JPH08291169A - Insecticidal tetrahydrofuran derivative - Google Patents

Abstract

PURPOSE: To obtain a tetrahydrofuran derivative, capable of manifesting excellent insecticidal activities, having low toxic nitroimino group and useful as an agrochemical, especially an insecticide. CONSTITUTION: This tetrahydrofuran derivative is expressed by formula I (R1 , R2 and R3 are each H or a 1-3C alkyl; R4 is H, a 1-3C alkyl, a 2-6C acyl or a 2-4C alkenyl), e.g. 3-(tetrahydro-3-furanyl)methyl-4-methyl-2-nitroimino-1-(1- propenyl)imidazoline. The derivative of formula I is readily obtained in high yield by reacting a compound of formula II [e.g. (tetrahydro-3-furanyl) methyltrifluoromethanesulfonate] with an imidazoline compound of formula III (R5 is an alkenyl group) [e.g. 4-methyl-2-nitroimino-1-(1-propenyl)imidazoline] in the presence a base (e.g. sodium hydroxide), preferably at ambient temperature to 150 deg.C for 0.1-15hr.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel tetrahydrofuran derivative and an insecticide containing the derivative as an active ingredient.

More specifically, the present invention relates to formula (1) (formula 2)

[0003]

Embedded image (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a C1 to C3 alkyl group, and R ₄ represents a hydrogen atom, a C1 to C3 alkyl group, a C2 to C4 acyl group, a C2 to C4 alkenyl. A tetrahydrofuran derivative represented by
And an insecticide containing the derivative as an active ingredient. The tetrahydrofuran derivative which is the compound of the present invention is useful as an agricultural chemical, particularly an insecticide in the agricultural field.

[0004]

2. Description of the Related Art Many amine compounds having a nitroimino group are conventionally known (Japanese Patent Laid-Open No. 61-1832).
71, JP 62-81382 A, JP 6
3-1567, etc.). These publications describe that a group of amine compounds containing a heterocyclic group in the molecule exhibit insecticidal activity. However, as a result of synthesizing these compounds and examining the insecticidal activity by the present inventors, it was found that not all amine derivatives having a heterocyclic group exhibit insecticidal activity. That is, among the compounds described in these publications, the compounds showing the activity to be seen are limited to amine derivatives having a thiazolylmethyl group or a pyridylmethyl group as a heterocyclic group, and this fact is described in J. Pestic
ide Sci. 18 , 41 (1993) and the like. Further, the only compounds currently being commercialized are derivatives having a pyridylmethyl group as a heterocyclic group.

[0005]

Therefore, the present invention does not have the above-mentioned pyridylmethyl group or thiazolylmethyl group as a heterocyclic group in the molecule, and exhibits excellent insecticidal activity,
Moreover, it is an object to provide a tetrahydrofuran derivative having a low toxicity nitroimino group.

[0006]

MEANS TO SOLVE THE PROBLEMS The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, the tetrahydrofuran derivative represented by the formula (1) has a pyridylmethyl group or a thiazolylmethyl group in the molecular structure. It has been found that it has an excellent insecticidal activity even though it is not present, and completed the present invention. That is, the present invention provides the formula (1)

[0007]

Embedded image (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a C1 to C3 alkyl group, and R ₄ represents a hydrogen atom, a C1 to C3 alkyl group, a C2 to C4 acyl group, a C2 to C4 alkenyl. A tetrahydrofuran derivative represented by
And an insecticide containing the derivative as an active ingredient. R ₁ , R ₂ in the above formula,
The most preferable substituent in R ₃ and R ₄ is a hydrogen atom, but typical examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group and an iso-propyl group, and a methyl group is preferable. . Typical examples of the acyl group for R ₄ include an acetyl group, an ethylcarbonyl group and a propylcarbonyl group, and an acetyl group is preferable.
Typical examples of the alkenyl group with respect to R ₄ include a vinyl group, an allyl group, a methylvinyl group and the like, and a methylvinyl group is preferable.

In the formula (1), when R ₄ represents R ₅ , the compound represented by the formula (1A) is represented by the following reaction formula (1)
It can be manufactured by

[0009]

[Chemical 4] (In the formula, R ₁ , R ₂ and R ₃ represent the above meanings, R ₅ represents an alkenyl group, X represents elimination of a halogen atom, a methanesulfonyl group, a toluenesulfonyloxy group, a trifluoromethanesulfonyloxy group or the like. Represents a group.)

That is, the compound represented by the formula (2) and the imidazolidine compound represented by the formula (3) are reacted in the presence of a base to allow easy and high-yield production. it can. As the base, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide, alkali metal hydrides such as sodium hydride and potassium hydride, Alkali metal alcoholates such as sodium methylate and sodium ethylate, alkali metal oxides such as sodium oxide, carbonates such as potassium carbonate and sodium carbonate, tripotassium phosphate, trisodium phosphate, dipotassium dihydrogen phosphate, monophosphate Phosphates such as disodium hydrogen, acetates such as sodium acetate and potassium acetate, organic bases such as 4- (dimethylamino) pyridine, DABCO, triethylamine and diazabicycloundecene can be used. Examples of the solvent include water, alcohols such as methanol, ethanol, propanol, butanol, etc., aromatic hydrocarbons such as benzene, toluene, xylene, etc., aliphatic hydrocarbons such as hexane, heptane, petroleum benzine, etc., dimethylformamide, dimethyl. Aprotic polar solvent such as acetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone, 1-methyl-2-pyrrolidinone, ethyl ether,
Diisopropyl ether, 1,2-dimethoxyethane,
Ethers such as tetrahydrofuran and dioxane, nitriles such as acetonitrile and propionitrile, and ketones such as acetone and diisopropyl ketone can be used. Although the reaction temperature and the reaction time can be varied over a wide range, the reaction temperature is generally -30 to 20.
0 ° C., preferably room temperature to 150 ° C., reaction time 0.01
~ 50 hours, preferably 0.1-15 hours.

The compound represented by the formula (2) in the reaction formula (1) is obtained by converting (tetrahydro-3-furanyl) methanols into thionyl chloride, phosphorus oxychloride, phosphorus tribromide, triphenylphosphine / tetrabromide. It can be produced by halogenation with a halogenating agent such as carbon or triphenylphosphine / carbon tetrachloride, or by sulfonation with a sulfonation agent such as tosyl chloride, methanesulfonyl chloride, trifluoromethanesulfonic anhydride.

In the formula (1), R ₄ is a hydrogen atom or R
_The compound represented by the formula (1B) and the formula (1C) when ₆ is represented can be produced by the reaction formula (2) (formula 5).

[0013]

[Chemical 5](In the formula, R₁ , R₂ , R₃ Represents the above meaning, R_Five Is
Represents an alkenyl group, R ₆ Represents an alkyl group or an acyl group
You )

The compound represented by the formula (3) is described in J. Am. Chem.
Soc., 70 , 430 (1948) and JP-A-5-279356. The compounds represented by the formulas (2) and (4) are known compounds or compounds which can be produced according to known methods.

The compound represented by the formula (1) of the present invention has an asymmetric carbon atom, and both the optically active isomer and the racemate thereof are included in the present invention. Further, the compound represented by the formula (1) of the present invention has two or more kinds of geometrical isomers because it contains two or more asymmetric carbons, and both single compounds and mixtures are included in the present invention. It

Conventionally, insecticidal compounds having a nitroimino group have been known. However, the active compounds to be found among these insecticidal compounds were limited to pyridine derivatives or thiazole derivatives. The compound represented by the formula (1) of the present invention exhibits an extremely excellent insecticidal action even though it does not have these pyridylmethyl group or thiazolylmethyl group in the molecule. Furthermore, in the compound represented by the formula (1) of the present invention, when the (tetrahydro-3-furanyl) methyl group is replaced by its isomer (tetrahydro-2-furanyl) methyl group, the compound is represented by the present invention. The insecticidal activity was remarkably reduced as compared with the compound represented by the formula (1). That is, the compound represented by the formula (1) of the present invention has (tetrahydro-
It has a 3-furanyl) methyl group.

The derivative represented by the formula (1) of the present invention has a strong insecticidal action and can be used as an insecticide in various scenes such as agriculture, horticulture, livestock, forestry, epidemics and houses. Further, the derivative represented by the formula (1) of the present invention exerts a proper controlling effect against harmful insects without causing any damage to plants, higher animals, environment and the like. Such pests include, for example, armyworm, tamanaga moth, white-spotted armyworm, hasmon armyworm, cabbage moth, armyworm,
Tamanaginuwaba, Nikamaiga, Kobunomaiga, Pteridophyta punctata, Rice beetle, Cotton bollworm, Potato moth, Pieris brassicae, Pleurotus coccinella, Green tea squirrel, Black-billed squirrel, Black squirrel moth, Mandarin moth,
Nashihime Shinui, Mameshin Muiga, Momo Shiniga,
Lepidopteran pests such as grape mossgrass, diamondback moth, moth, etc .; tobacco whitefly, whitefly, whitefly, white aphid, cotton aphid, snowy aphid, apple aphid, green peach aphid, Japanese aphid, black aphid, black aphid, bean aphid, miridae. Aphids, potato aphids, aphids, green leafhoppers, green leafhoppers, leafhopper planthoppers, planthopper plant, planthopper planthopper, leafhopper leafhopper, leafhopper leafhopper, leafhopper leafhopper,
Yano yanonensis, mulberry mealybugs, tangerine mealybugs, Iseria scale insects, southern green stink bug, bombardier helicopter bugs, Hemiptera such Nashigunbai; rice water weevil, Inedorooimushi, Kisujinomihamushi, Colorado potato beetle, cucurbit leaf beetle, Diabrotica sp
p., weevils, stag beetles, adzuki bean weevils, beetles, scorpion beetles, tobacco beetles, beetles, beetles, stag beetles,
Coleoptera pests such as flatworm, Culex pipiens; Culex pipiens, Culex pipiens, Aedes albopictus, Rice leaf moth, Fly soybean, Fly fly, Rice fly, Rice fly, Housefly,
Diptera pests such as onion flies, fruit flies, citrus fruit flies, beangrass flies and the like; Negia thrips, thrips thrips, thrips thrips, such as rice thrips, asclepias chinensis, thrips and octopus, asiaticus, asiatica, octopus, black-breasted thrips Orthoptera pests;
Hymenoptera pests such as turnip bees; Mites pests such as house dust mites, chiggers, and mites; other fleas
Examples include head lice, Yamato termites, millipedes, and gudge.

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

In formulating the compound of the present invention, no special conditions are required, and emulsions, wettable powders, powders, granules, fine granules and flowable granules can be prepared by a method well known in the art according to general agricultural chemicals. It can be prepared into any dosage form such as an agent, a microcapsule, an oil, an aerosol, a smoker, a poison bait, etc., and these can be used for various purposes according to their respective purposes. The term "carrier" as used herein refers to a synthetic or natural inorganic substance of a liquid, solid or gas that is formulated to help the active ingredient reach the site to be treated and to facilitate storage, transportation and handling of the active ingredient compound. Or, it means an organic substance.

Suitable solid carriers include, for example, montmorillonite, kaolinite, diatomaceous earth, clay, talc, vermiculite, gypsum, calcium carbonate, silica gel,
Inorganic substances such as ammonium sulfate, soybean flour, sawdust, wheat flour, pectin,
Methylcellulose, sodium alginate, petrolatum,
Examples include organic substances such as lanolin, liquid paraffin, lard, and vegetable oil.

Suitable liquid carriers include, for example, toluene,
Aromatic hydrocarbons such as xylene, cumene and solvent naphtha, paraffin hydrocarbons such as kerosene and mineral oil, halogenated hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride, ketones such as acetone, methyl ethyl ketone and cyclohexanone, Ethers such as dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc., esters such as ethyl acetate, acetic acid butyl ester, fatty acid glycerin ester, etc. acetonitrile, nitriles such as propionitrile Alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, dimethylformamide, di- Sulfoxide, water and the like.

Further, in order to enhance the potency of the compound represented by the formula (1) of the present invention, the following may be used alone or in combination depending on the purpose in consideration of the dosage form of the preparation, the application scene and the like. It is also possible to use such auxiliaries.

As auxiliary agents used for the purpose of emulsification, dispersion, spreading, wetting, binding, stabilization, etc., water-soluble bases such as lignin sulfonates, alkylbenzene sulfonates,
Alkyl sulfates, polyoxyethylene alkylaryl ethers, nonionic surfactants such as polyhydric alcohol esters, lubricants such as calcium stearate and wax, stabilizers such as isopropylhydrodiene phosphate, other methyl cellulose, carboxymethyl cellulose, Examples include casein and gum arabic.
However, these components are not limited to those described above.

Furthermore, these compounds represented by the formula (1) of the present invention can express more excellent insecticidal activity by using two or more kinds of them in combination, and other physiologically active substances such as allethrin, Tetramethrin, resmethrin, phenothrin, flamethrin, permethrin, cypermethrin, deltamethrin, cyhalothrin, cyfluthrin, fenpropatrine, tralomethrin, cycloprothrin, flucitrinate, fluvalinate, acrinathrin, tefluthrin, bifenthrin, enpentrin, betacyfluta. Synthetic pyrethroid insecticides such as cypermethrin and various isomers or pyrethrum extracts thereof; DDVP, cyanophos, fenthion, fenitrothion, tetrachlorvinphos, dimethylvinphos, Ropahosu, methyl parathion, temephos, phoxim, acephate, isofenphos, salithion, DEP, EPN, ethion, mecarbam, pyridafenthion, diazinon, pirimiphos-methyl, etrimfos, isoxathion, quinalphos, chlorpyrifos-methyl, chlorpyrifos, phosalone, phosmet,
Methidathion, oxydebrophos, bamidothion, malathion, fentoate, dimethoate, formothion, thiomethone, ethyl thiomethone, folate, terbufos, profenofos, prothiophos, sulprofos,
Organophosphorus insecticides such as pyraclofos, monocrotophos, naredo, fosthiazate, NAC, MTMC, MIP
Carbamate insecticides such as C, BPMC, XMC, PHC, MPMC, ethiophene carb, bendiocarb, pirimicarb, carbosulfan, benfulacarb, mesomil, oxamyl, aldicarb, etc., arylpropyl ethers such as etofenprox, halfenprox, etc. Insecticides, silyl ether compounds such as silafluofen. Insecticidal natural products such as nicotine sulfate, polynactin complex, avermectin, milbemectin, and BT agent, cartap, thiocyclam, bensultap, diflubenzuron, chlorfluazuron, teflubenzuron, triflumuron, flufenoxuron, flucycloxuron, hexaflumuron, Insecticides such as fluazuron, imidacloprid, nitenpyram, acetamiprid, pymetrozine, fipronil, buprofezin, phenoxycarb, pyriproxyfen, methoprene, hydroprene, quinoprene, endosulfan, diafenthiuron, triazuron, tebufenozide, benzoepine, dicofolene, chlorben, chlorben , Phenisobromolate, tetradiphone, CPCBS, BPPS, quinomethionate, amitraz, benzome , Hexthiazox, fenbutazin oxide, cyhexatin, dienochlor, clofentezine, pyridaben, fenpyroximate, phenazaquin, tebufenpyrad, pyrimidinamine and other insecticides, other insecticides, acaricides or fungicides, nematicides, herbicides , Plant growth regulators, fertilizers, soil conditioners, BT agents, microbial production toxins, natural or synthetic insect hormone disruptors, attractants, repellents, mixed with other pesticides such as entomopathogenic microorganisms and small animals By doing so, it is possible to prepare a multipurpose composition having more excellent efficacy, and a synergistic effect can be expected.

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

The insecticide of the compound represented by the formula (1) of the present invention contains the compound in an amount of 0.0000001 to 95% by weight, preferably 0.0001 to 50% by weight. To apply the insecticide of the present invention, generally 0.001 to 50
It is desirable to use it at a concentration of 00 ppm, preferably 0.01 to 1000 ppm. In addition, the application rate per 10a is generally 1 to 300 g of the active ingredient.

[0027]

EXAMPLES The contents of the present invention will be specifically described with reference to the following reference examples and examples, but the present invention is not limited thereto. Reference Example 1 (Tetrahydro-3-furanyl) methyl tosylate (Tetrahydro-3-furanyl) methanol 50 g, tosyl chloride 95 g, triethylamine 52 g, TH
A mixture of 450 ml of F was heated to reflux for 8 hours. The insoluble material was filtered off, the reaction solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 7) to give 114.5 g of 3- (tetrahydro-3-furanyl). Methyl tosylate was obtained.

Reference Example 2 (Tetrahydro-3-furanyl) methyl bromide Phosphorus tribromide 10 g, pyridine 0.8 g, ether 100
To the mixture of ml, 10 g of (tetrahydro-3-furanyl) methanol was added dropwise over 30 minutes, and then the mixture was stirred for 5.5 hours. The reaction solution was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (developing solvent; ethyl acetate: hexane =
It was purified by 1: 1) to obtain 8.6 g of (tetrahydro-3-furanyl) methyl bromide. ¹ HNMR (CDCl ₃ , ppm): 1.62-1.76 (1H, m), 2.05-2.16 (1H, m),
2.70 (1H, septet, J = 7.3), 3.40 (2H, dd, J = 1.5, J = 7.3), 3.45
-3.53 (1H, m), 3.60 (1H, dd, J = 5.1, J = 8.8), 3.80 (1H, t, J = 7.
3), 3.89-3.95 (1H, m)

Reference Example 3 [(Tetrahydro-3-furanyl) methyl] trifluoromethanesulfonate (Tetrahydro-3-furanyl) methanol 2.0 g,
Trifluoromethanesulfonic anhydride 5.9 g, pyridine 2.0 g, and dichloromethane 50 ml were stirred at room temperature for 1 hour. Water was poured into the reaction solution to separate the organic layer, 1N hydrochloric acid,
The extract was washed with water and a saturated saline solution, dried and concentrated to obtain 4.0 g of [(tetrahydro-3-furanyl) methyl] trifluoromethanesulfonate.

Reference Example 4 4-Methyl-2-nitroiminoimidazolidine 58 g of sodium chloride, 52 g of nitroguanidine, 1 part of water
While stirring 80 ml at 70 ° C., 40.8 g of 1,2-diaminopropane was added dropwise. After the completion of dropping, the mixture was stirred at the same temperature for 20 minutes and then cooled with ice while stirring. The generated solid was collected by filtration, washed with cold water and ethyl acetate (100 ml each), and dried.
7 g of 4-methyl-2-nitroiminoimidazolidine were obtained. ¹ HNMR (CDCl ₃ , ppm): 1.41 (3H, d, J = 6.6), 3.38 (1H, dd, J = 8.
1, J = 9.5), 3.92 (1H, t, J = 9.5), 4.19-4.27 (1H, m), 7.68 (1H,
br.), 7.92 (1H, br.)

Reference Example 5 4-Methyl-2-nitroimino-1- (1-propenyl) imidazolidine 4-Methyl-2-nitroiminoimidazolidine 10.0
g, propionaldehyde 8.05 g, potassium hydrogen sulfate 0.47 g, acetic anhydride 14.1 g, DMF 50 ml 6
After stirring at 0 ° C for 1 hour, the mixture was allowed to cool, discharged into 100 ml of water and stirred. The resulting precipitate was collected by filtration, 100 ml of water and 50 parts of ether.
By washing with ml, 8.80 g of a 10: 1 mixture of 4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine and 5-methyl-2-nitroimino-1- (1-propenyl) imidazolidine Got By purifying it by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 4), 7.55 g
To obtain 4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine. ¹ H NMR (CDCl ₃ , ppm): 1.44 (3H, d, J = 6.6), 1.72 (3H, dd, J = 1.
5, J = 6.6), 3.31 (1H, dd, J = 6.6, J = 9.5), 3.87 (1H.tJ = 9.5),
4.20-4.30 (1H, m) 4.88 (1H, dq, J = 13.9, J = 6.6), 6.86 (1H, dd, J = 1.5, J = 13.9),
8.32 (1H, br.)

Example 1 3- (Tetrahydro-3-furanyl) methyl-4-methyl-2-nitroimino-1-
(1-Propenyl) imidazolidine (Compound No. 1) 4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine 0.48 g, acetonitrile 5 ml
0.14 g of 60% sodium hydride at room temperature was added to
After stirring for 0 minutes, 1.1 g of (tetrahydro-3-furanyl) methyl] trifluoromethanesulfonate was added,
The mixture was stirred at 50 ° C for 1 hour. After allowing to cool, add 20 ml of water,
The mixture was extracted with 100 ml of ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate, and the solvent was evaporated. The obtained residue is purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 1) to give 3- (tetrahydro-3-furanyl) methyl-4-.
0.30 g of a 1: 1 diastereomixture of methyl-2-nitroimino-1- (1-propenyl) imidazolidine
I got ¹ HNMR (CDCl ₃ , ppm): 1.40 (1/2 * 3H, d, J = 6.6), 1.42 (1/2 * 3H,
d, J = 6.6), 1.55-1.68 (1H, m), 1.73 (3H, dd, J = 1.5, J = 6.6),
1.95-2.10 (1H, m), 2.54-2.66 (1H, m), 3.13 (1/2 * 1H, dd, J =
6.6, J = 14.7), 3.26 (1/2 * 1H, dd, J = 6.6, J = 14.7), 3.38-4.10
(8H, m), 4.98 (1H, dq, J = 14.7, J = 6.6), 6.44 (1H, dd, J = 1.5, J
= 14.7) IR (neat, cm ^-1 ): 1574,1419,1267

Example 2 1- (Tetrahydro-3-fura
Nyl) methyl-5-methyl-2-nitroiminoimidazo
Lysine (Compound No. 2) 3- (Tetrahydro-3-furanyl) methyl-4-meth
Lu-2-nitroimino-1- (1-propenyl) imida
0.15 g of a 1: 1 diastereomeric mixture of zolidine, 6
After refluxing 3 ml of normal hydrochloric acid and 6 ml of ethanol for 2 hours, dissolve
The solvent was distilled off and the resulting residue was subjected to silica gel column chromatography.
By purifying with Raffy (developing solvent; ethyl acetate),
1- (tetrahydro-3-furanyl) methyl-5-methyl
1: 1 dius of le-2-nitroiminoimidazolidine
0.07 g of a teleo mixture was obtained. ¹ HNMR (CDCl₃, ppm): 1.36 (1/2 * 3H, d, J = 6.6), 1.37 (1/2 * 3H,
d, J = 6.6), 1.58-1.70 (1H, m), 1.95-2.12 (1H, m), 2.60-2.72
(1H, m), 3.06 (1/2 * 1H, dd, J = 7.3, J = 13.9), 3.18 (1/2 * 1H, d
d, J = 7.3, J = 13.9), 3.33-3.39 (1H, m), 3.49-4.03 (7H, m), 8.
11 (1H, br.) IR (neat, cm^-1): 3399,1561,1447,1239

Example 3 1-Acetyl-3- (tetrahydro-3-furanyl) methyl-4-methyl-2-nitroiminoimidazolidine (Compound No. 3) 1- (Tetrahydro-3-furanyl) methyl-5 Methyl-2-nitroiminoimidazolidine 0.08 g, sodium hydride (60%) 0.04 g, acetonitrile 5
0.05 g of acetyl chloride was added to the mixture of ml, stirred at room temperature for 20 minutes, then discharged into 20 ml of water, extracted twice with methylene chloride, the obtained organic layer was dried over anhydrous sodium sulfate, and concentrated under reduced pressure. did. The obtained oily substance was purified by column chromatography (silica gel, developing solvent; ethyl acetate), and 1-acetyl-3- (tetrahydro-
0.08 g of a diastereomixture of 3-furanyl) methyl-4-methyl-2-nitroiminoimidazolidine was obtained. ¹ HNMR (CDCl ₃ , ppm): 1.39 (1/2 * 3H, d, J = 6.6), 1.40 (1/2 * 3H,
d, J = 6.6), 1.55-1.68 (1H, m), 2.00-2.14 (1H, m), 2.42 (3H,
s), 2.58-2.69 (1H, m), 3.18 (1/2 * 1H, dd, J = 7.3, J = 14.6), 3.
26 (1/2 * 1H, dd, J = 7.3, J = 14.6), 3.48-3.60 (2H, m), 3.72-4.
17 (6H, m) IR (neat, cm ^-1 ): 1722,1574,1487,1254

Example 4 3-{(4-methyl) tetrahydro-3-furanyl} methyl-4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine (Compound No. 4) According to Example 1. Carried out to give a 1: 1 diastereomeric mixture of 3-{(4-methyl) tetrahydro-3-furanyl} methyl-4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine. ¹ HNMR (CDCl ₃ , ppm): 1.07 (1/2 * 3H, d, J = 6.6), 1.08 (1/2 * 3H,
d, J = 6.6), 1.40 (1/2 * 3H, d, J = 6.6), 1.41 (1/2 * 3H, d, J = 6.
6), 1.73 (3H, dd, J = 1.5, J = 6.6), 1.91-2.09 (2H, m), 3.03-3.
60 (5H, m), 3.86-4.05 (4H, m), 4.98 (1H, sextet, J = 6.6), 6.4
5 (1H, dq, J = 13.9, J = 1.5) IR (neat, cm ^-1 ): 1668,1566,1420,1263

Example 5 3-{(5,5-dimethyl) tetrahydro-3-furanyl} methyl-4-methyl-2-
Nitroimino-1- (1-propenyl) imidazolidine (Compound No. 5) Carried out according to Example 1 to give 3-{(5,5-dimethyl)
Tetrahydro-3-furanyl} methyl-4-methyl-2
A 1: 1 diastereomeric mixture of -nitroimino-1- (1-propenyl) imidazolidine was obtained. ¹ HNMR (CDCl ₃ , ppm): 1.20 (3H, s), 1.30 (3H, s), 1.39 (1/2 * 3
H, d, J = 6.6), 1.41 (1/2 * 3H, d, J = 6.6), 1.73 (3H, dd, J = 1.5, J
= 6.6), 1.86-1.99 (1H, m), 2.60-2.73 (1H, m), 3.15 (1/6 * 1H,
dd, J = 6.6, J = 14.7), 3.25 (1/2 * 1H, dd, J = 6.6, J = 14.7), 3.38
-3.67 (3H, m), 3.89-4.10 (3H, m), 4.98 (1H, sextet, J = 6.6),
6.41-6.47 (1H, m) IR (neat, cm ^-1 ): 1560,1519,1428,1259

Example 6 3-{(5-methyl) tetrahydro-3-furanyl} methyl-4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine (Compound No. 6) According to Example 1. Was carried out to obtain a 1: 1 diastereomeric mixture of 3-{(5-methyl) tetrahydro-3-furanyl} methyl-4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine. ¹ HNMR (CDCl ₃ , ppm): 1.08-1.20 (1H, m), 1.26 (3H, d, J = 6.6),
1.40 (1/2 * 3H, d, J = 6.6), 1.41 (1/2 * 3H, d, J = 6.6), 1.73 (3H,
dd, J = 1.5, J = 6.6), 2.10-2.22 (1H, m), 2.55-2.70 (1H, m), 3.
10-3.25 (1H, m), 3.38-3.44 (1H, m), 3.52-3.62 (2H, m), 3.75
-3.84 (1H, m), 3.90-4.12 (3H, m), 4.90-5.04 (1H, m), 6.42-
6.48 (1H, m) IR (neat, cm ^-1 ): 1557,1518,1427,1259

Example 7 3- (Tetrahydro-3-furanyl) methyl-4-methyl-2-nitroimino-1-
(1-Propenyl) imidazolidine (Compound No. 7) Carried out according to Example 2 to give 3- (tetrahydro-3-furanyl) methyl-4-methyl-2-nitroimino-1-.
A 1: 1 diastereomeric mixture of (1-propenyl) imidazolidine was obtained. ¹ HNMR (CDCl ₃ , ppm): 1.07 (1/2 * 3H, d, J = 6.6), 1.08 (1/2 * 3H,
d, J = 6.6), 1.35 (1/2 * 3H, d, J = 6.6), 1.36 (1/2 * 3H, d, J = 6.
6), 2.00-2.19 (2H, m), 3.07 (1/2 * 1H, dd, J = 7.3, J = 13.9), 3.
22 (1/2 * 1H, dd, J = 7.3, J = 13.9), 3.30-3.37 (2H, m), 3.54-3.
70 (2H, m), 3.85-4.05 (4H, m), 8.10 (1H, br.) IR (neat, cm ^-1 ): 3400,1717,1563,1246

Next, the composition of the present invention will be specifically described with reference to formulation examples. In the following formulation examples, parts represent parts by weight. Formulation Example 1 20 parts of the compound of the present invention, 10 parts of Solpol 355S (manufactured by Toho Chemical Co., Ltd., a surfactant), and 70 parts of xylene were uniformly mixed with stirring to obtain an emulsion.

Formulation Example 2 10 parts of the compound of the present invention, 2 parts of sodium alkylnaphthalene sulfonate, 1 part of sodium lignin sulfonate, 5 parts of white carbon, 82 parts of diatomaceous earth, 100 parts of wettable powder by uniformly stirring and mixing the above. Got

Formulation Example 3 0.3 parts of the compound of the present invention and 0.3 part of white carbon are uniformly mixed, and 99.2 parts of clay and Dolores A (manufactured by Sankyo)
0.2 part was added and uniformly pulverized 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 lignin sulfonate, 94 parts of bentonite are uniformly pulverized and mixed, and then water is added and 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% of polyvinyl alcohol
After thoroughly stirring and mixing 5 parts of the aqueous solution, 75 parts of a 0.8% aqueous solution of xanthan gum was added and mixed again with stirring to obtain 100 parts of a flowable agent.

Formulation Example 6 10 parts of the compound of the present invention, carboxymethylcellulose 3
Parts, 2 parts of sodium ligninsulfonate, 1 part of dioctylsulfosuccinate sodium salt, and 84 parts of water were uniformly wet-ground 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, it will be specifically described by the following test examples. Test Example 1 Effect on Spodoptera frugiperda The compound of the present invention is used as an acetone solution of a predetermined concentration, and 3 ml is sprayed on rice seedlings (about 3 leaf stage) bundled in several pieces. After air-drying, the treated seedlings are covered with a wire netting cylinder, and then the female adult genus Astragalus L.
Zero of them were released and placed in a constant temperature room at 25 ° C, and 48 hours later, the mortality was examined. The results are shown in Table 1 (Table 1).

[0046]

[Table 1] Comparative compound: 3- (tetrahydro-2-furanyl) methyl-4-methyl-2-nitroimino-1- (1-propenyl) imidazolidine 1: 1 diastereomixture.

[0047]

The (tetrahydro-3-furanyl) methylamine derivative represented by the formula (1) of the present invention is a novel compound and has a high insecticidal activity and a broad insecticidal spectrum.
Therefore, it is represented by the formula (1) of the present invention (tetrahydro-
A pesticide containing a 3-furanyl) methylamine derivative has excellent properties as an insecticide and is useful.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shiroishi Shiroishi 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Kazutomi Onuma 1144 Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd. (72) Inventor Eiichi Yamada 1144 Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd. (72) Naoko Yasui 1144, Togo, Mobara-shi, Chiba Prefecture Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. Formula (1) (Formula 1) (In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom, a C1 to C3 alkyl group, and R ₄ represents a hydrogen atom, a C1 to C3 alkyl group, a C2 to C4 acyl group, a C2 to C4 alkenyl. Represents a group), which is a tetrahydrofuran derivative. 2. An insecticide comprising the compound represented by formula (1) according to claim 1 as an active ingredient.