JPH08295684A - Insecticidal (tetrahydro-3-furanyl)methyl derivative - Google Patents

Abstract

PURPOSE: To obtain the subject new compound derivative which is a specific (tetrahydro-3-furanyl)methyl derivative, having high insecticidal activities and a wide insecticidal spectrum and useful as an active ingredient, etc., of an insecticide used in the agricultural field. CONSTITUTION: This new (tetrahydro-3-furanyl)methyl derivative of formula I [R1 and R2 are each H or a (substituted)1-5C alkyl; B is NR5 (R5 is H, a 1-5C alkyl, a 2-5C alkenyl, etc.) when A is N while B is N hen A is NR4 ) (R4 is the same kind as that of R5 ); R3 is H, a (substituted)1-5C alkyl, a (substituted)2-5C alkenyl or a (substituted)2-5C alkynyl; X1 and X2 are each a halogen]. The derivative is useful as an active ingredient, etc., of an insecticide. The compound is obtained by treating a (substituted)(tetrahydro-3-furanyl) methylamine of formula II with a bis(alkylthio)nitromethylene derivative of formula III (R6 is a lower alkyl) and then reacting the resultant compound with amines of the formula HNR3 R5 , providing a compound of formula IV and subsequently treating the resultant compound of formula IV with a halogenating agent.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel (tetrahydro-
The present invention relates to a 3-furanyl) methyl derivative and an insecticide containing the derivative as an active ingredient. The (tetrahydro-3-furanyl) methyl derivative which is the compound of the present invention is useful as an agricultural chemical (particularly, an insecticide) in the agricultural field.

[0002]

2. Description of the Related Art An insecticidal compound having a dihalogenonitromethyl group has already been disclosed (JP-A-3-2048).
48, etc.). However, these patent publications specifically disclose only a compound having a nitrogen-containing unsaturated heterocycle or a phenyl group, and not a compound having a saturated heterocycle. In addition, as a result of further investigation by the present inventors, it was found that not all heterocycles show insecticidal activity. That is, the active compounds to be seen among these are limited to pyridine derivatives or thiazole derivatives. Furthermore, the only compounds currently being commercialized are derivatives having a pyridylmethyl group. That is, in the prior art, compounds containing a heterocycle in the molecule are said to exhibit insecticidal activity, but practical compounds were limited to derivatives having a pyridylmethyl group.

[0003]

Therefore, the problem to be solved by the present invention is to provide a novel (tetrahydro-3-furanyl) methyl which does not have the above-mentioned pyridylmethyl group or thiazolylmethyl group and exhibits excellent insecticidal activity. An object is to provide a derivative.

[0004]

Means and Actions for Solving the Problems As a result of intensive investigations by the present inventors to solve the above-mentioned problems, the (tetrahydro-3-furanyl) methyl derivative has a pyridylmethyl group or a thiazolylmethyl group in the molecular structure. The present invention was completed by finding that they have excellent insecticidal activity despite not having them.

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

[0006]

Embedded image [Wherein R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and when A is a nitrogen atom, B represents NR ₅ ; When A is NR ₄ , B represents a nitrogen atom (where R ₄ , R
₅ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkenyl group having 2 to 5 carbon atoms, and optionally substituted Represents an alkynyl group having 2 to 5 carbon atoms. ), R ₃ is a hydrogen atom, an optionally substituted C 1-5 alkyl group, an optionally substituted C 2-5 alkenyl group, or an optionally substituted Represents a good alkynyl group having 2 to 5 carbon atoms, X ₁ , X
Each ₂ independently represents a halogen atom. ] It is an insecticide characterized by containing the (tetrahydro-3-furanyl) methyl derivative represented by these, and this derivative as an active ingredient.

Typical examples of the alkyl group which may be optionally substituted for R ₁ and R ₂ in the above formula are methyl group, ethyl group, propyl group, n-butyl group, isopropyl group, isobutyl group and sec. Examples include -butyl group and tert-butyl group. Examples of the substituent of the alkyl group which may be optionally substituted include a methoxy group, an ethoxy group,
Propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-butyloxy group,
Alkoxy group such as tert-butyloxy group, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, etc., chlorine atom, bromine atom, iodine Atom, halogen atom of fluorine atom, hydroxyl group, oxo group, methanesulfonyl group, trifluoromethanesulfonyl group, sulfonyl group such as tosyl group, silyl group such as trimethylsilyl group, phenyl group,
Examples thereof include substituted or unsubstituted phenyl groups such as 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group and 4-methylphenyl group. Regarding R ₁ and R ₂ , a methyl group, an ethyl group, a propyl group, an isopropyl group and a hydrogen atom are preferable, a hydrogen atom, a methyl group and an ethyl group are more preferable, and a hydrogen atom and a methyl group are more preferable. It is a base.

Typical examples of the alkyl group which may be optionally substituted for R ₃ , R ₄ and R ₅ are each independently a methyl group, an ethyl group, a propyl group, an n-butyl group,
Isopropyl group, isobutyl group, sec-butyl group, t
An ert-butyl group and the like can be mentioned. As examples of the substituent of the alkyl group which may be optionally substituted, other than the above,
Methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group,
Alkoxy group such as sec-butyloxy group and tert-butyloxy group, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group and other alkylthio group, chlorine atom , Bromine atom, iodine atom, halogen atom of fluorine atom, hydroxyl group, oxo group,
Methanesulfonyl group, trifluoromethanesulfonyl group, sulfonyl group such as tosyl group, silyl group such as trimethylsilyl group, phenyl group, 2-chlorophenyl group, 3-
Examples thereof include substituted or unsubstituted phenyl groups such as chlorophenyl, 4-chlorophenyl group, 2-methylphenyl group, 3-methylphenyl group and 4-methylphenyl group.

Typical examples of the optionally substituted alkenyl group are vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1 -Methyl-1-propenyl group,
2-methyl-1-propenyl group, 3-methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-2-propenyl group, 3-methyl-2-propenyl group,
Examples thereof include a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group and a 4-pentenyl group. Examples of the substituent of the alkenyl group which may be optionally substituted include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-
Alkylthio group such as butyloxy group, tert-butyloxy group, etc., methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, chlorine atom, bromine Atom, iodine atom,
Halogen atom of fluorine atom, hydroxyl group, oxo group, methanesulfonyl group, trifluoromethanesulfonyl group, sulfonyl group such as tosyl group, silyl group such as trimethylsilyl group, phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl Group, a substituted or unsubstituted phenyl group such as a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group and the like.

Typical examples of the optionally substituted alkynyl group are propargyl group, 1-propynyl group,
Examples thereof include 1-butynyl group, 2-butynyl group and 3-butynyl group. Examples of the substituent of the alkynyl group which may be optionally substituted include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butyloxy group, isobutyloxy group, sec-butyloxy group, tert-
Alkoxy group such as butyloxy group, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group,
Alkylthio group such as tert-butylthio group, chlorine atom, bromine atom, iodine atom, halogen atom such as fluorine atom,
Hydroxyl group, oxo group, methanesulfonyl group, trifluoromethanesulfonyl group, sulfonyl group such as tosyl group, silyl group such as trimethylsilyl group, phenyl group, 2-chlorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 2-methyl group Examples thereof include substituted or unsubstituted phenyl groups such as phenyl group, 3-methylphenyl group and 4-methylphenyl group.

With respect to R ₃ , R ₄ and R ₅ , preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an allyl group, a propargyl group, a benzyl group, a p-chlorobenzyl group, 2- (methylthio) ethyl group, 3- (methylthio) propyl group, 2- (methoxy) ethyl group, 3- (methoxy) propyl group, and more preferably a hydrogen atom, a methyl group, an ethyl group, n-propyl. Group, isopropyl group, allyl group, propargyl group, benzyl group and 4-chlorobenzyl group, and more preferably hydrogen atom, methyl group and ethyl group.

Specific examples of the halogen atom for X ₁ and X ₂ are, independently of each other, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Regarding X ₁ and X ₂ , chlorine atom, fluorine atom and bromine atom are preferable, chlorine atom and bromine atom are more preferable, and chlorine atom is more preferable.

Typical examples of the present invention are shown below, but the compounds of the present invention are not limited to these. N-{(tetrahydro-3-furanyl) methyl} dichloronitroacetamidine N ¹ -{(tetrahydro-3-furanyl) methyl} -N ¹
-Methyldichloronitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- methyl dichloro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
^1, N ² - dimethyldichlorosilane nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
^1, N ¹ - dimethyl dichloro nitro acetamidine N - {(4-methyl-3-furanyl) methyl} dichloro nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ¹ - methyl dichloro nitro acetamidine N - {(4-methyl-3-furanyl) methyl}-N'-methyl-dichloro-nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ^1, N ² - dimethyldichlorosilane nitro acetamidine N ² - {(4-methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl dichloro nitro acetamidine N - {(5-methyl-3-furanyl) methyl} dichloro Nitroacetamidine N ¹ -{(5-methyltetrahydro-3-furanyl) Methyl} -N ¹ -methyldichloronitroacetamidine N-{(5-methyltetrahydro-3-furanyl) methyl} -N′-methyldichloronitroacetamidine N ¹ -{(5-methyltetrahydro-3-furanyl) methyl } -N ^1, N ² - dimethyldichlorosilane nitro acetamidine N ² - {(5- methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl dichloro nitro acetamidine N - {(tetrahydro-3-furanyl ) Methyl} dibronitroacetamidine N ¹ -{(tetrahydro-3-furanyl) methyl} -N ¹
-Methyldibromonitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- methyl dibromo nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
^1, N ² - dimethyl dibromo-nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
^1, N ¹ - dimethyl dibromo-nitro acetamidine N - {(4-methyl-3-furanyl) methyl} dibromo nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ¹ - methyl dibromo nitro acetamidine N - {(4-methyl-3-furanyl) methyl}-N'-methyl-dibromo-nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ^1, N ² - dimethyl dibromo-nitro acetamidine N ² - {(4-methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl dibromo-nitro acetamidine N - {(5-methyl-3-furanyl) methyl} dibromo Nitroacetamidine N ¹ -{(5-methyltetrahydro-3-furanyl) Methyl} -N ¹ - methyl dibromo nitro acetamidine N - {(5-methyl-3-furanyl) methyl}-N'-methyl-dibromo-nitro acetamidine N ¹ - {(5- methyl-3-furanyl) methyl } -N ^1, N ² - dimethyl dibromo-nitro acetamidine N ² - {(5- methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl dibromo-nitro acetamidine

N-{(tetrahydro-3-furanyl) methyl} difluoronitroacetamidine N ¹ -{(tetrahydro-3-furanyl) methyl} -N ¹
-Methyldifluoronitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- methyl difluoro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
^1, N ² - dimethyl-difluoro-nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
^1, N ¹ - dimethyl-difluoro-nitro acetamidine N - {(4-methyl-3-furanyl) methyl} difluoro nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ¹ - methyl difluoro nitro acetamidine N - {(4-methyl-3-furanyl) methyl}-N'-methyl-difluoro-nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ^1, N ² - dimethyl-difluoro-nitro acetamidine N ² - {(4-methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl-difluoro-nitro acetamidine N - {(5-methyl-3-furanyl) methyl} difluoro Nitroacetamidine N ¹ -{(5-methyltetrahydro- 3-furanyl) methyl} -N ¹ -methyldifluoronitroacetamidine N-{(5-methyltetrahydro-3-furanyl) methyl} -N′-methyldifluoronitroacetamidine N ¹ -{(5-methyltetrahydro-3 - furanyl) methyl} -N ^1, N ² - dimethyl-difluoro-nitro acetamidine N ² - {(5-methyl-3-furanyl) methyl} -N ^1, N ¹ - dimethyl-difluoro-nitro acetamidine N ¹ - {( Tetrahydro-3-furanyl) methyl} -N ¹
-Ethyldichloronitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- ethyl dichloro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ² - methyl dichloro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - Methyl -N ² - ethyl dichloro nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ¹ - methyl dichloro nitro acetamidine N ¹ - {(4-methyl-3-furanyl) methyl} -N ¹ - ethyl dichloro nitro acetamidine N - {(4-methyl-3-furanyl) methyl}-N'-ethyl-dichloro-nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ¹ - ethyl -N ² - methyl dichloro nitro acetamidine N ¹ - {(4- methyl tetrahydrophthalic -3-furanyl) methyl} -N ¹ -methyl-N ² -ethyldichloronitroacetamidine N ² -{(4-methyltetrahydro-3-furanyl) methyl} -N ¹ -ethyl-N ¹ -methyldichloronitroaceto amidine N ¹ - {(5- methyl-3-furanyl) methyl} -N ¹ - ethyl dichloro nits Acetamidine N - {(5-methyl-3-furanyl) methyl}-N'-ethyl-dichloro-nitro acetamidine

N ¹ -{(5-methyltetrahydro-3-
Furanyl) methyl} -N ¹ -ethyl-N ² -methyldichloronitroacetamidine N ¹ -{(5-methyltetrahydro-3-furanyl) methyl} -N ¹ -methyl-N ² -ethyldichloronitroacetamidine N ² - {(5-methyl-3-furanyl) methyl} -N ¹ - ethyl -N ¹ - methyl dichloro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N ¹
-Ethyldibromonitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- Ethyl dibromo-nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ² - methyl dibromo nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - Methyl -N ² - ethyl dibromo-nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ¹ - methyl dibromo nitro acetamidine N ¹ - {(4-methyl-3-furanyl) methyl} -N ¹ - ethyl-dibromo-nitro acetamidine N - {(4-methyl-3-furanyl) methyl}-N'-ethyl-dibromo-nitro acetamidine N ¹ - {(4- methyl-3-furanyl) methyl} -N ¹ - ethyl -N ² - methyl dibromo nitro acetamidine N ¹ - {(4- methyl tetrahydrophthalic -3-furanyl) methyl} -N ¹ -methyl-N ² -ethyldibromonitroacetamidine N ² -{(4-methyltetrahydro-3-furanyl) methyl} -N ¹ -ethyl-N ¹ -methyldibromonitroaceto amidine N ¹ - {(5- methyl-3-furanyl) methyl} -N ¹ - ethyl-dibromo nits Acetamidine N - {(5-methyl-3-furanyl) methyl}-N'-ethyl-dibromo-nitro acetamidine N ¹ - {(5- methyl-3-furanyl) methyl} -N ¹ - ethyl -N ² - methyl dibromo nitro acetamidine N ¹ - {(5-methyl-3-furanyl) methyl} -N ¹ - methyl -N ² - ethyl dibromo-nitro acetamidine N ² - {(5-methyl-3-furanyl) Methyl} -N ¹ -ethyl-N ¹ -methyldibromonitroacetamidine N ¹ -{(tetrahydro-3-furanyl) methyl} -N ¹
-Ethyldifluoronitroacetamidine N-{(tetrahydro-3-furanyl) methyl} -N '
- difluoromethyl nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ² - methyl difluoro nitro acetamidine N ¹ - {(tetrahydro-3-furanyl) methyl} -N
¹ - Methyl -N ² - difluoromethyl nitro acetamidine N ² - {(tetrahydro-3-furanyl) methyl} -N
¹ - ethyl -N ¹ - methyl difluoro nitro acetamidine N ¹ - {(4-methyl-3-furanyl) methyl} -N ¹ - difluoromethyl-nitro acetamidine N - {(4-methyl-3-furanyl) Methyl} -N'-ethyldifluoronitroacetamidine

N ¹ -{(4-methyltetrahydro-3-
Furanyl) methyl} -N ¹ -ethyl-N ² -methyldifluoronitroacetamidine N ¹ -{(4-methyltetrahydro-3-furanyl) methyl} -N ¹ -methyl-N ² -ethyldifluoronitroacetamidine N ² - {(4-methyl-3-furanyl) methyl} -N ¹ - ethyl -N ¹ - methyl difluoro nitro acetamidine N ¹ - {(5-methyl-3-furanyl) methyl} -N ¹ - difluoromethyl nitro acetamidine N - {(5-methyl-3-furanyl) methyl}-N'-difluoromethyl-nitro acetamidine N ¹ - {(5- methyl-3-furanyl) methyl} -N ¹ - ethyl -N ² -Methyldifluoronitroacetamidine N ¹ -{(5-methyltetrahydro-3-furanyl) Methyl} -N ¹ - methyl -N ² - difluoromethyl nitro acetamidine N ² - {(5- methyl-3-furanyl) methyl} -N ¹ - ethyl -N ¹ - methyl difluoro nitro acetamidine

The compound represented by the general formula (1) may exist as isomers (cis- and trans-isomers) and tautomers. In addition, an asymmetric carbon exists at the 3-position of the tetrahydrofuran ring, and it can exist as an optically active isomer, a racemate, and a mixture in an arbitrary ratio. Further, in the case of a compound having a substituent on the tetrahydrofuran ring, not only optical isomers but also diastereomers are present, which may be present as a single isomer or a mixture in an arbitrary ratio. All isomers and tautomers of this type, and mixtures thereof, are also included in the present invention. The compound represented by the general formula (1) can be easily produced by the following reaction formula (1) (chemical formula 3).

[0018]

Embedded image (In the formula, A, B, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , X
₁ and X ₂ have the same meanings as described above. )

That is, by reacting the compound represented by the general formula (2) with a halogenating agent, the compound can be easily produced in high yield. As a halogenating agent, N-chlorosuccinimide (NCS) is used to obtain a dichloro compound, N-bromosuccinimide (NBS) is used to obtain a dibromo compound, and N-fluoro-2,4 is used to obtain a difluoro compound. 6-trimethylpyridinium triflate or the like can be used. Although not necessary, benzoyl peroxide (BPO), α, α′-, as a reaction initiator
Diazobis (isobutyronitrile) (AIBN) or the like may be used. The reaction can be carried out without solvent or in various solvents. 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. Acetamide, dimethyl sulfoxide, 1,3-dimethyl-2-
Aprotic polar solvents such as imidazolidinone and 1-methyl-2-pyrrolidinone, ethers such as ethyl ether, diisopropyl ether, 1,2-dimethoxyethane, tetrahydrofuran and dioxane, acetonitrile,
Use of nitriles such as propionitrile, ketones such as acetone and diisopropyl ketone, esters such as ethyl acetate and methyl acetate, and halogenated hydrocarbons such as methylene chloride, 1,2-dichloroethane and chloroform. it can. In addition, preferable solvents are ethers, halogenated hydrocarbons and the like.

The reaction temperature and reaction time can be varied over a wide range, but in general, the reaction temperature is -30 to -30.
The temperature is 200 ° C., preferably −20 to 150 ° C., and the reaction time is 0.01 to 50 hours, preferably 0.1 to 15 hours.

The compound represented by the general formula (2) can be produced according to the following reaction formula (2) (chemical formula 4).

[0022]

[Chemical 4] (In the formula, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ have the same meanings as described above, and R ₆ represents a lower alkyl group.) That is, the compound represented by the general formula (2) is It is obtained by reacting a substituted or unsubstituted (tetrahydro-3-furanyl) methylamine represented by the general formula (3) with a bis (alkylthio) nitromethylene derivative represented by the general formula (4) in acetonitrile. It can be obtained by reacting the nitromethylene compound represented by the general formula (5) with an amine represented by the general formula (6) in alcohol or acetonitrile. The substituted or unsubstituted (tetrahydro-3-furanyl) methylamine derivative represented by the general formula (3) is represented by the following reaction formula (3) (Chemical formula 5) or (4) (Chemical formula 6). It can be produced according to the reaction formula.

[0023]

Embedded image (In the formula, R ₁ , R ₂ and R ₄ have the same meanings as described above, and R _1
7 represents a p-toluyl group, a methyl group, or a trifluoromethyl group. )

[0024]

[Chemical 6] (In the formula, R ₁ and R ₂ have the same meanings as described above.)

That is, the (tetrahydro-3-furanyl) methylamine derivative represented by the general formula (3) is the substituted or unsubstituted (tetrahydro-3-furanyl) methanol derivative represented by the general formula (7). From the sulfonic acid chloride derivative represented by the general formula (8), the general formula (9)
The phthalimide derivative represented by the general formula (10) is obtained from the reaction of the sulfonate derivative represented by the formula (1) with phthalimido potassium, and it is obtained by hydrazine decomposition. Alternatively, the sulfonate derivative represented by the general formula (9) can be directly reacted with the alkylamine derivative to obtain the amine derivative represented by the general formula (3). Further, the amine represented by the general formula (3) obtains an oxime represented by the general formula (13) from the 3-formyltetrahydrofuran derivative represented by the general formula (11) and hydroxylamine hydrochloride, and reduces the oxime. It can also be obtained.

Further, the (tetrahydro-3-furanyl) methanol derivative represented by the general formula (7) and the 3-formyltetrahydrofuran derivative represented by the general formula (11) or their alkyl-substituted compounds can be prepared by methods known in the literature or It can be easily and inexpensively synthesized by a similar method (Tetrahedron Letters, vo).
l. 26 (35), 4265-4268, J. Che
m. Soc, Chem. Comm. , 600-601
(1990), Bulletin de la Soc
iete Chimique de France 3
616, (1972), Tetrahedoron l
etters, vol. 21, 4927-4930).

The compound represented by the general formula (4) is
It is a known compound, for example, Chem. Be
r. , 100, 591-604.
Specific examples thereof include 1,1-bis (methylthio) -2-nitroethylene and 1,1-bis (ethylthio) -2-nitroethylene.

The derivative represented by the general 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 general 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.

Examples of such pests include armyworm, rice millet, hemlock worm, Tamana moth, cotton grasshopper, giant tobacco moth, bollworm, white beetle moth, corn borer, long-necked moth, cornweed moth, cornweed moth, cornweed moth, corn borer. , Cottontail bug, Potato moth, Pieris brassicae, Prunus densiflora, Chacococcinus pygmaea, Prunus chinensis, Mandarin moth, Grape beetle, Nashihime Shinkui, Codling moth, Stinkweed moth, Peach mosquito, Insect insects such as vinegrass moth, Chanojoga moth, Koga moth, Koga moth Whitefly,
On whitefly, whitefly, cotton aphid, cotton aphid, snowy aphid, apple aphid, apple aphid, green peach aphid, radish aphid, black phiphid aphid, bean aphid, citrus aphid, citrus aphid, stadium aphid, stamen aphis Aphid, green leafhopper, leafhopper leafhopper, potato leafhopper, leafhopper planthopper, leafhopper planthopper, brown planthopper, white-backed planthopper, leaf-hopper leafhopper, white-footed leafhopper, ruby aphid, olive leafworm, mosquito leafworm, green leafhopper Scale insects, scale insects, scale insects, mandarin oranges Na scale insects, Iseria scale insects, Ringokijirami, Diaphorina citri, southern green stink bug, bombardier helicopter bugs, USA co spring Naga bug, Hemiptera such Nashigunbai; rice water weevil,
Boll Weevil, Rice Beetle, Beetle Beetle, Colorado potato Beetle, Beetle Beetle, Diabrotica
spp., Chinese elephant, poplar beetle, Red weevil, Bean weevil, Azuki bean weevil, Lepidoptera, Weevil, Rana bubuei, Himekogane, Beetle beetle, Hemoptera scutellata, Beetle oleoptera, Beetle oleoptera, Beetle worm, Beetle, Beetle, Beetle, Beetle Acaca,
Diptera such as Chica mosquito, Anopheles albopictus, Aedes albopictus, Rice mosquito glyca, Soybean fly, Rice fly, Rice flesh fly, House fly, Black fly, Onion fly, Pleurotus cornucopia, Lilium melanogaster, Pleurotus cornucopia, L. scutellaria, Nymphalidae, Mikanomiba, etc .; Thysanoptera insects, such as black cockroaches, cockroaches, American cockroaches, German cockroaches, cobainago, locust grasshoppers, and other insect pests; Pests such as, house dust mite, chigger beetle, and mite mites; other fleas, lice, termites, millipedes, gudge It can be mentioned di-, centipede acids and the like.

The dichloronitromethyl derivative having an unsaturated heterocycle or a phenyl group has insecticidal activity.
Although it is already known from JP-A-3-204848 and the like, this publication only discloses a compound having a nitrogen-containing heterocycle or a phenyl group, and does not disclose a compound having a saturated heterocycle. Not not. Further, among these, the active compounds to be seen are limited to the pyridine derivative or the thiazole derivative and the 4-chlorobenzyl group. However, the compound represented by the general formula (1) of the present invention is characterized by having a (tetrahydro-3-furanyl) methyl group, and these derivatives show extremely excellent insecticidal action. Is amazing.

The excellent insecticidal activity according to the present invention appears only in the (tetrahydro-3-furanyl) methylamine derivative. When the oxygen atom of the tetrahydrofuran ring is replaced with a sulfur atom or a nitrogen atom, a high insecticidal activity is obtained. No activity is observed. Further, the position of the oxygen atom is also characteristic of the (tetrahydro-3-furanyl) methyl group,
No high insecticidal activity is observed with the (tetrahydro-2-furanyl) methyl derivative. That is, the compound of the present invention is characterized in that its insecticidal activity is found only in the (tetrahydro-3-furanyl) methylamine derivative having a very limited structure of a saturated heterocycle.

When the compound represented by the general 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 used for easy use as a controlling agent. It is generally compounded and applied.

The preparation of the compound represented by the general formula (1) of the present invention does not require any special conditions,
Emulsions, wettable powders, powders, granules, fine granules, water solutions, flowable agents, microcapsules, oils, aerosols, smoke agents, etc.
It can be adjusted to any dosage form such as poison bait and can be used for various purposes according to the respective purposes.

The term "carrier" as used herein refers to the synthesis or synthesis of a liquid, solid or gas formulated to help the active ingredient reach the site to be treated and to facilitate the storage, transportation and handling of the active ingredient compound. It means a natural inorganic or 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 lanolin, liquid paraffin, lard, organic substances such as vegetable oil, activated carbon and the like.

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, esters such as ethyl acetate, acetic acid butyl ester, fatty acid glycerin ester, etc. Nitrile such as acetonitrile, propionitrile, etc. 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 general formula (1) of the present invention, the following may be used individually 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 auxiliary agents such as

As an auxiliary agent 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 general formula (1) of the present invention can exhibit 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, Fenpropatorin, Tralomethrin, Cycloprothrin, Flucitrinate, Fluvalinate, Acrinathrin, Tefurthrin, Silafluorfen, Bifenthrin, Empentrin, Ardent, Benfluthrin, Betacyfluthrin, Zetacypers Synthetic pyrethroid insecticides such as phosphorus, palethrin, cyphenothrin, and imiprothrin and various isomers or pyrethrum extract thereof, DDVP, cyanophos, fenthion, fenitrothion, dichlorphenthion, tetrachlorvinphos, dimethylbinphos, chlorfenvin Phos, propaphos, methyl parathion, temephos,
Hoxime, acephate, isofenphos, salithion, DEP, EPN, ethione, mecarbam, pyridafenthion, diazinon, pirimiphosmethyl, etrimphos, isoxathione, quinalphos, chlorpyrifosmethyl, chlorpyrifos, phosalone, phosmet, methithione, estocks, bamidthione, malathion,
Organic phosphorus insecticides such as fentoate, dimethoate, formothione, thiomethone, ethylthiomethone, folate, terbufos, oxydeprophos, profenophos, prothiophos, sulprophos, pyraclofos, monocrotophos, naredo, fostiazate, NAC, MTMC,
MIPC, BPMC, XMC, PHC, MPMC, Ethiophene Carb, Bendiocarb, Pirimicarb, Carbosulfan, Benfuracarb, Bendiocarb,
Carbamate insecticides such as mesomil, oxamyl and aldicarb, arylpropyl ether insecticides such as etofenprox, flufenprox and halfenprox, silyl ether insecticides such as silafluofene, 1- (3-phenoxyphenyl ) -4-
(4-Ethoxyphenyl) -4-methylpentane, 1-
(3-phenoxy-4-fluorophenyl) -4- (4
-Ethoxyphenyl) -4-methylpentane and other aromatic alkane insecticides, nicotine sulfate, polynactin complex, insecticidal natural products such as avermectin and milbemectin, cartap, thiocyclam, bensultap, diflubenzuron, chlorfluazuron, teflubenzuron , Triflumuron, flufenoxuron, novaluron, flucycloxuron, hexaflumuron, fluazuron, imidacloprid, nitenpyram, fipronil, NI-25, pymetrozine, buprofezin, phenoxycarb, pyriproxyfen, methoprene, hydroprene, quinoprene, benzoepin, Insecticides such as pipericide, diafenthiuron, triazuron, tebufenozide, quelsen, CPCBS, BPPS, tetradiphone, amitraz, ven Mate, phenothiocarb, hexathiazox, phenbutatin oxide, dienochlor, clofentezine, pyridaben, fenpyroximate, tebufenpyrad, phenazaquin, pyrimidifen, agrimonte and other acaricides, 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, entomopathogenic microorganisms and small animals It is also possible to prepare a multipurpose composition having more excellent efficacy by mixing it with other pesticides and the like, and a synergistic effect can be expected.

The compound represented by the general 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-
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 phenetidine-acetone condensates. By adding an appropriate amount of the compounds or benzophenone compounds as a stabilizer, a composition having a more effective effect can be obtained.

The insecticide of the compound represented by the general formula (1) of the present invention contains 0.0000001 to 95% by weight of the compound.
Preferably 0.0001 to 50% by weight is contained. To apply the insecticide of the present invention, generally 0.001 to 0.001 of the active ingredient is used.
5000 ppm, preferably 0.01-1000 ppm
It is desirable to use it at the concentration of. In addition, the application rate per 10a is generally 1 to 300 g of the active ingredient.

[0042]

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. Example 1 N-{(tetrahydro-3-furanyl) methyl} -N '
-Methyldichloronitroacetamidine (Compound N
o. 1) 1-{(tetrahydro-3-furanyl) methylamino}
0.18 g of N-chlorosuccinimide (NCS) was added to a chloroform solution (10 ml) of 0.12-methylamino-2-nitroethylene 0.12 g, and the mixture was stirred at room temperature for 3 hours. The reaction solution was washed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 6: 4 → 4: 6) to obtain 0.16 g of the desired product as a yellow oil. Got as. ¹ HNMR (CDCl ₃ , ppm): 1.52-1.74 (1H, m), 1.92-2.10 (1H, m),
2.41-2.60 (1H, m), 3.10 (3H, br-s), 3.38-3.62 (2H, m), 3.66
-3.92 (4H, m) IR (neat, cm ^-1 ): 3329,2941,2870,1652,1594,1316,888

Example 2 N ¹ -{(tetrahydro-3-furanyl) methyl} -N
^1, N ² - dimethyldichlorosilane nitro acetamidine (Compound No.2) 1 - {(tetrahydro-3-furanyl) methylamino}
0.37 g of N-chlorosuccinimide (NCS) was added to a chloroform solution (14 ml) of 0.30 g of -1-methylamino-2-nitroethylene, and the mixture was stirred for 1 hour at room temperature. The reaction solution was washed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2 → 7: 3) to obtain 0.28 g of the desired product as a yellow oil. Got as. ¹ HNMR (CDCl ₃ , ppm): 1.55-1.68 (1H, m), 2.00-2.18 (1H, m),
2.59 (1H, septet, J = 6.6), 2.94 (3H, s), 3.18 (3H, s), 3.13-
3.31 (2H, m), 3.54 (1H, dd, J = 8.8, J = 5.1), 3.76 (1H, q, J = 8.
1), 3.83-3.92 (2H.m) IR (neat, cm ^-1 ): 2942,2871,1643,1593,1542,1331,1084,8
93

Example 3 N ² -{(tetrahydro-3-furanyl) methyl} -N
¹ , N ¹ -Dimethyldichloronitroacetamidine (Compound No. 3) 1-{(tetrahydro-3-furanyl) methylamino}
0.37 g of N-chlorosuccinimide (NCS) was added to a chloroform solution (14 ml) of 0.30 g of -1-methylamino-2-nitroethylene, and the mixture was stirred for 1 hour at room temperature. The reaction solution was washed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2 → 7: 3) to give 0.30 g of the desired product as a yellow oil. Got as. ¹ HNMR (CDCl ₃ , ppm): 1.53-1.65 (1H, m), 1.92-2.05 (1H, m),
2.44 (1H, septet, J = 6.6), 2.97 (6H, s), 3.36 (2H, d, J = 6.6),
3.46 (1H, dd, J = 8.1, J = 5.1), 3.69-3.86 (3H, m) IR (neat, cm ^-1 ): 2935,2865,1594,1329,1148,1066,890,75
7

Example 4 N-{(tetrahydro-3-furanyl) methyl} -N '
-Methyldibromonitroacetamidine (Compound N
o. 4) 1-{(tetrahydro-3-furanyl) methylamino}
0.97 g of N-bromosuccinimide (NBS) was added to a chloroform solution (20 ml) of 0.50 g of -1-methylamino-2-nitroethylene, and the mixture was stirred at room temperature for 3 hours. The reaction solution was washed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 6: 4 → 4: 6) to obtain 0.84 g of the desired product as a yellow oil. Got as. ¹ HNMR (CDCl ₃ , ppm): 1.48-1.76 (1H, br-s), 1.95-2.20 (1H, b
rs), 2.40-2.64 (1H, br-s), 3.08 (3H, br-d, J = 5.8), 3.25-
3.47 (2H, br-s), 3.50-4.00 (4H, m) IR (KBr, cm ^-1 ): 3328,2943,2870,1646,1583,1326,1064,82
8 Oil

Example 5 N ² -{(tetrahydro-3-furanyl) methyl} -N
¹ , N ¹ -Dimethyldibromonitroacetamidine (Compound No. 5) 1-{(tetrahydro-3-furanyl) methylamino}
0.87 g of N-chlorosuccinimide (NBS) was added to a chloroform solution (20 ml) of 0.50 g of -1-methylamino-2-nitroethylene, and the mixture was stirred at room temperature for 1 hour. The reaction solution was washed, dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, hexane: ethyl acetate = 8: 2 → 7: 3) to obtain 0.80 g of the desired product as a yellow oil. Got as. ¹ HNMR (CDCl ₃ , ppm): 1.56-1.80 (1H, m), 1.95-2.20 (1H, m),
2.25-2.70 (1H, m), 3.01-4.22 (12H, m) IR (KBr, cm ^-1 ): 2940,1653,1577,1328,1068 Oil

Reference Example 1 1-{(tetrahydro-3-furanyl) methylamino}
-1-Methylamino-2-nitroethylene 1-{(tetrahydro-3-furanyl) methylamino}
-1-methylthio-2-nitroethylene 4.0 g, 40
% Methylamine methanol solution 6.0 ml, a mixture of 1N sodium hydroxide aqueous solution 20 ml and ethanol 20 ml was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure and then purified by silica gel column chromatography (developing solvent; ethyl acetate: methanol = 9: 1) to give 3.2 g of 1-.
{(Tetrahydro-3-furanyl) methylamino} -1
-Methylamino-2-nitroethylene was obtained.

Reference Example 2 1-{(tetrahydro-3-furanyl) methylamino}
-1-Methylamino-2-nitroethylene 1-{(tetrahydro-3-furanyl) methylamino}
-1-methylthio-2-nitroethylene 1.79 g, 4
1% of 0% methylamine methanol solution, ethanol 3
0 ml of the mixture was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by column chromatography to obtain 1.54 g of 1-{(tetrahydro-3-furanyl) methylamino} -1-methylamino-2-nitroethylene. . ¹ HNMR (DMSO-d ₆ , ppm): 1.51-1.63 (1H, m), 1.90-2.04 (1H,
m), 2.42-2.54 (1H, m), 2.67-2.91 (3H, br), 3.05-3.25 (2H, b
r), 3.40-3.47 (1H, br), 3.59-3.81 (3H, br), 6.45-6.55 (1H,
br), 7.15-7.28 (1H, br), 9.90-10.1 (1H, br) IR (KBr, cm ^-1 ): 3186,1637,1584,1222,997 mp: 140.0-141.0 ℃

Reference Example 3 1-{(4-methyltetrahydro-3-furanyl) methylamino} -1-methylamino-2-nitroethylene 1-{(4-methyltetrahydro-3-furanyl) methylamino} -1 -Methylthio-2-nitroethylene 0.
A mixture of 30 g, 2% of a 40% methylamine methanol solution and 30 ml of methanol was stirred at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and the obtained oil was purified by column chromatography to give 0.16 g of 1-{(4-methyltetrahydro-3-furanyl) methylamino} -1-methylamino-2-nitroethylene. Got ¹ HNMR (DMSO-d ₆ , ppm): 1.00 (3H, d, J = 6.6Hz), 1.90-2.05 (2
H, m), 2.65-2.85 (3H, br.), 3.15-3.45 (3H, m), 3.75-3.90 (3
H, m), 6.47 (1H, br.) IR (KBr, cm ^-1 ): 3274,1628,1586,1367,1230,1011 mp: 127.5-129.0 ° C

Reference Example 4 1-{(5-methyltetrahydro-3-furanyl) methyi
Ruamino} -1-methylamino-2-nitroethylene 1-{(5-methyltetrahydro-3-furanyl) meth
Ruamino} -1-methylthio-2-nitroethylene 0.
2 g, 1.5 ml of 40% methylamine methanol solution,
A mixture of 10 ml of methanol was stirred at room temperature for 5 hours.
The reaction solution was concentrated under reduced pressure and the resulting oily substance was subjected to column chromatography.
Graphography (developing solvent; ethyl acetate: acetone = 7:
3) and 0.21 g of 1-{(5-methyltetra
Hydro-3-furanyl) methylamino} -1-methyla
Mino-2-nitroethylene was obtained. ¹ HNMR (CDCl₃, ppm): 1.12-1.30 (3H, m), 1.63-1.90 (1H, m),
2.19-2.29 (1H, m), 2.64 (1H, br.), 2.87 (3H * 1/2, d, J = 4.4H
z), 3.00 (3H * 1/2, d, J = 4.4Hz) .3.19-3.45 (2H, m), 3.68-4.1
3 (3H, m), 6.60 (1H, s), 10.20-10.25 (1H, br.) IR (KBr, cm^-1): 3189,2968,1637,1583,1541,1420,1387,12
22,1171,999,750,700 m.p .: 114.0-120.5 ° C

Reference Example 5 1-{(tetrahydro-3-furanyl) methylamino}
-1-Methylthio-2-nitroethylene (tetrahydro-3-furanyl) methylamine 7.0
A mixture of g, 1,1-bis (methylthio) -2-nitroethylene 12.5 g and acetonitrile 100 ml was heated under reflux for 5 hours. The reaction solution was concentrated under reduced pressure and then purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 1) to give 6.6 g of 1-{(tetrahydro-3-furanyl) methylamino} -1-methylthio-.
2-Nitroethylene was obtained.

Reference Example 6 1-{(4-methyltetrahydro-3-furanyl) methylamino} -1-methylthio-2-nitroethylene (4-methyltetrahydro-3-furanyl) methylamine 0.50 g, 1,1 A mixture of 0.74 g of -bis (methylthio) -2-nitroethylene and 10 ml of acetonitrile was heated under reflux for 5 hours. The reaction solution was concentrated under reduced pressure and then purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 1: 1) to give 0.50 g of 1-.
{(4-Methyltetrahydro-3-furanyl) methylamino} -1-methylthio-2-nitroethylene was obtained.

Reference Example 7 1-{(5-methyltetrahydro-3-furanyl) methylamino} -1-methylthio-2-nitroethylene (5-methyltetrahydro-3-furanyl) methylamine 0.80 g, 1,1 A mixture of -bis (methylthio) -2-nitroethylene 1.16 g and ethanol 40 ml was heated under reflux for 3 hours. The reaction solution was concentrated under reduced pressure and then purified by silica gel column chromatography (developing solvent; ethyl acetate: hexane = 4: 6) to obtain 0.72 g of 1-{(5-
Methyltetrahydro-3-furanyl) methylamino}-
1-Methylthio-2-nitroethylene was obtained.

Reference Example 8 (Tetrahydro-3-furanyl) methylamine N-{(tetrahydro-3-furanyl) methyl} phthalimide 1.50 g, 25% Na in a suspension solution of 8 ml of water.
1 ml of an OH aqueous solution was added, and the mixture was stirred at 70 ° C. for 3 hours. The reaction solution was added dropwise to a 10% HCl aqueous solution at 70 ° C., and the temperature was adjusted to 5
Stir for hours. Toluene (12 ml) was added while the reaction solution was warm, the aqueous layer was separated and made weakly alkaline with 50% NaOH aqueous solution, extracted with dichloromethane, dried and concentrated under reduced pressure to give 0.55 g of (tetrahydro-3-furanyl) methylamine. Got ¹ HNMR (CDCl ₃ , ppm): 1.36 (2H, br.), 1.52-1.64 (1H, m), 1.98
-2.10 (1H, m), 2.32 (1H, septet, J = 7.3Hz), 2.72 (2H, d, J = 7.
3Hz), 3.51 (1H, dd, J = 5.9Hz, J = 8.8Hz), 3.75 (1H, q, J = 7.3H
z), 3.82-3.91 (2H, m) IR (neat, cm ^-1 ): 3363,1660,1060

Reference Example 9 N-{(tetrahydro-3-furanyl) methyl} phthalimide (tetrahydro-3-furanyl) methyl tosylate 3
0.0g, potassium phthalimide 23.0g, DMF1
50 ml of the mixture was stirred at 80 ° C. for 8 hours. Water was poured into the reaction mixture, and the precipitated crystals were collected by filtration and 27.0 g of N-
{(Tetrahydro-3-furanyl) methyl} phthalimide was obtained. ¹ H NMR (CDCl ₃ , ppm): 1.69-1.81 (1H, m), 1.98-2.11 (1H, m),
2.74 (1H, septet, J = 7.3Hz) 3.61 (2H, dd, J = 5.9Hz, J = 8.1H
z), 3.65-3.88 (4H, m), 3.95 (1H, dt, J = 5.9Hz, J = 8.1Hz), 7.7
1-7.80 (2H, m), 7.84-7.89 (2H, m) IR (neat, cm ^-1 ): 1701,1399,1050,719

Reference Example 10 (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 (tetrahydro-
3-furanyl) methyl tosylate was obtained. ¹ HNMR (CDCl ₃ , ppm): 1.55 (1H, septet, J = 6.6Hz), 1.94-2.07
(1H, m), 2.46 (3H, s), 2.59 (1H, septet, J = 6.6Hz), 3.49 (1H,
dd, J = 5.1Hz, J = 9.5Hz), 3.64-3.81 (3H, m), 3.92 (1H, t, J = 8.
8Hz), 3.99 (1H, dd, J = 6.6Hz, J = 9.5Hz), 7.36 (2H, dJ = 8.1H
z), 7.79 (2H, d, J = 8.1Hz)

Reference Example 11 (Tetrahydro-3-furanyl) methyl bromide 10 g of phosphorus tribromide, 0.8 g of pyridine, 100 of ether
10 g of (tetrahydro-3-furanyl) methanol was added dropwise to the mixture of ml in 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 = 7.3Hz) 3.40 (2H, dd, J = 1.5Hz, J = 7.3H
z), 3.45-3.53 (1H, m), 3.60 (1H, dd, J = 5.1Hz, J = 8.8Hz), 3.8
0 (1H, t, J = 7.3Hz), 3.89-3.95 (1H, m)

Reference Example 12 (5-Methyltetrahydro-3-furanyl) methylamine hydrochloride (1) A solution of 13.0 g of (2-methyltetrahydro-4-furanyl) methanol and 12.5 g of triethylamine in 85 ml of tetrahydrofuran was cooled with ice. Methanesulfonyl chloride 14.1 g of tetrahydrofuran 10
The ml solution was added dropwise over 30 minutes. The reaction solution was stirred under ice-cooling for 1 hour and at room temperature for 2 hours, the insoluble material was filtered off, and the filtrate was concentrated under reduced pressure to obtain an oily substance and potassium phthalimide (20.7 g) of dimethylformamide 115.
The ml suspension solution was stirred at 80 ° C. for 3 hours. The reaction solution was allowed to cool to room temperature, ethyl acetate was added, and this was washed with water. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the obtained oily substance was purified by silica gel column chromatography (developing solvent: hexane: ethyl acetate = 2: 1) and recrystallized (acetic acid). Ethyl-
Hexane) to give N-{(5-methyltetrahydro-3-furanyl) methyl} phthalimide 22.1 g
Was obtained as colorless crystals. (2) N-{(5-methyltetrahydro-3-furanyl) methyl} phthalimide 21.0 g and hydrazine monohydrate (98%) 4.86 g ethanol 100 ml
The solution was heated to reflux for 2 hours. The reaction solution was allowed to cool to room temperature, 8.6 ml of concentrated hydrochloric acid was added thereto, and the mixture was stirred at room temperature for 1.5 hours. The insoluble matter was filtered off, the filtrate was concentrated under reduced pressure to remove ethanol, and then an aqueous sodium hydroxide solution was added to make the aqueous solution alkaline. This aqueous solution was extracted with dichloromethane, the organic layer was dried over anhydrous potassium carbonate and then concentrated under atmospheric pressure to obtain an oily substance, and 60 ml of ethyl acetate was added.
Was added, followed by hydrogen chloride-ethyl acetate solution (4
M) (30 ml) was added and the precipitated crystals were separated by filtration to obtain 5.70 g of (5-methyltetrahydro-3-furanyl) methylamine hydrochloride as colorless crystals. ¹ HNMR (CDCl ₃ , ppm): 1.12 (3H, s), 1.21 (3H, s), 1.41 (1H, dd,
J = 12.5Hz, J = 8.8Hz), 1.87-1.95 (1H, m), 2.50-2.63 (1H, m),
2.78 (2H, d, J = 7.3Hz), 3.48 (1H, dd, J = 8.8Hz, J = 6.6Hz), 3.8
3 (1H, dd, J = 8.8Hz, J = 7.3Hz)

Reference Example 13 (3-Methyltetrahydro-4-furanyl) methanol (1) Diethyl malonate 25.0 g of ethanol 50 m
1.72 g of sodium was added little by little to the 1 solution under ice cooling. Next, 7.3 g of ethyl α-bromopropionate was added dropwise, and after completion of the addition, the mixture was stirred at 60 ° C for 4 hours. Ethyl acetate was added to the reaction solution, which was washed with water, the organic layer was dried over anhydrous magnesium sulfate, and the organic layer was concentrated under reduced pressure to 2
17.4 g of crude oily substance of diethyl- {2- (1-ethoxycarbonyl) ethyl} malonate was obtained. (2) 2- {2 in a suspension of 5.10 g of lithium aluminum hydride in 100 ml of tetrahydrofuran under ice cooling.
Crude oily substance of diethyl-(1-ethoxycarbonyl) ethyl} malonate 17.4 g tetrahydrofuran 30 ml
The solution was added dropwise over 20 minutes. The reaction mixture was stirred for 1 hour under ice cooling and 5 hours at room temperature, and then 10 m of water under ice cooling.
1 was added dropwise over 20 minutes. The reaction mixture was heated under reflux for 1 hour, filtered, and concentrated under reduced pressure to give 2-hydroxymethyl-3-methyl-1,4-butanediol 7.70.
g was obtained as a colorless oil. (3) 7.70 g of 2-hydroxymethyl-3-methyl-1,4-butanediol and phosphoric acid (85%) 7.3
The ml mixture was stirred at 120 ° C. for 3 hours. The reaction mixture was allowed to cool to room temperature, water was added, and this was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and the oily substance obtained was distilled under reduced pressure (3-methyltetrahydro-4-
3.09 g of furanyl) methanol was obtained as a colorless oil.

Reference Example 14 (2-Methyltetrahydro-4-furanyl) methanol (1) Diethyl malonate 2 was added to a suspension of 6.55 g of sodium hydride in 90 ml of dimethylformamide under ice cooling.
A 5 ml solution of 5.0 g of dimethylformamide was added dropwise over 20 minutes. The reaction solution was stirred for 1 hour under ice cooling, and then 17.3 g of chloroacetone was added to 5 m of dimethylformamide.
1 solution was added, and the mixture was stirred under ice cooling for 1 hour and at room temperature for 6 hours. Ethyl acetate was added to the reaction solution, which was washed with water, and then the organic layer was dried over anhydrous magnesium sulfate.
The organic layer was concentrated under reduced pressure and the oily substance obtained was distilled under reduced pressure to obtain diethyl 2-oxopropylmalonate 14.8.
g was obtained as a yellow oil. ¹ HNMR (CDCl ₃ , ppm): 1.27 (6H, t, J = 7.3), 2.21 (3H, s), 3.06
(2H, d, J = 7.3), 3.86 (1H, t, J = 7.3), 4.20 (4H, q, J = 7.3) IR (neat, cm ^-1 ): 2985,2940,1732,1467,1448, 1406,1370,1
332,1273,1237,1161,1098,1050,1026,867 bp: 125-135 ° C (5mmHg) (2) 2-oxopropyl under ice-cooling in a suspension solution of 5.00g of lithium aluminum hydride in 100ml of tetrahydrofuran. A solution of 11.4 g of diethyl malonate in 30 ml of tetrahydrofuran was added dropwise over 20 minutes. The reaction solution was stirred under ice-cooling for 1 hour and at room temperature for 4.5 hours.
Under ice cooling, 10 ml of water was added dropwise over 20 minutes. The reaction solution was heated under reflux for 1 hour and then filtered, and the filtered product was suspended in 200 ml of ethanol and heated under reflux. The suspension was filtered, and the filtrate was combined with the above filtrate and concentrated under reduced pressure to obtain 7.08 g of 2-hydroxymethyl-1,4-pentanediol as a colorless oil. IR (neat, cm ^-1 ): 3313,2969,2928,1706,1457,1420,1375,1
091,1050 (3) A mixture of 7.08 g of 2-hydroxymethyl-1,4-pentanediol and 7.3 ml of phosphoric acid (85%) was stirred at 120 ° C for 3 hours. The reaction mixture was allowed to cool to room temperature, water was added, and this was extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to distill the resulting oil under reduced pressure (2-methyltetrahydro-4-furanyl).
2.69 g of methanol was obtained as a colorless oil.

Reference Example 15 3- (Methylaminomethyl) -4-ethyltetrahydrofuran (1) 11.5 g of (3-ethyltetrahydro-4-furanyl) methanol, 16.7 g of tosyl chloride, 9.10 g of triethylamine, 80 ml of tetrahydrofuran The mixture was boiled under reflux for 5 hours. After the reaction, 500m of water
The mixture was discharged to 1 l, extracted with 500 ml of ethyl acetate, washed with water, dried and concentrated under reduced pressure, and the obtained residue was purified by column chromatography (developing solvent; ethyl acetate: hexane = 1: 8). 7.60 g of 3- (tosyloxymethyl) -4-ethyltetrahydrofuran was obtained. (2) 3- (Tosyloxymethyl) -4-ethyltetrahydrofuran 2.50 g, anhydrous potassium carbonate 2.20
g, sodium iodide 0.30 g, methylamine 10 m
A mixture of 1 and 10 ml of ethanol was boiled under reflux for 11 hours. After completion of the reaction, discharge into 2N sodium hydroxide aqueous solution,
It was extracted with methylene chloride, dried, and concentrated under reduced pressure. 3-
2.10 g of (methylaminomethyl) -4-ethyltetrahydrofuran was obtained.

Synthesis of Comparative Compound N-{(tetrahydro-2-furanyl) methyl} -N '
-Methyldichloronitroacetamidine ¹ H NMR (CDCl ₃ , ppm): 1.55-2.15 (4H, m), 2.96-3.24 (3H, br-
d, J = 8.8), 3.26-4.20 (5H, m) IR (neat, cm ^-1 ): 3393,2975,1653,1597,1337,1069,889 Oil N- (4-chlorobenzyl) -N'- Methyldichloronitroacetamidine (compound No. 120 described in JP-A-3-204848) ¹ HNMR (CDCl ₃ , ppm): 7.25 (4H, br-s), 4.54 (2H, br-s), 3.15
(3H, br-s) IR (KBr, cm ^-1 ): 3342,1621,1592,1333,1092,894,774

Next, the composition of the present invention will be specifically described with reference to formulation examples. 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. In addition, a part represents a weight part.

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 a 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 parts of polyvinyl alcohol
% Of 5% aqueous solution was thoroughly mixed with stirring, then 75 parts of 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, carboxymethyl cellulose 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 litura planta The compound of the present invention was made into an acetone solution having a predetermined concentration and sprayed in an amount of 3 ml 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).

[0071]

[Table 1] Comparative compound 1: N-{(tetrahydro-2-furanyl) methyl} -N'-methyldichloronitroacetamidine Comparative compound 2: N- (4-chlorobenzyl) -N'-methyldichloronitroacetamidine (Patent Document 1) 3-204848 publication compound)

Test Example 2 Effect on Resistant Green Leafhopper The compound of the present invention is used as an acetone solution having a predetermined concentration and sprayed in an amount of 3 ml on rice seedlings (about 3 leaf stage) bundled in several pieces. After air-drying, the treated seedlings were covered with a wire netting cylinder, and an organic phosphorus agent and 10 carbamate-resistant leafhopper leafhoppers (10 adult females) were released for 25 times.
It was placed in a thermostatic chamber at 0 ° C. and the mortality was examined 48 hours later. The results are shown in Table 2 (Table 2).

[0073]

[Table 2] Comparative compound 1: N-{(tetrahydro-2-furanyl) methyl} -N'-methyldichloronitroacetamidine

Test Example 3 Effect on green peach aphid A potted eggplant seedling (4 to 5 leaf stage) grown in a greenhouse and infested with green peach aphid was diluted with 20 ml of a 1 ppm emulsion prepared according to Formulation Example 1. I sprayed them one by one.
After the treatment, the seedlings were allowed to stand in a greenhouse and the number of surviving insects was examined 2 days later to determine the mortality rate. The test was performed in duplicate. The results are shown in Table 3 (Table 3).

[0075]

[Table 3] Comparative compound 1: N-{(tetrahydro-2-furanyl) methyl} -N'-methyldichloronitroacetamidine Comparative compound 2: N- (4-chlorobenzyl) -N'-methyldichloronitroacetamidine 3-204848 publication compound)

[0076]

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

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Nobuyuki Kawahara 1144 Togo Togo, Mobara-shi, Chiba Mitsui Toatsu Chemical Co., Ltd.

Claims (2)

[Claims] 1. A compound represented by the general formula (1): [Wherein R ₁ and R ₂ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 5 carbon atoms, and when A is a nitrogen atom, B represents NR ₅ ; When A is NR ₄ , B represents a nitrogen atom (where R ₄ , R
₅ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 5 carbon atoms, an optionally substituted alkenyl group having 2 to 5 carbon atoms, and optionally substituted Represents an alkynyl group having 2 to 5 carbon atoms. ), R ₃ is a hydrogen atom, an optionally substituted C 1-5 alkyl group, an optionally substituted C 2-5 alkenyl group, or an optionally substituted Represents a good alkynyl group having 2 to 5 carbon atoms, X ₁ , X
Each ₂ independently represents a halogen atom. ] (Tetrahydro-3-furanyl) methyl derivative represented by this. 2. An insecticide comprising the (tetrahydro-3-furanyl) methyl derivative represented by the general formula (1) according to claim 1 as an active ingredient.