JPH04211683A - Dialkoxymethylimidazolidine derivative, its production and insecticide and intermediate containing the same as active ingredient - Google Patents

Abstract

PURPOSE:To obtain a new readily producible imidazolidine derivative having excellent insecticidal activity as an insecticide. CONSTITUTION:An imidazolidine derivative, e.g. 1-diethoxymethyl-2- nitroimino--3-(2-chloropyridin-5-ylmethyl) imidazolidine expressed by formula I (Z is 2-chloropyridin-5-yl or 2-chlorothiazol-5-yl; R1 and R2 are 1-6C alkyl, 1-3C haloalkoxyl or 1-3C alkoxy-substituted 1-3C alkyl; R1 and R2 together form 2-3C cyclic alkylene; n is 2 or 3). The aforementioned compound expressed by formula I is obtained by reacting a new compound expressed by formula II with a compound expressed by formula III (X is Cl or Br). Furthermore, the new compound expressed by formula II is obtained by reacting a compound expressed by formula IV with a nitroguanidine derivative expressed by formula V.

Description

[Detailed description of the invention]

0001

TECHNICAL FIELD The present invention relates to a novel imidazolidine derivative, a method for producing the same, an insecticide containing the derivative as an active ingredient, a novel intermediate, and a method for producing the same.

More specifically, the present invention provides the formula (1) (Chemical formula 10
)

0003

An imidazolidine derivative represented by the formula (2), a method for producing the same, an insecticide containing the derivative as an active ingredient, and the formula (2) (
11)

0004

[Chemical formula 11] The present invention relates to an intermediate represented by and a method for producing the same.

The imidazolidine derivative (1), which is a compound of the present invention, is useful as a pesticide (especially an insecticide) in the agricultural field, and the imidazolidine derivative (2) is useful in various industrial fields, especially as an intermediate for agricultural chemicals. It is useful as

[0006]

[Prior Art] Many insecticidal compounds having the same skeleton as the compound of the present invention represented by formula (1) have been known (Japanese Unexamined Patent Publication Nos. 62-81382 and 62-81382).
3-156786, etc.).

On the other hand, many compounds having the same skeleton as the intermediate of the compound (1) of the present invention represented by formula (2) have also been disclosed (Japanese Patent Application Laid-Open No. 156786/1986, etc.).

[0008]

[Problems to be solved by the present invention] The problems to be solved by the present invention are a novel imidazolidine derivative having excellent insecticidal activity, an easy method for producing the same, a highly active insecticide containing the same as an active ingredient, and The object of the present invention is to provide a new intermediate thereof.

[0009]

[Means and effects for solving the problem] As a result of intensive studies to solve the above problems, the present inventors discovered that a novel imidazolidine derivative represented by formula (1) has excellent insecticidal activity, and the present invention Completed the invention.

That is, the present invention is based on the formula (1) (Chemical formula 12)

[
0011

[Chemical formula 12]

(wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and R
1, R2 represents a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R1 , R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3. ), a method for producing the same, an insecticide containing it as an active ingredient, and a novel imidazolidine derivative represented by the formula (1).
) Novel intermediate (2) (Chemical formula 13)

00
13]

[Chemical formula 13]

(wherein R1 and R2 are a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms,
It represents a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R1 and R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3. ), and its manufacturing method.

In formula (1), Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group. In formulas (1) and (2), R1 and R2 are lower alkyl groups having 1 to 6 carbon atoms, and typical examples thereof include methyl group, ethyl group, n-propyl group, is
o-propyl group, n-butyl group, i-butyl group, sec
-butyl group, n-pentyl group, n-hexyl group, etc. When R1 and R2 represent a cyclic alkylene group, examples thereof include a dimethylene group and a trimethylene group. Typical examples of haloalkyl groups having 1 to 3 carbon atoms include 2-bromoethyl group, 2-chloroethyl group, 2-bromoethyl group,
, 2,2-trichloroethyl group, 2-fluoroethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, and the like. Typical examples of lower alkyl groups having 1 to 3 carbon atoms substituted with lower alkoxy having 1 to 3 carbon atoms include 2-methoxyethyl group, 2-ethoxyethyl group, 2-isopropoxyethyl group, 1-methoxy Examples include methyl-ethyl group.

The compound of formula (1) can be produced by the following method. (Chem.14)

[0017]

[Chemical formula 14]

(wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and R
1, R2 represents a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R1 , R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3, and X represents a chlorine atom or a bromine atom. ) i.e.
A compound represented by formula (2) and 2 represented by formula (3)
-chloro-5-halomethylpyridine or 2-chloro-
It can be easily synthesized by reacting 5-halomethylthiazole in various solvents in the presence of a deoxidizing agent.

As deoxidizing agents, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium hydride, potassium hydride, etc. Alkali metal hydrides, alkali metal alcoholates such as sodium methylate and sodium ethylate, alkali metal oxides such as sodium oxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, etc. hydrogen carbonates, hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate, phosphates such as trisodium phosphate and disodium phosphate, sodium acetate,
Acetate salts such as potassium acetate, triethylamine, DBU
, organic salts such as DIMAP, butyllithium, sodium amide, etc. can be used.

Examples of solvents include water, aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as hexane, heptane, and petroleum benzene;
Aprotic polar solvents such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran , ethers such as dioxane, nitriles such as acetonitrile and propionitrile, acetone,
Ketones such as diisopropyl ketone can be used.

Furthermore, the desired imidazolidine derivative (1) can also be obtained in high yield by using a phase transfer catalyst typified by tetrabutylammonium bromide, triethylbenzylammonium chloride, etc. as a catalyst.

Although the reaction temperature and reaction time can be varied over a wide range, generally the reaction temperature is -20 to
200°C, preferably 0-100°C, reaction time 0.0
The time is 1 to 30 hours, preferably 0.1 to 15 hours.

Compound (1) of the present invention includes the following isomers. (Chem.15)

[0024]

[Chemical formula 15]

In the above reaction formula, the starting material represented by formula (2) can be synthesized according to the following reaction formula. (Chem.16)

[0026]

[Chemical formula 16]

(In the formula, R is a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, or a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms. R1 and R2 are a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, or a lower alkoxy group having 1 to 3 carbon atoms substituted with 1 carbon number.
~3 lower alkyl group, and R1 and R2 represent a cyclic alkylene group having 2 to 3 carbon atoms. )

That is, the nitroguanidine derivative represented by formula (4) [Synthesis method literature: J. Am. Chem. S
oc. ,70. , 430 (1948)] and orthoformate derivatives [Synthesis method literature: Synthesis, 15
3 (1974)] can be easily synthesized in high yield. The compound represented by formula (2) is a novel compound synthesized for the first time by the present inventors, and this synthesis reaction itself is also a novel reaction discovered for the first time by the present inventors.

[0029] This reaction can be carried out without a solvent or in a solvent. As a solvent, aliphatic hydrocarbons such as benzene, toluene, xylene, chloroform, 1,2-
Halogenated hydrocarbons such as dichloroethane, ethers such as diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane, dimethylformamide, dimethylsulfoxide, sulfolane, 1,3-
Aprotic polar solvents such as dimethyl-2-imidazolidinone, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and methyl isobutyl ketone are used.

The reaction temperature and reaction time can be varied over a wide range, but generally the reaction temperature is between 50 and 3
00°C, preferably 70-200°C. This reaction is usually carried out under normal pressure conditions, but it can also be carried out under pressurized conditions as well.

Although not necessarily necessary, examples of catalysts include mineral acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and nitric acid, sulfonic acids such as p-toluenesulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid, formic acid, acetic acid, and benzoic acid. Lewis acids such as aluminum chloride, tin tetrachloride, zinc chloride, boron trifluoride, titanium tetrachloride, ammonium salts such as pyridine hydrochloride, tetrabutylammonium chloride, acid bases such as zirconium oxide, silica gel, alumina, etc. chemical oxides, etc. are used.

The reaction time is 0.1 to 30 hours, preferably 0.5 to 20 hours.

The amount of the orthoformate derivative (5) to be used may be any amount as long as it is 1.0 mol or more based on the nitroguanidine derivative (4), but economically it is 1.0 to 10.
0 mol is preferred.

[0034] This reaction is usually carried out under normal pressure conditions, but it can also be carried out under pressurized conditions.

Compound (2) of the present invention is an isomer of E and Z,
and tautomers, as shown below.
including. (Chem.17)

[0036]

[Chemical formula 17]

On the other hand, the chloropyridyl methyl halides represented by formula (3) are known compounds and can be synthesized by the method described in the literature [Synthesis method literature: J. Het
erocyclic Chem. ,16,333(1
979), J. Med. Chem. , 14,557 (1
971)], thiazolyl methyl halides are obtained by diazotizing 2-amino-5-alkoxycarbonylthiazoles, introducing a halogen atom, and reducing the resulting 2-halogeno- It can be obtained by converting 5-hydroxymethylthiazole into a halogen atom by a conventional method.

The derivative represented by formula (1) of the present invention has a strong insecticidal effect and can be used as an insecticide. The derivative represented by formula (1) of the present invention is effective against harmful insects without causing phytotoxicity to cultivated plants.
Demonstrates accurate pest control effects. As such pests,
Lepidopteran pests, such as green caterpillars, fall armyworms, corn borer moths, diamondback moths, and silver leaf moths; Hemiptera pests,
For example, black leafhopper, brown planthopper, brown planthopper, green leafhopper, green peach aphid, cotton aphid, false radish aphid, green stink bug, whitefly, etc.; Coleoptera pests such as red bean weevil, brown weevil, black lady beetle,
Orthoptera pests, such as the German cockroach, American cockroach, mole cricket, grasshopper, Japanese termite, house termite, etc.; Diptera pests, such as the house fly, Aedes aegypti, Culex mosquito, Culex pipiens, etc. .

When the compound represented by formula (1) of the present invention is actually applied, it can be used alone without adding other ingredients, but it may be added with a carrier to make it easier to use as a pest control agent. Generally, it is applied as follows.

The compounds of the present invention can be formulated into emulsions, wettable powders, powders, granules, fine granules, and oils by methods well known in the art in accordance with general agricultural chemicals, without requiring any special conditions. , aerosol, poison bait, etc., and can be used for various purposes depending on the purpose.

[0041] The carrier herein refers to a synthetic or natural inorganic or organic substance that is incorporated to help the active ingredient reach the site to be treated and to facilitate the storage, transportation, and handling of the active ingredient compound. means. Suitable solid carriers include clays such as montmorillonite and kaolinite;
Diatomaceous earth, white clay, talc, vermiculite, gypsum,
Examples include inorganic substances such as calcium carbonate, silica gel, and ammonium sulfate, vegetable organic substances such as soy flour, sawdust, and wheat flour, and urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as carbon tetrachloride, chloroform and dichloroethane, acetone, Ketones such as methyl ethyl ketone, ethers such as dioxane and tetrahydrofuran, methanol,
Examples include alcohols such as ethanol, propanol, and ethylene glycol, dimethylformamide, dimethyl sulfoxide, and water.

Furthermore, in order to enhance the efficacy of the compound represented by formula (1) of the present invention, the following may be used alone or in combination depending on the purpose, taking into account the dosage form of the preparation, the application situation, etc. Adjuvants may also be used.

For purposes of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as lignin sulfonates, nonionic surfactants such as alkylbenzene sulfonates, alkyl sulfate esters, calcium stearate, Examples include lubricants such as wax, stabilizers such as isopropylhydrodiene phosphate, and others such as methylcellulose, carboxymethylcellulose, casein, and gum arabic. However, these components are not limited to the above.

Furthermore, by combining two or more of these compounds represented by the formula (1) of the present invention, it is possible to exhibit more excellent insecticidal activity, and it is also possible to express more superior insecticidal activity by combining two or more of these compounds, and it is also possible to express more superior insecticidal activity by combining them with other physiologically active substances such as allethrin and N. - (chrysanthemoylmethyl)-3,4,5,6-tetrahydrophthalimide, 5-benzyl-3-furylmethyl chrysanthemate, 3-phenoxybenzyl chrysanthemate, 5-propargyl furfuryl chrysanthemate, and other known cyclopropanecarboxylic acid ester, 3-
Phenoxybenzyl 2,2-dimethyl-3-
(2,2-dichlorovinyl)-cyclopropane-
1-carboxylate, 3-phenoxy-α-
Cyanobenzyl 2,2-dimethyl-3- (2
,2-dichlorovinyl)-cyclopropane-1-
Carboxylate, 3-phenoxy-α-cyanobenzyl 2,2-dimethyl-3-(2,2
Synthetic pyrethroids such as -dibromovinyl)-cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl α-isopropyl-4-chlorophenylacetate and their various isomers or pyrethrum extract, O,O-diethyl-O
- (3-oxo-2-phenyl-2H-pyridazin-6-yl) phosphorothioate (Mitsui Toatsu Chemical registered trademark Offnac), O,O- dimethyl-
O-(2,2-dichlorovinyl)phosphate (D
DVP), O,O-dimethyl-O-(3-methyl-4-nitrophenyl)phosphorothioate, diazinon, O,O-dimethyl-O-4-cyanophenylphosphorothioate, O,O-dimethyl-
S- [α-(ethoxycarbonyl)benzyl]phosphorodithioate, 2-methoxy-4H- 1,
Organophosphorus insecticides such as 3,2-benzodioxaphosphorine-2-sulfide, O-ethyl-O-4-cyanophenylphosphonothioate, 1-naphthyl N-methylcarbamate (NAC), m-tolyl N - Methyl carbamate (MTMC), 2-
Dimethylamino-5,6-dimethylpyrimidine-
4-yl-dimethyl carbamate (pyrimer),
Carbamate insecticides such as 3,4-dimethylphenyl N-methylcarbamate and 2-isopropoxyphenyl N-methylcarbamate, 3-phenoxybenzyl 2-(4-chlorophenyl)-
2-methylpropyl ether, 3-phenoxy-
4-fluorobenzyl 2-(4-chlorophenyl)-2-methylpropyl ether, 3-
Arylpropyl ether insecticides such as phenoxybenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 3-phenoxy-4-fluorobenzyl 2-(4-ethoxyphenyl)-2-methylpropyl ether, 1
- (3-phenoxyphenyl)- 4- (4-
Chlorophenyl)-4-methylpentane, 1-(
3-phenoxy-4-fluorophenyl)-4
- (4-chlorophenyl)- 4-methylpentane, 1- (3-phenoxyphenyl)- 4- (
4-ethoxyphenyl)-4-methylpentane,
1-(3-phenoxy-4-fluorophenyl)-4-(4-ethoxyphenyl)-4-Aromatic alkane-based insecticides such as methylpentane, other insecticides, acaricides or fungicides, wireicides By mixing with insecticides, herbicides, plant growth regulators, fertilizers, BT agents, insect hormones, other agricultural chemicals, etc., it is possible to create multipurpose compositions with even greater efficacy, and synergistic effects can also be expected.

The compound represented by formula (1) of the present invention is stable against light, heat, oxidation, etc., but if necessary, it may be added with an antioxidant or an ultraviolet absorber, such as BHT (2,6-
di-t-butyl-4-methylphenol), B
Phenol derivatives such as HA (butylhydroxyanisole), bisphenol derivatives, and phenyl-α
- By adding an appropriate amount of arylamines such as naphthylamine, phenyl-β-naphthylamine, a condensate of phenetidine and acetone, or benzophenone compounds as a stabilizer, a composition with more stable effects can be obtained.

The insecticide of the compound represented by formula (1) of the present invention contains the compound in an amount of 0.0001 to 95% by weight, preferably 0.01 to 50% by weight.

When applying the insecticide of the present invention, the active ingredient is generally 0.01 to 5000 ppm, preferably 0.1 to 5000 ppm.
Preferably, it is used at a concentration of 1000 ppm.

[0049] The amount applied per 10a is generally 1 to 300 g of the active ingredient.

[0050]

[Examples] Next, the content of the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Synthesis Example 1 (Compound No. 1)
17.6 g of 1-diethoxymethyl-2-nitroiminoimidazolidine and 21.0 g of anhydrous potassium carbonate were added to 200 ml of dimethylformamide, and 7
While stirring at 0°C, a solution of 12.3 g of 2-chloro-5-chloromethylpyridine dissolved in 30 ml of dimethylformamide was added dropwise.

After the addition was completed, the reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 25.0 g of an oily residue. Purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)] to obtain 11.3 g of 1-diethoxymethyl-2-nitroimino-3-(2-chloropyridin-5-ylmethyl). Imidazolidine was obtained.

Synthesis Example 2 (Compound No. 3)
15.0 g of 1-(1-ethoxy-1-propoxy)methyl-2-nitroiminoimidazolidine, 11.6 g of anhydrous potassium carbonate, 11.3 g of 2-chloro-5-chloromethylpyridine, and 60 ml of dimethyl sulfoxide at 75°C. Stirred for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting oily residue was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)]. 4.7g of 1-(1
-ethoxy-1-propoxy)methyl-2-nitroimino-3-(2-chloropyridin-5-ylmethyl)imidazolidine was obtained.

Synthesis Example 3 (Compound No. 5)
1-[1-ethoxy-1-(2-methoxyethoxy)]
6.8 g of methyl-2-nitroiminoimidazolidine, 4.8 g of anhydrous potassium carbonate, 6.0 g of 2-chloro-5-chloromethylpyridine, and 20 ml of dimethyl sulfoxide were stirred at 70° C. for 1 hour.

The reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting oily residue was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)]. and 2.8 g of 1-[1-
Ethoxy-1-(2-methoxyethoxy)]methyl-2
-Nitroimino-3-(2-chloropyridin-5-ylmethyl)imidazolidine was obtained.

Synthesis Example 4 (Compound No. 6)
16.0 g of 1-[bis-(2-chloroethoxy)methyl]-2-nitroiminoimidazolidine, 13.0 g of anhydrous potassium carbonate, 13.0 g of 2-chloro-5-chloromethylpyridine, and 70 ml of dimethyl sulfoxide were heated at 70°C. The mixture was stirred for 1 hour. The reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting oily residue was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)]. and 14.0g of 1-
[Bis-(2-chloroethoxy)methyl]-2-nitroimino-3-(2-chloropyridin-5-ylmethyl)
Imidazolidine was obtained.

Synthesis Example 5 (Compound No. 7)
1-[1-ethoxy-1-(2,2,2-trifluoroethoxy)]methyl-2-nitroiminoimidazolidine 7.0 g, anhydrous potassium carbonate 7.0 g, 2-chloro-5
-7.0 g of chloromethylpyridine and 45 ml of dimethyl sulfoxide were stirred at 70°C for 1 hour.

The reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and the resulting oily residue was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)]. and 2.3 g of 1-[1-
Ethoxy-1-(2,2,2-trifluoroethoxy)
] Methyl-2-nitroimino-3-(2-chloropyridin-5-ylmethyl)imidazolidine was obtained.

Synthesis Example 6 (Compound No. 9)
6.0 g of 1-dimethoxymethyl-2-nitroiminoimidazolidine and 8.6 g of anhydrous potassium carbonate were added to 50 ml of dimethyl sulfoxide, and 5.0 g of 2-chloro-5-chloromethylpyridine was added to the mixture while stirring at 70°C. Dissolve 5g in 10ml of dimethyl sulfoxide,
After dropping at 0 minutes, stirring was continued for 30 minutes at the same temperature.

After the addition was completed, the reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 13.7 g of an oily residue. Column chromatography [silica gel,
Developing solvent: hexane-ethyl acetate (1:2)] to obtain 4.8 g of 1-dimethoxymethyl-2-nitroimino-3-(2-chloropyridin-5-ylmethyl)imidazolidine.

Synthesis Example 7 (Compound No. 10
) 5.5 g of 1-diethoxymethyl-2-nitroiminohexahydropyrimidine and 6.5 g of anhydrous potassium carbonate
was added to 50 ml of dimethylformamide, and 3.8 g of 2-chloro-5-chloromethylpyridine was dissolved in 10 ml of dimethylformamide and added dropwise to the mixture while stirring at 70°C, followed by continued stirring at the same temperature for 40 minutes. Ta.

After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 11.0 g of an oily residue. Column chromatography [silica gel,
Developing solvent: hexane-ethyl acetate (1:2)] to obtain 2.3 g of 1-diethoxymethyl-2-nitroimino-3-(2-chloropyridin-5-ylmethyl)hexahydropyrimidine.

Synthesis Example 8 (Compound No. 11
) 5.0 g of 1-diethoxymethyl-2-nitroiminoimidazolidine and 6.0 g of anhydrous potassium carbonate were added to 50 ml of dimethyl sulfoxide, and the mixture was heated at 70°C.
While stirring, 3.9 g of 2-chloro-5-chloromethylthiazole was dissolved in 5 ml of dimethyl sulfoxide.
After the addition, stirring was continued for 1.5 hours at the same temperature.

After the reaction was completed, the reaction solution was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure to obtain 9.8 g of an oily residue. Purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)],
5.4 g of 1-diethoxymethyl-2-nitroimino-
3-(2-chlorothiazol-5-ylmethyl)imidazolidine was obtained.

Representative examples of the compound represented by formula (1) that can be synthesized according to the same method as in Examples 1 to 8 are shown in Table 1 (Table 1), (Table 2), (Table 3), (Table 4). ), shown in Table 2 (Table 5).

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5] Next, a method for producing the intermediate represented by general formula (2) will be explained.

Synthesis Example 9 (Intermediate No. 1)
A mixture of 25 g of 2-nitroiminoimidazolidine, 100 g of ethyl orthoformate and 25 ml of 1,3-dimethyl-2-imidazolidinone was heated under reflux for 3 hours. After cooling to room temperature, it was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crystals were sludged with ether to obtain 32 g of 1-diethoxymethyl-2-nitroiminoimidazolidine.

Synthesis Example 10 (Intermediate No. 5
) 16.5 g of 2-nitroiminoimidazolidine, 18.0 g of ethylenedioxymethyl ethyl ether, about 4
The mixture was heated to reflux for an hour while removing the distillate with a Dean-Stark trap. After cooling to room temperature, the reaction mixture was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)] to obtain 1.9 g of ethylenedioxymethyl-2-nitroiminoimidazolidine. Ta.

Synthesis Example 11 (Intermediate No. 6
) 9.9 g of 2-nitroiminoimidazolidine and 18.0 g of n-propyl orthoformate were heated to reflux for about 4 hours while removing the distillate with a Dean-Stark trap. After cooling to room temperature, the reaction mixture was subjected to column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1
:2)] to obtain 2.8 g of 1-di-n-propoxymethyl-2-nitroiminoimidazolidine.

Synthesis Example 12 (Intermediate No. 9
) 2-nitroiminoimidazolidine 10g, 1,3-dimethyl-2-imidazolidinone 20ml, sulfuric acid 0.05
22.0 g of methyl orthoformate was added dropwise to the mixture at 150° C. over about 2 hours, and the mixture was further heated under reflux for 1.0 hour while removing the distillate with a Dean-Stark trap. After cooling to room temperature, it was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained crystals were sludged with ether to obtain 1.9 g of 1-dimethoxymethyl-2-nitroiminoimidazolidine.

Synthesis Example 13 (Intermediate No. 1
0) 10 g of 2-nitroiminohexahydropyrimidine,
Methyl orthoformate 2 was added to a mixture of 20 ml of 1,3-dimethyl-2-imidazolidinone and 0.05 g of sulfuric acid at 150°C.
0.0g was added dropwise over about 1.5 hours, and the distillate was
The mixture was further heated and refluxed for 1.0 hour while being removed using a Stark trap. After cooling to room temperature, it was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)] to obtain 1.5 g of 1-
Dimethoxymethyl-2-nitroiminohexahydropyrimidine was obtained.

Synthesis Example 14 (Intermediate No. 1
1) 10 g of 2-nitroiminohexahydropyrimidine,
A mixture of 12.4 g of ethyl orthoformate and 10 ml of 1,3-dimethyl-2-imidazolidinone was heated under reflux for 2.0 hours while removing the distillate with a Dean-Stark trap. After cooling to room temperature, it was poured into water and extracted with ethyl acetate. After washing with water and drying over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained oil was purified by column chromatography [silica gel, developing solvent: hexane-ethyl acetate (1:2)], and 2.3 g of 1
-diethoxymethyl-2-nitroiminohexahydropyrimidine was obtained.

Representative examples of the compound represented by formula (2) which can be synthesized according to the same method as in Examples 9 to 14 above are shown in the third example.
It is shown in the tables (Table 6), (Table 7), and (Table 8).

[0078]

[Table 6]

[0079]

[Table 7]

[0080]

[Table 8]

Next, the composition of the present invention will be specifically explained with reference to formulation examples.

Formulation Example 1 20 parts of the compound of the present invention produced in Example 1, Solpol 3
55S (manufactured by Toho Chemical, surfactant) 10 parts, xylene 7
0 parts and the above were uniformly stirred and mixed to obtain an emulsion.

[0083]

Formulation Example 2 20 parts of the compound of the present invention produced in Example 1, 2 parts of sodium alkylnaphthalene sulfonate, 5 parts of sodium ligninsulfonate, 5 parts of white carbon, 6 parts of diatomaceous earth
8 parts of the above were uniformly stirred and mixed to obtain a wettable powder.

Formulation Example 3 0.3 part of the compound of the present invention prepared in Example 1 is dissolved in acetone, and the acetone is evaporated while mixing with 99.7 parts of clay to obtain a powder.

Formulation Example 4 2 parts of the compound of the present invention produced in Example 1, 2 parts of sodium ligninsulfonate, and 96 parts of bentonite were uniformly pulverized and mixed, water was added and kneaded, and the mixture was granulated and dried. Obtain granules.

Next, in order to clarify that the compound represented by formula (1) of the present invention has excellent insecticidal activity, it will be specifically explained using the following test examples.

Test Example 1 Effect on the brown planthopper The emulsion prepared in Formulation Example 1 is diluted to a predetermined concentration, and 2 ml of the emulsion is sprayed onto several rice seedlings (approximately 3-leaf stage). After air drying,
The treated seedlings were covered with a wire mesh cylinder, 10 female adult brown planthoppers were released inside, and placed in a constant temperature room at 25°C, and the mortality rate was examined after 48 hours. The results are shown in Table 4 (Table 9). In addition, a compound of the following formula (Chemical formula 18) was used as a control drug.

[0089]

[Chemical formula 18]

[0090]

[Table 9] Table 4

Test Example 2 Effect on resistant black leafhopper The emulsion prepared in Formulation Example 1 is diluted to a predetermined concentration and 3 ml is sprayed on several rice seedlings (approximately 3-leaf stage). After air-drying, the treated seedlings were covered with a wire mesh cylinder, and 10 adult female leafhoppers resistant to organic phosphorus and carbamate were released into the inside, and placed in a constant temperature room at 25°C. After 48 hours, the mortality rate was examined. The results are shown in Table 5 (Table 10). Note that the same drug used in Test Example 1 was used as the control drug.

[0092]

[Table 10] Table 5

Test Example 3 Effect on Adzuki Bean Weevil The acetone solution of the compound of the present invention prepared in Example 1 was collected in a petri dish with a diameter of 9 cm, the acetone was evaporated, and 20 female adult adzuki bean weevils 2 to 3 days after emergence were collected. The heads were placed in a petri dish, and the mortality rate was examined after 48 hours at 25°C. The results are shown in Table 6 (Table 11). In addition, as a control drug, diazinon [O, O-D
iethyl O-(2-isopropyl-6-m
ethyl-4-pyrimidinyl)phosp
horothioate] was used.

[0094]

[Table 11] Table 6

Test Example 4 Effect on green peach aphid 20 ml of the diluted emulsion prepared according to Formulation Example 1 was sprayed onto potted eggplant seedlings (4-5 leaf stage) grown in a greenhouse and infested with green peach aphids. did. After treatment, the seedlings were placed in a greenhouse, and the number of parasitic insects was investigated 3 days later. The results are shown in Table 7 (Table 12). Note that the same drug used in Test Example 1 was used as the control drug.

[0096]

[Table 12] Table 7

[0097]

Effects of the Invention As is clear from the above explanation, the imidazolidine derivative represented by formula (1) of the present invention is an excellent compound having high insecticidal power and a wide insecticidal spectrum. The imidazolidine derivative represented by formula (1) of the present invention can be easily produced from the novel intermediate represented by formula (2) by the production method according to the present invention. Also,
The agricultural chemical containing the imidazolidine derivative represented by formula (1) of the present invention has excellent properties and is useful as an insecticide.

Claims (5)

[Claims] Claim 1: Formula (1) (Formula 1) [Formula 1] (wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and R1, R2
represents a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R
1 and R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3. ) An imidazolidine derivative represented by [Claim 2] Formula (2) (Chemical formula 2) [Chemical formula 2] (wherein, R1 and R2 are a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, and a lower haloalkyl group having 1 to 3 carbon atoms. represents a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group, and R1 and R2 represent a cyclic carbon number 2
-3 alkylene groups may be formed. n represents 2 and 3. ) and the compound represented by formula (3) (chemical formula (3)
) [Formula 3] (wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and X represents a chlorine atom or a bromine atom). Formula (1) (Chemical Formula 4) [Chemical Formula 4] (wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and R1, R2
represents a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R
1 and R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3. ) A method for producing an imidazolidine derivative represented by [Claim 3] Formula (1) (Chemical formula 5) [Chemical formula 5] (wherein, Z represents a 2-chloropyridin-5-yl group or a 2-chlorothiazol-5-yl group, and R1, R2
represents a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R
1 and R2 may form a cyclic alkylene group having 2 to 3 carbon atoms. n represents 2 and 3. ) An insecticide characterized by containing a compound represented by the following as an active ingredient. [Claim 4] Formula (2) (Chemical formula 6) [Chemical formula 6] (wherein R1 and R2 are a lower alkyl group having 1 to 6 carbon atoms, a lower haloalkyl group having 1 to 3 carbon atoms, and a lower haloalkyl group having 1 to 3 carbon atoms) represents a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group, and R1 and R2 represent a cyclic carbon number 2
-3 alkylene groups may be formed. n represents 2 and 3. ) An imidazolidine derivative represented by [Claim 5] A compound represented by formula (4) (chemical formula 7) [chemical formula 7] (wherein n represents 2 and 3) and a compound represented by formula (5) (chemical formula 8) [chemical formula 8] (formula Among them, R is a lower alkyl group having 1 to 6 carbon atoms, and 1 carbon number.
~3 lower haloalkyl group, a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R1 and R2 are lower alkyl groups having 1 to 6 carbon atoms, and a lower alkyl group having 1 to 6 carbon atoms; 3 lower haloalkyl group, carbon number 1 to 3
represents a lower alkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group, and R1 and R2 represent a cyclic lower alkyl group having 2 to 3 carbon atoms.
3 may form an alkylene group. Formula (2) (Chemical formula 9) [Chemical formula 9] (wherein, R1 and R2 are lower alkyl groups having 1 to 6 carbon atoms, 3 represents a lower haloalkyl group having 1 to 3 carbon atoms substituted with a lower alkoxy group having 1 to 3 carbon atoms, and R1 and R2 represent a cyclic carbon number 2 group.
-3 alkylene groups may be formed. n represents 2 and 3. ) A method for producing an imidazolidine derivative represented by