JP3258402B2 - N-vinyl imidazolidine derivative, process for producing the same, insecticide and intermediate containing the same as active ingredient - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

The N-vinylimidazolidine derivative of the present invention is useful as an agricultural chemical (especially an insecticide) in the agricultural field, and its intermediate is useful in various industrial fields, particularly as an intermediate of the agricultural chemical. is there.

[0003]

2. Description of the Related Art Conventionally, many insecticidal compounds having an imidazolidine derivative skeleton have been known. Many compounds having an imidazolidine skeleton have also been disclosed. For example, USP 4,742,060 describes the following formula (Formula 1)
In 6), there is a description of an imidazolidine derivative having an alkenyl group having 2 to 3 carbon atoms, wherein R may be substituted with a halogen atom, and that they have insecticidal activity. (2-Chloropyridin-5-ylmethyl) -2-nitroimino-3-allylimidazolidine (R is an allyl group) is shown.

[0004]

Embedded image As a method for producing them, a production method according to the following reaction formula (Formula 17) is disclosed.

[0005]

Embedded image

[0006]

There have been many pesticidal compounds having an imidazolidine skeleton, but these compounds are generally highly toxic, and are generally used as pesticides, for example, they remain in crops for a long period of time. If you do, there are many problems. In addition, it has high solubility in water, and when used as a spraying agent, there is a concern that it may contaminate groundwater and rivers. In the future, as environmental problems become more severe, there is a need for pesticides that are non-toxic, easy to decompose in the environment, do not remain, and do not pollute rivers. The present inventors have developed the synthesis of N-vinyl imidazolidine derivatives. And its biological activity. As a result, they succeeded in synthesizing a novel N-vinyl imidazolidine derivative not described in the literature, and found that the derivative exhibited an extremely excellent insecticidal action.

[0007] Accordingly, an object of the present invention is to provide a novel N-vinyl imidazolidine derivative which does not have the drawbacks of the above-mentioned existing imidazolidine derivatives, an easy production method thereof, and a high activity containing the same as an active ingredient. And an intermediate for the production of a novel N-vinyl imidazolidine derivative.

[0008]

The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the novel N-vinylimidazolidine derivative represented by the formula (1) has excellent insecticidal activity. We have found and completed the present invention.

That is, the present invention provides a compound of the formula (1)

[0010]

Embedded image (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, Z represents a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms; Is 2-chloropyridine-
Represents a 5-ylmethyl group or a 2-chlorothiazol-5-yl group. N-vinyl imidazolidine derivative represented by formula (2):

[0011]

Embedded image (Wherein, R ¹ and R ² each have the same meaning as described above.)
And a compound represented by the formula (3):

[0012]

Embedded image (Wherein, Z represents the above-mentioned meaning, and X represents a chlorine atom or a bromine atom), and the compound represented by the formula (1) is reacted with the compound represented by the formula (1). An insecticide comprising the compound represented by the formula (1) as an active ingredient, an N-vinylimidazolidine derivative represented by the formula (2), and a compound represented by the formula (4):

[0013]

Embedded image (Wherein, R ¹ and R ² each have the same meaning as described above.)
And a compound represented by the formula (5):

[0014]

Embedded image A method for producing an N-vinyl imidazolidine derivative represented by the formula (2), characterized by reacting a compound represented by the formula (2):

[0015]

Embedded image (Wherein, R ¹ and R ² each represent the same meaning as above;
³ and R ⁴ each represent an alkoxy group, an alkylthio group, an alkyl sulfoxide group, a phenoxy group, a phenylthio group, a phenyl sulfoxide group, or an alkylenedioxy group or an alkylenedithio group to which R ³ and R ⁴ are bonded. ) And a compound represented by the formula (5), and a method for producing an N-vinyl imidazolidine derivative represented by the formula (2) and a compound represented by the formula (7):

[0016]

Embedded image Wherein R represents a lower alkyl group; and a compound represented by the formula (8):

[0017]

Embedded image Wherein R ¹ and R ² have the same meanings as defined above, respectively, and are reacted.
(Formula 26)

[0018]

Embedded image (Wherein, R ¹ and R ² each have the same meaning as described above.)
And a method for producing an N-vinyl imidazolidine derivative represented by the formula:

That is, the present invention provides a compound of the formula (1)

[0020]

Embedded image (Wherein R ¹ and R ² represent the above-mentioned meanings), a method for producing the same, a method for producing the same, an insecticide containing the same as an active ingredient, and a method for producing the formula (1) New intermediate (2)

[0021]

Embedded image (Wherein, R ¹ and R ² represent the above-mentioned meanings) and their production methods.

R ¹ and R ² in the above formula have 1 carbon atoms.
Typical examples of the alkyl group of -18 are a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a n-butyl group, an iso-butyl group, a sec-butyl group,
t-butyl group, n-pentyl group, n-hexyl group, n-
Octyl group, n-decyl group, n-octadecyl group and the like. As the alkoxy group having 1 to 4 carbon atoms, a methoxy group,
An ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a sec-butoxy group and the like are mentioned. As the alkylthio group having 1 to 4 carbon atoms, a methylthio group, an ethylthio group, an n- Examples thereof include a propylthio group, an iso-propylthio group, and an n-butylthio group.

Examples of the substituent of the substituted phenyl group include a methyl group, an ethyl group, a propyl group, an iso-propyl group and a t-
An alkyl group having 1 to 4 carbon atoms such as a butyl group, a fluorine atom,
Chlorine atom, bromine atom, halogen atom of iodine atom, methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, se
An alkoxy group having 1 to 4 carbon atoms such as a c-butoxy group, a methylthio group, an ethylthio group, an n-propylthio group, an iso
1 to 4 carbon atoms such as -propylthio group, n-butylthio group, etc.
Alkylthio, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, difluorobromomethoxy, chloromethoxy, dichloromethoxy, trichloromethoxy, bromomethoxy, 2
-Chloroethoxy group, 2-bromoethoxy group, 1,1-
Difluoro-2,2-dichloroethoxy group, 1,1,
2,2-tetrafluoroethoxy group, 2,2,2-trifluoroethoxy group, 1,1-dibromo-2,2,2-
Trifluoroethoxy group, 2,2-dichloroethoxy group, 2,2,2-trichloroethoxy group, 1,2-dichloroethoxy group, 3-chloropropoxy group, 3-bromopropoxy group, 4-chlorobutoxy group, 4 A haloalkoxy group having 1 to 4 carbon atoms such as a bromobutoxy group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a perfluorobutyl group, a chloromethyl group, a dichloromethyl group, a trichloromethyl group, A haloalkyl group having 1 to 4 carbon atoms, such as -chloroethyl group and bromomethyl group;

The compound of the formula (1) can be prepared by the following reaction formula (1)
It can be produced by the following (Formula 29).

[0025]

Embedded image (In the formula, R ¹ , R ² , Z, and X have the same meanings as described above.) The compound (1) and the intermediate (2) include E and Z isomers.

That is, an N-vinyl imidazolidine derivative represented by the formula (2) and a 2-chloropyridin-5-ylmethyl halide represented by the formula (3) or 2-
It can be easily synthesized by reacting chlorothiazol-5-ylmethyl halides in various solvents in the presence of a deoxidizing agent.

Examples of the deoxidizing agent include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, sodium hydride and potassium hydride. Alkali metal hydrides, alkali metal alcoholates such as sodium methylate and sodium ethylate, alkali metal oxides such as sodium oxide, carbonates such as sodium carbonate and potassium carbonate, and carbonic acid such as sodium hydrogen carbonate and potassium hydrogen carbonate Hydrogen salts, hydrogen sulfates such as sodium hydrogen sulfate and potassium hydrogen sulfate, phosphates such as trisodium phosphate and disodium phosphate, acetates such as sodium acetate and potassium acetate, triethylamine, DBU, D
Organic bases such as IMAP, butyllithium, sodium amide and the like can be used.

Examples of the solvent include water, aromatic hydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbons such as hexane, heptane and petroleum benzine; dimethylformamide, dimethylacetamide, dimethylsulfoxide, Aprotic polar solvents such as 3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, ethyl ether, diisopropyl ether,
1,2-dimethoxyethane, tetrahydrofuran, ethers such as dioxane, acetonitrile, nitriles such as propionitrile, acetone, ketones such as diisopropyl ketone, methyl acetate, ethyl acetate, esters such as ethyl propionate, methanol, Alcohols such as ethanol, propanol and 2-ethylhexyl alcohol can be used.

Further, by using a phase transfer catalyst represented by tetrabutylammonium bromide, triethylbenzylammonium chloride or the like as a catalyst, the desired N-vinylimidazolidine derivative can be obtained in high yield.

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

Although not always necessary, a substituent of the compound represented by the formula (2) is reacted with a so-called protecting group, and then a derivative of the target compound (1) is synthesized and deprotected to give N-.
A vinyl imidazolidine derivative (1) can also be obtained.

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

[0033]

Embedded image (R ¹ , R ² , R ³ , R ⁴ , and R each represent the above-mentioned meaning.) That is, the compound represented by the formula (2) of the present invention is a 2-nitroimino represented by the formula (5). The compound can be easily synthesized at a high yield by reacting imidazolidine with the aldehyde represented by the formula (4) and the aldehyde equivalent represented by the formula (6). Further, the compound can be easily synthesized in a high yield by reacting 2-nitroimino-N-dialkoxymethyl imidazolidine represented by the formula (7) with a compound having active methylene represented by the formula (8). . However, it should be noted here that the compound represented by the formula (2) of the present invention is disclosed in US Pat.
060 cannot be produced.

Therefore, the compound represented by the formula (2)
This is a novel compound synthesized for the first time by the present inventors, and this synthesis reaction itself is also a novel reaction first discovered by the present inventors.

The compound A of the present invention represented by the formula (2)
The production method from Method C to Method C will be described in detail.

Method A: This reaction can be carried out without a solvent or in a solvent. As the solvent, methanol,
Ethanol, alcohols such as propanol, benzene, toluene, aromatic hydrocarbons such as xylene, chloroform, halogenated hydrocarbons such as 1,2-dichloroethane, dimethylformamide, dimethylacetamide,
Non-protonic polar solvents such as dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, ethers such as ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran, dioxane And nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone.

Although not always necessary, the catalyst includes 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, acetic acid, benzoic acid and formic acid. Carboxylic acids, Lewis acids such as aluminum chloride, tin tetrachloride, zinc chloride, boron trifluoride and titanium tetrachloride; ammonium salts such as pyridine hydrochloride and tetramethylammonium chloride; and hydrogen sulfate such as sodium hydrogen sulfate and potassium hydrogen sulfate. Salts, hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate, zirconium oxide, acid-base oxides such as silica gel and alumina, acid gases such as sulfur dioxide gas, carbon dioxide gas, and phenols are used.

The reaction temperature and the reaction time can be varied in a wide range, but generally the reaction temperature is from -80 to
The temperature is 300 ° C, preferably -30 to 200 ° C.

This reaction is generally carried out under normal pressure conditions, but can be carried out similarly under pressurized conditions.

The reaction time is 0.001 to 30 hours, preferably 0.01 to 20 hours.

The amount of the aldehyde derivative (4) used is 2-
0.1 to 3 relative to nitroimino imidazolidine (5)
The molar ratio is preferably 0 to 0.3 to 10.0 in terms of economy.

The compound represented by the formula (5) can be synthesized by the reaction of ethylenediamine or a hydrochloride thereof with 2-nitroimidazolidine [Synthesis method: J. Amer. Am. Chem. Soc. , 70 430 (1
948)].

Method B: It can be easily synthesized at a high yield by reacting the compound represented by the formula (6) with the 2-nitroiminoimidazolidine derivative represented by the formula (5).

This reaction can be carried out without a solvent or in a solvent. As the solvent, aromatic hydrocarbons such as benzene, toluene, xylene, chloroform, 1,2-
Aprotic polar solvents such as halogenated hydrocarbons such as dichloroethane, dimethylformamide, dimethylacetamide, dimethylsulfoxide, 1,3-dimethyl-2-imidazolidinone 1-methyl-2-pyrrolidinone;
Ethers such as ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane; nitriles such as acetonitrile and propionitrile; ketones such as acetone and diisopropyl ketone; alcohols such as methanol, ethanol and propanol. Can be used.

Although not always necessary, examples of the catalyst 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, acetic acid, benzoic acid and formic acid. Carboxylic acids, Lewis acids such as aluminum chloride, tin tetrachloride, zinc chloride, boron trifluoride and titanium tetrachloride; ammonium salts such as pyridine hydrochloride and tetramethylammonium chloride; acid-basic such as zirconium oxide, silica gel and alumina Oxides, hydrogensulfates such as sodium hydrogensulfate and potassium hydrogensulfate, hydrogencarbonates such as sodium hydrogencarbonate and potassium hydrogencarbonate, acid gases such as sulfurous gas and carbon dioxide, phenols and the like are used.

The reaction temperature and the reaction time can be varied in a wide range, but generally the reaction temperature is from -80 to
The temperature is 300 ° C, preferably -30 to 200 ° C.

This reaction is usually carried out under normal pressure conditions, but can be carried out similarly under pressurized conditions.

The reaction time is 0.001 to 30 hours, preferably 0.01 to 20 hours.

The amount of the ethane derivative (6) to be used is not particularly limited as long as it is 1.0 mol or more with respect to 2-nitroiminoimidazolidine (5), but is preferably 0.3 to 10.0 mol in terms of economy. The compound represented by (6) can also be obtained by acetalizing the aldehyde represented by (4) or by reacting a Grignard reagent with an orthoformate. In addition, it can be obtained by reacting methyl methylsulfinylmethyl sulfide with an alkyl halide, an aryl halide or the like [Synthesis method literature: Journal of Organic Synthetic Chemistry, Vol. 37, No. 11, (1979)] [Chemical Review No. 19, 75-96 (1978)] [Tet
rahedron Letters, No. 34, 31
51-3154 (1971)] [Tetrahedr
on Letters, no. 26,2681-268
4, (1972)].

Method C: An aldehyde equivalent represented by the formula (7) and a compound having an active methylene represented by the formula (8) can be easily synthesized in a high yield by a dehydration condensation reaction. .

The reaction temperature and the reaction time can be varied in a wide range, but generally the reaction temperature is from -80 to
The temperature is 300 ° C, preferably -30 to 200 ° C. The reaction time is 0.001-30 hours, preferably 0.01-20.
Time. The amount of the compound having active methylene used is based on the dialkoxymethyl imidazolidine derivative (7).
Any amount can be used as long as it is 1.0 mol or more, but from the economical point of view, it is not limited to 0.1 mol.
3 to 10.0 mol is preferred.

The dialkoxymethyl imidazolidine derivative represented by the formula (7) can be synthesized by reacting the imidazolidine derivative with orthoformates.
This reaction can be carried out without a solvent or in a solvent. As the solvent, an aprotic polar solvent such as dimethylformamide, dimethylsulfoxide, and 1,3-dimethyl-2-imidazolidinone is used. Reaction temperature is 50
~ 200 ° C, reaction time is 0.5 ~ 15hr. The amount of the orthoformate used is preferably 1 to 10 mole ratio to the imidazolidine derivative (5).

The compound represented by the formula (7) includes a tautomer (tautomer) represented by the following formula (3) (Formula 31).

[0054]

Embedded image (Wherein, R represents the same meaning as above.) On the other hand, 2-chloropyridine-5- represented by the formula (3)
Ilmethyl halide and 2-chloro-5-chloromethylthiazole are known compounds and can be synthesized by a method described in the literature [Synthesis method reference: J. Amer. Heter
oclicChem. , 16, 333 (197
9); Med. Chem. , 14,557 (19
71)].

The derivative represented by the formula (1) of the present invention has a strong insecticidal action and can be used as an insecticide. And the derivative represented by the formula (1) of the present invention, against cultivated plants, against harmful insects without causing phytotoxicity,
Exhibits an accurate control effect. As such pests,
Lepidopteran insect pests, for example, caterpillars, cutworms, Awanomeiga, Konaga, Nikameichu, Kombomeiga and the like;
Hemiptera pests, for example, black leafhoppers, brown planthoppers, brown planthoppers, brown aphids, peach aphids, cotton aphids, cotton aphids, radish aphids,
Green stink bugs, whiteflies, etc .; Coleoptera pests, such as adzuki beetles, weevil, beetle beetle, Japanese beetle, colorado potato beetle, rice water weevil, etc .;
House termites and the like; dipteran pests such as house flies, Aedes aegypti, Culex pipiens, Culex pipiens and the like can be mentioned.

The compound of the present invention has not only a high control effect on insect pests but also a very low acute toxicity as compared with a conventional compound having an imidazolidine skeleton, and can be used safely in any use. In addition, the compound of the present invention is rapidly decomposed by light or the like in a natural environment, has very little residue in crops, has low solubility in water, and has little outflow into groundwater and rivers. In addition, during the production of the compound of the present invention, by-products are produced very little, and it can be easily produced, which is industrially advantageous.

When the compound represented by the formula (1) of the present invention is actually applied, it can be used in a simple form without adding other components. However, a carrier is blended for easy use as a controlling agent. Generally, it is applied.

In formulating the compound of the present invention, no special conditions are required, and emulsions, wettable powders, powders, granules, fine granules, oils and the like can be prepared by a method well-known in the art according to general agricultural chemicals. , Aerosol, poison bait and the like, and can be used for various purposes depending on the purpose.

As used herein, the term "carrier" refers to a synthetic or natural inorganic or organic substance incorporated to help the active ingredient reach the site to be treated and to facilitate storage, transport, and handling of the active ingredient compound. Means

Suitable solid carriers include clays such as montmorillonite and kaolinite, diatomaceous earth, terra alba, talc, vermiculite, gypsum, calcium carbonate, silica gel, inorganic substances such as ammonium sulfate, and soybean flour, sawdust, flour and other vegetable substances. Organic substances and urea.

Suitable liquid carriers include aromatic hydrocarbons such as toluene, xylene and cumene, paraffinic hydrocarbons such as kerosene and mineral oil, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and ethers such as dioxane and tetrahydrofuran. Glymes such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; alcohols such as methanol, ethanol, propanol and ethylene glycol; phthalic esters such as dioctyl phthalate; dimethylformamide, dimethyl sulfoxide, and water.

Further, in order to enhance the efficacy of the compound represented by the formula (1) of the present invention, each of them may be used alone or in combination according to the purpose, taking into account the dosage form of the preparation, the application scene, etc. Various adjuvants can also be used.

For the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as lignin sulfonate, nonionic surfactants such as alkylbenzene sulfonate and alkyl sulfate, calcium stearate, 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 those described above.

Further, these compounds represented by the formula (1) of the present invention can exhibit more excellent insecticidal activity when used in combination of two or more kinds, and can also have other physiologically active substances such as allethrin, N -(Chrisantemoylmethyl) -3,4,5,6-tetrahydrophthalimide,
5-benzyl-3-furylmethyl chrysanthemate,
3-phenoxybenzyl chrysantemate, 5-propargylfurfuryl chrysantemate, other known cyclopropanecarboxylic acid esters, 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-dibromovinyl) -cyclopropane-1-carboxylate, 3-phenoxy-α-cyanobenzyl α-isopropyl-4
-Synthetic pyrethroid insecticides such as chlorophenylacetate, resmethrin, cyhalothrin, cyfluthrin, fenpropatrin, terralomethrin, cycloprothrin, flucitrinate, fulvalinate and the like, and various isomers or pyrethrum extract thereof, O, O-diethyl-O
-(3-oxo-2-phenyl-2H-pyridazine-6
-Yl) phosphorothioate (Mitsui Toatsu Chemicals Offnac), O, O-dimethyl-O- (2,2-dichlorovinyl) phosphate (DDVP), O, O-dimethyl-O- (3-methyl-4- Nitrophenyl) phosphorothioate, diazinon, O, O-dimethyl-O-4
-Cyanophenyl phosphorothioate, O, O-dimethyl-S- [α- (ethoxycarbonyl) benzyl] phosphorodithioate, 2-methoxy-4H-1,3,2-
Benzodioxaphosphorin-2-sulfide, O, O-
Diethyl-O-4-cyanophenylphosphonothioate, MPP, pirimiphosmethyl, isoxathion, chlorpyrifosmethyl, chlorpyrifos, ESP, propenophos, marathon, dimethoate, thiometon, ethylthiometon, hosalon, DMTP, prothiophos, sulprophos, pyraclophos, monocrotophos, CVP, Organophosphorus insecticides such as propafos, acephate, DEP, EPN, and ethion; 1-naphthyl N-methylcarbamate (NAC); m-tolyl N-methylcarbamate (MTMC); 2-dimethylamino-5,6-dimethylpyrimidine -4-yl-dimethylcarbamate (pyrimer), 3,4-dimethylphenyl N-methylcarbamate, 2-isopropoxyphenyl N-methylcarbamate, MIPC, BP C, XMC, ethiofencarb, bendiocarb, carbosulfan, benfuracarb, methomyl, oxamyl, carbamate insecticides such as thiodicarb, 3-phenoxybenzyl 2- (4
-Chlorophenyl) -2-methylpropyl ether,
3-phenoxy-4-fluorobenzyl 2- (4-chlorophenyl) -2-methylpropyl ether, 3-
Phenoxybenzyl 2- (4-ethoxyphenyl)-
2-methylpropyl ether, 3-phenoxy-4-
Fluorobenzyl 2- (4-ethoxyphenyl) -2
An arylpropyl ether-based insecticide such as 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-
Aromatic alkane insecticides such as 4-fluorophenyl) -4- (4-ethoxyphenyl) -4-methylpentane, nicotine sulfate, polynactin complex, insecticidal natural products such as avermectin, milbemectin, cartap, thiocyclam; Bensultap, diflubenzuron, chlorfluazuron, teflubenzuron, buprofezin,
Insecticides such as benzoepine, Kelsen, CPCBS, BP
Acaricides such as PS, tetradifon, amitraz, benzomate, phenothiocarb, hexathiazox, fenbutatin oxide, dienochlor, clofentezin, phenopiroximate, other insecticides, acaricides or fungicides, nematodes Pesticides, herbicides, plant growth regulators, fertilizers,
Soil improvement materials, molting inhibitors, JH activators, BT agents, toxins produced by microorganisms, natural or synthetic insect hormone disrupters,
By mixing with attractants, repellents, other pesticides such as entomopathogenic microorganisms and small animals, a multipurpose composition with even better efficacy can be produced, and a synergistic effect can be expected.

The compound represented by the formula (1) of the present invention is stable to light, heat, oxidation and the like, but if necessary, an antioxidant or an ultraviolet absorber such as BHT (2,6-
Phenol derivatives such as di-t-butyl-4-methylphenol) and BHA (butylhydroxyanisole); bisphenol derivatives; and arylamines such as phenyl-α-naphthylamine, phenyl-β-naphthylamine, and condensates of phenetidine and acetone. More effective compositions can be obtained by adding an appropriate amount of a benzophenone compound or a benzophenone compound as a stabilizer.

The insecticide of the compound represented by the 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.

To apply the insecticide of the present invention, the active ingredient is generally used in an amount of 0.01 to 5000 ppm, preferably 0.1 to 1 ppm.
It is desirable to use a concentration of 000 ppm.

The application rate per 10a is generally 1 to 300 g of the active ingredient.

[0069]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 (Compound No. 18) 1- {2- (3,4-dichlorophenyl) vinyl} -2
-Nitroimino imidazolidine 7.0 g, 2-chloro-
7.5 g of 5-chloromethylpyridine, potassium carbonate 6.
4 g of a mixture of 50 ml of dimethyl sulfoxide at 60 ° C.
For 1 hour. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ), and concentrated, and the resulting oily residue was subjected to column chromatography [silica.
Gel, developing solvent: ethyl acetate], and purify 5.7 g.
1- (2-chloropyridin-5-ylmethyl) -2-
Nitroimino-3- (3,4-dichlorophenylvinyl) -imidazolidine was obtained.

Example 2 (Compound No. 20) 1- {2- (3-cyanophenyl) vinyl} -2-nitroiminoimidazolidine 5.0 g, 2-chloro-5-chloromethylpyridine 7.4 g, carbonic acid 5.4 g of potassium,
A mixture of 50 ml of dimethyl sulfoxide was added at 60 ° C. for 1 hour.
and stirred. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated. Ethyl ether was added to the resulting oily residue, and the precipitated crystals were collected by filtration.
Drying yielded 5.9 g of 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3- {2- (3-cyanophenyl) vinyl} -imidazolidine.

Example 3 (Compound No. 23) 15.4 g of 1- (2,2-diphenylvinyl) -2-nitroiminoimidazolidine, 8.1 g of 2-chloro-5-chloromethylpyridine, potassium carbonate 6. A mixture of 9 g and dimethyl sulfoxide (80 ml) was stirred at 60 ° C. for 2 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated. The crude product obtained was added with 100 ml of ethyl acetate and recrystallized to obtain 13 g of 1- (2-chloroform). Pyridin-5-ylmethyl) -2-nitroimino-3- (2,2-diphenylvinyl) imidazolidine was obtained.

Example 4 (Compound No. 25) 1- {4- (2,2,2-trifluoroethoxy) phenylvinyl} -2-nitroiminoimidazolidine 5.0
g, 2-chloro-5-chloromethylpyridine 5.8 g,
8.4 g of potassium carbonate, 30 ml of dimethyl sulfoxide
Was stirred at 60 ° C. for 1 hr. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous MgSO 4).
₄ ) The oily residue obtained by concentration was separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate / hexane 4/1] to give 4.9 g of 1- (2-chloropyridine-5- Ylmethyl) -2-nitroimino-3
-{4- (2,2,2-trifluoroethoxy) phenylvinyl} -imidazolidine was obtained.

Example 5 (Compound No. 26) 1- (1-propenyl) -2-nitroiminoimidazolidine 6.0 g, potassium carbonate 7.0 g, DMSO 70 m
1, a mixture of 7.4 g of 2-chloro-5-chloromethylpyridine was stirred at 60 ° C. for 1 hr. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous MgSO 4).
O ₄ ) and the oily residue obtained by concentration were separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate / hexane 2/1] to obtain 8.6 g of 1- (2-chloropyridine-5). -Ylmethyl) -2-nitroimino-
3- (1-Propenyl) imidazolidine was obtained.

Example 6 (Compound No. 33) 3.7 g of 1- (2-ethyl-1-hexenyl) -2-nitroiminoimidazolidine, 3.3 g of 2-chloro-5-chloromethylpyridine, potassium carbonate 4 A mixture of 0.4 g and 20 ml of dimethyl sulfoxide was stirred at 60 ° C. for 1 hour. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ), and concentrated, and the resulting oily residue was subjected to column chromatography [silica gel, developing solvent: ethyl acetate / hexane 2/1]. Separated and purified by
4.3 g of 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3- (2-ethyl-1-hexenyl) imidazolidine were obtained.

Example 7 (Compound No. 35 Compound No. 36) 10.0 g of 1- (2-methoxyvinyl) -2-nitroiminoimidazolidine, 18.0 g of 2-chloro-5-chloromethylpyridine, potassium carbonate A mixture of 15.0 g and 150 ml of dimethyl sulfoxide was added at 70 ° C. for 2.0 hours.
Stirred. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated, and the resulting oily residue was subjected to column chromatography [silica gel,
Developing solvent: ethyl acetate].
(2-chloropyridin-5-ylmethyl) -2-nitroimino-3- (cis-2-methoxyvinyl) imidazolidine and 0.58 g of 1- (2-chloropyridin-5-
Ylmethyl) -2-nitroimino-3- (trans-
2-methoxyvinyl) imidazolidine was obtained.

Example 8 (Compound No. 37) 1- (2-phenoxyvinyl) -2-nitroiminoimidazolidine (2.8 g), 2-chloro-5-chloromethylpyridine (3.6 g), potassium carbonate (3.2 g), A mixture of 15 ml of dimethyl sulfoxide was stirred at 60 ° C. for 1 hour.
The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated. The resulting oily residue was separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate]. 3.0 g of 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3-
(2-phenoxyvinyl) -imidazolidine was obtained.

Example 9 (Compound No. 38) 1- (2-Formylvinyl) -2-nitroiminoimidazolidine 3.0 g, sodium hydride 0.7 g, DMF
30 ml of the mixture at 40 ° C. for 15 min. Stirred. After allowing to cool to room temperature, 3.2 g of 2-chloro-5-chloromethylpyridine was added, and the mixture was stirred at 60 ° C for 2 hr. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous M).
gSO ₄ ) and concentrate the oily residue obtained by column chromatography [silica gel, developing solvent: ethyl acetate].
And 2.3 g of 1- (2-chloropyridine-
5-ylmethyl) -2-nitroimino-3- (2-formylvinyl) imidazolidine was obtained.

Example 10 (Compound No. 42) 1- (2-ethylthiovinyl) -2-nitroiminoimidazolidine 8.0 g, 2-chloro-5-chloromethylpyridine 7.2 g, potassium carbonate 20.0 g , A mixture of 30 ml of dimethyl sulfoxide at 60 ° C. for 30 min. Stirred. Pour the reaction mixture into water, extract with ethyl acetate,
The oily residue obtained by washing with water, drying (anhydrous MgSO ₄ ) and concentration was separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate / hexane 4/1] to obtain 8.3 g of 1- ( 2-Chloropyridin-5-ylmethyl) -2-nitroimino-3- (2-ethylthiovinyl) imidazolidine was obtained.

Example 11 (Compound No. 43) 1- {2- (2-chloropyridin-5-yl) vinyl}
A mixture of 6.0 g of -2-nitroiminoimidazolidine, 8.0 g of 2-chloro-5-chloromethylpyridine, 6.8 g of potassium carbonate and 60 ml of dimethyl sulfoxide was added to 7
The mixture was stirred at 5 ° C for 2.5 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ), and concentrated. The resulting oily residue was separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate]. 0.9 g of 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3- {trans-2- (2
-Chloropyridin-5-yl) vinyl diimidazolidin was obtained.

Example 12 (Compound No. 45) 1- (2-phenylvinyl) -2-nitroiminoimidazolidine 6.9 g, 2-chloro-5-chloromethylthiazole 10.0 g, potassium carbonate 8.2 g, A mixture of 30 ml of dimethyl sulfoxide was stirred at 60 ° C. for 1 hour. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated. The resulting oily residue was separated and purified by column chromatography [silica gel, developing solvent: ethyl acetate]. 7.9 g of 1- (2-
Chlorothiazol-5-ylmethyl) -2-nitroimino-3- (2-phenylvinyl) -imidazolidin was obtained.

According to the same method as in Examples 1 to 12, representative examples of the compound of the formula (1) were synthesized together with the compounds of the above examples in Tables 1 (Tables 1 to 12) and 2 (Table 1).
It was shown in 3).

[0083]

[Table 1]

[0084]

[Table 2]

[0085]

[Table 3]

[0086]

[Table 4]

[0087]

[Table 5]

[0088]

[Table 6]

[0089]

[Table 7]

[0090]

[Table 8]

[0091]

[Table 9]

[0092]

[Table 10]

[0093]

[Table 11]

[0094]

[Table 12]

[0095]

[Table 13] Next, a method for producing an intermediate represented by the general formula (2) will be described in Examples.

Example 13 (Intermediate No. 1) 6.0 g of 2-nitroiminoimidazolidine, phenylacetaldehyde (50% in diethyl phthalate) 1
A mixture of 2.2 g, 60 ml of dimethylformamide and 0.05 g of boron trifluoride ether complex was added to 80
The mixture was stirred at C for 1 hour. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ), concentrated, and the precipitated crystals were sludged with ether, dried and dried to obtain 4.3 g of 1- (2-phenylvinyl). -2-Nitroimino imidazolidine was obtained.

Example 14 (Intermediate No. 9) Under a nitrogen atmosphere, 2.59 g of methyl methylsulfinyl methyl sulfide and 4.26 g of trifluorobenzyl chloride were dissolved in 30 ml of THF, and n- at -70 ° C.
29 ml of butyllithium (1.6 M hexane solution)
, And after the addition at -70 ° C for 40 min. 3 hours at room temperature
and stirred. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ), and the solvent was distilled off to obtain a black oily substance. 1.52 g of nitroimino imidazolidine and 20 ml of DMF were added to this oil, 1 ml of concentrated hydrochloric acid was added at 80 ° C., and the mixture was stirred at the same temperature for 4 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water, and dried (anhydrous MgS
After O ₄ ), the solvent was distilled off, and the solid obtained was sludged with ether to give yellow crystals of 1- {4- (2,2,2-trifluoroethoxy) phenylvinyl} -2-nitroiminoimidazo. 0.87 g of lysine was obtained.

Example 15 (Intermediate No. 20) A Grignard reagent was prepared by applying ultrasonic waves to a mixture of 5.0 g of 3,4-dichlorobenzyl chloride, 0.68 g of magnesium metal and 30 ml of ethyl ether at room temperature, and the magnesium metal was removed. When it disappeared, 4.2 g of ethyl orthoformate and 30 ml of toluene were added thereto, and ethyl ether was distilled off. Thereafter, the mixture was heated and refluxed for 1.5 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous Mg).
SO ₄ ) and 2.5 g of nitroimino imidazolidine, 1,3-dimethyl-to 6.5 g of an oily residue obtained by concentration.
90 ° C. to the mixture to which 25 ml of 2-imidazolidinone was added.
Then, 0.07 g of boron trifluoride ether complex was added thereto, and the mixture was stirred at the same temperature for 1.5 hr. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous MgSO 4).
O ₄ ) and concentrated, and ether was added to the obtained oily residue, and the precipitated crystals were collected by filtration, dried and 2.3 g of 1- (3,4-).
Dichlorophenylvinyl) -2-nitroiminoimidazolidine was obtained.

Example 16 (Intermediate No. 21) Under a nitrogen atmosphere, 3.48 g of methyl methylsulfinyl methyl sulfide was dissolved in 30 ml of THF, and -7
At 8 ° C., 18 ml of n-butyllithium (1.6 M hexane solution) was added dropwise, and the same temperature was applied for 10 min. Stir,
5.0 g of m-bromomethylbenzonitrile was added to THF 20
After the solution dissolved in ml was dropped, the mixture was stirred at the same temperature for 2 hours. Water was added to the reaction solution, extracted with ethyl acetate, washed with water and dried (anhydrous MgSO ₄ ), and the solvent was distilled off to obtain a colorless and transparent oil. To this oil was added 1.98 g of nitroimino imidazolidine and 20 ml of DMF.
Then, the mixture was stirred at the same temperature for 1 hour. Water is added to the reaction solution, extracted with ethyl acetate, washed with water, and dried (anhydrous MgSO ₄ ).
Thereafter, the solvent was distilled off, and the solid obtained was sludged with ether to give pale yellow crystals of 1- {2- (3-cyanophenyl).
0.73 g of vinyl II-2-nitroimino imidazolidine
I got

Example 17 (Intermediate No. 27) A mixture of 4.0 g of 2-nitroiminoimidazolidine, 20 ml of 1,3-dimethyl-2-imidazolidinone, 7.5 g of phosphorus oxychloride, and 2.7 g of propionaldehyde At room temperature for 30 min. Stirred. Pour the reaction mixture into water,
Extract with ethyl acetate, wash with water and dry (anhydrous Na ₂ S)
O ₄ ), concentrated and the precipitated crystals were sludged with ethyl acetate, collected by filtration and dried to obtain 1.7 g of 1- (1-propenyl) -2-nitroiminoimidazolidine.

Example 18 (Intermediate No. 35) A mixture of 8.1 g of 2-phenoxyethanol, 12.6 g of pyridinium chlorochromate and 100 ml of methylene chloride was stirred under ice cooling for 1.5 hr and at room temperature for 4 hr. The reaction mixture was separated by decantation, and the solvent was distilled off to obtain 10.6 g of an oily residue. To the obtained oily residue, nitroimino imidazolidine (5.1 g), boron trifluoride ether complex (0.07 g), and 1,3-dimethyl-2-imidazolidinone (30 ml) were added, and the mixture was added at 100 ° C.
The mixture was stirred for hr. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous MgSO ₄ ) and concentrated. The resulting oily residue was separated by column chromatography [silica gel, developing solvent: ethyl acetate]. .28 g of 1
-(2-Phenoxyvinyl) -2-nitroiminoimidazolidine was obtained.

Example 19 (Intermediate No. 38) 8.4 g of 2-nitroiminoimidazolidine, 70 ml of 1,3-dimethyl-2-imidazolidinone, 14.2 g of phosphorus oxychloride, 1,1,3,3 -A mixture of 20.3 g of tetraethoxypropane was stirred at 70 ° C for 2.5 hours.
The reaction mixture was poured into water, extracted with ethyl acetate, washed with water, dried (anhydrous Na ₂ SO ₄ ) and concentrated. The resulting oily residue was subjected to column chromatography [silica gel, developing solvent:
Ethyl acetate / hexane 2/1] to obtain 2.5 g of 1- (2-formylvinyl) -2-nitroiminoimidazolidine.

Example 20 (Intermediate No. 40) A mixture of 10.0 g of 2-ethylthioethanol, 24.4 g of pyridinium chlorochromate and 100 ml of methylene chloride was stirred for 2 hours under ice cooling. 13.2 g of nitroimino imidazolidine and phosphorus oxychloride were added to the methylene chloride layer separated from the reaction mixture by decantation.
5 g, 1,3-dimethyl-2-imidazolidinone
After adding 0 g, the mixture was heated under reflux for 2 hours. The reaction mixture was poured into water, extracted with ethyl acetate, washed with water and dried (anhydrous MgSO 4).
O ₄ ) and the oily residue obtained by concentration was separated by column chromatography [silica gel, developing solvent: ethyl acetate / hexane 3/1], and 2.3 g of 1- (2-ethylthiovinyl)- 2-Nitroimino imidazolidine was obtained.

Example 21 (Intermediate No. 43) 4.0 g of 2-nitroiminoimidazolidine, 4.7 g of 2-ethylhexylaldehyde, 0.05 g of boron trifluoride ether complex, 1,3-dimethyl-2-imidazo A mixture of 20 ml of lydinone was stirred at 120 ° C. for 3 hours. Pour the reaction mixture into water, extract with ethyl acetate,
After washing with water, drying (anhydrous MgSO ₄ ) and concentration, the precipitated crystals were sludged with ethyl acetate, collected by filtration and dried.
7 g of 1- (2-ethyl-1-hexenyl) -2-nitroiminoimidazolidine were obtained. Example 22 (Intermediate No. 27) 5.0 g of 2-nitroiminoimidazolidine and 4.5 g of propionaldehyde were dissolved in 25 ml of N, N-dimethylformamide, and 4.0 g of phosphorus pentachloride was added under ice cooling. The mixture was added over 10 minutes, and then stirred at 10 ° C. for 10 minutes. 20 ml of water and 20 ml of ethyl acetate were added to the reaction solution, and the precipitated crystals were collected by filtration and dried to obtain 4.3 g of 1- (1-propenyl) -2-nitroiminoimidazolidine.

Example 23 (Intermediate No. 32) 2.0 g of 2-nitroiminoimidazolidine and 3.4 g of n-decylaldehyde were dissolved in 20 ml of N, N-dimethylimidazolinone. 0.8 g to 2
It was added over 0 minutes and then stirred at 50 ° C. for 10 minutes. The reaction solution was poured into water, extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated to obtain 2.1 g of an oily substance in 1- (1).
-N-decenyl) -2-nitroiminoimidazolidine was obtained.

Example 24 (Intermediate No. 27) 4.0 g of 2-nitroiminoimidazolidine, 3.0 g of propionaldehyde, 6.0 g of acetic anhydride and 0.1 g of potassium hydrogen sulfate were added to 15 ml of N, N-dimethyl It was dissolved in formamide and stirred and reacted at 60 ° C. for 2 hours. 10 ml of ethyl acetate and 20 ml of hexane were added to the reaction solution,
Stirred for 0 minutes. The precipitated crystals were collected by filtration, washed with ethyl acetate, and dried to obtain 3.5 g of 1- (1-propenyl) -2.
-Nitroimino imidazolidine was obtained.

Representative examples of the compound of the formula (2) synthesized according to the same method as in Examples 13 to 24 are shown in Table 3 (Tables 14 to 24).

[0108]

[Table 14]

[0109]

[Table 15]

[0110]

[Table 16]

[0111]

[Table 17]

[0112]

[Table 18]

[0113]

[Table 19]

[0114]

[Table 20]

[0115]

[Table 21]

[0116]

[Table 22]

[0117]

[Table 23]

[0118]

[Table 24] Next, a method for producing the intermediate represented by the general formula (7) will be described with reference to Examples.

Example 25 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, the reaction solution was poured into water and extracted with ethyl acetate.
After washing with water and drying (anhydrous magnesium sulfate), the solvent was removed under reduced pressure. The obtained crystals were sludged with ether to obtain 32 g of 1-diethoxymethyl-2-nitroiminoimidazolidine.

Δ _TMS (CDCl ₃ ) (ppm): 1.24 (6H, t, J = 6.9 Hz),
3.44 to 3.87 (8H, m), 5.95 (1H, s), 8.36 (1H, s) ν _MAX (KBr) (cm ^-1 ): 3340,1570,1530,1470,1440,1280,12
20,1170,1090,1040,1010 mp: 100.2-101.8 ° C. Next, the composition of the present invention will be specifically described with reference to formulation examples.
In addition, in this preparation example, parts represent parts by weight.

Formulation Example 1 An emulsion was obtained by uniformly stirring and mixing 20 parts of the compound of the present invention, 10 parts of Solpol 355S (manufactured by Toho Chemical Co., surfactant) and 70 parts of xylene.

Formulation Example 2 10 parts of the compound of the present invention, 2 parts of sodium alkylnaphthalenesulfonate, 1 part of sodium ligninsulfonate, 5 parts of white carbon, and 82 parts of diatomaceous earth I got

Formulation Example 3 0.3 part of the compound of the present invention and 0.3 part of white carbon are uniformly mixed, and 99.2 parts of clay, Doreless A (manufactured by Sankyo)
0.2 parts were added and uniformly ground and mixed to obtain 100 parts of powder.

Formulation Example 4 2 parts of the compound of the present invention, 2 parts of white carbon, 2 parts of sodium ligninsulfonate and 94 parts of bentonite are uniformly pulverized and mixed, then water is added, kneaded, granulated and dried to obtain granules. 100 parts were obtained.

Formulation Example 5 20 parts of the compound of the present invention and 20 parts of polyvinyl alcohol
After sufficiently mixing and stirring 5 parts of a 5% aqueous solution, 75 parts of a 0.8% aqueous solution of xanthan gum was added and stirred and mixed again to obtain 100 parts of a flowable agent.

Formulation Example 6 10 parts of the compound of the present invention, carboxymethyl cellulose 3
Parts, 2 parts of sodium ligninsulfonate, 1 part of dioctylsulfosuccinate sodium salt, and 84 parts of water were uniformly wet-pulverized to obtain 100 parts of a flowable agent.

Next, in order to clarify that the compound represented by the formula (1) of the present invention has an excellent insecticidal activity, the present invention will be described in detail with reference to the following test examples.

Test Example 1 Effect on brown planthopper The emulsion prepared in Preparation Example 1 was diluted to a predetermined concentration, and 2 ml of the diluted rice seedlings (approximately 3 leaf stage) were sprayed onto several bundles of rice seedlings. After air-drying, the treated seedlings were covered with a wire mesh cylinder, 10 female adult adults of the brown planthopper were released inside and placed in a constant temperature room at 25 ° C., and the mortality was examined after 48 hours. The results are shown in Table 4 (Table 25).

[0129]

[Table 25] Control drug (1): 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3- {2- (4-chlorophenyl) ethyl} imidazolidine Control drug (2): 1- (2-chloropyridine -5-ylmethyl) -2-nitroimino-3-methoxymethylimidazolidine Test Example 2 Effect on resistant leafhopper Leafhopper prepared by diluting the emulsion prepared in Formulation Example 1 to a predetermined concentration and bundling several rice seedlings (about 3 leaf stage) ) To 3 ml. After air-drying, the treated seedlings were covered with a wire mesh cylinder, 10 female adults of the organic phosphorus agent and carbamate-resistant leafhopper leafhopper were released into the inside and placed in a constant temperature room at 25 ° C, and the mortality was examined after 48 hours. The results are shown in Table 5 (Table 26).

[0130]

[Table 26] Control drug (1): 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3- {2- (4-chlorophenyl) ethyl} imidazolidine Control drug (2): 1- (2-chloropyridine -5-ylmethyl) -2-nitroimino-3-methoxymethylimidazolidine Test Example 3 Effect on Azuki weevil Acetone solution of the compound of the present invention was collected in a 9 cm diameter petri dish, acetone was evaporated, and after eclosion, 2-3 20 adult female weevils of the day were released into a petri dish, and 25
After 48 hours at ℃, the mortality was investigated. The results are shown in Table 6 (Table 27).

[0131]

[Table 27] Test Example 4 Effect on peach aphid Growing in a greenhouse, 20 ml of the diluted solution of the emulsion prepared according to Formulation Example 1 was sprayed on potted eggplant seedlings (4 to 5 leaf stage) in which peach aphids were infested. After the treatment, the seedlings were placed in a greenhouse and three days later, the number of parasites was examined. The results are shown in Table 7 (Table 28).

[0132]

[Table 28] Test Example 5 Insecticidal effect on brown planthopper The emulsion prepared according to Formulation Example 1 was diluted to a predetermined concentration, and 2 ml of the diluted rice seedlings (approximately 3 leaf stage) were sprayed on the seedlings. After air-drying, the treated seedlings were covered with a wire mesh cylinder, 10 female adult female brown planthoppers were released and placed in a constant temperature room at 25 ° C. After 48 hours, the mortality was investigated, and the half lethal concentration (LC ₅₀ value) was determined. Was. The results are shown in Table 8 (Table 29).

Test Example 6 Insecticidal Effect on Resistant Leafhopper Leafhopper The emulsion prepared in Formulation Example 1 was diluted to a predetermined concentration, and 2 ml of the diluted rice seedlings (approximately three leaf stage) was sprayed on the seedlings. After air-drying, the treated seedlings were covered with a wire mesh cylinder, 10 female adult females of the organic phosphorus agent and carbamate-resistant leafhopper were released and placed in a constant temperature room at 25 ° C. After 48 hours, the mortality was examined, and half the lethal concentration was determined. (LC ₅₀ value) was determined. The results are shown in Table 8 (Table 29).

Test Example 7 Insecticidal effect on peach aphids [0134] Emulsion prepared according to Formulation Example 1 was obtained by growing in a greenhouse and diluting a potted eggplant seedling (4-5 leaf stage) with parasitism of peach aphids. A 20 ppm dilution of 10 ppm was sprayed. After the treatment, the seedlings were placed in a greenhouse, and three days later, the number of parasites was examined to determine the population density. The test was performed in duplicate. The results are shown in Table 8 (Table 29).

[0135]

[Table 29] Comparative compound 1: 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3-allylimidazolidine (compound described in US Pat. No. 4,742,060) Comparative compound 2: 1- (2-chloropyridin-5- (Ilmethyl) -2-nitroimino-3- (2-phenylethyl) imidazolidine These results show that the compound of the present invention exhibits an excellent insecticidal effect as compared with the compounds described in the prior art.

Test Example 8 Acute Toxicity Test for Mice A predetermined concentration of each test compound was dissolved in corn oil,
Weekly mice were gavaged. 1 after administration
The number of deaths was measured over time until day 4, and the half-lethal concentration (L
It was determined the D ₅₀ value). The test was performed on 10 animals per group. The results are shown in Table 9 (Table 30).

[0137]

[Table 30] Comparative compound 1: 1- (2-chloropyridin-5-ylmethyl) -2-nitroimino-3-allylimidazolidine (compound described in US Pat. No. 4,742,060) From the results of this test example, the compound of the present invention is regarded as a prior art. It turns out that toxicity is low and safe compared with the compound described.

[0138]

According to the present invention, the novel N- represented by the formula (1)
Vinyl imidazolidine derivatives are excellent compounds having high insecticidal activity and a broad insecticidal spectrum.

The novel N-vinylimidazolidine derivative of the present invention represented by the formula (1) can be easily produced from the novel intermediate of the formula (2) by the production method according to the present invention.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI C07D 401/14 C07D 401/14 417/06 417/06 (72) Inventor Hiroizumi Matsuno 1144 Togo, Mogo-shi, Chiba Pref. Mitsui Toatsu Within Chemical Co., Ltd. (72) Inventor Shiro Shiraishi 1144 Togo, Mobara-shi, Chiba Prefecture Inside Mitsui Toatsu Chemicals Co., Ltd. (72) Inventor Kazutomi Onuma 1144 Togo, Togo, Mobara-shi, Chiba Prefecture Inside Mitsui Toatsu Chemicals Inc. (72) Inventor Eiichi Yamada 1144 Togo, Mobara City, Chiba Pref.Inspector, Mitsui Toatsu Chemicals Co., Ltd.Tamoru Tominaga (56) References JP-A-63-267780 (JP, A) (58) Int.Cl. ⁷ , DB name) C07D 401/06 C07D 233/52 C07D 239/12 C07D 401/14 C07D 417/06 CA (STN) REGISTRY (STN)

Claims (16)

(57) [Claims] (1) Formula (1) (Formula 1) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, Z represents a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms; Is 2-chloropyridine-
Represents a 5-ylmethyl group or a 2-chlorothiazol-5-ylmethyl group. N-vinyl imidazolidine derivative represented by the formula: 2. The N according to claim 1, wherein R ² is a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group or a benzoylamino group.
-Vinyl imidazolidine derivatives. 3. The N-vinyl imidazolidine derivative according to claim 1, wherein R ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 4. A phenyl group R ² is substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, a phenyl group substituted by a benzoyl group, substituted with methylenedioxy group Phenyl group,
A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms,
The N-vinyl imidazolidine derivative according to claim 1, which is a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms. 5. A compound of the formula (2) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, A phenyl group substituted with a C1-4 alkylthio group, a phenyl group substituted with a C1-4 haloalkyl group, or a phenyl group substituted with a C1-4 haloalkoxy group. ) And a compound of formula (3) (Wherein, Z represents a 2-chloropyridin-5-ylmethyl group or a 2-chlorothiazol-5-ylmethyl group, and X represents a chlorine atom or a bromine atom). Expression (1)
(Formula 4) (Wherein, R ¹ , R ² , and Z each have the same meanings as described above). 6. A compound of the formula (1) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, Z represents a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms; Is 2-chloropyridine-
Represents a 5-ylmethyl group or a 2-chlorothiazol-5-ylmethyl group. An insecticide comprising a compound represented by the formula (1) as an active ingredient. 7. The N according to claim 6, wherein R ² is a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, or a benzoylamino group.
-Vinyl imidazolidine derivatives. 8. The insecticide according to claim 6, wherein R ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 9. R ² is substituted with a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, a phenyl group substituted with a benzoyl group, or a methylenedioxy group. Phenyl group,
A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms,
The insecticide according to claim 6, which is a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms. 10. A compound of the formula (2) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, A phenyl group substituted with a C1-4 alkylthio group, a phenyl group substituted with a C1-4 haloalkyl group, or a phenyl group substituted with a C1-4 haloalkoxy group. N-vinyl imidazolidine derivative represented by the formula: 11. The N-vinyl imidazolidine derivative according to claim 10, wherein R ² is a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group or a benzoylamino group. 12. The N-vinyl imidazolidine derivative according to claim 10, wherein R ² is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. 13. R ² is substituted with a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, a phenyl group substituted with a benzoyl group, or a methylenedioxy group. A phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms, The N-vinyl imidazolidine derivative according to claim 10, which is a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms. 14. A compound of the formula (4) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, A phenyl group substituted with a C1-4 alkylthio group, a phenyl group substituted with a C1-4 haloalkyl group, or a phenyl group substituted with a C1-4 haloalkoxy group. ) And a compound represented by the formula (5): Wherein a compound represented by the following formula is reacted: (Wherein, R ¹ and R ² have the same meanings as described above.) A method for producing an N-vinyl imidazolidine derivative represented by the formula: 15. A compound of the formula (6) (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, R represents a phenyl group substituted with an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a haloalkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a haloalkoxy group having 1 to 4 carbon atoms; ³ and R ⁴ represent an alkoxy group, an alkylthio group, an alkylsulfoxide group, a phenoxy group, a phenylthio group, and a phenylsulfoxide group, respectively. ) And a compound represented by the formula (5): Wherein a compound represented by the following formula is reacted: (Wherein, R ¹ and R ² each have the same meaning as described above.)
A method for producing an N-vinyl imidazolidine derivative represented by the formula: 16. The formula (7) (Wherein, R represents a lower alkyl group) and a compound represented by the formula (8): (R ¹ represents a hydrogen atom, a phenyl group, an alkyl group having 1 to 4 carbon atoms, and R ² represents a hydrogen atom, a phenoxy group, a benzyl group, a phenyl group, an aldehyde group, a 2-chloropyridin-5-ylmethyl group, a benzoyl group. Amino group, carbon number 1
An alkyl group of 18, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, a phenyl group substituted with a halogen atom, a phenyl group substituted with a cyano group, a phenyl group substituted with a phenyl group, A phenyl group substituted with a benzoyl group, a phenyl group substituted with a methylenedioxy group, a phenyl group substituted with an alkyl group having 1 to 4 carbon atoms, a phenyl group substituted with an alkoxy group having 1 to 4 carbon atoms, A phenyl group substituted with a C1-4 alkylthio group, a phenyl group substituted with a C1-4 haloalkyl group, or a phenyl group substituted with a C1-4 haloalkoxy group. Wherein the compound represented by the formula (2) is reacted. (Wherein, R ¹ and R ² each have the same meaning as described above.)
A method for producing an N-vinyl imidazolidine derivative represented by the formula: