomala ru)
focuprea), Colorado potato beetle (Leptinotarsa d
ecemlineata), Diablotheca (Diabrotica spp.),
Pine beetle (Monochamus alternatus), rice weevil (Lissorhoptrus oryzophilus), flat beetle (Lyctus bruneus); Lepidoptera, for example, Lymantria dispar, Malaco
soma neustria), Pteris rapae, Spodoptera litura, Spodoptera litura, Mamestra br
assicae), Nikameichiniu (Chilo tuppressalis),
Pyrausta nubilalis, Ephestia cautella, Adoxoph
yes orana), Codling moth (Carpocapsa pomonella),
Cabbage moth (Agrotis fucosa), Honey moth (Galleria)
mellonella), diamondback moth (Plutella maculipennis), Heliothis virescens, citrus fruit moth (Phyllocnistis citrella); Scale insects (Unaspis yanonensis) and green peach aphids (Myzus)
persicae), apple aphid (Aphis pomi) cotton aphid (Aphis gossypii), radish aphid (Rhopalosiphum pseudobrassicas), nasi gumbai (S
tephanitis nashi), blue stink bug (Nazara spp.),
Whitefly (Cimex lectularius), Whitefly (Trialeurodes vaporariorum), Whitefly (Psylla)
spp.); Orthoptera, for example, German cockroaches (Blatella germanica), American cockroaches (Periplaneta americana), and kerula (Gryllotalpa a)
fricana), grasshopper (Locusta migratoria migratoriode
s); Isoptera, for example, Yamato termite (deucotermes speratus), Coptotermes formosanus; Diptera, for example, Musca domestica, Aedes a
egypti), Fly (Hylemia platura), Culex pipiens, Culex pipiens, Anopheles slnen
sis), Culex tritaeniorhynchu
s), etc.

Furthermore, in the veterinary medicine field, the novel compounds of the present invention are effective for use against various harmful animal parasites (endo- and ectoparasites), such as insects and helminths. Examples of such animal parasites include the following pests.

Examples of insects include the fruit fly (Gastrophilus spp.) And the sand fly (Stomoxys).
spp.), white lice (Trichodectes spp.), reed turtle (R
hodnius spp.), dog flea (Ctenocephalides canis) and the like.

In the present invention, a substance having an insecticidal action against insects including all of them may be called an insecticide.

The active compound of formula (I) of the present invention can be made into a usual pharmaceutical form. And as such a form, a liquid preparation, emulsion, suspension, powder, foam, paste, granule, aerosol, active compound infiltration-natural and synthetic products, microcapsules, seed coatings, preparations equipped with a combustion device (For example, fumigation and fumigation cartridges, cans and coils for combustion equipment), and ULV (cold mist)
t), warm mist].

These preparations can be manufactured by a known method. Such a process comprises, for example, applying an active compound to a developing agent, ie a liquid diluent; a liquefied gas diluent; a solid diluent, or a carrier, optionally a surfactant, ie an emulsifier and / or dispersant and And / or by using a foam forming agent and mixing. If water is used as the spreading agent, organic solvents, for example, can also be used as auxiliary solvents.

Liquid diluents or carriers generally include aromatic hydrocarbons (eg, xylene, toluene, alkylnaphthalene, etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (eg, chlorobenzenes, ethylene chloride, chlorides). Methylene etc.), aliphatic hydrocarbons [eg cyclohexane etc., paraffins (eg mineral oil fraction etc.)], alcohols (eg butanol, glycol and their ethers, esters etc.), ketones (eg acetone,
Mention may also be made of methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone), strongly polar solvents (eg dimethylformamide, dimethylsulfoxide etc.) and water.

The liquefied gas diluent or carrier is a gas at room temperature and atmospheric pressure, examples of which include aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, and halogenated hydrocarbons.

As the solid diluent, soil natural minerals (for example, kaolin, clay, talc, chiyoke, quartz, attapal guide, montmorillonite, diatomaceous earth, etc.), soil synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.) Can be mentioned.

Solid carriers for granules include ground and fractionated rocks (eg, calcite, marble, pumice, sepiolite, dolomite, etc.), synthetic particles of inorganic and organic powders, and fine particles or organic materials ( For example, sawdust, coconut coconut, corn cob, tobacco stem and the like) 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, aryl sulfone). Acid salt, etc.)], and albumin hydrolysis products.

Dispersants include, for example, lignin sulfite waste liquor and methylcellulose.

Adhesives may also be used in the formulation (powder, granules, emulsions), such adhesives including carboxymethyl cellulose and natural and synthetic polymers (eg gum arabic, polyvinyl alcohol and polyvinyl acetate). You can

It is also possible to use colorants, which include 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 iron , Manganese, boron, copper, cobalt, molybdenum, zinc and their salts.

The formulation generally comprises from 0.1 to 95% by weight of the active ingredient,
Preferably 0.5 to 90% by weight can be contained.

The formula (I) active compounds of the present invention are in their commercially useful formulations and in the use forms prepared according to these formulations other active compounds, such as insecticides, baits, fungicides,
It can also be present as a mixture with acaricides, centrifuges, fungicides, growth regulators or herbicides. Here, examples of the insecticide include organic phosphorus agents, carbamate agents, carboxylate agents, chlorinated hydrocarbon agents, and insecticidal substances produced by microorganisms.

Further, the active compound of formula (I) of the present invention can be present as a mixture with a synergist, and such preparations and use forms can be those commercially useful. The synergist is a compound which amplifies the action of the active compound, which need not be active in and of itself.

The content of the active compounds of the formula (I) according to the invention in the commercially useful use forms can be varied within wide limits.

Useful concentrations of the active compounds of formula (I) according to the invention are, for example:
0.0000001 to 100% by weight, preferably 0.0001 to
It is 1% by weight.

The compound of the formula (I) of the present invention can be used in a usual method suitable for the use form.

When used as hygiene pests, pests on stored materials, active compounds are distinguished by their good residual stability in wood and soil, as well as their good stability to alkalis on lime materials. ing.

Next, the contents of the present invention will be specifically described with reference to Examples.
The present invention should not be limited to this.

Manufacturing Examples: -Example 1. Stir a mixture of 2-amino-1- (2-chloro-5-pyridylmethylamino) propane (2g), 1-nitro-2,2-bis (methylthio) ethylene (1.6g) and methanol (20ml). While refluxing for 5 hours. When the product is allowed to cool to room temperature, the desired product forms crystals and precipitates. Therefore, the product is suctioned, washed with methanol and dried. The desired pale yellow 1-
(2-chloro-5-pyridylmethyl) -4-methyl-2
-(Nitromethylene) imidazolidine (1.9 g) is obtained. mp.170-174 ° C Example 2. N- (3-methyl-5-isoxazolylmethyl) N '
A mixture of-(1-methyl-4-pyrazolylmethyl) trimethylenediamine (2.6g), 1-nitro-2,2-bis (methylthio) ethylene (1.6g) and ethanol (10ml) is refluxed for 15 hours. . After the ethanol was distilled off under reduced pressure, the tar-like residue was purified by silica gel column chromatography to give 1- (3-methyl-5-isoxazolylmethyl) 3- (1-methyl-4) as a viscous oil. -Pyrazolylmethyl) -2- (nitromethylene) tetrahydropyrimidine (0.7g) is obtained. ▲ n ²⁰ _D ▼ 1.5670 Example 3. 2- (2-Chloro-5-pyridylmethylamino) ethanol (7.5g) and well ground 1-nitro-2,2-
After mixing bis (methylthio) ethylene (6.6g), 110
Heat to ~ 120 ° C for 30 minutes. After generation of methyl mercaptan was completed, the mixture was allowed to cool to room temperature and purified by silica gel column chromatography to give 3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) oxazolidine (1.
7g) is obtained. mp.123-124 ° C Example 4. Dissolve potassium hydroxide (2.5 g) in ethanol (20 ml) and add 2- (2-methyl-5-pyrazinylmethylamino) ethanethiol (3.7 g) under a nitrogen gas atmosphere. The solution is cooled to 0 ° C., then 2,2-dichloronitroethylene (3.0 g) is added portionwise at 0-10 ° C. and then stirred at 10 ° C. for 1 hour. Ethanol is distilled off from the contents under reduced pressure, chloroform is added to the residue, and the mixture is washed with water and a 1% aqueous sodium hydroxide solution. By treating the genus Chloroform by a conventional method, the desired pale yellow 3- (2-methyl-5-pyridinylmethyl) -2- (nitromethylene) thiazolidine (2.0 g) is obtained. mp.147-150 ° C Example 5. N- (1,2,5-thiadiazol-3-ylmethyl) ethylenediamine (4.7g), nitroguanidine (3.4g), water
While mixing 20 ml, heat at 50-60 ° C for 1 hour and 70 ° C for 20 minutes. Then, if it is cooled slowly to 5 ° C, the target substance becomes crystals and precipitates. Therefore, if this is taken, washed with water and methanol, and dried, the desired 1- (1,2,5-
Thiadiazol-3-ylmethyl) -2- (nitroimino) imidazolidine (2.9 g) is obtained. mp.162 ~ 165
° C Example 6. A mixture of 2-nitroiminothiazolidine (2.9 g), anhydrous potassium carbonate (2.9 g), 2-chloro-5-pyridylmethyl chloride (3.2 g) and acetonitrile (50 ml) is refluxed for 5 hours while stirring well. After completion of the reaction, most of the acetonitrile was distilled off under reduced pressure, and water was added to the residue,
Since the target substance is separated as a solid, it is separated and then recrystallized from ethanol to give the desired 3- (2-
Chloro-5-pyridylmethyl) -2- (nitroimino)
Thiazolidine (3.8 g) is obtained. mp.137-138 ° C Example 7. 2-Nitroiminoimidazolidine (1.3g) is suspended in dry acetonitrile (30ml), 60% sodium hydride (0.4g) is added at room temperature and stirred at room temperature until the evolution of hydrogen ceases. Then, a 10 ml solution of 2-chloro-5-thiazolylmethyl chloride (1.7 g) in acetonitrile is added dropwise so as to keep the room temperature. After dropping, stir at room temperature for 3 hours,
Pour into ice water. After adding dichloromethane to extract the target substance, the dichloromethane layer is washed with water and a 1% sodium hydroxide aqueous solution. When the dichloromethane is distilled off under reduced pressure, the target substance is solidified, and the crystals are washed with ether and dried.
Target 1- (2-chloro-5-thiazolylmethyl) -2
-(Nitroimino) imidazolidine (1.4 g) is obtained. mp.147-150 ° C Example 8. Ethyl, nitro (tetrahydro-2H-1,3-thiazine-
2-ylidene) acetate (2.3 g), 2-chloro-5-
Example 7 using pyridyl methyl chloride (1.6 g)
A rubber-like substance is obtained by reacting in the same manner as. This was washed with hexane and ethanol, and the insoluble matter was purified by silica gel chromatography.
-(2-chloro-5-pyridylmethyl) tetrahydro-
2H-1,3-thiazine-2-ylidene] acetate (0.2
g) is obtained. mp.180-184 ° C Example 9. 2-Imino-3- (4-pyridylmethyl) thiazolidine (5.8 g) is added to concentrated sulfuric acid (20 ml) at -50 to 0 ° C to cause liquid liquefaction. Then fuming nitric acid (6 ml) was carefully added at the same temperature, and then the mixture was stirred at 0 to 5 ° C for 30 minutes. Pour the contents into ice and extract twice with dichloromethane. When the dichloromethane layer is treated by a conventional method, the desired 2-nitroimino-3 is obtained.
-(4-Pyridylmethyl) thiazolidine (1.4g) is obtained. mp.151-152 ° C Example 10 A mixture of 3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) thiazolidine (2.7 g), methyl vinyl ketone (3.5 g) and chloroform (30 ml) was added at 40 ° C. under a nitrogen gas stream at 48 ° C. Stir for an hour, then add fresh methyl vinyl ketone (3.5 g) and stir for an additional 48 hours at the same temperature. The volatiles were removed under reduced pressure and the residue was purified by silica gel chromatography to give the desired 3- (2-chloro-5-pyridylmethyl) -2- (1-nitro-4-oxopentylidene) thiazolidine (0.1g). Is obtained.
mp.75-80 ° C Example 11 1- (4-pyridylmethyl) -2- (nitromethylene)
Dihydroxane (30 ml) is added to tetrahydropyrimidine (2.3 g) and paraformaldehyde (0.5 g), and the mixture is heated at 70 to 80 ° C for 2 hours while stirring well. After the reaction, dioxane is concentrated under reduced pressure to 1/3 of its volume to precipitate crystals, so if this is taken and dried, the desired bis-
[Α-Nitro-1- (4-pyridylmethyl) tetrahydropyrimidine-2-ylidenemethyl] methane (1.8 g) is obtained. mp.222-223 ° C Example 12 1- (3-methyl-5-isoxazolylmethyl) -2
-(Nitromethylene) tetrahydropyrimidine (2.4g)
Is dissolved in dry dichloromethane (30 ml), chloral (1.6 g) is added at room temperature, and the mixture is stirred for 3 hours at 25 to 30 ° C. The target substance becomes crystals and precipitates, so take this,
After washing with ether and drying, the desired 1- (3-methyl-
5-isoxazolylmethyl) -2- (1-nitro-2
-Hydroxy-2-trichloromethylethylidene) tetrahydropyrimidine (3.1 g) is obtained. mp.128-130
C (decomposition) Example 13 1- (2-Chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine (2.5 g) is dissolved in dichloromethane (40 ml) and water (10 ml) is added. Bromine (1.6 g) dissolved in 10 ml of dichloromethane is added dropwise at 0 to 5 ° C within 10 minutes while stirring well. After stirring at that temperature for 10 minutes after dropping, the formed crystals were collected, washed with cold water and a small amount of dichloromethane, and dried to give 1- (2-chloro-5-pyridylmethyl) -2- (bromonitromethylene) imidazolidine. (2.5 g) is obtained. mp.110 ~ 115
C (decomposition) Example 14 1- (4-pyridylmethyl) -2- (nitromethylene)
Triturate tetrahydropyrimidine (1.2 g) and suspend in methanol (20 ml). 25% glyoxylic acid 1.
6 g and 2 drops of concentrated sulfuric acid are added and the mixture is stirred at room temperature for 3 hours. After adjusting the pH to 7, suction is carried out and the crystals are washed with water, methanol and ether and dried to give the desired 3- [1-
(4-Pyridylmethyl) -1H, 4H, 5H, 6H-tetrahydropyrimidin-2-yl] -3- (nitro) acrylic acid (1.1 g) is obtained. mp.150-155 ° C (decomposition) Example 15 1-Methylimidazole (1.6 g) was added to dichloromethane (50
ml), and phenyl chloroformate (3.1g) at 0 ℃ or below
And stir at that temperature for 30 minutes. Next, 1- (2-
Chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine (2.5 g) is added, and the mixture is stirred at room temperature for 24 hours. This mixture was washed with water, a 1% aqueous hydrochloric acid solution, a 1% aqueous sodium hydroxide solution, and dichloromethane was concentrated under reduced pressure from the dichloromethane layer to obtain glassy phenyl, nitro {1- (2-chloro-5-pyridylmethyl). -3-
Phenoxycarbonyl imidazolidine-2-ylidene}
Acetate (3.2 g) is obtained. Then leave this as it is,
It is dissolved in dimethylformamide (20 ml), sodium carbonate (1.7 g) is added, the mixture is stirred at room temperature for 3 days, water is added, and the mixture is extracted with dichloromethane. 1 dichloromethane layer
% Sodium hydroxide and water, and the product treated by a conventional method is further purified by silica gel chromatography to obtain the desired phenyl, nitro {1- (2-chloro-5
-Pyridylmethyl) imidazolidine-2-ylidene} acetate (0.2g) is obtained. mp.224-228 ° C (decomposition) Example 16 Dissolve 1- (3-methyl-5-isoxazoylmethyl) nitroiminoimidazolidine (1.1g) in dry dimethylformamide (15ml) and add 60% sodium hydride (0.2g) and stir at room temperature until hydrogen evolution stops. To do.

Next, 2-methyl-5-nitrobenzenesulfonyl chloride (1.2 g) was added and the contents were stirred overnight at room temperature,
Pour into ice water and extract with dichloromethane. If the dichloromethane layer is treated by a conventional method, the desired product remains as crystals, so if washed with ether and dried, the desired 1- (2-methyl-
5-nitrobenzenesulfonyl) -3- (3-methyl-
5-isoxazoylmethyl) -2- (nitroimino)
Imidazolidine (1.1 g) is obtained. mp.154-156 ° C Example 17 Dissolve 1- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine (1.3g) in dry dimethylformamide (15ml) and add 60% sodium hydride (0.2g) at room temperature until hydrogen evolution stops. Stir with.

The solution is then cooled to 0 ° C and 4-chlorobenzene-sulphenylenyl chloride (0.9g) is added at 0 ° C. After the addition is complete, stir at room temperature for 1 hour and pour the contents into ice water. The precipitated crystals are removed and recrystallized from ethyl acetate to obtain the desired 1
-(2-chloro-5-pyridylmethyl) -2-[(4-
Chlorophenylthio) -nitromethylene] imidazolidine (1.3 g) is obtained. mp.159-161 ° C Example 18 1- (2-Chloro-5-pyridylmethyl) -2- (nitromethylene) imidazolidine (1.3 g) is dissolved in dry difluoromethane (25 ml) and at room temperature a solution of benzenesulfonyl isocyanate (0.9) in dichloromethane 10 ml is added.
After stirring at room temperature for 2 hours, about half the amount of dichloromethane is concentrated under reduced pressure to precipitate crystals, which are taken, washed with ether and dried to obtain the desired N-benzenesulfonyl, 2- [1
-(2-Chloro-5-pyridylmethyl) imidazolidine-2-ylidene] 2-nitroacetamide (1 g) is obtained. mp.95-100 ° C Example 19 Stir a mixture of 2- (nitroimino) -1- (3-pyridylmethyl) imidazolidine (2.2g), 2-chloro-5-chloromethylpyridine (1.6g), potassium carbonate (1.4g), acetonitrile (30ml). While refluxing for 16 hours. Acetonitrile is distilled off under reduced pressure, dichloromethane is added to the residue, and the mixture is washed with water and a 1% sodium hydroxide aqueous solution. Dichloromethane was distilled off from the dichloromethane layer under reduced pressure, and the residue was purified by silica gel chromatography to obtain the desired 1- (2-chloro-5-pyridylmethyl) -3-.
(3-Pyridylmethyl) -2- (nitroimino) imidazolidine (2.1 g) is obtained. mp.143-144 ° C Example 20 Dissolve 1- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine (2.6g) in dry dimethylformamide (20ml) and add 60% sodium hydride (0.4g) to generate hydrogen at room temperature. Stir until stopped. Then, a solution of isopropyl bromide (1.5 g) in 5 ml of dry dimethylformamide is added at room temperature and stirred for 3 hours. The contents are then poured into water and the crystals formed are removed. When this crystal is recrystallized from ethanol,
-(2-Chloro-5-pyridylmethyl) -3-isopropyl-2- (nitroimino) imidazolidine (1.5 g) is obtained.

mp.138-142 ° C Example 21 A mixture of 3- (2-chloro-5-pyridylmethyl) -2- (nitromethylene) thiazolidine (2.7 g) and butyricquan hydride (8 ml) was stirred at 60 ° C. for 8 hours under a nitrogen gas stream. Subsequently, the mixture is concentrated at 1 mmHg and a bath temperature of 60 ° C. or lower, the residue is dissolved in dichloromethane and washed with a 1% sodium hydroxide aqueous solution. The dichloromethane layer was purified by silica gel column chromatography to give a viscous oily 1-
[3- (2-chloro-5-pyridylmethyl) thiazolidine-2-ylidene] 1-nitro-2-pentanone (0.15
g) is obtained.

(N ²⁰ _D) 1.6342 The compounds synthesized in the above-mentioned examples and the compounds of the general formula (I) of the present invention produced by the same production method are collectively shown in the following table. However, the "-" notation for R ³ and R ^{4 in} the table means that n is 0, and in this case, the ring structure means a hetero 5-membered ring.

In the general formula (I), when X is S (Table 1): In the general formula (I), when X is CH—R ⁸ (Table 2): In the general formula (I), when X is O (oxygen atom) (the third
table): In the general formula (I), Z is an optionally substituted pyridyl group, and X is N—R ⁷ (Table 4): The general formula (I) is represented by the following formula for convenience.

In Table 4, "-" in the column of W1 indicates that there is no substituent.
The column of R ² and R ⁵ "-" indicates that R ² and R ⁵ form together a connexion, a single bond.

In the general formula (I), X other than those shown in Table 4 is N—R ⁷
In case of (Table 5): When the compound of the general formula (I) has a structure corresponding to the following formula as described above (Table 6) Specific examples in which the compound of the general formula (I) has a structure corresponding to the following formula as described above (Table 7) Example 22 [Example of synthesizing compound of intermediate formula (II)] 2-Chloro-5-chloromethylpyridine (8.1 g) was added to a mixture of 1,2-diaminopropane (14.8 g), 40% aqueous sodium hydroxide solution (5 g) and acetonitrile (100 ml) at 0 ° C.
While stirring well, a solution of acetonitrile in 30 ml is added dropwise over 2 hours. After the dropping, the mixture is stirred for a while at room temperature, and then acetonitrile, water and excess 1,2-diaminopropane are distilled off from the contents under reduced pressure. The residue is suctioned off and the inorganic salt is removed to give the desired 2-amino-1- (2-chloro-5-pyridylmethylamino) propane (9.3 g).

N ¹⁷ _D 1.5450 By the same method as in Example 22 above, for example, the following compound was synthesized.

N-methyl-N'-3-pyridylmethylethylenediamine bp.140 ° C / 2.5mmHg 2-amino-2-methyl-1- (3-pyridylmethylamino) propane bp.115 ° C / 1.5mmHg 2-aminomethyl-2 -Methyl-1- (1-methyl-4
-Pyrazolylmethyl) propane ▲ n ²⁵ _D ▼ 1.5109 Example 23 [Example of synthesizing compound of intermediate formula (II)] A solution of N- (2-chloro-5-pyridylmethyl) ethylenediamine (18.6g), 1-methylpyrazole-4-carbaldehyde (11g) and benzene (150ml) was stirred for a while in a warm water bath to separate water. The base is obtained. Benzene and water are distilled off under reduced pressure and the residue is dissolved in 100 ml of ethanol. Sodium borohydride (3.8g) in this solution
Is added little by little at room temperature, and the mixture is stirred at room temperature for 1 day.
Ethanol is distilled off under reduced pressure, the residue is dissolved in dichloromethane and washed with water. If treated by a conventional method, the desired N- (2-chloro-5-pyridylmethyl) -N '-(1-methyl-4) is obtained.
-Pyrazolylmethyl) ethylenediamine is obtained as a viscous oil (23.5 g). N ²⁰ _D 1.5655 By the same method as in Example 23, for example, the following compound is synthesized.

N- (3-pyridylmethyl) -N '-(2-chloro-5
-Pyridylmethyl) ethylenediamine ▲ n ²⁰ _D ▼ 1.5846 N- (3-methyl-5-isoxazoylmethyl)-
N '-(1-Methyl-4-pyrazolylmethyl) trimethylene diamine ▲ n ²⁰ _D ▼ 1.5224 Example 24 [Example of synthesizing compound of intermediate formula (II)] 2-Aminoethanol (12.2 g) was added to acetonitrile (100
ml) and added to this solution at 10 ° C or lower
Acetonitrile 20 of 3-methylisoxazole (7 g)
Add the ml solution dropwise. After stirring at room temperature for a while after dropping,
The contents are distilled off under reduced pressure to acetonitrile and excess 2-aminoethanol, chloroform is added to the residue and the mixture is washed with a small amount of water. If treated by a conventional method, the desired 2- (3-methyl-
5-isoxazolylmethylamino) ethanol (4.4
g) is obtained.

N ²⁰ _D 1.5130 By the same method as in Example 24, for example, the following compound is synthesized.

3- (2-chloro-5-pyridylmethylamino) propanol ▲ n ²⁷ _D ▼ 1.5391 N- (4-pyridylmethyl) ethanolamine bp.148-
150 ° C / 3mmHg Example 25 [Example of compound of intermediate formula (II)] 2- (3-Methyl-5-isoxazolylmethylamino) ethanol (15.6 g) was dissolved in 100 ml of chloroform, and a catalytic amount of pyridine was added, and thionyl chloride (15
g) is added at room temperature. Subsequently, the contents are refluxed for 30 minutes and then the volatiles are distilled off under reduced pressure to obtain the corresponding chloride as a hydrochloride. mp136-139 ° C Next, potassium hydroxide (13.4g) is dissolved in ethanol (120ml) and hydrogen sulfide gas is blown into the solution to saturate it to prepare an alcohol solution of potassium hydrogen sulfide. The above-mentioned chloride hydrochloride is added to this alcohol solution at 25 to 30 ° C little by little with stirring. After the addition is complete, the contents are gently warmed and stirred at 60 ° C. for 2 hours. After cooling to room temperature, the inorganic salt is quickly sucked in, and the solution is concentrated to obtain the desired 2- (3-
Methyl-5-isoxazolylmethylamino) ethyl mercaptan (12.9 g) is obtained. N ²⁵ _D 1.5490 By the same method as in Example 25, for example, the following compound is synthesized.

2- (2-Methyl-5-pyrazinylamino) ethyl mercaptan ▲ n ²⁸ _D ▼ 1.5581 Example 26 [Example of compound of raw material formula (III)] Ethylene trithiocarbonate (2.72g) is heated with dimethylsulfate (2.52g) for 1 hour at 100 ° C. To the produced 2-methylmercapto-1,3-dithionium-methylsulfate, acetic acid (10 ml), triethylamine (2.02
g) are added sequentially. While cooling with ice to this mixture, 2,2,2-
Trifluoronitroethane (2.6g) was added dropwise and gradually added to 10
Warm to 0 ° C. and stir at this temperature for 4 hours. The reaction mixture is allowed to come to room temperature and left overnight. Crystals are precipitated when 100 ml of water is added. When the final crystals were taken and reconstituted from ethanol, the desired 1-nitro-2,2-ethylenedimercapto-1-trifluoromethyl-ethylene (4.
35 g) are obtained. mp.130-133 ° C. Example 27 [Example of compound of raw material formula (III)] To a 200 ml solution of 1-nitro-2-pentanone (13.1 g) in dimethyl sulfoxide, 20% aqueous sodium hydroxide solution (44 g) is added dropwise at 10 to 20 ° C. Then, at 10 degreeC, carbon disulfide (12g) is dripped, and it stirs at 0-10 degreeC for 2 hours.
Methyl iodide (57 g) was added dropwise to this mixture while cooling with ice, and the mixture was left at room temperature overnight. After the reaction is complete, the mixture is poured into ice water and extracted with methylene chloride. Subsequently, the organic layer is washed with water several times and dried over anhydrous sodium sulfate. After drying, purification by silica gel column chromatography (eluent toluene: hexane = 7: 3) gives the desired 1-butyroyl-1-nitro-2,2-bis (methylthio) ethylene (3 g).

N ²² _D 1.5880 By the same method as in Example 27, for example, the following compound is synthesized.

1-benzenesulfonyl-1-nitro-2,2-bis (methylthio) ethylene ▲ n ²⁰ _D ▼ 1.5868 Example 28 [Example of synthesizing compound of intermediate formula (VII)] 2-Nitroiminoimidazolidine (3.9 g) is dissolved in dry dimethylformamide (25 ml), and 60% sodium hydride (2.5 g) is stirred at room temperature little by little until hydrogen evolution stops. Next, this solution is -5 ° C.
After cooling, 4.7 g of phenyl chloroformate is added dropwise so that the internal temperature does not exceed 0 ° C. After the dropping, the mixture is stirred at room temperature for 1 hour and then poured into ice water. After adjusting the pH to 7 and extracting with dichloromethane, and distilling dichloromethane off from the extract under reduced pressure, crystals remain, so the crystals are washed with ether and dried to give the desired 1- (phenoxycarbonyl) -2. -(Nitroimino) imidazolidine (5.1 g) is obtained. mp.1
71 to 175 ° C. By the same method as in Example 28, for example, the following compound is synthesized.

1- (2-methyl-5-nitrobenzenesulfonyl)-
2- (nitroimino) imidazolidine mp.193-197 ° C 1- (2,4-dichlorobenzoyl) -2- (nitroimino) imidazolidine mp.184-186 ° C ] 2-Nitroiminoimidazolidine (3.6g), 3-chlorophenyl isocyanate (4.6g), dry acetonitrile
The 80 ml solution is refluxed for 3 hours. After cooling to room temperature, the formed crystals are filtered, washed with ether and dried to obtain the desired product.
-(3-Chlorophenylcarbamoyl) -2-nitroiminoimidazolidine (4.7g) is obtained.

mp.214-216 ° C Biological test: -Comparative compound A-1: Compounds described in West German Patent Publication No. 2,514,402 A-2: Same as A-3: A-2 and A-3 are compounds described in JP-A-59-196877. Example 30 (Biological test) Test for organic phosphorus agent resistant leafhopper leafhopper Preparation of reagent solution Solvent: 3 parts by weight of xylol Emulsifier: polyoxyethylene alkyl 1 part by weight of phenyl ether 1 part by weight of the active compound is mixed with said amount of solvent containing said amount of emulsifier in order to make a suitable active compound formulation, and the mixture is diluted with water to the given concentration.

Test method: To a rice plant planted in a pot having a diameter of 12 cm and having a plant height of about 10 cm, 10 ml of a diluted solution of the active compound prepared as above at a predetermined concentration was sprayed per pot. After the spray solution was dried, it was covered with a wire net with a diameter of 7 cm and a height of 14 cm, and 30 female adults of the leafhopper leafhopper, which is a strain resistant to the organophosphorus agent, were released into it and placed in a temperature-controlled room for 2 days to determine the number of dead insects. Insect kill rates were calculated. As a result, for example, compound No. 4, 11, 42, 48, 74, 111, 14
2,153,167,179,187,195,202,206,215,230,25
0, 266, 279, 301, 314, 323, 341, 348, 356, 360, 37
3,383,416 showed 100% control effect at an active ingredient concentration of 8 ppm, while Comparative Compound A-1 produced 6% at an active ingredient concentration of 40 ppm.
Pest control effect of 5%, A-2 is control effect 0% at active ingredient concentration 1000ppm, A-3 is 50% at active ingredient concentration 1000ppm, 200
The control effect was 40% at 40 ppm and 0% at 40 ppm.

Example 31 (Biological test) Test for planthoppers Test method: To a rice plant planted in a pot with a diameter of 12 cm and having a plant height of about 10 cm, 10 ml of a water-diluted solution of the active compound prepared in the same manner as in the above-mentioned examples at a given concentration was obtained. Sprayed. Diameter 7c after drying spray chemicals
m, 14 cm high wire mesh is covered, and 30 female adult brown planthoppers of a strain that are resistant to organophosphorus agents are released in it.
Two days after placing in a thermostatic chamber, the number of dead insects was examined and the insecticidal rate was calculated.

In the same manner as the above-mentioned method, the insecticidal rate for Sedro-loquan plant and organophosphorus-resistant Spodoptera frugiperda was calculated. As a result, for example, compound No. 4, 21, 42, 48, 56, 74, 11
1, 142, 166, 171, 189, 197, 208, 218, 266, 279, 29
4, 323, 348, 373 and 378 each show a 100% control effect against planthoppers at an active ingredient concentration of 40 ppm, while Comparative Compound A-1 shows a control effect of 50% or less at an active ingredient concentration of 40 ppm. It was just too much.

Example 32 (Biological test) Organophosphorus agent and test for carbamate-resistant peach aphid Test method: Organophosphorus agent bred on eggplant seedlings (genuine long eggplant) about 20 cm in height planted in a clay pot with a diameter of 15 cm , And about 200 peach aphids resistant to carbamate agent per seedling, and 1 day after the inoculation, a sufficient amount of a water-diluted solution of a predetermined concentration of the active compound prepared as in Example was sprayed using a spray gun. did,
After spraying, it was left in a greenhouse at 28 ° C, and the insecticidal rate was calculated 24 hours after spraying. The test was repeated twice. As a result, for example, compound Nos. 2, 4, 11, 21, 35, 42, 48, 74, 11
1, 142, 179, 188, 195, 208, 215, 242, 250, 266, 27
9, 340, 348, 360, 373, 383, 402, 418 active ingredient concentration
200ppm shows 100% control effect, while comparative compound A
-1 showed only 30% control effect at the active ingredient concentration of 200 ppm.

The biological tests shown in Examples 30, 31, and 32 above are representative examples of insecticidal use, and the compounds of the present invention exemplified here are also representative examples, and the present invention should be limited to these. Not a thing.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area A01N 43/54 D 43/56 A 43/72 43/76 43/78 D C07D 401/06 207 231 233 239 401/14 233 239 403/06 207 233 405/06 233 239 409/06 233 239 413/06 207 213 237 237 239 261 307 413/14 207 417/06 207 213 231 237 239 241 261 265 277 279 307 333 // C07C 323/22 7419-4H C07D 213/61 233/52 261/08 339/06 C07F 9/572 9155-4H 9/576 9155-4H 9/6527 9155-4H 9/6536 9155-4H

Claims (14)

[Claims] 1. A general formula In the formula, n represents 0 or 1, R ¹ , R ² , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ represent a hydrogen atom, Hydroxy or carbon number 1
4 is an alkyl group, X is S, O, N—R ⁷ or CH—R ⁸ , where R ⁷ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms (the alkyl group is An alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, cyano, chloro, diethylamino or trimethylsilyl may be substituted), chloro-substituted allyl, benzyl (the benzyl being methyl, methoxy). , Optionally substituted with at least one selected from chloro and nitro), an alkylcarbonyl group having an alkyl having 1 to 5 carbon atoms (the alkylcarbonyl group is methoxy, 2,4-dichlorophenoxy, chloro or Optionally substituted by bromine), benzoyl (wherein benzoyl is chloro, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy) , Optionally substituted with at least one selected from isopropyl and nitro), an alkoxycarbonyl group having an optionally substituted fluoroalkyl having 1 to 4 carbon atoms, phenoxycarbonyl (the phenoxycarbonyl is Optionally substituted with methyl or chloro),
Dimethylaminocarbonyl, phenylaminocarbonyl (the phenylaminocarbonyl may be substituted with methyl or chloro), an optionally substituted chloro-substituted alkylsulfonyl group having 1 to 4 carbon atoms, phenylsulfonyl (the phenylaminocarbonyl). Enylsulfonyl may be substituted with at least one selected from methyl, chloro and nitro), O, O-dimethylphosphono group, O-ethyl-Sn
- propyl phosphono group, group -CH ₂ -W or group -CO-W
(In the above group, W represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole or pyridine,
These rings may be substituted with a halogen atom or a lower alkyl group), and R ⁸ is a hydrogen atom or a carbon number of 1 to 2.
Represents an alkyl group, phenyl or benzyl, Y represents N or C—R ⁹ , wherein R ⁹ is a hydrogen atom, bromine, or an alkyl group having 1 to 2 carbon atoms (the alkyl group is fluoro, chloro, hydroxy). , An alkoxy having 1 to 2 carbon atoms,
It may be substituted with alkylthio having 1 to 2 carbons, cyano, dimethylamino, alkylcarbonyl having alkyl having 1 to 2 carbons, or alkoxycarbonyl having alkyl having 1 to 2 carbons), 1-hydroxy-
2,2,2-trichloroethyl group, an alkylcarbonyl group having an alkyl group having 1 to 4 carbon atoms (the alkylcarbonyl group may be substituted with methoxy or chloro),
A benzoyl group (the benzoyl group may be substituted with at least one selected from chloro, bromo, methoxy and methyl), an alkoxycarbonyl group having an optionally substituted fluoroalkyl group having 1 to 4 carbon atoms,
A phenoxycarbonyl group (the phenoxycarbonyl group may be substituted with chloro, methyl, methoxy or nitro), benzoylaminocarbonyl (the benzoylaminocarbonyl may be substituted with methyl, fluoro or chloro) Phenyl), phenylsulfonylaminocarbonyl (wherein the phenylsulfonylaminocarbonyl may be substituted with methyl or chloro), phenylthio (wherein the phenylthio may be substituted with methyl or chloro), or chloro-substituted. Optionally represents phenylsulfonyl, R represents a hydrogen atom or methyl, and Z represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole, thiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, pyridine, pyrimidine, pyridazine or pyrazine. These rings are lower alkyl groups which may be halogen-substituted, alkenyl groups having 2 to 3 carbon atoms which may be chloro-substituted, halogen atoms, propargyl, methoxy which may be fluoro-substituted, and fluoro-substituted. Optionally substituted with one or two selected from methylthio, methylsulfinyl, methylsulfonyl, thiocyanato, trichloroacetamide, nitro, cyano and methoxycarbonyl, provided that n is 0 or it indicates ^{1, R 1, R 2,} R 3, R 4, R 5 and R ⁶ are a hydrogen atom And, X represents NH, and when Y represents a CH, n represents 0 or ^{1, R 1, R 2,} R 3, R 4, R 5 and R ⁶ is a hydrogen atom, X is S And Y represents CH, and Z is an optionally substituted pyridyl group (the substituent is a halogen atom, an optionally halogenated lower alkyl group, nitro, cyano, or a fluoro-substituted group). Good methoxy, fluor optionally substituted methylthio, methylsulfinyl, methylsulfonyl and optionally substituted alkenyl group having 2 to 3 carbon atoms is shown), and n Represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents NH, Y represents N, and Z may be substituted. A good pyridyl group (wherein the substituent is a halogen atom or a halogen-substituted Optionally lower alkyl group, nitro, cyano, fluor optionally substituted methoxy, fluor optionally substituted methylthio, methylsulfinyl, methylsulfonyl, chloro optionally substituted alkenyl having 2 to 3 carbon atoms. Group, at least one selected from the group consisting of trichloroacetamide and methoxycarbonyl) is shown. 2. n is 0 or 1, R ¹ , R ² , R ⁵ and R ⁶ are each a hydrogen atom or methyl, R ³ and R ⁴ are each a hydrogen atom or methyl, X Is S,
O, an N-R ⁷ or CH-R ^8, wherein, R ⁷ is a hydrogen atom,
An alkyl group having 1 to 2 carbon atoms (wherein the alkyl group is methoxy,
Ethoxy, methylthio, ethylthio, cyano, chloro or trimethylsilyl may be substituted), allyl optionally substituted with chloro, benzyl optionally substituted with methyl and / or chloro, alkyl having 1 to 3 carbon atoms An alkylcarbonyl group having (wherein the alkylcarbonyl group may be substituted with methoxy, 2,4-dichlorophenoxy or chloro), benzoyl (wherein the benzoyl is selected from chloro, methyl, trifluoromethyl, methoxy and nitro). 1 to 2 carbon atoms which may be substituted with at least one) which may be substituted with fluoro.
Alkoxycarbonyl group having alkyl, phenoxycarbonyl optionally substituted with methyl or chloro, dimethylaminocarbonyl group, phenylaminocarbonyl optionally substituted with methyl or chloro, optionally chloro substituted methyl sulfonyl, methyl optionally substituted phenylalanine sulfonyl, O, O- dimethyl phosphono group, O- ethyl S-n-propyl phosphono group, group -CH ₂ -W or group (In the above group, W represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole or pyridine,
These rings may be substituted with chloro, bromine or methyl), R ⁸ represents a hydrogen atom, methyl, phenyl or benzyl, Y is N or C—R ⁹ , wherein R ⁹ Is a hydrogen atom, bromine, alkyl having 1 to 2 carbon atoms (the alkyl group may be substituted with fluoro, chloro, hydroxy, methoxy, cyano, dimethylamino, acetyl or methoxycarbonyl), or chloro substituted. Good acetyl,
Benzoyl, fluor optionally substituted carbon number 1
Alkoxycarbonyl group having 2 alkyl, phenoxycarbonyl optionally substituted with methyl or chloro, benzoylaminocarbonyl optionally substituted with methyl or chloro, phenylsulfonylaminocarbonyl optionally substituted with methyl, chloro Optionally substituted phenylthio or phenylsulfonyl, and R ⁹ is R is a hydrogen atom or methyl, and Z is from thiophene, pyrazole, isoxazole, thiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, pyridine, pyrimidine, pyridazine or pyrazine. A heterocycle group consisting of
At least one selected from chloro, bromo, methyl, fluoro-substituted methyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, nitro, cyano, trifluoromethoxy, trifluoromethylthio, allyl, trichloroacetamide and methoxycarbonyl. Optionally substituted, provided that n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents NH, and When Y represents CH, n represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents S, Y represents CH, And a pyridyl group in which Z may be substituted (the substituents are fluoro, chloro, bromo, methyl, fluoro-substituted methyl, nitro, cyano, methoxy, trifluoromethoxy, methylthio, trifluoromethyl Thio, methylsulfinyl Hui sulfonyl, indicating exhibits at least one selected from methylsulfonyl and allyl), and, n represents 0 or 1, R ^1, R ^2, R ^3, R ^4, R ⁵ and R ⁶ represents a hydrogen atom, X represents NH, Y represents N, and Z is an optionally substituted pyridyl group (the substituents are fluoro, chloro, bromo, methyl, fluoro-substituted methyl, nitro, Cyano, methoxy, trifluoromethoxy, methylthio, trifluoromethylthio, methylsulfinyl, methylsulfonyl, allyl, trichloroacetamide, and methoxycarbonyl)). The compound according to the item. 3. The formula: 1- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -2- (nitromethylene) pyrrolidine. 4. The formula: The compound according to claim 1 or 2, which is 1- (2-chloro-5-thiazolylmethyl) -2- (nitroimino) tetrahydropyrimidine represented by: 5. The formula: The compound according to claim 1 or 2, which is 1- (2-chloro-5-pyrimidinylmethyl) -2- (nitroimino) imidazolidine represented by: 6. The formula: 1- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -4-methyl-2- (nitromethylene) imidazolidine. 7. The formula: 1- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -3- (3-pyridylmethyl) -2- (nitromethylene) imidazolidine. 8. The formula: 1- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -2- (bromonitromethylene) imidazolidine. 9. The formula: 1- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -2- (1-nitro-2-oxopentylidene) imidazolidine. 10. The formula: Ethyl nitro [3- (2-chloro-5-
The compound according to claim 1 or 2, which is pyridylmethyl) thiazolidine-2-ylidene] acetate. 11. The formula: The compound according to claim 1 or 2, which is 1-acetyl-3- (2-chloro-5-pyridylmethyl) -2- (nitroimino) imidazolidine represented by: 12. The formula: N-phenylsulfonyl nitro [1-
(2-Chloro-5-pyridylmethyl) imidazolidine-
2-ylidene] acetamide.
Item or the compound according to Item 2. 13. The formula: 3- (2-chloro-5-pyridylmethyl) represented by
The compound according to claim 1 or 2, which is -2- (nitroimino) thiazolidine. 14. General formula In the formula, n represents 0 or 1, R ¹ , R ² , R ⁵ and R ⁶ each represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ³ and R ⁴ represent a hydrogen atom, Hydroxy or carbon number 1
4 is an alkyl group, X is S, O, N—R ⁷ or CH—R ⁸ , where R ⁷ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms (the alkyl group is 1 carbon atom). ~ 4 alkoxy group, alkylthio group having 1 to 4 carbon atoms, cyano, chloro, may be substituted with diethylamino or trimethylsilyl), chloro-substituted allyl, benzyl (the benzyl is methyl, methoxy, Optionally substituted with at least one selected from chloro and nitro), an alkylcarbonyl group having an alkyl having 1 to 5 carbon atoms, wherein the alkylcarbonyl group is methoxy, 2,4-dichlorophenoxy, chloro or Optionally substituted by bromine), benzoyl (wherein benzoyl is chloro, methyl, trifluoromethyl, methoxy, difluoromethoxy, trifluoromethoxy) Optionally substituted with at least one selected from isopropyl and nitro), an alkoxycarbonyl group having an optionally substituted fluoroalkyl having 1 to 4 carbon atoms, phenoxycarbonyl (the phenoxycarbonyl is methyl Or optionally substituted with chloro), dimethylaminocarbonyl, phenylaminocarbonyl (wherein the phenylaminocarbonyl may be substituted with methyl or chloro), and optionally substituted with chloro.
4, an alkylsulfonyl group, phenylsulfonyl (the phenylsulfonyl may be substituted with at least one selected from methyl, chloro and nitro), O, O
- dimethylphosphono group, O- ethyl -S-n-propyl phosphono group, in the group -CH ₂ -W or group -CO-W (the group, W is thiophene, pyrazole, heterocycle consisting of isoxazole or pyridine Group, these rings may be substituted with a halogen atom or a lower alkyl group), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, phenyl or benzyl, and Y represents N or shows the C-R ^9, wherein, R ⁹ is a hydrogen atom, bromine, fluor alkyl group (the alkyl group having 1 to 2 carbon atoms, chloro, hydroxy, carbons 1-2 alkoxy,
It may be substituted with alkylthio having 1 to 2 carbons, cyano, dimethylamino, alkylcarbonyl having alkyl having 1 to 2 carbons, or alkoxycarbonyl having alkyl having 1 to 2 carbons), 1-hydroxy-
2,2,2-trichloroethyl group, an alkylcarbonyl group having an alkyl group having 1 to 4 carbon atoms (the alkylcarbonyl group may be substituted with methoxy or chloro),
A benzoyl group (the benzoyl group may be substituted with at least one selected from chloro, bromo, methoxy and methyl), an alkoxycarbonyl group having an optionally substituted fluoroalkyl group having 1 to 4 carbon atoms,
A phenoxycarbonyl group (the phenoxycarbonyl group may be substituted with chloro, methyl, methoxy or nitro), benzoylaminocarbonyl (the benzoylaminocarbonyl may be substituted with methyl, fluoro or chloro) Phenyl), phenylsulfonylaminocarbonyl (wherein the phenylsulfonylaminocarbonyl group may be substituted with methyl or chloro), phenylthio (wherein the phenylthio may be substituted with methyl or chloro), or chloro-substituted. And optionally represents phenylsulfonyl, R represents a hydrogen atom or methyl, and Z represents a heterocyclic group consisting of thiophene, pyrazole, isoxazole, thiazole, 1,2,3-thiadiazole, 1,2,5-thiadiazole, pyridine, pyrimidine, pyridazine or pyrazine. These rings are lower alkyl groups which may be halogen-substituted, alkenyl groups having 2 to 3 carbon atoms which may be chloro-substituted, halogen atoms, propargyl, methoxy which may be fluoro-substituted,
Fluoro may be substituted with one or two selected from methylthio, methylsulfinyl, methylsulfonyl, thiocyanato, trichloroacetamide, nitro, cyano and methoxycarbonyl, provided that in the above, n Represents 0 or 1, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents NH, and Y represents CH, and n represents 0 or 1. R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ represent a hydrogen atom, X represents S, Y represents CH, and Z is an optionally substituted pyridyl group. The substituent is a halogen atom, an optionally halogen-substituted lower alkyl group, nitro, cyano, optionally fluoro-substituted methoxy, an optionally fluoro-substituted methylthio, methylsulfinyl, methylsulfonyl and chloro. When indicating at least one indicating a) is selected from an alkenyl group carbon atoms which may be have 2-3 substituents, and n represents 0 or ^{1, R 1, R 2,} R 3, R 4, R 5 And R ⁶ represents a hydrogen atom, X represents NH, Y represents N, and Z is an optionally substituted pyridyl group (the substituent is a halogen atom or an optionally substituted lower alkyl). Group, nitro, cyano, methoxy which may be substituted by fluoro, methylthio which may be substituted by fluoro, methylsulfinyl, methylsulfonyl, alkenyl group having 2 to 3 carbon atoms which may be substituted by chloro, trichloroacetamide And at least one selected from methoxycarbonyl), except that the heterocyclic compound represented by: is contained as an active ingredient.